Two-step efficient demulsification method of mannosylerythritol lipid

The two-step method with mannose erythritol lipid and salt treatment effectively addresses inefficiencies in demulsification, providing rapid and green oil phase separation with minimal environmental impact and equipment damage.

CN119215487APending Publication Date: 2024-12-31NANJING UNIV OF SCI & TECH
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Patent Information

Application Number
CN202411324302.4
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-09-23
Publication Date
2024-12-31

AI Technical Summary

Technical Problem

Conventional demulsification methods, including chemical and physical approaches, are inefficient, energy-intensive, and environmentally harmful, particularly in handling waste oil emulsions from oil refining, and existing biosurfactant methods cause equipment corrosion and are not mild enough.

Method used

A two-step method using mannose erythritol lipid as a salinity-sensitive biosurfactant for co-emulsification, followed by salt addition to achieve oil phase separation, leveraging its surface/interfacial activity and solubility changes in high-salinity environments.

Benefits of technology

The method achieves rapid, energy-efficient, and environmentally friendly oil phase separation with minimal equipment damage, suitable for various industrial applications.

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Abstract

The invention discloses a two-step efficient demulsification method of mannosylerythritol lipid. The method comprises the following steps: adding the mannosylerythritol lipid into an emulsion to be treated, and uniformly mixing to realize co-emulsification; wherein the mass volume ratio of the mannosylerythritol lipid to the emulsion to be treated is 2-15g / L; adding salt into the mixed emulsion, and standing at 10-50 DEG C to realize oil phase separation; wherein the mass volume ratio of the salt to the emulsion is 1-15g / L. The method is easy to operate, environmentally friendly and free of secondary pollution; the method has the characteristics of high demulsification activity, high oil phase separation speed, energy consumption reduction and the like, is mild in condition and small in damage to equipment and instruments, and can be used for demulsification in numerous industrial fields.
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Description

Technical Field

[0001] The invention belongs to the technical field of biosurfactants, and in particular relates to a two-step high-efficiency demulsification method for mannose erythritol lipids. Background Art

[0002] A large amount of waste oil (emulsion with a crude oil content of up to 50%) generated during oil extraction and processing, if discharged directly, will not only harm the environment, but also cause serious waste of oil resources. How to properly handle such a large amount of waste oil has become a common problem for oil refining companies. As oil fields increasingly use tertiary oil recovery to improve crude oil recovery, the emulsified crude oil produced contains natural surfactant substances such as asphaltene and colloid, forming a stable emulsion. How to destroy the stable emulsion to obtain high-quality products also urgently requires an efficient demulsification process. In addition, as oil resources are increasingly depleted and oil quality declines year by year, tertiary oil recovery technology will be increasingly used in oil field exploitation; the amount of waste oil generated during crude oil processing will be greater, and the composition of waste oil will be more complex and changeable, which will lead to more severe problems in the treatment of waste oil. With the help of demulsification means, oil phase separation can be achieved, the quality of crude oil in tertiary oil recovery can be improved, and the oil phase in the waste oil can also be recovered, which not only realizes the resource utilization of waste, but also is more conducive to the maximum utilization of resources and environmental protection. Therefore, the establishment of efficient, simple, green and environmentally friendly efficient demulsification technology has become a major problem that needs to be solved in the relevant fields.

[0003] Conventional physical demulsification methods include gravity sedimentation, electric field demulsification, ultrasonic demulsification, centrifugation, membrane separation, freezing / rewarming, etc., which are usually used alone or in combination, but most of them are inefficient and energy-intensive. Chemical demulsification is currently the most studied and widely used method. Chemical demulsifiers have gone through three generations since their development, namely fatty acid anionic surfactants, polyoxyethylene alkyl alcohol ethers and polyethers. Most of the widely used chemical demulsifiers are petroleum-based polymers, which are difficult to degrade and have great harm to the ecological environment. In addition, they have low treatment efficiency and poor universality. At present, a relatively novel demulsification method involves biosurfactant lipopeptide as a biodemulsifier. A pH-sensitive green biosurfactant lipopeptide is used as a demulsifier. First, it is simply mixed to stabilize the emulsion with the emulsifier in the emulsion, and then acid is added to allow the lipopeptide to precipitate from the oil-water interface, resulting in emulsion instability and achieving efficient demulsification and oil phase separation. However, the pH adjustment method uses acid conditions that are not mild enough, which will cause large equipment losses and rapid corrosion to the equipment. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a two-step efficient demulsification method for mannose erythritol lipid.

[0005] The embodiment of the present invention provides a two-step efficient demulsification method for mannose erythritol lipid, the method comprising:

[0006] Adding mannitol erythritol lipid to the emulsion to be treated and mixing evenly to achieve co-emulsification; wherein the mass volume ratio of mannitol erythritol lipid to the emulsion to be treated is 2-15 g / L;

[0007] Add salt to the mixed emulsion and let it stand at 10-50° C. to achieve oil phase separation; wherein the mass volume ratio of salt to emulsion is 1-15 g / L.

[0008] Furthermore, the mannose erythritol lipid is the fermentation liquid of aphid-mimicking yeast, or the concentrate of the fermentation liquid extracted with ethanol and subjected to rotary evaporation, or the purified mannose erythritol lipid.

[0009] Furthermore, the mass volume ratio of the mannitol erythritol lipid to the emulsion to be treated is 5-15 g / L.

[0010] Furthermore, the emulsion to be treated with the mannose erythritol lipid is fully mixed by shearing, shaking, stirring, vortex mixing or ultrasound.

[0011] Furthermore, when the emulsion to be treated is mixed with the mannitol erythritol lipid by shearing, a high-speed shearing machine is used for shearing at 15000 rpm for at least 5 minutes.

[0012] Furthermore, the salt is an inorganic salt or an organic salt; the inorganic salt is selected from potassium chloride, sodium chloride, and magnesium sulfate; the organic salt is selected from sodium acetate or sodium citrate.

[0013] Furthermore, the mass volume ratio of the salt to the emulsion is 10-15 g / L.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. The present invention adopts salinity-sensitive biosurfactant mannitol erythritol lipid as a demulsifier. The present invention achieves co-emulsification by adding mannitol erythritol lipid to the emulsion to be treated and mixing evenly, then adding salt to the mixed emulsion and standing at 10-50°C to achieve oil phase separation.

[0016] 2. Mannose erythritol lipid has excellent surface / interfacial activity and good green environmental friendly characteristics. The present invention is simple to operate, green and environmentally friendly, and will not produce secondary pollution; it has the characteristics of high demulsification activity, fast oil phase separation speed, energy saving, etc., and the conditions are mild, with little damage to equipment and instruments, and can be used for demulsification in many industrial fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative labor.

[0018] Figure 1 A schematic flow chart of a two-step efficient demulsification method for mannose erythritol lipids provided in an embodiment of the present invention;

[0019] Figure 2 A graph showing the change in mannose erythritol lipid solubility with salinity provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] It should be noted that, in the absence of conflict, the features in the following embodiments and implementations may be combined with each other.

[0022] like Figure 1 As shown, the embodiment of the present invention provides a two-step efficient demulsification method for mannose erythritol lipid, the method comprising:

[0023] Step S1, adding mannitol erythritol lipid to the emulsion to be treated and mixing evenly to achieve co-emulsification; wherein the mass volume ratio of mannitol erythritol lipid to the emulsion to be treated is 2-15 g / L.

[0024] Furthermore, the mannose erythritol lipids (MELs) are the fermentation liquid of the aphid-mimicking yeast, or the concentrate of the fermentation liquid extracted with ethanol and subjected to rotary evaporation, or the purified mannose erythritol lipids.

[0025] Mannose erythritol lipids include: MEL-A, MEL-B, MEL-C, MEL-D, and the general structural formula is as follows:

[0026]

[0027] Among them, MEL-A:R 1 =R 2 =Ac;MEL-B:R 1 =Ac,R2 =H;MEL-C:R 1 =H,R 2 =Ac;MEL-D:R 1 =R 2 =H; n 1 ,n 2 =6~10

[0028] Further, the emulsion to be treated with the mannose erythritol fat is fully mixed by shearing, shaking, stirring, vortex mixing or ultrasonication. Generally speaking, at a laboratory scale, when the emulsion to be treated is mixed with the mannose erythritol fat by shearing, a high-speed shearing machine is used to shear at least 5 minutes at 15000 rpm. In actual industrial applications, good mixing can be achieved with the help of a centrifugal pump, a static mixer, etc.

[0029] Furthermore, the mass volume ratio of the mannitol erythritol lipid to the emulsion to be treated is preferably 5-10 g / L.

[0030] Step S2, adding salt to the mixed emulsion and standing at 10-50° C. to achieve oil phase separation; wherein the mass volume ratio of salt to emulsion is 1-15 g / L.

[0031] Furthermore, the salt is an inorganic salt or an organic salt; the inorganic salt is selected from potassium chloride, sodium chloride, and magnesium sulfate; the organic salt is selected from sodium acetate or sodium citrate.

[0032] Furthermore, the mass volume ratio of salt to emulsion is preferably 10-15 g / L.

[0033] Furthermore, the higher the temperature, the better the treatment effect; the standing time varies slightly with the standing temperature, and the higher the temperature, the shorter the required standing time; efficient oil phase separation can be achieved by standing for 0.5-7h at room temperature (25°C).

[0034] Figure 2 The graph showing the change of mannose erythritol lipid solubility with salinity is shown in Figure 2 It can be seen that as the salt concentration increases and the standing time increases, the solubility of mannose erythritol lipid gradually decreases.

[0035] It should be noted that mannitol erythritol lipid has efficient surface / interfacial activity. Under stirring, shearing or shaking, it can be quickly adsorbed on the oil-water interface of the emulsion, and synergistically stabilize the emulsion with the emulsifier in the emulsion. Mannitol erythritol lipid is a non-ionic biosurfactant. In a high-salinity environment, its solubility decreases, and then it quickly desorbs from the emulsion interface, causing the emulsion particles to become unstable and the oil-water phase to separate. During the operation, the more mannitol erythritol lipid is added, the easier it is to achieve co-emulsification. For the same emulsion made from mannitol erythritol lipid, the greater the amount of salt added, the higher the demulsification efficiency, oil phase recovery rate and efficiency.

[0036] The method of first co-emulsification and then demulsification of the present invention is based on the efficient surface / interfacial activity of mannoerythritol lipids and the characteristic that they cannot be dissolved (or dispersed) in a high-salinity environment. It does not require special equipment and can achieve efficient demulsification and oil phase separation only by adjusting the dosage and salinity. It can be applied to demulsification in multiple industrial fields.

[0037] Example 1

[0038] Soybean oil and water were mixed in a volume ratio of 7:3, 5 g / L alkyl polyglycoside (APG) was added, and the mixture was sheared at 15000 rpm for 5 min using a high-speed shearing machine to prepare a soybean oil-water emulsion. The emulsion was very stable and had a demulsification rate of less than 3% when left standing at room temperature for 24 h.

[0039] 2, 5, 10, and 15 g / L of mannose erythritol lipids were added to the above emulsions, respectively. Mannose erythritol lipids are fermentation broths of mimic aphid yeast (including a mixture of multiple MELs). Then, the emulsions were sheared at 15,000 rpm for 1 min, 10 g / L of NaCl was added, and the emulsions were allowed to stand at room temperature for 0.5 h. The results are shown in Table 1 below. As can be seen from Table 1, the above treatments can achieve efficient oil separation.

[0040] Table 1

[0041] Mannose erythritol lipids (g / L) Oil phase recovery rate (%) 2 85.6±1.2 5 94.7±2.1 10 96.5±1.3 15 96.8±0.5

[0042] Example 2

[0043] Soybean oil and water were mixed in a volume ratio of 7:3, 5 g / L alkyl polyglycoside (APG) was added, and the mixture was sheared at 15000 rpm for 5 min using a high-speed shearing machine to prepare a soybean oil-water emulsion. The emulsion was very stable and had a demulsification rate of less than 3% when left standing at room temperature for 24 h.

[0044] 5 g / L of mannose erythritol lipid was added to the above emulsion. Mannose erythritol lipid is a crude product (containing a mixture of multiple MELs) purified from the fermentation broth of mimic aphid yeast. Then, it was sheared at 15000 rpm for 1 min, different concentrations of NaCl were added, and it was left to stand at room temperature for 0.5 h. The results are shown in Table 2 below. As can be seen from Table 2, the above treatments can achieve efficient oil separation.

[0045] Table 2

[0046]

[0047]

[0048] Comparative Example 1

[0049] Soybean oil and water were mixed in a volume ratio of 7:3, 5 g / L alkyl polyglycoside (APG) was added, and the mixture was sheared at 15000 rpm for 5 min using a high-speed shearing machine to prepare a soybean oil-water emulsion. The emulsion was very stable and had a demulsification rate of less than 3% when left standing at room temperature for 24 h.

[0050] Different concentrations of NaCl were added to the above emulsion and allowed to stand at room temperature for 0.5 h. It can be seen that it is difficult to achieve rapid and efficient emulsion demulsification when the alkyl glycoside is treated with salt alone.

[0051] Table 3

[0052] NaCl content (g / L) Oil phase recovery rate (%) 1 0 2 0 4 0 6 0 8 0 10 3.5±1.2 15 4.3±0.3

[0053] Comparative Example 2

[0054] Soybean oil and water were mixed in a volume ratio of 7:3, 5 g / L alkyl polyglycoside (APG) was added, and the mixture was sheared at 15000 rpm for 5 min using a high-speed shearing machine to prepare a soybean oil-water emulsion. The emulsion was very stable and had a demulsification rate of less than 3% when left standing at room temperature for 24 h.

[0055] 5g / L of rhamnolipid, 5g / L of sophorolipid, and 1g / L of lipopeptide (surfactin) were added to the above emulsion. Rhamnolipid is a biosurfactant produced by Pseudomonas aeruginosa fermentation, sophorolipid is a biosurfactant produced by yeast fermentation, and surfactin is a biosurfactant produced by Bacillus subtilis fermentation (a mixture of multiple surfactins). Then it was placed at 15000rpm and sheared for 1min, 10g / L of NaCl was added, and it was left to stand at room temperature for 0.5h. The results are shown in Table 4 below. As shown in Table 4, the above biosurfactants cannot achieve efficient and rapid demulsification.

[0056] Table 4

[0057] Types of biosurfactants Oil phase recovery rate (%) Rhamnolipid 0 Sophorolipids 5.1±1.3 Lipopeptide (surfactin) 0

[0058] Comparative Example 3

[0059] Soybean oil and water were mixed in a volume ratio of 7:3, 5 g / L alkyl polyglycoside (APG) was added, and the mixture was sheared at 15000 rpm for 5 min using a high-speed shearing machine to prepare a soybean oil-water emulsion. The emulsion was very stable and had a demulsification rate of less than 3% when left standing at room temperature for 24 h.

[0060] 5 g / L of mannose erythritol lipid was added to the emulsion, where the mannose erythritol lipid was a crude product purified from the fermentation broth of aphid-mimicking yeast (including a mixture of various MELs), and then sheared at 15,000 rpm for 1 minute and allowed to stand at room temperature for one month, and the emulsion demulsification rate was less than 5%.

[0061] In summary, the present invention uses salinity-sensitive biosurfactant mannitol erythritol lipid as a demulsifier. The present invention achieves co-emulsification by adding mannitol erythritol lipid to the emulsion to be treated and mixing evenly, then adding salt to the mixed emulsion, and standing at 10-50°C to achieve oil phase separation; mannitol erythritol lipid has excellent surface / interfacial activity and good green environmental friendly characteristics. The present invention is simple to operate, green and environmentally friendly, and will not produce secondary pollution; it has the characteristics of high demulsification activity, fast oil phase separation speed, energy saving, etc., and the conditions are mild, and the damage to equipment and instruments is small, and it can be used for demulsification in many industrial fields.

[0062] The above is only a preferred example of the present invention, and is not intended to limit the protection scope of the present invention. In addition to the above embodiments, the present invention may also have other implementations. Any technical solution formed by equivalent replacement or equivalent change falls within the protection scope required by the present invention.

Claims

1. A two-step efficient demulsification method for mannose erythritol lipid, characterized in that: The method comprises: Adding mannitol erythritol lipid to the emulsion to be treated and mixing evenly to achieve co-emulsification; wherein the mass volume ratio of mannitol erythritol lipid to the emulsion to be treated is 2-15 g / L; Add salt to the mixed emulsion and let it stand at 10-50° C. to achieve oil phase separation; wherein the mass volume ratio of salt to emulsion is 1-15 g / L.

2. A two-step efficient demulsification method for mannose erythritol lipid according to claim 1, characterized in that: The mannose erythritol lipid is the fermentation liquid of aphid-mimicking yeast, or the concentrate of the fermentation liquid extracted with ethanol and subjected to rotary evaporation, or the purified mannose erythritol lipid.

3. A two-step efficient demulsification method for mannose erythritol lipid according to claim 1, characterized in that: The mass volume ratio of the mannose erythritol lipid to the emulsion to be treated is 5-15 g / L.

4. A two-step efficient demulsification method for mannose erythritol lipid according to claim 1, characterized in that: The emulsion to be treated with mannose erythritol lipid added thereto is fully mixed and homogeneous by shearing, shaking, stirring, vortex mixing or ultrasonication.

5. A two-step efficient demulsification method for mannose erythritol lipid according to claim 3, characterized in that: When the emulsion to be treated is mixed with the mannitol erythritol lipid by shearing, a high-speed shearing machine is used for shearing at 15000 rpm for at least 5 minutes.

6. A two-step efficient demulsification method for mannose erythritol lipid according to claim 1, characterized in that: The salt is an inorganic salt or an organic salt; the inorganic salt is selected from potassium chloride, sodium chloride, and magnesium sulfate; the organic salt is selected from sodium acetate or sodium citrate.

7. A two-step efficient demulsification method for mannose erythritol lipid according to claim 1, characterized in that: The mass volume ratio of salt to emulsion is 10-15 g / L.