A petroleum antibacterial clay stabilizer and preparation method thereof

Abstract

The invention relates to the field of oilfield treatment agents, in particular to a petroleum antibacterial clay stabilizer and a preparation method thereof, which solves the problems in the prior art that clay stabilizers are easy to separate from the clay molecular layer, small-molecule clay stabilizers have poor adhesion, and large-molecule stabilizers are difficult to act on the clay interlayer. The antibacterial clay stabilizer is obtained by mixing a slow-release neutralization liquid with a stabilizing factor liquid, wherein the slow-release neutralization liquid comprises polyvinyl pyrrolidone, cationic metal releasing particles and a reducing agent; the stabilizing factor liquid comprises a stabilizing factor, deionized water, glacial acetic acid, polyether polyol and potassium hydroxide solution; the clay stabilizer of the invention is not only easy to insert into the clay interlayer with a relatively small molecular weight, but also has strong hydrophobicity of an external long chain, can effectively and stably retain colloidal molecules, thereby stably releasing metal cations and enhancing the clay anti-swelling effect.

Description

Technical Field

[0001] The invention relates to the technical field of oilfield treatment agents, and in particular to a petroleum antibacterial clay stabilizer and a preparation method thereof. Background Art

[0002] When conducting oil field exploitation, clay stabilizers need to be added during the construction links such as drilling, fracturing, and water injection to protect the reservoir clay, maintain the dense connection of the clay, and ensure the existence of pores to allow oil to flow through. The most important change in clay is hydration expansion. As clay particles come into contact with water and undergo hydration, their volume increases. During oil and gas field drilling, water injection exploitation, and hydraulic fracturing, the drilling fluid will cause the clay to swell, causing drill bit mud packing, unstable well wall, and bottom blockage, resulting in a series of changes and acidification. In the process of reservoir development, montmorillonite and kaolinite are the main materials, which have strong hydration expansion characteristics. Therefore, clay stabilizers are often used. Clay has a negative charge, which produces a repulsive force, allowing water molecules to enter between the crystal layers of clay minerals. The cations in the stabilizer structure interact with the negative charge on the clay surface, competing with water during the action, so that water and clay do not combine, thereby stabilizing the chemical substances of the clay and reducing the impact of hydration on the clay.

[0003] Existing clay stabilizers have been used and developed for a long time. Specifically, they are stabilizers that work on the anti-swelling inhibition principle, namely inorganic salts, organic cationic polymers and organic ammonium. Among them, the long-term use of inorganic salts will cause great damage to the formation, and the insoluble precipitation produced by the combination of inorganic salts and anions will damage the well wall, pipe fittings and oil pipelines, corrode the pipeline through the electrochemical effect, and reduce the life of the pipeline. In addition, pure inorganic salt stabilizers are not resistant to erosion and have weak adsorption.

[0004] In order to enhance stability and service life, a polymer stabilizer prepared by grafting macromolecules with organic cations is used. After dissolving in water, the organic cation groups are ionized and replaced with metal cations on the surface of the clay layer to reduce interlayer repulsion. Because the substitution forms a stronger link, the cationic surfactant is more stably combined with the clay, and the stability of the clay can be maintained for a longer period of time. The usage amount is also small. However, the polymer stabilizer is easily deactivated by reacting with anionic additives, so it is rarely used in complex environments.

[0005] Quaternary ammonium salt organic cationic surfactants have stronger electrostatic adsorption and the characteristics of multi-point adsorption. They are used in small amounts and have strong adsorption. However, ammonium salts are not resistant to high temperatures and are easily combined with OH- in the environment. Guar gum strong alkali systems are often used in water injection and fracturing processes, causing ammonium salts to fail. Among them, monovalent cationic ammonium stabilizers have poor temperature resistance and are easily decomposed into NH3. They have poor tolerance to toxic gases. Although polymer quaternary ammonium clay stabilizers with excessively large molecular weights have many adsorption sites and can stabilize clay for a long time, they have large molecular weights and cannot penetrate into the clay layers. They can only be adsorbed on the clay surface. Therefore, for clays with strong swelling properties, their stabilizing effect is not as good as that of small molecule quaternary ammonium stabilizers. Summary of the invention

[0006] In order to solve the problems that the quaternary ammonium clay stabilizer in the prior art has poor stability, is easily affected by temperature and alkaline environment and separated from the clay molecular layer, the small molecule clay stabilizer has poor adhesion, and the quaternary ammonium salt cation in the macromolecular stabilizer is difficult to act on the clay interlayer, the present invention provides a petroleum antibacterial clay stabilizer and a preparation method thereof, and the technical scheme adopted by the present invention is as follows:

[0007] A petroleum antibacterial clay stabilizer, which is obtained by mixing 20-40 parts of a slow-release neutralization liquid and 60-80 parts of a stabilizing factor liquid, wherein the slow-release neutralization liquid comprises polyvinyl pyrrolidone, cationic metal releasing particles and a reducing agent;

[0008] The stabilizing factor solution comprises 4-6 parts of stabilizing factor, 2-7 parts of deionized water, 1-3 parts of glacial acetic acid, 5-8 parts of polyether polyol and 3-5 parts of potassium hydroxide solution;

[0009] The stabilizing factor is obtained by reacting gluconolactone, organic polyamine and long-chain dibasic acid.

[0010] In the component of the stabilizing factor liquid used in the present application, the stabilizing factor acts on the clay molecular layer. The five-membered ring of glucose has a large number of hydroxyl groups and can be inserted into the clay layer. Both sides of the five-membered ring molecular chain layer are connected to the clay molecules by hydrogen bonds. The organic polyamine is the main substance that stabilizes the clay interlayer from external anions, preventing water molecules from diffusing into the clay, ensuring that the binding force between the clay structure will not decrease, and the original tight structure of the clay will not be destroyed. The long-chain dibasic acid, one end of which is connected to one side of the five-membered ring of glucose, and the other end of the long chain is located outside the clay molecular layer, which can It forms a hydrogen bond connection with the components in the sustained-release neutralization liquid, wherein the sustained-release neutralization liquid contains polyvinyl pyrrolidone and is coated with cationic metal releasing particles, which can continuously release metal cations in a clay environment. However, a single polyvinyl pyrrolidone has an amide group and has a certain hydration effect, which is friendly to the water environment. After coating the cationic metal releasing particles, it is easily washed away by water flow in an acidic or alkaline environment. Therefore, the carboxyl group at the other end of the long-chain dibasic acid is used to react with the amide group of polyvinyl pyrrolidone, and a connection is generated through hydrogen bonds, thereby stably maintaining the presence of the effective ingredients of the sustained-release neutralization liquid.

[0011] Furthermore, the sustained-release neutralization liquid also includes a non-ionic fluorocarbon surfactant, the added amount of the non-ionic fluorocarbon surfactant is 3-10% by weight of the sustained-release neutralization liquid, and the non-ionic fluorocarbon surfactant is obtained by reacting perfluoro-2,5-dimethyl-3,6-dioxonanoyl chloride with a long-chain alcohol.

[0012] During the research and development process of the present application, it was found that the polyvinyl pyrrolidone of the sustained-release neutralization liquid is in liquid form. In order to strongly protect the integrity of the cationic metal-releasing particles and prevent them from being corroded too quickly by the acid and alkaline substances in the environment, a non-ionic fluorocarbon surfactant is added to reduce the contact between the cationic metal-releasing particles and water. The FC group on the non-ionic fluorocarbon surfactant is a fluoroalkyl group, which not only has excellent surface activity, but also can resist corrosion from a variety of chemical substances, can be oleophobic and hydrophobic, and has strong stability. It can maintain performance and stability at high temperatures, and fluoroalkanes have a certain antibacterial effect. Therefore, when using polyvinyl pyrrolidone in the environment of oil field exploitation, it can also inhibit the growth of foreign harmful bacteria and prevent microorganisms from corroding polyvinyl pyrrolidone.

[0013] The addition of polyether polyols facilitates the entry of stabilizing factors into the intermolecular layers of clay.

[0014] Furthermore, the number of carbon atoms in the long-chain alcohol is 3-8.

[0015] Furthermore, the cationic metal releasing particles are one of hydroxyaluminum, silver nitrate, copper nitrate, magnesium chloride, and chromium hydroxide.

[0016] Furthermore, the reducing agent is one of sodium borohydride, hydrazine hydrate or sodium hypophosphite, and the molar ratio of the reducing agent to the cationic metal releasing particles is 1-3:3.

[0017] Furthermore, the antibacterial clay stabilizer includes the preparation of a slow-release neutralization liquid stabilizer and a stabilizer factor liquid, and the preparation method of the stabilizer factor is as follows:

[0018] The organic polyamine is reacted with gluconolactone to obtain reactant A, and then reactant A is mixed with a long-chain dibasic acid for reaction, wherein the ratio of the hydroxyl group in the reactant to the carboxyl group of the long-chain dibasic acid is 3:1-2, to obtain reactant B, and then reactant B is reacted with p-hydroxycinnamic acid to obtain a stabilizing factor, wherein the molar ratio of the p-hydroxycinnamic acid ester to the long-chain dibasic acid is 1:1.

[0019] In the process of preparing the stabilizing factor, the present application found that in the combination of glucose and lauric acid as the prototype, the methyl end has certain limitations in improving the hydrophobic effect. Only relying on the effect of the internal "sticky" clay molecular layer and the external hydrophobic long chain, the inhibition rate of clay expansion only reached 60-70%. Therefore, for further inhibiting clay expansion, the present application uses a long-chain dibasic acid with two terminal carboxyl groups. After one end is linked to glucose, the other end is esterified with p-hydroxycinnamic acid to form reactant A. Therefore, the long-chain dibasic acid has a benzene ring and a carboxyl group at the end away from glucose, and an asymmetric electron cloud is distributed on the benzene ring, so it has a strong hydrophobic ability. The electron cloud density on the methyl alkane is relatively uniform, so the hydrophobicity is weaker. The carboxyl group close to the benzene ring can not only provide strong hydrophobicity, but also has the effect of isolating water molecules for the amide group of polyvinyl pyrrolidone, thereby reducing the hydration of polyvinyl pyrrolidone.

[0020] The five-membered ring of glucose is located in the clay interlayer, and the long chain of the long-chain dibasic acid is located on the clay surface outside the clay interlayer. The benzene ring on the cinnamic acid forms a hydrophobic structure, and the carboxyl group at its end can cooperate with the acyl group on the polyvinyl pyrrolidone to form a small amount of hydrogen bond connection.

[0021] Furthermore, the organic polyamine includes one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethylenepolyamine, and the long-chain dibasic acid is one of decacarbon dibasic acid, elevencacarbon dibasic acid, twelvecacarbon dibasic acid, tridecacarbon dibasic acid, tetradecacarbon dibasic acid, pentadecanoic acid, hexadecanoic acid or octadecanoic acid.

[0022] Furthermore, the preparation steps of the sustained-release neutralization solution are as follows:

[0023] Polyvinyl pyrrolidone is placed in water to form a polyvinyl pyrrolidone aqueous solution, and then the salt solution of the cationic metal releasing particles is added to the polyvinyl pyrrolidone aqueous solution. After stirring for reaction, a reducing agent is added dropwise until the solution changes color and the reaction is completed.

[0024] Furthermore, the concentration of the polyvinyl pyrrolidone aqueous solution is 1-4%, and the weight ratio of the polyvinyl pyrrolidone to the cationic metal releasing particles is 5:2-3.

[0025] The petroleum antibacterial clay stabilizer of the present application can be applied to petroleum exploitation in various environments.

[0026] The beneficial effects of the present invention are:

[0027] 1. In addition to using a clay stabilizer, the present application also uses a slow-release neutralizing liquid. The cations of the slow-release neutralizing liquid are slowly discharged under the action of a small amount of water, and combine with the anions on the surface of the clay layer to prevent the diffusion of the clay layer, thereby effectively enhancing the ability of the small molecule clay stabilizer to resist anions. The molecules are only connected by hydrogen bonds between the carboxyl group and the amide group, which does not affect the insertion of the small molecule clay stabilizer into the clay sheet, and can strongly inhibit clay expansion.

[0028] 2. The present application transforms the existing glycoside-based clay stabilizer on the basis of using a sustained-release neutralizing liquid, so that the long molecular chain has a benzene ring and a carboxyl group, wherein the carboxyl group enhances the connecting effect of the sustained-release neutralizing liquid, while the benzene ring enhances the hydrophobicity, and the benzene ring is located close to the carboxyl connecting site, which can spatially image the carboxyl group and the amide group, thereby increasing the hydrophobicity and protecting the polyvinyl pyrrolidone, so that it forms a sustained-release effect, thereby forming a long-term clay stabilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The figure is a line graph showing the relationship between the anti-swelling rate and the number of washing times of the embodiments of the present invention.

[0030] Figure 2 It is a line graph showing the relationship between the anti-swelling rate and the number of water washings of the comparative example of the present invention. DETAILED DESCRIPTION

[0031] The following will refer to the attached Figure 1 To Attachment Figure 2 The embodiments of the present invention are described in detail. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0032] Preparation Example 1

[0033] Preparation of stabilizing factor solution

[0034] Diethylenetriamine and gluconolactone were mixed in a molar ratio of 1:1, added into a sufficient amount of N,N-dimethylformamide to dissolve, heated to 90°C, and reacted for 5 hours to obtain reactant A;

[0035] Then, dodecane dicarboxylic acid is added to the mixed solution of reactant A, the molar ratio of dodecane dicarboxylic acid to gluconolactone is 0.5:1, the ratio of hydroxyl group to carboxyl group of dodecane dicarboxylic acid is 3:1, the catalyst is sulfuric acid, the esterification temperature is 60°C, the esterification time is 0.5h, and reactant B is obtained. p-hydroxycinnamic acid is added to reactant B for esterification reaction, the molar ratio of p-hydroxycinnamic ester to long-chain dicarboxylic acid is 1:1, the catalyst is sulfuric acid, the esterification temperature is 80°C, and the esterification time is 4h, and a stabilizing factor is obtained.

[0036] Preparation Example 2

[0037] Preparation of stabilizing factor solution

[0038] Triethylenetetramine and gluconolactone were mixed in a molar ratio of 1:1, added into a sufficient amount of N,N-dimethylformamide to dissolve, heated to 90° C., and reacted for 5 hours to obtain reactant A;

[0039] Then, decanedicarboxylic acid is added to the mixed solution of reactant A, the molar ratio of decanedicarboxylic acid to gluconolactone is 1:1, the ratio of hydroxyl group to carboxyl group of decanedicarboxylic acid is 3:2, the catalyst is sulfuric acid, the esterification temperature is 60°C, the esterification time is 1h, and reactant B is obtained. p-hydroxycinnamic acid is added to reactant B for esterification reaction, the molar ratio of p-hydroxycinnamic ester to decanedicarboxylic acid is 1:1, the catalyst is sulfuric acid, the esterification temperature is 80°C, and the esterification time is 3h, and a stabilizing factor is obtained.

[0040] Preparation Example 3

[0041] Preparation of stabilizing factor solution

[0042] Tetraethylenepentamine and gluconolactone were mixed in a molar ratio of 1:1 and added into a sufficient amount of N,N-dimethylformamide to dissolve, and the temperature was raised to 90°C and reacted for 5 hours to obtain reactant A.

[0043] Then, tetradecanedioic acid is added to the mixed solution of reactant A, the molar ratio of tetradecanedioic acid to gluconolactone is 1:1, the ratio of hydroxyl group to carboxyl group of tetradecanedioic acid is 3:2, the catalyst is sulfuric acid, the esterification temperature is 60°C, the esterification time is 0.5h, and reactant B is obtained. p-hydroxycinnamic acid is added to reactant B for esterification reaction, the molar ratio of p-hydroxycinnamic ester to tetradecanedioic acid is 1:1, the catalyst is sulfuric acid, the esterification temperature is 80°C, and the esterification time is 5h, and a stabilizing factor is obtained.

[0044] Preparation Example 4 - Comparison, using lauric acid instead of long-chain dibasic acid

[0045] Preparation of stabilizing factor solution

[0046] Triethylenetetramine and gluconolactone were mixed in a molar ratio of 1:1 and added into a sufficient amount of N,N-dimethylformamide to dissolve, and the temperature was raised to 90°C and reacted for 5 hours to obtain reactant A.

[0047] Then, lauric acid is added to the mixed solution of reactant A, the molar ratio of lauric acid added to gluconolactone is 0.5:1, the ratio of hydroxyl group to carboxyl group of lauric acid is 3:1, the catalyst is sulfuric acid, the esterification temperature is 60°C, the esterification time is 0.5h, and reactant B is obtained. p-Hydroxycinnamic acid is added to reactant B for esterification reaction, the molar ratio of p-hydroxycinnamic ester to lauric acid is 1:1, the catalyst is sulfuric acid, the esterification temperature is 80°C, and the esterification time is 4h, to obtain a stabilizing factor.

[0048] Preparation Example 5 - Comparison, esterification without using p-hydroxycinnamic acid

[0049] Preparation of stabilizing factor solution

[0050] Diethylenetriamine and gluconolactone were mixed in a molar ratio of 1:1, added into a sufficient amount of N,N-dimethylformamide to dissolve, heated to 90° C., and reacted for 5 hours to obtain reactant A;

[0051] Then, dodecanedioic acid is added to the mixed solution of reactant A, the molar ratio of dodecanedioic acid to gluconolactone is 0.5:1, the ratio of hydroxyl group to carboxyl group of dodecanedioic acid is 3:1, the catalyst is sulfuric acid, the esterification temperature is 60°C, and the esterification time is 0.5h to obtain a stabilizing factor.

[0052] Except for diethylenetriamine, triethylenetetramine and tetraethylenepentamine, other organic polyamines with the same functional groups can react with gluconolactone; in addition, any one of 15-carbon dicarboxylic acid, 16-carbon dicarboxylic acid or 18-carbon dicarboxylic acid can be used as long-chain dicarboxylic acid, all of which can achieve the effect of the above preparation example.

[0053] Preparation Example 6

[0054] Preparation of sustained-release neutralization solution

[0055] Polyvinyl pyrrolidone is placed in water to form a 3% polyvinyl pyrrolidone aqueous solution, and silver nitrate is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, sodium borohydride, is added dropwise at a molar ratio of sodium borohydride to silver nitrate of 2:1 to complete the reaction.

[0056] Preparation Example 7

[0057] Preparation of sustained-release neutralization solution

[0058] Polyvinyl pyrrolidone is placed in water to form a 2% polyvinyl pyrrolidone aqueous solution, and hydroxyaluminum is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2.5 between polyvinyl pyrrolidone and silver nitrate. After stirring for reaction, a reducing agent hydrazine hydrate is added dropwise, and the molar ratio of hydrazine hydrate to hydroxyaluminum is 3:1, to complete the reaction.

[0059] Preparation Example 8

[0060] Preparation of sustained-release neutralization solution

[0061] Polyvinyl pyrrolidone is placed in water to form a 4% polyvinyl pyrrolidone aqueous solution, copper nitrate is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2, and after stirring for reaction, sodium borohydride, a reducing agent, is added dropwise at a molar ratio of sodium borohydride to copper nitrate of 2:1 to complete the reaction.

[0062] Perfluoro-2,5-dimethyl-3,6-dioxonanoyl chloride and n-propanol are mixed at room temperature in a molar ratio of 1:1.2, and then a small amount of triethylamine is added dropwise. After reacting for 10 hours, anhydrous copper sulfate is used to remove water and filter to obtain a nonionic fluorocarbon surfactant.

[0063] Add the above nonionic fluorocarbon surfactant into the sustained-release neutralization solution at a mass ratio of 5% of the sustained-release neutralization solution, and mix.

[0064] Preparation Example 9

[0065] Preparation of sustained-release neutralization solution

[0066] Polyvinyl pyrrolidone is placed in water to form a polyvinyl pyrrolidone aqueous solution with a concentration of 1%, and magnesium chloride is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, sodium hypophosphite, is added dropwise, and the molar ratio of sodium hypophosphite to magnesium chloride is 1:1 to complete the reaction.

[0067] Perfluoro-2,5-dimethyl-3,6-dioxonanoyl chloride and n-pentanol are mixed at room temperature in a molar ratio of 1:1.2, and then a small amount of triethylamine is added dropwise. After reacting for 10 hours, anhydrous copper sulfate is used to remove water and filter to obtain a nonionic fluorocarbon surfactant.

[0068] Add the above nonionic fluorocarbon surfactant into the sustained-release neutralization solution at a mass ratio of 3% of the sustained-release neutralization solution, and mix.

[0069] Preparation Example 10

[0070] Preparation of sustained-release neutralization solution

[0071] Polyvinyl pyrrolidone is placed in water to form a polyvinyl pyrrolidone aqueous solution with a concentration of 3%, and chromium hydroxide is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, hydrazine hydrate, is added dropwise at a molar ratio of hydrazine hydrate to chromium hydroxide of 2:1 to complete the reaction.

[0072] Perfluoro-2,5-dimethyl-3,6-dioxonanoyl chloride and n-hexanol were mixed at room temperature in a molar ratio of 1:1.2, and then a small amount of triethylamine was added dropwise. After reacting for 10 hours, anhydrous copper sulfate was used to remove water and filter to obtain a nonionic fluorocarbon surfactant.

[0073] Add the above nonionic fluorocarbon surfactant into the sustained-release neutralization solution at a mass ratio of 10% of the sustained-release neutralization solution, and mix.

[0074] Preparation Example 11 - Comparison, increasing the maximum amount of reducing agent

[0075] Polyvinyl pyrrolidone is placed in water to form a 3% polyvinyl pyrrolidone aqueous solution, and silver nitrate is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, sodium borohydride, is added dropwise at a molar ratio of sodium borohydride to silver nitrate of 5:1 to complete the reaction.

[0076] Preparation Example 12 - Comparison, increasing the concentration of polyvinyl pyrrolidone aqueous solution

[0077] Polyvinyl pyrrolidone is placed in water to form a 10% polyvinyl pyrrolidone aqueous solution, and silver nitrate is added to the polyvinyl pyrrolidone aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, sodium borohydride, is added dropwise at a molar ratio of sodium borohydride to silver nitrate of 4:1 to complete the reaction.

[0078] Preparation Example 13 - Comparison, trehalose was used to coat cationic metal-releasing particles instead of polyvinyl pyrrolidone

[0079] Polyvinyl pyrrolidone was placed in water to form a 5% trehalose aqueous solution, and silver nitrate was added to the trehalose aqueous solution at a molar ratio of 5:2. After stirring for reaction, a reducing agent, sodium borohydride, was added dropwise at a molar ratio of sodium borohydride to silver nitrate of 4:1 to complete the reaction.

[0080] Example 1

[0081] Preparation of a petroleum antibacterial clay stabilizer

[0082] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0083] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 1, and the sustained-release neutralizing agent is the sustained-release neutralizing solution of Preparation Example 6.

[0084] First, a stabilizing factor solution is prepared by mixing 6 parts of polyether polyol with 5 parts of deionized water by weight, and then adding 5 parts of stabilizing factor, 2 parts of glacial acetic acid and 4 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0085] Then, 30 parts by weight of the stabilizing factor liquid and 70 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0086] Example 2

[0087] Preparation of a petroleum antibacterial clay stabilizer

[0088] The polyether polyol is one of PPG, POP and PTMEG, and POP is selected in this embodiment;

[0089] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 2, and the sustained-release neutralizing agent is the sustained-release neutralizing solution of Preparation Example 7.

[0090] First, a stabilizing factor solution is prepared by mixing 5 parts of polyether polyol with 2 parts of deionized water by weight, and then adding 4 parts of stabilizing factor, 1 part of glacial acetic acid and 3 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0091] Then, 20 parts by weight of the stabilizing factor liquid and 80 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0092] Example 3

[0093] Preparation of a petroleum antibacterial clay stabilizer

[0094] The polyether polyol is one of PPG, POP and PTMEG, and PTMEG is selected in this embodiment;

[0095] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 3, and the sustained-release neutralizing agent is the sustained-release neutralizing solution of Preparation Example 8.

[0096] First, a stabilizing factor solution is prepared by mixing 8 parts of polyether polyol with 7 parts of deionized water by weight, and then adding 6 parts of stabilizing factor, 3 parts of glacial acetic acid and 5 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0097] Then, 40 parts by weight of the stabilizing factor liquid and 60 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0098] Example 4

[0099] The difference between this embodiment and embodiment 1 is that the stabilizing factor is the stabilizing factor prepared in preparation example 1, and the sustained-release neutralizing agent is the sustained-release neutralizing solution prepared in preparation example 9.

[0100] Example 5

[0101] The difference between this embodiment and embodiment 1 is that the stabilizing factor is the stabilizing factor prepared in preparation example 2, and the sustained-release neutralizing agent is the sustained-release neutralizing liquid prepared in preparation example 10.

[0102] Comparative Example 1

[0103] Preparation of a petroleum antibacterial clay stabilizer

[0104] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0105] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 4, and the sustained-release neutralizing agent is the sustained-release neutralizing solution prepared in Preparation Example 6.

[0106] First, a stabilizing factor solution is prepared by mixing 7 parts of polyether polyol with 4 parts of deionized water by weight, and then adding 5 parts of stabilizing factor, 2 parts of glacial acetic acid and 4 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0107] Then, 30 parts by weight of the stabilizing factor liquid and 70 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0108] Comparative Example 2

[0109] Preparation of a petroleum antibacterial clay stabilizer

[0110] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0111] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 5, and the sustained-release neutralizing agent is the sustained-release neutralizing solution prepared in Preparation Example 6.

[0112] First, a stabilizing factor solution is prepared by mixing 6 parts of polyether polyol with 3 parts of deionized water by weight, and then adding 6 parts of stabilizing factor, 2 parts of glacial acetic acid and 3 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0113] Then, 30 parts by weight of the stabilizing factor liquid and 70 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0114] Comparative Example 3

[0115] Preparation of a petroleum antibacterial clay stabilizer

[0116] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0117] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 1, and the sustained-release neutralizing agent is the sustained-release neutralizing solution of Preparation Example 11.

[0118] First, a stabilizing factor solution is prepared by mixing 8 parts of polyether polyol with 7 parts of deionized water by weight, and then adding 4 parts of stabilizing factor, 1 part of glacial acetic acid and 3 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0119] Then, 20 parts by weight of the stabilizing factor liquid and 80 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0120] Comparative Example 4

[0121] Preparation of a petroleum antibacterial clay stabilizer

[0122] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0123] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 1, and the sustained-release neutralizing agent is the sustained-release neutralizing liquid of Preparation Example 12.

[0124] First, a stabilizing factor solution is prepared by mixing 5 parts of polyether polyol with 7 parts of deionized water by weight, and then adding 6 parts of stabilizing factor, 3 parts of glacial acetic acid and 5 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0125] Then, 40 parts by weight of the stabilizing factor liquid and 60 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0126] Comparative Example 5

[0127] Preparation of a petroleum antibacterial clay stabilizer

[0128] The polyether polyol is one of PPG, POP and PTMEG, and PPG is selected in this embodiment;

[0129] The stabilizing factor of this example is the stabilizing factor prepared in Preparation Example 1, and the sustained-release neutralizing agent is the sustained-release neutralizing solution of Preparation Example 13.

[0130] First, a stabilizing factor solution is prepared by mixing 6 parts of polyether polyol and 6 parts of deionized water by weight, and then adding 5 parts of stabilizing factor, 1 part of glacial acetic acid and 4 parts of potassium hydroxide solution in sequence, and homogenizing at a speed of 200 rpm / min for 30 minutes to obtain a stabilizing factor solution;

[0131] Then, 30 parts by weight of the stabilizing factor liquid and 70 parts by weight of the slow-release neutralizing liquid were mixed to obtain a petroleum antibacterial clay stabilizer.

[0132] Experiments and data

[0133] The clay stability test was conducted on the antibacterial clay stabilizer in the above-mentioned Examples 1 to 5 and Comparative Examples 1 to 5, and the test experiments included an anti-swelling test, a water wash resistance test, and an antibacterial effect test.

[0134] Anti-swelling experiment: The petroleum antibacterial clay stabilizer was prepared into concentrations of 0.5%, 1%, 1.5%, and 2%, and then infiltrated into montmorillonite type bentonite according to the corresponding concentrations for 1 hour. The Fangpeng performance test was carried out according to the performance evaluation method of clay stabilizer for water injection in accordance with SY / T 5971-1994.

[0135] In the water wash resistance test, the petroleum antibacterial clay stabilizer was prepared into a concentration of 1%, and then impregnated with montmorillonite type bentonite for 1 hour. The liquid matter was then removed by centrifuge. Alkaline water with a pH value of 9-12 was added and centrifuged at 1000 rpm / min for 10 minutes. The water was filtered out to calculate the expanded volume of the bentonite and the anti-swelling rate. The total number of tests was 20 times.

[0136] Antibacterial effect experiment: After 20 times, the bentonite was sampled and cultured with culture medium to observe the number of colonies.

[0137] The anti-swelling rate of the blank hydrochloride solution with the same volume concentration on clay was 64.6%.

[0138] The results of the expansion test are shown in Table 1, and the results are the anti-expansion rate (%). The results in Table 1 are as follows:

[0139] Table 1

[0140]

[0141] The anti-swelling rate of the clay in the first, fifth, tenth, fifteenth and twentieth washings of the embodiment was subjected to a water washing resistance test, and the anti-swelling rate was recorded, as shown in Table 2.

[0142] Table 2

[0143] 1 5 10 15 20 Example 1 91.4 91.2 91.0 90.5 89.1 Example 2 90.1 89.9 89.8 89.6 88.8 Example 3 88.7 88.5 88.4 88.2 87.7 Example 4 91.2 91.1 91.0 90.4 90.1 Example 5 88.7 88.4 88.5 88.3 87.9

[0144] The anti-swelling rate of the clay in the first, fifth, tenth, fifteenth and twentieth washings of the comparative example was subjected to a water washing resistance test, and the anti-swelling rate was recorded, as shown in Table 3.

[0145] Table 3

[0146]

[0147]

[0148] The number of colony growth is shown in Table 4:

[0149]

[0150] analyze

[0151] First, according to the data of Example 1 and Example 2, it can be seen from the anti-swelling rate data before and after 20 water washings that the petroleum antibacterial clay stabilizer of the present invention has a good anti-swelling rate and adsorption, high stability, is not easy to detach, and can maintain the stability of the clay for a long time.

[0152] According to the data of Comparative Example 1, the anti-swelling rate of the clay stabilizer in Comparative Example 1 is poor, and the concentration cannot be too high. Too high a concentration causes the anti-swelling rate to decrease, and the results of the water washing experiment show that the clay stabilizer has a large loss in an alkaline environment and is obviously unstable, which proves that the use of long-chain dibasic acids has a connecting effect on liquid polyvinyl pyrrolidone, which can effectively prevent polyvinyl pyrrolidone from being washed away, thereby retaining cationic metal factors and continuously releasing cations to the clay layer.

[0153] According to the data of Comparative Example 2, the clay stabilizer of Comparative Example 2 has excellent anti-swelling efficiency in the initial use, which is as high as the anti-swelling rate of the embodiment of the present application. However, after 20 water washing experiments, there is a significant decrease, which proves that the carboxyl group has partial connection ability, but it will be lost in an alkaline environment for a long time, thereby disconnecting the connection with polyvinyl pyrrolidone, which proves that p-hydroxycinnamic acid can effectively ensure the connection between the carboxyl group and polyvinyl pyrrolidone and slow down the washing away of polyvinyl pyrrolidone.

[0154] According to the experimental data of Comparative Example 3, the anti-swelling rate of the comparative example, whether before or after washing, cannot reach a good level compared with that of Examples 1-5, proving that a large amount of reducing agent will cause polyvinyl pyrrolidone and cations to be strongly reduced, thereby failing to release sufficient cations, which is equivalent to the presence of no cation-releasing particles, and the relevant active sites are also occupied by some groups on polyvinyl pyrrolidone, so the anti-swelling effect is extremely poor. The amount of reducing agent used in this application is a critical factor.

[0155] According to the experimental data of Comparative Example 4, the anti-swelling effect of Comparative Example 4 before and after water washing is poor, which proves that a higher polyvinyl pyrrolidone solution makes it difficult for cations to be discharged and combined with anions, or it may make the reducing agent unable to react with some metal cations, and the metal particles cannot produce an effective connection effect and are easily washed away.

[0156] According to the experimental data of Comparative Example 5, the clay stabilizer of Comparative Example 5 has a strong anti-swelling effect before water washing, but after 20 water washings, it has greatly decreased. It can be seen that the clay stabilizer of Comparative Example 5 does not use polyvinyl pyrrolidone, but uses trehalose to coat the cationic metal particles. At the beginning, trehalose can rely on its own adsorption to link with the clay outside and slowly release cations, but multiple flushings in an alkaline environment cause trehalose to separate from the clay surface. This is because trehalose has no amide group and cannot form hydrogen bonds with carboxyl groups. Therefore, in terms of adsorption stability, the use of polyvinyl pyrrolidone is the key to the clay anti-swelling agent of this application.

[0157] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. A petroleum antibacterial clay stabilizer, characterized in that: The antibacterial clay stabilizer is obtained by mixing 20-40 parts of a slow-release neutralization liquid with 60-80 parts of a stabilizing factor liquid, wherein the slow-release neutralization liquid comprises polyvinyl pyrrolidone, cationic metal releasing particles and a reducing agent; The weight ratio of the polyvinyl pyrrolidone to the cationic metal releasing particles is 5:2-3; The molar ratio of the reducing agent to the cationic metal releasing particles is 1-3:1; The stabilizing factor solution comprises 4-6 parts of stabilizing factor, 2-7 parts of deionized water, 1-3 parts of glacial acetic acid, 5-8 parts of polyether polyol and 3-5 parts of potassium hydroxide solution; The stabilizing factor is obtained by reacting gluconolactone, organic polyamine, p-hydroxycinnamic acid and long-chain dibasic acid; The molar ratio of the p-hydroxycinnamic acid to the long-chain dibasic acid is 1:

1. When the p-hydroxycinnamic acid is not added into the reaction process, the ratio of the hydroxyl group in the reactant to the carboxyl group of the long-chain dibasic acid is 3:1-2.

2. A petroleum antibacterial clay stabilizer according to claim 1, characterized in that: The sustained-release neutralization liquid also includes a nonionic fluorocarbon surfactant, the addition amount of which is 3-10% by weight of the sustained-release neutralization liquid. The nonionic fluorocarbon surfactant is obtained by reacting perfluoro-2,5-dimethyl-3,6-dioxonanoyl chloride with a long-chain alcohol.

3. A petroleum antibacterial clay stabilizer according to claim 2, characterized in that: The long-chain alcohol has 3-8 carbon atoms.

4. The petroleum antibacterial clay stabilizer according to claim 1, characterized in that: The cationic metal releasing particles are one of hydroxyaluminum, silver nitrate, copper nitrate, magnesium chloride and chromium hydroxide.

5. The petroleum antibacterial clay stabilizer according to claim 1, characterized in that: The reducing agent is one of sodium borohydride, hydrazine hydrate or sodium hypophosphite.

6. A method for preparing a petroleum antibacterial clay stabilizer according to any one of claims 1 to 5, characterized in that: The antibacterial clay stabilizer includes the preparation of a slow-release neutralization liquid stabilizer and a stabilizer factor liquid. The preparation method of the stabilizer factor is as follows: The organic polyamine is reacted with gluconolactone to obtain reactant A, and then reactant A is mixed with a long-chain dibasic acid for reaction, wherein the ratio of the hydroxyl group in the reactant to the carboxyl group of the long-chain dibasic acid is 3:1-2 to obtain reactant B, and then reactant B is reacted with p-hydroxycinnamic acid to obtain a stabilizing factor.

7. The method for preparing a petroleum antibacterial clay stabilizer according to claim 6, characterized in that: The organic polyamine includes one of diethylenetriamine, triethylenetetramine or tetraethylenepentamine, and the long-chain dibasic acid is one of decacarbon dibasic acid, elevencacarbon dibasic acid, twelvecacarbon dibasic acid, tridecacarbon dibasic acid, tetradecacarbon dibasic acid, pentadecanoic acid, hexadecanoic acid or octadecanoic acid.

8. The method for preparing a petroleum antibacterial clay stabilizer according to claim 6, characterized in that: The preparation steps of the sustained-release neutralization solution are as follows: Polyvinyl pyrrolidone is placed in water to form a polyvinyl pyrrolidone aqueous solution, and then the salt solution of the cationic metal releasing particles is added to the polyvinyl pyrrolidone aqueous solution. After stirring for reaction, a reducing agent is added dropwise until the solution changes color and the reaction is completed.

9. The method for preparing a petroleum antibacterial clay stabilizer according to claim 8, characterized in that: The concentration of the polyvinyl pyrrolidone aqueous solution is 1-4%.

10. Use of the petroleum antibacterial clay stabilizer according to any one of claims 1 to 5 in petroleum production.

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