CN111454744B

CN111454744B - Demulsifier modified net film and preparation method and application thereof

Info

Publication number: CN111454744B
Application number: CN201910058648.7A
Authority: CN
Inventors: 靳健; 秦俊岭
Original assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Current assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date: 2019-01-22
Filing date: 2019-01-22
Publication date: 2022-02-11
Anticipated expiration: 2039-01-22
Also published as: CN111454744A

Abstract

The invention discloses a modified net membrane of a demulsifier, a preparation method and application thereof. The modified net membrane of the demulsifier comprises a porous net membrane and a demulsifier molecular brush, wherein the demulsifier molecular brush is composed of demulsifier molecules anchored on the surface of the porous net membrane. The preparation method comprises the following steps: the demulsifier modified net film has larger pore diameter, improves the oil-water flux, enhances the oil-water treatment efficiency, can be used for oil-water separation devices for crude oil demulsification in the petrochemical industry, such as three-phase separators, oil skimming tanks, settling tanks, air flotation and the like, can be repeatedly used, reduces the using amount of the demulsifier, and avoids the demulsifier from entering an oil phase and a water phase to influence the crude oil refining and wastewater treatment processes; meanwhile, the manufacturing process is simple and the cost is low.

Description

Demulsifier modified net film and preparation method and application thereof

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a modified net membrane of a demulsifier for demulsification of crude oil, a preparation method of the modified net membrane, and application of the modified net membrane in the field of oil-water separation.

Background

In both oil extraction and oil refining, crude oil is dehydrated, and a commonly used method is to add a demulsifier to the crude oil. The demulsifier molecules are rapidly diffused to an oil-water interface under the action of heat energy and mechanical energy, an interface film formed by a natural emulsifier on the oil-water interface is damaged, the oil-water interface is unstable, water drops or oil drops are mutually condensed and enlarged, and the oil and water phases are separated by virtue of density difference. The demulsifier has fast dehydration, is particularly suitable for ocean oil fields with high water content of produced liquid, but has high cost because of large liquid production amount and the need of adding a large amount of demulsifier for oil removal. In addition, a large amount of demulsifiers enter the petroleum refining link along with the oil phase, and influence on the petroleum refining process is possibly caused; the demulsifier entering the water phase increases the difficulty of wastewater treatment. Thus, reducing the amount of demulsifier used, finding alternative techniques is a long and arduous task.

In recent years, microfiltration membranes and nanofiltration membranes are beginning to be applied to small scales of oil fields, and the microfiltration membranes and the nanofiltration membranes are used for intercepting fine emulsified oil drops by means of the principle of pore size screening so as to separate oil from water. Although the manufacturing cost of the microfiltration membrane and the nanofiltration membrane is high, the microfiltration membrane and the nanofiltration membrane can be repeatedly used, the use of chemical additives is reduced, and certain significance in energy conservation and environmental protection is achieved. But the method has small aperture, low membrane flux and low efficiency of treating oil-water mixed liquid, and cannot be used as the mainstream technology of oil-water separation in the petrochemical industry.

The demulsifier is used in the oil exploitation and refining processes, and can quickly demulsify emulsified oil drops or emulsified water drops to promote the separation of crude oil and water. Although this process is simple and effective, the large amount of demulsifier is consumed by the petroleum industry because of the large amount of oil-water mixture that is produced or refined. And the demulsifier can not be recycled, and can enter the next process flow along with the crude oil or water, thereby influencing the refining of the crude oil or the treatment of oily wastewater and causing the problem of environmental protection. Therefore, how to get rid of the dependence on the demulsifier is always a technical development direction. The microfiltration membrane or the nanofiltration membrane is used for oil-water separation and can be repeatedly used, but the separation membrane has high manufacturing cost, low flux and easy pollution, and is not suitable for large-scale popularization and application.

Disclosure of Invention

The invention aims to combine the advantages of a demulsifier and the advantages of a filter membrane and provide a demulsifier modified net membrane and a preparation method thereof so as to overcome the defects in the prior art.

The invention also aims to provide application of the modified omentum of the demulsifier in the field of oil-water separation.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a demulsifier modified omentum, which comprises a porous omentum and a demulsifier molecular brush, wherein the demulsifier molecular brush is composed of demulsifier molecules anchored on the surface of the porous omentum.

In some embodiments, the breaker molecule comprises any one or a combination of two or more of polyoxyethylene polyoxypropylene alkyl alcohol, polyoxyethylene polyoxypropylene propylene glycol ether, polyoxyethylene alkylphenol formaldehyde resin, polyoxyethylene polyoxypropylene ethylenediamine, polyoxyethylene polyoxypropylene diethylenetriamine, polyoxyethylene polyoxypropylene pentaethylenehexamine, and polyoxypropylene phenolic resin.

The embodiment of the invention also provides a preparation method of the modified net membrane of the demulsifier, which comprises the following steps: and at least adopting a physical coating and/or chemical grafting mode to anchor the demulsifier molecules on the surface of the porous net membrane through a bonding material, thereby forming a demulsifier molecule brush consisting of the demulsifier molecules on the surface of the porous net membrane to obtain the demulsifier modified net membrane.

The embodiment of the invention also provides the demulsifier modified omentum prepared by the method.

The embodiment of the invention also provides application of the demulsifier modified omentum in the field of oil-water separation.

Correspondingly, the embodiment of the invention also provides an oil-water separation device, which comprises:

a fluid channel; and

and the demulsifier modified omentum is arranged in the fluid channel.

Correspondingly, the embodiment of the invention also provides an oil-water separation method, which comprises the following steps:

providing the demulsifier modified net film;

and (3) enabling the emulsified oil-water mixed system to pass through the demulsifier modified net film to realize oil-water separation.

Compared with the prior art, the invention has the advantages that:

1) the modified net membrane of the demulsifier provided by the invention has the advantages of simple manufacturing process, easily obtained raw materials and low cost;

2) the demulsifier modified net film provided by the invention has the function of the demulsifier, and the demulsifier is anchored on the net film, cannot run off along with oil and water, can be repeatedly used, reduces the using amount of the demulsifier, and is economic and environment-friendly;

3) on the premise of playing the function of the demulsifier, the modified net film of the demulsifier provided by the invention properly increases the aperture of the net film, only enables floating oil to be intercepted, and dispersed oil drops, emulsified oil and dissolved oil can freely pass through and interact with the molecular brush of the demulsifier to be demulsified, thereby improving the oil-water flux and enhancing the oil-water treatment efficiency;

4) the invention integrates the advantages of the demulsifier and the net film, can be used for oil-water separation devices aiming at crude oil demulsification, such as a three-phase separator, an oil skimming tank, a settling tank, air flotation and the like in the petrochemical industry, reduces the possibility that the demulsifier enters an oil phase, a water phase and a downstream process flow, and avoids the influence of the demulsifier on petroleum refining and wastewater treatment processes.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention.

The principle of the scheme may be as follows: the inventor synthesizes the advantages of the demulsifier and the separation membrane and provides a thought of coating or chemically grafting the demulsifier on the surface of the porous net membrane. And modifying the demulsifier on the porous net membrane to form a demulsifier molecular brush, and contacting or repeatedly contacting the emulsified oil water with the demulsifier molecular brush to cause demulsification. The demulsifier is fixed on the porous net film and can not run off along with oil and water, and can be used repeatedly. The aperture of the porous net film of the fixed demulsifier is larger than the size of dispersed oil drops, so that the sufficient oil-water flux is ensured, and the demulsification efficiency is improved. Based on the above thought, the inventor anchors the demulsifier molecules on the porous net membrane with larger pore diameter to form the demulsifier molecular brush.

The technical solution, its implementation and principles, etc. will be further explained as follows.

In one aspect of the technical scheme, the invention relates to a demulsifier modified omentum, which comprises a porous omentum and a demulsifier molecular brush, wherein the demulsifier molecular brush is composed of demulsifier molecules anchored on the surface of the porous omentum.

Further, the demulsifier molecule is a nonionic polyether compound, and specifically includes one or a combination of two or more of polyoxyethylene polyoxypropylene alkyl alcohol, polyoxyethylene polyoxypropylene propylene glycol ether, polyoxyethylene alkylphenol formaldehyde resin, polyoxyethylene polyoxypropylene ethylenediamine, polyoxyethylene polyoxypropylene diethylenetriamine, polyoxyethylene polyoxypropylene pentaethylenehexamine, and polyoxypropylene phenol resin, but is not limited thereto.

Further, the demulsifier molecules are modified on the surface of the porous net membrane and play a role in demulsifying when the emulsified oil-water mixture passes through.

Furthermore, a certain specific group or chain segment on the demulsifier molecule is anchored on the porous net membrane through a physical and chemical reaction, other molecular chain segments are free, and in an oil-water mixture, the free demulsifier molecular chains are in contact with emulsified oil drops to break the oil-water interface so as to demulsify the emulsified oil drops.

In some embodiments, the breaker molecules are anchored to the porous omentum surface via a binding material.

Further, the adhesive material may be an anti-corrosive primer, a coupling agent, etc., but is not limited thereto.

Further, the anti-corrosion primer includes any one or a combination of two or more of perchloroethylene anti-corrosion paint, chlorinated rubber anti-corrosion paint, high chlorinated polyethylene anti-corrosion paint, epoxy anti-corrosion paint, polyurethane anti-corrosion paint, acrylic acid anti-corrosion paint, and the like, but is not limited thereto.

Further, the coupling agent includes any one or a combination of two or more of a lignin coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, an aluminum-zirconate coupling agent, a phosphate coupling agent, and the like, but is not limited thereto.

In some embodiments, the material of the porous mesh film includes, but is not limited to, metal mesh, non-woven fabric, various types of fiber membranes, and the like.

In some embodiments, the porous mesh membrane has a relatively large pore size of about 100 to 1000 μm. Unlike a common oil-water separation filter membrane, the porous net membrane has large pore size, so that only floating oil is trapped, and dispersed oil drops, emulsified oil and dissolved oil can freely pass through and interact with a demulsifier molecular brush to be demulsified.

The demulsifier modified omentum provided by the invention anchors demulsifier molecules on a porous omentum with a larger aperture to form a demulsifier molecular brush, the demulsifier molecular brush ensures the demulsification effect of crude oil, and the larger aperture of the omentum improves the oil-water flux.

In some embodiments, the calculation is in unit areaThe content of the molecules of the demulsifier modified omentum surface demulsifier is 0.0004g/cm²～0.8g/cm²。

As another aspect of the technical scheme of the invention, the invention also relates to a preparation method of the modified omentum of the demulsifier, which comprises the following steps: and at least adopting a physical coating and/or chemical grafting mode to anchor the demulsifier molecules on the surface of the porous net membrane through a bonding material, thereby forming a demulsifier molecule brush consisting of the demulsifier molecules on the surface of the porous net membrane to obtain the demulsifier modified net membrane.

In some embodiments, the bonding material may be, but is not limited to, an anti-corrosive primer, a coupling agent, and the like.

In some embodiments, the preparation method may specifically include: at least mixing demulsifier molecules and anticorrosive primer uniformly to form slurry, transferring the slurry to the surface of the porous net film and curing to prepare the demulsifier modified net film;

or dissolving demulsifier molecules in a solvent to form demulsifier solution, treating the porous net membrane by using a coupling agent, transferring the demulsifier solution to the surface of the porous net membrane, and anchoring the demulsifier molecules on the surface of the porous net membrane to prepare the demulsifier modified net membrane.

Further, the preparation method specifically comprises the following steps: and dissolving demulsifier molecules in a solvent, and then uniformly mixing with the anticorrosive primer to form the slurry.

Further, the curing temperature is between room temperature and 100 ℃, and the curing time is 1-24 hours.

Wherein, as a more specific embodiment, the preparation method may comprise: (1) dissolving a demulsifier in a solvent, and uniformly mixing the demulsifier with the anticorrosive primer to obtain demulsifier slurry; transferring the demulsifier slurry to the surface of the porous net film by brushing, spraying, dip-coating and other methods, and heating and curing to form a demulsifier modified net film;

or (2) dissolving the demulsifier in a solvent to form a demulsifier solution; cleaning the porous net membrane with an organic solvent, airing, then immersing in a coupling agent solution for surface treatment, then immersing in a demulsifier solution, and forming the demulsifier modified net membrane after 1-24 hours at room temperature-100 ℃.

Further, the density of the demulsifier grafted to the surface of the porous membrane can be adjusted by controlling the amount of the demulsifier transferred to the surface of the porous membrane. Specifically, the mass concentration of the slurry or the demulsifier solution is 0.01-20 wt%.

Further, the solvent includes any one or a combination of two or more of methanol, ethanol, propanol, isopropanol, butanol, octanol, ethylene glycol, benzene, toluene, xylene, acetone, butanone, water, and the like, but is not limited thereto.

Further, the temperature of the surface treatment is room temperature to 100 ℃, and the time is 1-24 hours.

Furthermore, the method for transferring the demulsifier slurry and the demulsifier solution on the surface of the porous net membrane can use methods such as brushing, spraying, dipping and the like, and the process is simple.

Further, in order to accelerate the curing or grafting reaction of the demulsifier and the porous net film, heating and drying can be carried out.

As another aspect of the present invention, it also relates to the demulsifier-modified omentum prepared by the foregoing method.

The embodiment of the invention also provides application of the modified net film of the demulsifier in the field of oil-water separation, and the modified net film of the demulsifier can be used in oil-water separation devices in the petrochemical industry.

Accordingly, another aspect of the embodiments of the present invention also provides an oil-water separation device, including:

a fluid channel; and

and the demulsifier modified omentum is arranged in the fluid channel.

Further, the oil-water separation device includes, but is not limited to, an oil-water separation device for crude oil demulsification, such as a three-phase separator, a skimming tank, a settling tank, or an air flotation device.

Correspondingly, another aspect of the embodiments of the present invention further provides an oil-water separation method, including:

providing the demulsifier modified net film;

and (3) passing the emulsified oil-water mixed system through the demulsifier modified net film to enable crude oil in the emulsified oil-water mixed system to interact with the demulsifier molecular brush layer to demulsify, thereby realizing oil-water separation.

Further, the emulsified oil-water mixed system comprises crude oil.

In the oil-water separation method, the oil-water mixing system is repeatedly contacted with the demulsifier modified net film to achieve rapid demulsification.

By the technical scheme, the modified net film of the demulsifier has larger aperture, improves the oil-water flux, enhances the oil-water treatment efficiency, can be used for an oil-water separation device for crude oil demulsification, such as a three-phase separator, a skimming tank, a settling tank, air flotation and the like in the petrochemical industry, can be repeatedly used, and reduces the using amount of the demulsifier so as to prevent the demulsifier from entering an oil phase and a water phase to influence the crude oil refining and wastewater treatment processes; meanwhile, the manufacturing process is simple and the cost is low.

The technical solution of the present invention is explained in more detail below with reference to several preferred embodiments.

Example 1

(1) Dissolving 1g of demulsifier polyoxyethylene polyoxypropylene alkyl alcohol in 19g of xylene solvent to prepare 5 wt% demulsifier solution; and adding 10g of perchloroethylene anticorrosive paint into the demulsifier solution, and uniformly stirring for later use.

(2) Cleaning stainless steel mesh (aperture 300 μm) with petroleum ether, cleaning for 3 times, and air drying.

(3) Brushing the anticorrosive paint solution prepared in the step (1) on the stainless steel net film prepared in the step (2), and naturally drying.

Tests prove that the modified omentum of the demulsifier prepared by the embodiment has demulsification effect on emulsified oil water.

Example 2

(1) Dissolving 2g of demulsifier polyoxyethylene alkylphenol formaldehyde resin in 18g of xylene solvent to prepare 10 wt% demulsifier solution; and adding 10g of polyurethane anticorrosive paint into the demulsifier solution, and uniformly stirring for later use.

(2) The glass fiber web (average pore size 200 μm) was washed with acetone, 3 times, and dried.

(3) And (3) immersing the glass fiber net in the step (2) into the anticorrosive paint solution in the step (1), immersing and taking out, repeating for 3 times, and naturally drying.

Example 3

(1) Dissolving 0.002g of demulsifier polyoxyethylene polyoxypropylene pentaethylenehexamine into 19.998g of xylene solvent to prepare 0.01 wt% demulsifier solution; and adding 10g of acrylic acid anticorrosive paint into the demulsifier solution, and uniformly stirring for later use.

(2) The nonwoven webs (pore size 100 μm) were washed with acetone and toluene, 3 times each, and dried.

(3) And (3) immersing the non-woven fabric in the step (2) into the anti-corrosion paint solution in the step (1), immersing and taking out for three times, and naturally airing.

Example 4

(1) 1g of demulsifier polyoxyethylene polyoxypropylene alkyl alcohol is dissolved in 19g of methanol solvent to prepare 5 wt% demulsifier solution, and the demulsifier solution is placed in a water bath at 80 ℃.

(2) Silane coupling agent, water and methanol were mixed in a ratio of 1: 2: 7, preparing a coupling agent solution, and placing the coupling agent solution in a water bath at the temperature of 80 ℃; the stainless steel net (aperture 300 μm) cleaned with petroleum ether is immersed in the coupling agent solution for 24 hours, taken out, washed with anhydrous methanol for 3 times, and dried.

(3) And (3) immersing the stainless steel mesh membrane prepared in the step (2) into the demulsifier solution in the step (1), immersing for 12 hours at 80 ℃, taking out, washing for 3 times by using anhydrous methanol, and airing.

Example 5

(1) 4g of demulsifier polyoxyethylene alkylphenol formaldehyde resin is dissolved in 16g of xylene solvent to prepare 20wt% demulsifier solution, and the solution is placed in a water bath at 70 ℃.

(2) Mixing titanate coupling agent, water and ethanol according to the proportion of 1: 1: 8, preparing a coupling agent solution, and placing the coupling agent solution in a water bath at 70 ℃; the glass fiber net (average pore diameter 200 μm) cleaned with acetone was immersed in the coupling agent solution for 24 hours, taken out, washed with anhydrous methanol 3 times, and dried.

(3) And (3) immersing the glass fiber net prepared in the step (2) into the demulsifier solution in the step (1), immersing for 1 hour at 100 ℃, taking out, washing for 3 times by using dimethylbenzene, and airing.

Example 6

(1) 0.2g of demulsifier polyoxyethylene polyoxypropylene pentaethylenehexamine is dissolved in 19.8g of xylene solvent to prepare 1 wt% demulsifier solution, and the solution is placed in a water bath at 90 ℃.

(2) An aluminum-zirconate coupling agent, water and butanol were mixed in a ratio of 1: 3: 16, preparing a coupling agent solution, and placing the coupling agent solution in a water bath at 90 ℃; the nonwoven web (pore size 100 μm) cleaned with acetone and toluene was immersed in the coupling agent solution for 48 hours, taken out, rinsed 3 times with acetone, and air dried.

(3) And (3) immersing the non-woven fabric in the step (2) into the demulsifier solution in the step (1), immersing for 24 hours at room temperature, taking out, and washing for 3 times by using dimethylbenzene.

Example 7

(1) 0.5g of demulsifier polyoxypropylene phenolic resin is dissolved in 19.5g of xylene solvent to prepare 2.5 wt% demulsifier solution.

(2) Mixing lignin coupling agent, water and isopropanol according to a ratio of 2: 3: 15 to prepare a coupling agent solution; the stainless steel net (aperture 200 μm) cleaned by acetone is immersed in the coupling agent solution for 24 hours, taken out and washed by acetone for 3 times, and then placed in a vacuum oven for drying at 100 ℃.

(3) And (3) soaking the stainless steel net in the step (2) into the demulsifier solution in the step (1), soaking at room temperature for 24 hours, taking out, washing with xylene for 3 times, and drying in a vacuum oven at 100 ℃.

In addition, the inventor also refers to the mode of example 1-example 7, tests are carried out by using other raw materials and conditions listed in the specification, and the modified net film of the demulsifier which has demulsification effect on emulsified oil water, has high oil water flux and high oil water treatment efficiency is also prepared.

It should be understood that the above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. All the technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.

Claims

1. A preparation method of a demulsifier modified omentum is characterized by comprising the following steps:

at least mixing emulsion breaker molecules and the anticorrosive primer uniformly to form slurry, transferring the slurry to the surface of the porous net film to anchor the emulsion breaker molecules on the surface of the porous net film, and curing to form an emulsion breaker molecule brush consisting of the emulsion breaker molecules on the surface of the porous net film to prepare an emulsion breaker modified net film;

or dissolving demulsifier molecules in a solvent to form demulsifier solution, performing surface treatment on the porous net membrane by using a coupling agent at room temperature to 100 ℃ for 1-24 hours, transferring the demulsifier solution to the surface of the porous net membrane to anchor the demulsifier molecules on the surface of the porous net membrane, and thus forming a demulsifier molecule brush consisting of the demulsifier molecules on the surface of the porous net membrane to prepare a demulsifier modified net membrane;

wherein the concentration of the slurry or the demulsifier solution is 0.01-20 wt%; the demulsifier molecule is selected from one or a combination of more than two of polyoxyethylene polyoxypropylene alkyl alcohol, polyoxyethylene alkylphenol formaldehyde resin, polyoxyethylene polyoxypropylene ethylenediamine, polyoxyethylene polyoxypropylene diethylenetriamine, polyoxyethylene polyoxypropylene pentaethylenehexamine and polyoxypropylene phenolic resin, and the anticorrosion primer is selected from one or a combination of more than two of perchloroethylene anticorrosion paint, chlorinated rubber anticorrosion paint, high chlorinated polyethylene anticorrosion paint, epoxy anticorrosion paint, polyurethane anticorrosion paint and acrylic anticorrosion paint;

the modified net membrane of the demulsifier comprises a porous net membrane and a demulsifier molecular brush, wherein the demulsifier molecular brush is composed of an anchorThe demulsifier molecules fixed on the surface of the porous omentum; the pore diameter of the porous net membrane is 100-1000 mu m, and the content of demulsifier molecules on the surface of the demulsifier modified net membrane is 0.0004g/cm calculated by unit area²～0.8g/ cm²。

2. The method of claim 1, wherein: the molecule of the demulsifier is polyoxyethylene polyoxypropylene propylene glycol ether.

3. The method of claim 1, wherein: the coupling agent is selected from any one or the combination of more than two of lignin coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconate coupling agent, aluminum-zirconate coupling agent and phosphate coupling agent.

4. The method according to claim 1, comprising: and dissolving demulsifier molecules in a solvent, and then uniformly mixing with the anticorrosive primer to form the slurry.

5. The method of claim 1, wherein: the curing temperature is between room temperature and 100 ℃, and the curing time is 1 to 24 hours.

6. The method of claim 4, wherein: the solvent is selected from any one or combination of more than two of methanol, ethanol, propanol, isopropanol, butanol, octanol, glycol, benzene, toluene, xylene, acetone, butanone and water.

7. The production method according to claim 1, characterized by comprising: and transferring the slurry or the demulsifier solution to the surface of the porous net film by brushing, spraying or dipping.

8. The method of claim 1, wherein: the porous net film is selected from metal net, non-woven fabric or fiber film.

9. Use of the demulsifier-modified omentum prepared by the method of any one of claims 1 to 8 in the field of oil and water separation.

10. An oil-water separator, characterized by comprising:

a fluid channel; and

a demulsified modified omentum prepared by the method of any one of claims 1-8 disposed in the fluid passageway.

11. The oil-water separator according to claim 10, wherein: the oil-water separation device is selected from a three-phase separator, an oil skimming tank, a settling tank or an air floatation device.

12. An oil-water separation method is characterized by comprising the following steps:

providing a demulsifier-modified omentum prepared by the method of any of claims 1-8;

13. The oil-water separation method according to claim 12, characterized in that: the emulsified oil-water mixed system is crude oil.