Stabilizer for stably dispersing heavy oil asphaltene at high temperature and preparation method thereof

Abstract

The invention provides a stabilizer for stably dispersing heavy oil asphaltene at a high temperature and a preparation method thereof, the stabilizer comprises at least two of components A, B, C, D and E. The component A is an organic anhydride substance with alkylamine, alkylaniline, naphthylamine or aminopyridine on a side chain, the component B is an organic amide polymer, the component C is a fluorine-containing ultrahigh surfactant, and the component D is a fluorine-containing ultrahigh surfactant. The component D is an organic acid ester polymer with a dodecylbenzene sulfonic acid substituent group or an alkyl aminophenylboronic acid substituent group, and the component E is an organic acid anhydride polymer with an alkyl straight chain or branched chain. The stabilizer composition disclosed by the invention has the advantages of cheap and easily available raw materials, simple preparation process and low cost; the action time with oil product asphaltene is short, and the oil product asphaltene stabilizing agent still has a very good stabilizing effect on heavy oil asphaltene at a high temperature of 150-300 DEG C.

Description

Technical Field

[0001] The invention relates to the technical field of asphaltene stabilizers, and in particular to a stabilizer for stably dispersing heavy oil asphaltene at high temperature and a preparation method thereof. Background Art

[0002] Asphaltene is the component with the largest molecular weight, the strongest polarity, and the most complex structure in heavy oil. It is also the component with the largest intermolecular force and the most unstable in heavy oil. When the ambient temperature, pressure, or oil composition of the heavy oil changes, the stability of asphaltene is easily destroyed and flocculated and deposited. In the process of oil extraction, storage, transportation, and processing, asphaltene deposition will cause pipeline scaling, storage deposition, equipment blockage and coking, which has become a difficult problem that needs to be solved urgently in order to reduce costs and increase efficiency in related industries.

[0003] Adding asphaltene stabilizer can delay or inhibit the precipitation of asphaltene into the "second liquid phase", or make asphaltene evenly dispersed in the oil phase to form an asphaltene suspension, which is one of the most economical and effective methods to solve asphaltene deposition. The structure of asphaltene stabilizer generally contains polar groups or aromatic groups and non-polar groups. Polar groups usually include hydroxyl, sulfonic acid, carboxyl, amine, and amide, and non-polar groups are generally long-chain alkyl groups. Polar groups or aromatic groups form hydrogen bonds, π-π, acid-base interactions, dipole interactions, etc. with asphaltene molecules or aggregates, while long alkyl chains play a certain role in entanglement, blocking, and thus weakening or preventing the aggregation of asphaltene molecules. There are many types of asphaltene stabilizers currently developed, including small molecule surfactant type, non-polymer type, ionic liquid and high molecular polymer type. However, most asphaltene stabilizers can only be used in mining and storage at room temperature, and there are few related research reports on asphaltene stabilizers at high temperatures. Therefore, the development of high-temperature asphaltene stabilizers has broad application prospects.

[0004] Chinese patent CN108117867A relates to a method for synthesizing and purifying a petroleum asphaltene stabilizer used in the process of petroleum blending and dilution. First, the reactants 3-aminophenylboronic acid or 3-aminobenzenesulfonic acid and polyisobutylene succinic anhydride are dissolved in an aromatic solvent, reacted under the action of zinc perchlorate catalyst at 110°C-140°C, and then subjected to water-organic solvent extraction, reduced pressure distillation and vacuum drying to obtain an asphaltene stabilizer. The preparation process of this patent requires catalytic reaction, extraction, distillation and drying, which has high preparation costs, and the polar group types in the structure of the obtained asphaltene stabilizer are single, and there are fewer action sites with asphaltene. At the same time, the asphaltene stabilizer has poor thermal stability. If it is added to the oil product after residual oil hydrogenation at 150°C-300°C, it will decompose, and it cannot achieve the purpose of preventing the oil product from aggregating and clogging in the pipeline and equipment after thermal high separation.

[0005] Chinese patent CN107629776A discloses a method for synthesizing and purifying a heavy oil asphaltene stabilizer used in the process of heavy oil blending and dilution. First, reactants such as polyisobutylene succinic anhydride and aniline dissolved in an aromatic solvent react for 3h-9h at 100℃-150℃ and under the action of catalyst zinc perchlorate; the mixture after the reaction is then subjected to water-organic solvent extraction, reduced pressure distillation and vacuum drying to obtain an asphaltene stabilizer. The preparation process of this patent requires the process of catalytic reaction, extraction, distillation and drying, which has high preparation costs, and the polar group type in the structure of the obtained asphaltene stabilizer is single, and it has fewer action sites with asphaltene. At the same time, the asphaltene stabilizer has poor thermal stability. If it is added to the oil product after residual oil hydrogenation at 150℃~300℃, it will decompose, and it cannot achieve the purpose of preventing the oil product from aggregating and clogging in the pipeline and equipment after thermal high separation.

[0006] Chinese patent CN114196391A discloses an acid liquid system for asphaltene reservoirs and its preparation method, which belongs to the field of petroleum extraction. The acid liquid system includes the following components in mass percentage: hydrochloric acid 12%-20%, polyacrylamide thickener 0.3%-0.6%, fluorocarbon drainage agent 0.5%-2%, aldehyde ketone amine condensate corrosion inhibitor 1%-3%, iron ion stabilizer 0.5%-2%, asphaltene dissolving dispersant 10%-30%, and the balance is water. The acid liquid system for asphaltene reservoirs is suitable for the acidification of asphaltene reservoirs, especially the acidification of asphaltene carbonate reservoirs, and can dissolve and disperse the asphaltene in the reservoir to obtain a good acidification effect. The patent introduces components such as hydrochloric acid, which are acidic overall. If added after the residue hydrogenation reactor, it will cause corrosion to the subsequent pipelines and reduce the operating life of the device.

[0007] Chinese patent CN111334250A discloses a heavy oil asphaltene stabilizer composition and its preparation method, the composition comprises at least two components: component A, one or more of the group consisting of N, N-dimethylamide, alkyl pyrrolidone and polyisobutylene succinimide; component B, organic amine compounds containing boric acid groups; component C, one or more of the group consisting of dodecylbenzenesulfonic acid, alkylaminophenylboric acid and oleic acid; component D, span-80; component E, p-alkylaniline and / or m-alkylaniline. The asphaltene stabilizer in the patent has a good effect at room temperature, but poor thermal stability. If it is added to the oil product after residual oil hydrogenation at 150℃ to 300℃, it will decompose, and it cannot achieve the purpose of preventing the oil product from agglomerating and clogging in the pipeline and equipment after thermal high separation. Summary of the invention

[0008] The purpose of the present invention is to provide a stabilizer for stably dispersing heavy oil asphaltene at high temperature, thereby solving the problem of poor thermal stability of the stabilizer in the prior art.

[0009] The present invention also aims to provide a method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature.

[0010] To achieve the above object, the present invention provides a stabilizer for stably dispersing heavy oil asphaltene at high temperature, comprising at least two of components A, B, C, D, and E, wherein:

[0011] Component A is an organic acid anhydride substance with alkylamine, alkylaniline, naphthylamine or aminopyridine on the side chain, and has the following molecular structure:

[0012] Among them, R 1 for n = 10-40;

[0013] R 2 CH 3 -(CH 2 ) m -NH-, m = 6-12, or R 4 CH 3 -(CH 2 ) n -, n = 6-12,

[0014] Component B is an organic amide polymer with the following molecular structure:

[0015]

[0016] Among them, R 1 for n = 10-40;

[0017] R 2 For -NH 2 or -NHB(OH) 2 or

[0018] Component C is a fluorinated ultra-high surfactant. n F 2n+1 CONHC 3 H 6 (CH 3 ) 2 , wherein n = 7-9;

[0019] Component D is an organic acid ester polymer having a dodecylbenzenesulfonic acid substituent or an alkylaminophenylboronic acid substituent;

[0020] Component E is an organic acid anhydride polymer with a linear or branched alkyl chain and has the following molecular structure:

[0021]

[0022] in:

[0023] R is m = 7-16, or n=10-40.

[0024] The stabilizer for stably dispersing heavy oil asphaltene at high temperature of the present invention is characterized in that the mass ratio of component A, component B, component C, component D and component E is 0-10: 0-8: 0-5: 0-5: 0-10, wherein at least two components are not 0 at the same time.

[0025] The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature of the present invention is characterized in that at least two of component A, component B, component C, component D and component E are mixed with a solvent and stirred evenly to obtain the stabilizer.

[0026] The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature according to the present invention is characterized in that the solvent is one or more of benzene, toluene, xylene, naphtha, catalytic cracking gasoline, straight-run diesel, catalytic cracking diesel, coker diesel, straight-run wax oil and hydrocracking wax oil.

[0027] The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature of the present invention is characterized in that the mass ratio of the total amount of component A, component B, component C, component D and component E to the solvent is 20%-60%.

[0028] The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature of the present invention is characterized in that stirring is carried out at 10° C.-60° C. for 10 minutes-12 hours.

[0029] Beneficial effects of the present invention: The raw materials of the stabilizer composition of the present invention are cheap and easily available, the preparation process is simple and the cost is low; the reaction time with oil asphaltene is short, and it still has a good stabilizing effect on heavy oil asphaltene at high temperature of 150°C-300°C. DETAILED DESCRIPTION

[0030] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0031] Test method for stability performance of stabilizer

[0032] (1) The asphaltene stabilizer composition was prepared into a stabilizer-toluene mother solution M of 50 g / L.

[0033] (2) Prepare 10 g / L asphaltene-toluene mother liquor N.

[0034] (3) Take a certain volume of 10g / L mother solution N and n-heptane and mix them evenly to form a mixed solution P, so that V in P 甲苯 :V 正庚烷 =1:7, place the P solution in two autoclaves, react at 100℃ for 6h and 350℃ for 3h respectively, take out the product q after the autoclave returns to room temperature, let it stand for 24 hours, filter out the precipitated asphaltene, take the supernatant and use UV-visible spectrophotometer to measure its absorbance D at a wavelength of 710nm 0 .

[0035] (4) Take a certain volume of mother solution M and N and mix them evenly, then add a certain volume of n-heptane to form a mixed solution S, so that V in S 甲苯 :V 正庚烷 =1:7, the S solution was placed in two autoclaves respectively, the reaction conditions and treatment conditions of (3) were repeated, and the absorbance D of the product was measured. w .

[0036] (6) The stabilization efficiency of asphaltene stabilizer at low and high temperatures is calculated according to the following formula:

[0037]

[0038] Example 1

[0039] 2.5 g of component A (N-dodecyl polyisobutylene maleimide) and 2.5 g of component B (N-polyethyleneamine polyisobutylene maleimide) were added to a mixing container, and then 25 g of toluene was added, and the mixture was stirred and mixed at 30° C. for 30 minutes to obtain an asphaltene stabilizer composition a. An asphaltene stabilizer composition b and an asphaltene stabilizer composition c having a mass ratio of component A to component B of 3:1 and a mass ratio of component B of 1:3 were prepared in the same manner.

[0040] The stability performance of the asphaltene stabilizer composition a, asphaltene stabilizer composition b, and asphaltene stabilizer composition c on the asphaltene of Daqing hydrogenated oil was measured according to the stability performance test method of the stabilizer described in this patent. The low-temperature stability efficiency of the compounded asphaltene stabilizer composition a is 82.0%, and the high-temperature stability efficiency is 57.6%; the low-temperature stability efficiency of the asphaltene stabilizer composition b is 98.3%, and the high-temperature stability efficiency is 63.2%; the low-temperature stability efficiency of the asphaltene stabilizer composition c is 81.5%, and the high-temperature stability efficiency is 71.3%.

[0041] Example 2

[0042] Add 3.75 g of component A (N-dodecyl polyisobutylene maleimide) and 1.25 g of component C (C 9 F 19 CONHC 3 H 6 (CH 3 ) 2 ), and then add 6g of naphtha and 6g of catalytic cracking diesel, and stir and mix thoroughly at 10°C for 40 minutes to obtain an asphaltene stabilizer composition d. An asphaltene stabilizer composition e having a mass ratio of component A to component C of 4:1 was prepared in the same manner.

[0043] The stability performance of the asphaltene stabilizer composition d and the asphaltene stabilizer composition e on the asphaltene of Daqing hydrogenated oil was measured according to the stability performance test method of the stabilizer described in this patent. The low temperature stability efficiency of the compounded asphaltene stabilizer composition d was 99.5% and the high temperature stability efficiency was 70.2%; the low temperature stability efficiency of the asphaltene stabilizer composition e was 98.1% and the high temperature stability efficiency was 65.4%.

[0044] Example 3

[0045] 3.75 g of component E (polyethylene maleic anhydride) and 1.25 g of component C (C 9 F 19 CONHC 3 H 6 (CH 3 ) 2 ), and then 8.5 g of hydrocracked wax oil was added, and the mixture was stirred and mixed at 60° C. for 10 minutes to obtain an asphaltene stabilizer composition f. An asphaltene stabilizer composition g having component E and component C in a mass ratio of 4:1 was prepared in the same manner.

[0046] The stability performance of the asphaltene stabilizer composition f and asphaltene stabilizer composition g on the asphaltene of Daqing hydrogenated oil was measured according to the stability performance test method of the stabilizer described in this patent. The low temperature stability efficiency of the compounded asphaltene stabilizer composition f was 98.5% and the high temperature stability efficiency was 63.3%; the low temperature stability efficiency of the asphaltene stabilizer composition g was 98.1% and the high temperature stability efficiency was 60.5%.

[0047] Example 4

[0048] 2.5 g of component A (N-dodecyl polyisobutylene maleimide), 1.25 g of component E (polyethylene maleic anhydride) and 1.25 g of component C (C 9 F 19 CONHC 3 H 6 (CH3 ) 2 ), and then 25 g of straight-run diesel was added, and the mixture was stirred and mixed at 60° C. for 2 hours to obtain an asphaltene stabilizer composition h. The same method was used to prepare asphaltene stabilizer composition i and asphaltene stabilizer composition j, in which the mass ratios of component A, component E and component C were 1:2:1 and 1:1:2 respectively.

[0049] According to the stability performance test method of the stabilizer described in this patent, the stability performance of the obtained asphaltene stabilizer composition h, asphaltene stabilizer composition i, and asphaltene stabilizer composition j on the asphaltene of Daqing hydrogenated oil was measured. The low-temperature stability efficiency of the compounded asphaltene stabilizer composition h was 98.5%, and the high-temperature stability efficiency was 69.1%; the low-temperature stability efficiency of the asphaltene stabilizer composition i was 93.0%, and the high-temperature stability efficiency was 55.9%; the low-temperature stability efficiency of the asphaltene stabilizer composition j was 80.3%, and the high-temperature stability efficiency was 42.1%.

[0050] Example 5

[0051] 2 g of component A (N-dodecyl polyisobutylene maleimide), 2 g of component B (N-polyethyleneamine polyisobutylene maleimide) and 1 g of component D (dodecylbenzenesulfonic acid substituted polyhexadecyl acrylate) were added to a mixing container in sequence, and then 25 g of benzene was added, and the mixture was stirred and mixed at 30° C. for 12 hours to obtain an asphaltene stabilizer composition k. In the same manner, asphaltene stabilizer composition t and asphaltene stabilizer composition o were prepared in which the mass ratios of component A, component B and component D were 2:1:1 and 1:2:1, respectively.

[0052] The stability performance of the obtained asphaltene stabilizer composition k, asphaltene stabilizer composition t, and asphaltene stabilizer composition o on Daqing hydrogenated oil asphaltene was measured according to the stability performance test method of the stabilizer described in this patent. The low-temperature stability efficiency of the compounded asphaltene stabilizer composition k is 85.2%, and the high-temperature stability efficiency is 52.1%; the low-temperature stability efficiency of the asphaltene stabilizer composition t is 80.3%, and the high-temperature stability efficiency is 45.8%; the low-temperature stability efficiency of the asphaltene stabilizer composition o is 77.6%, and the high-temperature stability efficiency is 40.3%.

[0053] Example 6

[0054] In the mixing container, add 2g of component A (N-dodecyl polyisobutylene maleimide), 2g of component C (C 9 F 19 CONHC 3 H 6 (CH 3 ) 2) and 1g of component D (dodecylbenzenesulfonic acid substituted polyhexadecyl acrylate), and then 25g of coker diesel were added, and the mixture was stirred and mixed at 30°C for 5 hours to obtain an asphaltene stabilizer composition u. The asphaltene stabilizer composition v and asphaltene stabilizer composition w were prepared in the same way, wherein the mass ratios of component A, component C and component D were 2:1:1 and 1:2:1 respectively.

[0055] According to the stability performance test method of the stabilizer described in this patent, the stability performance of the obtained asphaltene stabilizer composition u, asphaltene stabilizer composition v, and asphaltene stabilizer composition w on Daqing hydrogenated oil asphaltene was measured. The low temperature stability efficiency of the compounded asphaltene stabilizer u is 78.1%, and the high temperature stability efficiency is 52.5%; the low temperature stability efficiency of the asphaltene stabilizer v is 74.9%, and the high temperature stability efficiency is 50.8%; the low temperature stability efficiency of the asphaltene stabilizer w is 70.6%, and the high temperature stability efficiency is 61.2%.

[0056] Example 7

[0057] 2.5 g of component A (N-dodecyl polyisobutylene maleimide), 1.25 g of component E (polyethylene maleic anhydride) and 1.25 g of component C (C 9 F 19 CONHC 3 H 6 (CH 3 ) 2 ), and then add 100 mL of catalytic cracking gasoline, and stir and mix thoroughly at 60° C. for 40 minutes to obtain an asphaltene stabilizer composition z.

[0058] The stability performance of the asphaltene stabilizer composition Z on the asphaltene of Daqing hydrogenated oil was measured according to the stability performance test method of the stabilizer described in this patent. The low temperature stability efficiency of the compounded asphaltene stabilizer composition Z was 97.5% and the high temperature stability efficiency was 67.1%.

[0059] Comparative Example 1

[0060] The stabilizer was prepared according to the scheme provided in Example 2 of Chinese Patent CN111334250A. 50g of component A (polyisobutylene succinimide) and 50g of component D (Span80) were added to a mixing container, and then 100g of toluene was added, and the mixture was stirred and mixed at 30°C for 40 minutes to obtain an asphaltene stabilizer composition a'.

[0061] The stability performance of the obtained asphaltene stabilizer composition a' on Daqing hydrogenated oil asphaltene was measured according to the stabilizer stability performance test method described in this patent. The low temperature stability efficiency of the compounded asphaltene stabilizer composition a' was 31.3% and the high temperature stability efficiency was 5.3%.

[0062] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A stabilizer for stably dispersing heavy oil asphaltene at high temperature, characterized in that: It includes at least two of components A, B, C, D, and E, wherein: Component A is an organic acid anhydride substance with alkylamine, alkylaniline, naphthylamine or aminopyridine on the side chain, and has the following molecular structure: Among them, R1 is n = 10-40; R2 is CH3-(CH2) m -NH-, m = 6-12, or R4 is CH3-(CH2) n -, n = 6-12, or Component B is an organic amide polymer with the following molecular structure: Among them, R1 is n = 10-40; R2 is -NH2 or -NHB(OH)2 or Component C is a fluorinated ultra-high surfactant. n F 2n+1 CONHC3H6(CH3)2, wherein n=7-9; Component D is an organic acid ester with a dodecylbenzenesulfonic acid substituent or an alkylaminophenylboronic acid substituent. Polymer-like; Component E is an organic acid anhydride polymer with a linear or branched alkyl chain and has the following molecular structure: in: R is m = 7-16, or n=10-40.

2. The stabilizer for stably dispersing heavy oil asphaltene at high temperature according to claim 1, characterized in that: The mass ratio of component A, component B, component C, component D and component E is 0-10: 0-8: 0-5: 0-5: 0-10, wherein at least two components are not 0 at the same time.

3. The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature according to claim 1 or 2, characterized in that: At least two of component A, component B, component C, component D and component E are mixed with a solvent and stirred evenly to obtain the stabilizer.

4. The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature according to claim 3, characterized in that: The solvent is one or more of benzene, toluene, xylene, naphtha, catalytic cracking gasoline, straight-run diesel, catalytic cracking diesel, coker diesel, straight-run wax oil and hydrocracking wax oil.

5. The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature according to claim 3, characterized in that: The mass ratio of the total amount of component A, component B, component C, component D and component E to the solvent is 20%-60%.

6. The method for preparing a stabilizer for stably dispersing heavy oil asphaltene at high temperature according to claim 3, characterized in that: The mixture is stirred at 10°C to 60°C for 10 minutes to 12 hours.

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