CN109553988B - Asphaltene dispersant compositions and methods of dispersing asphaltene deposits - Google Patents

Asphaltene dispersant compositions and methods of dispersing asphaltene deposits Download PDF

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CN109553988B
CN109553988B CN201710882167.9A CN201710882167A CN109553988B CN 109553988 B CN109553988 B CN 109553988B CN 201710882167 A CN201710882167 A CN 201710882167A CN 109553988 B CN109553988 B CN 109553988B
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CN109553988A (en
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李�诚
王小伟
田松柏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)

Abstract

The invention provides an asphaltene dispersant composition and a method for dispersing asphaltene deposits. The asphaltene dispersant composition of the present invention comprises an ester-based polymer, a sorbitan fatty acid ester, and/or an alkylbenzene, the structure of the ester-based polymer being:
Figure DDA0001419387740000011
wherein the group T represents the backbone of the ester-based polymer; group B is selected from O, S; y radicals R, equal to or different from each other, are each independently selected from C1‑10A hydrocarbyl group; y groups A, equal to or different from each other, are each independently selected from O, S or NH; r' is preferably C1‑10A hydrocarbyl group; y is preferably an integer between 1 and 6; two of the repeating units NbEach independently selected from H or-R '-BH, wherein R' is preferably C1‑10A hydrocarbyl group, at least one selected from-R' -BH; m is an integer between 1 and 10. The dispersant composition of the present invention has very excellent dispersing properties and is particularly suitable for use as a dispersant for asphaltene deposits.

Description

Asphaltene dispersant compositions and methods of dispersing asphaltene deposits
Technical Field
The present invention relates to a dispersant composition, and in particular to a dispersant composition for dispersing asphaltene deposits.
Background
Asphaltenes, generally defined as petroleum components that are insoluble in n-heptane and soluble in toluene, are a class of materials defined by solubility, which is the highest relative molecular mass, the most polar and the most difficult to process component of heavy oil. The presence of asphaltenes makes heavy oil have the characteristics of a colloid system, and when the environment where the asphaltenes are located is changed due to changes in temperature, pressure or components, the asphaltenes are easy to flocculate and deposit, so that adverse effects are brought to the production, storage and transportation and processing of petroleum. In the process of oil exploitation, the flocculation and deposition of asphaltene can cause the reduction of the permeability and the reversion of the wettability of rocks, so that permanent oil deposit damage is caused, and peripheral equipment such as well pipes, separators and the like can be blocked, so that the production efficiency is seriously reduced; in the process of transporting and storing petroleum, the flocculation and deposition of the asphaltene can cause the scaling of a pumping pipeline and related treatment equipment thereof, and the transmission efficiency is seriously influenced; in the process of processing petroleum, asphaltene is used as a raw coke precursor to deposit on the surface of a hot solid (such as the wall of a reactor, the wall of a heating furnace tube and the wall of a heat exchanger), which can cause coking and inactivation of a catalyst or coking and scaling of a device, thereby reducing the production efficiency and bringing difficulty to processing and utilization of heavy oil.
One of the most cost effective ways to prevent flocculation and deposition of asphaltenes is to add chemical additives (dispersants and/or inhibitors). Common chemical additives include alkylphenols, alkylsulfonic acids, alkylpyrrolidones, alkylphenol ethoxylates, fatty acid ester polyols, alkyl phenolic resins, oil-soluble polymers, novel ionic liquids, and the like. The literature does not conclude exactly the same for the dispersing and inhibiting effect of chemical additives, which may be related to the kind and structure of asphaltenes, solvent conditions and the method of evaluation of the chemical additives. Although most chemical additives have been used in oil fields for many years, there is still a lot of research work on finding more effective, more economical (cheap, readily available materials), safer to human, more environmentally friendly chemical additives.
There are some known asphaltene dispersants in the prior art. CA 2029465 and CA 2075749 disclose combinations of alkylphenol-formaldehyde resins with hydrophilic-lipophilic vinyl polymers. Dodecyl Benzene Sulfonic Acid (DBSA) has asphaltene-dispersing properties described in published papers such as US 4414035 and D.L. Chang, H.S. Fogler (SPE article No. 25185, 1993) and Francia Marcano (Energy & Fuels, 2015, 29 (5): 2813-2822).
Disclosure of Invention
The invention provides an asphaltene dispersant composition and a method for dispersing asphaltene deposits.
The asphaltene dispersant composition of the present invention comprises an ester-based polymer, a sorbitan fatty acid ester, and/or an alkylbenzene, the structure of the ester-based polymer being:
Figure BDA0001419387730000021
wherein the group T represents the backbone of the ester-based polymer; group B is selected from O, S, preferably O; y radicals R, equal to or different from each other, are each independently selected from C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); y groups A, equal to or different from each other, are each independently selected from O, S or NH, preferably O or S; r' is preferably C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); y is preferably an integer between 1 and 6, preferably an integer between 1 and 3, most preferably 1; two of the repeating units NbEach independently selected from H or-R '-BH, wherein R' is preferably C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl), at least one is selected from-R' -BH, more preferably two NbEach independently selected from-R' -BH; m is an integer between 1 and 10, preferably between 1 and 5, most preferably 2.
According to the invention, as the matrix polymer of the ester-based polymer, for example, polyolefins, polyethers, polyesters, preferably polyolefins, including but not limited to C, may be used2-20Homopolymers or copolymers of olefins, more preferably C2-10Examples of homopolymers or copolymers of olefins include, for example, polyethylene, polypropylene, polybutene, polyisobutylene, polypentene, polyhexene, polyoctene, polynonane, and polydecene. The molecular weight of the ester-based polymer is preferably 600-10500, and more preferably 800-4500.
The invention also provides a preparation method of the ester-based polymer, which comprises the following steps:
1) will be provided with
Figure BDA0001419387730000022
And
Figure BDA0001419387730000023
and/or
Figure BDA0001419387730000024
By acylation reaction to produce
Figure BDA0001419387730000025
A step (2); wherein the group B is selected from O, S, preferably O; y radicals R, equal to or different from each other, are each independently selected from C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); y groups A, equal to or different from each other, are each independently selected from O, S or NH, preferably O or S; r' is preferably C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl); y is preferably an integer between 1 and 6, preferably an integer between 1 and 3, most preferably 1; the above-mentioned
Figure BDA0001419387730000031
Two of NbEach independently selected from H or-R '-BH, wherein R' is preferably C1-10Hydrocarbyl (preferably C)1-6Straight or branched alkyl, further preferably C1-4Straight or branched chain alkyl), at least one is selected from-R' -BH, more preferably two NbEach independently selected from-R' -BH;
2) will contain-COOH groups and/or
Figure BDA0001419387730000032
A step of esterification reaction of the polymer of the group and the product of the step 1).
The preparation method of the ester-based polymer has the same definition as the above groups.
Described in step 1)
Figure BDA0001419387730000033
The alcohol amine and/or thiol amine can be selected, preferably the alcohol amine and/or thiol amine containing two hydroxyl groups or thiol groups, more preferably the C1-C10 alcohol amine and/or thiol amine containing two hydroxyl groups or thiol groups, for example, one or more of ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, ethanediol amine, propanediol amine, butanediamine amine, pentanedioamine, hexanediol amine, ethanethiol amine, propanethiol amine, butanethiol amine, pentanethioamine, hexanthiol amine, ethanedithiol amine, propanethiol amine, butanethiol amine, pentanethioamine, hexanthiol amine, ethanedithiol amine, propanethiol amine, butanethiol amine, hexanthiol amine; the above-mentioned
Figure BDA0001419387730000034
Ethers containing hydroxyl and carboxyl groups, ethers containing sulfhydryl and carboxyl groups, ethers containing amino and carboxyl groups, preferably etherification products of alkylene glycol and hydroxy acid, etherification products of alkylene dithiol and hydroxy acid, etherification products of alcohol amine and hydroxy acid, more preferably etherification products of alkylene glycol of C1-C5 and hydroxy acid of C1-C5, etherification products of alkylene dithiol of C1-C5 and hydroxy acid of C1-C5, etherification products of alcohol amine of C1-C5 and hydroxy acid of C1-C5, such as 2- (2-hydroxyethoxy) -acetic acid, 3- (2-hydroxyethoxy) -propionic acid, 3- (2-hydroxyethoxy) -butyric acid, 2- (3-hydroxypropoxy) -acetic acid, 2- (4-hydroxybutoxy) -propionic acid, One or more of 2- (2-hydroxyethylthio) -acetic acid, 3- (2-hydroxyethylthio) -propionic acid, 3- (2-hydroxyethylthio) -butyric acid, 2- (3-hydroxypropylthio) -acetic acid and 2- (4-hydroxybutylthio) -propionic acid; the above-mentioned
Figure BDA0001419387730000035
Oxalactones, thialactones, azalides may be selected, with oxalactones being preferred; examples which may be mentioned include oxetanone, oxetanolactone (dioxadione), valerolactone, oxacaprolactone, oxaheptolactone, oxaoctalactone, thietanolactone, thietanelactone, and thietanolactoneOne or more of lactones, thia-octanolactones, aza-propiolactones, aza-butyrolactones, aza-valerolactones, aza-caprolactones, aza-heptanolactones, and aza-octanolactones.
The alcohol amine is preferably a compound of the formula:
Figure BDA0001419387730000041
wherein R is1And R2May be the same or different and are each independently selected from the group consisting of C1-C10 alkylene groups, preferably C1-C4 alkylene groups.
The above-mentioned
Figure BDA0001419387730000042
Preferred are compounds having the general formula:
Figure BDA0001419387730000043
wherein R is3And R4May be the same or different and are each independently selected from C1-C10 alkyl, preferably H or C1-C4 alkyl.
In the step 1), the
Figure BDA0001419387730000044
And
Figure BDA0001419387730000045
and/or
Figure BDA0001419387730000046
The molar ratio of the two is generally 1: 0.1-10, preferably 1: 0.5-5, more preferably 1: 0.9-1.1;
the reaction temperature in the step 1) is preferably 50-150 ℃, and more preferably 80-120 ℃;
the reaction pressure in the step 1) is preferably 0.1 to 10MPa, more preferably 0.1 to 5 MPa;
the reaction time in the step 1) is preferably 0.1h-10h, more preferably 4h-8 h;
in step 1), an inert gas is preferably introduced, and nitrogen gas is more preferably introduced.
The solvent may or may not be added in the reaction of step 1). When the solvent is selected, one or more of butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, cyclooctane, nonane, undecane, dodecane, benzene, toluene, xylene, cumene, vegetable oil, carbon tetrachloride, dichloroethane and liquid paraffin, preferably toluene and/or xylene, may be added. The amount of the solvent may be varied from its conventional amount, and preferably the solvent is used in the amount of
Figure BDA0001419387730000047
10-200% of the mass. The solvent can be removed after the reaction is complete in a manner known to those skilled in the art.
The catalyst may or may not be added in the reaction of step 1). When a catalyst is selected for addition, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieves may be added, with silica being preferred. The amount of the catalyst is preferably the amount of
Figure BDA0001419387730000051
0.1 to 20% by mass, preferably 0.5 to 2% by mass.
Said group containing-COOH and/or in step 2)
Figure BDA0001419387730000052
The polymers of the radicals preferably contain q-COOH groups and/or
Figure BDA0001419387730000053
Polymers of groups, wherein q is a-COOH group and/or
Figure BDA0001419387730000054
The ratio of the total number of groups to the number of polymer molecules, which is an average value, may be non-integer, and q is preferably selected in the range of 1. ltoreq. q.ltoreq.10, more preferablySelecting q is more than or equal to 1 and less than or equal to 5; said molecule containing q-COOH groups and/or
Figure BDA0001419387730000055
The polymers of the radicals preferably contain q-COOH groups and/or
Figure BDA0001419387730000056
Polyolefins, polyethers, polyesters of the group. Said group containing-COOH and/or
Figure BDA0001419387730000057
The molecular weight of the polymer of the group is preferably 500 to 10000, more preferably 600 to 6000, and further preferably 600 to 3000.
In said step 2), said compound containing-COOH groups and/or
Figure BDA0001419387730000058
Polymers of radicals (with-COOH groups and/or
Figure BDA0001419387730000059
Calculated by groups) to the product of step 1) is generally 1:0.1 to 10, preferably 1:0.5 to 5, more preferably 1:0.9 to 1.1;
the reaction temperature in the step 2) is preferably 100-300 ℃, and more preferably 120-200 ℃;
the reaction pressure in the step 2) is preferably 0.1 to 10MPa, more preferably 0.1 to 5 MPa;
the reaction time in the step 2) is preferably 0.1h-10h, more preferably 2h-8 h;
in step 2), an inert gas is preferably introduced, and nitrogen gas is more preferably introduced.
The solvent may or may not be added in the reaction of step 2). When the solvent is selected to be added, one or more of butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, cyclooctane, nonane, undecane, dodecane, benzene, toluene, xylene, cumene, vegetable oil, carbon tetrachloride, dichloroethane, and liquid paraffin may be added. The amount of the solvent may vary from that ofIn an amount which is preferably equal to the amount of the catalyst, said catalyst preferably contains-COOH groups and/or
Figure BDA0001419387730000061
The polymer mass of the radical is between 10% and 200%. The solvent can be removed after the reaction is complete in a manner known to those skilled in the art.
The catalyst may or may not be added in the reaction of step 2). When a catalyst is selected for addition, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieves may be added, with silica being preferred. The amount of the catalyst is preferably such that the catalyst contains-COOH groups and/or
Figure BDA0001419387730000062
The amount of the polymer of the radical is 0.1 to 20%, preferably 0.5 to 2%.
Said group containing-COOH and/or in step 2)
Figure BDA0001419387730000063
The polymer of the group is preferably a product of addition reaction of a polymer having-C ═ C-bonds with alkenyl acids and/or alkenyl acid anhydrides, more preferably a product of addition reaction of a polymer having u-C ═ C-bonds in the molecule with alkenyl acids and/or alkenyl acid anhydrides, wherein u is a ratio of the total number of-C ═ C-groups in the polymer to the number of polymer molecules, and may be a non-integer because it is an average value, and u is preferably selected from the range of 1. ltoreq. u.ltoreq.10, more preferably 1. ltoreq. u.ltoreq.5; further preferred are addition reaction products of polyolefins, polyethers and polyesters containing u-C ═ C-bonds in the molecule, and alkenyl acids and/or alkenyl acid anhydrides.
More preferably, the polymer having a — C ═ C-bond is preferably a polymer having 1 to 2-C ═ C-bonds in the molecule, more preferably a polyolefin having 1 to 2-C ═ C-bonds in the molecule, and further preferably a polymer having one-C ═ CH in the molecule after olefin polymerization2A bonded polyalphaolefin.
The molecular weight of the polymer having an — C ═ C-bond is preferably 500 to 10000, more preferably 600 to 6000, and still more preferably 600 to 3000. Said compound containing-C ═ C-bondsPolyolefin, preferably C2-20Homopolymers or copolymers of olefins, more preferably C2-20Polymers of alpha-olefins.
The alkenyl acid and/or alkenyl anhydride is preferably C3-10Alkenyl acids and/or alkenyl anhydrides, more preferably C4-10The alkenyl diacid and/or alkenyl dianhydride can be selected from one or more of acrylic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, butenedioic acid, glutaconic acid, hexenedioic acid, heptenoic acid, octenoic diacid, nonenedioic acid, decenedioic acid, maleic anhydride, butenedioic anhydride, glutaconic anhydride, hexenedioic anhydride, heptenoic dianhydride, octenoic dianhydride, nonenoic dianhydride, and decenoic dianhydride, for example.
The molar ratio between the polymer containing-C ═ C-bonds and the alkenyl acid and/or the alkenyl anhydride (calculated as-C ═ C-bonds) is generally 1:0.1 to 10, preferably 1:0.5 to 5, more preferably 1:0.9 to 1.1;
the reaction temperature between the polymer containing-C ═ C-bonds and the alkenyl acids and/or alkenyl anhydrides is preferably 100-; the reaction pressure is preferably 0.1 to 10MPa, more preferably 0.1 to 5 MPa; the reaction time is preferably 0.1h to 10h, more preferably 0.5h to 10 h; the reaction is preferably carried out with an inert gas, more preferably with nitrogen.
The reaction between the polymer having — C ═ C-bonds and the alkenyl acid and/or the alkenyl anhydride may or may not be carried out with a solvent. When the solvent is selected for addition, one or more of water, DMF, NMP, acetone, DMSO, butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, cyclooctane, nonane, undecane, dodecane, benzene, toluene, xylene, cumene, vegetable oils, carbon tetrachloride and dichloroethane may be added, preferably toluene and/or xylene. The amount of the solvent may be from its conventional amount, preferably from 10% to 200% of the mass of the polymer containing-C ═ C-bonds. The solvent can be removed after the reaction is complete in a manner known to those skilled in the art.
The reaction between the polymer having — C ═ C-bonds and the alkenyl acid and/or the alkenyl anhydride may or may not be carried out with a catalyst. When a catalyst is selected for addition, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieves may be added, with silica being preferred. The amount of the catalyst is preferably 0.1 to 20%, preferably 0.5 to 2%, by mass of the polyolefin having — C ═ C-bonds.
According to the present invention, after the preparation process of the ester-based polymer is completed, the ester-based polymer is obtained after removing the catalyst and the solvent, if any, from the finally obtained reaction mixture by any conventionally known means. The ester-based polymer of the present invention is particularly suitable for use as a dispersant and/or a polymerization inhibitor, and particularly suitable for use as an asphaltene dispersant and/or a polymerization inhibitor.
The sorbitan fatty acid ester is preferably a sorbitan fatty acid ester containing a C4-C30 hydrocarbon group, more preferably a sorbitan fatty acid ester containing a C8-C20 hydrocarbon group, and may be, for example, one or more of sorbitan lauric acid monoester, sorbitan myristic acid monoester, sorbitan palmitic acid monoester, sorbitan oleic acid monoester and sorbitan stearic acid monoester, and may be available under the trade designations span20 (span 20), span40 (span 40) and span 60(span 60).
The alkylbenzene is preferably an alkyl-substituted benzene having 7 to 20 carbon atoms in total, and may be a mono-substituted benzene, or a poly-substituted benzene, and more preferably an alkyl-substituted benzene having 8 to 16 carbon atoms in total, and may be one or more selected from 1-ethyl-2, 3-xylene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1, 2-dimethyl-4-ethylbenzene and 1, 2-dimethyl-3-ethylbenzene. The alkylbenzene is most preferably tetraalkyl substituted benzene with the total number of carbon atoms of 8-12.
In the dispersant composition of the present invention, the ester-based polymer accounts for 30% to 90%, preferably 40% to 80%, of the total mass of the composition, and the sorbitan fatty acid ester and/or alkylbenzene accounts for 10% to 70%, preferably 20% to 60%, of the total mass of the composition. When the sorbitan fatty acid ester and the alkylbenzene are added into the dispersant composition, the mass ratio of the sorbitan fatty acid ester to the alkylbenzene is 10: 1-1: 10, preferably 5: 1-1: 5.
The invention provides a method for dispersing asphaltene deposits, which comprises the following steps: the dispersant composition described above is added to the crude oil to be treated. The dispersant composition is preferably added in an amount of 0.001-1% by mass, most preferably 0.005-0.1% by mass, based on the crude oil to be treated.
The dispersant composition of the present invention has very excellent dispersing properties and is particularly suitable for use as a dispersant for asphaltene deposits.
Detailed Description
In a specific embodiment, the dispersion effect of the dispersant of the present invention was evaluated by the sample preparation method of ASTM D7061-2012 and the evaluation method of the chemical additive of asphaltene in the published article "Stable Dispersion Effect of chemical additive to asphaltene" (Licheng, King Xiaowei, Selaginella tamariscina, Stable Dispersion Effect of chemical additive to asphaltene. Petroleum institute (Petroleum processing), 2016.32 (5): page 1005-1012.).
The specific experimental process is as follows: the preparation mass ratio is 1: 9 oil-like-toluene sample solution. Weighing a certain amount of the sample solution, adding a certain amount of dispersant, stirring for 30min by using a magnetic stirrer, transferring 2mL of the sample solution containing the dispersant to be mixed with 23mL of n-heptane, immediately transferring to a sample cell, and measuring by using a Turbiscan stability analyzer. The experimental determination temperature is 30 ℃, the scanning time is 3h, and the scanning interval is 1 min.
The degree of change in light intensity within 3h is defined as ISP, see formula (1):
Figure BDA0001419387730000081
in the formula: xiThe average value of the intensity of the back scattered light (or the intensity of transmitted light) obtained at different heights of the sample cell is scanned each time; xTIs XiAverage value of (2), i.e. XT＝(X1+X2+…+Xn) N; n is the number of scans, 181.
The ISP value reflects the degree of instability of the system, with a larger value indicating a more unstable system and a more easily flocculated asphaltene to settle. Defining the extent of ISP value variation (C)ISP) To compare the degree of dispersion stability of the asphaltene by the dispersant visually and quantitatively, see formula (2):
Figure BDA0001419387730000091
in the formula: ISP (Internet service provider)0ISP number for the sample before addition of dispersantiIs the ISP value of the sample after addition of dispersant i. Therefore, only when CISP<0, the dispersant has the effect of dispersing and stabilizing the asphaltenes, and CISPThe smaller the dispersant, the more pronounced the effect of the dispersant.
Literature results indicate when ISP in a sample<3, or CISP<At-75%, the sample did not delaminate significantly, indicating that the asphaltene concentration in the sample was low or that the dispersant was able to substantially disperse asphaltene precipitation in the hydrocarbon mixture.
Preparation example 1
10.5 g of diethanolamine (compound 1, available from Beijing Ethicoki technology Co., Ltd.) and 10.2 g of 1, 4-dioxane-2-one (compound 2, available from Beijing Ethicoki technology Co., Ltd.) were mixed uniformly and added to a 50 ml round bottom flask, heated to 100 ℃ for reaction for 6 hours, the compounds 1 and 2 were in a molten state during the heating, and cooled and left to stand to obtain N, N-bis- (2-hydroxyethyl) -2-hydroxyethoxyacetamide (compound 3, see the following formula) (20 g) as a colorless oil, which was used in the next reaction without purification.
Polyisobutylene maleic anhydride (compound 4, n 15, Mn 994) (0.5 eq) was added to a 50 ml round bottom flask and nitrogen was passed for 5 minutes, then heated to 160 ℃, stirred at 160 ℃ for 30 minutes, compound 3 was added to the solution and the reaction was continued at 160 ℃ for 3.5 hours, cooled to room temperature to give compound 5, i.e. compound L-01, as a yellow oil.
An exemplary reaction is as follows:
Figure BDA0001419387730000092
example 1
80% by weight of L01 and 20% by weight of span20 (available from Bester reagent) were mixed and stirred at 100 ℃ to obtain dispersant composition EE-01.
Example 2
80% by weight of L01 and 20% by weight of span40 (available from Bester reagent) were mixed and stirred at 100 ℃ to obtain dispersant composition EE-02.
Example 3
80% by weight of L01 was mixed with 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-03.
Example 4
80% by weight of L01 was mixed with 20% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-04.
Example 5
60% by weight of L01 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,4, 5-tetramethylbenzene (SJB available from YinoKay technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition E-01.
Example 6
60% by weight of L01 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinakai technologies, Inc. of Beijing) at 100 deg.C and stirred to obtain dispersant composition E-02.
Example 7
70% by weight of L01 was mixed with 10% by weight of span20 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition E-03.
Example 8
60% by weight of L01 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-01.
Example 9
60% by weight of L01 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-02.
Example 10
70% by weight of L01 was mixed with 10% by weight of span40 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-03.
Preparation example 2
13.3 g of diisopropanolamine (compound 6, available from Beijing YinuoKai science and technology Co., Ltd.) and 10.2 g of 1, 4-dioxane-2-one (compound 2) were uniformly mixed and added into a 50 ml round-bottom flask, and the mixture was heated to 100 ℃ to react for 6 hours, wherein the compounds 1 and 2 were in a molten state during heating, and then cooled and stood to obtain N, N-bis- (2-hydroxyisopropyl) -2-hydroxyethoxyacetamide (compound 7) (23 g) as a colorless oil which was used for the next reaction without purification.
Polyisobutylene maleic anhydride PIBSA (compound 4, n 15, Mn 994) (0.5 eq) was added to a 50 ml round bottom flask, purged with nitrogen for 5 minutes, then heated to 160 ℃, stirred at 160 ℃ for 30 minutes, compound 3 was added to the solution, the reaction was continued at 160 ℃ for 3.5 hours, and cooled to room temperature to give compound 8, i.e. yellow oil L-02.
An exemplary reaction is as follows:
Figure BDA0001419387730000121
example 11
80% by weight of L02 and 20% by weight of span20 (available from Bester reagent) were mixed and stirred at 100 ℃ to obtain dispersant composition EE-05.
Example 12
80% by weight of L02 and 20% by weight of span40 (available from Bester reagent) were mixed and stirred at 100 ℃ to obtain dispersant composition EE-06.
Example 13
80% by weight of L02 was mixed with 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-07.
Example 14
80% by weight of L02 was mixed with 20% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-08.
Example 15
60% by weight of L02 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,4, 5-tetramethylbenzene (SJB available from YinoKay technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition E-04.
Example 16
60% by weight of L02 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinakai technologies, Inc. of Beijing) at 100 deg.C and stirred to obtain dispersant composition E-05.
Example 17
70% by weight of L02 was mixed with 10% by weight of span20 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition E-06.
Example 18
60% by weight of L02 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-04.
Example 19
60% by weight of L02 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-05.
Example 20
70% by weight of L02 was mixed with 10% by weight of span40 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-06.
Preparation example 3
After 10.5 g of diethanolamine (compound 1) and 10.2 g of 1, 4-dioxane-2-one (compound 2) are uniformly mixed, the mixture is added into a 50 ml round bottom flask, the mixture is heated to 100 ℃ to react for 6 hours, the compounds 1 and 2 are in a molten state during heating, and the mixture is cooled and stood to obtain N, N-bis- (2-hydroxymethyl) -2-hydroxyethoxyacetamide (compound 3) (20 g) colorless oil which is directly used for the next reaction without purification.
Polyisobutylene maleic anhydride (compound 9, n-18, Mn-1162) (0.5 eq) was added to a 50 ml round bottom flask, purged with nitrogen for 5 minutes, then heated to 160 ℃, stirred at 160 ℃ for 30 minutes, compound 3 was added to the solution, the reaction was continued at 160 ℃ for 3.5 hours, and cooled to room temperature to give compound 10, i.e. L-03, as a yellow oil.
An exemplary reaction is as follows:
Figure BDA0001419387730000141
example 21
80% by weight of L03 was mixed with 20% of span20 (available from Bester reagent) at 100 ℃ with stirring to give dispersant composition EE-09.
Example 22
80% by weight of L03 and 20% by weight of span40 (available from Bester reagent) were mixed and stirred at 100 ℃ to obtain dispersant composition EE-10.
Example 23
80% by weight of L03 was mixed with 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-11.
Example 24
80% by weight of L03 was mixed with 20% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EE-12.
Example 25
60% by weight of L03 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,4, 5-tetramethylbenzene (SJB available from YinoKay technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition E-07.
Example 26
60% by weight of L03 was mixed with 5% span20 (available from Bester reagent) and 35% of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinakai technologies, Inc. of Beijing) at 100 deg.C and stirred to obtain dispersant composition E-08.
Example 27
70% by weight of L03 was mixed with 10% by weight of span20 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition E-09.
Example 28
60% by weight of L03 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyy technologies, Inc., Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-07.
Example 29
60% by weight of L03 was mixed with 5% by weight of span40 (available from Bester reagent) and 35% by weight of 1,2,3,4, 5-pentamethylbenzene (WJB available from Yinaoka technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-08.
Example 30
70% by weight of L01 was mixed with 10% by weight of span40 (available from Bester reagent) and 20% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinocyk technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain dispersant composition EB-09.
Comparative example 1
Uniformly mixing 10.5 g of diethanolamine (compound 1, available from Beijing Ethickory technologies, Ltd.) and 10.0 g of valerolactone (compound 11, available from Beijing Ethickory technologies, Ltd.) and adding into a 50 ml round-bottom flask, heating to 100 ℃ for reaction for 6 hours, wherein the compounds 1 and 2 are in a molten state during heating, cooling and standing to obtain 5-hydroxy-N, N-bis- (2-hydroxyethyl) -valeramide (compound 13, shown in the following formula) (20 g) as colorless oil which is directly used for the next reaction without purification.
Polyisobutylene maleic anhydride (compound 4, n 15, Mn 994) (0.5 eq) was added to a 50 ml round bottom flask and nitrogen was passed for 5 minutes, then heated to 160 ℃, stirred at 160 ℃ for 30 minutes, compound 3 was added to the solution and the reaction continued at 160 ℃ for 3.5 hours, cooled to room temperature to give compound 14, compound D-01, as a yellow oil.
An exemplary reaction is as follows:
Figure BDA0001419387730000171
comparative example 2
60% by weight of D01 was mixed with 5% by weight of span20 (available from Bester reagent) and 35% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinakai science Co., Ltd., Beijing) at 100 ℃ and stirred to obtain dispersant composition ED-01.
Comparative example 3
Referring to the literature (green synthesis and application research of polyisobutylene succinic acid alcohol amine, cheng liu lock, master's academic thesis, nanjing university), polyisobutylene maleic anhydride PIBSA (compound 4, n ═ 15, Mn ═ 994) was esterified with 2 times equivalent of Triethanolamine (TEA) to give product D-02.
The specific reaction conditions are as follows: n (PIBSA)/n (TEA) 1:2, preheating PIBSA to 160 ℃, slowly adding TEA while stirring, controlling the feeding speed, and after the dropwise addition is finished, keeping the temperature for reaction for 3.5 hours.
60% by weight of D-02 was mixed with 5% by weight of span20 (available from Bester reagent) and 35% by weight of 1,2,4, 5-tetramethylbenzene (SJB available from Yinakai technologies, Inc. of Beijing) at 100 ℃ and stirred to obtain a dispersant composition ED-02.
Example 31
The asphaltene dispersants L-01, L-02, L-03, D-01, D-02, EE-01, EE-02, EE-03, EE-04, EE-05, EE-06, EE-07, EE-08, EE-09, EE-10, EE-11, EE-12, E-01, E-02, E-03, E-04, E-05, E-06, E-07, E-08, E-09, EB-01, EB-02, EB-03, EB-05, EB-01, EB-03, EB-05, ED-02, FAD-07, EB-08, EB-09, ED-01, ED-02, and commercial dispersants L-01, L-03, D-01, D-02, EE-10 are evaluated by using the Tahe slag reduction (THVR) with a boiling point, span20, span40, 1,2,4, 5-tetramethylbenzene (SJB available from Beijing YinuoKai technology Co., Ltd.), 1,2,3,4, 5-pentamethylbenzene (WJB available from Beijing YinuoKai technology Co., Ltd.), and lubricating oil ashless dispersant polyisobutenamide TAD (produced by petrochemical Co., Ltd.) exhibited a dispersing effect on asphaltenes in the n-toluene-slag reducing system at the added amounts (ratio of additive mass to slag reducing mass) of 50ppm and 100 ppm. The results of the blank test and the test after the addition of additives are shown in Table 1.
TABLE 1 evaluation results of dispersant dispersion efficiency (with blank test)
Figure BDA0001419387730000181
Figure BDA0001419387730000191
For the samples after addition of chemical additives, when ISP<3, and CISP<At-75%, no precipitate was produced in the sample. As can be seen from the test results in Table 1, the asphaltene dispersant composition of the invention is present at the same addition levelCISPAll values are less than-75%, and CISPThe values are significantly less than the control, indicating that the dispersant composition of the present invention is effective in dispersing asphaltene precipitation in hydrocarbon mixtures.

Claims (37)

1. An asphaltene dispersant composition comprising a sorbitan fatty acid ester and an ester-based polymer, or comprising a sorbitan fatty acid ester, an alkylbenzene, and an ester-based polymer, wherein the ester-based polymer has the structure:
Figure FDA0002990151770000011
wherein the group T represents the backbone of the ester-based polymer; group B is selected from O, S; y radicals R, equal to or different from each other, are each independently selected from C1-10A hydrocarbyl group; y groups A, equal to or different from each other, are each independently selected from O, S or NH; r' is C1-10A hydrocarbyl group; y is an integer between 1 and 6; two of the repeating units NbEach independently selected from H or-R '-BH wherein R' is C1-10A hydrocarbyl group, at least one selected from-R' -BH; m is an integer between 1 and 10; the group T is a polyolefin; the molecular weight of the ester-based polymer is 600-10500.
2. The composition of claim 1 wherein group B is selected from O; y radicals R are each independently selected from C1-6A linear or branched alkyl group; y groups A are each independently selected from O or S; r' is C1-6A linear or branched alkyl group; y is an integer between 1 and 3; r' is C1-6A linear or branched alkyl group; m is an integer of 1 to 5.
3. The composition according to claim 1, wherein y groups R are each independently selected from C1-4A linear or branched alkyl group; r' is C1-4A linear or branched alkyl group; y is 1; r' is C1-4Straight or branched chain alkyl, two NbEach independently selected from-R' -BH; m is 2.
4. The composition of claim 1 wherein the polyolefin is C2-20Homopolymers or copolymers of olefins.
5. The composition of claim 1, wherein the ester-based polymer has a molecular weight of 800 to 4500.
6. The composition of claim 1, wherein the ester-based polymer is prepared by a method comprising:
1) will be provided with
Figure FDA0002990151770000012
And
Figure FDA0002990151770000013
by acylation reaction to produce
Figure FDA0002990151770000014
A step (2); wherein group B is selected from O, S; y radicals R, equal to or different from each other, are each independently selected from C1-10A hydrocarbyl group; y groups A, equal to or different from each other, are each independently selected from O, S or NH; r' is C1-10A hydrocarbyl group; y is an integer between 1 and 6; the above-mentioned
Figure FDA0002990151770000021
Two of NbEach independently selected from H or-R '-BH wherein R' is C1-10A hydrocarbyl group, at least one selected from-R' -BH;
2) will contain-COOH groups and/or
Figure FDA0002990151770000022
A step of esterification reaction of the polymer of the group and the product of the step 1).
7. The composition of claim 6, wherein the groupsB is selected from O; y radicals R are each independently selected from C1-6A linear or branched alkyl group; y groups A are each independently selected from O or S; r' is C1-6A linear or branched alkyl group; y is an integer between 1 and 3; r' is C1-6Straight or branched chain alkyl, two NbEach independently selected from-R' -BH.
8. A composition according to claim 6, wherein y groups R are each independently selected from C1-4A linear or branched alkyl group; r' is C1-4A linear or branched alkyl group; y is 1; r' is C1-4Straight or branched chain alkyl.
9. The composition of claim 6, wherein the composition of step 1) is
Figure FDA0002990151770000023
Is an alcohol amine and/or a thiol amine; the above-mentioned
Figure FDA0002990151770000024
Selected from ethers containing hydroxyl and carboxyl, ethers containing sulfhydryl and carboxyl; the above-mentioned
Figure FDA0002990151770000025
One or more selected from the group consisting of oxalactones, thialactones, and azalides.
10. The composition of claim 9, wherein the composition of step 1) is
Figure FDA0002990151770000026
Is C containing two hydroxy or mercapto groups1-C10Alcohol amines and/or thiol amines; the above-mentioned
Figure FDA0002990151770000027
Selected from the etherification products of alkylene glycols with hydroxy acids, the etherification of alkylene dithiols with hydroxy acidsA product; the above-mentioned
Figure FDA0002990151770000028
Selected from oxalactones.
11. The composition of claim 9, wherein the composition of step 1) is
Figure FDA0002990151770000029
Is C containing two hydroxy or mercapto groups1-C10Alcohol amines and/or thiol amines; the above-mentioned
Figure FDA0002990151770000031
Is selected from C1-C5Alkylene glycol of (2) with C1-C5Etherification product of hydroxy acid(s), C1-C5Alkylene dithiols with C1-C5Etherification products of hydroxy acids.
12. The composition of claim 6, wherein the composition of step 1) is
Figure FDA0002990151770000032
One or more selected from ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, ethanediolamine, propanediamine, butanediamine, pentanediolamine, hexanediolamine, ethanethiol, propanethiol, butanethiol, pentanethiolamine, hexanethiolamine, ethanedithiol, propanedithiolamine, butanedithiolamine, pentanethiolamine, hexanethiolamine, propanedithiolamine, butanedithiolamine, pentanethiolamine, hexanethi; the above-mentioned
Figure FDA0002990151770000033
Selected from the group consisting of 2- (2-hydroxyethoxy) -acetic acid, 3- (2-hydroxyethoxy) -propionic acid, 3- (2-hydroxyethoxy) -butyric acid, 2- (3-hydroxypropoxy) -acetic acid, 2- (4-hydroxybutoxy) -propionic acid, 2- (2-hydroxyethylthio) -acetic acid, 3- (2-hydroxyethylthio) -propionic acid, 3- (2-hydroxyethylthio) -butyric acid, 2- (3-hydroxypropylthio) -acetic acid and 2- (4-hydroxybutylthio) -propionic acidOne or more of (a); the above-mentioned
Figure FDA0002990151770000034
One or more selected from the group consisting of oxaprolactone, oxabutyrolactone, oxavalerolactone, oxaheptolactone, oxaoctalactone, thiapropiolactone, thiabutyrolactone, thiavalerolactone, thiacaprolactone, thiaheptolactone, and thiaoctalactone.
13. The composition of claim 9 wherein said alcohol amine is selected from the group consisting of compounds of the formula:
Figure FDA0002990151770000035
wherein R is1And R2May be the same or different and are each independently selected from C1～C4Alkylene group between;
the above-mentioned
Figure FDA0002990151770000036
Selected from compounds having the following general formula:
Figure FDA0002990151770000037
wherein R is3And R4Can be the same or different and are respectively and independently selected from H or C1～C4An alkyl group.
14. The composition according to claim 6, wherein the compound of step 2) contains-COOH groups and/or
Figure FDA0002990151770000041
The polymer of the group is a polymer containing q-COOH groups and/or
Figure FDA0002990151770000042
Polymers of groups, wherein q is a-COOH group and/or
Figure FDA0002990151770000043
The ratio of the total number of the groups to the number of polymer molecules, and the value range of q is more than or equal to 1 and less than or equal to 10; said molecule containing q-COOH groups and/or
Figure FDA0002990151770000044
The polymer of the group is a polymer containing q-COOH groups and/or
Figure FDA0002990151770000045
A polyolefin of the group.
15. The composition of claim 14, wherein q is in the range of 1. ltoreq. q.ltoreq.5.
16. Composition according to claim 6, characterized in that it contains-COOH groups and/or
Figure FDA0002990151770000046
The molecular weight of the polymer of the group is 500-10000.
17. Composition according to claim 6, characterized in that it contains-COOH groups and/or
Figure FDA0002990151770000047
The molecular weight of the polymer of the group is 600-6000.
18. Composition according to claim 6, characterized in that it contains-COOH groups and/or
Figure FDA0002990151770000048
Of polymers of radicalsThe molecular weight is 600-3000.
19. The composition according to claim 6, wherein, in the step 1), the composition is
Figure FDA0002990151770000049
And
Figure FDA00029901517700000410
the molar ratio of the components is 1: 0.1-10; the reaction temperature in the step 1) is 50-150 ℃; the reaction pressure in the step 1) is 0.1-10 MPa; the reaction time in the step 1) is 0.1-10 h; in said step 2), said compound containing-COOH groups and/or
Figure FDA00029901517700000411
The molar ratio of the polymer of the group to the product of the step 1) is 1: 0.1-10; the reaction temperature in the step 2) is 100-300 ℃; the reaction pressure in the step 2) is 0.1-10 MPa; the reaction time in the step 2) is 0.1-10 h.
20. The composition according to claim 6, wherein, in the step 1), the composition is
Figure FDA0002990151770000051
And
Figure FDA0002990151770000052
the molar ratio of the components is 1: 0.5-5; the reaction temperature in the step 1) is 80-120 ℃; the reaction pressure in the step 1) is 0.1-5 MPa; the reaction time in the step 1) is 4-8 h; in said step 2), said compound containing-COOH groups and/or
Figure FDA0002990151770000053
The molar ratio of the polymer of the group to the product of the step 1) is 1: 0.5-5; the reaction temperature in the step 2) is 120-200 ℃; the above-mentionedThe reaction pressure in the step 2) is 0.1-5 MPa; the reaction time in the step 2) is 2-8 h.
21. The composition according to claim 6, wherein the compound of step 2) contains-COOH groups and/or
Figure FDA0002990151770000054
The polymer of the group is a product of addition reaction of a polymer containing-C ═ C-bonds with alkenyl acids and/or alkenyl anhydrides.
22. The composition according to claim 6, wherein the compound of step 2) contains-COOH groups and/or
Figure FDA0002990151770000055
The polymer of the group is a product of addition reaction of a polymer containing u-C-bonds in a molecule and alkenyl acid and/or alkenyl anhydride, wherein u is the ratio of the total number of-C-groups in the polymer to the number of polymer molecules, and the value range of u is more than or equal to 1 and less than or equal to 10.
23. The composition of claim 22, wherein u is selected from the range of 1. ltoreq. u.ltoreq.5.
24. A composition according to claim 21, wherein the polymer containing-C-bonds is a polyolefin containing 1 to 2-C-bonds in the molecule.
25. A composition according to claim 24, wherein the polyolefin containing-C ═ C-bonds is selected from C2-20Homopolymers or copolymers of olefins.
26. A composition according to claim 24, wherein the polyolefin containing-C ═ C-bonds is selected from C2-20Polymers of alpha-olefins.
27. The composition of claim 21 wherein said alkenyl acid and/or anhydride is C3-10Alkenyl acids and/or C3-10An alkenyl anhydride.
28. The composition of claim 21 wherein said alkenyl acid and/or anhydride is C4-10Alkenyl diacid and/or C4-10Alkenyl dicarboxylic anhydrides.
29. The composition of claim 21, wherein said alkenyl acid and/or anhydride is selected from the group consisting of one or more of acrylic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, butenedioic acid, glutaconic acid, hexenedioic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, maleic anhydride, glutaconic anhydride, hexenedioic anhydride, heptenoic anhydride, octenoic anhydride, nonenoic anhydride, and decenoic anhydride.
30. Composition according to one of claims 1 to 29, characterized in that the fatty acid sorbitan ester is a fatty acid sorbitan ester containing C4～C30A hydrocarbon based sorbitan fatty acid ester.
31. Composition according to one of claims 1 to 29, characterized in that the fatty acid sorbitan ester is a fatty acid sorbitan ester containing C8～C20A hydrocarbon based sorbitan fatty acid ester.
32. The composition according to any one of claims 1 to 29, wherein the alkylbenzene is an alkyl-substituted benzene having a total number of carbon atoms of from 7 to 20.
33. The composition according to any one of claims 1 to 29, wherein the alkylbenzene is an alkyl-substituted benzene having a total number of carbon atoms of 8 to 16.
34. The composition according to one of claims 1 to 29, characterized in that said ester-based polymer represents 30% to 90% of the total mass of the composition and said sorbitan fatty acid ester and alkylbenzene represent 10% to 70% of the total mass of the composition.
35. The composition according to one of claims 1 to 29, characterized in that said ester-based polymer represents from 30% to 90% of the total mass of the composition and said sorbitan fatty acid ester represents from 10% to 70% of the total mass of the composition.
36. The composition according to one of claims 1 to 29, characterized in that a sorbitan fatty acid ester and an alkylbenzene are added simultaneously to the dispersant composition, and the mass ratio between the sorbitan fatty acid ester and the alkylbenzene is 10:1 to 1: 10.
37. A method of dispersing asphaltene deposits comprising: adding the dispersant composition as described in one of claims 1 to 36 to the crude oil to be treated.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1498230A (en) * 2001-03-28 2004-05-19 �ÿ���˹ʯ�ͻ�ѧ��Ʒ��˾ Mid-range vinylidene content polyisobufylene and production thereof
CN101220116A (en) * 2007-01-09 2008-07-16 天津市波菲特石油科技有限公司 Polyisobutylene amine
CN101260329A (en) * 2008-04-18 2008-09-10 东南大学 Special-purpose polyisobutene amine for gasoline and diesel oil clean dispersing agent and preparation method thereof
CN102057023A (en) * 2008-04-25 2011-05-11 雪佛龙奥伦耐有限责任公司 A lubricating oil additive composition and method of making the same
WO2012039900A2 (en) * 2010-09-23 2012-03-29 Shrieve Chemical Products, Inc. α-OLEFIN / VINYL PYRROLIDINONE COPOLYMERS AS ASPHALTENE DISPERSANTS
CN103755844A (en) * 2013-12-12 2014-04-30 南京理工大学 Method for preparing polyisobutylene succinic acid triethanolamine ester
CN105062451A (en) * 2015-07-20 2015-11-18 辽宁瑞达石油技术有限公司 Multifunctional oil-based cold production viscosity reducer
CN105086975A (en) * 2015-08-11 2015-11-25 中国石油化工股份有限公司 Thin oil modifier for preventing asphaltene from accumulating
CN109553782A (en) * 2017-09-26 2019-04-02 中国石油化工股份有限公司 Composite dispersing agent and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1498230A (en) * 2001-03-28 2004-05-19 �ÿ���˹ʯ�ͻ�ѧ��Ʒ��˾ Mid-range vinylidene content polyisobufylene and production thereof
CN101220116A (en) * 2007-01-09 2008-07-16 天津市波菲特石油科技有限公司 Polyisobutylene amine
CN101260329A (en) * 2008-04-18 2008-09-10 东南大学 Special-purpose polyisobutene amine for gasoline and diesel oil clean dispersing agent and preparation method thereof
CN102057023A (en) * 2008-04-25 2011-05-11 雪佛龙奥伦耐有限责任公司 A lubricating oil additive composition and method of making the same
WO2012039900A2 (en) * 2010-09-23 2012-03-29 Shrieve Chemical Products, Inc. α-OLEFIN / VINYL PYRROLIDINONE COPOLYMERS AS ASPHALTENE DISPERSANTS
CN103755844A (en) * 2013-12-12 2014-04-30 南京理工大学 Method for preparing polyisobutylene succinic acid triethanolamine ester
CN105062451A (en) * 2015-07-20 2015-11-18 辽宁瑞达石油技术有限公司 Multifunctional oil-based cold production viscosity reducer
CN105086975A (en) * 2015-08-11 2015-11-25 中国石油化工股份有限公司 Thin oil modifier for preventing asphaltene from accumulating
CN109553782A (en) * 2017-09-26 2019-04-02 中国石油化工股份有限公司 Composite dispersing agent and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"沥青质分散剂与阻聚剂研究进展";李诚等;《石油炼制与化工》;20170412;第48卷(第4期);第99-108页 *

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