CN115305074A - Water-based crude oil pour point depressant, preparation method and application thereof - Google Patents
Water-based crude oil pour point depressant, preparation method and application thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention belongs to the technical field of oilfield chemicals, and particularly relates to a water-based crude oil pour point depressant, a preparation method and application thereof. The invention provides a water-based crude oil pour point depressant, a preparation method and application thereof, wherein the water-based crude oil pour point depressant comprises a pour point depressing main agent, an emulsifying agent, a stabilizing agent and a pour point depressing auxiliary agent; the pour point depressing main agent is an alcoholysis product of a methacrylate-crotonic acid-oleic acid terpolymer. The water-based crude oil pour point depressant provided by the invention is stable in state and safe to use, can be compatible with hydraulic fracturing fluid and tertiary oil recovery fluid, effectively prevents wax precipitation of a shaft, reduces the condensation point of crude oil, and thus improves the recovery ratio of crude oil.
Description
Technical Field
The application relates to the technical field of oilfield chemicals, in particular to a water-based crude oil pour point depressant, a preparation method and application thereof.
Background
The hydraulic fracturing is to inject fracturing fluid into an underground coal seam or rock stratum through ground equipment by utilizing the pressure transfer function of the fluid to press open cracks of the coal seam or the rock stratum to form a plurality of permeable zones with flow conductivity to communicate cracks of a reservoir stratum, thereby achieving the purpose of efficiently exploiting resources.
In the process of hydraulic fracturing, a large volume of low temperature water-based fluid is pumped at high pressure into the reservoir formation, which can fracture the formation, allowing the crude oil to pool with the fractures into the production tubing. In the process, the low-temperature fluids fracture the stratum, but simultaneously reduce the temperature of the stratum, so that long carbon chain paraffin in the crude oil is condensed into the stratum fracture, the crude oil is blocked, and the yield is reduced. Conventional pour point depressants, wax inhibitors, are dissolved in organic solvents and are incompatible with hydraulic fracturing fluids and therefore cannot be used in hydraulic fracturing. Therefore, it is necessary to develop a water-based pour point depressant product, which is compatible with hydraulic fracturing fluid and tertiary oil recovery fluid, can be used in a large amount in the hydraulic fracturing and tertiary oil recovery processes to prevent wax precipitation of a shaft and reduce the condensation point of crude oil, thereby improving the recovery rate of the crude oil.
In view of this, the present invention is proposed.
Disclosure of Invention
The invention aims to provide a water-based crude oil pour point depressant and a preparation method thereof, wherein the water-based crude oil pour point depressant is compatible with hydraulic fracturing fluid and tertiary oil recovery fluid, so that the water-based crude oil pour point depressant can be used in a large amount in the hydraulic fracturing and tertiary oil recovery processes to prevent wax precipitation of a shaft and reduce the condensation point of crude oil, thereby improving the recovery ratio of the crude oil.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a water-based pour point depressant for crude oil, which comprises a pour point depressant main agent, an emulsifier, a stabilizer and a pour point depressant auxiliary agent;
the pour point depressing main agent is an alcoholysis product of a methacrylate-crotonic acid-oleic acid terpolymer.
In the application, an alcoholysis product of a methacrylate-crotonic acid-oleic acid terpolymer is used as a pour point depressing main agent, an alcoholysis type methacrylate-crotonic acid-oleic acid terpolymer is of a comb-shaped structure, and alkyl branched chains in the comb-shaped structure can act with colloid and asphaltene in high-condensation-point crude oil to prevent the colloid asphaltene from forming a three-dimensional network structure. So that wax crystal molecules are not easy to mutually wind to form macromolecules, thereby enhancing the pour point depressing and viscosity reducing effects.
The pour point depressing main agent, the emulsifier, the stabilizer and the pour point depressing auxiliary agent are in a weight ratio of (20 to 40): (1 to 4): (0.5 to 1.5): (1 to 5).
In the application, the pour point depressant is formed by compounding the pour point depressant main agent, the emulsifier, the stabilizer and the pour point depressant auxiliary agent in a specific proportion, so that the pour point depressant provided by the application is stable in state and excellent in pour point depression effect, and has a certain effect of relieving corrosion of an oil well casing.
The emulsifier is a mixture of OP-4 and OP-10;
preferably, the mass ratio of OP-4 to OP-10 in the emulsifier is (1 to 3): (5 to 10).
In the application, the emulsifier is formed by compounding OP-4 and OP-10 in a specific mass ratio, so that the emulsifying and dispersing effect is more excellent.
Preferably, the mass ratio of OP-4 to OP-10 in the emulsifier is (1 to 2): (5 to 9).
The stabilizer is one or more of sodium hydroxymethyl cellulose, sodium hydroxyethyl cellulose and polyacrylate.
The pour point depressing auxiliary agent comprises one or more of bactericide, corrosion inhibitor and scale inhibitor;
in the application, the pour point depressing additive is added, and comprises one or more of a bactericide, a corrosion inhibitor and a scale inhibitor, and the scale inhibitor effectively solves the scaling problem and avoids the problems of heat transfer effect reduction, local corrosion of equipment and pipelines and the like caused by scaling; the bactericide can avoid the problems of corrosion of the product of microorganisms to metal, pipeline blockage or battery corrosion caused by oxygen concentration difference and the like; the corrosion inhibitor can relieve the corrosivity of corrosive gases such as dissolved oxygen, hydrogen sulfide, carbon dioxide and the like on equipment and pipelines.
Preferably, the mass ratio of the bactericide to the corrosion inhibitor to the scale inhibitor in the pour point depressant additive is (1 to 3): (1 to 3): (1 to 3).
In the application, the bactericide, the corrosion inhibitor and the scale inhibitor are compounded according to a specific mass ratio to prepare the pour point depressing auxiliary agent, and the bactericide, the corrosion inhibitor and the scale inhibitor have synergistic effect, so that the sterilization, scale inhibition and corrosion inhibition effects are enhanced, and the function of protecting an equipment pipeline is achieved.
The invention also provides a preparation method of the water-based crude oil pour point depressant, which comprises the following steps:
heating the pour point depressant main agent to 70 to 90 ℃, stirring for 30min to 40min, adding an emulsifier, continuously stirring for 30min to 50min, adding deionized water, stirring for 60min to 90min, adding a pour point depressant auxiliary agent, stirring for 60min to 75min, adding a stabilizer, and stirring for 30min to 45min to obtain the water-based crude oil pour point depressant.
In the application, the pour point depressant for the water-based crude oil is prepared by compounding a pour point depressant main agent with an emulsifier, a pour point depressant auxiliary agent and a stabilizer. The pour point depressant can be used in a shaft to prevent wax precipitation in the shaft, reduce the condensation point of crude oil and improve the extraction rate of the crude oil.
The preparation method of the pour point depressing main agent comprises the following steps: adding methacrylate, crotonic acid and oleic acid into a solvent, keeping the temperature at 70-90 ℃, stirring for 30min-45min, adding an initiator, and reacting for 5-7h to obtain a terpolymer; heating to 110-120 ℃, adding higher aliphatic alcohol, stirring for 6-8 h until the water yield reaches the theoretical water yield, and obtaining the alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer.
In the method, methacrylate, crotonic acid and oleic acid are polymerized to obtain a terpolymer, and then alcoholysis is carried out on the terpolymer and a higher aliphatic alcohol to obtain an alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer. The alcoholysis product is used as a pour point depressing main agent in the application, the alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer is of a comb-shaped structure, and alkyl branched chains in the comb-shaped structure can act with colloid and asphaltene in high-freezing-point crude oil, so that the growth of wax crystal nuclei can be effectively inhibited, a network structure formed by crosslinking of the wax crystal nuclei is damaged, and the freezing point of the crude oil is effectively reduced.
The mass ratio of the methacrylate to the crotonic acid to the oleic acid is (7 to 8): (2 to 6): (5 to 9);
the initiator comprises benzoyl peroxide or azobisisobutyronitrile;
in the application, benzoyl peroxide or azobisisobutyronitrile is added as an initiator to improve the polymerization rate. The azodiisobutyronitrile is an oil-soluble azo initiator, and the azo initiator has stable reaction, is a first-order reaction, has no side reaction and is better controlled. Can increase the polymerization reaction rate, inhibit the precipitated wax crystal structure from generating a crosslinking effect, and lead the wax crystal structure to be polymerized quickly.
The higher fatty alcohols include tetradecanol, hexadecanol and octadecanol.
The using amount of the initiator is 0.05-0.15% of the total mass of the methacrylate, the crotonic acid and the oleic acid;
the polymerization reaction rate is gradually increased along with the increase of the dosage of the initiator, the self-crosslinking effect of the precipitated wax crystal structure is inhibited, the rapid polymerization can be realized, and the action effect is obvious when the dosage of the initiator is 0.05-0.15 percent of the total mass of the methacrylate, the crotonic acid and the oleic acid. Because each monomer in the reaction system is well polymerized. With the continuous increase of the dosage, the effect is not obvious, so that the initiator dosage can achieve better effect within the range.
Preferably, the mass ratio of the higher aliphatic alcohol to the terpolymer is (1 to 5): 1.
it is another object of the present invention to provide the use of the above water-based pour point depressant for crude oil in the recovery and transportation of crude oil.
The invention has the following beneficial effects:
1. the water-based crude oil pour point depressant provided by the invention is stable in state, is not easy to delaminate, and can relieve the corrosion of an oil well casing; the water-soluble paint can be dissolved in water, so that the safety of the paint is greatly improved, and meanwhile, a storage tank and a pipeline which are used on site can be directly cleaned by water, so that the injection process flow is greatly simplified, and the workload and the working strength are greatly reduced; the additive can be compatible with hydraulic fracturing fluid and tertiary oil recovery fluid, can be used in the hydraulic fracturing and tertiary oil recovery processes in a large amount, prevents wax precipitation of a shaft, reduces the condensation point of crude oil, and accordingly improves the recovery rate of the crude oil.
2. The preparation method of the water-based crude oil pour point depressant provided by the invention has the advantages of low cost, simple process flow, strong operability, good completeness and repeatability and capability of realizing large-scale industrial continuous production.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example in conjunction with the description. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
In the following embodiments, reagents or apparatuses used are not indicated by manufacturers, and are conventional products commercially available, unless otherwise specified.
Example 1
Preparation of pour point depressing main agent
Adding 7kg of methacrylate, 2kg of crotonic acid and 5kg of oleic acid into 39kg of aromatic solvent, keeping the temperature at 70 ℃, stirring for 30min, adding 7g of initiator benzoyl peroxide, and reacting for 5h to obtain a terpolymer; taking 5kg of the terpolymer, heating the temperature to 110 ℃, adding 5kg of hexadecanol, stirring for 6h until the water yield reaches the theoretical water yield, and obtaining the alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer, which is marked as a pour point depressing main agent 1.
The preparation of the water-based crude oil pour point depressant comprises the following steps:
weighing 20kg of pour point depressant main agent 1, heating to 70 ℃, stirring for 30min, adding 286gOP-4 and 714gOP-10, continuing to stir for 30min, then adding 38.5kg of deionized water, stirring for 60min, then adding 333g of bactericide, 333g of corrosion inhibitor and 334g of scale inhibitor, stirring for 60min, finally adding 0.5kg of stabilizer sodium carboxymethylcellulose, and stirring for 30min to obtain the water-based crude oil pour point depressant, wherein the sample is marked as sample 1.
Example 2
Preparation of pour point depressing main agent
Adding 7kg of methacrylate, 4kg of crotonic acid and 9kg of oleic acid into 25kg of aromatic solvent, keeping the temperature at 90 ℃ and stirring for 45min, adding 16g of azodiisobutyronitrile serving as an initiator, and reacting for 7h to obtain a terpolymer; taking 5kg of the terpolymer, heating the temperature to 120 ℃, adding 10kg of octadecanol, stirring for 8h until the water yield reaches the theoretical water yield, and obtaining an alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer, which is marked as a pour point depressing main agent 2.
The preparation method of the water-based crude oil pour point depressant comprises the following steps:
weighing 40kg of pour point depressant 2, heating to 90 ℃, stirring for 40min, adding 571g of OP-4 and 3429g of OP-10, continuing stirring for 50min, then adding 24.5kg of deionized water, stirring for 90min, then adding 1250g of bactericide, 1250g of corrosion inhibitor and 2500g of scale inhibitor, stirring for 75min, finally adding 1.5kg of sodium hydroxyethyl cellulose as a stabilizer, and stirring for 45min to obtain the water-based crude oil pour point depressant, which is marked as sample 2.
Example 3
Preparation of pour point depressing main agent
Adding 8kg of methacrylate, 6kg of crotonic acid and 9kg of oleic acid into 34kg of aromatic hydrocarbon solvent, keeping the temperature at 80 ℃, stirring for 40min, adding 25.3g of initiator benzoyl peroxide, and reacting for 6h to obtain a terpolymer; taking 5kg of the terpolymer, heating the temperature to 115 ℃, adding 20kg of tetradecanol, stirring for 7h until the water yield reaches the theoretical water yield, and obtaining an alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer, which is marked as a pour point depressing main agent 3.
The preparation of the water-based crude oil pour point depressant comprises the following steps:
weighing 30kg of pour point depressant main agent 3, heating to 80 ℃, stirring for 35min, adding 375g of OP-4 and 2625g of OP-10, continuing to stir for 40min, then adding 27.5kg of deionized water, stirring for 80min, then adding 1000g of bactericide, 2000g of corrosion inhibitor and 1000g of scale inhibitor, stirring for 70min, finally adding 1.5kg of stabilizer polyacrylate, and stirring for 40min to obtain the water-based crude oil pour point depressant, which is marked as sample 3.
Example 4
Preparation of pour point depressing main agent
Adding 8kg of methacrylate, 5kg of crotonic acid and 5kg of oleic acid into 32kg of aromatic solvent, stirring at the temperature of 80 ℃ for 40min under heat preservation, adding 27g of azodiisobutyronitrile serving as an initiator, and reacting for 6h to obtain a terpolymer; taking 5kg of the terpolymer, heating the temperature to 115 ℃, adding 25kg of hexadecanol, stirring for 7h until the water yield reaches the theoretical water yield, and obtaining an alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer, which is marked as a pour point depressing main agent 4.
The preparation method of the water-based crude oil pour point depressant comprises the following steps:
weighing 30kg of pour point depressant main agent 4, heating to 80 ℃, stirring for 35min, adding 364gOP-4 and 1636gOP-10, continuing to stir for 40min, then adding 32kg of deionized water, stirring for 80min, then adding 1200g of bactericide, 600g of corrosion inhibitor and 1200g of scale inhibitor, stirring for 70min, finally adding 1kg of stabilizer polyacrylate, and stirring for 40min to obtain the water-based crude oil pour point depressant, wherein the sample is marked as sample 4.
Comparative example 1
The difference from sample 1 is that no emulsifier was used and the rest is the same.
Comparative example 2
The difference from sample 1 is that no stabilizer is used, and the rest is the same.
Comparative example 3
The difference from sample 1 is that the preparation of the pour point depressant is not subject to alcoholysis, i.e. the pour point depressant is methacrylate-crotonic acid-oleic acid terpolymer, and the rest is the same.
Comparative example 4
According to the method of the examples provided by an oilfield pour point depressant and a preparation method thereof (CN 113087836A), the pour point depressant is prepared:
(1) 150.66g of vinyl acetate (1.75 mol), 37.04g of vinyl benzoate (0.25 mol), 57.07g of caprolactone (0.5 mol) and 100.10g of caprolactone methacrylate (0.5 mol) were charged into the reactor;
(2) Then adding 1000g of mixed benzene, 377.00g of toluene, 500g of xylene (10 times) and 0.1877g of titanium isopropoxide catalyst (1 per thousand), starting nitrogen protection and stirring, and heating to 50 ℃;
(3) Dissolving 5.631g (3%) LPO in 50.68g benzene, controlling the temperature to be 50-95 ℃, dropwise adding 10% benzene solution of an initiator, controlling the temperature to be 85-95 ℃ after dropwise adding, and reacting for 10-15 hours to obtain an intermediate product A1;
(4) 68.35g (3%) of fumaric acid-vinyl acetate-fluorobutyl acrylate copolymer 113.92g (5%) of Tween-40 are mixed and stirred uniformly to obtain the oilfield pour point depressant.
Test example 1
In the test example, pour point depression amplitude test experiments are carried out on crude oil in a certain area of the victory oil field by using the pour point depressants prepared in examples 1 to 4 and comparative examples 1 to 2 respectively according to the method in GB/T26985-2018, and the pour point test experiments are carried out on each group of pour point depressants at the temperature of 80 ℃. The test results are shown in table 1.
TABLE 1 pour point depression amplitude test results
As can be seen from Table 1, the pour point depressant for crude oil provided in examples 1 to 4 has a large pour point depressing range, effectively prevents wax precipitation in a shaft, lowers the pour point of crude oil, and is stable in state, and the systems of comparative examples 1 to 2 are unstable and cannot be applied in the field. The pour point depressing main agent of the comparative example 3 is not subjected to alcoholysis, namely, the methacrylate-crotonic acid-oleic acid terpolymer is adopted as the pour point depressing main agent, so that the pour point depressing amplitude is obviously reduced.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. The water-based crude oil pour point depressant is characterized by comprising a pour point depressant main agent, an emulsifier, a stabilizer and a pour point depressant auxiliary agent;
the pour point depressing main agent is an alcoholysis product of a methacrylate-crotonic acid-oleic acid terpolymer.
2. The pour point depressant according to claim 1, wherein the pour point depressant is prepared from the main pour point depressant, the emulsifier, the stabilizer and the pour point depressant in a weight ratio of (20 to 40): (1 to 4): (0.5 to 1.5): (1 to 5).
3. The pour point depressant of claim 1 or 2, wherein the emulsifier is a mixture of OP-4 and OP-10.
4. The pour point depressant of claim 1 or 2, wherein the stabilizer is one or more of sodium hydroxymethyl cellulose, sodium hydroxyethyl cellulose, and a polyacrylate.
5. The pour point depressant of claim 1 or 2, wherein the pour point depressant additive comprises one or more of a bactericide, a corrosion inhibitor, and a scale inhibitor.
6. A preparation method of the water-based crude oil pour point depressant according to any one of claims 1 to 5, which is characterized by comprising the following steps of:
heating the pour point depressant main agent to 70 to 90 ℃, stirring for 30min to 40min, adding an emulsifier, continuously stirring for 30min to 50min, adding deionized water, stirring for 60min to 90min, adding a pour point depressant auxiliary agent, stirring for 60min to 75min, adding a stabilizer, and stirring for 30min to 45min to obtain the water-based crude oil pour point depressant.
7. The method according to claim 6, wherein the preparation method of the pour point depressant main agent comprises the following steps: adding methacrylate, crotonic acid and oleic acid into a solvent, keeping the temperature at 70-90 ℃, stirring for 30min-45min, adding an initiator, and reacting for 5-7h to obtain a terpolymer; heating to 110-120 ℃, adding higher aliphatic alcohol, stirring for 6-8 h until the water yield reaches the theoretical water yield, and obtaining the alcoholysis product of the methacrylate-crotonic acid-oleic acid terpolymer.
8. The method according to claim 7, wherein the mass ratio of methacrylate, crotonic acid and oleic acid is (7 to 8): (2 to 6): (5 to 10);
the initiator comprises benzoyl peroxide or azobisisobutyronitrile;
the higher fatty alcohols include tetradecanol, hexadecanol and octadecanol.
9. The method of claim 8, wherein the amount of the initiator is 0.05% to 0.15% of the total mass of the methacrylate, the crotonic acid and the oleic acid.
10. Use of the water-based crude oil pour point depressant according to any one of claims 1 to 5 in the processes of crude oil extraction and transportation.
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| CN107448777A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院化学研究所 | A kind of glutinous pour point reducer composition of crude oil nanometer drop and its preparation method and application |
| CN108456279A (en) * | 2018-04-26 | 2018-08-28 | 杨冰川 | A kind of pour point depressant for crude oil and the preparation method and application thereof |
| CN113480989A (en) * | 2021-06-02 | 2021-10-08 | 德仕能源科技集团股份有限公司 | Quadripolymer pour point depressant for high-freezing-point crude oil and preparation method thereof |
| CN113444190A (en) * | 2021-06-03 | 2021-09-28 | 德仕能源科技集团股份有限公司 | Polymer for crude oil pour point depression and preparation method and application thereof |
| CN114605586A (en) * | 2022-02-25 | 2022-06-10 | 中海油(天津)油田化工有限公司 | Polyacrylic acid higher alcohol ester pour point depressant and preparation method thereof |
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