CN113480989A - Quadripolymer pour point depressant for high-freezing-point crude oil and preparation method thereof - Google Patents
Quadripolymer pour point depressant for high-freezing-point crude oil and preparation method thereof Download PDFInfo
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- CN113480989A CN113480989A CN202110615108.1A CN202110615108A CN113480989A CN 113480989 A CN113480989 A CN 113480989A CN 202110615108 A CN202110615108 A CN 202110615108A CN 113480989 A CN113480989 A CN 113480989A
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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
- C09K8/588—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 polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
Abstract
The application discloses a quadripolymer pour point depressant for high-freezing-point crude oil and a preparation method thereof, belonging to the technical field of oil field chemicals. The quadripolymer pour point depressant for the high freezing point crude oil consists of a first substance and a second substance; the first substance is a nano modified montmorillonite composite material formed by copolymerizing modified montmorillonite and four monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide; the second substance is alcoholysis type terpolymer formed by alcoholysis of octadecyl methacrylate-maleic anhydride-acrylamide terpolymer. The first substance and the second substance in the quadripolymer pour point depressant for the high pour point crude oil act synergistically, the pour point and the viscosity of the high pour point crude oil are reduced, and the low-temperature fluidity of the high pour point crude oil is improved, so that the high pour point crude oil is convenient to extract and transport.
Description
Technical Field
The application relates to a quadripolymer pour point depressant for high-freezing-point crude oil and a preparation method thereof, belonging to the technical field of oil field chemicals.
Background
The high-solidifying point crude oil is formed by mixing complex hydrocarbons, has high wax content, can be solidified at normal temperature, blocks oil well pipelines and oil extraction equipment, and has great influence on the exploitation and the transportation of the crude oil. At present, a heating conveying process is mainly adopted, and the conveying method has the defects of high fuel consumption, small variation range of allowed quantity and the like. From the viewpoint of reducing energy consumption and production cost and improving the safety of pipeline operation, the chemical pour point depressant is added into the high-freezing crude oil, and the method is the simplest and most effective method for realizing normal-temperature and even low-temperature transportation of the high-freezing crude oil.
The existing commercial pour point depressant has poor pour point depressing effect on high pour point crude oil, so the development of the pour point depressant for the high pour point crude oil ensures that the high pour point crude oil still keeps better fluidity at normal temperature or even low temperature, and is the key for solving the problems of serious wax deposition of a shaft, blockage of a drill bit and the like.
Disclosure of Invention
In order to solve the problems, the application provides a quadripolymer pour point depressant for high pour point crude oil and a preparation method and application thereof.
According to one aspect of the present application, there is provided a tetrapolymer-based pour point depressant for high pour point crude oil, consisting of a first substance and a second substance;
the first substance is a nano modified montmorillonite composite material formed by copolymerizing modified montmorillonite and four monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide;
the second substance is alcoholysis type terpolymer formed by alcoholysis of octadecyl methacrylate-maleic anhydride-acrylamide terpolymer.
Preferably, the weight ratio of the first substance to the second substance is 1: (1.5 to 3).
Preferably, the molar ratio of the monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide in the first substance is (2-3): 1: (1-2): (1-2).
Preferably, the molar ratio of the monomers of octadecyl methacrylate, maleic anhydride and acrylamide in the second substance is (3-4): 1: (1-2).
Preferably, the size of the modified montmorillonite is 200-300 nm.
According to another aspect of the present application, there is provided a method for preparing a tetrapolymer-based pour point depressant for high freezing point crude oil, comprising the steps of:
and adding the first substance and the second substance into dimethylbenzene, and performing ultrasonic dispersion uniformly to obtain the quadripolymer pour point depressant for the high-freezing-point crude oil.
Preferably, the first substance comprises the following preparation steps:
adding modified montmorillonite into absolute ethyl alcohol, continuously stirring until the modified montmorillonite is uniformly dispersed in the absolute ethyl alcohol, adding monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide, keeping the temperature of 65-75 ℃ for 10min under the protection of nitrogen, adding azodiisobutyronitrile, reacting for 6-8 hours, centrifuging, washing and drying to obtain the first substance.
Preferably, the modified montmorillonite comprises the following preparation steps:
mixing montmorillonite with pure water to prepare a suspension of 5-8%, and heating to 65 ℃;
and adding the aqueous solution of dodecyl benzene sulfonate into the suspension under the condition of continuously stirring, reacting for 7-8 hours, cooling and standing, centrifuging, washing, drying, and grinding into powder to obtain the modified montmorillonite.
Preferably, the second substance comprises the following preparation steps:
adding azodiisobutyronitrile into a mixture of monomers of octadecyl methacrylate, maleic anhydride and acrylamide, and carrying out polymerization reaction at the temperature of 60-70 ℃ under the protection of nitrogen for 5-6 hours to obtain an octadecyl methacrylate-maleic anhydride-acrylamide terpolymer;
mixing the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer with high-carbon alcohol, carrying out alcoholysis reaction at the temperature of 100-110 ℃ by taking p-toluenesulfonic acid as a catalyst for 4-5 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a second substance;
the high-carbon alcohol is selected from one of high-carbon dodecanol, high-carbon tetradecanol, high-carbon hexadecanol and high-carbon octadecanol;
the molar ratio of the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer to the higher alcohol is 1: (1-2).
According to still another aspect of the present application, there is provided a use of the above-mentioned tetrapolymer-based pour point depressant for high pour point crude oil or the tetrapolymer-based pour point depressant for high pour point crude oil prepared by the above-mentioned preparation method in high pour point crude oil.
Benefits of the present application include, but are not limited to:
1. the quadripolymer pour point depressant for the high freezing point crude oil has the advantages that the first substance and the second substance act synergistically, the freezing point and the viscosity of the high freezing point crude oil are reduced, the low-temperature fluidity of the high freezing point crude oil is improved, and the high freezing point crude oil is convenient to extract and transport.
2. The utility model provides a quadripolymer class pour point depressant for high congealing point crude oil, long chain molecule can with the wax crystal effect in the high congealing crude oil, colloid, asphaltene effect in polar group and the high congealing crude oil play the effect that the viscidity falls that congeals simultaneously.
3. According to the preparation method of the quadripolymer pour point depressant for the high-freezing-point crude oil, the preparation process of the first substance and the preparation process of the second substance are simple, the operation is convenient, and the popularization and the use are facilitated.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1
The preparation method of the quadripolymer pour point depressant for the high freezing point crude oil comprises the following preparation steps:
adding the first substance and the second substance into dimethylbenzene, and performing ultrasonic dispersion uniformly to obtain a quadripolymer pour point depressant for the high-freezing-point crude oil;
the weight ratio of the first substance to the second substance is 1: (1.5 to 3).
Wherein the first substance is a nano modified montmorillonite composite material formed by copolymerizing modified montmorillonite and four monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide;
the preparation of the first substance comprises the following steps:
adding modified montmorillonite into absolute ethyl alcohol, continuously stirring until the modified montmorillonite is uniformly dispersed in the absolute ethyl alcohol, adding monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide, keeping the temperature at 65-75 ℃ for 10min under the protection of nitrogen, adding azodiisobutyronitrile, reacting for 6-8 hours, centrifuging, washing and drying to obtain a first substance;
the molar ratio of monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide in the first substance is (2-3): 1: (1-2): (1-2);
the using amount of the azodiisobutyronitrile is 0.5 percent of that of the methacrylic acid octadecyl ester, the maleic anhydride, the polyethylene glycol and the acrylamide;
the preparation of the modified montmorillonite comprises the following steps:
mixing montmorillonite with pure water to prepare a suspension of 5-8%, and heating to 65 ℃;
adding the aqueous solution of dodecyl benzene sulfonate into the suspension under the condition of continuous stirring, reacting for 7-8 hours, cooling and standing, centrifuging, washing, drying, and grinding into powder to prepare modified montmorillonite;
the size of the modified montmorillonite is 200-300 nm.
The second substance is alcoholysis type terpolymer consisting of alcoholysis type octadecyl methacrylate-maleic anhydride-acrylamide terpolymer;
the second substance comprises the following preparation steps:
adding azodiisobutyronitrile into a mixture of monomers of octadecyl methacrylate, maleic anhydride and acrylamide, and carrying out polymerization reaction at the temperature of 60-70 ℃ under the protection of nitrogen for 5-6 hours to obtain an octadecyl methacrylate-maleic anhydride-acrylamide terpolymer;
mixing the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer with high-carbon alcohol, carrying out alcoholysis reaction at the temperature of 100-110 ℃ by taking p-toluenesulfonic acid as a catalyst for 4-5 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a second substance;
when the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer is prepared, the molar ratio of the monomers octadecyl methacrylate, maleic anhydride and acrylamide in the second substance is (3-4): 1: (1-2); the using amount of the azodiisobutyronitrile is 0.5 percent of the total mole number of the mixture of the octadecyl methacrylate, the maleic anhydride and the acrylamide;
when preparing the alcoholysis type octadecyl methacrylate-maleic anhydride-acrylamide terpolymer, the molar ratio of the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer to the higher alcohol is 1: (1-2); the higher alcohol is selected from one of higher dodecanol, higher tetradecanol, higher hexadecanol and higher octadecanol.
The specific implementation conditions are as follows:
TABLE 1 conditions for carrying out the examples and comparative examples
Example 2 characterization
In the embodiment, the crude oil with high freezing point is used as the experimental oil, the wax content of the experimental oil is 30%, the freezing point is 45 ℃, the content of colloid asphaltene is 10-15%, the viscosity is 900-1400 mPa & S, and the freezing point of the crude oil pour point depressant is detected according to the GB/T510-.
In this example, the viscosity is a viscosity value at 60 ℃ of a tetrapolymer-based pour point depressant for high pour point crude oil.
TABLE 2 Performance test results of tetrapolymer pour point depressant for high pour point crude oil
| Sample numbering | Freezing point/. degree.C | Reduction in amplitude/deg.C | Viscosity mPa.s |
| 1 | 24 | 21 | 480 |
| 2 | 22 | 23 | 410 |
| 3 | 15 | 30 | 240 |
| 4 | 20 | 25 | 350 |
| 5 | 23 | 22 | 430 |
| 6 | 21 | 24 | 390 |
| 7 | 19 | 26 | 300 |
| 8 | 17 | 28 | 260 |
| 9 | 18 | 27 | 280 |
| Comparative example 1 | 25 | 20 | 550 |
| Comparative example 2 | 32 | 13 | 640 |
| Comparative example 3 | 30 | 15 | 600 |
| Comparative example 4 | 31 | 14 | 610 |
| Comparative example 5 | 31 | 14 | 630 |
When the mass ratio of the first substance to the second substance is 1:2.5, the coagulation and viscosity reducing effects are the best. The pour point depressing effect is increased and then decreased along with the increase of the content of the second substance, because the formed pour point depressing agent structure in the compound system has a long enough carbon chain structure, the content of the polar functional group is proper, the pour point depressing effect is better, and when the content of the second substance is lower or higher, the polar molecules in the system generate cross-linking effect due to low or high content, so that the pour point depressing effect is decreased.
The montmorillonite is a lamellar silicate mineral with nano-sized particles, after the montmorillonite is organically modified by a surfactant, the interlayer spacing of a crystal structure is increased, the hydrophilicity of the particles is changed into hydrophobicity, and organic matters are favorably introduced between the layers, so that the modified nano montmorillonite also has a certain pour point depressing and viscosity reducing effect; when long-chain molecules are introduced on the surface or between layers of the nano modified montmorillonite, polar groups in the montmorillonite can interact with colloid and asphaltene in the high-coagulation crude oil to form hydrogen bonds with the colloid and the asphaltene, so that the colloid and the asphaltene are prevented from agglomerating, and the effects of reducing coagulation and reducing viscosity are achieved.
The first substance is compounded with the alcoholysis type octadecyl methacrylate-maleic anhydride-acrylamide terpolymer, and compared with the compounding of the first substance and the non-alcoholysis type octadecyl methacrylate-maleic anhydride-acrylamide terpolymer, the condensation reduction and viscosity reduction effects are both obviously improved, because the content of polar groups in the alcoholysis type octadecyl methacrylate-maleic anhydride-acrylamide terpolymer is increased, the polar effect is enhanced, wax crystal molecules are not easy to mutually twine to form macromolecules, and the polar groups can form hydrogen bonds with colloid and asphaltene, so the condensation reduction and viscosity reduction effects are enhanced; the first substance formed by the copolymerization of the nano modified montmorillonite and four monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide can be used as a nucleation point of paraffin wax crystallization due to the small size effect and the special nucleation effect of the nano montmorillonite, prevents the paraffin wax from crystallizing into larger wax blocks, introduces strong polar groups between montmorillonite layers, and the strong polar groups can react with colloid and asphaltene in the high condensation point crude oil to form hydrogen bonds and prevent the colloid asphaltene from forming a three-dimensional network structure. The first substance and the second substance act synergistically to reduce the condensation point and viscosity of the high-condensation-point crude oil and improve the low-temperature fluidity of the high-condensation-point crude oil, so that the high-condensation-point crude oil is convenient to extract and transport.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A quadripolymer pour point depressant for high freezing point crude oil is characterized by consisting of a first substance and a second substance;
the first substance is a nano modified montmorillonite composite material formed by copolymerizing modified montmorillonite and four monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide;
the second substance is alcoholysis type terpolymer formed by alcoholysis of octadecyl methacrylate-maleic anhydride-acrylamide terpolymer.
2. The tetrapolymer-based pour point depressant for high pour point crude oil according to claim 1, wherein the weight ratio of the first substance to the second substance is 1: (1.5 to 3).
3. The quadripolymer pour point depressant for high pour point crude oil according to claim 1, wherein the molar ratio of monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide in the first substance is (2-3): 1: (1-2): (1-2).
4. The tetrapolymer pour point depressant for high freezing point crude oil according to claim 1, wherein the molar ratio of monomers of octadecyl methacrylate, maleic anhydride and acrylamide in the second substance is (3-4): 1: (1-2).
5. The tetrapolymer pour point depressant for high pour point crude oil according to claim 1, wherein the size of the modified montmorillonite is 200 to 300 nm.
6. A method for producing a tetrapolymer-based pour point depressant for high pour point crude oil according to any one of claims 1 to 5, comprising the steps of:
and adding the first substance and the second substance into dimethylbenzene, and performing ultrasonic dispersion uniformly to obtain the quadripolymer pour point depressant for the high-freezing-point crude oil.
7. The method for preparing the tetrapolymer pour point depressant for high freezing point crude oil according to claim 6, wherein the first substance comprises the following preparation steps:
adding modified montmorillonite into absolute ethyl alcohol, continuously stirring until the modified montmorillonite is uniformly dispersed in the absolute ethyl alcohol, adding monomers of octadecyl methacrylate, maleic anhydride, polyethylene glycol and acrylamide, keeping the temperature of 65-75 ℃ for 10min under the protection of nitrogen, adding azodiisobutyronitrile, reacting for 6-8 hours, centrifuging, washing and drying to obtain the first substance.
8. The method for preparing the quadripolymer pour point depressant for high pour point crude oil according to claim 6, wherein the modified montmorillonite comprises the following preparation steps:
mixing montmorillonite with pure water to prepare a suspension of 5-8%, and heating to 65 ℃;
and adding the aqueous solution of dodecyl benzene sulfonate into the suspension under the condition of continuously stirring, reacting for 7-8 hours, cooling and standing, centrifuging, washing, drying, and grinding into powder to obtain the modified montmorillonite.
9. The method for preparing the tetrapolymer-based pour point depressant for high freezing point crude oil according to claim 6, wherein the second substance comprises the following preparation steps:
adding azodiisobutyronitrile into a mixture of monomers of octadecyl methacrylate, maleic anhydride and acrylamide, and carrying out polymerization reaction at the temperature of 60-70 ℃ under the protection of nitrogen for 5-6 hours to obtain an octadecyl methacrylate-maleic anhydride-acrylamide terpolymer;
mixing the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer with high-carbon alcohol, carrying out alcoholysis reaction at the temperature of 100-110 ℃ by taking p-toluenesulfonic acid as a catalyst for 4-5 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a second substance;
the high-carbon alcohol is selected from one of high-carbon dodecanol, high-carbon tetradecanol, high-carbon hexadecanol and high-carbon octadecanol;
the molar ratio of the octadecyl methacrylate-maleic anhydride-acrylamide terpolymer to the higher alcohol is 1: (1-2).
10. Use of the tetrapolymer-based pour point depressant for high pour point crude oil according to any one of claims 1 to 5 or the tetrapolymer-based pour point depressant for high pour point crude oil prepared by the preparation method according to any one of claims 6 to 9 in high pour point crude oil.
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Application publication date: 20211008 |