CN116948115A - Demulsifier containing nanoparticle structure and preparation method and application thereof - Google Patents

Abstract

The invention provides a demulsifier containing a nanoparticle structure, and a preparation method and application thereof. The demulsifier is prepared from components including a hydrophobic monomer, a hydrophilic monomer, a nano functional monomer and a crosslinkable monomer. The nano material is introduced into the demulsifier, so that the adsorptivity and the surface activity of the demulsifier at an oil-water interface can be greatly improved, the demulsification speed, the demulsification efficiency and the demulsification range are improved, and meanwhile, the production condition is mild and safe, and the high-temperature and high-pressure condition is not required.

Description

Demulsifier containing nanoparticle structure and preparation method and application thereof

Technical Field

The invention relates to the technical field of oilfield chemicals, in particular to a demulsifier containing a nanoparticle structure, and a preparation method and application thereof.

Background

In the petroleum exploitation and transportation process, crude oil and water are usually in emulsion, especially the application of a new tertiary oil recovery technology, so that the components and structures of the oil-containing emulsion are more and more complex, and the crude oil treatment difficulty is increased. Chemical demulsification is the most commonly used demulsification method at present, and the interfacial property of oil water or the strength of an interfacial film is changed mainly through chemical agents, so that demulsification is achieved. Most of the emulsion uses high molecular polyether as a main component, and is also suitable for emulsions with different complexity degrees by compounding with other reagents. The demulsifier used at present has the problems of gradually decreasing demulsification efficiency, large dosage, poor applicability, high cost, environmental pollution and the like, so the development of the green demulsifier with strong universality and high demulsification efficiency is urgent.

The nano particles have unique high dispersion performance, large specific surface area and multiple active sites, and the dispersibility of the nano particles can be optimized through functional modification, so that the hydrophilicity/lipophilicity of the particles is enhanced; in addition, the surface of the nanoparticle contains a large amount of unsaturated bonds, and is easily modified by various functional groups. After the demulsifier is combined with the nano particles, the modified nano particles are utilized to open the water-in-oil external oil layer structure, penetrate through the emulsion layer, and break the interface after being combined with water molecules so as to generate demulsification. Can realize high-efficiency demulsification, effectively solve the problem of poor universality of the existing demulsifier, can obviously improve the demulsification quality, the demulsification efficiency and the demulsification range, and is more environment-friendly.

Disclosure of Invention

The invention provides a demulsifier containing a nanoparticle structure, a preparation method and application thereof, wherein a nano functional monomer with reactivity, such as a modified nano silicon dioxide functional monomer, a hydrophilic monomer such as acrylic acid, an acrylic ester hydrophobic monomer and a crosslinkable monomer are polymerized by emulsion, so that the demulsifier molecule contains two structures of nanoparticles and acrylic ester at the same time, and the two structures are synergistic, thereby enhancing the surface activity, the adsorptivity and the diffusion permeation wetting performance of the demulsifier and improving the demulsification speed and the demulsification efficiency.

The invention aims at providing a demulsifier containing a nanoparticle structure, which is prepared from components including a hydrophobic monomer, a hydrophilic monomer, a nano functional monomer and a crosslinkable monomer.

The hydrophobic monomer is acrylic ester, preferably at least one of butyl acrylate, methyl methacrylate, lauryl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, dodecyl acrylate and stearyl acrylate.

The hydrophilic monomer is at least one of acrylic acid, methacrylic acid or maleic anhydride.

The crosslinkable monomer is an olefin containing two or more unsaturated double bonds, preferably at least one of diethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol dimethacrylate, butanediol diacrylate, acrylamide, N-methylolacrylamide, N' -methylenebisacrylamide and divinylbenzene.

The nano functional monomer is modified nano silicon dioxide.

The modified nano silicon dioxide is obtained by adopting a modifier to carry out surface modification on nano silicon dioxide particles, wherein the modifier is vinyl silanes, preferably vinyl triethoxysilane.

Based on 100 parts by weight of the total reaction monomers (i.e., the total weight of the hydrophobic monomer, the hydrophilic monomer, the nano-functional monomer and the crosslinkable monomer), the hydrophobic monomer is 70-98 parts, preferably 80-95 parts; 1 to 20 parts of hydrophilic monomer, preferably 5 to 10 parts; the nanometer functional monomer is 0.1-10 parts, preferably 0.5-5 parts; the crosslinkable monomer is 0.001 to 3 parts, preferably 0.1 to 0.5 part.

The second purpose of the invention is to provide a preparation method of the demulsifier, which comprises the step of reacting a hydrophobic monomer, a hydrophilic monomer, a nano functional monomer, a crosslinkable monomer, an emulsifier and an initiator to obtain the demulsifier.

On the basis of the technical scheme, the hydrophobic monomer is acrylic ester, preferably at least one of butyl acrylate, methyl methacrylate, lauryl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, dodecyl acrylate and stearyl acrylate; the hydrophilic monomer is at least one of acrylic acid, methacrylic acid or maleic anhydride; the nano functional monomer is modified nano silicon dioxide; the crosslinkable monomer is selected from olefins containing two or more unsaturated double bonds, preferably at least one of diethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol dimethacrylate, butanediol diacrylate, acrylamide, N-methylolacrylamide, N' -methylenebisacrylamide and divinylbenzene.

On the basis of the technical scheme, the modified nano-silica can be obtained by adopting a vinyl silane modifier to carry out surface modification on nano-silica particles, and the modifier is preferably vinyl triethoxysilane. The surface modification method may employ a method commonly used in the art.

Based on the technical scheme, the total weight of the reaction monomers is taken as 100 parts, the hydrophobic monomers are 70-98 parts, preferably 80-95 parts, such as 70 parts, 75 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts and the like.

Based on the above technical scheme, the total weight of the reaction monomers is taken as 100 parts, and the hydrophilic monomers are 1 to 20 parts, preferably 5 to 10 parts, for example 1 part, 3 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 15 parts, 20 parts and the like.

Based on the above technical scheme, the total weight of the reaction monomers is taken as 100 parts, and the nano functional monomers are 0.1-10 parts, preferably 0.5-5 parts, for example, 0.1 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and the like.

Based on the above technical scheme, the crosslinkable monomer is 0.001-3 parts, preferably 0.1-0.5 parts, for example 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 1 part, 2 parts, 3 parts and the like based on 100 parts of the total weight of the reaction monomers.

Based on the technical scheme, the emulsifier is one or more of alkylphenol ethoxylates (such as OP-10), petroleum sulfonate, sodium dodecyl sulfonate, sodium alkylbenzenesulfonate and sodium dodecyl sulfate.

The emulsifier is 2-15%, preferably 5-10% of the total mass of the hydrophilic monomer and the hydrophobic monomer.

On the basis of the technical scheme, the initiator can be one or more of various conventional initiators, preferably one or more of inorganic peroxy initiators, water-soluble oxidation-reduction systems and water-soluble azo compounds. The inorganic peroxy initiator is preferably one or more of ammonium persulfate and potassium persulfate; the water-soluble oxidation-reduction system is preferably one or more of potassium persulfate, sodium persulfate, hydrogen peroxide and sodium thiosulfate, ferrous chloride and ascorbic acid; the water-soluble azo compound is preferably one or more of dimethyl 2, 2-azobisisobutyrate, 2-azo [2- (2-imidazolinyl) propane ] dihydrochloride and azobisisobutylamidine hydrochloride.

The initiator is 0.1 to 1%, preferably 0.2 to 0.6% of the total mass of the hydrophilic monomer and the hydrophobic monomer.

Preferably, the preparation method can comprise the following steps:

(1) Dissolving an emulsifying agent in a solvent, and adding a hydrophobic monomer for emulsification to obtain emulsion;

(2) Adding a nano functional monomer and a crosslinkable monomer into the emulsion obtained in the step (1), and adding part of initiator solution under an inert atmosphere;

(3) Adding the hydrophilic monomer solution and the residual initiator solution into the reaction system in the step (2) together, continuing the constant-temperature reaction, and stopping the reaction to obtain the demulsifier.

The solvent is water, and the solvent is 2-6 times, preferably 3-4 times, of the total mass of the reaction monomers.

In the step (2), the reaction temperature is 50-80 ℃ and the reaction time is 2-4 hours.

In the step (3), the reaction time is 2.5-3.5 hours.

The invention further provides an application of the demulsifier or the demulsifier obtained by the preparation method in crude oil demulsification.

The demulsifier can be used for treating crude oil water-in-oil emulsion.

When applied to crude oil demulsification, the treatment method comprises contacting a crude oil water-in-oil emulsion with a demulsifier, which may be used in the same or different amounts as the prior art.

The demulsifier comprises an acrylic polymer containing a nanoparticle structure, and is formed by polymerizing a hydrophobic monomer, a hydrophilic monomer, a nano functional monomer and a crosslinkable monomer.

The demulsifier can be an aqueous solution containing the polymer, an emulsion product prepared by the preparation method, or an aqueous solution of a solid product prepared by the preparation method.

The demulsifier can also be compounded with other existing demulsifiers.

The essential difference between the invention and the prior art is that:

the acrylic ester non-polyether demulsifier with the nano material introduced can greatly improve the adsorptivity and the surface activity of the demulsifier at an oil-water interface due to the special surface property of the nano material, the nano particles and the acrylic ester long-chain structure can play a synergistic effect, the diffusion permeation wetting property is enhanced, the demulsification speed, the demulsification efficiency and the demulsification range are improved, and meanwhile, the production condition is mild and safe, and the high-temperature and high-pressure condition is not needed.

The beneficial effects of the invention are as follows:

the acrylic ester non-polyether demulsifier containing the nano functional monomer provided by the invention has good adsorptivity and surface activity, strong diffusion permeation wettability, can improve demulsification and dehydration effects, shortens oil-water separation time, provides technical support for gathering, transporting and storing of oil well produced liquid, and has wide application prospect.

The demulsifier provided by the invention can be used for preparing corresponding demulsifiers by selecting copolymers with different proportions according to different crude oil water-in-oil emulsions, can be used independently, and can be used by being compounded with other existing demulsifiers according to the properties of the crude oil water-in-oil emulsions so as to improve the universality of the demulsifier.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.

In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.

The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.

According to a preferred embodiment of the invention, the preparation method of the invention comprises the following steps:

step 1, preparing a nano silicon dioxide functional monomer: adding nano silicon dioxide, absolute ethyl alcohol, distilled water and ammonia water into a three-neck flask, performing ultrasonic dispersion for 30 minutes, slowly dropwise adding vinyl triethoxysilane under the stirring condition, reacting in a water bath at the temperature of 30 ℃ for 18 hours after dropwise adding, and obtaining the nano silicon dioxide functional monomer after centrifugation and drying.

And 2, dissolving the emulsifier in water, adding the acrylic ester hydrophobic monomer, and emulsifying under high-speed stirring.

And step 3, adding the prepared nano silicon dioxide functional monomer particles and the crosslinkable monomer solution, uniformly stirring, transferring into a reaction kettle, heating to 50-80 ℃, continuously introducing nitrogen, adding part of initiator solution, and reacting for 2-4 hours.

And step 4, uniformly mixing the rest initiator solution and the hydrophilic monomer solution, dropwise adding the mixture into a reaction kettle, finishing dropwise adding within 0.5 hour, continuing to react for 2-3 hours, stopping the reaction, and discharging the mixture at normal temperature to obtain the milky uniform emulsion.

Example 1

The operation steps are as follows:

step 1, preparing a modified nano silicon dioxide functional monomer, namely sequentially adding 1.5g of nano silicon dioxide, 100ml of absolute ethyl alcohol, 17.22g of distilled water and 1.58ml of 28% ammonia water into a 250ml three-neck flask, dispersing for 30 minutes by ultrasonic waves, slowly dropwise adding 0.22g of vinyltriethoxysilane into the three-neck flask under the stirring condition, reacting in a water bath at 30 ℃ for 18 hours after the vinyltriethoxysilane is dropwise added, and centrifuging and drying to obtain the nano silicon dioxide functional monomer.

Step 2, weighing 50g of deionized water in a beaker, adding 1g of sodium dodecyl sulfate and 0.5g of alkylphenol ethoxylate OP-10 under stirring, mixing for 20 minutes, adding 18g of acrylic acid-2-ethylhexyl ester, and emulsifying for 5-30 minutes at a rotating speed of 5000r/min to obtain emulsion. 10g of deionized water was weighed, and 0.06g of 2-azo (2-amidinopropane) dihydrochloride (V50) as an initiator was added thereto and stirred uniformly to prepare an initiator solution.

And 3, adding 0.15g of prepared modified nano silicon dioxide particles and 0.03g of trihydroxymethyl propyl triacrylate into the emulsion, stirring uniformly, transferring into a reaction kettle, heating to 60 ℃, starting stirring, replacing air, continuously introducing nitrogen, adding 7g of the initiator solution, and reacting at constant temperature for 3 hours.

And 4, dissolving 1.0g of acrylic acid in 10g of deionized water, adding the rest of initiator solution, uniformly stirring, dropwise adding into the emulsion, finishing dropwise adding within 0.5 hour, continuing to perform constant-temperature reaction for 2-3 hours, stopping the reaction, and discharging at normal temperature.

Example 2

The operation steps are as follows:

step 1 a modified nanosilica functional monomer was prepared as in example 1.

Step 2, weighing 50g of deionized water in a beaker, adding 1g of sodium dodecyl sulfate and 0.5g of alkylphenol ethoxylate OP-10 g under stirring, mixing for 20 minutes, adding 12g of acrylic acid-2-ethylhexyl ester and 6g of butyl acrylate, and emulsifying for 5-30 minutes at a rotating speed of 5000r/min to obtain emulsion. 10g of deionized water was weighed, and 0.06g of 2-azo (2-amidinopropane) dihydrochloride (V50) as an initiator was added thereto and stirred uniformly to prepare an initiator solution.

And 3, adding 0.3g of prepared modified nano silicon dioxide particles and 0.04g of trihydroxymethyl propyl triacrylate into the emulsion, uniformly stirring, then transferring into a reaction kettle, starting stirring, heating to 60 ℃, replacing air, continuously introducing nitrogen, adding 7g of the initiator solution, and reacting at constant temperature for 3 hours.

And 3, dissolving 1.5g of acrylic acid in 10g of deionized water, adding the rest of initiator solution, uniformly stirring, dropwise adding into the emulsion, finishing dropwise adding within 0.5 hour, continuing to perform constant-temperature reaction for 2-3 hours, stopping the reaction, and discharging at normal temperature.

Example 3

The operation steps are as follows:

step 1 a modified nanosilica functional monomer was prepared as in example 1.

Step 2, weighing 50g of deionized water in a beaker, adding 1g of sodium dodecyl sulfate and 0.5g of alkylphenol ethoxylate OP-10 g under stirring, mixing for 20 minutes, adding 12g of 2-ethylhexyl acrylate and 6g of butyl acrylate, and emulsifying for 5-30 minutes at a rotating speed of 5000r/min to obtain emulsion. 10g of deionized water was weighed, and 0.08 g of 2-azo (2-amidinopropane) dihydrochloride (V50) as an initiator was added thereto and stirred uniformly to prepare an initiator solution.

And 3, adding 0.5g of prepared modified nano silicon dioxide particles and 0.05g of trihydroxymethyl propyl triacrylate into the emulsion, uniformly stirring, then transferring into a reaction kettle, starting stirring, heating to 60 ℃, replacing air, continuously introducing nitrogen, and adding 7g of the initiator solution for constant-temperature reaction for 3 hours.

And 4, dissolving 1.5g of acrylic acid in 10g of deionized water, adding the rest of initiator solution, uniformly stirring, dropwise adding into the emulsion, finishing dropwise adding within 0.5 hour, continuing to perform constant-temperature reaction for 2-3 hours, stopping the reaction, and discharging at normal temperature.

Example 4

The operation steps are as follows:

step 1 a modified nanosilica functional monomer was prepared as in example 1.

Step 2, weighing 40g of deionized water in a beaker, adding 1g of sodium dodecyl sulfate and 0.5g of OP-10 under stirring, mixing for 20 minutes, adding 8g of butyl acrylate and 2g of lauryl methacrylate, and emulsifying for 5-30 minutes at a rotating speed of 5000r/min to obtain emulsion. 10g of deionized water is weighed, 0.06g of initiator potassium persulfate is added, and the mixture is stirred uniformly to prepare an initiator solution.

And 3, adding 0.3g of prepared modified nano silicon dioxide particles and 0.04g of trihydroxymethyl propyl triacrylate into the emulsion, uniformly stirring, then transferring into a reaction kettle, starting stirring, heating to 70 ℃, replacing air, continuously introducing nitrogen, adding 7g of the initiator solution, and reacting at constant temperature for 3 hours.

And 4, dissolving 1.2g of acrylic acid in 10g of deionized water, adding the rest of initiator solution, uniformly stirring, dropwise adding into the emulsion, finishing dropwise adding within 0.5 hour, continuing to perform constant-temperature reaction for 2-3 hours, stopping the reaction, and discharging at normal temperature.

Comparative example 1

The operation steps are as follows:

step 1, weighing 50g of deionized water in a beaker, adding 1g of sodium dodecyl sulfate and 0.5g of OP-10 under stirring, mixing for 20 minutes, adding 18g of 2-ethylhexyl acrylate, and emulsifying for 5-30 minutes at a rotating speed of 5000r/min to obtain emulsion. 10g of deionized water was weighed, and 0.06g of 2-azo (2-amidinopropane) dihydrochloride (V50) as an initiator was added thereto and stirred uniformly to prepare an initiator solution.

And 2, adding 0.03g of tri-hydroxy methyl propyl triacrylate into the emulsion, uniformly stirring, then transferring into a reaction kettle, starting stirring, heating to 60 ℃, replacing air, continuously introducing nitrogen, and adding 7g of the initiator solution for constant-temperature reaction for 3 hours.

And 3, dissolving 1.4g of acrylic acid in 10g of deionized water, adding the rest of initiator solution, uniformly stirring, dropwise adding into the emulsion, finishing dropwise adding within 0.5 hour, continuing to perform constant-temperature reaction for 2-3 hours, stopping the reaction, and discharging at normal temperature.

Comparative example 2

The demulsifier used in the field of the Shengli oil field estuary oil extraction plant is polyoxyethylene polyoxypropylene ether and is provided by the Shengli chemical industry.

Application example 1

The demulsifiers of examples 1-4 and comparative examples 1-2 were used to evaluate the demulsification performance of crude oil emulsion at the east-east joint station of the oil works at the estuary of the victory oil field, and the demulsification performance of the crude oil demulsifier was evaluated by an evaluation method specified by the petroleum and natural gas industry standard SY-T5281-2000 using a performance detection method (bottle test method), wherein the field demulsification temperature was 72℃and the test temperature was reduced by 6℃than the field temperature.

The results are shown in Table 1 below.

TABLE 1 demulsification Performance evaluation results

Experiments prove that under the condition that the actual demulsification temperature is reduced by 6 ℃ compared with the on-site demulsification temperature, the demulsification effect of the demulsifier prepared by the method is obviously higher than that of the acrylate demulsifier and the polyether demulsifier without modified nano silicon dioxide particles, and the demulsification speed and the demulsification efficiency are improved. Among them, the demulsification effect of example 2, example 3 and example 4 is superior to that of the demulsifier used in the field of the east joint station.

The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (10)

1. A demulsifier containing nano-particle structure is prepared from hydrophobic monomer, hydrophilic monomer, nano-functional monomer and cross-linking monomer.

2. The demulsifier of claim 1, wherein:

the hydrophobic monomer is acrylic ester, preferably at least one of butyl acrylate, methyl methacrylate, lauryl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, dodecyl acrylate and stearyl acrylate; and/or the number of the groups of groups,

the hydrophilic monomer is at least one of acrylic acid, methacrylic acid and maleic anhydride; and/or the number of the groups of groups,

the crosslinkable monomer is olefin containing two or more unsaturated double bonds, preferably at least one of diethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol dimethacrylate, butanediol diacrylate, acrylamide, N-methylolacrylamide, N' -methylenebisacrylamide and divinylbenzene; and/or the number of the groups of groups,

the nano functional monomer is modified nano silicon dioxide.

3. The demulsifier of claim 1, wherein:

based on 100 parts of the total weight of the reaction monomers, the hydrophobic monomer is 70-98 parts, preferably 80-95 parts; 1 to 20 parts of hydrophilic monomer, preferably 5 to 10 parts; the nanometer functional monomer is 0.1-10 parts, preferably 0.5-5 parts; the crosslinkable monomer is 0.001 to 3 parts, preferably 0.1 to 0.5 part.

4. The demulsifier as claimed in claim 2, wherein:

the modified nano silicon dioxide is obtained by adopting a modifier to carry out surface modification on nano silicon dioxide particles, wherein the modifier is vinyl silanes, preferably vinyl triethoxysilane.

5. The method of preparing a demulsifier according to any one of claims 1 to 4, comprising reacting a hydrophobic monomer, a hydrophilic monomer, a nano-functional monomer, a crosslinkable monomer, an emulsifier and an initiator to obtain the demulsifier.

6. The preparation method according to claim 5, characterized by comprising the steps of:

(1) Dissolving an emulsifying agent in a solvent, and adding a hydrophobic monomer for emulsification to obtain emulsion;

(2) Adding a nano functional monomer and a crosslinkable monomer into the emulsion obtained in the step (1), and adding part of initiator solution under inert atmosphere for reaction;

(3) Adding the hydrophilic monomer solution and the residual initiator solution into the reaction system in the step (2) together, continuing the constant-temperature reaction, and stopping the reaction to obtain the demulsifier.

7. The method of manufacturing according to claim 6, wherein:

in the step (2), the reaction temperature is 50-80 ℃ and the reaction time is 2-4 hours;

in the step (3), the reaction time is 2.5-3.5 hours.

8. The method of manufacturing according to claim 6, wherein:

the emulsifier is at least one of alkylphenol ethoxylates, petroleum sulfonate, sodium dodecyl sulfonate, sodium alkylbenzenesulfonate and sodium dodecyl sulfate;

the initiator is at least one of inorganic peroxy initiator, water-soluble oxidation-reduction system and water-soluble azo compound.

9. The method of manufacturing according to claim 6, wherein:

the initiator is 0.1-1% of the total mass of the hydrophilic monomer and the hydrophobic monomer, preferably 0.2-0.6%;

the emulsifier is 2-15% of the total mass of hydrophilic monomer and hydrophobic monomer, preferably 5-10%;

the solvent is water, and the solvent is 2-6 times, preferably 3-4 times, of the total mass of the reaction monomers.

10. Use of a demulsifier according to any one of claims 1 to 4 or obtainable by a process according to any one of claims 5 to 9 in the demulsification of crude oil.