CN114478908B - Temperature-resistant and salt-resistant polymer containing cyclic structure and preparation method and application thereof - Google Patents
Temperature-resistant and salt-resistant polymer containing cyclic structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, and a preparation method and application thereof. The polymer is represented by the following formula (III). The invention adopts functional monomer containing molecular cyclic structure such as benzene ring and heterocycle as steric hindrance group to improve the salt ion compression resistance of polymer molecular chain, not easy to curl, more stretching molecular chain, larger hydrodynamic volume, better salt resistance and tackifying effect, and simultaneously ensures proper molecular weight (100-500 ten thousand) and good injectability in low-permeability oil layer.
Description
Technical Field
The invention relates to the field of petroleum exploitation, in particular to the field of tertiary oil recovery polymer flooding in the petroleum exploitation process, and more particularly relates to a temperature-resistant and salt-resistant polymer containing a ring structure, a preparation method and application thereof, in particular to a polymer for oil recovery under the conditions of low permeability, sewage injection allocation process and high-temperature and high-mineralization degree oil reservoirs.
Background
Polymer flooding in tertiary oil recovery technology is the most widely used technical means at present. The polymer flooding mainly increases the viscosity of the water phase through the high molecular water-soluble polymer, thereby improving the oil-water fluidity ratio, increasing the flow resistance of the dominant water flow channel, reducing the permeability of the dominant channel, increasing the injection pressure, expanding the wave volume of the injected liquid, driving the crude oil in the oil layer which can not be entered by the water flooding, improving the recovery ratio of the crude oil, and the average improvement range of the recovery ratio can reach more than 10 percent. One of the key points in polymer research for oil recovery is therefore the stable tackifying properties of the polymer under various reservoir conditions. The tackifier commonly used in polymer flooding at present is high molecular weight partially hydrolyzed polyacrylamide, but because polyacrylamide is sensitive to high mineralization degree and high temperature, the viscosity of the polyacrylamide is extremely severely reduced under the high-salt and high-temperature conditions, so that clear water injection allocation or polymer concentration and consumption increase are generally required to obtain a good flooding effect.
The conventional polyacrylamide is usually partially hydrolyzed polyacrylamide HPAM containing a certain carboxylic acid group, the structure is shown as a formula (I), b+c is the polymerization degree of the polyacrylamide, namely, one acrylamide monomer molecule is taken as a chain unit, the number of repeated chain units connected with each other is higher, the longer the single polymer chain is, the larger the molecular weight is, b is expressed as the polymerization amount of the acrylamide monomer on the polymer chain, and c is expressed as the number of anionic carboxyl groups on the polymer chain, and the hydrolysis degree of the polymer is expressed. b+c is typically in the range of 1 ten thousand to 40 ten thousand. And c is 10-40% of the sum of b+c, the preparation process is shown in a formula (II), the acrylamide monomer with the equivalent weight of b is added with water to prepare an aqueous solution with proper concentration, 17-30%, then the acrylic acid monomer with the equivalent weight of c is added, alkali is added to neutralize to be neutral, nitrogen is introduced at the temperature of 0-30 ℃ to deoxidize, then various initiating aids and initiating agents are added to polymerize, so as to obtain a partially hydrolyzed polyacrylamide gel block, and the partially hydrolyzed polyacrylamide gel block is cut and granulated by a granulator, dried, ground and sieved to obtain a partially hydrolyzed polyacrylamide product.
The conventional polyacrylamide has poor salt resistance in the application of a high-salt oil reservoir, the requirement of high viscosity of a polymer solution can be met by greatly increasing the dosage (50%, even 1 time and several times), the cost of the dosage of the polymer is one of main determinants of the cost of the whole polymer flooding, the economic feasibility and the economic benefit of the polymer flooding are directly influenced, and the popularization and the application of the polymer flooding are also directly restricted.
In addition, the viscosity of the solution prepared from the conventional polyacrylamide by the oilfield hypersalinity produced water is greatly reduced compared with that prepared from clear water. The problem is directly related to recycling of produced sewage in oil extraction operation of an oil field, and the environmental protection problem caused by the produced sewage also directly influences the economic benefit and feasibility of polymer flooding.
The polymer has the main functions of increasing the viscosity of an injected aqueous solution, reducing the oil-water fluidity ratio and reducing the 'finger-feeding' series flow phenomenon caused by the heterogeneity of water in an oil reservoir, wherein the main component of the polymer is polyacrylamide, the common high molecular weight polyacrylamide for oil displacement is curled under the compression action of salt ions under the condition of higher salt concentration due to the salt sensitivity effect, the hydrodynamic volume is greatly reduced, the macroscopic apparent viscosity is greatly reduced, and the viscosity requirement of the polyacrylamide for oil displacement is difficult to be achieved. Moreover, the acid, alkali, high calcium and magnesium concentration or the temperature exceeding 80 ℃ can cause accelerated hydrolysis reaction, so that polyacrylamide is degraded, even precipitation is generated, and the viscosity is almost zero, so that the displacement capacity is lost. Therefore, the polymer with good stable tackifying performance under the conditions of high temperature and high salt becomes a focus research direction of attention at home and abroad in recent years.
Disclosure of Invention
An object of the present invention is to provide a temperature-resistant and salt-resistant polymer containing a cyclic structure; the invention mainly adopts functional monomers containing molecular cyclic structures such as benzene ring (R substituted sodium p-styrenesulfonate) and heterocycle (N-acryloylmorpholine) as steric hindrance groups, so as to improve the salt ion compression resistance of polymer molecular chains, prevent the polymer molecular chains from curling easily, enable the molecular chains to stretch more, enable the hydrodynamic volume to be larger, have better salt resistance and tackifying effects, ensure proper molecular weight and ensure good injectability in low-permeability oil layers.
Another object of the present invention is to provide a method for preparing the cyclic structure-containing temperature-resistant and salt-resistant polymer;
it is a further object of the present invention to provide the use of the cyclic structure-containing temperature-resistant and salt-resistant polymer.
In order to achieve the above object, in one aspect, the present invention provides a heat-resistant and salt-resistant polymer having a cyclic structure as shown in formula (III):
wherein a is 100-1 ten thousand, b is 1-25 ten thousand, c is 1-8 ten thousand, and d is 100-1 ten thousand; r is selected from H, methyl or ethyl.
According to the invention, by adding the functional monomer with the cyclic structure, when the polymer is compressed by salt ions in saline water, the anti-curling performance of the polymer molecular chain is enhanced, namely, the rigidity of the polymer molecular chain is increased, and under the condition of similar molecular chains, the viscosity in the saline water is higher than that of polyacrylamide.
According to some embodiments of the invention, the polymer has a viscosity average molecular weight of 100 to 500 tens of thousands.
Because acrylamide and the monomer reactivity ratio of the cyclic structure have larger difference, the molecular weight of the copolymer is greatly reduced after the monomer with the cyclic structure is added, and the low-molecular-weight polymer has better adaptability and injection performance to low-permeability oil reservoirs, so that the technical feasibility of polymer flooding in the low-permeability oil reservoirs is improved.
According to some embodiments of the invention, the polymer is obtained by polymerization of acrylamide, acrylic acid, R-substituted sodium p-styrenesulfonate and acryloylmorpholine as monomers (reaction monomers); wherein R is 2-R-sodium p-styrenesulfonate, and R is selected from H, methyl or ethyl.
Sodium p-styrenesulfonate is shown in formula (a), and acryloylmorpholine is shown in formula (d):
according to some specific embodiments of the invention, the polymer is obtained by polymerization of 16-20 parts of acrylamide, 2-5 parts of acrylic acid, 0.2-2.6 parts of R-substituted sodium p-styrene sulfonate and 0.5-2.0 parts of acryloylmorpholine based on 100 parts of the total mass of the prepared polymer.
According to some embodiments of the invention, wherein the polymer is prepared from the following monomers in the composition ratio: acrylic acid accounts for 5-25% of the total monomer mass, R-substituted sodium p-styrenesulfonate accounts for 0.07-0.7% of the total monomer mass, the total monomer mass of the acryloylmorpholine accounts for 0.2-1.0%, and the balance is acrylamide.
According to some specific embodiments of the invention, the polymer is obtained by polymerization reaction of acrylamide, acrylic acid, R-substituted sodium p-styrenesulfonate and acryloylmorpholine serving as monomers, 3-aminopropionitrile serving as a catalyst, ammonium persulfate serving as an oxidant, sodium bisulfate serving as a reducing agent and azodiisoheptanenitrile serving as an initiator.
According to some specific embodiments of the invention, the polymer is obtained by polymerization reaction of 15-25 parts of acrylamide, 2-5 parts of acrylic acid, 0.2-2.0 parts of R-substituted sodium p-styrene sulfonate and 0.5-2.0 parts of acryloylmorpholine serving as monomers, 0.01-0.08 part of 3-aminopropionitrile serving as a catalyst, 0.0001-0.0008 part of ammonium persulfate serving as an oxidant, 0.0002-0.002 part of sodium bisulfite serving as a reducing agent, 0.01-0.05 part of azo-diisoheptanenitrile serving as an initiator and the balance of water based on 100 parts of the total mass of the prepared polymer.
The invention adopts a composite initiation system combining a redox initiation system and an azo initiation system, ensures that various functional monomers of the polymer can be successfully polymerized on a polymer molecular main chain under the condition of multi-element copolymerization, and simultaneously ensures that the lower residual monomer content meets the environmental protection requirement.
According to some embodiments of the invention, the polymerization reaction is initiated at a temperature of 15-40 ℃.
According to some embodiments of the invention, the polymerization comprises deoxygenation prior to initiating the polymerization, and then initiating the polymerization.
According to some embodiments of the invention, the deoxygenation treatment comprises a step of introducing nitrogen into the reaction solution (mixed solution of reaction monomer and reaction medium).
According to some specific embodiments of the invention, the polymerization reaction comprises uniformly mixing a reaction monomer and a reaction medium, regulating the pH value to 6.5-7.5 by alkali, carrying out deoxidization treatment, then adding a composite initiation system consisting of a catalyst 3-aminopropionitrile, an oxidant ammonium persulfate, a reducing agent sodium bisulphite and an initiator azo-diisoheptanenitrile, and carrying out polymerization reaction to obtain the polymer.
According to some embodiments of the invention, the reaction medium is water.
According to some embodiments of the invention, the polymer is obtained by polymerization, and further comprises the steps of granulating the polymer colloid, drying at 50-90 ℃, grinding and crushing the dried particles, and sieving for 18-80 meshes.
According to some embodiments of the invention, the drying temperature is 70 ℃.
According to some embodiments of the invention, wherein the polymerization comprises: mixing and dissolving an Acrylamide Monomer (AM) by using water (pure water), adding Acrylic Acid (AA), adding sodium hydroxide for neutralization to adjust the pH, then adding R-substituted sodium p-styrene sulfonate and acryloylmorpholine, introducing nitrogen to remove oxygen with polymerization inhibition effect in the aqueous solution, adding an oxidation-reduction and azo composite initiation system for initiation, and performing polymerization reaction at the initiation temperature of 15-40 ℃ to obtain polymer colloid; granulating the polymer colloid, drying at the temperature below 70 ℃, grinding and crushing the dried particles, and sieving the particles with 18-80 meshes to obtain a final sample.
On the other hand, the invention also provides a preparation method of the cyclic structure-containing temperature-resistant and salt-resistant polymer, wherein the method comprises the step of carrying out polymerization reaction by taking acrylamide, acrylic acid, R-substituted sodium p-styrenesulfonate and acryloylmorpholine as monomers to obtain the polymer.
According to some embodiments of the invention, the method of the invention comprises:
the first step, 100 parts of raw materials comprise the following components in parts by weight:
15-25 parts of Acrylamide (AM),
2-8 parts of Acrylic Acid (AA),
0.2 to 2.0 parts of R-substituted sodium p-styrenesulfonate (SSS),
0.5-2.0 parts of Acryloylmorpholine (ACMO),
3-aminopropionitrile (H) 2 NCH 2 CH 2 CN) polymerization catalyst 0.01-0.08 parts
Ammonium persulfate ((NH) 4 ) 2 S 2 O 8 ) 0.0001 to 0.0008 part,
sodium bisulfite (Na) 2 SO 3 ) 0.0002 to 0.002 parts of a compound,
azodiisoheptonitrile (C) 12 H 24 N 4 ) 0.01-0.05 part of a compound,
the balance being water.
In the first step, firstly, adding the acrylamide AM and the acrylic acid AA added in the formula into water in sequence to prepare a solution, and then adjusting the pH value of the aqueous solution to 7.0+/-0.5 by using sodium hydroxide; adding R substituted sodium p-styrenesulfonate, then adding acryloylmorpholine, fully and uniformly stirring, putting into a refrigerator for cooling, reducing the temperature to 15-40 ℃ according to the performance requirements of different products, adding 3-aminopropionitrile after blowing nitrogen to deoxidize for 10min, adding azodiisoheptonitrile after continuously deoxidizing for 20min, adding ammonium persulfate after continuously deoxidizing for 20min, adding sodium bisulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And secondly, after the sealing, the temperature of the solution is raised to the highest value (the polymerization reaction is exothermic, the highest temperature is 60-90 ℃ according to different reaction rates, polymerization concentration and initial temperature), naturally cooling for 2 hours, the viscous solution obtained in the first step is changed into jelly-shaped semitransparent gum, the gum is granulated into colloidal particles, 1-3 parts of hydrolyzer sodium hydroxide and 0.1-1 part of reducer sodium bisulphite are added into every 100 parts of colloidal particles according to parts by weight, granulating is carried out after hydrolysis for 1-2 hours at 90-92 ℃, and the colloidal particles are dried, crushed and screened after granulating, so that the temperature-resistant salt-resistant polymer is obtained.
In still another aspect, the invention also provides application of the cyclic structure-containing temperature-resistant and salt-resistant polymer in polymer flooding of low-permeability oil reservoirs (polymer flooding of low-permeability oil reservoirs by injection-blended sewage).
According to some embodiments of the invention, wherein the low permeability reservoir has a formation permeability of 20×10 -3 μm 2 -100×10 -3 μm 2 。
In summary, the invention provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, and a preparation method and application thereof. The polymer of the invention has the following advantages:
the polymer provided by the invention can overcome the defects of the conventional polyacrylamide, such as single structure, flexible molecular chain, poor salt resistance, rejection and compression of inorganic salt ions on polymer carboxyl, curling of the polymer molecular chain, reduced tackifying capability, low viscosity of the produced sewage in an oilfield, high cost and the like. According to the invention, the monomer with a cyclic structure (such as benzene ring and heterocycle) is introduced on the polyacrylamide molecular chain, so that the compressive rigidity of the molecular chain is improved, and the resistance of shrinkage and rotation of molecular chain links is improved, thereby improving the curling degree of the polymer molecular chain in salt water, retaining larger hydrodynamic volume, and macroscopically improving the salt resistance under the premise of lower molecular weight.
The polymer molecular chain has higher rigidity and high compression strength due to the cyclic structure (such as benzene ring and heterocycle), so that the molecular chain is more stretched, the ductility of the polymer molecular chain in the flowing process of the polymer solution is enhanced, namely, the polymer molecular chain has better linearity, thereby realizing better injection performance than the conventional polyacrylamide and solving the problem of difficult polymer injection in a low-permeability oil reservoir.
The reactivity ratio of the copolymerized cyclic structure (such as benzene ring and heterocycle) monomer and acrylamide is more different, the compound initiation system can effectively polymerize the cyclic structure monomer onto a polymer main chain, but because the reactivity ratio difference of the cyclic structure (such as benzene ring and heterocycle) monomer has larger influence on the molecular weight of the polymer, the molecular weight of the polymer can be controlled to be reduced to a range of 100 ten thousand to 500 ten thousand according to the application condition requirement of the low-permeability reservoir, and the small molecular weight polymer has good matching property with the low permeability of the reservoir, and is also beneficial to the smooth injection of the polymer in the low-permeability reservoir.
Drawings
FIG. 1 is an infrared plot of the product of example 1.
FIG. 2 is an infrared plot of the product of example 2.
FIG. 3 is an infrared plot of the product of example 3.
FIG. 4 is an infrared plot of the product of example 4.
FIG. 5 is an infrared plot of the product of example 5.
FIG. 6 is an infrared plot of the product of example 6.
FIG. 7 is an infrared plot of the product of example 7.
Detailed Description
The following detailed description of the invention and the advantages achieved by the embodiments are intended to help the reader to better understand the nature and features of the invention, and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 725g of distilled water into a 1L wide-mouth bottle, adding 200g of acrylamide monomer AM, then adding 50g of acrylic acid monomer AA, uniformly mixing, starting the stirring speed to 1000 revolutions per minute, uniformly mixing, completely dissolving, then regulating the pH of an aqueous solution to 7.0+/-0.5 by using sodium hydroxide, then adding 8g of sodium p-styrenesulfonate under the stirring condition, then adding 6g of acryloylmorpholine, and then cooling to 15 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding polymerization catalyst 3-aminopropionitrile 1.5g, continuously introducing nitrogen to deoxidize for 20min, adding azodiisoheptonitrile 1.2g, introducing nitrogen to deoxidize for 20min, adding ammonium persulfate 0.008g, adding sodium bisulfate 0.02g after 2min, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The polymerized monomer with double bond is harmful to environment, so the detection of residual monomer content is carried out in the inspection standard of the polyacrylamide product, and the method for measuring the residual monomer content is shown in national standard GB12005.5-89. It can be seen that the residual monomer content (residual content of all monomers added) of the examples is very low (see Table 1), i.e. the monomers involved in the polymerization, including acrylamide, acrylic acid, sodium R-p-styrene sulfonate, acryloylmorpholine, have mostly opened double bonds to participate in the polymerization, effectively attaching to the polymer molecular chain. The infrared spectrum of the finished product purified by washing with anhydrous alcohol is shown in figure 1, -CONH 2 The absorption peak of C=O in (2) is 1660cm -1 About, the S=O absorption peak in the sulfonic acid group of AMPS is 1185cm -1 Left and right, 1560, 770cm -1 About benzene ring absorption peak 1115cm -1 The left and right are morpholine ring absorption peaks. FIG. 1 also shows that sodium p-styrenesulfonate containing a benzene ring and acryloylmorpholine containing a heterocycle are both efficiently polymerized into a polymer.
Example 2
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 722g of distilled water into a 1L wide-mouth bottle, adding 240g of acrylamide monomer AM, adding 50g of acrylic acid monomer AA, uniformly mixing, stirring at a speed of 1000 rpm, uniformly mixing, completely dissolving, regulating the pH of an aqueous solution to 7.0+/-0.5 by using sodium hydroxide, adding 10g of sodium p-styrenesulfonate under the stirring condition, then adding 7g of acryloylmorpholine, and cooling to 18 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding polymerization catalyst 3-aminopropionitrile 1.8g, continuously introducing nitrogen to deoxidize for 20min, adding azodiisoheptonitrile 2.4g, introducing nitrogen to deoxidize for 20min, adding ammonium persulfate 0.008g, adding sodium bisulfate 0.02g after 2min, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers which participate in polymerization comprise acrylamide, acrylic acid, sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in figure 2, and figure 2 shows that sodium p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Example 3
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 721g of distilled water into a 1L wide-mouth bottle, adding 220g of acrylamide monomer AM, adding 35g of acrylic acid monomer AA, uniformly mixing, starting the stirring speed to 1000 revolutions per minute, uniformly mixing, completely dissolving, then regulating the pH of an aqueous solution to 7.0+/-0.5 by using sodium hydroxide, adding 8g of sodium p-styrenesulfonate under the stirring condition, then adding 6g of acryloylmorpholine, and then cooling to 20 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding 3.6g of polymerization catalyst 3-aminopropionitrile, continuously introducing nitrogen to deoxidize for 20min, adding 1.8g of azodiisoheptonitrile, introducing nitrogen to deoxidize for 20min, adding 0.010g of ammonium persulfate, adding 2min, adding 0.03g of sodium bisulphite, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers which participate in polymerization comprise acrylamide, acrylic acid, sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in figure 3, and figure 3 shows that sodium p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Example 4
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 721g of distilled water into a 1L wide-mouth bottle, adding 230g of acrylamide monomer AM, then adding 40g of acrylic acid monomer AA, uniformly mixing, starting the stirring speed to 1000 revolutions per minute, uniformly mixing, completely dissolving, then regulating the pH of an aqueous solution to 7.0+/-0.5 by using sodium hydroxide, adding 8g of sodium p-styrenesulfonate under the stirring condition, then adding 8g of acryloylmorpholine, and then cooling to 25 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding 2.4g of polymerization catalyst 3-aminopropionitrile, continuously introducing nitrogen to deoxidize for 20min, adding 1.2g of azodiisoheptonitrile, introducing nitrogen to deoxidize for 20min, adding 0.0010g of ammonium persulfate, adding 2min, adding 0.03g of sodium bisulfate, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers which participate in polymerization comprise acrylamide, acrylic acid, sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in fig. 4, and fig. 4 shows that sodium p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Example 5
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 701g of distilled water into a 1L wide-mouth bottle, adding 210g of acrylamide monomer AM, adding 50g of acrylic acid monomer AA, uniformly mixing, stirring at a speed of 1000 rpm, uniformly mixing, completely dissolving, regulating the pH of an aqueous solution to 6.7+/-0.5 by using sodium hydroxide, adding 10g of sodium p-styrenesulfonate under the stirring condition, then adding 8g of acryloylmorpholine, and cooling to 25 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding 3.5g of polymerization catalyst 3-aminopropionitrile, continuously introducing nitrogen to deoxidize for 20min, adding 2.4g of azodiisoheptonitrile, introducing nitrogen to deoxidize for 20min, adding 0.016g of ammonium persulfate, adding 2min, adding 0.06g of sodium bisulphite, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers which participate in polymerization comprise acrylamide, acrylic acid, sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in fig. 5, and fig. 5 shows that sodium p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Example 6
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 681g of distilled water into a 1L wide-mouth bottle, adding 210g of acrylamide monomer AM, adding 50g of acrylic acid monomer AA, uniformly mixing, starting the stirring speed to 1000 rpm, uniformly mixing, completely dissolving, regulating the pH of an aqueous solution to 6.7+/-0.2 by using sodium hydroxide, adding 10g of sodium 2-methyl-p-styrenesulfonate under the stirring condition, adding 6g of acryloylmorpholine, and cooling to 25 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding 3.5g of polymerization catalyst 3-aminopropionitrile, continuously introducing nitrogen to deoxidize for 20min, adding 3.6g of azodiisoheptonitrile, introducing nitrogen to deoxidize for 20min, adding 0.012g of ammonium persulfate, adding 2min and then adding 0.05g of sodium bisulfate, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers participating in polymerization comprise acrylamide, acrylic acid, 2-methyl-sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in fig. 6, and fig. 6 shows that both sodium 2-methyl-p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Example 7
The embodiment provides a temperature-resistant and salt-resistant polymer containing a cyclic structure, which is prepared by the following steps:
adding 661g of distilled water into a 1L wide-mouth bottle, adding 210g of acrylamide monomer AM, adding 45g of acrylic acid monomer AA, uniformly mixing, starting the stirring speed to 1000 revolutions per minute, uniformly mixing, completely dissolving, then regulating the pH of an aqueous solution to 6.7+/-0.2 by using sodium hydroxide, adding 8.0g of sodium 2-ethyl-p-styrenesulfonate under the stirring condition, then adding 5g of acryloylmorpholine, and then cooling to 25 ℃; transferring into a heat-insulating Dewar flask, introducing high-purity nitrogen with concentration of more than 99.99% to deoxidize for 10min, adding 4.0g of polymerization catalyst 3-aminopropionitrile, continuously introducing nitrogen to deoxidize for 20min, adding 3.6g of azodiisoheptonitrile, introducing nitrogen to deoxidize for 20min, adding 0.012g of ammonium persulfate, adding 2min and then adding 0.05g of sodium bisulfate, continuously introducing nitrogen until the solution becomes viscous, and sealing.
Standing for 12h after the temperature of the solution rises to the highest value, changing the reaction system into a micelle, taking out the micelle from the Dewar flask, and cutting into colloidal particles with the diameter of 2-3mm by using a granulator. 100g of the colloidal particles are put into a beaker, 1.5g of round granular sodium hydroxide serving as a hydrolyzer and 0.1g of sodium bisulphite serving as a reducing agent are poured into the beaker, the mixture is uniformly stirred, sealed and put into a constant-temperature water bath at 90 ℃ for hydrolysis for 2 hours, then the mixture is taken out and granulated by a granulator, after the granulation is completed, the mixture is uniformly spread on a wire mesh, the wire mesh is put into a baking oven for drying at 60 ℃ for about 5 hours, and the dried particles are taken out, crushed and sieved by a crusher for 0.1-1.0mm, so that a fine granular finished product is obtained. The residual monomer content was determined according to national standard GB12005.5-89. The total residual content of each monomer is shown in Table 1, namely, the monomers participating in polymerization comprise acrylamide, acrylic acid, 2-ethyl-sodium p-styrenesulfonate and acryloylmorpholine, most of which have opened double bonds to participate in polymerization, and are effectively connected to a polymer molecular chain. The infrared spectrum of the finished product purified by washing with absolute alcohol is shown in fig. 7, and fig. 7 shows that both sodium 2-ethyl-p-styrenesulfonate containing benzene ring and acryloylmorpholine containing heterocycle are effectively polymerized into the polymer.
Evaluation of experimental examples:
the conventional polyacrylamide products of examples 1-7 and similar molecular weights were characterized and the specific test results are shown below.
1. Salt resistance and tackifying properties, the results are shown in Table 1:
in order to ensure that the measured viscosity is truly reliable, i.e. that the measured viscosity value is the viscosity of the aqueous polymer solution, excluding the influence of insoluble swollen particles, the water solubility index of the polymer is also measured according to oilfield standards: water insoluble content and filtration factor. The viscosity of the polymer solution measured under conditions ensuring good water solubility.
The test of the intrinsic viscosity and the molecular weight of the solution is carried out according to the medium petroleum enterprise standard Q/SY 119-2014;
wherein, the water insoluble substances are detected according to the medium petroleum enterprise standard Q/SY 119-2014, and the standard requirement is less than or equal to 0.20 percent;
wherein, the filtering factor is detected according to the medium petroleum enterprise standard Q/SY 119-2014, and the standard requirement is less than or equal to 2.0.
The viscosity testing method specifically comprises the following steps: taking 1.00g of polymer sample, slowly and uniformly adding the polymer sample into 199.00g of 30,000mg/L mineralized sodium chloride brine, stirring the mixture for 2 hours at a rotating speed of 400r/min, diluting the mixture to a polymer concentration of 3500mg/L, and measuring the mixture at 90 ℃;
TABLE 1 salt resistance and tackiness-imparting Properties of the inventive Polymer and comparative example
Comparative example the polyacrylamide was a product produced by Daqing refining company.
As can be seen from Table 1, examples 1-7 have a molecular weight in the range of 100 to 500 tens of thousands, and a viscosity significantly greater than that of the comparative polyacrylamide product having a molecular weight similar thereto, while maintaining good water solubility.
2. The temperature resistance and tackifying performance are shown in Table 2:
the viscosity test method specifically comprises the following steps: a sample of the polymer (1.00 g) was taken, slowly and uniformly added to 199.00g of 30,000mg/L mineralized sodium chloride brine, and after stirring at 400r/min for 2 hours, diluted to the test concentration and measured at 90 ℃.
TABLE 2
From Table 2, it can be seen that the comparative polyacrylamide products of examples 1 to 7 have a significantly higher viscosity at various concentrations than those of similar molecular weights under the conditions of 3 thousands of mineralization and high temperature and salt at 90 ℃.
3. Salt resistance and results are shown in Table 3:
the viscosity test method specifically comprises the following steps: the viscosity test method specifically comprises the following steps: 1.00g of polymer sample was taken, and was slowly and uniformly added to 199.00g of 5,000mg/L and 30,000mg/L mineralized sodium chloride brine, respectively, and after stirring at 400r/min for 2 hours, the polymer sample was diluted to a polymer concentration of 3500mg/L, and the results were shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the polyacrylamide of examples 1-7 and comparative example showed a large decrease in solution viscosity as the mineralization degree of brine increased from 5,000mg/L to 30,000 mg/L. This is because salt ions have a repulsive effect on ionic groups on the polymer molecular chains, and increasing the salt ion concentration causes the polymer molecular chains to be further compressed and curled, the hydrodynamic volume is greatly reduced, and macroscopic appearance is a larger reduction in viscosity. However, the examples 1-7 contain cyclic structure molecular groups, so that the salt ion compression resistance of the polymer molecular chain is improved, the molecular chain is not easy to curl in high-concentration saline water, and the retention viscosity value and the viscosity retention rate of the polymer molecular chain after the salt concentration is increased are both obviously larger than those of the comparative polyacrylamide product with similar molecular weight.
3. Low permeability reservoir good injectability
Polymer injectability test polymer solutions (5600 mg/L sodium chloride in simulated saline, stirring at 400r/min for 2 hours, diluting to 1500mg/L,50 ℃) prepared under the same conditions are adopted, mechanical impurities are removed by filtering through a filter screen, a certain volume of polymer solutions are injected into cores with different permeabilities, and whether the injection pressure is rapidly increased to an out-of-range or not is observed, so as to judge the injectability of the polymer. The results are shown in Table 4.
TABLE 4 Table 4
The evaluation criteria in table 4 are:
the injection pressure was stabilized at 0.2MPa or lower at an injection rate of 0.1ml/min, and it was determined that the injectability was good; the injection pressure is in the range of 0.2MPa-1.0MPa, tends to be stable, and is judged to be difficult to inject; the injection pressure exceeding 1.0Mpa is determined to be clogging.
It can be seen from table 4 that the salt-resistant polymers of the present invention exhibit good low permeability reservoir injectability.
Claims (10)
1. A temperature-resistant and salt-resistant polymer containing a cyclic structure as shown in formula (III):
wherein a is 100-1 ten thousand, b is 1-25 ten thousand, c is 1-8 ten thousand, and d is 100-1 ten thousand; r is selected from H, methyl or ethyl,
the polymer is prepared by carrying out polymerization reaction on 15-25 parts of acrylamide, 2-8 parts of acrylic acid, 0.2-2.0 parts of R-substituted sodium p-styrene sulfonate and 0.5-2.0 parts of acryloylmorpholine serving as monomers, wherein the total mass of the prepared polymer is 100 parts.
2. The polymer of claim 1, wherein the polymer has a viscosity average molecular weight of 100-500 tens of thousands.
3. The polymer according to claim 1, wherein the polymer is obtained by polymerization of acrylamide, acrylic acid, R-substituted sodium p-styrenesulfonate and acryloylmorpholine as monomers; wherein R is 2-R-sodium p-styrenesulfonate, and R is selected from H, methyl or ethyl.
4. The polymer according to claim 3, wherein the polymer is obtained by polymerization reaction using 3-aminopropionitrile as a catalyst, ammonium persulfate as an oxidant, sodium bisulphite as a reducing agent and azobisisoheptonitrile as an initiator.
5. The polymer according to claim 3, wherein the polymer is obtained by polymerizing 0.01 to 0.08 part of 3-aminopropionitrile as a catalyst, 0.0001 to 0.0008 part of ammonium persulfate as an oxidizing agent, 0.0002 to 0.002 part of sodium bisulfite as a reducing agent, 0.01 to 0.05 part of azobisisoheptonitrile as an initiator, and the balance of water based on 100 parts by weight of the total polymer thus prepared.
6. A polymer according to claim 3, wherein the polymerization reaction is initiated at a temperature of 15-40 ℃.
7. A polymer according to claim 3, wherein the polymerization reaction comprises an oxygen scavenging treatment prior to initiation of the polymerization reaction, followed by initiation of the polymerization reaction.
8. The polymer according to claim 3, wherein the polymerization reaction comprises uniformly mixing a reaction monomer and a reaction medium, regulating the pH value to 6.5-7.5 with alkali, carrying out deoxidization treatment, adding a composite initiation system consisting of a catalyst 3-aminopropionitrile, an oxidant ammonium persulfate, a reducing agent sodium bisulphite and an initiator azo-diisoheptanenitrile, and carrying out polymerization reaction to obtain the polymer.
9. A preparation method of a heat-resistant and salt-resistant polymer with a cyclic structure shown in a formula (III),
wherein a is 100-1 ten thousand, b is 1-25 ten thousand, c is 1-8 ten thousand, and d is 100-1 ten thousand; r is selected from H, methyl or ethyl,
the method comprises the steps of taking the total mass of the prepared polymer as 100 parts, taking 15-25 parts of acrylamide, 2-8 parts of acrylic acid, 0.2-2.0 parts of R-substituted sodium p-styrene sulfonate and 0.5-2.0 parts of acryloylmorpholine as monomers, and taking the rest of components as water for polymerization reaction.
10. The use of a cyclic structure-containing temperature-resistant salt-resistant polymer as claimed in any one of claims 1 to 8 in displacement operations of low permeability produced wastewater injection polymers; the low permeability is 20×10 -3 -100×10 -3 μm 2 。
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| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
| CN103998567A (en) * | 2012-01-20 | 2014-08-20 | S.P.C.M.公司 | Process for the enhanced recovery of oil by injection of a polymer solution |
| CN106520107A (en) * | 2016-11-07 | 2017-03-22 | 重庆科技学院 | Acryloyl morpholine polymer oil-displacing agent and preparation method thereof |
| CN109837079A (en) * | 2019-02-15 | 2019-06-04 | 大庆再创科技有限公司 | A kind of high injection salt resistance polymers for oil recovery, three-component compound system and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
| CN103998567A (en) * | 2012-01-20 | 2014-08-20 | S.P.C.M.公司 | Process for the enhanced recovery of oil by injection of a polymer solution |
| CN106520107A (en) * | 2016-11-07 | 2017-03-22 | 重庆科技学院 | Acryloyl morpholine polymer oil-displacing agent and preparation method thereof |
| CN109837079A (en) * | 2019-02-15 | 2019-06-04 | 大庆再创科技有限公司 | A kind of high injection salt resistance polymers for oil recovery, three-component compound system and preparation method thereof |
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