D'ELIA VALERIO (TH)
ARAYACHUKIAT SUNATDA (TH)
| CLAIMS 1. An epoxide based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i); wherein: X is selected from halide, acetate, benzoate, tetrafluoroborate, hexafluorophosphate, perchlorate, sulphate, nitrate, phosphate, cyanide, and thiocyanate; A is selected from nitrogen or phosphorous; and R1, R2, and R3 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R1, R2, and R3 are taken together to form a heteroaryl ring. 2. The ionic liquid according to claim 1 , wherein X is halide. 3. The ionic liquid according to claim 2, wherein X is chloride . 4. The ionic liquid according to claim 1 , wherein A is phosphorous. 5. The ionic liquid according to claim 1, wherein R1, R2, and R3 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms, linear or branched alkoxy group having 2 to 12 carbon atoms, phenyl, or benzyl. 6. The ionic liquid according to claim 5, wherein R1, R2, and R3 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. 7. The ionic liquid according to claim 6, wherein R1, R2, and R3 are independently selected from linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms. 8. The ionic liquid according to claim 7, wherein R1 is octyl. 9. The ionic liquid according to claim 7, wherein R2 is octyl. 10. The ionic liquid according to claim 7, wherein R3 is octyl. 11. The ionic liquid according to any one of claims 1 to 10, wherein said ionic liquid is trioctyl(oxiran-2-ylmethyl)phosphonium chloride. 12. A demulsifier composition comprising the ionic liquid according to any one of claims 1 to 1 1. 13. A wax removal composition in crude oil production process comprising the ionic liquid according to any one of claims 1 to 1 1. 14. A composition for extracting crude oil from oil sand comprising the ionic liquid according to any one of claims 1 to 1 1. 15. A method for preparing the ionic liquid according to any one of claims 1 to 1 1, comprising a step of reacting an epoxide compound having structure (ii) and a nucleophile compound having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks; wherein: Y is selected from halide, acetate, thioacetate, -toluenesulfonyl, trifluoromethanesulfonyl, linear or branched alkoxy group having 2 to 40 carbon atoms, aryloxy group, alkanoate group having 1 to 5 carbon atoms, or thioether; M is selected from nitrogen or phosphorous; and R4, R5, and R6 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R4, R5, and R6 are taken together to form a heteroaryl ring. 16. The method according to claim 15, wherein the reaction is conducted at the temperature of 25 to 35 °C for 12 to 36 hours. 17. The method according to claim 15, wherein Y is halide. 18. The method according to claim 17, wherein Y is chloride. 19. The method according to claim 15, wherein M is phosphorous. 20. The method according to claim 15, wherein R4, R5, and R6 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms, linear or branched alkoxy group having 2 to 12 carbon atoms, phenyl, or benzyl. 21. The method according to claim 20, wherein R4, R5, and R6 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. 22. The method according to claim 21, wherein R4, R5, and R6 are independently selected from linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms. 23. The method according to claim 22, wherein R4 is octyl. 24. The method according to claim 22, wherein R5 is octyl. 25. The method according to claim 22, wherein R6 is octyl. 26. A demulsification process of crude-oil emulsion in a form of triphasic mixture comprising steps of: a) adding the ionic liquid according to any one of claims 1 to 1 1 into crude-oil emulsion until a concentration of the ionic liquid is in the range of 10 to 50 % v/v; b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least three phases; and c) separating each phase of the mixture. 27. The demulsification process according to claim 26, wherein the concentration of the ionic liquid in step a) is in the range of 10 to 35 % v/v. 28. The demulsification process according to claim 26, wherein step b) is conducted at the temperature of 50 to 80 °C for 0.5 to 2 hours. 29. The demulsification process according to claim 26 further comprises a step of recovering the phase of ionic liquid after conducting step c). 30. The demulsification process according to claim 26, wherein said process is conducted to separate the crude-oil emulsion having water content in the range of 20 to 60 % v/v. 31. A demulsification process of crude-oil emulsion in a form of disposable use comprising steps of: a) adding the ionic liquid according to any one of claims 1 to 11 into crude-oil emulsion until a concentration of the ionic liquid is in the range of 30 to 500 ppm; b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least two phases; and c) separating each phase of the mixture. 32. The demulsification process according to claim 31, wherein the concentration of the ionic liquid in step a) is in the range of 30 to 300 ppm. 33. The demulsification process according to claim 31, wherein step b) is conducted at the temperature of 50 to 80 °C for 0.5 to 2 hours. 34. The demulsification process according to claim 31, wherein said process is conducted to separate the crude-oil emulsion having water content in the rage of 20 to 60 % v/v. 35. A process of wax removal from petroleum well fluid comprising steps of: a) contacting the ionic liquid according to any one of claims 1 to 11 to petroleum well fluid, wherein a concentration of the ionic liquid is in the range of 10 to 50 % v/v; b) transferring the mixture obtained from step a) into dehydration tank and setting the mixture aside for 0.5 to 2 hours until the mixture is separated into at least three phases; and c) separating each phase of the mixture. 36. The process of wax removal according to claim 35, wherein the concentration of the ionic liquid in step a) is in the range of 10 to 30 % v/v. 37. The process of wax removal according to claim 35, wherein said process further comprises a step of separating gaseous phase from the mixture of the petroleum well fluid and the ionic liquid in step a) prior to conducting step b). 38. The process of wax removal according to claim 35, wherein step b) is conducted at the temperature of 35 to 90 °C. 39. The process of wax removal according to claim 35 further comprises a step of recovering the phase of ionic liquid after conducting step c). 40. A process for extracting crude oil from oil sand comprising steps of: a) contacting the ionic liquid according to any one of claims 1 to 11 to crude oil sand inside petroleum production well, wherein a concentration of the ionic liquid is in the range of 10 to 70 % v/v; b) mixing the obtained mixture and setting the mixture aside for 1 to 5 hours until the mixture is separated into at least three phases; and c) separating each phase of the mixture. 41. The process for extracting crude oil from oil sand according to claim 40, wherein the concentration of the ionic liquid in step a) is in the range of 50 to 70 % v/v. 42. The process for extracting crude oil from oil sand according to claim 40, wherein said process further comprises a step of separating gaseous phase from the mixture of the crude oil sand and the ionic liquid in step a) prior to conducting step b). 43. The process for extracting crude oil from oil sand according to claim 40, wherein step b) is conducted at the temperature of 35 to 80 °C. 44. The process for extracting crude oil from oil sand according to claim 40 further comprises a step of recovering the phase of ionic liquid after conducting step c). 45. A use of the ionic liquid according to any one of claims 1 to 11 in a demulsification process of crude-oil emulsion in a form of triphasic mixture. 46. A use of the ionic liquid according to any one of claims 1 to 11 in a demulsification process of crude-oil emulsion in a form of disposable use. 47. A use of the ionic liquid according to any one of claims 1 to 11 for a process of wax removal from from petroleum well fluid. 48. A use of the ionic liquid according to any one of claims 1 to 1 1 for extracting crude oil from oil sand. |
FIELD OT THE INVENTION
The present invention relates to the field of chemistry, in particular, to an epoxide based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid.
BACKGROUND OF THE INVENTION
Crude oil is liquid petroleum containing mixed hydrocarbon compounds as its main compositions. In addition, it may contain other compounds such as water, petroleum wax, asphalt, sulphur (S), nitrogen (N), oxygen (O), etc. Therefore, the crude oil obtained through drilling cannot be used immediately, but needed to be separated of each hydrocarbon prior to the utilization.
Crude-oil emulsion is crude oil having water drops distributed inside said crude oil. The crude-oil emulsion can be formed as water-in-oil emulsion (W/O emulsion), oil-in-water emulsion (O/W emulsion), and other complex emulsions. This crude-oil emulsion can be found in every step of petroleum process, from drilling, refining, producing, transporting, etc. Therefore, in order to obtain good quality crude oil, it is necessary to remove water from the crude oil.
Petroleum wax is derived from high molecular weight hydrocarbons as complex mixtures of both linear and branched hydrocarbons. Normally, there are about 3 to 44 % of said complex mixtures in the crude oil. When the temperature of the crude oil reduces to one certain point, said complex mixtures will change their phase into solid wax and accumulate in the petroleum production process, such as production pipe or transportation pipe, which causes a reduction of flow rates of the petroleum fluid in the pipes. Therefore, the removal of wax from the crude oil or the prevention of wax formation in the pipe is very necessary in the petroleum industry.
The use of chemical compounds in demulsification, and removal and/or prevention of the wax formation is the well-known technique in petroleum industry because it is the low cost technique and can be operated easily and efficiency. The ionic liquid is the chemical compound comprising group(s) of organic cation binding to group(s) of anion that can be organic or inorganic molecule. Owning to various structures of the ionic liquid, the ionic liquid can have many properties such as increasing the solubility of many solutions. Therefore, the ionic liquid is a promising compound to be applied for the petroleum industry.
From literature reviews, the demulsification of the crude-oil emulsion by the ionic liquid has been disclosed in several following documents.
US 2014/0360920 A1 discloses a process for separating water-in-oil emulsion of the crude oil using the ionic liquid derived from amino acid, such as methane sulfonate of alkyl amino acid ester having 8 to 22 carbon atoms. The process could be conducted by adding said ionic liquid in which the concentration of the ionic liquid was between 50 to 150 ppm followed by mixing the mixture at the temperature about 25 to 80 °C. The mixture was set aside to be separated for at least 24 hours. However, the demulsification process according to the disclosure needed a long separation time.
US 201 1/0186515 A1 discloses the demulsification process of water-in-oil emulsion using the ionic liquid that can be selected from alkylpyrimidium, 1,3-dialkyl-imidazolium, 1,2,3-trialkyl-imidazolium, 1 , 1 -dialkyl-piperidine, and 1 , 1 -dialkyl-pyrrolidinium. Said demulsification process of water-in-oil emulsion could be done by mixing said ionic liquid into emulsion, heating at about 90 to 120 °C at 0.5 to 200 bars in order to separate water from oil. Nevertheless, said process needed higher temperature and pressure, which required higher cost than the process without the need of temperature and pressure.
CN 107286976 B discloses a use of ionic liquid for separating water from the crude oil. Such ionic liquid is N- alkyl trimethylammonium bromide or N- alkyl trimethylammonium chloride. However, the disclosed method for preparing the ionic liquid was complicated because it comprised many steps of reaction and purification.
WO 2017/099706 A1 discloses a demulsification composition for separating water from the cmde oil in the petroleum well. The demulsification composition comprises alkanolamide, alkoxylated alcohol, and amine-oxide. However, due to each complex structure of the ionic liquid in said composition, the preparation process of each ionic liquid was complicated and needed many steps.
However, although there have been several disclosures of the ionic liquid, the disclosed ionic liquid in those documents needs a long operational time for demulsification and may need heat and pressure in their processes which increase the operational cost. Moreover, the above method to prepare the ionic liquids are complicate. Therefore, there is still a need to obtain the ionic liquid with good efficiency, which can be prepared by simple method, is environmental friendly, and is suitable for the demulsification process of crude- oil emulsion. For all reasons above, this invention provides an epoxide based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid in the demulsification process, wax removal process, and process for extracting crude oil from oil sand of said ionic liquid.
SUMMARY OF INVENTION
In one embodiment, this invention relates to an epoxide based ionic liquid for demulsification of water- in-oil emulsion (W/O emulsion) having structure (i);
wherein:
X is selected from halide, acetate, benzoate, tetrafluoroborate, hexafluorophosphate, perchlorate, sulphate, nitrate, phosphate, cyanide, and thiocyanate; A is selected from nitrogen or phosphorous; and
R 1 , R 2 , and R 3 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R 1 , R 2 , and R 3 are taken together to form a heteroaryl ring. In another embodiment, this invention relates to a method for preparing the epoxide based ionic liquid according to the present invention comprising a step of reacting an epoxide compound having structure (ii) and a nucleophile compound having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks; wherein:
Y is selected from halide, acetate, thioacetate, -toluenesulfonyl, trifluoromethanesulfonyl, linear or branched alkoxy group having 2 to 40 carbon atoms, aryloxy group, alkanoate group having 1 to 5 carbon atoms, or thioether;
M is selected from nitrogen or phosphorous; and
R 4 , R 5 , and R 6 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R 4 , R 5 , and R 6 are taken together to form a heteroaryl ring.
In another embodiment, this invention relates to a demulsification process of crude- oil emulsion in a form of triphasic mixture comprising steps of: a) adding the ionic liquid according to the present invention into crude-oil emulsion until a concentration of the ionic liquid is in the range of 10 to 50 % v/v;
b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least three phases; and
c) separating each phase of the mixture. In another embodiment, this invention relates to a demulsification process of crude- oil emulsion in a form of disposable use comprising steps of: a) adding the ionic liquid according to the present invention into crude-oil emulsion until a concentration of the ionic liquid is in the range of 30 to 500 ppm; b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least two phases; and
c) separating each phase of the mixture.
In another embodiment, this invention relates to a process of wax removal from petroleum well fluid comprising the step of: a) contacting the ionic liquid according to the present invention to petroleum well fluid, wherein a concentration of the ionic liquid is in the range of 10 to 50 % v/v;
b) transferring the mixture obtained from step a) into dehydration tank and setting the mixture aside for 0.5 to 2 hours until the mixture is separated into at least three phases; and
c) separating each phase of the mixture.
In another embodiment, this invention relates to a process for extracting crude oil from oil sand comprising the step of: a) contacting the ionic liquid according to the present invention to crude oil sand inside petroleum production well, wherein a concentration of the ionic liquid is in the range of 10 to 70 % v/v;
b) mixing the obtained mixture and setting the mixture aside for 1 to 5 hours until the mixture is separated into at least three phases; and
c) separating each phase of the mixture.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a crude-oil emulsion separation of (a) ionic liquid of Sample 1 after about 5 minutes, (b) ionic liquid of Sample 1 after about 2 hours, (c) ionic liquid of Sample 8 after about 2 hours, and (d) ionic liquid of Sample 11 after about 2 hours.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an epoxide based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid, in which will be described according to embodiments as the detailed description and drawings show in the following. Any aspect being described here is meant to include the application to the other aspects of this invention, unless stated otherwise.
Definition
Technical terms or scientific terms used here have definitions as by person skilled in the art unless stated otherwise.
Any tools, equipment, methods, or chemicals named here mean tools, equipment, methods, or chemicals being used commonly by person skilled in the art unless stated otherwise that they are tools, equipment, methods, or chemicals specific only in this invention. Use of singular noun or singular pronoun with “comprising” in claims or specification means“one” and including“one or more,”“at least one,” and“one or more than one” too.
All compositions and/or methods disclosed and claims in this application aim to cover embodiments from any action, performance, modification, or adjustment without any experiment that significantly different from this invention, and obtain with obj ect with utility and resulted as same as the present embodiment according to person ordinary skilled in the art although without specifically stated in claims. Therefore, substitutable or similar object to the present embodiment, including any little modification or adjustment that clearly seen by person skilled in the art should be construed as remains in spirit, scope, and concept of invention as appeared in appended claims.
Throughout this application, term“about” means any number that appeared or showed here that could be varied or deviated from any error of equipment, method, or personal using said equipment or method.
Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.
In one embodiment, this invention relates to an epoxide based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i); wherein:
X is selected from halide, acetate, benzoate, tetrafluoroborate, hexafluorophosphate, perchlorate, sulphate, nitrate, phosphate, cyanide, and thiocyanate; A is selected from nitrogen or phosphorous; and
R 1 , R 2 , and R 3 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R 1 , R 2 , and R 3 are taken together to form a heteroaryl ring. In a preferred exemplary embodiment, X is halide. More preferably, X is chloride.
In a preferred exemplary embodiment, A is phosphorous.
In another exemplary embodiment, R 1 , R 2 , and R 3 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms, linear or branched alkoxy group having 2 to 12 carbon atoms, phenyl, or benzyl. In a preferred exemplary embodiment, R 1 , R 2 , and R 3 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. More preferably, R 1 , R 2 , and R 3 are independently selected from linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms.
In another exemplary embodiment, R 1 is octyl. In another exemplary embodiment, R 2 is octyl.
In another exemplary embodiment, R 3 is octyl. In another exemplary embodiment, said ionic liquid is trioctyl (oxiran-2- ylmethyl)phosphonium chloride.
In another embodiment, this invention relates to a demulsifier composition comprising the ionic liquid according to the present invention. In another embodiment, this invention relates to a wax removal composition in crude oil production process comprising the ionic liquid according to the present invention.
In another embodiment, this invention relates to a composition for extracting crude oil from oil sand comprising the ionic liquid according to the present invention.
In another embodiment of the invention, this invention relates to a method for preparing the epoxide based ionic liquid according to the present invention comprising a step of reacting an epoxide compound having structure (ii) and a nucleophile compound having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks;
wherein: Y is selected from halide, acetate, thioacetate, y?-toluenesulfonyl, trifluoromethanesulfonyl, linear or branched alkoxy group having 2 to 40 carbon atoms, aryloxy group, alkanoate group having 1 to 5 carbon atoms, or thioether;
M is selected from nitrogen or phosphorous; and
R 4 , R 5 , and R 6 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 40 carbon atoms, linear or branched alkoxy group having 2 to 40 carbon atoms, aromatic with or without substituted group, or R 4 , R 5 , and R 6 are taken together to form a heteroaryl ring. In a preferred exemplary embodiment, the reaction is conducted at the temperature of 25 to 35 °C for 12 to 36 hours.
In a preferred exemplary embodiment, Y is halide. More preferably, Y is chloride.
In a preferred exemplary embodiment, M is phosphorous.
In another exemplary embodiment, R 4 , R 5 , and R 6 are independently selected from hydrogen, linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms, linear or branched alkoxy group having 2 to 12 carbon atoms, phenyl, or benzyl.
In a preferred exemplary embodiment, R 4 , R 5 , and R 6 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. More preferably, R 4 , R 5 , and R 6 are independently selected from linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms.
In another exemplary embodiment, R 4 is octyl.
In another exemplary embodiment, R 3 is octyl.
In another exemplary embodiment, R 6 is octyl.
In another embodiment of the invention, this invention relates to a demulsification process of crude-oil emulsion in a form of triphasic mixture comprising steps of: a) adding the ionic liquid according to the present invention into crude-oil emulsion until a concentration of the ionic liquid is in the range of 10 to 50 % v/v;
b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least three phases; and
c) separating each phase of the mixture.
In another exemplary embodiment, the concentration of the ionic liquid in step a) is in the range of 10 to 35 % v/v.
In another exemplary embodiment, step b) is conducted at the temperature of 50 to
80 °C for 0.5 to 2 hours. In another exemplary embodiment, the demulsification process according to the present invention further comprises a step of recovering the phase of ionic liquid after conducting step c).
In another exemplary embodiment, said process is conducted to separate the crude- oil emulsion having water content in the range of 20 to 60 % v/v.
In another embodiment of the invention, this invention relates to a demulsification process of crude-oil emulsion in a form of disposable use comprising steps of: a) adding the ionic liquid according to the present invention into crude-oil emulsion until a concentration of the ionic liquid is in the range of 30 to 500 ppm; b) mixing the obtained mixture at the temperature of 35 to 80 °C and holding said temperature for 5 minutes to 2 hours until the mixture is separated into at least two phases; and c) separating each phase of the mixture.
In another exemplary embodiment, the concentration of the ionic liquid in step a) is in the range of 30 to 300 ppm.
In another exemplary embodiment, step b) is conducted at the temperature of 50 to 80 °C for 0.5 to 2 hours.
In another exemplary embodiment, said process is conducted to separate the crude- oil emulsion having water content in the rage of 20 to 60 % v/v. In another embodiment of the invention, this invention relates to a process of wax removal from petroleum well fluid comprising steps of: a) contacting the ionic liquid according to the present invention to petroleum well fluid, wherein a concentration of the ionic liquid is in the range of 10 to 50 % v/v; b) transferring the mixture obtained from step a) into dehydration tank and setting the mixture aside for 0.5 to 2 hours until the mixture is separated into at least three phases; and c) separating each phase of the mixture.
In another exemplary embodiment, the concentration of the ionic liquid in step a) is in the range of 10 to 30 % v/v.
In another exemplary embodiment, said process further comprises a step of separating gaseous phase from the mixture of the petroleum well fluid and the ionic liquid in step a) prior to conducting step b).
In another exemplary embodiment, step b) is conducted at the temperature of 35 to
90 °C.
In another exemplary embodiment, the process of wax removal according to the present invention further comprises a step of recovering the phase of ionic liquid after conducting step c).
In another embodiment of the invention, this invention relates to a process for extracting crude oil from oil sand comprising steps of: a) contacting the ionic liquid according to the present invention to crude oil sand inside petroleum production well, wherein a concentration of the ionic liquid is in the range of 10 to 70 % v/v; b) mixing the obtained mixture and setting the mixture aside for 1 to 5 hours until the mixture is separated into at least three phases; and c) separating each phase of the mixture. In another exemplary embodiment, the concentration of the ionic liquid in step a) is in the range of 50 to 70 % v/v.
In another exemplary embodiment, said process further comprises a step of separating gaseous phase from the mixture of the crude oil sand and the ionic liquid in step a) prior toconducting step b). In another exemplary embodiment, step b) is conducted at the temperature of 35 to
80 °C. In another exemplary embodiment, the process for extracting crude oil from oil sand according to the present invention further comprises a step of recovering the phase of ionic liquid after conducting step c).
In another embodiment, this invention relates to a use of the ionic liquid according to the present invention in a demulsification process of crude-oil emulsion in a form of triphasic mixture.
In another embodiment, this invention relates to a use of the ionic liquid according to the present invention in a demulsification process of crude-oil emulsion in a form of disposable use. In another embodiment, this invention relates to a use of the ionic liquid according to the present invention for a process of wax removal from petroleum well fluid.
In another embodiment, this invention relates to a use of the ionic liquid according to the present invention for extracting crude oil from oil sand.
For the better understanding of the invention, examples of the ionic liquid according to the present invention will be shown, in which the following examples are for demonstrating of the embodiment of this invention only, not for limitation of the scope of this invention.
Example 1: A synthesis of the epoxide based ionic liquid according to the present invention Trioctyl(oxiran-2-ylmethyl)phosphonium chloride ionic liquid (Sample 1) having structure (iv) was prepared by the reaction between epichlorohydrin and trioctylphosphine having the equimolar- amount at the temperature about 20 to 30 °C for about 1 day.
Example 2 to 14: The synthesis of comparative ionic liquid
Comparative Samples 2 to 14 of the ionic liquid were prepared by adding of epichlorohydrin (about 0.5 mole) into round bottom flask. Then, phenol was added at about 1 % mole of the epichlorohydrin and tetrabutylammonium iodide was added at about 2 % mole of the epichlorohydrin into the round bottom flask containing epichlorohydrin. The reaction mixture reacted with CO 2 (1 bar using balloon) at room temperature for about 10 days. The obtained product was purified by column chromatography.
The product obtained from the above step reacted with the compounds according to
Table 1 at the temperature about 60 °C for about 2 weeks in order to obtain the comparative Samples 2 to 14.
Properties of the ionic liquid
The properties of the ionic liquids according to Samples 1 to 14 were tested for water solubility and density. Moreover, titration of said ionic liquid Samples with the silver nitrate solution (AgNO 3 ) was investigated in order to evaluate whether or not the ionic liquid was obtained from the synthesis. The results are shown in Table 2. Table 1: Compounds used in the synthesis of comparative Sample 2 to 14
Table 2: Properties of the ionic liquid
As shown in Table 2, Samples 4, 12, and 14 provided negative results when titrated with silver nitrate solution because ionic liquids were not obtained from the reactions. Therefore, Samples 4, 12, and 14 were not subject to further tests. Moreover, Samples 2 to 7 were water soluble, not suitable for using in a demulsification process, and were not subject to further tests. Therefore, only Samples 1, 8 to 11, and 13 were subject to tests for the efficiency of the separation of water from crude oil.
An efficiency of the separation of water from crude oil sample
The ionic liquid samples were investigated for the separation of water from crude oil sample. The crude oil about 100 mL was added into test bottle and was heated up to about 60 °C. Then, about 10 mL of each ionic liquid sample was added into the crude oil sample. The controlled sample was the crude oil without adding the ionic liquid. The mixture samples of crude oil and ionic liquid were shaken at about 240 rpm for about 2 minutes and were left in the water bath at the temperature about 60 °C for about 2 hours. The amount of water and oil was recorded at about 5, 10, 15, 30, 60, and 120 minutes. The efficiency of the ionic liquid according to this invention was compared to the commercial reagent (EPT).
After the demulsification test, the water content in oil phase (WC) was analyzed by adding about 10 mL of the oil phase from the test bottle into about 50 mL of the testing solution. The testing solution could be prepared by dropping about 1 to 2 drops of about 25 % v/v of the commercial demulsifier solution (F46) into about 50 mL of toluene. Then, the mixture of crude oil and testing solution was heated at about 60 °C until the mixture was uniformed, and said temperature was hold for about 3 to 5 minutes. The obtained mixture was centrifuged at the temperature about 40 °C at about 550 rpm for about 3 minutes in order to separate water from oil. Then, the separated water at the bottom was measured.
Table 3: Content of water, emulsion, and water content in oil phase
Note:
- Controlled sample 1 was crude oil without addition of the ionic liquid for controlling the negative result.
- Controlled sample 2 was crude oil subject to the addition of the commercial reagent (EPT) for controlling the positive result.
As shown in Table 3, the ionic liquid according to the present invention (Sample 1) had a better efficiency to separate water from oil than the commercial reagent (EPT). The separation of water from oil using Sample 1 was done within about 5 minutes. There was no water found in the obtained oil phase from the separation. Moreover, although comparative Sample 8 and 1 1 could separate water from oil, but they took longer time and lower efficiency than the ionic liquid according to the present invention (Sample 1). When considering Figure 1, it was found that the ionic liquid of Sample 1 (Figure 1 (a) and (b)) could form the triphasic mixture whereas other comparative samples such as Samples 8 and 11 (Figure 1 (c) and (d)) did not show the triphasic mixture. The formation of the triphasic mixture provided an advantage because the phase of ionic liquid could easily be separated from the system in order to be recovered. Moreover, the ionic liquid according to the present invention from the triphasic mixture was separated and used in the demulsification of the crude oil again without any purification process. The results were shown in Table 4. It was found that the ionic liquid according to the present invention could be reused without needed of the purification process, wherein the separation efficiency of the ionic liquid was slightly decreasing (when comparing to the ionic liquid subjected to the purification process prior to the reuse).
Table 4: Content of water, emulsion, and water content in oil phase
Apart from the demulsification of the triphasic mixture, the ionic liquid of Sample 1 was also tested for the separation of water from crude oil sample as the disposable use reagent. Said testing could be conducted by adding about 100 mL of crude oil sample into test bottle and 30 and 300 ppm of ionic liquid of Sample 1 were added into crude oil sample. The mixture between crude oil and ionic liquid was shaken at about 230 rp for about 5 minutes. Then, the mixture was set aside in the water bath at the temperature about 60 °C for about 2 hours. The water separated (WS) content was recorded at 2 hours. The water content in oil phase (WC) after the demulsification was analyzed by the method described above. The separation efficiency (E) was calculated from the total water content (TWC): wherein,
Total water content (TWC) = WS + [(100 - WS) / 100] x WC, and
Separation efficiency (E) = (WS / TWC) x 100.
As shown in Table 5, it was found that the ionic liquid according to the present invention could be applied as a disposable use reagent in the demulsification of water-in-oil crude oil emulsion effectively.
Table 5: Separation efficiency of the ionic liquid as the disposable use reagent
A wax removal from the crude oil could also be conducted by contacting the ionic liquid according to the present invention at the concentration of the ionic liquid in the range of about 10 to 50 % v/v by the addition of the ionic liquid according to the present invention into petroleum production well to contact with the well fluid. The obtained mixture was then transferred via the production tube to the wellhead and then further transferred to a gas separation tank. The obtained mixture from the gas separation tank was then transferred via the flowline to the dehydration tank for about 0.5 to 2 hours until the mixture was separated into at least three phases. Then, each phase of liquid was separated and the ionic liquid was recovered for further use. Said operation provided the following technical result such as said ionic liquid increased the solubility of the wax in crude oil and prevented the accumulation of the wax in the production pipe and avoided the clogging of the pipe from the wax.
An extraction of crude oil from the oil sand using the ionic liquid could also be conducted by the addition of the ionic liquid according to the present invention at the concentration of the ionic liquid in the range of about 10 to 70 % v/v to mix with crude oil sand in the petroleum production well. Then, the mixture was mixed and set aside for about 1 to 5 hours until the mixture was separated into at least three phases. Then the mixture was separated and the ionic liquid was recovered for further use.
BEST MODE OF THE INVENTION Best mode or preferred embodiment of the invention is as provided in the description of the invention.