An ion regulator and its preparation method and application

Abstract

The present invention discloses an ion regulator, a preparation method and an application thereof. The ion regulator is formed by hydrogen bonding carboxylic acid and protein; the carboxylic acid is one or more of acrylic acid, crotonic acid and cinnamic acid; the protein is one or more of whey protein, soy protein and collagen. The ion regulator of the present invention can bind to cations in water to prevent scaling and avoid oil pipe corrosion; the ion regulator of the present invention belongs to the carboxylic acid compound and can effectively regulate the formation of agglomerated particles, while the low-charge organic matter in the hydrogen-bonded protein macromolecules can chelate with divalent cations, thereby stabilizing the ions in the fluid, controlling its agglomeration process, and thus preventing scaling. At the same time, the ions are combined to form nanoparticles, so that the size of the agglomerated particles can be controlled, and the agglomerated particles can be used for plugging, turning high-valent ions into "waste".

Description

Technical Field

[0001] The invention relates to an ion control agent and a preparation method and application thereof, belonging to the technical field of oil field exploitation. Background Art

[0002] Oilfield produced water usually contains a large amount of ions, such as Ca 2+ Mg 2+ As oil production deepens, the number of high-temperature and high-salt oil wells gradually increases, and the ion concentration in the produced water increases, causing serious scaling and corrosion, which brings economic losses and safety problems to the oil production process.

[0003] The existing method for controlling ion aggregation and deposition in produced water involves adding scale inhibitors to the produced water. For example, CN104479663A proposes a scale inhibitor for oilfield reinjection water, comprising the following components, by weight: 1-2 parts Lygodium japonicum, 0.5-3 parts Nicotiana odorifera, 1-2 parts poloxamer, 2-4 parts povidone, 0.5-1 part chlorobutanol, 8-12 parts bis(trifluoromethanesulfonyl)imide, 3-6 parts nicotinic acid, 4-6 parts sodium citrate, 20-30 parts ethanol, and 50-65 parts water. This oilfield reinjection water scale inhibitor has excellent dispersion and stabilization effects on iron oxide and zinc salts, but it is unclear whether it has a certain scale inhibition effect on calcium salts, magnesium salts, and other salts. In particular, the complex composition of this scale inhibitor makes it difficult to meet the high efficiency requirements of on-site construction. For example, prior art CN1306944A discloses a composite corrosion and scale inhibitor comprising the following components: based on 100% by weight of the composition, 1-20% of a hydroxyphosphinoacetic acid compound, 1-25% of an isopropenylphosphonic acid polymer, 1-35% of a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid, 1-10% of a zinc salt (calculated as zinc), and the remainder being water. This scale inhibitor exhibits a moderate scale inhibition effect on produced water.

[0004] However, the design ideas of the existing technologies are all to chelate the cations in the produced water to achieve the purpose of controlling scaling. These methods not only increase the cost of corrosion and scale prevention, but also make the ions in the produced water not effectively utilized. In this paper, an ion regulator is proposed that can stabilize the ions in the produced water through the dual effects of complexation and charge. Summary of the Invention

[0005] The present invention aims to provide an ion control agent that can bind ions in produced water to prevent scaling and achieve controllable agglomerated particle size. The agent also features a simple preparation method and rapid and effective ion control. This allows for the utilization of ions in produced water and reduces production costs.

[0006] The ion regulator provided by the present invention is formed by connecting carboxylic acid and protein via hydrogen bonds;

[0007] The carboxylic acid is one or more of acrylic acid, crotonic acid and cinnamic acid;

[0008] The protein is one or more of whey protein, soy protein and collagen.

[0009] The present invention also provides a method for preparing the ion regulator, comprising the following steps:

[0010] In an inert atmosphere, the carboxylic acid and ammonium persulfate are reacted in water to carry out reaction I, and then the protein and triethylamine are added to continue reaction II to obtain the product.

[0011] Preferably, the ammonium persulfate is added in the form of an aqueous solution thereof with a mass concentration of 2-3%, and the added amount is a material ratio of 1 mL: 2-3 g to the carboxylic acid.

[0012] Preferably, the reaction I lasts for 1 to 1.5 hours, and the reaction II lasts for 1 to 1.5 hours;

[0013] The temperature of the reaction I and the reaction II is 50-70°C.

[0014] Preferably, the mass ratio of the carboxylic acid, the protein and the triethylamine is 20-30:10-15:1-3.

[0015] The ion regulator of the present invention can be used to prevent scaling of oil pipes;

[0016] When used, the ion regulator and the solution to be treated are mixed for 10 to 30 minutes.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The ion regulator of the present invention can bind cations in water, preventing scaling and oil pipe corrosion. The ion regulator belongs to the carboxylic acid class and can effectively control the formation of agglomerated particles. The low-charge organic matter in hydrogen-bonded protein macromolecules can chelate with divalent cations, thereby stabilizing ions in the fluid and controlling their aggregation, thereby preventing scaling. The ions also bind to form nanoparticles, achieving controllable agglomerated particle size. The agglomerated particles can also be used for plugging, turning high-valent ions into valuable assets. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a particle size distribution diagram of agglomerated particles formed by the mineralized water treated in Example 1 of the application example of the present invention.

[0020] Figure 2 This is the infrared characterization spectrum of the product prepared in Comparative Example 1 of the present invention.

[0021] Figure 3This is the infrared characterization spectrum of the product prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0022] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0023] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0024] Example 1

[0025] In a three-necked flask connected to a condensing reflux apparatus, 68 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 20 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 60°C. After 1 hour, the addition was complete to achieve carboxylic acid oligomerization. Then, 10 g of whey protein and 2 g of triethylamine were added. After continuing the reaction for 1 hour, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 59.6%.

[0026] Example 2

[0027] In a three-necked flask connected to a condensing reflux apparatus, 52 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 30 g of cinnamic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 50°C. After 1.5 hours, the addition was complete to achieve carboxylic acid oligomerization. Then, 15 g of soy protein and 3 g of triethylamine were added. After continuing the reaction for 1 hour, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 59.2%.

[0028] Example 3

[0029] In a three-necked flask connected to a condensing reflux apparatus, 61 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 25 g of crotonic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 70°C. After 1 hour, the addition was complete to achieve carboxylic acid oligomerization. Then, 12 g of collagen and 2 g of triethylamine were added. After continuing the reaction for 1.5 hours, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 58.8%.

[0030] Example 4

[0031] In a three-necked flask connected to a condensing reflux apparatus, 60 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 27 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 60°C. After 1.5 hours, the addition was complete to achieve carboxylic acid oligomerization. Then, 10 g of whey protein and 3 g of triethylamine were added. After continuing the reaction for 1.5 hours, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 58.3%.

[0032] Example 5

[0033] In a three-necked flask connected to a condensing reflux apparatus, 62 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 25 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 60°C. After 1 hour, the addition was complete to achieve carboxylic acid oligomerization. Then, 10 g of whey protein and 2 g of triethylamine were added. After continuing the reaction for 1 hour, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 57.5%.

[0034] Example 6

[0035] In a three-necked flask connected to a condensing reflux apparatus, 66 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 22 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 50°C. After 1.5 hours, the addition was complete to achieve carboxylic acid oligomerization. Then, 12 g of whey protein and 2 g of triethylamine were added. After continuing the reaction for 1.5 hours, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 57.9%.

[0036] Example 7

[0037] In a three-necked flask connected to a condensing reflux apparatus, 56 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 28 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 60°C. After 1.5 hours, the addition was complete to achieve carboxylic acid oligomerization. Then, 13 g of whey protein and 3 g of triethylamine were added. After continuing the reaction for 1.5 hours, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 57.2%.

[0038] Example 8

[0039] In a three-necked flask connected to a condensing reflux apparatus, 52 g of water was added and nitrogen was passed through to remove oxygen. After half an hour, 30 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 70°C. After 1 hour, the addition was complete to achieve carboxylic acid oligomerization. Then, 15 g of whey protein and 3 g of triethylamine were added. After continuing the reaction for 1 hour, the mixture was washed with ethanol three times for purification to obtain an ion regulator with a yield of 58.1%.

[0040] Comparative Example 1

[0041] The only difference from Example 1 was that the raw materials were added simultaneously. Specifically, the raw materials were directly mixed to obtain a reagent. Specifically, 60 g of water, 20 g of carboxylic acid, 10 mL of whey protein, and 10 mL of 2% ammonium persulfate solution were added to a three-necked flask connected to a condenser reflux apparatus. Nitrogen was passed through the flask to remove oxygen. The mixture was reacted at 60°C for 2 hours to obtain the product. The product contained polymers of protein and carboxylic acid, polymers of carboxylic acid and carboxylic acid, and polymers of protein and carboxylic acid oligomers, with excessive byproducts.

[0042] Figure 2The infrared characterization spectrum of the product of this comparative example is shown in the figure. -1 The peak at 1403cm is the CN stretching vibration peak. -1 The peak at 1635 cm is the -CH stretching vibration peak. -1 and 1724cm -1 The peak at 3396 cm is the C=O peak in the carboxyl group. -1 The peak at is the stretching vibration peak of -OH in the carboxyl group. The product contains characteristic functional groups of both carboxylic acid and protein. Therefore, it is speculated that the simultaneous addition of the raw materials will produce byproducts of protein-carboxylic acid polymerization or protein-carboxylic acid oligomer polymerization.

[0043] Comparative Example 2

[0044] The difference from Example 1 is that whey protein is not added. Specifically, 68 g of water was added to a three-necked flask connected to a condensation reflux device, and nitrogen was passed through to remove oxygen. After half an hour, 20 g of acrylic acid and 10 mL of 2% ammonium persulfate solution were added dropwise at a reaction temperature of 60°C. After 1 hour, the addition was completed to achieve carboxylic acid oligomerization. Then, 2 g of triethylamine was added, and the reaction was continued for 1 hour. After purification, the ion regulator carboxylic acid oligomer was obtained by washing with ethanol three times. The structural formula of the carboxylic acid oligomer is: .

[0045] Figure 3 This is the infrared characterization spectrum of the product of this comparative example. As shown in the figure, 1678cm -1 The peak at 3547cm is the C=O peak in the carboxyl group. -1 The peak at is the -OH stretching vibration peak in the carboxyl group.

[0046] Comparative Example 3

[0047] The difference from Example 1 was that no acrylic acid was added. Specifically, 68 g of water was added to a three-necked flask connected to a condensing reflux apparatus, and nitrogen was passed through to remove oxygen. After half an hour, 10 mL of a 2% ammonium persulfate solution was added dropwise at a reaction temperature of 60°C. After one hour, 10 g of whey protein and 2 g of triethylamine were added. The reaction was continued for another hour, and then purified to obtain an ion control agent. The results showed that the protein did not react with other substances.

[0048] Application examples,

[0049] The ion regulators of Examples 1 and 2 were added to mineralized water of the same concentration at different concentrations, and the particle size test was performed 2 hours later.

[0050] Table 1 Particle size of the ion regulators of Examples 1 and 2 after adding to mineralized water

[0051]

[0052] Table 2 Composition of mineralized water

[0053]

[0054] From the data in Table 1, it can be seen that the greater the concentration of the ion control agent, the larger the size of the agglomerated particles. In addition, the size of the agglomerated particles formed by the ion control agent in Example 1 is smaller than that of the agglomerated particles formed by the ion control agent in Example 2.

[0055] The ion regulators of Examples 3 and 4 were added to 200 ml of mineralized water at different concentrations, and the water was observed for 6 days to measure the amount of ion aggregation (large particles visible to the naked eye).

[0056] Table 3 Ion aggregation amount after adding the ion regulators of Examples 1 and 2 to mineralized water

[0057]

[0058] It can be seen from the data in Table 3 that when the ion regulator is added to the mineralized water, no large particles are generated within 6 days, indicating that the ion regulator has a good effect in regulating ions.

[0059] The ion regulators of Examples 1-4 and Comparative Examples 2-3 were added to mineralized water with varying divalent ion concentrations, and titrated after 2 hours. The amount of ion regulator added was 1 g / L. The ion concentrations in the treated mineralized water were recorded for each example and comparative example, as shown in Table 4.

[0060] Table 4 Treatment results of different mineralized waters in Examples 1-4 and Comparative Examples 2-3

[0061]

[0062] As can be seen from Table 4, Examples 1-4 can significantly reduce the concentration of divalent ions in mineralized water, and the size of the bound ions can be controlled to be nanometer-sized, and almost no particles or agglomerates visible to the naked eye are formed. Figure 1 As can be seen, the particle size is at the nanometer level. In Comparative Examples 2 and 3, the agents can only bind a small amount of ions, or the ions are directly precipitated. Because large particles are generated, the ion concentration after treatment is low, and the particle size of Comparative Examples 2 and 3 is visible to the naked eye.

Claims

1. An ion regulator, formed by hydrogen bonding between carboxylic acid and protein, the specific preparation method comprising the following steps: In an inert atmosphere, the carboxylic acid and ammonium persulfate are reacted in water in step I, and then the protein and triethylamine are added to continue the reaction in step II to obtain the product; The mass ratio of the carboxylic acid, the protein and the triethylamine is 20-30:10-15:1-3.

2. The ion regulator according to claim 1, characterized in that: The carboxylic acid is one or more of acrylic acid, crotonic acid and cinnamic acid.

3. The ion regulator according to claim 1 or 2, characterized in that: The protein is one or more of whey protein, soy protein and collagen.

4. The ion regulator according to claim 1 or 2, characterized in that: The ammonium persulfate is added in the form of an aqueous solution with a mass concentration of 2-3%, and the added amount is a material ratio of 1 mL to 2-3 g of the carboxylic acid.

5. The ion regulator according to claim 1 or 2, characterized in that: The time of the reaction I is 1 to 1.5 hours, and the time of the reaction II is 1 to 1.5 hours; The temperature of the reaction I and the reaction II is 50-70°C.

6. Use of the ion regulator according to any one of claims 1 to 5 in preventing scaling of oil pipes.

7. The use according to claim 6, characterized in that: The mixing time of the ion regulator and the solution to be treated is 10 to 30 minutes.

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