CN111334250B - Thickened oil asphaltene stabilizer composition and preparation method thereof - Google Patents
Thickened oil asphaltene stabilizer composition and preparation method thereof Download PDFInfo
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 134
- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 45
- 229960002317 succinimide Drugs 0.000 claims abstract description 25
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 18
- -1 alkyl pyrrolidone Chemical compound 0.000 claims abstract description 16
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 14
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005642 Oleic acid Substances 0.000 claims abstract description 4
- 125000005619 boric acid group Chemical group 0.000 claims abstract description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 88
- 238000002156 mixing Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 8
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 abstract description 25
- 230000000087 stabilizing effect Effects 0.000 abstract description 19
- 239000003027 oil sand Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 description 34
- 239000010779 crude oil Substances 0.000 description 14
- 230000003993 interaction Effects 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000010998 test method Methods 0.000 description 7
- SOANRMMGFPUDDF-UHFFFAOYSA-N 2-dodecylaniline Chemical compound CCCCCCCCCCCCC1=CC=CC=C1N SOANRMMGFPUDDF-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000003113 dilution method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- 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
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention discloses a thickened oil asphaltene stabilizer composition and a preparation method thereof, wherein the composition comprises at least two components: one or more of the components A, N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide; a component B, an organic amine compound containing a boric acid group; one or more of the components C, dodecylbenzene sulfonic acid, alkylaminobenzene boric acid and oleic acid; component D, span-80; component E, para-alkylaniline and/or meta-alkylaniline. The asphaltene stabilizing agent with the proportion has the highest asphaltene stabilizing efficiency of 96.2% on Canadian oil sand asphalt.
Description
Technical Field
The invention belongs to the field of improving the stability of asphaltene in a thick oil blending and diluting process, and particularly relates to a thick oil asphaltene stabilizer composition and a preparation method thereof.
Background
Because the content of polar components such as colloid, asphaltene and the like in the thick oil is high, the thick oil has the characteristics of high viscosity, high relative density and poor fluidity at low temperature. At present, the viscosity of the thickened oil is reduced, the pipeline transportation standard is reached, and the safe transportation of the pipeline is ensured to become a hot spot and a difficult point of the thickened oil transportation technology. The common thick oil viscosity reduction method mainly comprises the following steps: heating viscosity-reducing method, emulsifying viscosity-reducing method, hydrothermal viscosity-reducing method, thermal viscosity-reducing method, diluting agent viscosity-reducing method, etc. The heating viscosity reduction is commonly used for underground exploitation of thick oil and short-distance pipeline transportation, and is not suitable for long-distance pipeline transportation in complex terrain environments; the emulsification viscosity-reducing method relates to complex technological processes such as emulsification, demulsification and the like, and reduces the pipeline transportation capacity due to the addition of water; the dilution viscosity reduction method is a dilution viscosity reduction method for adding thin oil into thick oil; the hydrothermal viscosity reduction method and the pyrolysis viscosity reduction method are both methods for reducing the viscosity of the thickened oil by thermal cracking or catalyzing the hydrothermal pyrolysis of the crude oil macromolecules into small molecules under relatively mild conditions, and the method is suitable for underground crude oil exploitation or is used as a thickened oil pretreatment process before pipe transportation.
Blending low viscosity thin oils is the most efficient and simplest method of reducing the viscosity of thick oils. The asphaltene in the thick oil has the greatest molecular weight and the strongest polarity, and is the most unstable component with the strongest interaction force in the thick oil. During dilution of thick oil with thin oil or when the conveying conditions change to a certain range, the stability of asphaltene is reduced to cause flocculation and sedimentation. Asphaltene deposition can cause problems such as reduction of the effective sectional area of the pipeline, reduction of the conveying efficiency of the pipeline conveying equipment and the like, and pipeline blockage can occur in severe cases. Therefore, in order to inhibit the deposition of asphaltenes and ensure the safety of the pipeline of the diluted crude oil, it is necessary to develop an asphaltene stabilizer in the dilution process of the thickened oil.
The crude oil is a colloid dispersion system, the asphaltene is dispersed in the crude oil as colloidal particles, and the colloid is adsorbed on the surface of the asphaltene to form a protective layer, but the protective layer is dissolved into the crude oil due to the change of the property of the crude oil and the change of the solubility of the colloid in the dilution process and the heating process, so that the colloid protective layer is thinned, and the stability of the asphaltene is reduced. To maintain asphaltene stability, an asphaltene stabilizer is required. Stabilization mechanism of asphaltene stabilizers: the asphaltene stabilizer is a surfactant, contains hydrophilic polar groups and lipophilic nonpolar groups, wherein the polar groups can be combined with the polar groups in the asphaltene on the surface of the asphaltene through interactions such as hydrogen bonding, acid-base interaction, van der Waals interaction and the like, and the nonpolar groups of the asphaltene stabilizer extend into a crude oil medium to play a role in space stabilization of the asphaltene, inhibit mutual approaching and aggregation of the asphaltene, and play a role in stabilizing the asphaltene. Because asphaltene molecules in different crude oils contain different polar groups, different asphaltene stabilizers are required; the amount of gum in crude oil also affects the amount of asphaltene stabilizer required. Thus, for a particular crude oil, it is necessary to design the molecular weight of the asphaltene stabilizer based on the crude oil composition, in particular the asphaltene content and molecular composition, and to experimentally optimize the amount of asphaltene stabilizer used to determine the optimal formulation of the asphaltene stabilizer.
The polar groups are typically hydroxyl, sulfonate, carboxyl, amine, and the like. At present, a plurality of different types of asphaltene stabilizers, such as polyisobutylene succinimide, polyisobutylene maleic anhydride, dodecylbenzene sulfonic acid, organic amines, organic acids, etc., have been developed at home and abroad.
Patent WO2014078243A1 reports that bis (2-hydroxyethyl) amide has a good dispersion polymerization inhibiting effect on asphaltenes. Another patent, US7122112B2, reports an asphaltene dispersant containing both amide and carboxylic acid head groups, increasing the polarity and acidity of the stabilizer head functions, enhancing the interaction between the remaining asphaltene groups.
CN102876306a gives an asphaltene deposit dispersant containing 50-95% ketone, 5-45% asphaltene stabilizer, and the balance solvent, mainly for clear deposits in the well bore in heavy oil recovery processes, and also for removal of asphaltene deposits in surface pipelines, equipment. The stabilizer is large in dosage and is not suitable for stabilizing asphaltene in the crude oil dilution process.
CN107057094a prepares a high-efficiency asphalt aggregation inhibitor which has a strong affinity for crude oil asphalt, and through pi-pi interaction, intermolecular binding is generated with asphalt molecules in the thick oil, and aggregation between asphalt molecules and colloid molecules is prevented. The asphalt aggregation inhibitor and the asphaltene form pi-pi interaction, and the conjugated aromatic ring numbers of the synthetic components are lower than the aromatic ring numbers of the asphaltene, so that the pi-pi interaction degree of the asphalt aggregation inhibitor and the asphaltene is lower than the pi-pi interaction between asphaltene molecules, the inhibition effect is affected, and meanwhile, the stability effect of the asphaltene of the thick oil with high asphaltene content is not clear due to the lower concentration of the asphaltene in the patent example.
CN107629776a provides a method for preparing an asphaltene stabilizer in the process of diluting thick oil. Firstly, reacting reactants such as polyisobutylene succinic anhydride, aniline and the like dissolved in an aromatic hydrocarbon solvent for 3-9h at the temperature of 100-150 ℃ under the action of a catalyst zinc perchlorate; the reacted mixture is extracted by water-organic solvent, distilled under reduced pressure and dried in vacuum to obtain the asphaltene stabilizer, and the synthesized asphaltene stabilizer has the highest asphaltene stabilizing efficiency of 98.2% on Canadian oil sand asphalt. The asphalt stabilizer has the defects that the preparation process is complex, the cost of the stabilizer is high, the synthesized stabilizer has single polar group, the multi-group anchoring effect of the stabilizer and the asphalt is not facilitated, and the long-term stabilizing effect of the asphalt is affected.
Different stabilizers have different stabilizing effects on different thickened oil asphaltenes. Because asphaltenes contain a variety of polar groups, it is desirable that the asphaltene stabilizer have different polar groups that act upon it to provide better stability to the asphaltene. The introduction of multiple polar groups on the molecule of one asphaltene stabilizer is a very challenging synthetic task, while asphaltene stabilizers with different polar groups are compounded in a certain proportion, and the effect of stabilizing asphaltene is easier to achieve by utilizing the synergistic effect of the asphaltene stabilizers. In the compounding process, the competitive adsorption of the compound components on the interface and the synergistic effect between the interface components after adsorption are required to be considered, so that a compounding scheme with less stabilizer consumption, high strength of an interface adsorption layer and good asphaltene stabilizing effect is obtained.
Disclosure of Invention
The invention mainly aims to provide a thickened oil asphaltene stabilizer composition and a preparation method thereof, which are used for solving the problem of poor asphaltene stability caused by insufficient group types of interaction between a single stabilizer and asphaltene.
In order to achieve the above object, the present invention provides a thickened oil asphaltene stabilizer composition comprising at least two components:
one or more of the group consisting of components A, N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide, wherein the N, N-dimethylamide, the alkyl pyrrolidone and the polyisobutylene succinimide sequentially have the structures shown in the following formulas I, II and III:
wherein R is 1 H, CH of a shape of H, CH 3 -(CH 2 ) m -or
m＝7-15，n＝10-50；
R 3 Is H or
R 2 Is H or CH 3 -(CH 2 ) m -，m＝8-16；
R is CH 3 -(CH 2 ) i -，i＝7-11；
The component B, the organic amine compound containing boric acid group, has the structure shown in the following formula IV:
wherein R is 1 H, CH of a shape of H, CH 3 -(CH 2 ) m -or
m＝7-15，n＝10-50；
R 2 Is H or CH 3 -(CH 2 ) m -，m＝7-14；
One or more of the components C, dodecylbenzene sulfonic acid, alkylaminobenzene boric acid and oleic acid;
component D, span-80;
component E, para-alkylaniline and/or meta-alkylaniline.
The thickened oil asphaltene stabilizer composition of the present invention, wherein the composition preferably comprises at least one of component a and component B.
The invention relates to a thickened oil asphaltene stabilizer composition, wherein the component B is 1-polyisobutylene succinimide-3-phenylboric acid.
The thickened oil asphaltene stabilizer composition of the invention, wherein in the para-alkylaniline and/or meta-alkylaniline, the alkyl carbon chain length is preferably 8-16.
The thickened oil asphaltene stabilizer composition of the present invention wherein the alkyl group is preferably a straight chain alkyl group or a branched alkyl group.
The heavy oil asphaltene stabilizer composition of the invention, wherein preferably, based on the total mass of the composition component A, component B, component C, component D and component E, the mass content of the component A is 0-70%, the mass content of the component B is 0-70%, the mass content of the component C is 0-68%, the mass content of the component D is 0-68%, and the mass content of the component E is 0-33%; and the mass content of at least two of the component A, the component B, the component C, the component D and the component E is different from 0 percent.
The heavy oil asphaltene stabilizer composition disclosed by the invention further comprises a solvent, wherein the ratio of the mass of the solvent to the total mass of the component A, the component B, the component C, the component D and the component E is preferably 1:1-1:3.
The heavy oil asphaltene stabilizer composition disclosed by the invention is characterized in that the solvent is toluene, and the ratio of the mass of the toluene to the total mass of the component A, the component B, the component C, the component D and the component E is preferably 1:1.
The thickened oil asphaltene stabilizer composition further preferably comprises a component A, a component B, a component C, a component D and a component E, wherein the mass content of the component A is 0-70%, the mass content of the component B is 0-70%, the mass content of the component C is 0-68%, the mass content of the component D is 0-68%, and the mass content of the component E is 0-33% based on the total mass of the component A, the component B, the component C, the component D and the component E; and the mass content of the component A, the component B, the component C, the component D and the component E is not 0 percent.
In order to achieve the above object, the present invention also provides a preparation method of the above heavy oil asphaltene stabilizer composition, which comprises the following steps:
step 1, adding at least two of the component A, the component B, the component C, the component D and the component E into a mixer and uniformly mixing;
step 2, adding a solvent into a mixer;
and 3, stirring the mixture in the mixer at the temperature of 10-50 ℃ for 15-60 minutes to obtain the thickened oil asphaltene stabilizer composition.
The invention has the beneficial effects that:
(1) The stabilizer composition disclosed by the invention is simple in preparation process, low in cost, energy-saving and environment-friendly.
(2) The stabilizing agent has good stabilizing effect on the heavy oil asphaltene even under the condition of keeping standing, and is beneficial to the stable transportation of the mixed thin and heavy oil in a pipeline.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The invention discloses a heavy oil asphaltene stabilizer composition, which comprises at least two components:
the component A is a compound containing amide or imide, specifically one or more of N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide, and the N, N-dimethylamide, the alkyl pyrrolidone and the polyisobutylene succinimide sequentially have the structures shown in the following formulas I, II and III:
wherein R is 1 H, CH of a shape of H, CH 3 -(CH 2 ) m -or
m＝7-15，n＝10-50；
R 3 Is H or
R 2 Is H or CH 3 -(CH 2 ) m -，m＝8-16；
R is CH 3 -(CH 2 ) i -，i＝7-11；
The component B, the organic amine compound containing boric acid group, has the structure shown in the following formula IV:
wherein R is 1 H, CH of a shape of H, CH 3 -(CH 2 ) m -or
m＝7-15，n＝10-50；
R 2 Is H or CH 3 -(CH 2 ) m -，m＝7-14；
Component B is further preferably 1-polyisobutene succinimidyl-3-phenylboronic acid.
One or more of the components C, dodecylbenzene sulfonic acid, alkylaminobenzene boric acid and oleic acid;
component D, span-80;
component E, para-alkylaniline and/or meta-alkylaniline. Wherein, in the para-alkylaniline and/or the meta-alkylaniline, the alkyl carbon chain length is preferably 8-16. The alkyl group may be a straight chain alkyl group or a branched alkyl group.
Wherein the composition should comprise at least two of the above component a, component B, component C, component D and component E, preferably at least one of component a and component B. Based on the total mass of the composition component A, the composition component B, the composition component C, the composition component D and the composition component E, the mass content of the composition component A is 0-70%, the mass content of the composition component B is 0-70%, the mass content of the composition component C is 0-68%, the mass content of the composition component D is 0-68%, and the mass content of the composition component E is 0-33%; and the mass content of at least two of the component A, the component B, the component C, the component D and the component E is different from 0 percent.
More preferably, the composition comprises a component A, a component B, a component C, a component D and a component E, wherein the mass content of the component A is 0-70%, the mass content of the component B is 0-70%, the mass content of the component C is 0-68%, the mass content of the component D is 0-68%, and the mass content of the component E is 0-33% based on the total mass of the component A, the component B, the component C, the component D and the component E of the composition; and the mass content of the component A, the component B, the component C, the component D and the component E is not 0 percent.
In addition, a solvent, preferably toluene, may be further included in the stabilizer composition, and the ratio of the mass of the solvent to the total mass of the component a, the component B, the component C, the component D, and the component E may be 1:1 to 1:3, and more preferably 1:1.
Moreover, the invention also provides a preparation method of the thickened oil asphaltene stabilizer composition, which comprises the following steps:
step 1, adding at least two of the component A, the component B, the component C, the component D and the component E into a mixer and uniformly mixing;
step 2, adding a solvent into a mixer;
and 3, stirring the mixture in the mixer at the temperature of 10-50 ℃ for 15-60 minutes to obtain the thickened oil asphaltene stabilizer composition.
The asphaltene stabilizer composition obtained by the method can enable different types of asphaltenes to achieve a stabilizing effect more easily due to the mutual synergistic effect among the components, and the adopted mixing means are simple and easy to operate and easy to apply industrially.
Stabilization performance test method of stabilizer
(1) The asphaltene stabilizer composition is formulated into a concentration of stabilizer toluene solution R.
(2) 10g/L of asphaltene toluene solution P was prepared.
(3) 1mL of 10g/L asphaltene toluene solution and 9mL of n-heptane were uniformly mixed to form a mixed solution M, the M solution was allowed to stand for 24 hours, and the absorbance D of the supernatant of the M solution after standing was measured at a wave of 410nm using an ultraviolet-visible spectrophotometer 0 。
(4) And (3) uniformly mixing a certain volume of R solution and 1mL of P solution, adding a certain volume of n-heptane to ensure that the volume of n-heptane and toluene in the mixed solution is 9:1, and uniformly stirring and mixing to obtain a mixed solution S.
(5) The mixed solution S was allowed to stand for 24 hours.
(6) Measuring absorbance D of supernatant of the S solution after standing at a wavelength of 410nm with an ultraviolet-visible spectrophotometer w 。
(7) The stabilizing efficiency of the asphaltene stabilizer was calculated according to the following formula:
example 1
50g of component A (polyisobutylene succinimide) and 50g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) were added to a mixing vessel, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 30 minutes to obtain an asphaltene stabilizer composition a.
66.6g of component A (polyisobutylene succinimide) and 33.3g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) were added to a mixing vessel, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 30 minutes to obtain an asphaltene stabilizer composition B.
Into a mixing vessel were charged 33.3g of component A (polyisobutylene succinimide) and 66.6g of component B (1-polyisobutylene succinimide-3-phenylboric acid), and 100g of toluene was further added, followed by thoroughly stirring and mixing at 30℃for 30 minutes, to obtain an asphaltene stabilizer composition c.
The stability properties of the obtained asphaltene stabilizer composition a, asphaltene stabilizer composition b, and asphaltene stabilizer composition c against asphaltene were measured according to the above-described stability property test method of stabilizers. The stabilizing efficiency of the compounded asphaltene stabilizer composition a, the asphaltene stabilizer composition b and the asphaltene stabilizer composition c on asphaltene of Canadian oil sand asphalt respectively reaches 94.4%, 86.5% and 93.9%.
Example 2
Into a mixing vessel, 50g of component A (polyisobutylene succinimide) and 50g of component D (Span 80) were added, and 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 40 minutes to obtain an asphaltene stabilizer composition D.
66.6g of component A (polyisobutylene succinimide) and 33.3g of component D (Span 80) were added to a mixing vessel, and 100g of toluene was further added thereto, and the mixture was thoroughly stirred and mixed at 30℃for 40 minutes to obtain an asphaltene stabilizer composition e.
Into a mixing vessel were charged 33.3g of component A (polyisobutylene succinimide) and 66.6g of component D (Span 80), and 100g of toluene were further added, and the mixture was thoroughly stirred and mixed at 30℃for 40 minutes to obtain an asphaltene stabilizer composition f.
The stability properties of the obtained asphaltene stabilizer composition d, asphaltene stabilizer composition e, and asphaltene stabilizer composition f to asphaltene were measured according to the above-described stability property test method of stabilizers. The stabilizing efficiency of the compounded asphaltene stabilizer composition d, the asphaltene stabilizer composition e and the asphaltene stabilizer composition f on asphaltene of Canadian oil sand asphalt respectively reaches 95.7%, 95.2% and 96.2%.
Example 3
50g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) and 50g of component D (Span 80) were sequentially added to a mixing vessel, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 40 minutes to obtain an asphaltene stabilizer composition g.
50g of component A (polyisobutylene succinimide) and 50g of component C (dodecylbenzenesulfonic acid) were added to a mixing vessel, and 100g of toluene was further added thereto, followed by mixing with stirring at 30℃for 40 minutes, to obtain an asphaltene stabilizer composition h.
50g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) and 50g of component C (dodecylbenzenesulfonic acid) were added to a mixing vessel, and 100g of toluene was further added thereto, followed by thoroughly stirring and mixing at 30℃for 40 minutes, to obtain an asphaltene stabilizer composition i.
50g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) and 50g of component E (dodecylaniline) were added to a mixing vessel, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 40 minutes to obtain an asphaltene stabilizer composition j.
The stability properties of the obtained asphaltene stabilizer composition g, asphaltene stabilizer composition h, asphaltene stabilizer composition i, and asphaltene stabilizer composition j to asphaltene were measured according to the stability property test method of the above-described stabilizers. The stabilizing efficiency of the compounded asphaltene stabilizer composition g, the asphaltene stabilizer composition h, the asphaltene stabilizer composition i and the asphaltene stabilizer composition j on asphaltene of Canadian oil sand asphalt respectively reaches 95.5%, 93.2%, 92.5% and 94.0%.
Example 4
In a mixing vessel, 33.3g of component A (polyisobutylene succinimide), 33.3g of component B (polyisobutylene succinimide phenylboronic acid) and 33.3g of component D (Span 80) were sequentially added, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 35℃for 40 minutes to obtain an asphaltene stabilizer composition k.
Into a mixing vessel were charged 25g of component A (polyisobutylene succinimide), 50g of component B (polyisobutylene succinimide phenylboronic acid) and 25g of component D (Span 80), and 100g of toluene was further added, followed by thoroughly stirring and mixing at 35℃for 40 minutes, to obtain an asphaltene stabilizer composition I.
40g of component A (polyisobutylene succinimide), 40g of component B (1-polyisobutylene succinimide-3-phenylboronic acid) and 20g of component D (Span 80) were added to a mixing vessel, and 100g of toluene was added thereto, followed by thoroughly stirring and mixing at 35℃for 40 minutes, to obtain an asphaltene stabilizer composition m.
The stability properties of the resulting asphaltene stabilizer composition k, asphaltene stabilizer composition l, and asphaltene stabilizer composition m to asphaltene were measured according to the stability property test method of the stabilizer described above. The stabilizing efficiency of the compounded asphaltene stabilizer composition k, the asphaltene stabilizer composition l and the asphaltene stabilizer composition m on asphaltene of Canadian oil sand asphalt respectively reaches 89.0%, 92.4% and 89.7%.
Example 5
33.3g of component B (1-polyisobutylene succinimide-3-phenylboronic acid), 33.3g of component C (dodecylbenzenesulfonic acid) and 33.3g of component D (Span 80) were sequentially added to a mixing vessel, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 50 minutes to obtain an asphaltene stabilizer composition n.
Into a mixing vessel were charged 40g of component B (1-polyisobutylene succinimide-3-phenylboronic acid), 40g of component C (dodecylbenzenesulfonic acid) and 20g of component D (Span 80), and 100g of toluene were further added, followed by thoroughly stirring and mixing at 30℃for 50 minutes, to obtain an asphaltene stabilizer composition o.
Into a mixing vessel were charged 25g of component B (1-polyisobutylene succinimide-3-phenylboronic acid), 50g of component C (dodecylbenzenesulfonic acid) and 25g of component D (Span 80), and 100g of toluene were further added, followed by thoroughly stirring and mixing at 30℃for 50 minutes, to obtain an asphaltene stabilizer composition p.
The stability properties of the resulting asphaltene stabilizer composition n, asphaltene stabilizer composition o, and asphaltene stabilizer composition p were measured according to the stability property test method of the stabilizers described above. The stabilizing efficiency of the compounded asphaltene stabilizer n, asphaltene stabilizer composition o and asphaltene stabilizer composition p on asphaltene of Canadian oil sand asphalt respectively reaches 94.7%, 92.8% and 89.5%.
Example 6
In a mixing vessel, 33.3g of component A (polyisobutylene succinimide), 33.3g of component C (dodecylbenzenesulfonic acid) and 33.3g of component D (Span 80) were sequentially added, and 100g of toluene was further added, followed by thoroughly stirring and mixing at 30℃for 50 minutes, to obtain an asphaltene stabilizer composition q.
Into a mixing vessel were charged 40g of component A (polyisobutylene succinimide), 40g of component C (dodecylbenzenesulfonic acid) and 20g of component D (Span 80), and 100g of toluene were further added, and the mixture was thoroughly stirred and mixed at 30℃for 50 minutes to obtain an asphaltene stabilizer composition r.
Into a mixing vessel were charged 20g of component A (polyisobutylene succinimide), 40g of component C (dodecylbenzenesulfonic acid) and 40g of component D (Span 80), and 100g of toluene were further added, and the mixture was thoroughly stirred and mixed at 30℃for 50 minutes to obtain an asphaltene stabilizer composition s.
The stability properties of the resulting asphaltene stabilizer composition q, asphaltene stabilizer composition r, and asphaltene stabilizer composition s were measured according to the stability property test method of the stabilizer described above. The stabilizing efficiency of the compounded asphaltene stabilizer q, asphaltene stabilizer r and asphaltene stabilizer s on asphaltene of Canadian oil sand asphalt respectively reaches 78.1%, 91.9% and 92.8%.
Example 7
In a mixing vessel, 33.3g of component A (polyisobutylene succinimide), 33.3g of component B (polyisobutylene succinimide phenylboric acid) and 33.3g of component E (dodecylaniline) were sequentially added, 100g of toluene was further added, and the mixture was thoroughly stirred and mixed at 30℃for 50 minutes to obtain an asphaltene stabilizer composition t.
31.25g of component A (polyisobutylene succinimide), 37.5g of component B (polyisobutylene succinimide phenylboronic acid) and 31.25g of component E (dodecylaniline) were added to a mixing vessel, and 100g of toluene was further added thereto, followed by thoroughly stirring and mixing at 30℃for 50 minutes, to obtain an asphaltene stabilizer composition u.
29.41g of component A (polyisobutylene succinimide), 41.17g of component B (polyisobutylene succinimide phenylboronic acid) and 29.41g of component E (dodecylaniline) were added to a mixing vessel, and 100g of toluene was further added thereto, followed by thoroughly stirring and mixing at 30℃for 50 minutes, to obtain an asphaltene stabilizer composition v.
The stability properties of the resulting asphaltene stabilizer composition t, asphaltene stabilizer composition u, and asphaltene stabilizer composition v were measured according to the stability property test method of the stabilizer described above. The stabilizing efficiency of the compounded asphaltene stabilizer t, asphaltene stabilizer u and asphaltene stabilizer v on asphaltene of Canadian oil sand asphalt respectively reaches 75.1%, 89.2% and 91.1%.
The stable efficiency is optimized by above proportion to be more than 95 percent: component a, d=1:1 or 2:1 or 1:2; component B, d=1:1; component B, C, d=1:1:1.
Because the asphalt of Canadian oil sand has higher O, S, N element content, obvious absorption peaks of-OH, -NH-, -C=O exist, and the components A (polyisobutylene succinimide), B (1-polyisobutylene succinimide-3-phenylboric acid), C (dodecylbenzenesulfonic acid) and D (Span 80) have imide, boric acid and sulfonic acid groups, wherein the head groups of the imide form hydrogen bonds with the asphalt, and the boric acid and sulfonic acid groups have acid-base action with the alkaline groups in the asphalt, so that the aggregation of the asphalt is weakened or prevented, and the sedimentation and deposition of the asphalt are inhibited. Due to the fewer-COOH groups in asphaltenes, the-NH groups in E (dodecylaniline) 2 The effect of the compound containing E (dodecylaniline) for stabilizing the oil sand asphalt is poor because the compound has weaker effect on asphalt groups.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A thickened oil asphaltene stabilizer composition, which is characterized by comprising a component A, a component D and a solvent, wherein the mass ratio of the component A to the component D is 1:1, 2:1 or 1:2; or consists of a component B, a component D and a solvent, wherein the mass ratio of the component B to the component D is 1:1; or comprises a component B, a component C, a component D and a solvent, wherein the mass ratio of the component B to the component C to the component D is 1:1:1,
wherein, one or more of the group consisting of components A, N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide are provided, and the N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide have the structures shown in the following formulas I, II and III in sequence:
wherein R is 1 Is that
n＝10-50；
R 3 Is H or
R 2 Is H or CH 3 -(CH 2 ) m -，m＝8-16；
R is CH 3 -(CH 2 ) i -，i＝7-11；
The component B, the organic amine compound containing boric acid group, has the structure shown in the following formula IV:
wherein R is 1 H, CH of a shape of H, CH 3 -(CH 2 ) m -or
m＝7-15，n＝10-50；
R 2 Is H;
one or more of the components C, dodecylbenzene sulfonic acid, alkylaminobenzene boric acid and oleic acid;
component D, span-80.
2. A thickened oil asphaltene stabilizer composition as claimed in claim 1, wherein component B is 1-polyisobutylene succinimide-3-phenylboronic acid.
3. The thickened oil asphaltene stabilizer composition as claimed in claim 1, wherein the solvent is toluene.
4. A process for the preparation of a thickened oil asphaltene stabiliser composition as claimed in any one of claims 1 to 3 characterised in that the process comprises the steps of:
step 1, adding the components into a mixer and uniformly mixing;
step 2, adding a solvent into a mixer;
and 3, stirring the mixture in the mixer at the temperature of 10-50 ℃ for 15-60 minutes to obtain the thickened oil asphaltene stabilizer composition.
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