CN106833578B - Polyamid-amine-alkyl ester bitumen dispersants for high-viscosity oils - Google Patents
Polyamid-amine-alkyl ester bitumen dispersants for high-viscosity oils Download PDFInfo
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- CN106833578B CN106833578B CN201710044314.5A CN201710044314A CN106833578B CN 106833578 B CN106833578 B CN 106833578B CN 201710044314 A CN201710044314 A CN 201710044314A CN 106833578 B CN106833578 B CN 106833578B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—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
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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
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
The invention discloses a polyamide-amine-alkyl ester asphalt dispersant for high-coagulation heavy oil. The asphalt dispersant consists of a main agent and a solvent, wherein the main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula of the asphalt dispersant is as follows:
in the formula:
Description
Technical Field
The invention relates to a dendritic macromolecular compound which is used in the process of thick oil exploitation and can help asphalt to disperse, in particular to an asphalt dispersant which is used for high-coagulation thick oil and is prepared from polyamide-amine-alkyl ester.
Background
The reserve of the thickened oil resources accounts for a large proportion of the total reserve of the oil and gas resources in the world. With the continuous improvement of petroleum resource exploitation technology and the continuous exhaustion of light crude oil resources, high-condensation heavy oil resources increasingly attract the attention of petroleum workers. Therefore, how to exploit and utilize the high-viscosity oil to make the high-viscosity oil become a mobile energy reserve becomes a difficult problem which is always researched in the petroleum industry. The addition of a small amount of pour point depressant to crude oil to improve the low temperature flow properties of thick oils is a currently widely used and effective method. However, because the composition of crude oil in the stratum is complex, many oil reservoirs face the problems of high salinity, high wax content, high asphaltene and the like, and the use of the emulsification viscosity reducer faces the difficulties of later demulsification and the like.
The heavy oil contains more colloid and asphaltene, has high viscosity and poor flow property, and is a very effective exploitation method by heating or diluting. Generally, under stable reservoir conditions, saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene components in heavy oil are in a thermodynamic equilibrium state, and changes in the physical and chemical properties of the reservoir during development can cause significant changes in the flow and phase states of reservoir fluids, destroy the equilibrium state of the asphaltene components in the crude oil, cause flocculation and deposition of the asphaltene components in the crude oil, and cause blockage of the stratum, a wellbore and production equipment.
The article 'evaluation of performance of thick oil colloid asphaltene dispersion blocking remover and field application' reported by the university of Xian Petroleum uses water-based asphalt high-temperature dispersion stabilizer for organic matter blocked oil wells of marine oil extraction plants. The agent consists of a dispersant, a proper cosolvent, a C-F, Si-F surfactant and water, and has the action mechanism of dissolving, dispersing, mixing and dissolving to form a stable low-viscosity system, so that the agent cannot be separated out in a layering way under the stratum condition and at low temperature, the viscosity of thick oil is reduced, and the flow capacity of crude oil in the stratum is improved. The basic principle is to add a certain amount of aqueous surfactant solution to crude oil to form an oil-in-water emulsion or dispersion system. However, this method has disadvantages that the amount of the dispersant is more than 16%, the cost is high, and a large amount of water is contained therein, and the crude oil is transported to a destination and then subjected to demulsification and dehydration, thereby requiring an additional demulsification process, and requiring an increased cost for treating waste water after demulsification.
ZL 02155597.4 'oil well cleaning and blocking remover' provides a cleaning and blocking remover for oil wells in petroleum development, which is prepared by compounding aromatic hydrocarbon, ethanol, organic acid salt, paraffin emulsifying dispersant and high-efficiency detergent according to a certain proportion, and can dissolve organic matters such as colloid, asphaltene and wax, enhance the fluidity of crude oil and inhibit the expansion of reservoir clay. The main component is aromatic hydrocarbon material, and the detergent component is still fluorine-containing surfactant. The dosage patent of the cleaning and blocking remover does not relate to the dosage patent, and the economy is difficult to evaluate.
"synthesis of novel dendritic polyamidoamine with ethylenediaminetetraacetic acid as core" (synthetic chemistry), published by wangchen et al, 2014, 22 "literature provides a series of novel methods for synthesizing dendritic polyamidoamine macromolecules. According to experimental research, the dendritic molecule with the polar functional group containing the amido and the tertiary amine functional group can be used for the high wax-content thick oil asphaltene dispersant. The polyamide-amine-alkyl ester organic compound is used for the high-congealing-oil asphalt dispersant and is not reported in any document or patent.
Disclosure of Invention
The invention provides a polyamide-amine-alkyl ester asphalt dispersant for high-coagulation thick oil aiming at the defects of the prior art, and the dispersant has the characteristics of high temperature resistance, salt resistance and viscosity reduction performance.
The polyamide-amine-alkyl ester asphalt dispersant for high-coagulation thickened oil is characterized by comprising a main agent and a solvent, wherein the main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula of the dendritic organic compound is as follows:
in the formula:
the solvent is one of benzene, toluene, xylene and trimethylbenzene.
The mass ratio of the main agent to the solvent is 1: 1-99, and preferably 1: 9.
The preparation method of the polyamide-amine-alkyl ester asphalt dispersant for high-coagulation thick oil comprises the following specific steps:
(1) weighing the solvent according to the proportion, adding the solvent into a beaker, heating while stirring, wherein the heating temperature is 40-50 ℃, the heating time is 20-30 min, the stirring speed is 200-300 rpm, the stirring time is 10-20 min, and naturally cooling to room temperature after the heating time is over;
(2) adding the main agent in the proportion into the solvent, heating while stirring, wherein the heating temperature is 50-60 ℃, the heating time is 20-30 min, the stirring speed is 300-500 rpm, the stirring time is 20-30 min, and a mixture is obtained after the heating time is finished;
(3) and cooling the mixture to 30-40 ℃, keeping the temperature constant for 30-40 min, stirring for 20-30 min, and naturally cooling to room temperature after the constant temperature time is over to obtain the asphaltene dispersant.
The polyamide-amine-alkyl ester molecules are easy to combine with the asphaltene due to the existence of a plurality of amide polar functional groups, and the ester-based antenna is easier to penetrate into the asphaltene lamellar structure, so that the adsorption force of the asphaltene lamellar structure is weakened; by introducing tertiary amine groups, the tertiary amine groups react with the asphaltenes, the hydrogen bond effect of molecular bonds of the asphaltenes is destroyed, the mutual repulsive force between the asphaltenes is enhanced, the asphaltene molecules combined with the dendritic molecules are not easy to interact to form large crystals, the anti-deposition capability and the dispersity are improved, and the purpose of reducing the viscosity of the high-viscosity oil is finally achieved; in addition, the asphaltene dispersant has stronger polar groups, and can act synergistically with the pour point depressant to change the growth form of wax crystals and destroy the network structure, thereby improving the flow property of the high-pour-point thickened oil. The existence of the solvent in the dispersant has a synergistic effect, and the mixing degree of asphaltene molecules and the dispersant is enhanced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the asphalt dispersant has the advantages of wide raw material source, simple synthesis process, clean and pollution-free process, and easily obtained, transported and stored products;
(2) the asphalt dispersant has the characteristics of small using amount, safety and stability, and remarkable economic benefit;
(3) the asphalt dispersant has good temperature and salt resistance, can resist the temperature of 220 ℃ and the mineralization degree of 230000 mg/L;
(4) the asphalt dispersant has good universality and good dispersion effect on asphaltene, and can reduce the viscosity of high-coagulation heavy oil by more than 85% when the dosage is 100 ppm.
Detailed Description
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1: asphaltene dispersant A and preparation method thereof
(1) The asphaltene dispersant A comprises the following components
Main agent 5.0g
The solvent was benzene 5.0g
The main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula is as follows:
in the formula:
(2) preparation method of asphaltene dispersant A
① weighing 5.0g of solvent benzene, adding into a beaker, heating while stirring, wherein the heating temperature is 40 ℃, the heating time is 20min, the stirring speed is 200rpm, the stirring time is 15min, and naturally cooling to room temperature after the heating time is over;
② adding 5.0g of main agent into the solvent benzene, heating while stirring, wherein the heating temperature is 55 ℃, the heating time is 30min, the stirring speed is 400rpm, the stirring time is 20min, and a mixture is obtained after the heating time is over;
③ cooling the mixture to 30 ℃, keeping the temperature constant for 40min, stirring for 20min, and naturally cooling to room temperature after the constant temperature time is over to obtain the asphaltene dispersant A.
The preparation method of the main agent comprises the following specific preparation methods according to the prior documents:
in the formula:
example 2: asphaltene dispersant B and preparation method thereof
(1) The asphaltene dispersant B comprises the following components
Main agent 1.0g
The solvent is 99.0g of trimethylbenzene
The main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula is as follows:
in the formula:
(2) preparation method of asphaltene dispersant B
①, weighing 99.0g of solvent trimethylbenzene, adding into a beaker, stirring while heating, wherein the heating temperature is 45 ℃, the heating time is 25min, the stirring speed is 260rpm, the stirring time is 10min, and naturally cooling to room temperature after the heating time is over;
② adding 1.0g of main agent into the trimethylbenzene solvent, heating while stirring, wherein the heating temperature is 50 ℃, the heating time is 25min, the stirring speed is 300rpm, the stirring time is 25min, and a mixture is obtained after the heating time is over;
③, cooling the mixture to 35 ℃, keeping the temperature constant for 35min, stirring for 25min, and naturally cooling to room temperature after the constant temperature time is over to obtain the asphaltene dispersant B.
The preparation method of the main agent refers to example 1.
Example 3: asphaltene dispersant C and preparation method thereof
(1) The asphaltene dispersant C comprises the following components
Main agent 2.0g
The solvent was 18.0g of toluene
The main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula is as follows:
in the formula:
(2) preparation method of asphaltene dispersant C
① weighing 18.0g of solvent toluene, adding into a beaker, stirring while heating, wherein the heating temperature is 50 ℃, the heating time is 30min, the stirring speed is 300rpm, the stirring time is 20min, and naturally cooling to room temperature after the heating time is over;
② adding 2.0g of main agent into the solvent toluene, heating while stirring, wherein the heating temperature is 60 ℃, the heating time is 20min, the stirring speed is 500rpm, the stirring time is 30min, and a mixture is obtained after the heating time is over;
③, cooling the mixture to 40 ℃, keeping the temperature constant for 30min, stirring for 30min, and naturally cooling to room temperature after the constant temperature time is over to obtain the asphaltene dispersant C.
The preparation method of the main agent refers to example 1.
Example 4
The asphaltene dispersants A, B and C prepared in examples 1, 2 and 3 are added into high-viscosity thick oil F provided by a pure girder oil extraction factory in a victory oil field according to 100ppm and stirred uniformly, and the basic parameters of the thick oil F are as follows: the solidification point was 53 ℃ and the content of asphaltenes was 18.5%, and the viscosity was 10949 mPas (50 ℃).
The effect of reducing the viscosity of the high-coagulation thickened oil F (50 ℃) is determined according to the SY/T0520-2008 crude oil viscosity determination standard, and the test results are shown in Table 1.
TABLE 1 viscosity reduction Effect of asphaltene dispersants on high viscosity oil F (50 ℃ C.)
As can be seen from Table 1, when the amount of the asphaltene dispersant A, B and the amount of the asphaltene dispersant C are 100ppm, the viscosity of the high-viscosity heavy oil F of the pure-beam oil production plant of the victory oil field can be respectively reduced by 86.2%, 87.3% and 89.5%, and the reduction range is larger than 85%, wherein the viscosity reduction effect of the asphaltene dispersant C is preferably more than 89.0%, and the viscosity reduction effect is good.
Example 5
The asphaltene dispersants A, B and C prepared in examples 1, 2 and 3 are added to the high-viscosity oil G provided by the oil extraction plant of Wangjiagang of Shengli oil field at 100ppm and stirred uniformly, and the basic parameters of the high-viscosity oil G are as follows: the solidification point was 47 ℃ and the asphaltene content was 16.8%, and the viscosity was 5686 mPas (50 ℃).
The effect of reducing the viscosity of the high-viscosity oil G (50 ℃) is determined according to SY/T0520-2008 crude oil viscosity determination standards, and the test results are shown in Table 2.
TABLE 2 viscosity reduction Effect of asphaltene dispersants on high-viscosity oil G (50 ℃ C.)
As can be seen from Table 2, when the amount of the asphaltene dispersants A, B and C is 100ppm, the viscosity of the high-viscosity oil G of the pure-beam oil production plant of the victory oil field can be respectively reduced by 86.5%, 87.0% and 88.2%, and the reduction range is larger than 85%; wherein, the viscosity reduction effect of the asphaltene dispersant C is preferably more than 88.0 percent, and the viscosity reduction effect is good.
Example 6
The asphaltene dispersants A, B and C prepared in examples 1, 2 and 3 are added into high-viscosity heavy oil H provided by a petroleum extraction plant in the river of the Shengli oil field at 100ppm and stirred uniformly, and the basic parameters of the heavy oil H are as follows: the solidification point was 55 ℃, the asphaltene content was 20.5%, and the viscosity (50 ℃) was 25605 mPas.
The effect of reducing the viscosity of the high-coagulation heavy oil H (50 ℃) is determined according to the SY/T0520-2008 crude oil viscosity determination standard, and the test results are shown in Table 3.
TABLE 3 viscosity reduction Effect of asphaltene dispersants on high viscosity oil H (50 ℃ C.)
As can be seen from Table 3, when the amount of the asphaltene dispersant A, B and the amount of the asphaltene dispersant C are 100ppm, the viscosity of the high-viscosity heavy oil H of the pure-beam oil extraction plant of the victory oil field can be respectively reduced by 85.7%, 86.4% and 89.0%, and the reduction range is larger than 85%, wherein the viscosity reduction effect of the asphaltene dispersant C is preferably 89.0%, and the viscosity reduction effect is good.
In conclusion, the asphaltene dispersant disclosed by the invention has an asphaltene dispersing effect on various high-coagulation thickened oils, and can reduce the viscosity of high-coagulation thickened oils F, G and H by more than 85%, wherein the mass ratio of the main agent to the solvent is 1: the viscosity reduction rate reaches over 88% at 9 hours, which shows that the asphaltene dispersant has good asphalt dispersing effect, and meanwhile, the asphaltene dispersant has the advantages of small addition amount, low cost and simple synthesis method, and can meet the requirements of on-site exploitation and transportation of high-viscosity oil and the like.
Claims (4)
1. The polyamide-amine-alkyl ester asphalt dispersant for high-coagulation thickened oil is characterized by comprising a main agent and a solvent, wherein the main agent is a dendritic organic compound with a plurality of amide groups, ester groups and amine functional groups, and the molecular formula of the dendritic organic compound is as follows:
in the formula:
the solvent is one of benzene, toluene, xylene and trimethylbenzene.
2. The polyamide-amine-alkyl ester asphalt dispersant for high-viscosity oil according to claim 1, wherein the mass ratio of the main agent to the solvent is 1: 1-99.
3. The dispersing agent for asphalt of high-viscosity oil according to claim 2, wherein the mass ratio of the main agent to the solvent is 1: 9.
4. A process for the preparation of a polyamidoamine-alkyl ester bitumen dispersant for high-viscosity oils according to any of claims 1 to 3, characterized in that said process comprises the following steps:
(1) weighing the solvent according to the proportion, adding the solvent into a beaker, heating while stirring, wherein the heating temperature is 40-50 ℃, the heating time is 20-30 min, the stirring speed is 200-300 rpm, the stirring time is 10-20 min, and naturally cooling to room temperature after the heating time is over;
(2) adding the main agent in the proportion into the solvent, heating while stirring, wherein the heating temperature is 50-60 ℃, the heating time is 20-30 min, the stirring speed is 300-500 rpm, the stirring time is 20-30 min, and a mixture is obtained after the heating time is finished;
(3) and cooling the mixture to 30-40 ℃, keeping the temperature constant for 30-40 min, stirring for 20-30 min, and naturally cooling to room temperature after the constant temperature time is over to obtain the asphaltene dispersant.
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| CN110776606B (en) * | 2019-10-31 | 2022-01-07 | 四川瑞冬科技有限公司 | Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof |
| CN113480446B (en) * | 2021-05-27 | 2023-12-01 | 佳化化学科技发展（上海）有限公司 | Amine compound, polymer polyol and preparation method and application thereof |
| CN114075120B (en) * | 2021-10-27 | 2024-01-23 | 深圳飞世尔新材料股份有限公司 | PH stabilizer, preparation method thereof, cleaning agent for molybdenum-aluminum-molybdenum coated glass and preparation method thereof |
| CN117285708B (en) * | 2023-11-24 | 2024-01-30 | 西南石油大学 | Asphaltene dispersion stabilizer and preparation method thereof |
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