CN110835313A - Water-soluble oil washing agent for thick oil and preparation method thereof - Google Patents
Water-soluble oil washing agent for thick oil and preparation method thereof Download PDFInfo
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- CN110835313A CN110835313A CN201810940101.5A CN201810940101A CN110835313A CN 110835313 A CN110835313 A CN 110835313A CN 201810940101 A CN201810940101 A CN 201810940101A CN 110835313 A CN110835313 A CN 110835313A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/22—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to carbon atoms of six-membered aromatic rings
- C07C305/24—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to carbon atoms of six-membered aromatic rings of non-condensed six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention discloses a water-soluble oil washing agent for thick oil, which has the following molecular formula:
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to a water-soluble oil washing agent for thick oil and a preparation method thereof.
Background
The heavy oil resource accounts for a considerable proportion of the oil and gas resources in the world. According to statistics, the heavy oil and the super heavy oil account for more than 20% of the reserves of the proven crude oil in the world, and along with the continuous reduction of light easy-to-extract crude oil, the heavy oil extraction increasingly draws attention of various countries.
In the middle and later stages of water injection development of oil fields, comprehensive water content rises, formation pressure drops and oil layer temperature drops. Along with the reduction of the pressure and the temperature of the oil layer, the viscosity of the crude oil rises, the fluidity is poor, and oil layer capillaries are blocked, so that a large amount of crude oil is retained in the oil layer and is difficult to extract.
At present, methods capable of replacing water flooding mining mainly comprise steam flooding, dilution and chemical viscosity reduction, wherein the steam flooding and dilution mining have high cost and are difficult to popularize in large areas of oil fields. The chemical method has the advantages of less investment, simple process and quick response, and is widely applied to oil fields.
As is known, the recovery ratio of oil is closely related to the sweep efficiency and the sweep coefficient, and the recovery ratio of crude oil is equal to the product of the sweep efficiency and the sweep coefficient, so that the recovery ratio of crude oil needs to be further improved in the later stage of water injection exploitation of an oil field. Therefore, the research and development of the efficient oil washing agent can effectively improve the oil recovery rate of petroleum, and is an important means of tertiary oil recovery technology.
Most of the conventional oil washing agents are sensitive to the degree of mineralization and are particularly limited by the concentrations of metal calcium ions and magnesium ions, so that the conventional oil washing agents cannot be widely applied to oil fields; in addition, in order to improve the viscosity reduction and oil displacement effects, part of the oil washing agent uses inorganic base, so that the burden of oil-water separation in the later period is increased. For example, in patent ZL201210553355, "a long-acting active sand control oil washing agent and a preparation method thereof", although the long-acting active sand control oil washing agent has an obvious oil washing effect and a sand control effect, due to the use of hydroxide, the long-acting active sand control oil washing agent is difficult to popularize on a large scale in an oil field.
Disclosure of Invention
The invention provides a water-soluble oil washing agent for thick oil and a preparation method thereof aiming at the defects of the prior art, and the oil washing agent has the advantages of no alkali, strong salt resistance, low critical micelle concentration, strong surface activity, simple synthesis process and low cost.
The invention aims to provide a water-soluble oil washing agent for thick oil, which is prepared by reacting hydroquinone with dibromo halohydrocarbon to generate an intermediate, and then reacting the intermediate with chlorosulfonic acid, wherein the molecular formula of the water-soluble oil washing agent is as follows:
wherein n is a natural number, and n is more than or equal to 8 and less than or equal to 14.
The invention also aims to provide a preparation method of the water-soluble oil washing agent for the thick oil, which comprises the following steps:
(1) dissolving hydroquinone in solvent ethanol, heating to 60-80 ℃, keeping the temperature constant for 20-40 min, cooling to room temperature, adding dibromohalohydrocarbon, heating to 75-80 ℃, reacting while stirring at the stirring speed of 400-500 rpm for 20-40 h, cooling to room temperature after the reaction is finished, transferring the reaction liquid to a distillation flask, distilling under reduced pressure to remove the solvent ethanol, adding water into the residue, and extracting with diethyl ether to obtain an organic layer, namely an intermediate;
(2) dissolving the intermediate into chloroform as a solvent, cooling the intermediate to-8 to-12 ℃ by using an ice salt bath, slowly dropwise adding chlorosulfonic acid into the intermediate while stirring under the protection of inert gas, wherein the dropwise adding speed is 5 to 8 drops/min at the stirring speed of 300 to 500rpm, continuing to react for 30 to 50min after complete dropwise adding, then adjusting the pH value to 9 to 11 by using sodium hydroxide, evaporating chloroform as the solvent under reduced pressure to obtain a light yellow liquid, dissolving the light yellow liquid into distilled water, and extracting the light yellow liquid by using n-butyl alcohol to obtain the final product, namely the water-soluble oil washing agent.
The molar ratio of the hydroquinone to the dibromo-halogenated hydrocarbon to the chlorosulfonic acid is 1: 0.4-0.5: 4-5, and preferably 1:0.48: 4.5.
The dosage of the solvent ethanol is 10-20 times of the mass of the hydroquinone; the amount of the water is 3-6 times of the mass of the hydroquinone; the amount of the diethyl ether is 5-8 times of the mass of the hydroquinone; the dosage of the solvent chloroform is 10-15 times of the mass of hydroquinone; the inert gas is nitrogen or argon; the using amount of the distilled water is 5-10 times of the mass of the hydroquinone; the dosage of the n-butanol is 8-14 times of the mass of the hydroquinone.
The preparation formula of the water-soluble oil washing agent for the thickened oil is as follows:
the water-soluble oil washing agent is an anionic surfactant, has four sulfonic acid groups, belongs to a multi-head surfactant molecule, has good solubility in water, can be firstly adsorbed to the surface of oil sand when contacting with the oil sand, reduces the positive charge strength of the surface of sand body, and quickly peels crude oil from the oil sand, so that the oil washing agent has higher surface activity and lower critical micelle concentration than the conventional surfactant with single hydrophilic oleophilic groups, and therefore, the required dosage is lower; meanwhile, as the molecule is provided with two benzene rings with rigid structures, the molecule has better temperature resistanceCan, in addition, a high valent cation such as Ca2+，Mg2+Na on the molecule+After ion exchange, no precipitate is generated, and the compound can still exert the effects of oil displacement and oil washing in the stratum.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the water-soluble oil washing agent has the advantages of simple synthesis process, clean and pollution-free process, and easily obtained, transported and stored product;
(2) the water-soluble oil washing agent has remarkable temperature resistance and salt tolerance, the temperature resistance reaches over 180 ℃, the calcium and magnesium ion resistance concentration reaches 8000mg/L, and the total ion resistance concentration reaches 200000 mg/L;
(3) the water-soluble oil washing agent has low dosage and high viscosity reduction rate, and when the dosage is 200ppm, the viscosity of the thickened oil can be reduced by more than 96.0 percent, and the oil washing efficiency can reach more than 95 percent.
Detailed Description
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
(1) Dissolving 1mol of hydroquinone in 1101g of solvent ethanol, heating to 60 ℃, keeping the temperature for 20min, cooling to room temperature, adding 0.4mol of 1, 8-dibromooctane, then heating to 75 ℃, 78 and 80 ℃, reacting while stirring, wherein the stirring speed is 400rpm, the reaction time is 20h, cooling to room temperature after the reaction is finished, transferring the reaction solution to a distillation flask, carrying out reduced pressure distillation to remove the solvent ethanol, then adding 330.3g of water to the residue, and extracting with 550.5g of diethyl ether to obtain an organic layer, namely an intermediate;
(2) dissolving the intermediate into 1101g of chloroform solvent, cooling to-8 ℃ by using a ice salt bath, slowly dropwise adding 4mol of chlorosulfonic acid into the mixture while stirring under the protection of inert gas nitrogen, wherein the dropwise adding speed is 5 drops/min at the stirring speed of 300rpm, continuously reacting for 30min after complete dropwise adding, then adjusting the pH to 9 by using sodium hydroxide, and carrying out reduced pressure evaporationExtracting solvent chloroform to obtain light yellow liquid, dissolving the light yellow liquid in 550.5g distilled water, extracting with 880.8g n-butanol to obtain final product water-soluble oil detergent A1。
Generating water-soluble oil washing agent A for thick oil1The reaction equation of (a) is as follows:
through testing, the emulsifying viscosity reducer A1When the dosage is 200ppm, the viscosity of the crude oil with the viscosity of 12560mPa.s can be reduced by 97.2 percent at 50 ℃, the oil washing efficiency reaches 96.5 percent, and the oil washing and viscosity reduction effects are good.
Example 2
(1) Dissolving 1mol of hydroquinone in 1560g of solvent ethanol, heating to 72 ℃, keeping the temperature for 25min, cooling to room temperature, adding 0.48mol of 1, 12-dibromododecane, heating to 78 ℃, reacting while stirring, wherein the stirring speed is 450rpm, the reaction time is 35h, cooling to room temperature after the reaction is finished, transferring the reaction liquid to a distillation flask, carrying out reduced pressure distillation to remove the solvent ethanol, adding 440.4g of water into the residue, and extracting with 660.6g of diethyl ether to obtain an organic layer, namely an intermediate;
(2) dissolving the intermediate into 1456g solvent chloroform, cooling to-10 deg.C with ice salt bath, slowly adding 4.5mol chlorosulfonic acid under stirring at a speed of 320rpm under protection of inert gas nitrogen, continuing to react for 40min after complete dripping, adjusting pH to 10 with sodium hydroxide, distilling off solvent chloroform under reduced pressure to obtain yellowish liquid, dissolving the yellowish liquid in 760.5g distilled water, extracting with 1120.5g n-butanol to obtain final product water-soluble oil washing agent A2。
Generating water-soluble oil washing agent A for thick oil2The reaction equation of (a) is as follows:
through testing, the emulsifying viscosity reducer A2When the dosage is 200ppm, the viscosity of the crude oil with the viscosity of 21565mPa.s can be reduced by 98.5% at 50 ℃, the oil washing efficiency reaches 98.2%, and the oil washing and viscosity reduction effects are good.
Example 3
(1) Dissolving 1mol of hydroquinone in 2202g of solvent ethanol, heating to 80 ℃, keeping the temperature for 40min, cooling to room temperature, adding 0.5mol of 1, 14-dibromotetradecane, heating to 80 ℃, reacting while stirring, wherein the stirring speed is 500rpm, the reaction time is 40h, cooling to room temperature after the reaction is finished, transferring the reaction solution to a distillation flask, carrying out reduced pressure distillation to remove the solvent ethanol, adding 660.6g of water to the residue, and extracting with 880.8g of diethyl ether to obtain an organic layer, namely an intermediate;
(2) dissolving the intermediate into 1651.5g of chloroform solvent, cooling to-12 ℃ by using a ice salt bath, slowly dripping 5mol of chlorosulfonic acid into the solvent under the protection of inert gas nitrogen while stirring, wherein the dripping speed is 8 drops/min at the stirring speed of 500rpm, continuing to react for 50min after the dripping is completely finished, adjusting the pH to 11 by using sodium hydroxide, evaporating the chloroform solvent under reduced pressure to obtain a light yellow liquid, dissolving the light yellow liquid into 1101g of distilled water, extracting by using 1541.4g of n-butyl alcohol to obtain the final product, namely the water-soluble oil washing agent A3。
Generating water-soluble oil washing agent A for thick oil3The reaction equation of (a) is as follows:
through testing, the emulsifying viscosity reducer A3When the dosage is 200ppm, the viscosity of the crude oil with the viscosity of 18657mPa.s can be reduced by 97.7% at 50 ℃, the oil washing efficiency reaches 97.3%, and the oil washing and viscosity reduction effects are good.
Claims (10)
1. A water-soluble oil washing agent for thick oil has the following molecular formula:
wherein n is a natural number, and n is more than or equal to 8 and less than or equal to 14.
2. The preparation method of the water-soluble oil washing agent for thick oil according to claim 1, characterized by comprising the following steps:
(1) dissolving hydroquinone in solvent ethanol, heating to 60-80 ℃, keeping the temperature constant for 20-40 min, cooling to room temperature, adding dibromohalohydrocarbon, heating to 75-80 ℃, reacting while stirring at the stirring speed of 400-500 rpm for 20-40 h, cooling to room temperature after the reaction is finished, transferring the reaction liquid to a distillation flask, distilling under reduced pressure to remove the solvent ethanol, adding water into the residue, and extracting with diethyl ether to obtain an organic layer, namely an intermediate;
(2) dissolving the intermediate into chloroform as a solvent, cooling the intermediate to-8 to-12 ℃ by using an ice salt bath, slowly dropwise adding chlorosulfonic acid into the intermediate while stirring under the protection of inert gas, wherein the dropwise adding speed is 5 to 8 drops/min at the stirring speed of 300 to 500rpm, continuing to react for 30 to 50min after complete dropwise adding, then adjusting the pH value to 9 to 11 by using sodium hydroxide, evaporating chloroform as the solvent under reduced pressure to obtain a light yellow liquid, dissolving the light yellow liquid into distilled water, and extracting the light yellow liquid by using n-butyl alcohol to obtain the final product, namely the water-soluble oil washing agent.
3. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the molar ratio of the hydroquinone, the dibromo-halogenated hydrocarbon and the chlorosulfonic acid is 1: 0.4-0.5: 4-5.
4. The method for preparing a water-soluble oil washing agent for thick oil according to claim 2 or 3, characterized in that the molar ratio of hydroquinone, dibromohalogenated hydrocarbon and chlorosulfonic acid is 1:0.48: 4.5.
5. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the amount of the solvent ethanol is 10-20 times of the mass of the hydroquinone, and the amount of the water is 3-6 times of the mass of the hydroquinone.
6. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the amount of the diethyl ether is 5-8 times of the mass of the hydroquinone.
7. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the amount of chloroform as a solvent is 10-15 times of the mass of hydroquinone.
8. The method for preparing a water-soluble oil washing agent for thick oil according to claim 2, characterized in that the inert gas is nitrogen or argon.
9. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the amount of the distilled water is 5-10 times of the mass of the hydroquinone.
10. The preparation method of the water-soluble oil washing agent for the thick oil according to claim 2, characterized in that the amount of the n-butanol is 8-14 times of the mass of the hydroquinone.
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| US5092405A (en) * | 1990-12-21 | 1992-03-03 | Texaco Inc. | Alkoxylated surfactant system for heavy oil reservoirs |
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| CN106587245A (en) * | 2016-11-17 | 2017-04-26 | 烟台智本知识产权运营管理有限公司 | Oil removing agent used for treating sewage produced by thermal recovery of thickened oil and preparation method thereof |
| CN106749892A (en) * | 2016-11-17 | 2017-05-31 | 烟台智本知识产权运营管理有限公司 | A kind of degreaser of heavy crude heat extraction sewage and preparation method thereof |
| CN106866473A (en) * | 2017-01-19 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of high-content wax viscous crude wax is brilliant, asphaltene dispersants |
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2018
- 2018-08-17 CN CN201810940101.5A patent/CN110835313B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5092405A (en) * | 1990-12-21 | 1992-03-03 | Texaco Inc. | Alkoxylated surfactant system for heavy oil reservoirs |
| WO2008020908A2 (en) * | 2006-08-16 | 2008-02-21 | Exxonmobil Upstream Research Company | Core annular flow of heavy crude oils in transportation pipelines and production wellbores |
| CN102051164A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Surfactant for oil field and preparation method of surfactant |
| CN103881675A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Long-acting active sand-controlling oil washing agent and preparation method thereof |
| CN104164226A (en) * | 2013-05-20 | 2014-11-26 | 北京德美高科科技有限责任公司 | High temperature oil washing agent |
| CN106587245A (en) * | 2016-11-17 | 2017-04-26 | 烟台智本知识产权运营管理有限公司 | Oil removing agent used for treating sewage produced by thermal recovery of thickened oil and preparation method thereof |
| CN106749892A (en) * | 2016-11-17 | 2017-05-31 | 烟台智本知识产权运营管理有限公司 | A kind of degreaser of heavy crude heat extraction sewage and preparation method thereof |
| CN106866473A (en) * | 2017-01-19 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of high-content wax viscous crude wax is brilliant, asphaltene dispersants |
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