CN105218744B - A kind of profile control agent and its synthetic method and application - Google Patents

Abstract

The invention discloses a profile control agent and its synthesis method and application. The synthesis method of the profile control agent includes: (1) performing bulk polymerization after mixing the oil production sludge with the first water phase, granulating, drying, crushing and sieving the rubber blocks obtained by the bulk polymerization to obtain different granules (2) mixing the solid particles with the second water phase to obtain a granular solid whose particle diameter is greater than that of the solid particles; (3) mixing the granular solid After being mixed with the oil phase, the emulsion polymerization is carried out, and the emulsion polymerization product is separated to obtain the profile control agent; the oil production sludge is a product obtained by drying the sludge generated in the oil field water treatment process after deoiling. The profile control agent synthesized by the method can obtain different particle sizes, and the obtained profile control agent has better strength and performance effects.

Description

A kind of profile control agent and its synthesis method and application

technical field

The present invention relates to a profile control agent and its synthesis method and application, in particular to a profile control agent synthesis method, the profile control agent synthesized by the method and the application of the profile control agent in oil well production.

Background technique

The profile control technology of water injection wells is a major technical measure for oil stabilization and water control when oilfield development enters the medium-high water cut period.

For some special types of reservoirs that have been put into development in recent years, such as low-permeability reservoirs, ultra-low-permeability reservoirs, and high-temperature reservoirs, they gradually enter the medium-high water cut period after water injection development. For such reservoirs, it is difficult to meet the profile control requirements of the oilfield by using the existing profile control methods.

Among the existing granular profile control agents: inorganic profile control agents with cement, fly ash, etc. It is difficult to inject into reservoirs with low permeability and ultra-low permeability. Particle profile control agents based on polymers and cross-linked polymers are generally aggregated into blocks and then crushed, dried, and sieved to obtain particles of different particle sizes. Usually, the particles obtained by this method have larger particle sizes. , unable to meet the particle size requirements of low-permeability reservoirs; on the other hand, the mechanical crushing and drying process destroys the original particle strength, resulting in a decline in the performance of the profile control agent. The more obvious the strength damage of the agent is, the more the performance declines.

Oilfield oil production sludge is a kind of waste produced in the oil production process. At present, it is mainly disposed of by landfill, which pollutes the environment and wastes resources. In the profile control and water plugging, the oil production sludge is made into the profile control agent used in the oil field and re-injected into the underground oil reservoir, which can realize the full utilization and harmless treatment of the oil production sludge.

CN1796484A discloses a preparation method of a copolymerized cross-linked profile control agent. The profile control agent disclosed in the invention is a profile control agent prepared by copolymerizing acrylamide and acrylic acid as monomers, N,N'-methylenebisacrylamide as a crosslinking agent, and adding kaolin or bentonite as a reinforcing agent. The profile control process of this method is simple, but the production process requires drying, crushing, and screening, which requires a large investment in equipment, the performance of the profile control agent is reduced, and the particle size is difficult to meet the requirements of low-permeability reservoirs, and the temperature resistance is also low.

CN1781860A discloses a method for preparing a bulky particle profile control agent by using oil production sludge. The profile control agent is to add oil production sludge, oxidizing agent and reducing agent to the ternary copolymerization system of acrylic acid, acrylamide and crosslinking agent. Carry out adiabatic free radical polymerization to form rubber blocks, then granulate, dry and crush to the required particle size, which can be applied to the deep profile adjustment of large pore reservoirs in oil fields, but this method still has the process of destroying the strength and performance of the profile control agent, etc. question.

CN101575966B discloses a method for underground polymerization of oil production sludge for water plugging and profile control. The method mixes acrylic acid, acrylamide, crosslinking agent and initiator into 15-25% of oil production sludge, and injects oilfield water or tap water into the ground, Under the action of reservoir temperature, a polymerization reaction occurs to form a three-dimensional network structure plugging substance wrapped with sludge, which plays a role in sealing underground fractures and holes. This method changes the above-ground polymerization process into an underground polymerization process, which can save corresponding procedures and equipment. However, the reservoir conditions are complex, the polymerization conditions are uncontrollable, and the injected chemical agents are easily absorbed, resulting in excessive dosage of agents and poor product performance. Stablize.

It can be seen that the existing technology uses oil recovery sludge to prepare profile control agents, but there are still problems such as the strength and performance of profile control agents being destroyed during processing, and the preparation conditions are poorly controlled. It cannot provide good performance of profile control agents and reduce strength damage and is easy to prepare. 1. A method for synthesizing a profile control agent with good temperature resistance.

Contents of the invention

The object of the present invention is to provide a profile control agent and its synthesis method and application in order to solve the problems in the prior art that the process of synthesizing the profile control agent greatly damages the strength of the profile control agent, the synthesis is complicated and the high temperature resistance is poor.

In order to achieve the above object, the present invention provides a synthetic method of a profile control agent, which comprises the following steps: (1) performing bulk polymerization after mixing the oil production sludge with the first water phase, and performing bulk polymerization on the rubber block obtained by the bulk polymerization Granulating, drying, pulverizing and sieving to obtain solid particles of different particle sizes, wherein the first aqueous phase contains polymerized monomers, the first crosslinking agent and the first water-soluble initiator; (2) the The solid particles are mixed with the second water phase to obtain granular solids, and the particle size of the granular solids is larger than the particle size of the solid particles, wherein the second water phase contains polymerized monomers, a second crosslinking agent and The second water-soluble initiator; (3) carry out emulsion polymerization after mixing the granular solid with the oil phase, and separate the emulsion polymerization product to obtain the profile control agent; wherein, the polymerized monomers are acrylamide and 2-acrylamide -2-Methylpropanesulfonic acid; the oil production sludge is the product obtained by drying the sludge produced in the process of oilfield water treatment after deoiling.

The present invention also provides the profile control agent synthesized by the method provided by the present invention, the average particle diameter of the profile control agent is 20-1000 μm, and the plugging strength of the profile control agent is 0.5-8 MPa/m.

The present invention also provides the application of the profile control agent provided by the present invention in oil well production.

When oil production sludge is used alone for profile control, its injectability is poor and its particle size is small, making it difficult to effectively block channeling of injected water. The synthesis method provided by the invention, on the one hand, uses oil production sludge as a raw material, avoids environmental pollution caused by sludge landfill and disposal, and achieves harmless treatment of oil production sludge. After the profile control agent is prepared according to the above method, the oil production sludge is wrapped by the three-dimensional structure formed by the copolymer, which improves the plugging ability. In addition, since the main component of oil production sludge is inorganic solids, the temperature resistance and strength of the profile control agent formed by copolymerization of organic monomers are improved. On the other hand, although adding the first water phase of oil production sludge to carry out bulk polymerization, the obtained rubber blocks still need to be crushed and sieved, but the method of the present invention adopts the technology of repolymerization to strengthen the strength and performance of the dissecting agent, and at the same time Free regulation of the particle size of the profile control agent is realized. The monomer 2-acrylamido-2-methylpropanesulfonic acid in the profile control agent provided by the invention has relatively high temperature resistance, and also helps to improve the temperature resistance of the profile control agent.

By adopting the synthesis method provided by the invention, required profile control agents with different average particle diameters can be synthesized, and the synthesized profile control agents have better strength and performance effects.

Other features and advantages of the present invention will be described in detail in the following detailed description.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a method for synthesizing a profile control agent, the method comprising the following steps: (1) performing bulk polymerization after mixing the oil production sludge with the first water phase, granulating and drying the rubber block obtained by the bulk polymerization , crushing and sieving to obtain solid particles of different particle sizes, wherein the first aqueous phase contains polymerized monomers, the first crosslinking agent and the first water-soluble initiator; (2) combining the solid particles with the second The two water phases are mixed to obtain granular solids, the particle size of which is larger than that of the solid particles, wherein the second water phase contains polymerizable monomers, a second crosslinking agent and a second water-soluble initiator (3) carry out emulsion polymerization after mixing the granular solid with the oil phase, and separate the emulsion polymerization product to obtain the profile control agent; wherein, the polymerized monomers are acrylamide and 2-acrylamide-2-methyl propanesulfonic acid; the oil production sludge is the product obtained by drying the sludge produced in the oil field water treatment process after deoiling.

In the method provided by the invention, the first aqueous phase (which contains acrylamide and 2-acrylamide-2-methyl propanesulfonic acid, and the first cross-linking agent) to carry out bulk polymerization to obtain a solid particle product; then use the solid particle to mix with the second water phase, and at this time, the solid particle will absorb the second water phase to expand in volume and become the second water phase for absorption. The granular solid with larger particle size of the two water phases; then put the granular solid into the oil phase, under the condition of emulsion polymerization, due to the second water-soluble initiator contained in the second water phase absorbed by the granular solid The role of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid and the second crosslinking agent contained in the second aqueous phase as polymerized monomers can be carried out on the basis of the aforementioned granular solid Emulsion polymerization is used to obtain the final profile control agent product.

In the method provided by the present invention, in step (2), the amount of solid particles absorbing the second aqueous phase is different, and granular solids with different particle sizes can be obtained. The polymerization reaction of step (3) is carried out on the granular solid that has been volume-expanded, and the monomer component and the second crosslinking agent in the second aqueous phase absorbed by the granular solid are polymerized to form a larger aggregate material particles, that is, profile control agents with different particle sizes can be obtained. When a profile control agent with a larger particle size is needed, the synthesized profile control agent can be used as solid particles to repeat the steps of the method provided by the present invention.

The existing technology adopts the method of preparing profile control agents from large to small, and obtains bulk polymers by bulk polymerization, and then obtains profile control agents with different particle sizes by crushing and sieving. The plugging strength is reduced due to the destruction, and the particle shape of the profile control agent obtained by crushing is not uniform and the particle size is random. Although the product obtained by pulverizing the step (1) bulk polymerization is also pulverized in the method of the present invention, the solid particles obtained are also repolymerized, and the solid particles are used as a starting point for preparing the final profile control agent in a small amount. The proportion of the final profile control agent is very small, and the obtained profile control agent still has good strength and performance. The method of the present invention adopts the method of changing from small to large, starting with a profile control agent with a small particle size, and continuing to polymerize on the profile control agent with a small particle size to form profile control agents with different particle sizes with controllable particle sizes. Damage to the strength of the profile control agent in the prior art is avoided.

According to the present invention, the result of step (1) operation can provide step (2) with starting solid particles with uniform particle size and suitable particle size. If the particle size of the solid particles is smaller, the subsequent steps can have a larger range for adjusting the particle size of the profile control agent. The solid particles in step (2) may be properly selected in particle size, and may be selected according to the particle size of the final required profile control agent. The particle size of the solid particles may be, for example, less than 40 μm, preferably 10-40 μm. Preferably, the weight ratio of the oil recovery sludge to the first water phase in step (1) is 0.1-0.2:1, preferably 0.15-0.2:1.

According to the present invention, preferably, in the first aqueous phase, the weight ratio of the polymerized monomer, the first crosslinking agent and the first water-soluble initiator is 10-1000:1-2:1, preferably the weight ratio The ratio is 50-800:1-1.5:1. The first crosslinking agent may preferably be N,N'-methylenebisacrylamide. Using the first cross-linking agent within the above range can help the polymerization product of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid monomers to be formed into solid particles, and can make the resulting solid particles have Appropriate water absorption can absorb an appropriate amount of the second water phase when mixed with the second water phase in step (2), and further facilitate the control of the particle size of the obtained granular solid. The first water-soluble initiator may not be particularly limited, for example, may be sulfite and persulfate, such as sodium sulfite and potassium persulfate, and may preferably be potassium persulfate.

According to the present invention, preferably, based on the total weight of the first aqueous phase, the total content of polymerized monomers is 30-50% by weight, preferably 35-45% by weight. In the first aqueous phase, acrylamide and 2-acrylamido-2-methylpropanesulfonic acid can be mixed in any ratio, preferably, the weight of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid The ratio is 0.5-2.3:1. The first water phase can be prepared by dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the first crosslinking agent in water first, then adding alkali to adjust the pH value, and then adjusting the pH value when the pH is 3-7. It is prepared by adding the first water-soluble initiator under certain conditions. The base may preferably be sodium hydroxide.

According to the present invention, preferably, the reaction temperature of the bulk polymerization is 25-50°C, and the reaction time of the bulk polymerization is 2-6h; preferably, the reaction temperature is 40-50°C, and the reaction time for 2-4h. In addition, the stirring rate of the bulk polymerization is 200-500 rpm, preferably 300-500 rpm.

In the synthesis method of the profile control agent provided by the present invention, a preferred embodiment of step (1) is: under bulk polymerization conditions, the oil production sludge and the first water phase are then subjected to bulk polymerization to obtain a rubber block Granulating, drying, pulverizing and sieving to obtain solid particles of different particle sizes, the weight ratio of the oil production sludge to the first water phase is 0.1-0.2:1; wherein, the first water phase contains The monomer acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, the first crosslinking agent and the first water-soluble initiator have a weight ratio of 10-1000:1-2:1. Step (1) can obtain solid particles with suitable particle size, which is beneficial to the synthesis method of the whole profile control agent provided by the present invention to further obtain profile control agents with different particle sizes.

In the present invention, the solid particles obtained in step (1) can be directly used as a profile control agent with a small particle size, and the profile control agent with different particle size increases can also be obtained through further polymerization in steps (2) and (3). Select the solid particles obtained by sieving with a suitable particle size to carry out step (2), and mix with the second water phase to make the solid particles absorb the second water phase. The solid particles after absorbing the second water phase will expand in volume and increase in particle size to become granular solids. The granular solids are further subjected to emulsion polymerization in the oil phase, which can be beneficial to obtain dispersed particles of polymerized product solids, avoiding The polymerized product coalesced into a large solid.

According to the present invention, in step (2), the weight ratio between the solid particles and the second water phase can be adjusted to control the desired particle size of the finally obtained profile control agent. Preferably, the weight ratio of the solid particles to the second aqueous phase in step (2) is 1:1-20, preferably 1:5-20.

In the present invention, in the step (2), the volume of the solid particles expands and the particle size increases due to the absorption of the second aqueous phase. Preferably, the particle size-to-length ratio of the solid particles to the granular solid in step (2) may be 1:1-10, preferably 1:3-8.

In the present invention, step (3) is used to further polymerize the granular solid obtained in step (2), so that the polymerized monomer and the second crosslinking agent in the second water phase contained in the granular solid can be dissolved in the second water Polymerized and cross-linked under the action of a neutral initiator, and integrated with the solid particles obtained in step (1), it can be used as a profile control agent. The second aqueous phase can contain acrylamide and 2-acrylamide-2-methylpropanesulfonic acid as polymerized monomers, and they can be mixed in any ratio. Preferably, acrylamide and 2-acrylamide- The weight ratio of 2-methylpropanesulfonic acid is 0.5-2.3:1. The monomer 2-acrylamido-2-methylpropanesulfonic acid can help improve the temperature resistance of the synthesized profile control agent.

According to the present invention, preferably, in the second water phase, the weight ratio of the polymerized monomer to the second crosslinking agent and the second water-soluble initiator can be 10-1000:1-2:1, preferably For 50-800:1-1.5:1. The second crosslinking agent may preferably be N,N'-methylenebisacrylamide. The second water-soluble initiator may not be particularly limited, for example, may be sulfite and persulfate, such as sodium sulfite and potassium persulfate, and may preferably be potassium persulfate.

According to the present invention, preferably, in the second water phase, based on the total weight of the second water phase, the total content of polymerized monomers can be 30-50% by weight, preferably 35-45% by weight .

In the present invention, the second water phase can be dissolved in water by first dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the second crosslinking agent, then adding alkali to adjust the pH value, and then It is prepared by adding the second water-soluble initiator under the conditions of 3-7. The base may preferably be sodium hydroxide.

According to the present invention, the polymerization reaction in step (3) is carried out in the oil phase, which is beneficial to obtain dispersed solid particles of the polymerized product and prevents the polymerized product from agglomerating into large solids. Preferably, the oil phase contains an organic solvent and an emulsifier, and the weight ratio of the emulsifier to the organic solvent is 1:5-100, preferably 1:20-80. The organic solvent and emulsifier may not be particularly limited, the organic solvent may preferably be cyclohexane, and the emulsifier may preferably be Span 80. The amount of the above emulsifier used can be beneficial to control the polymerization reaction to obtain a polymerization product with a suitable particle size.

According to the present invention, when the emulsion polymerization is carried out in step (3), the addition amount of the granular solid and the oil phase is not particularly limited, as long as the polymerization can be completed. Preferably, the weight ratio of the granular solid to the oil phase may be 0.1-1:1, preferably 0.2-0.8:1. The usage amount of the above-mentioned oil phase is beneficial to the dispersion of granular solids.

According to the present invention, preferably, the temperature of the emulsion polymerization in step (3) is 35-60°C, and the time of the emulsion polymerization is 2-6h; preferably, the temperature is 40-60°C, and the The time is 3-6h. The stirring speed of the emulsion polymerization reaction is 200-500rpm, preferably the stirring speed is 300-500rpm.

In the present invention, also require the profile control agent of bigger particle size according to actual application, can carry out step (2)-(3) in the synthetic method of profile control agent provided by the invention again with the profile control agent that step (3) obtains ), as a solid particle in step (2), continue to synthesize a profile control agent with a larger particle size. That is to say, the method provided by the present invention may also include performing steps (2)-(3) on the obtained profile control agent, wherein the profile control agent may be used as solid particles in step (2).

In the present invention, the separation in step (3) can be a separation technique commonly used in the art, for example, it can be static separation of solids and liquids.

The present invention also provides the profile control agent synthesized by the method provided by the present invention, the average particle diameter of the profile control agent is 20-1000 μm, and the plugging strength of the profile control agent is 0.5-8MPa/m; preferably, the The temperature resistance of the profile control agent is 75-110°C, and the salt tolerance of the profile control agent is below 25×10 ⁴ mg/L. Wherein, when the average particle size is small, such as less than 50 μm, the solid particles synthesized in the method provided by the present invention can be used as the profile control agent.

In the present invention, the plugging strength of the profile control agent can be measured by the profile control agent performance evaluation device produced by Jiangsu Hua'an Petroleum Scientific Research Instrument Factory. The specific method is as follows: (1) Fill the 60-mesh quartz sand into the sand-filling pipe with a diameter of 2.5 cm x 100 cm in length; (2) Put the sand-filling pipe into the profile control agent performance evaluation device, and raise the temperature of the device to the point where the profile control agent is evaluated. The temperature of the plugging strength is kept constant for 2-4 hours; (3) The profile control agent of 1 times the pore volume is injected into the sand filling pipe, and the temperature is kept constant for 24 hours; (4) The brine (concentration in NaCl is 0-25× 10 ⁴ mg/L) was injected into the sand pack pipe to displace the profile control agent. When the displacement reaches the balance of the pressure difference between the two ends of the sand pack pipe, record the pressure difference at this time as the plugging strength of the profile control agent. The plugging strength of the profile control agent is the pressure difference at both ends of the sand packing pipe divided by the length of the sand packing pipe (for filling with 60-mesh quartz sand). The larger the value, the higher the plugging strength of the profile control agent. Test the plugging strength of the profile control agent at different temperatures and brine concentrations. When a certain temperature or brine concentration, the plugging strength of the profile control agent is significantly reduced, then this temperature or brine concentration is the temperature resistance temperature of the profile control agent or salt tolerance.

The present invention also provides the application of the profile control agent provided by the present invention in oil well production.

The present invention will be described in detail below by way of examples.

In the following examples, the particle sizes of the obtained solid particles, granular solids and profile control agents were measured by optical microscopic imaging method using UV-g microscopic particle size analysis instrument of Shanghai No. 6 Optical Instrument Factory.

All raw materials are commercially available.

Example 1

This example is used to illustrate the synthesis method of the profile control agent provided by the present invention.

(1) Add 10g of deionized water, 7g of acrylamide, 3g of 2-acrylamido-2-methylpropanesulfonic acid, and 0.08g of N,N'-methylenebisacrylamide into a stirred container, and stir to dissolve; Then add 30% by weight of NaOH solution to adjust the pH to 4, add 0.050 g of K ₂ S ₂ O ₈ to dissolve, and pass nitrogen gas for 20 minutes to obtain the first aqueous phase;

Add 5g of oil production sludge and an appropriate amount of water into a reactor equipped with a stirring, reflux condensing device, and a nitrogen conduit, and stir to form a slurry. Under the protection of nitrogen, quickly add the above-mentioned first water phase into the reactor, mix it with the mud in it, stop stirring when the temperature rises to 40°C, and continue to heat up to 50°C for bulk polymerization for 2 hours. After the reaction is completed, the product gel Block granulation, drying, crushing, and sieving, and the average particle size of solid particles is determined to be 15 μm;

(2) Add 80g of cyclohexane and 2.5g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60°C, stir for 30 minutes, then cool to 50°C, pass Inject nitrogen gas to remove oxygen for 30 minutes to obtain an oil phase; add 10 g of deionized water, 7 g of acrylamide, 3 g of 2-acrylamido-2-methylpropanesulfonic acid, N,N′-methylenebis 0.05 g of acrylamide was stirred and dissolved; then 30% by weight of NaOH solution was added to adjust the pH to 4, and then 0.050 g of K ₂ S ₂ O ₈ was added to dissolve, and nitrogen gas was introduced for 20 minutes to obtain the second aqueous phase;

After drying the solid particles in (1), take 2 g and add them to 20 g of the second aqueous phase, and fully absorb water to swell until no obvious aqueous solution exists. At this time, all the obtained particles are granular solids;

(3) The granular solid was added to the reactor containing the oil phase, under nitrogen protection, 50°C and a stirring speed of 400rpm, the polymerization reaction was carried out for 2 hours, and then the temperature was raised to 60°C to continue the reaction for 2 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent A1, and the measured average particle size was 150 μm.

The plugging strength of A1 was determined to be 5 MPa/m, the temperature resistance reached 110°C, and the salt resistance capacity reached 25×10 ⁴ mg/L.

Example 2

This example is used to illustrate the synthesis method of the profile control agent provided by the present invention.

(1) Add 15g of deionized water, 5g of acrylamide, 5g of 2-acrylamido-2-methylpropanesulfonic acid, and 0.01g of N,N'-methylenebisacrylamide into a stirred container, and stir to dissolve; Then add 30% by weight of NaOH solution to adjust the pH to 7; add 0.01g of K ₂ S ₂ O ₈ to dissolve, and pass nitrogen gas for 20 minutes to obtain the first aqueous phase;

Add 5g of oil production sludge and an appropriate amount of water into a reactor with a stirring, reflux condensing device, and a nitrogen conduit, and stir to form a slurry. Under the protection of nitrogen, quickly add the above-mentioned first water phase to the reactor, and stir to raise the temperature to 40 Stop stirring at ℃, continue to heat up to 50 ℃ to carry out bulk polymerization reaction for 4 hours, after the reaction is completed, the product rubber block is granulated, dried, crushed, and sieved, and the average particle size of the solid particles is determined to be 40 μm;

(2) Add 100 g of cyclohexane and 1.0 g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60° C., stir for 30 minutes, cool to 50° C., and pass Nitrogen was added to deoxygenate for 30 minutes to obtain an oil phase; 15 g of deionized water, 5 g of acrylamide, 5 g of 2-acrylamido-2-methylpropanesulfonic acid, and N,N′-methylenebis 0.01 g of acrylamide was stirred and dissolved; then 30% by weight of NaOH solution was added to adjust the pH to 7; 0.010 g of K ₂ S ₂ O ₈ was added to dissolve, and nitrogen gas was introduced for 20 minutes to obtain the second aqueous phase;

Add 1.25 g of the solid particles in (1) to 16 g of the second aqueous phase, fully absorb water and swell until there is no obvious aqueous solution, and at this time, all of the solid particles are obtained;

(3) The granular solid was added to the reactor containing the oil phase, under nitrogen protection, 50°C and a stirring speed of 400rpm, the polymerization reaction was carried out for 2 hours, and then the temperature was raised to 60°C to continue the reaction for 2 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent A2, and the measured average particle size was 480 μm.

It is determined that the plugging strength of A2 reaches 6MPa/m, the temperature resistance reaches 110°C, and the salt resistance reaches 25×10 ⁴ mg/L.

Example 3

This example is used to illustrate the synthesis method of the profile control agent provided by the present invention.

(1) Add 20g of deionized water, 3.5g of acrylamide, 7g of 2-acrylamido-2-methylpropanesulfonic acid, and 0.10g of N,N'-methylenebisacrylamide into a stirred container, and stir to dissolve ;Add 30% by weight of NaOH solution to adjust the pH to 5; add 0.30g of K ₂ S ₂ O ₈ to dissolve, and pass nitrogen gas for 20 minutes to obtain the first aqueous phase;

Add 6g of sludge and an appropriate amount of water into a reactor equipped with stirring, reflux condensing device, and nitrogen conduit, and stir to form a slurry. Under the protection of nitrogen, quickly add the above-mentioned first water phase to the reactor, and stir to raise the temperature to 40°C Stop stirring at the same time, continue to heat up to 50 ℃ and carry out the bulk polymerization reaction for 3 hours, after the reaction is completed, the product rubber block is granulated, dried, pulverized, sieved, and the average particle size of the solid particles is determined to be 10 μm;

(2) Add 100g of cyclohexane and 5g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60°C, stir for 30 minutes, cool to 50°C, and feed Deoxygenate with nitrogen for 30 minutes to obtain an oil phase; add 20 g of deionized water, 3.5 g of acrylamide, 7 g of 2-acrylamido-2-methylpropanesulfonic acid, N,N′-methylenebis 0.10 g of acrylamide was stirred and dissolved; then 30% by weight of NaOH solution was added to adjust the pH to 5; 0.10 g of K ₂ S ₂ O ₈ was added to dissolve, and nitrogen gas was introduced for 20 minutes to obtain the second aqueous phase;

Add 10 g of the solid particles in (1) into 10 g of the second aqueous phase, fully absorb water and swell until no obvious aqueous solution exists, and at this time, all of the solid particles are obtained in granular form;

(3) The granular solid was added to the reactor containing the second oil phase, and the polymerization reaction was carried out under nitrogen protection at 35° C. and a stirring speed of 400 rpm for 2 hours, and then the temperature was raised to 50° C. to continue the reaction for 4 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent A3 with an average particle size of 20 μm.

It is determined that the plugging strength of A3 reaches 4.5MPa/m, the temperature resistance reaches 100°C, and the salt resistance reaches 20×10 ⁴ mg/L.

Example 4

This example is used to illustrate the synthesis method of the profile control agent provided by the present invention.

(1) Add 80g of cyclohexane and 2.5g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60°C, stir for 30 minutes, then cool to 50°C, pass Inject nitrogen gas to remove oxygen for 30 minutes to obtain an oil phase; add 10 g of deionized water, 7 g of acrylamide, 3 g of 2-acrylamido-2-methylpropanesulfonic acid, N,N′-methylenebis 0.05 g of acrylamide was stirred and dissolved; then 30% by weight of NaOH solution was added to adjust the pH to 6; 0.050 g of K ₂ S ₂ O ₈ was added to dissolve, and nitrogen gas was introduced for 20 minutes to obtain the second aqueous phase;

Add 3 g of dried profile control agent A1 with an average particle size of 150 μm into the above-mentioned second water phase, fully absorb water and swell until there is no obvious aqueous solution, and at this time, all granular solids are obtained;

(2) The granular solid was added to the reactor containing the oil phase, under nitrogen protection, 50°C and a stirring speed of 400rpm, the polymerization reaction was carried out for 2 hours, and then the temperature was raised to 60°C to continue the reaction for 2 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent A4, and the measured average particle size was 1000 μm.

It is determined that the plugging strength of A4 reaches 6.5MPa/m, the temperature resistance reaches 110°C, and the salt resistance reaches 25×10 ⁴ mg/L.

Comparative example 1

Add 10g of deionized water, 7g of acrylamide, 3g of 2-acrylamido-2-methylpropanesulfonic acid, 0.08g of N,N'-methylenebisacrylamide into a stirred container, stir to dissolve, and then add 30 After adjusting the pH to 4 by weight % NaOH solution, add 0.050g of K ₂ S ₂ O ₈ to dissolve, feed nitrogen for 20 minutes to obtain an aqueous solution; add 5 g of Sludge and an appropriate amount of water are stirred into a slurry. Under the protection of nitrogen, the above aqueous solution is quickly added to the reactor, and the stirring is stopped when the temperature is raised to 40°C, and the temperature is continued to rise to 50°C for bulk polymerization for 2 hours. After the reaction is completed, the product The rubber blocks were granulated, dried, crushed, and sieved to obtain the profile control agent B1 with an average particle size of 150 μm.

It is determined that the plugging strength of the profile control agent B1 reaches 2MPa/m, the temperature resistance reaches 90°C, and the salt tolerance reaches 20×10 ⁴ mg/L.

Comparative example 2

(1) Add 10g of deionized water, 10g of acrylamide, and 0.08g of N,N'-methylenebisacrylamide into a stirred container, stir and dissolve, then add 30% by weight NaOH solution to adjust the pH to 4, then add Dissolve 0.050g of K ₂ S ₂ O ₈ and pass nitrogen gas for 20 minutes to obtain the first water phase; add 5 g of sludge and appropriate amount of water into a reactor equipped with stirring, reflux condensing device, and nitrogen gas conduit, and stir to form a slurry , under the protection of nitrogen, quickly add the above-mentioned first water phase into the reactor, stop stirring when the temperature is raised to 40°C, continue to heat up to 50°C for bulk polymerization reaction for 2 hours, after the reaction is completed, the product rubber block is granulated and baked Drying, crushing and sieving, the average particle size of the solid particles is determined to be 15 μm;

(2) Add 80g of cyclohexane and 2.5g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60°C, stir for 30 minutes, then cool to 50°C, pass Add nitrogen gas to remove oxygen for 30 minutes to obtain an oil phase; add 10 g of deionized water, 10 g of acrylamide, and 0.08 g of N,N'-methylenebisacrylamide into a stirred container, and stir to dissolve; then add 30% by weight of NaOH After the pH of the solution was adjusted to 4, 0.050 g of K ₂ S ₂ O ₈ was added to dissolve it, and nitrogen gas was introduced for 20 minutes to obtain the second aqueous phase;

Take 2g of the solid particles in (1) and add them to 20g of the second aqueous phase, fully absorb water and swell until there is no obvious aqueous solution, and at this time, all of the particles are granular solids;

(3) The granular solid was added to the reactor containing the oil phase, under nitrogen protection, 50°C and a stirring speed of 400rpm, the polymerization reaction was carried out for 2 hours, and then the temperature was raised to 60°C to continue the reaction for 2 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent B2, and the measured average particle size was 150 μm.

It is determined that the plugging strength of the profile control agent B2 reaches 3MPa/m, the temperature resistance reaches 70°C, and the salt tolerance reaches 15×10 ⁴ mg/L.

Comparative example 3

(1) Add 10 g of deionized water, 7 g of acrylamide, 3 g of 2-acrylamido-2-methylpropanesulfonic acid, N,N'- 0.08g of methylbisacrylamide, stir to dissolve, then add 30% by weight of NaOH solution to adjust the pH to 4, then add 0.050g of K ₂ S ₂ O ₈ to dissolve; under nitrogen protection, stir and stop stirring when the temperature rises to 40°C , continue to heat up to 50 ° C for bulk polymerization for 2 hours, after the reaction is completed, the product rubber block is granulated, dried, crushed, and sieved, and the average particle size of the solid particles is determined to be 15 μm;

(2) Add 80g of cyclohexane and 2.5g of Span 80 into a reactor with stirring, reflux condensing device, and nitrogen conduit, heat to a temperature of 60°C, stir for 30 minutes, then cool to 50°C, pass Inject nitrogen gas to remove oxygen for 30 minutes to obtain an oil phase; add 10 g of deionized water, 7 g of acrylamide, 3 g of 2-acrylamido-2-methylpropanesulfonic acid, N,N′-methylenebis 0.08 g of acrylamide was stirred and dissolved; then 30% by weight of NaOH solution was added to adjust the pH to 4, and then 0.050 g of K ₂ S ₂ O ₈ was added to dissolve, and nitrogen gas was passed in for 20 minutes to obtain an aqueous phase;

Take 2g of the solid particles in (1) and add them to 20g of the water phase, fully absorb water and swell until there is no obvious aqueous solution, and at this time, all the obtained particles are granular solids;

(3) The granular solid was added to the reactor containing the oil phase, under nitrogen protection, 50°C and a stirring speed of 400rpm, the polymerization reaction was carried out for 2 hours, and then the temperature was raised to 60°C to continue the reaction for 2 hours. After cooling and standing still, the lower product was separated to obtain the profile control agent B3, and the measured average particle size was 150 μm.

The plugging strength of B3 was determined to be 4.8 MPa/m, the temperature resistance reached 100°C, and the salt resistance capacity reached 22×10 ⁴ mg/L.

From the results of the above examples and comparative examples, it can be seen that by using the synthesis method of the profile control agent provided by the present invention, the free control of the particle size of the profile control agent can be realized, and the strength and performance of the profile control agent can be enhanced. However, the profile control agent not obtained by the method of the present invention in Comparative Example 1 is directly obtained after crushing, so the strength and temperature and salt resistance of the profile control agent are destroyed. In Comparative Example 2, there is no polymerized monomer 2-acrylamido-2-methylpropanesulfonic acid, and the obtained profile control agent has poor temperature resistance. In the synthesis method in Comparative Example 3, oil production sludge was not added, and the obtained profile control agent was slightly inferior in strength and performance. The profile control agent synthesis method provided by the present invention not only realizes the full utilization and harmless treatment of oil production sludge, but also can conveniently obtain products with different particle sizes, and the profile control agent synthesized has better strength, durability temperature performance and salt tolerance.

Claims (10)

1. a kind of synthetic method of profile control agent, this method comprises the following steps：

(1) polymerisation in bulk is carried out after oil exploitation sludge is mixed with the first aqueous phase, the blob of viscose that the polymerisation in bulk is obtained granulated, Drying, crushing and screening, obtain the solid particle of different-grain diameter, wherein, first aqueous phase contains polymerized monomer, the first crosslinking Agent and the first water soluble starter；The particle diameter of the solid particle is less than 40 μm；

(2) solid particle is mixed with the second aqueous phase, obtains granular solids, the particle diameter of the granular solids is more than described The particle diameter of solid particle, wherein, second aqueous phase contains polymerized monomer, the second crosslinking agent and the second water soluble starter；

(3) emulsion polymerization is carried out after the granular solids are mixed with oil phase, separation emulsion polymeric product obtains profile control agent；

Wherein, the polymerized monomer is acrylamide and 2- acrylamide-2-methylpro panesulfonic acids；The oil exploitation sludge is oil field The sludge produced in water treatment procedure dries obtained product after oil removing；

In step (3), the weight ratio of the granular solids and the oil phase is 0.1-1：1；

The oil phase contains organic solvent and emulsifying agent, and the weight ratio of the emulsifying agent and the organic solvent is 1:5-100；

The temperature of the emulsion polymerization is 35-60 DEG C, and the time of the emulsion polymerization is 2-6h.

2. according to the method described in claim 1, wherein, the weight of oil exploitation sludge described in step (1) and first aqueous phase Than for 0.1-0.2:1.

3. according to the method described in claim 1, wherein, in first aqueous phase, polymerized monomer, the first crosslinking agent and the first water The weight ratio of soluble initiator is 10-1000:1-2:1；On the basis of the gross weight of first aqueous phase, the polymerized monomer Content is 30-50 weight %.

4. according to the method described in claim 1, wherein, the reaction temperature of the polymerisation in bulk is 25-50 DEG C, and the body gathers The reaction time of conjunction is 1-4h.

5. the method according to any one in claim 1-4, wherein, solid particle described in step (2) and described the The weight ratio of two aqueous phases is 1：1-20.

6. the method according to any one in claim 1-4, wherein, in second aqueous phase, polymerized monomer, second are handed over Join agent, the weight ratio of the second water soluble starter is 10-1000:1-2:1；On the basis of the gross weight of second aqueous phase, institute The content for stating polymerized monomer is 30-50 weight %.

7. the method according to any one in claim 1-4, wherein, this method also includes again entering obtained profile control agent Row step (2)-(3), wherein, profile control agent is used as the solid particle in step (2).

8. the profile control agent of the method synthesis in claim 1-7 described in any one, the average grain diameter of the profile control agent is 20-1000 μm, the plugging strength of the profile control agent is 0.5-8MPa/m.

9. profile control agent according to claim 8, wherein, the heatproof temperature of the profile control agent is 75-110 DEG C, the profile control The salt resistance ability of agent is 25 × 10⁴Below mg/L.

10. application of the profile control agent described in claim 8 or 9 in oil mining.