WO2020162841A2 - A cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid - Google Patents
A cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid Download PDFInfo
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- WO2020162841A2 WO2020162841A2 PCT/TH2020/000003 TH2020000003W WO2020162841A2 WO 2020162841 A2 WO2020162841 A2 WO 2020162841A2 TH 2020000003 W TH2020000003 W TH 2020000003W WO 2020162841 A2 WO2020162841 A2 WO 2020162841A2
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- Prior art keywords
- ionic liquid
- mixture
- carbon atoms
- linear
- oil
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 92
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 12
- 239000010779 crude oil Substances 0.000 claims abstract description 81
- 230000008569 process Effects 0.000 claims abstract description 62
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 37
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 19
- -1 tetrafluoroborate Chemical group 0.000 claims abstract description 17
- 239000003027 oil sand Substances 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Chemical group SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000010452 phosphate Chemical group 0.000 claims abstract description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 87
- 239000012071 phase Substances 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000003208 petroleum Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 150000004820 halides Chemical group 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000007762 w/o emulsion Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001805 chlorine compounds Chemical group 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012038 nucleophile Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- DUYAAUVXQSMXQP-UHFFFAOYSA-M thioacetate Chemical group CC([S-])=O DUYAAUVXQSMXQP-UHFFFAOYSA-M 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 14
- 239000001993 wax Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012169 petroleum derived wax Substances 0.000 description 2
- 235000019381 petroleum wax Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KNYXMWUJWMQBMZ-UHFFFAOYSA-M [Cl-].C(CCCCCCC)[P+](CC1OC(OC1)=O)(CCCCCCCC)CCCCCCCC Chemical compound [Cl-].C(CCCCCCC)[P+](CC1OC(OC1)=O)(CCCCCCCC)CCCCCCCC KNYXMWUJWMQBMZ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Definitions
- the present invention relates to the field of chemistry, in particular, to a cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid.
- 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.
- W/O emulsion water-in-oil emulsion
- O/W emulsion oil-in- water emulsion
- 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.
- 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.
- 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 l,l-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.
- ionic liquid is N- alkyl trimethylammonium bromide or N- alkyl trimethylammonium chloride.
- 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 crude oil in the petroleum well.
- the demulsification composition comprises alkanolamide, alkoxylated alcohol, and amine-oxide.
- the preparation process of each ionic liquid was complicated and needed many steps.
- 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.
- the above method to prepare the ionic liquids are complicate.
- 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.
- this invention relates to a cyclic carbonate based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i);
- X is selected from halide, acetate, benzoate, tetrafluoroborate, hexafluorophosphate, perchlorate, sulphate, nitrate, phosphate, cyanide, and thiocyanate;
- A is selected from nitrogen or phosphorous
- 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 , andR 3 are taken together to form a heteroaryl ring.
- this invention relates to a method for preparing the cyclic carbonate based ionic liquid according to the present invention comprising steps of: a) preparing a cyclic carbonate compound by reacting an epoxide compound having structure (ii) with carbon dioxide in the presence of a catalyst selected from phenolic compound, metal halide salt, imidazolium catalyst, ammonium catalyst, phosphonium catalyst, or a mixture thereof at a carbon dioxide pressure of 1 to 10 bars, temperature of 25 to 85 °C for 2 to 10 hours;
- 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; b) reacting the product obtained from step a) with a nucleophile having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks;
- M is selected from nitrogen or phosphorous
- 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 , andR 6 are taken together to form a heteroaryl ring.
- 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 from 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
- 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;
- 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;
- step 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;
- 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;
- Figure 1 shows a crude-oil emulsion separation of (a) ionic liquid of Sample 7 after about 2 minutes, (b) ionic liquid of Sample 10 after about 2 hours, (c) ionic liquid of Sample 12 after about 2 hours.
- the present invention relates to a cyclic carbonate 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.
- Amy aspect being described here is meant to include the application to the other aspects of this invention, 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.
- 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 object 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.
- 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.
- this invention relates to a cyclic carbonate based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i);
- X is selected from halide, acetate, benzoate, tetrafluoroborate, hexafluorophosphate, perchlorate, sulphate, nitrate, phosphate, cyanide, and thiocyanate;
- A is selected from nitrogen or phosphorous
- 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 , andR 3 are taken together to form a heteroaryl ring.
- X is halide. More preferably, X is chloride.
- A is phosphorous
- R 1 , R 2 , andR 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.
- 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.
- R 1 is octyl
- R 2 is octyl.
- R 3 is octyl.
- said ionic liquid is trioctyl ((2-oxo- 1,3 -dioxolan- 4-yl)methyl)phosphonium chloride.
- 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.
- this invention relates to a composition for extracting crude oil from oil sand comprising the ionic liquid according to the present invention.
- this invention relates to a method for preparing the cyclic carbonate based ionic liquid according to the present invention comprising steps of: a) preparaing a cyclic carbonate compound by reacting an epoxide compound having structure (ii) with carbon dioxide in the presence of a catalyst selected from phenolic compound, metal halide salt, imidazolium catalyst, ammonium catalyst, phosphonium catalyst, or a mixture thereof at a carbon dioxide pressure of 1 to 10 bars, temperature of 25 to 85 °C for 2 to 10 hours;
- 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; b) reacting the product obtained from step a) with a nucleophile having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks;
- M is selected from nitrogen or phosphorous
- 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 , andR 6 are taken together to form a heteroaryl ring.
- the reaction is conducted at the temperature of 25 to 35 °C for 12 to 36 hours.
- Y is halide. More preferably, Y is chloride.
- M is phosphorous
- R 4 , R 5 , and 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.
- 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 independently, are selected linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms.
- R 4 is octyl.
- R 5 is octyl.
- R 6 is octyl
- 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 from 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.
- the concentration of the ionic liquid in step a) is in the range of 10 to 35 % v/v.
- step b) is conducted at the temperature of 50 to 80 °C for 0.5 to 2 hours.
- the demulsification process according to the present invention further comprises a step of recovering the phase of ionic liquid after conducting step c).
- 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.
- the concentration of the ionic liquid in step a) is in the range of 30 to 300 ppm.
- step b) is conducted at the temperature of 50 to 80 °C for 0.5 to 2 hours.
- said process is conducted to separate the crude- oil emulsion having water content in the range of 20 to 60 % v/v.
- 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.
- step a) the concentration of the ionic liquid in step a) is in the range of 10 to 30 % v/v.
- 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).
- step b) is conducted at the temperature of 35 to
- the process of wax removal according to the present invention farther comprises a step of recovering the phase of ionic liquid after conducting step c).
- 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.
- the concentration of the ionic liquid in step a) is in the range of 50 to 70 % v/v.
- 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).
- step b) is conducted at the temperature of 35 to 80 °C.
- 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).
- 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.
- 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.
- Step 1 Epichlorohydrin (about 0.5 mole) was added 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 CO2 (1 bar using balloon) at room temperature for about 4 to 10 hours. The obtained product was purified by column chromatography.
- Step 2 The product obtained from step 1 reacted with the compounds according to Table 1 at the equimolar amount, at the temperature about 60 °C for about 2 weeks in order to obtain the ionic liquid samples.
- Samples 3, 11, and 14 provided negative results when titrated with silver nitrate solution because ionic liquids were not obtained from the reactions. Therefore, Samples 3, 11, and 14 were not subjected to further tests. Moreover, Samples 1 to 6 were water soluble, not suitable for using in a demulsification process, and were not subjected to further tests. Therefore, only Samples 7 to 10, and 12 to 13 were subjected to test for the efficiency of the separation of water from crude oil.
- 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).
- the water content in the oil phase 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.
- the mixture of crude oil and testing solution was heated at about 60 °C until the mixture was uniform, 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 the oil phase
- Controlled sample 1 was crude oil without addition of the ionic liquid for controlling the negative result.
- Controlled sample 2 was crude oil subjected to the addition of the commercial reagent
- the ionic liquid in Sample 12 was suitable for the application of demulsification process.
- the ionic liquid Sample 12 from the piphasic 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 Sample 12 could be reused without purification, 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 the oil phase
- the ionic liquid of Sample 12 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 12 were added into crude oil sample. The mixture between crude oil and ionic liquid was shaken at about 230 rpm 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 the 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
- 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.
- a was 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 the 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.
Abstract
This invention relates to a cyclic carbonate based ionic liquid, a preparation of such ionic liquid, and a use of the ionic liquid in a demulsification process, a process of wax removal from the crude oil, and a process for extracting crude oil from the oil sand. Said ionic liquid has 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.
Description
A CYCLIC CARBONATE BASED IONIC LIQUID, A METHOD OF PREPARING THE IONIC LIQUID, AND A USE OF SAID IONIC LIQUID
FIELD OF THE INVENTION
The present invention relates to the field of chemistry, in particular, to a cyclic carbonate 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 l,l-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 crude 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 a cyclic carbonate based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i);
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, andR3 are taken together to form a heteroaryl ring.
In another embodiment, this invention relates to a method for preparing the cyclic carbonate based ionic liquid according to the present invention comprising steps of:
a) preparing a cyclic carbonate compound by reacting an epoxide compound having structure (ii) with carbon dioxide in the presence of a catalyst selected from phenolic compound, metal halide salt, imidazolium catalyst, ammonium catalyst, phosphonium catalyst, or a mixture thereof at a carbon dioxide pressure of 1 to 10 bars, temperature of 25 to 85 °C for 2 to 10 hours;
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; b) reacting the product obtained from step a) with a nucleophile having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks;
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, andR6 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 from 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 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 embodiment, 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.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a crude-oil emulsion separation of (a) ionic liquid of Sample 7 after about 2 minutes, (b) ionic liquid of Sample 10 after about 2 hours, (c) ionic liquid of Sample 12 after about 2 hours. DESCRIPTION OF THE INVENTION
The present invention relates to a cyclic carbonate 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.
Amy 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 object 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 a cyclic carbonate based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) having structure (i);
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, andR3 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, R1, R2, andR3 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, R1, R2, and R3 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. More
preferably, R1, R2, and R3 are independently selected from linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms.
In another exemplary embodiment, R1 is octyl.
In another exemplary embodiment, R2 is octyl. In another exemplary embodiment, R3 is octyl.
In another exemplary embodiment, said ionic liquid is trioctyl ((2-oxo- 1,3 -dioxolan- 4-yl)methyl)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 cyclic carbonate based ionic liquid according to the present invention comprising steps of: a) preparaing a cyclic carbonate compound by reacting an epoxide compound having structure (ii) with carbon dioxide in the presence of a catalyst selected from phenolic compound, metal halide salt, imidazolium catalyst, ammonium catalyst, phosphonium catalyst, or a mixture thereof at a carbon dioxide pressure of 1 to 10 bars, temperature of 25 to 85 °C for 2 to 10 hours;
R' M
R5' Re
(iii) wherein,
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, andR6 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, R4, R5, and 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, R4, R5, and R6 are independently selected from linear or branched aliphatic hydrocarbon having 2 to 12 carbon atoms. More preferably, R4, R5, and R6 independently, are selected linear or branched aliphatic hydrocarbon having 4 to 10 carbon atoms.
In another exemplary embodiment, R4 is octyl.
In another exemplary embodiment, R5 is octyl.
In another exemplary embodiment, R6 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 from 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 range 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, step a) 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 farther 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 to conducting 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
The synthesis of the cyclic carbonate based ionic liquid
All cyclic carbonate based ionic liquid samples were prepared as the following. Step 1: Epichlorohydrin (about 0.5 mole) was added 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 CO2 (1 bar using balloon) at room temperature for about 4 to 10 hours. The obtained product was purified by column chromatography.
Step 2: The product obtained from step 1 reacted with the compounds according to Table 1 at the equimolar amount, at the temperature about 60 °C for about 2 weeks in order to obtain the ionic liquid samples.
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 silver nitrate solution (AgNCb) 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 Samples 1 to 14
As shown in Table 2, Samples 3, 11, and 14 provided negative results when titrated with silver nitrate solution because ionic liquids were not obtained from the reactions. Therefore, Samples 3, 11, and 14 were not subjected to further tests. Moreover, Samples 1 to 6 were water soluble, not suitable for using in a demulsification process, and were not subjected to further tests. Therefore, only Samples 7 to 10, and 12 to 13 were subjected to test for the efficiency of the separation of water from crude oil.
An efficacy 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 the 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 uniform, 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 the 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 subjected to the addition of the commercial reagent
(EPT) for controlling the positive result.
As shown in Table 3, the ionic liquid Samples 7, 10, and 12 had a good efficiency to separate water from crude oil. There was no water found in the obtained oil phase from
the separation. When considering Figure 1, it was found that Samples 7 and 10 (Figure 1 (a) and (b)) did not show any formation of triphasic mixture whereas Sample 12 (Figure 1 (c)) showed the triphasic mixture. The separation efficiency of ionic liquid in Samples 7, 10, and 12 was similar. 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.
Therefore, the ionic liquid in Sample 12 was suitable for the application of demulsification process.
Moreover, the ionic liquid Sample 12 from the piphasic 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 Sample 12 could be reused without purification, 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 the oil phase
Apart from the demulsification of the triphasic mixture, the ionic liquid of Sample 12 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 12 were added into crude oil sample. The mixture between crude oil and ionic liquid was shaken at about 230 rpm 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 the 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 was 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 the 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.
Claims
1. A cyclic carbonate based ionic liquid for demulsification of water-in-oil emulsion (W/O emulsion) according to structure (i);
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, andR3 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((2-oxo-l,3-dioxolan-4-yl)methyl)phosphonium chloride.
12. A demulsifier composition comprising the ionic liquid according to any one of claims 1 to 11.
13. A wax removal composition in crude oil production process comprising the ionic liquid according to any one of claims 1 to 11.
14. A composition for extracting crude oil from oil sand comprising the ionic liquid according to any one of claims 1 to 11.
15. A method for preparing the ionic liquid according to any one of claims 1 to 11, comprising the step of: a) preparaing a cyclic carbonate compound by reacting an epoxide compound having structure (ii) with carbon dioxide in the presence of a catalyst selected from phenolic compound, metal halide salt, imidazolium catalyst, ammonium catalyst, phosphonium catalyst, or a mixture thereof at a carbon dioxide pressure of 1 to 10 bars, temperature of 25 to 85 °C for 2 to 10 hours;
Y is selected from halide, acetate, thioacetate, p-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; b) reacting the product obtained from step a) with a nucleophile having structure (iii) at the temperature of 25 to 120 °C for 1 hour to 3 weeks;
R4- M
/ L
R5 R6
Oii) wherein,
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, andR6 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 11 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 from 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 range 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 petroleum well fluid .
48. A use of the ionic liquid according to any one of claims 1 to 11 for extracting crude oil from oil sand.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TH1901000298A TH1901000298A (en) | 2019-01-16 | Ionic liquid with a basic component of cyclic carbonate Method of preparation of ionic liquids and the use of such ionic liquids. | |
| TH1901000298 | 2019-01-16 |
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| WO2020162841A2 true WO2020162841A2 (en) | 2020-08-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111909094A (en) * | 2020-08-28 | 2020-11-10 | 河南大学 | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid |
| WO2020162841A3 (en) * | 2019-01-16 | 2021-02-18 | Ptt Exploration And Production Public Company Limited | A cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid |
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| US3475458A (en) * | 1967-08-11 | 1969-10-28 | Shell Oil Co | Production of epoxy ammonium salts |
| BRPI0905253B1 (en) * | 2009-12-28 | 2020-02-18 | Petroleo Brasileiro S.A. - Petrobras | PROCESS FOR THE TREATMENT OF WATER / OIL EMULSIONS |
| US9093722B2 (en) * | 2010-09-30 | 2015-07-28 | Uchicago Argonne, Llc | Functionalized ionic liquid electrolytes for lithium ion batteries |
| MX2011003848A (en) * | 2011-04-11 | 2012-10-29 | Mexicano Inst Petrol | Dehydrating and desalting median, heavy and extra-heavy oils using ionic liquids and their formulations. |
| WO2020162841A2 (en) * | 2019-01-16 | 2020-08-13 | Ptt Exploration And Production Public Company Limited | A cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020162841A3 (en) * | 2019-01-16 | 2021-02-18 | Ptt Exploration And Production Public Company Limited | A cyclic carbonate based ionic liquid, a method of preparing the ionic liquid, and a use of said ionic liquid |
| CN111909094A (en) * | 2020-08-28 | 2020-11-10 | 河南大学 | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid |
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