阅读说明：本技术 一种生物发酵纳米酶调堵驱油剂及其制备方法 (Biological fermentation nano-enzyme regulated and blocked oil displacement agent and preparation method thereof ) 是由 夏文杰 于 2021-09-28 设计创作，主要内容包括：本发明公开了一种生物发酵纳米酶调堵驱油剂及其制备方法,属于油气开发技术领域。生物发酵纳米酶调堵驱油剂,包括以下组分：生物发酵制备生物活性分子、表面活性剂、表面改性二氧化硅及醇；其制备方法：包括以下步骤：在10℃-40℃的水中,将生物发酵制备生物活性分子按照配制比例配制成水溶液,并充分搅拌；再按照配制比例加入表面改性二氧化硅,并充分搅拌；然后加入醇,并充分搅拌；最后加入表面活性剂,充分搅拌,即可。在低浓度或低温下,它在油藏中起到降低界面张力、增溶、乳化等效果；在高温高浓度下,油藏中封堵高渗层、底水和边水；同时它也可以实现油藏原位堵水,可应用于多种油藏,可大规模应用于油田增产领域。(The invention discloses a biological fermentation nano-enzyme regulating and plugging oil displacement agent and a preparation method thereof, belonging to the technical field of oil and gas development. The biological fermentation nano enzyme regulating and plugging oil displacement agent comprises the following components: preparing bioactive molecules, a surfactant, surface modified silicon dioxide and alcohol by biological fermentation; the preparation method comprises the following steps: the method comprises the following steps: preparing bioactive molecules prepared by biological fermentation into aqueous solution according to a preparation proportion in water with the temperature of 10-40 ℃, and fully stirring; adding the surface modified silicon dioxide according to the preparation proportion, and fully stirring; then adding alcohol and fully stirring; and finally, adding a surfactant, and fully stirring. At low concentration or low temperature, it has the effects of reducing interfacial tension, solubilizing, emulsifying and the like in an oil reservoir; plugging a high-permeability layer, bottom water and side water in an oil reservoir at high temperature and high concentration; meanwhile, the method can realize in-situ water shutoff of the oil reservoir, can be applied to various oil reservoirs, and can be applied to the field of oil field production increase in a large scale.)

1. A bio-fermentation nano enzyme regulating and plugging oil displacement agent is characterized in that:

the bio-fermentation nano enzyme regulating and plugging oil displacement agent comprises the following components: biologically fermenting to prepare bioactive molecule, surfactant, surface modified silicon dioxide and alcohol.

2. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 1, which is characterized in that:

the bio-fermentation nano enzyme regulating and plugging oil displacement agent comprises the following components in percentage by weight:

3. the bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 2, characterized in that:

the bioactive molecule prepared by biological fermentation is sugar ester or lipopeptide.

4. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 3, characterized in that:

the surfactant is one or more of alcamines, phospholipids, fatty alcohol-polyoxyethylene ether sodium sulfate and betaine.

5. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 3, characterized in that:

the surface modified silicon dioxide is a mixture of conventional silicon dioxide and hydrophobic modified silicon dioxide, and the particle size range of the surface modified silicon dioxide is between 5nm and 70 nm.

6. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 3, characterized in that:

the alcohol is one or more of methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, butanediol, pentanediol, cyclohexanol and pentanol.

7. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 3, characterized in that:

the biological fermentation preparation of bioactive molecules is obtained by separating fermentation liquor products fermented by microbial strains;

wherein the microbial strain comprises one or more of Pseudomonas, Bacillus, Acinetobacter, Candidas, Rhodococcus, and Moesziomyes.

8. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 7, which is characterized in that:

the culture medium for fermenting the microbial strains comprises the following components in percentage by weight:

the pH value of a culture medium for fermenting the microbial strains is 6-8;

the conditions for the fermentation of the microbial strains are as follows:

the fermentation temperature is 20-37 ℃, the stirring speed is 100-300 rpm, the ventilation quantity is 0.1-0.6 vvm, and the fermentation time is 24-90 h.

9. The bio-fermentation nano-enzyme regulated and blocked oil-displacing agent according to claim 7, which is characterized in that:

the culture medium for fermenting the microbial strains comprises the following components in percentage by weight:

the pH value of a culture medium for fermenting the microbial strains is 6-7;

the conditions for the fermentation of the microbial strains are as follows:

the fermentation temperature is 20-37 ℃, the stirring speed is 100-300 rpm, the ventilation quantity is 0.1-0.6 vvm, and the fermentation time is 24-48 h.

10. A preparation method of a biological fermentation nano enzyme regulating and plugging oil displacement agent is characterized by comprising the following steps:

the method comprises the following steps:

preparing bioactive molecules prepared by biological fermentation into aqueous solution according to a preparation proportion in water with the temperature of 10-40 ℃, and fully stirring; adding the surface modified silicon dioxide according to the preparation proportion, and fully stirring; then adding alcohol and fully stirring; and finally, adding a surfactant, and fully stirring.

Technical Field

The invention belongs to the technical field of oil and gas development, and particularly relates to a biological fermentation nano-enzyme regulating and plugging oil displacement agent and a preparation method thereof.

Background

With the continuous development of oil and gas fields, the high water content of oil well produced liquid is a common problem in the development process, the contradiction between layers and in layers is prominent, the heterogeneity is enhanced, so that phenomena such as dominant channels, even water coning or water channeling and the like can be formed in the formation, the phenomenon that the oil well is exposed to water or flooded in advance is caused, the water drive efficiency is low or invalid circulation is formed, and the final recovery ratio is low.

In order to solve the above problems, the oil layer profile control technology is more and more important in oil field development. The profile control and water shutoff is to improve the sweep coefficient of water injection by plugging a high permeable stratum so as to achieve the purpose of improving the recovery ratio. The profile control and water plugging oil displacement agent plays a determining role in the profile control and water plugging effects.

However, the existing profile control and water shutoff technology still has some problems. Such as: in actual use, the existing profile control agent often has the problems of insufficient plugging strength, small plugging radius and no plugging formation in a target area due to high underground temperature, high salinity or poor seepage capability of an oil reservoir, so that the plugging efficiency is low, the plugging effective period is short, and the plugging failure is caused. Especially for low permeability oil reservoir, especially for low permeability, the injection capacity of the plugging and oil-displacing agent is a very large restriction condition. Meanwhile, if edge water or bottom water exists, the strength is not enough, and effective plugging is not formed. Or the existing cement water shutoff agent has high strength, but has operation risks of fast solidification, difficult blockage removal and the like.

For example, the chinese invention patent, application No.: CN202011353845.0, publication No.: CN112480895A discloses a pH response type oil displacement agent composition, an oil displacement agent, a preparation method and an application thereof, and the technical scheme is as follows: "the oil-displacing agent composition comprises chitosan and a surfactant; the mass ratio of the two is (5-8): (2-5). The oil displacement agent comprises chitosan, a surfactant, a pH regulator and water; the mass ratio of the chitosan to the surfactant is (5-8): (2-5); the total mass of the chitosan and the surfactant accounts for 0.05-0.15 wt% of the mass concentration of the total oil displacement agent; the pH value of the oil displacement agent is 6.33-6.58%. But there are serious problems: due to adsorption retention of the surfactant in the porous medium, the smaller pore throat is blocked, so that the permeability of the reservoir is reduced, and the environment of the reservoir is polluted.

Therefore, it is very necessary to provide an environment-friendly type profile control and plugging oil displacement agent which has high profile control and water plugging effects, strong reservoir universality (especially high-temperature and high-salinity reservoirs), high injectivity and adjustable strength and curing time. Meanwhile, the emulsion has the function of slowly releasing the surfactant after crosslinking or curing, and achieves the effects of emulsifying, reducing interfacial tension and the like; finally, the oil recovery efficiency is improved.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems in the prior art, the invention provides a bio-fermentation nano-enzyme regulating and plugging oil-displacing agent and a preparation method thereof, wherein the prepared oil-displacing agent has certain fluid property at low temperature, is expressed as a fluid with extremely strong emulsifying capacity and reduced interfacial tension, forms a network structure of unsaturated bond polymerization and vitrified metal crosslinking at high temperature, is tightly combined with stratum minerals, has strong water molecule wrapping capacity, strong rigidity and low dehydration rate; the emulsion slowly releases surface active substances at high temperature for a long time, and has the functions of emulsifying capacity and reducing interfacial tension; therefore, the high-regulating-blocking oil displacement agent not only has the capacity of improving swept volume, but also has the function of improving oil washing efficiency.

2. Technical scheme

In order to solve the above problems, the present invention adopts the following technical solutions.

A biological fermentation nano enzyme regulating and plugging oil displacement agent comprises the following components: biologically fermenting to prepare bioactive molecule, surfactant, surface modified silicon dioxide and alcohol. The components are mixed according to a certain proportion, and form flowable liquid at low temperature or low concentration, and the liquid has the functions of solubilizing, emulsifying, reducing interfacial tension and the like; at high temperatures or high concentrations, colloids of different strengths can be formed.

In the bio-fermentation nano-enzyme plugging oil-displacing agent, the bio-fermentation nano-enzyme plugging oil-displacing agent comprises the following components in percentage by weight:

in the bio-fermentation nano enzyme regulated and blocked oil displacement agent, the bio-fermentation prepared bioactive molecules are sugar esters or lipopeptides.

In the bio-fermentation nano-enzyme regulated and blocked oil displacement agent, the surfactant is one or more of alcohol amines, phospholipids, fatty alcohol-polyoxyethylene ether sodium sulfate and betaine.

In the bio-fermentation nano-enzyme regulated and blocked oil displacement agent, the surface modified silicon dioxide is a mixture of conventional silicon dioxide and hydrophobic modified silicon dioxide, and the particle size range of the surface modified silicon dioxide is between 5nm and 70 nm.

In the bio-fermentation nano-enzyme plugging and oil-displacing agent, the alcohol is one or more of methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, butanediol, pentanediol, cyclohexanol and pentanol.

In the bio-fermentation nano-enzyme regulated and blocked oil displacement agent, the bio-fermentation prepared bioactive molecules are obtained by separating fermentation liquor products fermented by microbial strains;

wherein the microbial strain comprises one or more of Pseudomonas, Bacillus, Acinetobacter, Candidas, Rhodoco ccus, and Moesziomyes.

In the bio-fermentation nano-enzyme regulated and blocked oil displacement agent, a culture medium for microbial strain fermentation comprises the following components in percentage by weight:

the pH value of a culture medium for fermenting the microbial strains is 6-8;

the conditions for the fermentation of the microbial strains are as follows:

the fermentation temperature is 20-37 ℃, the stirring speed is 100-300 rpm, the ventilation quantity is 0.1-0.6 vvm, and the fermentation time is 24-90 h.

In the bio-fermentation nano-enzyme regulated and blocked oil displacement agent, a culture medium for microbial strain fermentation comprises the following components in percentage by weight:

the pH value of a culture medium for fermenting the microbial strains is 6-7;

the conditions for the fermentation of the microbial strains are as follows:

the fermentation temperature is 20-37 ℃, the stirring speed is 100-300 rpm, the ventilation quantity is 0.1-0.6 vvm, and the fermentation time is 24-48 h.

The preparation method of the biological fermentation nano-enzyme regulated and blocked oil displacement agent comprises the following steps:

preparing bioactive molecules prepared by biological fermentation into aqueous solution according to a preparation proportion in water with the temperature of 10-40 ℃, and fully stirring; adding the surface modified silicon dioxide according to the preparation proportion, and fully stirring; then adding alcohol and fully stirring; and finally, adding a surfactant, and fully stirring. Particularly, the emulsion is flowable liquid at low temperature, and has the functions of solubilization, emulsification, interface tension reduction and the like; at high temperature, colloids with different strengths can be formed; the method is used for resource development of oil and gas fields or for thick oil gathering and transportation.

In conclusion, the bio-fermentation nano enzyme regulating and plugging oil displacement agent prepared by bio-fermentation, a surfactant, surface modified silicon dioxide, alcohol and the like are mixed according to different proportions, and the effects of reducing interfacial tension, solubilizing, emulsifying and the like are achieved in an oil reservoir at low concentration or low temperature; plugging a high-permeability layer, bottom water and side water in an oil reservoir at high temperature and high concentration; has the functions of blocking water, increasing swept volume, reducing water content and improving recovery ratio. The method can realize in-situ water shutoff of the oil reservoir, can be applied to various oil reservoirs, and can be applied to the field of oil field production increase in a large scale.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) the prepared biological fermentation nano enzyme plugging oil displacement agent is a thermodynamically stable nano emulsion system, the system is suitable for a wider temperature and mineralization range, can be suitable for various oil reservoir geological environments and fluids, and can be stored for a long time;

(2) the prepared biological fermentation nano enzyme regulating and blocking oil displacement agent takes a biological active agent with biological fermentation as a core, helps silicon dioxide to be stably dispersed in a continuous phase, and does not generate interface bridging polymerization; the structure can be well transported in pores, and the organic hydrophobic phase can be transported to a deeper and farther place; meanwhile, the surface of the material has high viscoelasticity, so that the material cannot crack and polymerize in transportation and can be automatically released when encountering crude oil;

(3) the bioactive agent obtained by biological fermentation greatly improves the application performance of the profile control agent, has certain fluid properties at low temperature, and is expressed as fluid with extremely strong emulsifying capacity and reduced interfacial tension and resistance; under high temperature, a network structure of unsaturated bond polymerization and vitrified metal crosslinking is formed, and is tightly combined with stratum minerals, the water molecule wrapping capacity is strong, the rigidity is strong, and the dehydration rate is low; the emulsion slowly releases surface active substances at high temperature for a long time, and has the functions of emulsifying capacity and reducing interfacial tension; therefore, the high-plugging oil displacement agent has the capacity of improving swept volume and the effect of improving oil washing efficiency.

Drawings

FIG. 1 is a diagram of the effect of the plugging and oil displacing agent of the present invention at low temperature;

FIG. 2 shows the solubilizing effect of the modified flooding formulation of the present invention;

FIG. 3 is a graph showing the oil-water interfacial tension test in accordance with the present invention;

FIG. 4 is a structural diagram of a plugging and flooding agent of the present invention;

FIG. 5 is an effect diagram of the plugging-regulating flooding preparation of the invention used for plugging in a physical simulation core test.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As mentioned in the background art, the existing plugging agent has poor plugging effect on high temperature oil reservoirs or used under high temperature conditions, or cannot be injected into low permeability oil reservoirs, and the like, and in order to improve the effect, the inventor firstly considers that a material capable of performing biodegradation is adopted as an improvement direction from the viewpoint of environmental protection. In the experiment, the inventor obtains the fermentation liquor of the engineering bacteria by the principle of the fermentation process, separates and extracts bioactive molecules from the fermentation liquor, has the characteristics of water retention, thickening, high-temperature polymerization, high-temperature metal bridging, stability, heat resistance, salt resistance and the like due to the fact that biological sugar has multiple hydroxyl groups and unsaturated bonds, and has the advantages of simple preparation process, environmental friendliness and easy performance adjustment. Based on this, the inventors further thought that the blocking strength is improved by hydrophobic association, or hydrogen bonding, or metal chelate bridging of the bioactive molecule with the surface modified silica. The plugging system has the excellent characteristics of strong water solubility, high temperature resistance, acid and alkali resistance, salt resistance, environmental friendliness and the like. The water plugging agent has the characteristics of easy injection, easy plugging, high strength and the like in the water plugging application of the oil field, and can be widely applied to steam channeling and oil reservoirs with high water content. The bio-based plugging material brought by the bio-fermentation method is beneficial to improving the economic benefit and the environmental protection benefit of oil field exploitation.

The advantageous effects of the present application will be further described with reference to specific examples.

The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set any limit to the actual scope of the present invention, and the scope of the present invention is not limited thereto.

Unless otherwise indicated, the following examples refer to formulations wherein the% are by weight.

Example 1

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 3 wt% of bioactive molecule, 10 wt% of surfactant, 4 wt% of hydrophobic surface modified silicon dioxide and 1 wt% of ethanol; the balance being water. The bioactive molecule is prepared by Pseudomonas fermentation, the surfactant is fatty alcohol polyoxyethylene ether sulfate AES, and the mixture is uniformly mixed according to the preparation method to obtain the plugging and flooding agent A.

Wherein the biological activity isThe molecule is prepared by fermentation of Pseudomonas, and the preparation conditions are as follows: the culture medium for preparing fermentation product from Pseudomonas contains 0.5% of vegetable oil, 0.5% of corn syrup and vitamins, and 0.1% of KH₂PO₄0.01-0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 6. The preparation conditions are as follows: the reaction temperature is between 20 ℃, the stirring speed is 100rpm, the aeration rate is 0.1vvm, and the reaction time is 72 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 4%; concentrating at 40 deg.C to obtain effective components with concentration of 30%; is used for preparing a plugging and oil displacing preparation A.

The preparation process of the oil plugging and flooding regulating preparation A can adopt the following steps: adding hydrophobic modified silicon dioxide into a certain amount of clear Pseudomonas fermentation product according to a proportion, fully stirring, then adding 1% ethanol, and fully stirring; finally, 10% of AES is added, and the mixture is fully stirred.

Example 2

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 9 wt% of bioactive molecule, 3 wt% of surfactant, 10 wt% of hydrophobic surface modified silicon dioxide and 3 wt% of ethanol; the balance being water. Wherein the bioactive molecule is prepared by Pseudomonas fermentation, the surfactant adopts fatty alcohol polyoxyethylene ether sulfate AES, and the mixture is uniformly mixed according to the preparation method, so that the plugging and flooding control preparation B is obtained.

The bioactive molecule is prepared by the fermentation of Pseudomonas, and the preparation conditions are as follows: the culture medium for preparing fermentation product from Pseudomonas may contain 10% vegetable oil, 3% corn syrup and vitamins, and 1.0% KH₂PO₄0.5% of NaNO₃0.2 percent of yeast powder and 0.2 percent of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is between 37 ℃, the stirring speed is 300rpm, the aeration rate is 0.4vvm, and the reaction time is 72 hours; the obtained fermentation liquor is subjected toRemoving thalli and floating residual vegetable oil by a high-speed centrifuge to obtain middle layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane to obtain a clarified fermentation product, wherein the concentration of effective substances is 5%; concentrating at 60 deg.C to obtain effective component with concentration of 30%; used for preparing a biological nano preparation B.

The preparation process of the oil plugging and flooding regulating preparation B can adopt the following steps: adding hydrophobic modified silicon dioxide into a certain amount of clear Pseudomonas fermentation product according to a proportion, fully stirring, then adding 3% ethanol, and fully stirring; finally, 3 percent of AES is added and fully stirred.

Example 3

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 15 wt% of bioactive molecule, 2 wt% of surfactant, 15 wt% of hydrophobic surface modified silicon dioxide and 6 wt% of ethanol; the balance being water. The bioactive molecule is prepared by Bacillus fermentation, the surfactant adopts fatty alcohol-polyoxyethylene ether sulfate AES, and the mixture is uniformly mixed according to the preparation method to obtain the plugging and flooding agent C.

The bioactive molecule is prepared by Bacillus fermentation under the following conditions: the culture medium for preparing fermentation product from Bacillus may contain vegetable oil 0.5%, corn syrup 3%, vitamins 0.1%₂PO₄0.01% of NaNO₃0.2 percent of yeast powder and 0.2 percent of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is 32 ℃, the stirring speed is 300rpm, the aeration rate is 0.3vvm, and the reaction time is 72 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 2%; concentrating at 60 deg.C to obtain effective component with concentration of 30%; is used for preparing a plugging and oil displacing preparation C.

The preparation process of the oil plugging and flooding regulating preparation C can adopt the following steps: adding hydrophobic modified silicon dioxide into a certain amount of clear Bacillus fermentation products according to a proportion, fully stirring, then adding 6% ethanol, and fully stirring; finally, AES 2% is added, and the mixture is fully stirred.

Example 4

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 16 wt% of bioactive molecule, 5 wt% of surfactant, 9 wt% of hydrophobic surface modified silica, 3 wt% of propanol; the balance being water. The bioactive molecule is prepared by Bacillus fermentation, the surfactant is fatty alcohol phospholipid, and the preparation method is adopted to mix the surfactant and the fatty alcohol phospholipid uniformly to obtain the plugging-regulating oil displacement preparation D.

The bioactive molecule is prepared by Bacillus fermentation under the following conditions: the culture medium for preparing fermentation product from Bacillus may contain vegetable oil 1.5%, corn syrup and vitamins 3%, and KH 0.8%₂PO₄0.01% of NaNO₃0.2 percent of yeast powder and 0.1 percent of xanthan gum. The pH value of the special culture medium is 7. The preparation conditions are as follows: the reaction temperature is 30 ℃, the stirring speed is 200rpm, the aeration is 0.5vvm, and the reaction time is 7 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 3%; concentrating at 60 deg.C to obtain effective component with concentration of 30%; used for preparing a plugging and oil displacing preparation D.

The preparation process of the oil plugging and flooding control preparation D can adopt the following steps: adding hydrophobic modified silicon dioxide into a certain amount of clear Bacillus fermentation products according to a proportion, fully stirring, then adding 3% propanol, and fully stirring; finally, 5% of fatty alcohol phospholipid is added and fully stirred.

Example 5

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 20 wt% of bioactive molecule, 3 wt% of surfactant, 15 wt% of hydrophobic surface modified silicon dioxide, 5 wt% of butanol and 2 wt% of ethanol; the balance being water. The bioactive molecule is prepared by Acinetobacter fermentation, the surface active agent adopts betaine, and the surface active agent and the betaine are uniformly mixed according to the preparation method to obtain the plugging and oil displacing preparation E.

The bioactive molecule is prepared by Acinetobacter fermentation, and the preparation conditions are as follows: the culture medium for Acinetobacter to produce fermentation product may contain 3.5% vegetable oil, 3% corn syrup and vitamins, and 0.5% KH₂PO₄0.2% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 7. The preparation conditions are as follows: the reaction temperature is 32 ℃, the stirring speed is 300rpm, the aeration rate is 0.3vvm, and the reaction time is 72 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 1.8%; concentrating at 50 deg.C to obtain effective components with concentration of 30%; used for preparing a plugging and oil displacing preparation E.

The preparation process of the oil plugging and flooding regulating preparation E can adopt the following steps: adding hydrophobic modified silicon dioxide into a certain amount of clear Acinetobacter fermentation product according to a proportion, fully stirring, then adding 5 wt% of butanol and 2 wt% of ethanol, and fully stirring; finally, 3% of betaine is added and fully stirred.

Example 6

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 10 wt% of bioactive molecule, 6 wt% of surfactant, 20 wt% of hydrophobic surface modified silica, 3 wt% of butanol, 2 wt% of propanol; the balance being water. The bioactive molecule is prepared by Acinetobacter fermentation, the surfactant is fatty alcohol phospholipid, and the mixture is uniformly mixed according to the preparation method to obtain the plugging and oil displacing preparation F.

The bioactive molecule is prepared by Acinetobacter fermentation, and the preparation conditions are as follows: the culture medium for Acinetobacter to produce fermentation product may contain 6.5% vegetable oil, 2.4% corn syrup and vitamins, and 0.4% KH₂PO₄0.2% of NaNO₃0.25% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is 30 ℃, the stirring speed is 200rpm, the aeration is 0.6vvm, and the reaction time is 72 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 2.2%; concentrating at 40 deg.C to obtain effective components with concentration of 30%; is used for preparing a plugging and oil displacing preparation F.

The preparation process of the oil plugging and flooding regulating preparation F can adopt the following steps: fully stirring a certain amount of clear Acinetobacter fermentation product with 20% of hydrophobic surface modified silicon dioxide according to a proportion, then adding 3% of butanol and 2% of propanol, and fully stirring; finally, 6 percent of fatty alcohol phospholipid is added and fully stirred.

Example 7

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 2 wt% of bioactive molecule, 6 wt% of surfactant, 15 wt% of hydrophobic surface modified silica, 2% of ethylene glycol; the balance being water. The bioactive molecule is prepared by Candidas fermentation, the surfactant is fatty alcohol phospholipid, and the surfactant and the fatty alcohol phospholipid are uniformly mixed according to the preparation method to obtain the plugging and oil displacing preparation G.

The bioactive molecule is prepared by Candidas fermentation under the following conditions: the culture medium for preparing fermentation product from Candidas may contain vegetable oil 10%, corn syrup 6%, vitamins 0.4% KH₂PO₄0.4% of NaNO₃0.25% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 6. The preparation conditions are as follows: the reaction temperature is 24 ℃, the stirring speed is 200rpm, the aeration rate is 0.6vvm, and the reaction time is 90 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain lower-layer viscous liquid, wherein the concentration of effective substances is 20%; concentrating at 40-60 deg.C to obtain 60% effective component; used for preparing a plugging and oil displacing preparation G.

The preparation process of the oil plugging and flooding agent G can adopt the following steps: fully stirring a certain amount of clear Candidas fermentation products with 15% of hydrophobic surface modified silicon dioxide according to the proportion, then adding 2% of hexanediol, and fully stirring; finally, 6 percent of fatty alcohol phospholipid is added and fully stirred.

Example 8

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 5 wt% bioactive molecule, 2 wt% surfactant, 5 wt% hydrophobic surface modified silica, 6% ethylene glycol; the balance being water. The bioactive molecule is prepared by Candidas fermentation, the surface active agent adopts betaine, and the surface active agent and the betaine are uniformly mixed according to the preparation method, so that the plugging-regulating oil displacement agent H is obtained.

The bioactive molecule is prepared by Candidas fermentation under the following conditions: the culture medium for preparing fermentation product from Candidas may contain vegetable oil 8%, corn syrup 10%, vitamins, and KH 0.4%₂PO₄0.4% of NaNO₃0.25% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is 26 ℃, the stirring speed is 200rpm, the aeration is 0.3vvm, and the reaction time is 90 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain lower-layer viscous liquid, wherein the concentration of effective substances is 20%; concentrating at 40 deg.C to obtain 60% effective component; used for preparing a plugging and oil displacing preparation H.

The preparation process of the oil plugging and flooding regulating preparation H can adopt the following steps: fully stirring a certain amount of clear Candidas fermentation products with 5% of hydrophobic surface modified silicon dioxide according to the proportion, then adding 6% of glycol, and fully stirring; finally, 6% of betaine is added and fully stirred.

Example 9

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 6 wt% of bioactive molecule, 20 wt% of surfactant, 12 wt% of hydrophobic surface modified silica, 6% of propylene glycol; the balance being water. The bioactive molecule is prepared by Rhodococcus fermentation, the surfactant is AES, and the preparation method is adopted, and the mixture is uniformly mixed, so that the plugging and oil displacing preparation I is obtained.

Wherein the bioactive molecule is prepared by Rhodococcus fermentation under the following conditions: the culture medium for Rhodococcus to prepare fermentation product may contain 5% vegetable oil, 1% corn syrup and vitamins, and 0.5% KH₂PO₄0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is 30 ℃, the stirring speed is 300rpm, the aeration rate is 0.5vvm, and the reaction time is 85 hours; removing thallus from the obtained fermentation liquor by a high-speed centrifuge to obtain upper-layer liquid, and controlling the ratio of the upper-layer hydrophobic phase to the water to be 2:1 to obtain a fermentation product; is used for preparing a plugging and oil displacing preparation I.

The preparation process of the oil plugging and flooding regulating preparation I can adopt the following steps: fully stirring a certain amount of clear Rhodococcus fermentation product with 12% of hydrophobic surface modified silicon dioxide according to the proportion, then adding 6% of ethylene glycol, and fully stirring; finally, 20 percent of AES is added and fully stirred.

Example 10

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 10 wt% of bioactive molecule, 20 wt% of surfactant, 15 wt% of hydrophobic surface modified silicon dioxide, 4% of propylene glycol and 3% of ethanol; the balance being water. The bioactive molecule is prepared by Rhodococcus fermentation, the surfactant is fatty alcohol phosphate, and the preparation method is adopted to mix the surfactant and the fatty alcohol phosphate uniformly to obtain the plugging and oil displacing preparation J.

Wherein the bioactive molecule is prepared by Rhodococcus fermentation under the following conditions: the culture medium for Rhodococcus to prepare fermentation product may contain 5% vegetable oil, 1% corn syrup and vitamins, and 0.5% KH₂PO₄0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 6. Prepared stripA piece: the reaction temperature is 30 ℃, the stirring speed is 300rpm, the aeration rate is 0.3vvm, and the reaction time is 85 hours; removing thallus from the obtained fermentation liquor by a high-speed centrifuge to obtain upper-layer liquid, and controlling the ratio of the upper-layer hydrophobic phase to the water to be 2:1 to obtain a fermentation product; is used for preparing a plugging and oil displacing preparation J.

The preparation process of the oil plugging and flooding regulating preparation J can adopt the following steps: fully stirring a certain amount of clear Rhodococcus fermentation product with 15% of hydrophobic surface modified silicon dioxide according to a proportion, then adding 4% of propylene glycol and 3% of ethanol, and fully stirring; finally, 20 percent of fatty alcohol phosphate is added and fully stirred.

Example 11

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 20% of bioactive molecules, 7% of surfactant, 9% of hydrophobic surface modified silicon dioxide, 3% of propylene glycol and 3% of ethanol; the balance being water. The bioactive molecule is prepared by fermenting Moesziomyes, the surfactant is fatty alcohol phosphate, and the fatty alcohol phosphate is uniformly mixed according to the preparation method to obtain the plugging and flooding regulating preparation K.

The bioactive molecule is prepared by fermentation of Moesziomyes under the following conditions: the medium for fermentation of Moesziomyes may contain 5% vegetable oil, 1% corn syrup and vitamins, 0.5% KH₂PO₄0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 8. The preparation conditions are as follows: the reaction temperature is 30 ℃, the stirring speed is 300rpm, the aeration rate is 0.6vvm, and the reaction time is 85 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge to obtain lower-layer viscous liquid, wherein the concentration of effective substances is 30%, and concentrating the lower-layer viscous liquid to 60% to obtain a fermentation product; is used for preparing a plugging and oil displacing preparation K.

The preparation process of the oil plugging and flooding regulating preparation K can adopt the following steps: fully stirring a certain amount of clear Moesziomyes fermentation product with 9% of hydrophobic surface modified silicon dioxide according to a proportion, then adding 3% of propylene glycol and 3% of ethanol, and fully stirring; finally adding 7% of fatty alcohol phosphate, and fully stirring.

Example 12

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 2% of bioactive molecule, 3% of surfactant, 16% of hydrophobic surface modified silicon dioxide and 4% of propylene glycol; the balance being water. The bioactive molecule is prepared by fermentation of Moesziomyes, and the surfactant is fatty alcohol phosphate, and is uniformly mixed according to the preparation method to obtain the plugging and oil displacing preparation L.

The bioactive molecule is prepared by fermentation of Moesziomyes under the following conditions: the medium for fermentation of Moesziomyes may contain 8% vegetable oil, 8% corn syrup and vitamins, 0.5% KH₂PO₄0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 6. The preparation conditions are as follows: the reaction temperature is between 27 ℃, the stirring speed is 300rpm, the aeration rate is 0.6vvm, and the reaction time is 90 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge to obtain lower-layer viscous liquid, wherein the concentration of effective substances is 30%, and concentrating the lower-layer viscous liquid to 60% to obtain a fermentation product; is used for preparing a plugging and oil displacing preparation L.

The preparation process of the oil plugging and flooding regulating preparation L can adopt the following steps: fully stirring a certain amount of clear Moesziomyes fermentation product with 16% of hydrophobic surface modified silicon dioxide according to a proportion, then adding 4% of propylene glycol, and fully stirring; finally, 2 percent of fatty alcohol phosphate is added and fully stirred.

Example 13

The bio-fermentation nano-enzyme regulated and blocked oil displacement agent is prepared from the following components in percentage by weight: 2% of bioactive molecule I, 2% of bioactive molecule II 5%, AES 2%, fatty alcohol phosphate 3%, 19% of hydrophobic surface modified silicon dioxide and 4% of propylene glycol; the balance being water. Wherein the bioactive molecule I is prepared by the fermentation of Pseudomonas; the bioactive molecule II is prepared by fermentation of Moesziomyes, and is uniformly mixed according to the preparation method to obtain the plugging and oil displacing preparation M.

The bioactive molecule I is prepared by Pseudomonas fermentation, and the preparation conditions are as follows: the culture medium for preparing fermentation product from Pseudomonas may contain 6% vegetable oil, 2% corn syrup and vitamins, and 0.7% KH₂PO₄0.01% of NaNO₃0.2 percent of yeast powder and 0.1 percent of xanthan gum. The pH value of the special culture medium is 6. The preparation conditions are as follows: the reaction temperature is between 33 ℃, the stirring speed is 200rpm, the aeration is 0.4vvm, and the reaction time is 80 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge so as to obtain middle-layer liquid, and removing residual suspended particles or flocs by an organic fiber membrane so as to obtain a clear fermentation product, wherein the concentration of effective substances is 4%; concentrating at 50 deg.C to obtain effective components with concentration of 30%; is used for preparing a plugging and oil displacing preparation M.

The bioactive molecule II is prepared by fermentation of Moesziomyes under the following conditions: the medium for fermentation of Moesziomyes may contain 8% vegetable oil, 8% corn syrup and vitamins, 0.5% KH₂PO₄0.5% of NaNO₃0.1% of yeast powder and 0.1% of xanthan gum. The pH value of the special culture medium is 6-8. The preparation conditions are as follows: the reaction temperature is 26 ℃, the stirring speed is 300rpm, the aeration rate is 0.4vvm, and the reaction time is 90 hours; removing thalli and floating residual vegetable oil from the obtained fermentation liquor by a high-speed centrifuge to obtain lower-layer viscous liquid, wherein the concentration of effective substances is 30%, and concentrating the lower-layer viscous liquid to 60% to obtain a fermentation product; is used for preparing a plugging and oil displacing preparation M.

The preparation process of the oil plugging and flooding regulating preparation M can adopt the following steps: fully stirring a certain amount of clear bioactive molecule I and bioactive molecule II fermentation products with 19% of hydrophobic surface modified silicon dioxide according to a proportion, then adding 4% of propylene glycol, and fully stirring; finally, 2 percent of AES and 3 percent of fatty alcohol phosphate are added and fully stirred.

Example 14

The plugging and oil displacing preparation prepared in the examples 1 to 13 is used for testing oil washing, interfacial tension reduction, freezing point reduction and viscosity reduction at low temperature or low concentration; effect of blocking strength at high temperature.

The experimental method comprises the following steps:

crude oil sand preparation, 2 g of crude oil is obtained from a certain oil field; selecting 10 g of 1:1 mixed quartz sand with the mesh numbers of 200 and 500; 5 g of quartz sand is poured into a 20 ml glass tube, then 2 g of crude oil is added, and the crude oil and the quartz sand are aged for 2 days at 60 ℃ so that the crude oil and the quartz sand are completely contacted and infiltrated, and the oil sand is obtained.

2 g of plugging and oil displacement regulating preparation A-L are respectively added into the oil sand, and the use concentration is 1-5%. The results of the experiment are shown in FIG. 1. As can be seen from figure 1, the plugging and oil displacing agent has an obvious cleaning effect at low temperature.

The results of the tests on the oil yield, the viscosity of the oil and the freezing point depression are shown in table l.

TABLE 1 Effect at Low temperatures (less than 45 ℃) or at Low concentrations (less than 10%)

Wherein, fig. 2 shows the solubilizing effect of the plugging and oil displacing preparation, and the results show that the plugging and oil displacing preparation has excellent effects of reducing viscosity, reducing pour point, washing oil and the like at low temperature or low concentration.

Example 15

The plugging and flooding formulations of examples 1-13 were used to reduce oil-water interfacial tension at low temperatures or low concentrations.

The experimental method comprises the following steps:

selecting the plugging and oil displacing preparation, preparing a 3% aqueous solution, testing the oil-water interfacial tension by using a spinning drop method, wherein the rotating speed is 5000rpm, selecting 2 different oil phases for testing, and referring to a test result in figure 3. As can be seen from fig. 3, an ultra-low interfacial tension can be formed with the crude oil.

Example 16

The plugging and flooding formulations of examples 1-13 were used for gel strength at high temperature and high concentration.

The experimental method comprises the following steps:

selecting the plugging and oil displacing preparation, preparing a 20% aqueous solution by using stratum water, placing the aqueous solution in an environment with the temperature of more than 70 ℃ for 3 days, and observing the gelling strength, wherein the observation structure is shown in a figure 4 and a test result table 2. As can be seen from table 2, different agents form colloids of different strengths at high temperatures.

TABLE 2 gel Strength Effect at high temperature and high concentration

Example 17

The plugging and oil displacing preparation in examples 1 to 13 was used for physical simulation core test plugging effect.

The experimental method comprises the following steps:

(1) filling a model with quartz sand in a certain ratio (160-;

(2) vacuumizing saturated water by the model, converting the weight of the water saturated into the sintered rock core into the volume of a water phase according to the density of formation water, namely, obtaining a pore volume V pore, and calculating the porosity phi;

(3) measuring the permeability Kw with water;

(4) injecting 25% of plugging and oil displacing preparation solution with 0.1PV, then injecting 0.2PV of water, closing the pump, and closing valves at two ends of the core holder for 16 hours.

(5) And continuing to inject water slowly, and recording the pressure change. The pressure curves for the different phases are plotted on a single graph.

Representative results are shown in fig. 5, where injection pressure was significantly doubled before and after occlusion.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.