Cashew Nutshell Liquid Alkoxylate Carboxylate as a New Renewable Surfactant Composition for Enhanced Oil Recovery Applications

Abstract

The present invention contains methods, of making a cashew nutshell liquid alkoxylate carboxylate surfactant by alkoxylation of a natural alkylphenol using propylene oxide (PO) and/or ethylene oxide (EO) followed by a carboxymethylation reaction. The cashew nutshell liquid alkoxylate sulfate surfactant of the present invention is made by a facile and cost effective method. The natural hydrophobe surfactant of the present invention find uses in EOR applications where it is used for solubilization and mobilization of oil optionally containing asphaltene, wax, naphthenate, and for environmental cleanup. Another advantage is that the composition is a renewable based surfactant that is non-toxic and biodegradable.

Claims

1.-24. (canceled)

25. A composition of formula (I) ##STR00005## wherein R is aliphatic hydrocarbon with 15 C-atoms having 1 to 3 double bonds or being saturated, A is CH.sub.2COOM n is a number from 1 to 70, m from 1 to 150, and M is a counter ion to the carboxylate group.

26. The composition according to claim 25, wherein n is a number from 2 to 60.

27. The composition according to claim 25, wherein m is a number from 2 to 140.

28. The composition of claim 25, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 21, 22, 23, 24, 25, 28, 30, 35, 40, 45, 50, 55, 60, 65 or 70.

29. The composition of claim 25, wherein m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 21, 22, 23, 24, 25, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 110, 120, 130, 140 or 150.

30. The composition of claim 25, wherein n is 30 to 40, and m is 15 to 25.

31. The composition of claim 25, wherein M is selected from the group consisting of H, Li, Na, K, Mg, Ca, Sr, and NH.sub.4.

32. The composition of claim 25, wherein of all residues R, 35-45 molar % are tri-unsaturated, 18-28 molar % are di-unsaturated, 30-40 molar % are mono-unsaturated and 0-4 molar % are saturated.

33. A method of making a composition of formula (I) ##STR00006## wherein R is aliphatic hydrocarbon with 15 C-atoms having 1 to 3 double bonds or being saturated, A is CH.sub.2COOM n is a number from 1 to 70, m from 1 to 150, and M is a counter ion to the carboxylate group, comprising the steps of alkoxylating a cashew nutshell liquid comprising Cardanol with 1 to 70 moles of propylene oxide and 1 to 150 moles of ethylene oxide in the presence of a basic catalyst, and subsequently carboxymethylating the alkoxylated Cardanol.

34. The method of claim 33, wherein carboxymethylation is effected by reacting the alkoxylated Cardanol with chloroacetic acid.

35. The method of claim 33, wherein the basic catalyst is KOH, NaOH, NaOMe, LiOH, NH.sub.4OH, SrOH.sub.2, CaOH.sub.2 or any combination thereof.

36. The method of claim 33, wherein the number of ethylene oxide units is 15 to 25, and the number of propylene oxide units is 30 to 40.

37. The method of claim 36, comprising the steps of: propoxylating the Cardanol with propylene oxide (PO) in the presence of KOH or any other suitable alkaline catalyst to form a propoxylated Cardanol, wherein the mole ratio of the Cardanol:PO is 1:(30 to 40); ethoxylating the propoxylated Cardanol with ethylene oxide (EO) in the presence of KOH or any other alkaline catalyst to form a Cardanol-PO-EO, wherein the mole ratio of the Cardanol-PO:EO is 1:(15 to 25); and carboxymethylating the Cardanol-PO-EO by a chloroacetic acid, or its salts, carboxymethylation process to make the Cardanol alkoxy carboxylate surfactant having the formula Cardanol-PO-EO-CH.sub.2COO-M.

38. A composition comprising at least one composition according to claim 25, one or more alkalinity generating agents, and a solvent, wherein the at least one composition and the one or more alkalinity generating agents are dissolved in the solvent.

39. The composition of claim 38, wherein the one or more alkalinity generating agents comprise alkaline earth metal hydroxides, NaOH, NaOMe, LiOH, KOH, NH.sub.4OH, Na.sub.2CO.sub.3, NaHCO.sub.3, NaOAc, CaCO.sub.3, Na-metaborate, Na-silicate, Na-orthosilicate, EDTANa.sub.4, other polycarboxylates or any combinations thereof.

40. The composition of claim 38, wherein the solvent comprises water, hard brine, hard water, polymer containing solutions, gas foam or any combinations thereof.

41. The composition of claim 38, wherein the composition contains from 0.1 to 5 wt.-% alkalinity generating agents.

42. A method of enhanced oil recovery (EOR) from a hydrocarbon bearing formation comprising the steps of: injecting a composition of formula (I) ##STR00007## wherein R is aliphatic hydrocarbon with 15 C-atoms having 1 to 3 double bonds or being saturated, A is CH.sub.2COOM n is a number from 1 to 70, m from 1 to 150, and M is a counter ion to the carboxylate group into the hydrocarbon bearing formation at a temperature from 25 to 150 C., wherein the composition is present in water, hard water or hard brine, and further comprises more than 0.05 wt.-% of one or more alkalinity generating agents; and injecting a polymer solution or a gas foam to recover the oil.

43. The method of claim 42, wherein the one or more alkalinity generating agents comprise alkali earth metal hydroxides, NaOH, NaOMe, LiOH, KOH, NH.sub.4OH, Na.sub.2CO.sub.3, NaHCO.sub.3, NaOAc, CaCO.sub.3, Na-metaborate, Na-silicate, Na-orthosilicate, EDTANa.sub.4, other polycarboxylates or any combinations thereof.

44. The method of claim 42, wherein the hydrocarbon bearing formation comprises one or more paraffin based crude oils, asphaltene based crude oils, naphthenate based crude oils or combinations and mixtures thereof.

Description

EXAMPLES

[0128] Percentages are weight percent unless noted otherwise.

TABLE-US-00001 TABLE 1 Cardanol + PO + EO + Carboxylate mole chloroacetic acid sodium salt per Sample # mole PO mole EO Cardanol-PO-EO mole 1 35 20 1.1 2 35 30 1.1 3 35 40 1.1 4 35 50 1.1 5 10 10 1.1 6 10 20 1.1 7 20 10 1.1 8 20 20 1.1 9 50 20 1.1 10 50 30 1.1 11 50 50 1.1 12 50 70 1.1 13 50 100 1.1 14 50 150 1.1 15 75 75 1.1 16 (C) 0 5 1.1 17 (C) 0 10 1.1 18 (C) 7 0 1.1 19 (C) 10 0 1.1

[0129] The alkoxylates 18 and 19 turned out to be insoluble in water. They will transfer only into the oil phase and do not contribute to the microemulsion.

TABLE-US-00002 TABLE 2 Microemulsion phase behavior of 2% sample 1 NaCl Concentration Oil Solubilization Oil Solubilization (wt %) (cc/cc) OIL (cc/cc) WATER 0 1 2 2 4 3 6 6 8 10 10 18 80 12 35 35 14 50 8 16 4 18 3 20 2

TABLE-US-00003 TABLE 3 Microemulsion phase behavior with 2% alkaline generating agent sodium hydroxyde of 2% sample 1 NaCl Concentration Oil Solubilization Oil Solubilization (wt %) (cc/cc) OIL (cc/cc) WATER 0 5 2 8 4 12 6 16 8 25 10 45 92 12 71 67 14 37 16 8 18 4 20 1

TABLE-US-00004 TABLE 4 Microemulsion phase behavior of 2% sample 16 NaCl Concentration Oil Solubilization Oil Solubilization (wt %) (cc/cc) OIL (cc/cc) WATER 0 0 2 0 4 0 1 6 0 3 8 0 6 10 0 6 12 0 6 14 2 6 16 5 4 18 4 20 1

[0130] The IFT calculated from Chun-Huh's formula as previously described is as follows

[0131] Sample 1 without alkali

[00004]${}_0=\frac{V_O}{V_S}.Math.\left({\mathrm{cm}}^3.Math.\text{/}.Math.{\mathrm{cm}}^3\right)=0.3/{35}^2=2.449{10}^{-4}$
.sub.0=1.6610.sup.4Sample 1 with alkali

.sub.0=0.312Sample 16 without alkali

[0132] A .sub.0 of 10.sup.3 or less is considered to be ultra low IFT.

[0133] In general, a solubilization ratio of 10 cc/cc of oil in the microemulsion phase or higher is regarded as reflecting a system with ultra-low IFT.

BRIEF DESCRIPTION OF THE DRAWINGS

[0134] FIG. 1 is a solubilization plot for the system comprising 0.15% C.sub.15-17 ABS (Alkylbenzenesulfonic acid salt), 0.15% cardanol-35PO-20EO Sulfate, 0.15% Butylglycol.