阅读说明：本技术 十二烷基聚氧乙烯醚硫酸钠-杆菌肽化合物及复合驱油剂 (Dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound and composite oil displacement agent ) 是由 宋文枫 赵越 章骏 魏小芳 田茂章 黄佳 于 2019-04-02 设计创作，主要内容包括：本发明提供了一种十二烷基聚氧乙烯醚硫酸钠-杆菌肽化合物及复合驱油剂。该十二烷基聚氧乙烯醚硫酸钠-杆菌肽化合物的化学结构式如下：<Image he="391" wi="700" file="DDA0002015499200000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。本发明提供了包含有由十二烷基聚氧乙烯醚硫酸钠与杆菌肽反应得到的十二烷基聚氧乙烯醚硫酸钠-杆菌肽化合物的十二烷基聚氧乙烯醚硫酸钠-杆菌肽复合驱油剂。该复合驱油剂可很好地实现与采油功能菌的复配形成一种微生物-化学复合驱油剂。该微生物-化学复合驱油剂既具有微生物驱对原油降解降黏功效又具有化学驱的乳化降黏效果,且通过生物携载方式,扩大化学驱油剂在油层中的波及体积和分散效率,有效提高微生物与化学剂的协同反应效率,实现1+1>2的目的。(The invention provides a dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound and a composite oil displacement agent. The chemical structural formula of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound is as follows: . The invention provides a dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent which comprises a dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound obtained by reacting dodecyl polyoxyethylene ether sodium sulfate with bacitracin. The compound oil displacement agent can be well compounded with oil extraction functional bacteria to form a microorganism-chemical compound oil displacement agent. The microbial-chemical compound oil displacement agent has the functions of degrading and reducing viscosity of crude oil by microbial floodingThe oil displacement agent has the effects of emulsifying and viscosity reducing of chemical flooding, and the swept volume and the dispersion efficiency of the chemical oil displacement agent in an oil layer are enlarged through a biological carrying mode, so that the synergistic reaction efficiency of microorganisms and chemical agents is effectively improved, and 1+1>2, in the process.)

1. A sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound, wherein the structural formula of the sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound is as follows:

2. a dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound oil displacement agent, wherein, the compound oil displacement agent contains dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound obtained by the reaction of dodecyl polyoxyethylene ether sodium sulfate and bacitracin; preferably, the sodium laureth sulfate-bacitracin compound is the sodium laureth sulfate-bacitracin compound of claim 1.

3. The preparation method of the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent as claimed in claim 2, wherein the preparation method comprises:

adding sodium dodecyl polyoxyethylene ether sulfate into a bacitracin compound solution, and reacting to obtain the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent, wherein the mass ratio of the bacitracin compound to the sodium dodecyl polyoxyethylene ether sulfate is 1: 1.5-3; preferably, the reaction is carried out at 37-40 ℃ for 6-12 h.

4. The preparation method according to claim 3, wherein the bacitracin compound solution has a mass concentration of 40% to 60%; preferably, the bacitracin compound solution is formed by dissolving bacitracin compounds in water, wherein the bacitracin compounds are prepared by the steps of:

1) culturing the bacterial strain inoculated into the culture medium in an air bath shaker until the bacteria grow to the late logarithmic phase, centrifuging, and collecting the bacteria; preferably, the centrifugation is performed at 6000-10000 rpm for 10-20 min; further preferably, the centrifugation is carried out for 15min at 8000 revolutions per minute, and thalli are collected;

2) washing the collected thallus with dilute sulfuric acid to remove impurities, and suspending the thallus to prepare a suspension; preferably, the suspension has an absorbance of 1 at a wavelength of 600nm as measured with a 1cm cuvette;

3) subpackaging the suspension, centrifuging and collecting lower layer bacterial bodies; preferably, the centrifugation is performed at 6000-; further preferably, the centrifugation is centrifugation at 8000 revolutions per minute for 10 min;

4) eluting the collected lower layer bacterial body, performing centrifugal separation, and performing chromatographic separation and purification on the upper layer capsular solution to obtain a bacitracin compound; preferably, the elution is carried out by eluting with clear water at 38-40 ℃ for 10-12 h; further preferably, the elution is with clear water at 40 ℃ for 12 h.

5. The production method according to claim 4, wherein in step 1), the strain is any strain containing bacitracin compounds in metabolites; preferably, the cultivation is carried out at 63-68 ℃ and at 160-180r/min, further preferably, the cultivation is carried out at 65 ℃ and 170 r/min.

6. The production method according to claim 4, wherein the pH of the dilute sulfuric acid in step 2) is 2 to 3; preferably, the dilute sulfuric acid has a pH of 2.

7. A microorganism-chemical compound oil-displacing agent, wherein the microorganism-chemical compound oil-displacing agent is prepared by compounding the lauryl polyoxyethylene ether sodium sulfate-bacitracin compound oil-displacing agent of claim 2 and oil extraction functional bacteria; preferably, the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent is prepared by the preparation method of any one of claims 3 to 6.

8. The microorganism-chemical composite oil displacement agent according to claim 7, wherein the sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound in the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent is modified on the surface of oil recovery functional bacteria.

9. The microbial-chemical composite oil-displacing agent according to claim 7, which is obtained by the following production method:

1) adding 200mL of culture medium inoculated with the strain into a 500mL triangular flask, placing the triangular flask in an air bath shaker for culture at 65 ℃ and 170r/min, when the strain grows to the late logarithmic phase, centrifuging at 8000r/min for 15min to collect cells, washing with dilute sulfuric acid with the pH value of 2 to remove impurities, suspending the strain, preparing a suspension with the light absorption value of 1 measured by a 1cm cuvette at the wavelength of 600nm, subpackaging 20mL of each suspension, centrifuging at 8000 rpm for 10min, and collecting the lower-layer bacterial cells;

2) eluting the bacterial body with clear water at 40 deg.C for 12h, centrifuging, collecting the upper layer capsular solution, performing chromatographic separation, and purifying to obtain bacitracin compound;

3) placing the bacitracin compound solution with the mass concentration of 40-60% in a water bath at 39 ℃, adding dodecyl polyoxyethylene ether sodium sulfate which is 2.5 times of the mass of the bacitracin compound, and reacting for 12 hours to obtain the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent;

4) adding the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent obtained in the step 3) into a bacterial culture medium, transferring the mixture into an oil extraction functional bacteria microbial inoculum to form a mixture, wherein the volume ratio of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent to the oil extraction functional bacteria microbial inoculum is 10:1-5:1, and culturing and proliferating for 24-36h until the solution is measured to have a light absorption value of 1 by using a 1cm cuvette under the wavelength of 600nm to obtain the microorganism-chemical composite oil displacement agent.

10. A method for preparing the microorganism-chemical composite oil-displacing agent according to any one of claims 7 to 9, wherein the method comprises:

adding the lauryl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent of claim 2 into a bacterial culture medium, transferring oil recovery functional bacteria to form a mixture, culturing and proliferating to obtain the microorganism-chemical composite oil displacement agent;

preferably, the culture proliferation is culture proliferation until the solution has an absorbance of 1 at a wavelength of 600nm as measured by a 1cm cuvette;

preferably, the oil recovery functional bacteria are transferred in a functional bacteria microbial inoculum, wherein the volume ratio of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent to the oil recovery functional bacteria microbial inoculum is 10:1-5: 1; more preferably, the volume ratio is 10: 1;

preferably, the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent is prepared by the preparation method of any one of claims 3 to 6.

Technical Field

The invention belongs to the technical field of tertiary oil recovery, relates to preparation and application of a microorganism-chemical composite oil displacement agent, and particularly relates to a sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound and a composite oil displacement agent.

Background

Along with the rapid development of national economy, the demand of petroleum is continuously increased, the contradiction between petroleum consumption and supply is more prominent, and in order to solve the contradiction, besides increasing exploration strength and continuously searching petroleum resources, the method is also one of effective ways for improving the crude oil recovery ratio of developed oil fields.

The Microbial enhanced oil recovery-MEOR (Microbial enhanced oil recovery-MEOR) is a technology for improving the recovery of crude oil by utilizing the natural biochemical action (biodegradation and metabolites) of living cells of microorganisms. The microorganism and/or nutrient solution with oil extraction function is injected into the oil reservoir, so that oil extraction functional bacteria grow and reproduce in the oil reservoir, the physical (surface and interface properties) and chemical properties (crude oil components) of crude oil are changed through the biochemical action of the microorganism, the molecular chain length and the shear viscosity of the crude oil are reduced, the fluidity of the crude oil is improved, and the recovery ratio of the crude oil is improved.

Although the microbial oil recovery technology can well solve the problem of crude oil fluidity of heavy oil reservoirs such as Xinjiang oil fields, the chemical oil displacement agent is still required to be matched for oil displacement in order to achieve higher crude oil recovery. Although the simple mixing of the two components has the advantages of simple operation and low operation cost, the diffusion speeds of the two components after entering an oil layer are greatly different, the separation is easy to occur, and the synergistic oil displacement effect cannot be achieved. How to realize the good combination of microbial oil displacement and chemical oil displacement and improve the recovery ratio of crude oil become important problems which people pay attention to widely and need to solve urgently.

The chemical oil-displacing agent is modified on the surface of the microorganism with the oil extraction function, and enters an oil layer through the synergistic loading of the microorganism, so that the problem of separation of the chemical oil-displacing agent and the microorganism is solved, and the important way of realizing the synergistic oil displacement of the chemical oil-displacing agent and the microorganism is realized.

However, the addition of chemical oil displacement agents and the reaction process thereof often destroy the physiological functions of microorganisms, reduce the oil displacement effect of the microorganisms, and even cause the microorganisms to die in a large scale, so that the microbial oil displacement cannot be realized. In addition, the addition of the chemical oil displacement agent can also cause the reduction of the movement capacity and the permeability of microorganisms, and the substantial oil displacement effect on low-permeability oil reservoirs is difficult to generate. Therefore, the selection of chemical agents, the addition method, the control of the addition amount and the control of reaction conditions become the key points of the microbial-chemical complex oil displacement.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a composite oil displacement agent of sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound.

The invention also aims to provide the lauryl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent, which can be well compounded with oil extraction functional bacteria to form a microorganism-chemical composite oil displacement agent.

The invention also aims to provide a microbial-chemical composite oil displacement agent suitable for oil displacement of oil fields, in particular to oil displacement of high-viscosity oil fields.

In order to solve the technical problems, the invention is realized by adopting the following technical scheme.

The invention provides a sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound, which has the structural formula as follows:

the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound with the structure can be obtained by reacting dodecyl polyoxyethylene ether sodium sulfate with bacitracin compounds, and the chemical reaction formula is as follows:

the invention provides a dodecyl polyoxyethylene N-vinyl ether sodium sulfate-bacitracin composite oil displacement agent, which comprises a dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound obtained by reacting dodecyl polyoxyethylene ether sodium sulfate with bacitracin; preferably, the sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound is the sodium dodecyl polyoxyethylene ether sulfate-bacitracin compound with the structure.

The invention provides a preparation method of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent, which comprises the following steps:

adding sodium dodecyl polyoxyethylene ether sulfate into a bacitracin compound solution, and reacting to obtain the sodium dodecyl polyoxyethylene ether sulfate-bacitracin composite oil displacement agent, wherein the mass ratio of the bacitracin compound to the sodium dodecyl polyoxyethylene ether sulfate is 1: 1.5-3.

In the above preparation method, preferably, the reaction is carried out at 37 to 40 ℃ for 6 to 12 hours.

In the above preparation method, the bacitracin compound solution preferably has a mass concentration of 40% to 60%, and in the preparation method, the mass concentration of the bacitracin compound solution does not affect the reaction itself, but has some influence on the final yield of the reaction.

In the above preparation method, preferably, the bacitracin compound solution is formed by dissolving bacitracin compounds in water, wherein the bacitracin compounds are prepared as follows:

1) culturing the bacterial strain inoculated into the culture medium in an air bath shaker until the bacteria grow to the late logarithmic phase, centrifuging, and collecting the bacteria;

2) washing the collected thallus with dilute sulfuric acid to remove impurities, and suspending the thallus to prepare a suspension;

3) subpackaging the suspension, centrifuging and collecting lower layer bacterial bodies;

4) and eluting the collected lower layer bacterial body, performing centrifugal separation, taking the upper layer capsular solution, performing chromatographic separation and purification, and obtaining the bacitracin compound.

In the above method for preparing bacitracin compounds, preferably, the centrifugation in step 1) is centrifugation at 6000-10000 rpm for 10-20 min; further preferably, the centrifugation is at 8000 revolutions per minute for 15 min.

In the above-mentioned method for producing a bacitracin compound, preferably, the medium in step 1) is 200 mL.

In the above method for producing bacitracin compounds, preferably, the culturing of the strain inoculated into the medium in step 1) is carried out using a 500mL Erlenmeyer flask as a container.

In the above method for producing a bacitracin compound, preferably, the strain in step 1) is any strain containing a bacitracin compound in a metabolite.

In the above-mentioned method for producing bacitracin compounds, preferably, the culturing in step 1) is carried out at 63-68 ℃ and 160-180 r/min; further preferably, the culturing is carried out at 65 ℃ and 170 r/min.

In the above-mentioned method for producing bacitracin compounds, preferably, the suspension in step 2) has an absorbance of 1 as measured at a wavelength of 600nm using a 1cm cuvette.

In the above method for producing bacitracin compounds, preferably, the ph value of said dilute sulfuric acid in step 2) is 2 to 3; further preferably, the pH of the dilute sulfuric acid is 2.

In the above method for preparing bacitracin compounds, preferably, the centrifugation of step 3) is centrifugation at 6000-; further preferably, the centrifugation is at 8000 revolutions per minute for 10 min.

In the above method for producing bacitracin compounds, preferably, the dispensing in step 3) is performed in 20mL portions.

In the above method for preparing bacitracin compounds, preferably, the elution in step 4) is an elution with clear water at 38-40 ℃ for 10-12 h; further preferably, the elution is carried out at 40 ℃ for 12h with clear water.

In the above method for preparing bacitracin compounds, the retention time of the supernatant capsular solution may be determined according to the retention time of a standard sample of bacitracin compounds when performing the chromatographic separation in step 4). In chromatographic analysis, the time from the start of sample injection to the time when the concentration of the component is at its maximum after the column, i.e. the time from the start of sample injection to the time when the peak of a chromatographic peak of a component appears, is referred to as the retention time of the component.

The dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound oil displacement agent obtained by the preparation method can be purified to obtain the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound.

The invention also provides a microorganism-chemical compound oil-displacing agent which is prepared by compounding the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound oil-displacing agent and oil extraction functional bacteria.

In the microbial-chemical composite oil-displacing agent, preferably, the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil-displacing agent is prepared by the preparation method of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil-displacing agent.

In the above-mentioned microbial-chemical composite oil-displacing agent, preferably, the sodium laureth sulfate-bacitracin compound in the sodium laureth sulfate-bacitracin composite oil-displacing agent is modified on the surface of the oil recovery functional bacteria.

In the above-mentioned microbial-chemical complex oil-displacing agent, preferably, the microbial-chemical complex oil-displacing agent is prepared by the following preparation method:

1) adding 200mL of culture medium inoculated with the strain into a 500mL triangular flask, placing the triangular flask in an air bath shaker for culture at 65 ℃ and 170r/min, when the bacteria grow to the late logarithmic phase, centrifuging at 8000r/min for 15min to collect cells, washing with dilute sulfuric acid (pH value is 2) to remove impurities, suspending the bacteria, preparing suspension (1cm cuvette) with the light absorption value of 1 at the wavelength of 600nm, subpackaging 20mL of each part, centrifuging at 8000 rpm for 10min, and collecting the bacteria at the lower layer;

2) eluting the bacterial body with clear water at 40 deg.C for 12h, centrifuging, collecting upper layer capsular solution, performing chromatographic separation, and purifying to obtain bacitracin compound (in chromatographic separation, the retention time of upper layer capsular solution can be determined according to the retention time of standard sample of bacitracin compound);

3) placing the bacitracin compound solution with the mass concentration of 40-60% in a water bath at 39 ℃, adding dodecyl polyoxyethylene ether sodium sulfate which is 2.5 times of the mass of the bacitracin compound, and reacting for 12 hours to obtain the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent;

4) adding the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent obtained in the step 3) into a bacterial culture medium, transferring the oil extraction functional bacteria microbial inoculum to form a mixture, wherein the volume ratio of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent to the oil extraction functional bacteria microbial inoculum is 10:1-5:1, and culturing and proliferating for 24-36h until the mixture in the culture medium has a light absorption value of 1 measured by a 1cm cuvette under the wavelength of 600nm, thus obtaining the microorganism-chemical composite oil displacement agent.

The invention also provides a preparation method of the microbial-chemical composite oil displacement agent, which comprises the following steps:

adding the lauryl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent into a bacterial culture medium, transferring oil extraction functional bacteria to form a mixture, and culturing and proliferating to obtain the microorganism-chemical composite oil displacement agent.

In the above method for preparing a microbial-chemical composite oil-displacing agent, preferably, the culture proliferation is a culture proliferation in which the mixture in the culture medium has an absorbance of 1 measured at a wavelength of 600nm with a 1cm cuvette.

In the above method for preparing the microbial-chemical composite oil-displacing agent, the culture and proliferation time is preferably 24-36 h.

In the preparation method of the microorganism-chemical compound oil-displacing agent, preferably, the transferring of the oil recovery functional bacteria is performed by transferring an oil recovery functional bacteria microbial inoculum, wherein the volume ratio of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound oil-displacing agent to the oil recovery functional bacteria microbial inoculum is 10:1-5: 1; more preferably, the volume ratio is 10: 1.

In the preparation method of the microbial-chemical composite oil-displacing agent, preferably, the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil-displacing agent is prepared by the preparation method of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil-displacing agent. The technical scheme provided by the invention researches the oil displacement by taking the synergistic effect of microorganisms and chemical agent oil into consideration, provides a brand-new microorganism-chemical compound oil displacement system, and provides a solution for improving the crude oil recovery ratio of an oil field. Compared with the prior art, the invention has the following beneficial effects:

(1) the method is simple, has strong operability and applicability, and can meet the requirements of actual oil field production.

(2) The microbial-chemical compound oil displacement agent provided by the invention has the effects of degrading and reducing viscosity of the microbial flooding on crude oil and the effects of emulsifying and reducing viscosity of the chemical flooding, and can enlarge the swept volume and the dispersion efficiency of a chemical agent in an oil layer in a biological carrying mode, effectively improve the synergistic reaction efficiency of the microbes and the chemical agent and realize the purpose of 1+1> 2.

(3) The dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent provided by the invention can well realize coexistence with oil extraction functional bacteria, and provides favorable conditions for growth and propagation of the oil extraction functional bacteria.

(4) The dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound provided by the invention has good emulsifying property on crude oil, is a good surfactant for oil displacement, and can be modified on the surface of oil extraction functional bacteria.

(5) The microbial-chemical composite oil-displacing agent prepared by the preparation method successfully modifies alkyl polyoxyethylene ether-bacitracin compounds on the surface of oil extraction functional bacteria.

Drawings

FIG. 1 is an infrared image of a sodium laureth sulfate-bacitracin compound provided in example 1.

FIG. 2 is a comparison graph of the emulsification stability characterization curves of the microbial-chemical composite oil displacement agent, water, oil recovery functional bacteria, and the emulsification of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent and the white oil respectively.

FIG. 3 is a diagram showing the growth of microbial colonies in the sodium laureth sulfate-bacitracin complex oil-displacing agent provided in example 1.

FIG. 4 is a comparison graph of the effect of reducing the crude oil viscosity of the microbial-chemical composite oil displacement agent, the oil recovery functional bacteria and the lauryl polyoxyethylene ether sodium sulfate obtained by compounding the lauryl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent and the oil recovery functional bacteria.

FIG. 5 is a comparison graph of oil displacement sweep efficiency of a microbial-chemical composite oil displacement agent and a dodecyl polyoxyethylene ether sodium sulfate chemical oil displacement agent obtained by compounding a dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent with oil recovery functional bacteria.

FIG. 6 is a comparison graph of the load efficiency of the dodecyl polyoxyethylene ether sodium sulfate-bacitracin compound, the dodecyl polyoxyethylene ether sodium sulfate and the oil recovery functional bacteria when they are compounded.

FIG. 7 is a comparison graph of the emulsified particle size distribution of the microorganism-chemical composite oil displacement agent, the oil recovery functional bacteria and the dodecyl polyoxyethylene ether sodium sulfate crude oil obtained by compounding the dodecyl polyoxyethylene ether sodium sulfate-bacitracin composite oil displacement agent and the oil recovery functional bacteria.

FIG. 8 is a physical simulation of the flooding apparatus used for sweep efficiency verification.

Fig. 9 is a schematic diagram of a sweep efficiency validation core injection slug.

FIG. 10 is a schematic diagram of a core injection slug from a sweep efficiency validation control experiment.

Detailed Description

The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.