CN114644727B - Polymer asphaltene inhibitor, preparation method thereof, compound system and application - Google Patents
Polymer asphaltene inhibitor, preparation method thereof, compound system and application Download PDFInfo
- Publication number
- CN114644727B CN114644727B CN202011494862.6A CN202011494862A CN114644727B CN 114644727 B CN114644727 B CN 114644727B CN 202011494862 A CN202011494862 A CN 202011494862A CN 114644727 B CN114644727 B CN 114644727B
- Authority
- CN
- China
- Prior art keywords
- asphaltene
- inhibitor
- asphaltene inhibitor
- solvent
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003112 inhibitor Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010779 crude oil Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 230000008021 deposition Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- -1 n-octadecyl Chemical group 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 42
- 239000002245 particle Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 230000005764 inhibitory process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- KWHDXJHBFYQOTK-UHFFFAOYSA-N heptane;toluene Chemical compound CCCCCCC.CC1=CC=CC=C1 KWHDXJHBFYQOTK-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000035859 Drug effect increased Diseases 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a polymer asphaltene inhibitor, a preparation method, a compound system and application thereof, and belongs to the technical field of asphaltene inhibitors. The structure of the asphaltene inhibitor is shown in the following formula, wherein x, y and z are the total molar ratio of each block, and x+y+z=1; r is n-octadecyl, the preparation method comprises the step of polymerization reaction of octadecyl methacrylate, styrene and vinyl sulfonic acid, and the inhibitor has good effect, good stability, wide application range, safety, reliability, economy and practicality, effectively solves the problem of asphaltene deposition in the storage and transportation process of heavy crude oil, and reduces the production safety risk and the running cost.
Description
Technical Field
The invention belongs to the technical field of asphaltene inhibitors, and particularly relates to a polymer asphaltene inhibitor, a preparation method, a compound system and application thereof.
Background
In the crude oil production process, asphaltene accumulation phenomenon can occur from the inside of stratum to pumps, oil pipes, wellheads, safety valves, oil outlet pipelines and ground facilities, the average content of asphaltene in heavy crude oil produced by an oil field is 20.35%, so that the formation of organic solid sediment is a serious problem affecting the petroleum industry, no chemical auxiliary agent capable of effectively inhibiting the asphaltene deposition for a long time is found at present, and the asphaltene deposition phenomenon of the oil field is not effectively solved.
Asphalt dispersants commonly used in oil fields are mainly prepared by stabilizing asphaltenes in crude oil so that they are in an equilibrium state without aggregation and precipitation.
Chinese patent application 02131111.0 discloses an asphaltene precipitation inhibitor composition useful in the recovery under reservoir conditions (high temperature, high pressure), crude oil gathering and processing, and the like. It consists of the following components: a) An amphiphilic compound having the structure:
wherein the method comprises the steps of，R 1 Is C 6 -C 15 R is an alkyl chain of 2 Is a hydrophilic polar functional group, R 1 And R is R 2 Para or meta; b) An enhancer selected from oil-soluble surfactants; c) A solvent that can dissolve components a) and b) selected from n-alkanes having a carbon number of 5 or greater than 5; in the composition, the weight ratio of the amphiphilic compound to the reinforcing agent is 50:1 to 1:2. The raw materials used in the inhibitor composition provided by the invention are industrial chemical raw materials, and the inhibitor composition has the characteristics of low price and safe use, but has unexpected synergistic enhancement effect on inhibiting asphaltene precipitation after being combined according to a certain proportion.
Chinese patent application 201610349079.8 discloses an asphaltene deposition inhibitor composition comprising a vegetable oil, a compound of formula C n H m SN 2 O 2 Nitrogen-containing sulfur-oxygen heteroatom compounds of the formula C t F 2t+1 C 6 H 4 SO 3 And a synergist shown as X. The invention also relates to a preparation method of the inhibitor composition, and the raw materials used in the method are easy to biodegrade, and have the advantages of environmental protection and low cost. The asphaltene inhibition rate of the asphaltene deposition inhibitor composition provided by the invention can reach more than 87%.
The literature (BA crude oil asphaltene property and action mechanism of deposition inhibitor, li Aiying, zhang Wenxiu, shu Fuchang and the like, chemical industry progress) discloses the inhibition effect of different types of inhibitors, wherein the inhibition rate of FAE183 can reach 91.43% when the addition amount is 100mg/L and the temperature is 90 ℃, the particle size of asphaltene particles can be reduced, the inhibitor FAE183 can prevent association between asphaltene molecules, and the main action mechanism is acid-base action, the basic group of the inhibitor and the acidic group of the asphaltene molecules are in action, and hydrogen bonding action and dipole action are assisted.
The existing inhibitors for solving asphaltene deposition mainly have the following problems:
(1) The filling concentration of the medicament is high, and the production cost is increased;
(2) The effect of the medicament is greatly influenced by the conveying condition, the storage environment and the temperature;
(3) The effective working time of the medicament is short, the performance is unstable, and the effect is poor.
Therefore, aiming at the problems existing in the prior art, the invention provides the asphaltene inhibitor which has the advantages of good effect, good stability, wide application range, safety, reliability, economy and practicality, effectively solves the problem of asphaltene deposition in the storage and transportation process of heavy crude oil, and reduces the production safety risk and the operation cost.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a polymer asphaltene inhibitor, a preparation method, a compound system and application thereof, which effectively solve the problem of asphaltene deposition in the heavy crude oil storage and transportation process and reduce the production safety risk and the operation cost.
In order to achieve the above object, the present invention has the following technical scheme:
first, the present invention provides an asphaltene inhibitor having the structure shown in the following formula:
x, y, z are the overall molar ratios of the blocks, x+y+z=1.
Wherein R is n-octadecyl.
In another aspect, the present invention provides a method for preparing the above asphaltene inhibitor, comprising the step of polymerizing stearyl methacrylate, styrene, and vinylsulfonic acid.
Preferably, the preparation method specifically comprises the following steps: and (3) dissolving octadecyl methacrylate, styrene and vinylsulfonic acid in a solvent, adding an initiator in a protective gas environment, and reacting at 65-75 ℃ for 5-7 hours to obtain the polymer asphaltene inhibitor.
Wherein,
the molar ratio of the octadecyl methacrylate to the styrene to the vinylsulfonic acid is 3-5:1:2-3.
The solvent is at least one selected from benzene, toluene and xylene, and preferably xylene.
The shielding gas includes, but is not limited to, nitrogen, inert gas, etc., and further preferably nitrogen.
The initiator is at least one selected from benzoyl peroxide and 2, 4-dichloro benzoyl peroxide, and is more preferably benzoyl oxide.
The reaction temperature is further preferably 70 ℃.
The reaction time is further preferably 6 hours.
In yet another aspect, the present invention provides a formulation system of the above polymeric asphaltene inhibitor, comprising the above polymeric asphaltene inhibitor, a dispersant, and a solvent.
Preferably, the mass ratio of the polymeric asphaltene inhibitor, dispersant and solvent is from 1:2 to 3:3 to 4, more preferably 1:3:4.
Preferably, the dispersing agent is at least one selected from nonylphenol, petroleum sulfonate, dodecylbenzene sulfonate and alkylphenol ethoxylates.
Preferably, the solvent is selected from carbon tetrachloride, chloroform, 200 # At least one of solvent oil and kerosene.
Finally, the invention provides the application of the polymer asphaltene inhibitor or the compound system thereof in the exploitation, gathering and processing processes of heavy crude oil and condensate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer asphaltene inhibitor has the advantages of simple preparation process, wide raw material sources and low cost;
(2) The asphaltene inhibitor has strong adaptability, and is suitable for crude oil with different water contents and different compositions;
(3) The asphaltene inhibitor has the advantages of small dosage and good inhibition effect;
(4) The asphaltene inhibitor can well delay asphaltene deposition points, reduce deposition amount and reduce deposit size.
Drawings
FIG. 1 is a graph of the characterization of a polymer prepared according to the present invention;
FIG. 2 is a graph of n-heptane absorbance at various volume fractions;
FIG. 3 is a graph of absorbance versus system for different concentrations of inhibitor;
FIG. 4 is a particle size distribution of asphaltenes in different n-heptane-toluene solvents (without inhibitor);
FIG. 5 is a particle size distribution (200 ppm) of asphaltenes in different n-heptane-toluene solvents;
FIG. 6 is a particle size distribution (400 ppm) of asphaltenes in different n-heptane-toluene solvents;
FIG. 7 is a particle size distribution (800 ppm) of asphaltenes in different n-heptane-toluene solvents;
FIG. 8 is the effect of n-heptane concentration on particle size distribution (55%) and average particle size;
FIG. 9 is the effect of n-heptane concentration on particle size distribution and average particle size (60%);
FIG. 10 is the effect of n-heptane concentration on particle size distribution (65%) and average particle size;
FIG. 11 is the effect of n-heptane concentration on particle size distribution (70%) and average particle size;
figure 12 is an effect of inhibitors on average particle size.
Detailed Description
In order that the manner in which the above recited features and advantages of the present invention are obtained, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. In the interest of clarity, not all features of an actual implementation are described. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. It will be appreciated that in the development of any such actual embodiment, numerous implementation details must be made in order to achieve the developer's specific goals. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention.
In order to make the objects and features of the present invention more comprehensible, embodiments accompanied with figures are described in detail below. It should be noted that the drawings are in a very simplified form and all employ non-precise ratios, and are merely convenient and clear to aid in the description of the embodiments of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
In the examples below, octadecyl methacrylate was purchased from Dongguan Yongzheng chemical Co., ltd.
Example 1
Octadecyl methacrylate, styrene and vinylsulfonic acid are dissolved in dimethylbenzene according to a molar ratio of 3:1:2 to prepare a solution with a monomer concentration of 20%, and an initiator benzoyl peroxide which is 0.7% of the mass of the monomer is added in a nitrogen environment to react for 6 hours at 70 ℃ to obtain the polymer asphaltene inhibitor 1.
Example 2
Octadecyl methacrylate, styrene and vinylsulfonic acid are dissolved in dimethylbenzene according to a molar ratio of 5:1:2 to prepare a solution with a monomer concentration of 20%, and an initiator benzoyl peroxide which is 0.7% of the mass of the monomer is added in a nitrogen environment to react for 6 hours at 70 ℃ to obtain the polymer asphaltene inhibitor 2.
Example 3
Octadecyl methacrylate, styrene and vinylsulfonic acid are dissolved in dimethylbenzene according to a molar ratio of 5:1:3 to prepare a solution with a monomer concentration of 20%, and an initiator benzoyl peroxide which is 0.7% of the mass of the monomer is added in a nitrogen environment to react for 6 hours at 70 ℃ to obtain the polymer asphaltene inhibitor 3.
Result detection
1. Inhibition test
In a mixed system of 10g of thick oil and 15g of condensate oil, the proportions of a solvent, a dispersing agent and a polymer asphaltene inhibitor are respectively regulated, the mixture is centrifuged for 10min at 5500rpm for 30min under ultrasound, the upper solution is poured, the mixture is treated for 12h at 65 ℃, and the sediment mass is weighed, so that the formula of the asphaltene inhibitor is obtained through screening.
The solvent is carbon tetrachloride, the dispersant is petroleum sulfonate, and the polymer asphalt inhibitor is polymer asphalt inhibitor 3.
TABLE 1 asphaltene inhibitor System compounding test
The mass of the solvent is first fixed and the ratio of dispersant to inhibitor is optimized. As is clear from the table, the ratio of the dispersant to the inhibitor was 3:1, and the effect of inhibiting asphaltene deposition was best, and was 93% or more.
The ratio of dispersant to inhibitor was then fixed and the ratio of solvent was selected, as seen from the table, the asphaltene deposition inhibition effect increased with the addition of solvent, but the increase was not significant when the solvent addition was exceeded by a certain amount, so that the final formulation optimized to give an asphaltene inhibitor was (number 9) solvent: dispersing agent: inhibitor = 4:3:1.
Because the thickened oil and the condensate oil are miscible when the blending ratio of the condensate oil is below 0.4, the blending ratios of 0.6, 0.8, 1.0, 1.3 and 1.5 are respectively used as research objects, and the influence of the addition amount of the asphaltene inhibition dispersing agent on the sediment under different blending ratios is respectively optimized.
TABLE 2 Effect of asphaltene inhibitor addition on sediment
As can be seen from the table, the addition amount of the asphaltene inhibitor has a critical value in the range of 0.6 to 1.5, and the inhibiting effect of the asphaltene inhibitor is not obvious when the concentration of the asphaltene inhibitor is lower than the critical value. When the concentration of the asphaltene inhibitor exceeds a critical value, the inhibition effect is greatly increased. This is because the two phases formed by the thickened oil and the condensate are only nearly miscible when the inhibitor concentration reaches a certain level.
As shown in the table, when the condensate oil mixing ratio is less than 1.0, the addition of the asphaltene inhibitor is more than 2%, the inhibition effect is better, and the inhibition rate can reach more than 90%. When the mixing ratio of the condensate oil reaches more than 1.0, the inhibition effect can reach 60-80% when 2% of the inhibitor is added, and the inhibition effect can reach more than 90% when 3% -4% of the inhibitor is needed to be added.
TABLE 3 inhibition test results for Polymer asphaltene inhibitors 1-3
2. Asphaltene deposit point test
The effect of the inhibitor on the initial precipitation point of asphaltenes was characterized by means of an ultraviolet-visible spectrophotometer, the specific experimental protocol of which is as follows.
Preparing model oil: firstly preparing an asphaltene-toluene solution with the concentration of 500ppm as a mother solution by taking the extracted asphaltene; and taking a proper amount of mother solution, gradually adding n-heptane and toluene into the mother solution in different proportions, wherein the volume fractions of the n-heptane are respectively 30v%, 40v%, 45v%, 50v%, 55v%, 60v%, 65v% and 70v%, and finally diluting the mother solution into toluene-n-heptane solution with asphaltene concentration of 100ppm, so as to obtain 8 groups of model oil samples. The sample was dispersed in an ultrasonic water bath for 2 hours and then allowed to stand for 4 hours for analysis.
Testing of initial precipitation points: the above samples were centrifuged at 9500rmp for 20min, and the supernatants were diluted twice with toluene, and their absorption spectra at a wavelength range of 200-800nm at room temperature were measured with an ultraviolet-visible spectrophotometer at 1nm intervals. The scanning speed is slow, and the slit width is 2.0nm. At the same time, to eliminate background effects, the reference cuvette was filled with the same toluene/n-heptane mixture. The characteristic absorption peak of asphaltenes is around 280.
TABLE 4 absorbance of supernatants at different n-heptane volume fractions
TABLE 5 influence of different concentration of inhibitors on the absorbance of the system
TABLE 6 Polymer asphaltene inhibitor 1-3 precipitation Point test
3. Deposit size
Test target: asphaltene inhibitor 3.
Asphaltene particle size assessment is by dynamic light scattering techniques, DLS data is used to measure the hydrodynamic radius of particles in a fluid. The pure simulated oil and the treated simulated oil were analyzed to determine the particle size distribution of asphaltenes in various systems.
From the measurement of the initial point of precipitation, an n-heptane volume fraction of 50% was obtained as the initial point of asphaltene precipitation, and an asphaltene (asphaltene: 100 ppm) -toluene-n-heptane solution was prepared, and the n-heptane volume fractions were respectively: 50%, 55%, 60%, 65% and 70%, and the 5 groups of solutions were subjected to ultrasonic treatment for 2 hours and then allowed to stand for 4 hours, and the particle size distribution was measured.
It can be seen from fig. 4 that the asphaltene particles are uniformly distributed in size, the distribution morphology is unimodal, and the size of the asphalt aggregate becomes larger as the proportion of n-heptane in the asphalt-n-heptane-toluene system increases.
To compare the effect of different amounts of inhibitor on the size of the aggregate asphaltene, 4 groups of 100ppm asphaltene in 30/70 toluene-n-heptane solutions were prepared, in which different concentrations of inhibitor were added (amounts of inhibitor added were 800ppm, 400ppm, 200ppm, 0ppm, respectively)
As can be seen from fig. 5-12, the average particle size of the precipitate decreases significantly when the inhibitor is added. As the inhibitor concentration increases, the asphaltene precipitation particle size decreases. The greater the inhibitor concentration, the smaller the precipitate particle size at the same n-heptane volume fraction. With the same inhibitor addition, the asphaltene particle size decreases with increasing n-heptane volume fraction. The size of the asphaltene precipitate generated under different addition amounts of the inhibitor can also be obtained, and the addition of the inhibitor has better dispersion effect on the asphaltene precipitate.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. An asphaltene inhibitor characterized by the following formula:
x, y, z are the overall molar ratio of the blocks, x+y+z=1; the leftmost structural unit containing R in the above formula is a structural unit derived from n-octadecyl methacrylate;
the asphaltene inhibitor is prepared by the following method: dissolving octadecyl methacrylate, styrene and vinylsulfonic acid in a solvent, adding an initiator in a protective gas environment, and reacting at 70 ℃ for 6 hours to obtain the polymer asphaltene inhibitor; the molar ratio of the octadecyl methacrylate to the styrene to the vinylsulfonic acid is 5:1:3; the solvent is xylene.
2. The method for preparing the asphaltene inhibitor according to claim 1, wherein octadecyl methacrylate, styrene and vinylsulfonic acid are dissolved in a solvent, an initiator is added under a protective gas environment, and the reaction temperature is 70 ℃ and the reaction time is 6 hours, so that the polymer asphaltene inhibitor can be obtained; the molar ratio of the octadecyl methacrylate to the styrene to the vinylsulfonic acid is 5:1:3; the solvent is xylene.
3. The method of claim 2, wherein the initiator is benzoyl peroxide.
4. A polymeric asphaltene inhibitor compounding system according to claim 1, comprising the polymeric asphaltene inhibitor of claim 1, a dispersant, and a solvent.
5. The compounding system of claim 4, wherein the mass ratio of the polymeric asphaltene inhibitor, dispersant, and solvent is 1:2-3:3-4.
6. Use of the polymeric asphaltene inhibitor of claim 1 or the compounding system of claim 4 in heavy crude oil and condensate recovery, gathering and processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494862.6A CN114644727B (en) | 2020-12-17 | 2020-12-17 | Polymer asphaltene inhibitor, preparation method thereof, compound system and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494862.6A CN114644727B (en) | 2020-12-17 | 2020-12-17 | Polymer asphaltene inhibitor, preparation method thereof, compound system and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114644727A CN114644727A (en) | 2022-06-21 |
| CN114644727B true CN114644727B (en) | 2023-11-14 |
Family
ID=81989711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011494862.6A Active CN114644727B (en) | 2020-12-17 | 2020-12-17 | Polymer asphaltene inhibitor, preparation method thereof, compound system and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114644727B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029318A1 (en) * | 2008-09-15 | 2010-03-18 | Halliburton Energy Services, Inc. | Compositions and methods for hindering asphaltene deposition |
| CN101712787A (en) * | 2008-10-08 | 2010-05-26 | 中国石油天然气集团公司 | Sulfonic acid-containing organic macromolecule reaction type crude oil flow modifying agent |
| CN102492410A (en) * | 2011-12-06 | 2012-06-13 | 中国石油天然气股份有限公司 | Thick oil soluble viscosity reducer and preparation method thereof |
| CN104232050A (en) * | 2014-09-05 | 2014-12-24 | 纳百科创(北京)技术开发有限公司 | Compound oil-soluble viscosity reducer for reducing viscosity of thickened oil and preparation method of compound oil-soluble viscosity reducer |
| CN104628934A (en) * | 2015-03-17 | 2015-05-20 | 西南石油大学 | Anionic oil-soluble heavy oil viscosity reducer and preparation method thereof |
| CN105199699A (en) * | 2015-10-15 | 2015-12-30 | 中国石油大学(华东) | Low-cost oil-soluble viscosity reducer for viscosity reduction of thick oil and preparation method of low-cost oil-soluble viscosity reducer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6727872B2 (en) * | 2016-03-18 | 2020-07-22 | キヤノン株式会社 | Toner and toner manufacturing method |
-
2020
- 2020-12-17 CN CN202011494862.6A patent/CN114644727B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029318A1 (en) * | 2008-09-15 | 2010-03-18 | Halliburton Energy Services, Inc. | Compositions and methods for hindering asphaltene deposition |
| CN101712787A (en) * | 2008-10-08 | 2010-05-26 | 中国石油天然气集团公司 | Sulfonic acid-containing organic macromolecule reaction type crude oil flow modifying agent |
| CN102492410A (en) * | 2011-12-06 | 2012-06-13 | 中国石油天然气股份有限公司 | Thick oil soluble viscosity reducer and preparation method thereof |
| CN104232050A (en) * | 2014-09-05 | 2014-12-24 | 纳百科创(北京)技术开发有限公司 | Compound oil-soluble viscosity reducer for reducing viscosity of thickened oil and preparation method of compound oil-soluble viscosity reducer |
| CN104628934A (en) * | 2015-03-17 | 2015-05-20 | 西南石油大学 | Anionic oil-soluble heavy oil viscosity reducer and preparation method thereof |
| CN105199699A (en) * | 2015-10-15 | 2015-12-30 | 中国石油大学(华东) | Low-cost oil-soluble viscosity reducer for viscosity reduction of thick oil and preparation method of low-cost oil-soluble viscosity reducer |
Non-Patent Citations (3)
| Title |
|---|
| 化学添加剂对草桥稠油胶体体系的影响规律及机理探究;马洋洋;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第07期);B019-343 * |
| 油溶性降黏剂的制备及性能评价;刘旭超 等;《油田化学》;第35卷(第3期);第512-516页 * |
| 阙国和.《石油组成与转化化学》.东营：中国石油大学出版社,2008,(第1版),第607页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114644727A (en) | 2022-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Acevedo et al. | Adsorption of asphaltenes and resins on organic and inorganic substrates and their correlation with precipitation problems in production well tubing | |
| Taraneh et al. | Effect of wax inhibitors on pour point and rheological properties of Iranian waxy crude oil | |
| Zakaria et al. | A novel polymer-assisted emulsified-acid system improves the efficiency of carbonate matrix acidizing | |
| Shi et al. | Synthesis and evaluation of a hyperbranched copolymer as viscosity reducer for offshore heavy oil | |
| BRPI0920581B1 (en) | hydrate inhibition method in a fluid | |
| WO2017173266A1 (en) | Dispersants and dissolvers for removal of asphaltene deposits | |
| Ghosh et al. | Laboratory treatment of HPAM polymers for injection in low permeability carbonate reservoirs | |
| EP2167606A1 (en) | Dispersing sulfide scales in oil and gas production systems | |
| Huang et al. | Synthesis, characterization and evaluation of a quadripolymer with low molecular weight as a water based drilling fluid viscosity reducer at high temperature (245° C) | |
| Mao et al. | Novel terpolymers as viscosity reducing agent for Tahe super heavy oil | |
| Zheng et al. | Preparation and mechanism of hyperbranched heavy oil viscosity reducer | |
| MX2007012339A (en) | Wax-containing materials. | |
| Chen et al. | Study of asphaltene dispersion and removal for high-asphaltene oil wells | |
| WO2016073574A1 (en) | Encapsulated production chemicals | |
| Quan et al. | The effect of a kind of hyperbranched polyester with different carbon length on flowability for crude oil | |
| CN114644727B (en) | Polymer asphaltene inhibitor, preparation method thereof, compound system and application | |
| Taherian et al. | The mechanistic investigation on the effect of the crude oil/brine interaction on the interface properties: A study on asphaltene structure | |
| Patil et al. | Crude oil characterization with a new dynamic emulsion stability technique | |
| CN104449813A (en) | Emulsion breaker for oil-water separation by efficiently treating crude oil with high clay component content on offshore oil field | |
| Chang et al. | Peptization and coagulation of asphaltenes in apolar media using oil-soluble polymers | |
| Leitenmueller et al. | Treatment of Produced Polymer-Containing Water with a Water Treatment Pilot Unit in the Matzen Field, Austria | |
| Adizov et al. | Analysis of efficiency of chemical reagents used in destruction of oil emulses in local deposits | |
| Adams et al. | Evaluation of wax inhibitor performance through various techniques | |
| Zhang et al. | The study on interactions between stabilizers and asphaltenes | |
| Fraser et al. | Limitations of common oilfield scale inhibitor chemistries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |