CN111763509B - Thick oil viscosity reducer and preparation method thereof - Google Patents
Thick oil viscosity reducer and preparation method thereof Download PDFInfo
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- CN111763509B CN111763509B CN201910257468.1A CN201910257468A CN111763509B CN 111763509 B CN111763509 B CN 111763509B CN 201910257468 A CN201910257468 A CN 201910257468A CN 111763509 B CN111763509 B CN 111763509B
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Abstract
The invention provides a thick oil viscosity reducer, a preparation method thereof and a thick oil modification method, wherein the thick oil viscosity reducer comprises the following components: copper salt of fatty acid, fatty acid amide, hydrocarbon organic solvent, assistant and water. The heavy oil viscosity reducer comprises, by total mass of the heavy oil viscosity reducer, 100%, 20-40% of fatty acid copper salt, 15-25% of fatty acid amide, 25-40% of organic solvent, 3-8% of auxiliary agent and the balance of water.
Description
Technical Field
The invention provides a thick oil viscosity reducer and a preparation method thereof, in particular to a method for modifying thick oil by using the thick oil viscosity reducer.
Background
The heavy oil is heavy crude oil with high viscosity, high density, high colloid and asphaltene content, high contents of hetero atoms such as sulfur, nitrogen, oxygen, nickel, vanadium and other metals, low hydrogen-carbon atom ratio and difficult extraction by a conventional method. At present, the heavy oil exploitation methods mainly include physical methods (such as steam stimulation and steam flooding) and chemical methods (such as in-situ combustion and active water viscosity reduction), wherein the thermal exploitation method is the main method for heavy oil exploitation, but the investment cost is high, and recently, the chemical modification viscosity reduction method increases the temperature required by the reaction by injecting steam, and also achieves a certain progress, but cannot achieve the required effect when the formation temperature is low. The air injection oil extraction technology has the advantages of rich air source and low cost, and is more and more paid more attention by people in recent years.
CN105327716A proposes a catalyst for oxidizing and reducing viscosity of thick oil by injecting air, which is composed of acrylate polymer, metal hydroxide, metal linoleate, benzoic acid and petroleum sulfonate. The viscosity of the thick oil is reduced mainly by means of the combined action of the pour point depression of the polymer and the oxidative upgrading of the catalyst.
CN103396779A proposes a thickened oil air injection moderating catalytic oxidation emulsion catalyst and a preparation method thereof, N-lauroyl ethylenediamine triacetic acid transition metal salt and an emulsifier are adopted for oxidation and viscosity reduction, and the air injection pressure in the patent is higher than 3.2 MPa.
CN1987043A proposes a method for producing oil by injecting air into thickened oil and using it to moderate catalytic oxidation, i.e. during the process of producing thickened oil by injecting steam, a water-soluble or oil-soluble, high-temperature resistant, bifunctional catalyst with catalytic oxidation and cracking is injected, and a certain amount of air is injected, during soaking or steam flooding, the thickened oil undergoes the reactions of moderate catalytic oxidation and cracking, so as to lighten the crude oil and reduce the viscosity of the crude oil, improve the surface activity of the crude oil, and make the viscosity reduction rate of the thickened oil reach more than 90%. The catalyst is a composite catalyst composed of a metal salt catalyst, a basic assistant and an activator, wherein the metal salt catalyst relates to an inorganic metal salt or a micromolecular organic acid salt (such as oxalate or acetate or benzoate) as the catalyst.
The catalysts used in the above patents are mostly water-soluble or small-molecular organic acid metal salts, and the hydrophobic chains in the self structure are short, and no specific description is made on the oxidation modification effect of the thick oil, such as the change of the acid value.
Disclosure of Invention
The invention provides a thick oil viscosity reducer, which comprises the following components: copper salt of fatty acid, fatty acid amide, hydrocarbon organic solvent, assistant and water.
In a specific embodiment, the copper salt of fatty acid is at least one of a copper salt of lauric acid, a copper salt of coconut oil acid, and a copper salt of palmitic acid.
In one embodiment, the fatty acid amide is an amide compound formed from a first fatty acid and an amine compound; the first fatty acid is C 12 To 18 At least one of fatty acids; the amine compound is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and polyethylene polyamine.
In one embodiment, the hydrocarbon organic solvent is diesel and/or kerosene.
In a specific embodiment, the auxiliary agent comprises at least one of ethylenediamine, ammonium phosphate, ammonium bicarbonate, ammonia, sodium hydroxide, and sodium citrate.
In a specific embodiment, the viscosity reducer for thick oil comprises, by 100% of the total mass of the viscosity reducer for thick oil, 20% to 40% of copper salt of fatty acid, 15% to 25% of fatty acid amide, 25% to 40% of hydrocarbon organic solvent, 3% to 8% of auxiliary agent, and the balance of water.
The second invention provides a method for preparing the heavy oil viscosity reducer, which comprises the following steps: the fatty acid copper salt, the fatty acid amide, the auxiliary agent and the water are added into the hydrocarbon organic solvent one by one and mixed evenly at the temperature of 35 ℃ to 45 ℃.
In one embodiment, the mixing is homogeneous at 38 ℃ to 42 ℃.
In one embodiment, the copper salt of fatty acid is isolated by reacting copper hydroxide with a second fatty acid at 70 to 100 ℃ for 2 to 3 hours, the second fatty acid being at least one of lauric acid, coconut oil acid and palmitic acid.
In one embodiment, the copper salt of fatty acid may also be formed by reacting (in a reactor) a milled second fatty acid, which is at least one of lauric acid, coconut oil acid, and palmitic acid, with an oxide of copper at 70 ℃ to 100 ℃.
In a specific embodiment, the second fatty acid is selected from at least one of lauric acid, coconut oil acid, and palmitic acid.
The third invention provides a method for modifying thick oil, which comprises the following steps:
adding 10 to 90 percent of water and 0.5 to 1.5 percent of the thick oil viscosity reducer into thick oil by taking the total mass of the thick oil, the water and the thick oil viscosity reducer as described in any one of the invention or the thick oil viscosity reducer prepared by the method as described in the second invention as 100 percent, stirring and mixing uniformly, and then placing in a reaction kettle; injecting air under the pressure of 0.5 to 3 MPa; heating to 100-200 ℃, and carrying out catalytic oxidation for 5-72 h to obtain the upgraded thick oil.
In one embodiment, the water is 12.5% to 30%, the viscosity reducer is 1%, and the pressure of injected air is 1 to 2 MPa; and (4) carrying out catalytic oxidation for 12 to 48 hours.
The invention has the beneficial effects that:
(1) the thick oil viscosity reducer solves the problem of high temperature required by high-temperature hydrothermal catalytic viscosity reduction, has good compatibility with thick oil, can reduce the viscosity of the thick oil at a lower temperature, particularly can be well dispersed in the thick oil to carry out homogeneous catalytic reaction to modify the thick oil, has good cracking effect, generates light components, generates organic acid and alkaline substances to form a surfactant, has emulsifying and stripping properties, enables the thick oil to better strip polar components in the thick oil from the surface of minerals, and achieves the effect of reducing the viscosity of the thick oil under the combined action of the organic acid and the alkaline substances.
(2) The catalyst can promote the generation of acidic substances in the catalytic oxidation of thick oil by injecting air, so that the acid value of the oxidized crude oil is improved, and the generation of active components is facilitated.
(3) The thick oil viscosity reducer and the viscosity reduction method effectively reduce the viscosity of crude oil, and can improve the recovery efficiency when used for thick oil exploitation. Wherein the content of the light component can be increased by 0.2 to 5 percent, the content of the acidic component is increased, and the viscosity reduction rate reaches 30 to 95 percent.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
Unless otherwise specified, the reagents used in the following examples are commercially available.
Example 1
Preparation of No. 1 viscosity reducer
Weighing 20.6 parts by mass of crystal water copper chloride and 9.6 parts by mass of sodium hydroxide, dissolving in 40 parts by mass of water, mixing and stirring at 40 ℃ for 10min, filtering, and washing with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of coconut oil acid, stirring and reacting at 70 ℃ for 3h, then adding a certain amount of water, washing, carrying out suction filtration and separation to obtain copper cocoate, and carrying out vacuum drying at 60 ℃ for 4 h. Mixing 20 parts by mass of copper cocoateIn the kettle, 40 parts by mass of diesel oil and 20 parts by mass of C are sequentially added 16 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 16 Alkyl group), 3 parts by mass of sodium hydroxide, and 17 parts by mass of water. Stirring at 40 deg.C for 20min to obtain 1# viscosity reducer.
Example 2
Preparation of No. 2 viscosity reducer
Weighing 18 parts by mass of copper nitrate and 7.5 parts by mass of sodium hydroxide, dissolving in 28 parts by mass of water, mixing and stirring at 40 ℃ for 20min, filtering, and washing with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of palmitic acid (palmitic acid), stirring at 100 ℃ for reaction for 2 hours, then adding a certain amount of water, washing with water, performing suction filtration and separation to obtain copper palmitate, and performing vacuum drying at 60 ℃ for 4 hours. 40 parts by mass of copper palmitate are taken and put into a mixing kettle, and 25 parts by mass of kerosene 15 parts by mass of C are sequentially added 16 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 16 Alkyl group), 6 parts by mass of ammonia water, and 14 parts by mass of water. Stirring at 39 ℃ for 20min at high speed to obtain the No. 2 viscosity reducer.
Example 3
Preparation of No. 3 viscosity reducer
Weighing 18 parts by mass of copper nitrate and 7.5 parts by mass of sodium hydroxide, dissolving in 28 parts by mass of water, mixing and stirring at 40 ℃ for 20min, filtering, and washing with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of palmitic acid, stirring and reacting for 2 hours at 75 ℃, then adding a certain amount of water, washing with water, performing suction filtration and separation to obtain the copper palmitate, and performing vacuum drying for 4 hours at 60 ℃. 20 parts by mass of copper palmitate is taken and put into a mixing kettle, and 20 parts by mass of C mixed solvent of 20 parts by mass of diesel oil and 15 parts by mass of kerosene is added in turn 12 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 12 Alkyl group), 3 parts by mass of sodium hydroxide, and 22 parts by mass of water. Stirring at 41 deg.C for 20min to obtain 3# viscosity reducer.
Example 4
Preparation of No. 4 viscosity reducer
Weighing 22 parts by mass of copper nitrate and 9.3 parts by mass of sodium hydroxide, and dissolving in 30 parts by mass of sodium hydroxideMixing and stirring the components in water at 40 ℃ for 30min, filtering and washing the mixture with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of lauric acid, stirring and reacting for 2.5 hours at 80 ℃, then adding a certain amount of water, washing with water, carrying out suction filtration and separation to obtain copper laurate, and carrying out vacuum drying for 4 hours at 60 ℃. Adding 30 parts by mass of copper laurate into a mixing kettle, and sequentially adding 25 parts by mass of C which is a mixed solvent of 15 parts by mass of diesel oil and 15 parts by mass of kerosene 18 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 18 Alkyl group), 3 parts by mass of ethylenediamine, 12 parts by mass of water. Stirring at 42 deg.C for 20min to obtain 4# viscosity reducer.
Example 5
Preparation of No. 5 viscosity reducer
Weighing 22 parts by mass of copper nitrate and 9.3 parts by mass of sodium hydroxide, dissolving in 30 parts by mass of water, mixing and stirring at 20 ℃ for 30min, filtering, and washing with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of lauric acid, stirring and reacting at 85 ℃ for 2.5h, then adding a certain amount of water, washing with water, carrying out suction filtration and separation to obtain copper laurate, and carrying out vacuum drying at 60 ℃ for 4 h. Taking 40 parts by mass of copper laurate, adding a mixed solvent of 10 parts by mass of diesel oil and 15 parts by mass of kerosene, and 15 parts by mass of C in sequence into a mixing kettle 14 Fatty acid amide (structural formula is ROCHCH) 2 CH 2 NHCOR where R is linear C 14 Alkyl group), 6 parts by mass of ammonium phosphate, and 14 parts by mass of water. Stirring at high speed for 20min at 38 ℃ to obtain the 5# viscosity reducer.
Example 6
Preparation of No. 6 viscosity reducer
20.6 parts by mass of crystal water copper chloride and 9.6 parts by mass of sodium hydroxide are dissolved in 40 parts by mass of water, mixed and stirred for 10min at 70 ℃, filtered and washed with water to obtain pure copper hydroxide. Transferring to a reaction kettle, adding 40 parts by mass of coconut oil acid, stirring and reacting at 90 ℃ for 3h, then adding a certain amount of water, washing, carrying out suction filtration and separation to obtain copper cocoate, and carrying out vacuum drying at 60 ℃ for 4 h. Adding 40 parts by mass of copper cocoate oleate into a mixing kettle, and sequentially adding 25 parts by mass of diesel oil and 15 parts by mass of C 16 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCORWherein R is a straight chain C 16 Alkyl group), 8 parts by mass of ammonium hydrogencarbonate and 12 parts by mass of water. Stirring at 35 deg.C for 20min to obtain 6# viscosity reducer.
Example 7
Preparation of 7# viscosity reducer
Weighing 38 parts by mass of copper oxide, adding 40 parts by mass of coconut oil acid, stirring and reacting for 4 hours at 80 ℃, adding an ethanol water solution, filtering and separating to obtain copper cocoate, and drying for 4 hours in vacuum at 60 ℃. Adding 30 parts by mass of copper cocoate oleate into a mixing kettle, and sequentially adding 30 parts by mass of kerosene and 20 parts by mass of C 16 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 16 Alkyl group), 8 parts by mass of sodium citrate, 12 parts by mass of water. Stirring at high speed for 20min at 45 ℃ to obtain the 7# viscosity reducer.
Example 8
Preparation of No. 8 viscosity reducer
Weighing 30 parts by mass of copper oxide, adding 40 parts by mass of palmitic acid, stirring and reacting for 5 hours at 80 ℃, adding an ethanol water solution, filtering and separating to obtain the copper palmitate, and drying for 4 hours in vacuum at 60 ℃. 20 parts by mass of copper palmitate are taken and put into a mixing kettle, 40 parts by mass of kerosene and 15 parts by mass of C are sequentially added 16 Fatty acid amide (structural formula ROCHCH) 2 CH 2 NHCOR where R is linear C 16 Alkyl group), 3 parts by mass of sodium citrate, and 22 parts by mass of water. Stirring at 37 deg.C for 20min to obtain 8# viscosity reducer.
Example 9
According to the condition that the mass percent of the viscosity reducer in an oil-water mixture (the volume ratio of oil to water is 7:3) is 1.0 percent, the viscosity reducers 1# to 8# prepared in examples 1 to 8 and 100g of thick oil with the water content of 30 percent are mixed and stirred uniformly, then the mixture is added into a reaction kettle, air with the pressure of 0.5 to 3MPa (shown in table 1) is injected, the mixture is kept at 150 ℃ for 8 to 24 hours, and the acid values before and after the reaction are measured by a titration method.
The results are shown in Table 1.
TABLE 1 heavy oil Change before and after reaction
As can be seen from Table 1, the acid values of the viscosity reducer products No. 1, No. 2 and No. 6 were high when the reaction time was 8 hours. When the reaction time was 24 hours and the air pressure was 3MPa, the acid value decreased and decarboxylation occurred.
Example 10
According to the condition that the volume percentage of the viscosity reducer in an oil-water mixture (the volume ratio of thick oil to water is shown in table 2) is 1.0%, the viscosity reducers 1# to 8# prepared in examples 1 to 8 and 100g of the oil-water mixture are uniformly mixed, then the mixture is added into a reaction kettle, air with the pressure of 1 to 1.5MPa is injected, the mixture is kept at the temperature of 150 ℃ for 8 to 24 hours, and the viscosity of a mixed system after oxidation is measured after the reaction is finished. The viscosity was measured using a BROOKFIELD, Inc. DV-III viscometer, USA. The viscosity of the thick oil was 154152 mPas at 60 ℃. Specific conditions and results are shown in table 2 below.
TABLE 2 viscous oil changes before and after reaction
Experiments show that when the oil-water ratio is 7:1, the crude oil is coked after the 4# catalyst and the 1# catalyst are oxidized under the conditions of 1MPa catalytic oxidation for 9 hours and 2.0MPa catalytic oxidation for 8 hours respectively, and the low water content is not beneficial to the oxidation and viscosity reduction of the thick oil. The viscosity reduction rate of 2#, 4#, 5# and 6# can reach more than 90% under the proper reaction condition.
While the invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that various changes can be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (6)
1. A viscosity reducer for thick oil comprises the following components: copper salt of fatty acid, fatty acid amide, hydrocarbon organic solvent, auxiliary agent and water;
the auxiliary agent comprises at least one of ethylenediamine, ammonium phosphate, ammonium bicarbonate, ammonia water, sodium hydroxide and sodium citrate;
by taking the total mass of the thick oil viscosity reducer as 100%, 20-40% of fatty acid copper salt, 15-25% of fatty acid amide, 25-40% of hydrocarbon organic solvent, 3-8% of auxiliary agent and the balance of water;
the fatty acid copper salt is at least one of copper laurate salt, copper cocoate salt and copper palmitate salt;
the fatty acid amide is an amide compound formed by a first fatty acid and an amine compound; the first fatty acid is C 12-18 At least one of fatty acids; the amine compound is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and polyethylene polyamine.
2. The thick oil viscosity reducer according to claim 1, wherein the hydrocarbon organic solvent is diesel oil and/or kerosene.
3. A method for producing the thick oil viscosity reducer of claim 1 or 2, comprising the steps of:
the fatty acid copper salt, the fatty acid amide, the auxiliary agent and the water are added into the hydrocarbon organic solvent in sequence and mixed evenly at 35 ℃ to 45 ℃.
4. The method of claim 3, wherein the mixing is homogeneous at 38 ℃ to 42 ℃.
5. A method of upgrading heavy oil comprising the steps of:
adding 10 to 90 percent of water and 0.5 to 1.5 percent of the thick oil viscosity reducer into thick oil, stirring and uniformly mixing the mixture and then placing the mixture into a reaction kettle, wherein the total mass of the thick oil, the water and the thick oil viscosity reducer according to the claim 1 or 2 or the thick oil viscosity reducer prepared by the method according to the claim 3 or 4 is 100 percent; injecting air under the pressure of 0.5 to 3 MPa; heating to 100-200 ℃, and carrying out catalytic oxidation for 5-72 h to obtain the modified thick oil.
6. The method according to claim 5, wherein the water is 12.5 to 30%, the viscosity reducer for thick oil is 1%, and the pressure of injected air is 1 to 2 MPa; and (4) carrying out catalytic oxidation for 12 to 48 hours.
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| CN103396779A (en) * | 2013-08-07 | 2013-11-20 | 中国海洋石油总公司 | Thick oil air injection relaxation catalytic oxidation emulsion catalyst and preparation method thereof |
| CA3045622A1 (en) * | 2016-11-30 | 2018-06-07 | Prince Energy Llc | Compositions for use in drilling fluids |
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| CN103396779A (en) * | 2013-08-07 | 2013-11-20 | 中国海洋石油总公司 | Thick oil air injection relaxation catalytic oxidation emulsion catalyst and preparation method thereof |
| CA3045622A1 (en) * | 2016-11-30 | 2018-06-07 | Prince Energy Llc | Compositions for use in drilling fluids |
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