PH self-adaptive oil absorption tow for recycling underwater spilled oil

Abstract

The invention discloses a pH (Potential of Hydrogen) self-adaptive oil absorption tow for recycling underwater spilled oil. Comprising a plurality of acidic oil-absorbing filaments and alkaline oil-absorbing filaments which are arranged at intervals, and deformation layers are arranged between the adjacent acidic oil-absorbing filaments and alkaline oil-absorbing filaments; when the external pH value is smaller than the neutral pH value, the deformation layer is bent towards one side of the alkaline oil absorption filaments, and the sectional area of the acidic oil absorption filaments is enlarged; when the pH value is greater than the neutral pH value, the deformation layer is bent towards one side of the acidic oil-absorbing filaments, and the sectional area of the alkaline oil-absorbing filaments is enlarged; when the pH value is smaller than the neutral pH value, the oil absorption capacity of the acidic oil absorption filaments is higher than that of the alkaline oil absorption filaments; when the pH value is larger than the neutral pH value, the oil absorption capacity of the acid oil absorption filaments is lower than that of the alkaline oil absorption filaments. The device has the beneficial effects that under the condition that the total sectional area is not changed, efficient adsorption of spilled oil can be realized under wide pH values.

Description

Technical Field

[0001] The invention relates to the technical field of oil spill collection, in particular to a pH self-adaptive oil absorbing thread bundle for recovering underwater oil spill. Background Art

[0002] With the rapid development of the economy, global crude oil production activities are constantly increasing, especially the output of offshore oil is increasing year by year. The depth of offshore oil development in the world shows a trend of deepening year by year, gradually moving from shallow water to deep water, but the risk of oil spills is also gradually increasing. Toxic substances such as volatile organic compounds and polycyclic aromatic hydrocarbons contained in oil spills are toxic to marine organisms, interfere with the growth and development of marine organisms, and pose a threat to deep-sea biodiversity. In addition, oil spills also have potential effects on human health, have a negative impact on production activities in specific sea areas, and interfere with the sustainable development of the marine economy. Therefore, the oil industry of various countries pays great attention to the prevention of underwater oil spills and carries out research and development of oil spill disposal technologies under various special environments, such as underwater recovery hoods and adsorption recovery and other efficient disposal technologies. The underwater recovery hood is arranged above the underwater oil spill point. Underwater spilled oil floats up under its own buoyancy, is collected by the recovery hood, and then recovered to the ship on the sea surface through a hose. Oil absorbent materials such as oil absorbent filaments can efficiently absorb and recover oil spills due to their strong adsorption capacity and reusability, and are a research hotspot in the field of marine environmental governance. The oil-absorbing filaments are coated on the inner surface of the recovery cover. Their oil-absorbing and flow-conducting properties can promote the collection of spilled oil to the top of the recovery cover, thereby facilitating the recovery of underwater spilled oil.

[0003] The adsorption process of oil spills in seawater by oil absorbent materials is affected by multiple environmental parameters such as temperature, salinity and pH value. In particular, the pH value of the oil-water interface can change the microscopic charge distribution on the surface of the oil absorbent material, change the strength of the forces between molecules such as hydrogen bonds, and affect the efficient adsorption and recovery of oil spills. Although the marine environment is relatively stable near the neutral pH value, oil spills from blowouts during underwater drilling often leak together with drilling fluids and formation fluids, thus affecting the pH value of the oil-water interface in the adjacent sea area. Commonly used drilling fluids contain a certain amount of alkaline additives such as calcium hydroxide, sodium hydroxide and sodium carbonate, which have the purpose of stabilizing the well wall and protecting the reservoir. In particular, dispersed drilling fluids are usually controlled at an alkaline pH value of 8 to 12. In addition, the pH value of some formation fluids is acidic, and the acidification operation during crude oil extraction will also significantly reduce the pH value of the formation fluid, even as low as pH 2. Since the pH value of the adjacent sea area fluctuates widely due to the simultaneous leakage of underwater blowout oil spills and drilling fluids and formation fluids, achieving efficient adsorption under a wide range of pH values ​​is one of the key points in the development of oil absorbing materials.

[0004] In order to solve the problem of efficient adsorption of oil absorbent materials under a wide range of pH values, surface modification of the oil absorbent materials themselves is the main method adopted at home and abroad. There are many limiting factors in the modification of oil absorbent materials, and it is difficult to achieve stable adsorption of oil spills in a wider pH range. Considering that underwater blowout oil spills often leak together with drilling fluids and formation fluids, and the pH value of the oil-water interface in the adjacent sea area fluctuates widely, the existing methods cannot meet the needs of oil spill recovery. Summary of the invention

[0005] The purpose of the present invention is to provide a pH adaptive oil absorption fiber bundle for underwater oil spill recovery, which is composed of acidic oil absorption fibers, alkaline oil absorption fibers and a deformation layer. The cross-sectional areas of the acidic oil absorption fibers and the alkaline oil absorption fibers are changed by the deformation layer. Under the condition of ensuring that the total cross-sectional area remains unchanged, efficient oil spill absorption can be achieved under a wide range of pH values.

[0006] To achieve the above object, the present invention adopts the following technical solutions, including:

[0007] A plurality of acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils are arranged at intervals, and a deformation layer is provided between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the deformation layer bends toward the acidic oil-absorbing fibrils to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is higher than that of the alkaline oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is lower than that of the alkaline oil-absorbing fibrils;

[0008] Wherein, the acidic oil-absorbing filaments are made of polystyrene-poly (acrylic acid)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 1;

[0009]

[0010] The alkaline oil-absorbing filaments are composed of polystyrene-poly (4-vinyl pyridine)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 2;

[0011]

[0012] The deformation layer is composed of cellulose phosphate-polycaprolactone-polytoluene diisocyanate-polyethylene glycol, and the structural formula is shown in Formula 3;

[0013]

[0014] Wherein a, b, c, d, e, f, g, h and i are the polymerization degrees, a is 100-300, b is 50-200, c is 100-300, d is 100-300, e is 50-200, f is 10-50, g is 10-50, h is 100-300, and i is a natural number of 100-300.

[0015] Preferably, the cross-sections of the acidic oil-absorbing fibrils and the alkaline oil-absorbing fibrils are triangular.

[0016] Preferably, the cross-section of the acidic oil-absorbing fibrils and the alkaline oil-absorbing fibrils is quadrilateral.

[0017] The beneficial effect of the present invention is that the cross-sectional areas of the acidic oil-absorbing fibrils and the alkaline oil-absorbing fibrils are changed by the deformation layer, and under the condition of ensuring that the total cross-sectional area remains unchanged, efficient adsorption of spilled oil can be achieved under a wide range of pH values. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 1 of the present invention (when the external pH value is equal to the neutral pH value).

[0019] Figure 2 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 1 of the present invention (when the external pH value is less than the neutral pH value).

[0020] Figure 3 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 1 of the present invention (when the external pH value is greater than the neutral pH value).

[0021] Figure 4 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 2 of the present invention (when the external pH value is equal to the neutral pH value).

[0022] Figure 5 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 2 of the present invention (when the external pH value is less than the neutral pH value).

[0023] Figure 6 This is a schematic cross-sectional view of a pH adaptive oil absorbing fiber bundle for underwater oil spill recovery in Example 2 of the present invention (when the external pH value is greater than the neutral pH value). DETAILED DESCRIPTION

[0024] The invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement it according to the description.

[0025] It should be understood that terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or other elements or combinations thereof.

[0026] Example 1

[0027] like Figure 1-3 As shown, a pH adaptive oil absorbing thread bundle 1 for underwater oil spill recovery of the present invention comprises:

[0028] A plurality of acidic oil-absorbing fibrils 110 and alkaline oil-absorbing fibrils 120 are arranged at intervals, and a deformation layer 130 is provided between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils 120 to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils 110; when the pH value is greater than the neutral pH value, the deformation layer 130 bends toward the acidic oil-absorbing fibrils 110 to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils 120; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils 110 is higher than that of the alkaline oil-absorbing fibrils 120; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils 110 is lower than that of the alkaline oil-absorbing fibrils 120. The cross-sections of the acidic oil-absorbing fibrils 110 and the alkaline oil-absorbing fibrils 120 are triangular;

[0029] A plurality of acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils are arranged at intervals, and a deformation layer is provided between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the deformation layer bends toward the acidic oil-absorbing fibrils to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is higher than that of the alkaline oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is lower than that of the alkaline oil-absorbing fibrils;

[0030] Wherein, the acidic oil-absorbing filaments are made of polystyrene-poly (acrylic acid)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 1;

[0031]

[0032] The alkaline oil-absorbing filaments are composed of polystyrene-poly (4-vinyl pyridine)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 2;

[0033]

[0034] The deformation layer is composed of cellulose phosphate-polycaprolactone-polytoluene diisocyanate-polyethylene glycol, and the structural formula is shown in Formula 3;

[0035]

[0036] Wherein a, b, c, d, e, f, g, h and i are the polymerization degrees, a is 100-300, b is 50-200, c is 100-300, d is 100-300, e is 50-200, f is 10-50, g is 10-50, h is 100-300, and i is a natural number of 100-300.

[0037] Example 2

[0038] like Figure 4-6 As shown, a pH adaptive oil absorbing thread bundle 1 for underwater oil spill recovery of the present invention comprises:

[0039] A plurality of intervally arranged acidic oil-absorbing fibrils 110 and alkaline oil-absorbing fibrils 120, with a deformation layer 130 between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils 120 to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils 110; when the pH value is greater than the neutral pH value, the deformation layer 130 bends toward the acidic oil-absorbing fibrils 110 to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils 120; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils 110 is higher than that of the alkaline oil-absorbing fibrils 120; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils 110 is lower than that of the alkaline oil-absorbing fibrils 120. The cross-sections of the acidic oil-absorbing fibrils 110 and the alkaline oil-absorbing fibrils 120 are quadrilaterals;

[0040] A plurality of acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils are arranged at intervals, and a deformation layer is provided between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the deformation layer bends toward the acidic oil-absorbing fibrils to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is higher than that of the alkaline oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is lower than that of the alkaline oil-absorbing fibrils;

[0041] Wherein, the acidic oil-absorbing filaments are made of polystyrene-poly (acrylic acid)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 1;

[0042]

[0043] The alkaline oil-absorbing filaments are composed of polystyrene-poly (4-vinyl pyridine)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 2;

[0044]

[0045] The deformation layer is composed of cellulose phosphate-polycaprolactone-polytoluene diisocyanate-polyethylene glycol, and the structural formula is shown in Formula 3;

[0046]

[0047] Wherein a, b, c, d, e, f, g, h and i are the polymerization degrees, a is 150-250, b is 100-150, c is 150-250, d is 150-250, e is 100-150, f is 20-40, g is 20-40, h is 150-250, and i is a natural number of 150-250.

[0048] In summary, the pH adaptive oil absorbing fiber bundle 1 for underwater oil spill recovery of the present invention changes the cross-sectional area of ​​the acidic oil absorbing fiber 110 and the alkaline oil absorbing fiber 120 through the deformation layer 130, and can achieve efficient adsorption of oil spills under a wide range of pH values ​​while ensuring that the total cross-sectional area remains unchanged.

[0049] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A pH adaptive oil absorbing tow for underwater oil spill recovery, characterized in that: include: A plurality of acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils are arranged at intervals, and a deformation layer is provided between adjacent acidic oil-absorbing fibrils and alkaline oil-absorbing fibrils; when the external pH value is less than the neutral pH value, the deformation layer bends toward the alkaline oil-absorbing fibrils to expand the cross-sectional area of ​​the acidic oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the deformation layer bends toward the acidic oil-absorbing fibrils to expand the cross-sectional area of ​​the alkaline oil-absorbing fibrils; when the pH value is less than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is higher than that of the alkaline oil-absorbing fibrils; when the pH value is greater than the neutral pH value, the oil absorption capacity of the acidic oil-absorbing fibrils is lower than that of the alkaline oil-absorbing fibrils; Wherein, the acidic oil-absorbing filaments are made of polystyrene-poly (acrylic acid)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 1; The alkaline oil-absorbing filaments are composed of polystyrene-poly (4-vinyl pyridine)-polytoluene diisocyanate-polyethylene glycol sponge, and the structural formula is shown in Formula 2; The deformation layer is composed of cellulose phosphate-polycaprolactone-polytoluene diisocyanate-polyethylene glycol, and the structural formula is shown in Formula 3; Wherein a, b, c, d, e, f, g, h and i are the polymerization degrees, a is 100-300, b is 50-200, c is 100-300, d is 100-300, e is 50-200, f is 10-50, g is 10-50, h is 100-300, and i is a natural number of 100-300.

2. The pH adaptive oil absorbing tow for underwater oil spill recovery according to claim 1, characterized in that: The cross sections of the acidic oil-absorbing fibrils and the alkaline oil-absorbing fibrils are triangular.

3. The pH adaptive oil absorbing tow for underwater oil spill recovery according to claim 1, characterized in that: The cross sections of the acidic oil-absorbing fibrils and the alkaline oil-absorbing fibrils are quadrilateral.

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