Anti-sticking structure as well as preparation method and application thereof
By processing a two-dimensional dot matrix groove structure on the surface of the pipeline substrate and forming sealed air pockets with femtosecond laser treatment, the problem of adhesion blockage in CO2 hydrate transportation is solved, and efficient hydrophobic performance and stable anti-adhesion effect are achieved.
Patent Information
- Application Number
- CN202510443193.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-09
- Publication Date
- 2025-07-11
AI Technical Summary
CO2 hydrate is prone to adhere to the pipe wall during transportation, resulting in clogging, and the existing hydrophobic coatings have poor durability and are prone to fall off.
The grooves arranged in two-dimensional dot matrix are processed on the surface of the pipeline substrate. The grooves are hexagonal, square or round, and sealed air pockets are formed by femtosecond laser treatment to improve hydrophobic performance and integrate them with the substrate.
Effectively reduce the wettability of CO2 hydrate and pipeline, prevent adhesion, improve anti-adhesion performance and maintain structural stability, contact angles up to 128.929~133.059°, and adhesion force as low as 3.9758~2.9153mN/m.
Smart Images
Figure CN120292358A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of CO2 hydrate transportation, and particularly to an anti-adhesion structure, a preparation method thereof and an application thereof. Background Art
[0002] The combustion of fossil fuels has led to a continuous increase in greenhouse gases. Among them, the excessive emission of CO2 is the main reason for the intensification of global warming. In order to mitigate the impact of greenhouse gases on the earth's climate, the capture, transportation and utilization of CO2 have become the top priorities at present.
[0003] At present, the technology of CO2 capture, transportation and utilization based on hydrates is safe, economical and efficient, and is an internationally recognized effective technical solution to address climate change, significantly reduce carbon emissions and ultimately achieve carbon neutrality; each volume of CO2 hydrate can store 170 times the volume of CO2. Among them, the transportation of CO2 hydrates plays a bridging role in the technology of hydrate-based CO2 capture, transportation and utilization, and is a key link in carbon capture, utilization and storage. However, when transporting CO2 hydrates, there is a pre-melted layer on the surface of CO2 hydrate particles, which makes the hydrate particles have a certain wettability in the fluid, resulting in the adhesion between the hydrate particles and the transportation pipeline wall; at the same time, a liquid bridge will be formed between the pre-melted layer on the surface of CO2 hydrate particles and the pipeline wall surface. After the formation of the liquid bridge, capillary force is generated through capillary action, causing the hydrates to continuously adhere, ultimately leading to pipeline blockage.
[0004] The wettability of water to solids is a common interfacial phenomenon. Hydrophobic surfaces can effectively improve wettability, thereby reducing the adhesion force between hydrate particles and the wall surface, and reducing the risk of blockage of CO2 hydrate transportation pipelines. Currently, the commonly used method to form a hydrophobic surface is to coat a hydrophobic coating on the pipeline surface. However, the durability of the coating is poor and it is easily peeled off under the scouring of CO2 hydrates, and it may lose its anti-adhesion performance for hydrates after long-term use. Summary of the Invention
[0005] The purpose of the present invention is to provide an anti-adhesion structure, a preparation method thereof and an application thereof. The anti-adhesion structure provided by the present invention can effectively prevent the adhesion of CO2 hydrates, and at the same time, the anti-adhesion structure and the pipeline matrix are of an integral structure and will not be washed off.
[0006] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:
[0007] The present invention provides an anti-adhesion structure, including a matrix and grooves arranged on the surface of the matrix; the grooves are arranged in a two-dimensional lattice on the surface of the matrix; the projected shape of the grooves on the surface of the matrix is a regular hexagon, a square or a circle.
[0008] Preferably, when the projected shape of the groove on the substrate surface is a regular hexagon, the grooves are arranged in a honeycomb lattice.
[0009] Preferably, when the projected shape of the groove on the substrate surface is a regular hexagon, the side length of the groove is 80 - 120 μm, the depth is 40 - 60 μm, and the spacing is 40 - 60 μm.
[0010] Preferably, when the projected shape of the groove on the substrate surface is a square or a circle, the grooves are arranged in a square lattice.
[0011] Preferably, when the projected shape of the groove on the substrate surface is a square, the side length of the groove is 130 - 170 μm, the depth is 40 - 60 μm, and the spacing is 40 - 60 μm.
[0012] Preferably, when the projected shape of the groove on the substrate surface is a circle, the diameter of the groove is 130 - 170 μm, the depth is 40 - 60 μm, and both the horizontal spacing and the vertical spacing are 40 - 60 μm.
[0013] The present invention also provides a preparation method of the anti - sticking structure according to the above - mentioned technical solution, including:
[0014] Processing the surface of the substrate with femtosecond laser to obtain the anti - sticking structure.
[0015] Preferably, the laser wavelength of the femtosecond laser is 1030 - 1050 nm, the pulse width is 400 - 900 fs, the repetition frequency is 400 - 1000 kHz, and the scanning speed is 0.01 - 0.1 m / s.
[0016] The present invention also provides an application of the anti - sticking structure according to the above - mentioned technical solution or the anti - sticking structure obtained by the preparation method according to the above - mentioned technical solution in a pipeline for CO2 hydrate transportation.
[0017] Preferably, the inner wall of the pipeline is the anti - sticking structure according to the above - mentioned technical solution or the anti - sticking structure obtained by the preparation method according to the above - mentioned technical solution.
[0018] The present invention provides an anti - sticking structure, which includes a substrate and grooves arranged on the surface of the substrate; the grooves are arranged in a two - dimensional lattice on the substrate surface; the projected shape of the grooves on the substrate surface is a regular hexagon, a square or a circle. By arranging grooves with a specific structure on the substrate surface, the present invention can effectively reduce the contact area between CO2 hydrate and the substrate surface; at the same time, the groove structure effectively increases the surface roughness of the substrate. The groove structure realizes the encapsulation of air in the environment, forms a sealed air cavity, effectively improves the hydrophobic property, reduces the wettability between CO2 hydrate and the substrate, and effectively improves the anti - sticking property; and makes CO2 hydrate contact with the convex structure formed by the sealed air cavity, further reducing the contact area between CO2 hydrate and the substrate surface, thereby effectively improving the anti - sticking property of the anti - sticking structure; and the groove structure in the anti - sticking structure and the substrate are an integral structure, and will not fall off under the scouring of CO2 hydrate, effectively improving the stability and firmness of the anti - sticking structure and further improving the anti - sticking property. The results of the examples show that the contact angle of the anti - sticking structure provided by the present invention is as high as 128.929 - 133.059°, and the adhesion force can be as low as 3.9758 - 2.9153 mN / m. Description of the Drawings
[0019] Figure 1 Microstructure photograph of the anti - sticking structure of Example 1;
[0020] Figure 2 Microstructure photograph of the anti - sticking structure of Example 2;
[0021] Figure 3 Microstructure photograph of the anti - sticking structure of Example 3;
[0022] Figure 4 Histogram of the contact angles of the anti - sticking structures of Examples 1 - 3 and the pipe wall structure of Comparative Example 1;
[0023] Figure 5 Histogram of the adhesion forces between the anti - sticking structures of Examples 1 - 3 and the pipe wall structure of Comparative Example 1 and CO2 hydrate. Detailed Description of the Invention
[0024] The present invention provides an anti - sticking structure, which includes a substrate and grooves arranged on the surface of the substrate; the grooves are arranged in a two - dimensional lattice on the substrate surface; the projected shape of the grooves on the substrate surface is a regular hexagon, a square or a circle.
[0025] As an implementation manner of the present invention, the substrate can be 304 stainless steel, X80 pipeline steel or X90 pipeline steel.
[0026] As an embodiment of the present invention, the projected shape of the groove on the surface of the substrate is a regular hexagon, and the grooves are arranged in a honeycomb lattice. In the present invention, by defining the arrangement of grooves with a regular hexagon projected shape, the intermittent distribution of adjacent grooves is made more uniform, the cavitation formed in the grooves is made more continuous, further reducing the contact between the CO2 hydrate and the substrate, and further improving the anti-sticking performance of the anti-sticking structure.
[0027] As an embodiment of the present invention, when the projected shape of the groove on the surface of the substrate is a regular hexagon, the side length of the groove can be 80 - 120 μm, or 90 - 110 μm, or 95 - 100 μm; the depth of the groove can be 40 - 60 μm, or 45 - 55 μm, or 48 - 50 μm; the spacing of the grooves can be 40 - 60 μm, or 45 - 55 μm, or 48 - 50 μm. In the present invention, by defining the size of the groove with a regular hexagon projected shape, the formed sealing cavitation is made more firm and stable, enabling the cavitation to fully play the isolation role, effectively reducing the contact area and improving the hydrophobic performance, and further improving the anti-sticking performance of the anti-sticking structure.
[0028] As another embodiment of the present invention, the projected shape of the groove on the surface of the substrate is a square, and the grooves are arranged in a square lattice. In the present invention, by defining the shape and arrangement of the grooves, their distribution on the substrate is more regular, which helps to fully play the hydrophobic role of the sealing cavitation and further improve the anti-sticking performance of the anti-sticking structure.
[0029] As an embodiment of the present invention, when the projected shape of the groove on the surface of the substrate is a square, the side length of the groove can be 130 - 170 μm, or 140 - 160 μm, or 150 - 155 μm; the depth of the groove can be 40 - 60 μm, or 45 - 55 μm, or 48 - 50 μm; the spacing of the grooves can be 40 - 60 μm, or 45 - 55 μm, or 48 - 50 μm. In the present invention, by defining the size of the groove with a square projected shape, sufficient isolation of the CO2 hydrate can be achieved, and at the same time, the formed cavitation is arranged evenly, further reducing the contact between the hydrate and the substrate and further improving the anti-sticking performance.
[0030] As another embodiment of the present invention, when the projected shape of the groove on the surface of the substrate is a circle, the grooves are arranged in a square lattice. In the present invention, by defining the shape and arrangement of the grooves, their distribution on the substrate is more neat, which helps to fully play the hydrophobic role of the sealing cavitation and further improve the anti-sticking performance of the anti-sticking structure.
[0031] As an embodiment of the present invention, when the projected shape of the groove on the surface of the substrate is circular, the diameter of the groove can be 130 - 170 μm, can also be 140 - 160 μm, or can also be 150 - 155 μm; the depth of the groove can be 40 - 60 μm, can also be 45 - 55 μm, or can also be 48 - 50 μm; the lateral spacing and longitudinal spacing of the grooves are both 40 - 60 μm, can also be 45 - 55 μm, or can also be 48 - 50 μm. In the present invention, by defining the size of the groove, while achieving sufficient isolation of CO₂ hydrate, the hydrophobic effect of the cavitation is fully exerted, the cavitation rupture is avoided, and the anti-sticking performance of the anti-sticking structure is further improved.
[0032] The anti-sticking structure provided by the present invention utilizes the groove and the sealed cavitation formed in the groove to fully isolate the contact between the CO₂ hydrate and the substrate, and at the same time effectively improve the hydrophobic property of the substrate surface, reduce the wettability of the hydrate to the substrate, thereby effectively improving the anti-sticking performance of the anti-sticking structure; at the same time, the groove is arranged on the surface of the substrate and is an integral structure with the substrate, effectively avoiding the problem of the anti-sticking structure falling off under the scouring of the CO₂ hydrate, effectively improving the stability and firmness of the anti-sticking structure, and further improving the anti-sticking performance.
[0033] The present invention also provides a preparation method of the anti-sticking structure described in the above technical solution, including:
[0034] Using femtosecond laser to process the surface of the substrate to obtain the anti-sticking structure.
[0035] As an embodiment of the present invention, the laser wavelength of the femtosecond laser can be 1030 - 1050 nm, can also be 1035 - 1045 nm, or can also be 1038 - 1040 nm; the pulse width of the femtosecond laser can be 400 - 900 fs, can also be 500 - 800 fs, or can also be 600 - 700 fs; the repetition frequency of the femtosecond laser can be 400 - 1000 kHz, can also be 600 - 900 kHz, or can also be 700 - 800 kHz; the scanning speed of the femtosecond laser can be 0.01 - 0.1 m / s, can also be 0.02 - 0.08 m / s, or can also be 0.05 - 0.06 m / s; the power of the femtosecond laser can be 7 - 13 W, can also be 8 - 12 W, or can also be 9 - 10 W. In the present invention, by defining the process parameters of the femtosecond laser, sufficient treatment of the substrate surface is achieved, a specific anti-sticking structure is formed, and its anti-sticking performance is further improved. In the embodiments of the present invention, the device of the femtosecond laser is an ultraviolet femtosecond laser.
[0036] The preparation method provided by the present invention forms physical anti-sticking through specific treatment methods, improves the isolation effect of the groove structure on hydrates by directly treating the substrate surface, and at the same time improves the hydrophobic effect of the cavities in the grooves, thereby effectively improving the anti-sticking performance of the anti-sticking structure.
[0037] The present invention also provides an application of the anti-sticking structure described in the above technical solution or the anti-sticking structure obtained by the preparation method described in the above technical solution in a pipeline for transporting CO2 hydrates.
[0038] As an implementation manner of the present invention, the inner wall of the pipeline is the anti-sticking structure described in the above technical solution or the anti-sticking structure obtained by the preparation method described in the above technical solution.
[0039] To further illustrate the present invention, the following describes in detail the anti-sticking structure provided by the present invention, its preparation method and application in conjunction with embodiments, but they cannot be understood as limiting the protection scope of the present invention.
[0040] Example 1
[0041] An anti-sticking structure is composed of the inner wall of a 304 stainless steel pipe and grooves provided on the inner wall surface of the 304 stainless steel pipe; the projection shape of the grooves on the substrate surface is a regular hexagon; the grooves are arranged in a honeycomb lattice; the side length of the grooves is 100 μm, the depth is 50 μm, and the spacing is 50 μm.
[0042] The microscopic structure photograph of the anti-sticking structure taken by using a 3D confocal microscope (OLYMPUS, LEXT OLS5000, Japan) is as Figure 1 shown.
[0043] The preparation method of the anti-sticking structure is as follows:
[0044] The substrate surface is processed by using an ultraviolet femtosecond laser (Monaco 345-20-25) to obtain an anti-sticking structure; wherein the laser wavelength of the femtosecond laser is 1030 nm, the pulse width is 600 fs, the repetition frequency is 700 kHz, the scanning speed is 0.05 m / s, and the power is 10 W.
[0045] Example 2
[0046] An anti-sticking structure is composed of the inner wall of a 304 stainless steel pipe and grooves provided on the inner wall surface of the 304 stainless steel pipe; the projection shape of the grooves on the substrate surface is a square; the grooves are arranged in a square lattice; the side length of the grooves is 150 μm, the depth is 50 μm, and the spacing is 50 μm.
[0047] Microstructure photos of the anti-adhesion structure taken by a 3D confocal microscope (OLYMPUS, LEXT OLS5000, Japan) are as follows Figure 2 as shown
[0048] The preparation method of the anti-adhesion structure is as follows
[0049] The surface of the substrate is processed by an ultraviolet femtosecond laser to obtain the anti-adhesion structure; the laser wavelength of the femtosecond laser is 1030 nm, the pulse width is 600 fs, the repetition frequency is 700 kHz, the scanning speed is 0.05 m / s, and the power is 10 W
[0050] Example 3
[0051] An anti-adhesion structure is composed of the inner wall of a 304 stainless steel tube and grooves arranged on the surface of the inner wall of the 304 stainless steel tube; the projected shape of the grooves on the substrate surface is circular; the grooves are arranged in a square lattice; the side length of the grooves is 150 μm, the depth is 50 μm, and the horizontal and vertical spacings are both 50 μm
[0052] Microstructure photos of the anti-adhesion structure taken by a 3D confocal microscope (OLYMPUS, LEXT OLS5000, Japan) are as follows Figure 3 as shown
[0053] The preparation method of the anti-adhesion structure is as follows
[0054] The surface of the substrate is processed by an ultraviolet femtosecond laser to obtain the anti-adhesion structure; the laser wavelength of the femtosecond laser is 1030 nm, the pulse width is 600 fs, the repetition frequency is 700 kHz, the scanning speed is 0.05 m / s, and the power is 10 W
[0055] Comparative Example 1
[0056] A pipe wall structure is the inner wall of a 304 stainless steel tube
[0057] Test Example 1
[0058] The contact angles of the anti-adhesion structures of Examples 1-3 and the pipe wall structure of Comparative Example 1 were measured using a dynamic / static contact angle meter (SL200B / Ke, Konos Industry Co., Ltd., USA), and the results are shown in Table 1 and Figure 4 as shown
[0059] Table 1 Contact angle record table of the anti-adhesion structures of Examples 1-3 and the pipe wall structure of Comparative Example 1
[0060] Example Example 1 Example 2 Example 3 Comparative Example 1 Contact Angle (deg) 133.059 130.536 128.929 78.751
[0061] As can be seen from Table 1, the contact angle of the anti-sticking structure provided in the embodiments of the present invention is significantly higher than that of the untreated pipe wall surface of the comparative example, indicating that the anti-sticking structure provided by the present invention can effectively improve the hydrophobic performance of the inner wall surface of the pipeline, and thus effectively improve the anti-sticking performance.
[0062] Test Example 2
[0063] Spray droplets (water droplets) on a glass fiber by the spraying method, and scrape the sprayed droplets with the end of another glass fiber to form droplets with a diameter of about 1 mm at the end of the glass fiber. Quickly immerse the droplets in liquid nitrogen and keep them for 30 seconds to freeze the water droplets into ice particles. Install the glass fiber with ice particles at the end in a reaction kettle at a temperature of -3°C, and introduce CO2 gas to 2.5 MPa, and the ice particles cannot be melted during this period. Use the charging and discharging method to discharge the gas to 1.5 MPa and then re-inflate to 2.5 MPa until hydrate particles are generated.
[0064] After the hydrate particles are generated, continue to raise the temperature to 1.5°C, and keep the hydrate particles stable for 1 h under the conditions of 2.5 MPa and 1.5°C, and then contact them with the anti-sticking structures of Examples 1 to 3 and the pipe wall structure of Comparative Example 1 for 10 s respectively; use a high-pressure micro-mechanical force measuring device (HP-MMF) to measure the adhesion force between the CO2 hydrate and the anti-sticking structures of Examples 1 to 3 and the pipe wall structure of Comparative Example 1 under the conditions of 2.5 MPa and 1.5°C respectively. The results obtained are shown in Table 2 and Figure 5 as shown.
[0065] Table 2 Record table of the adhesion force between the anti-sticking structures of Examples 1 to 3 and the pipe wall structure of Comparative Example 1 and CO2 hydrate
[0066] Example Example 1 Example 2 Example 3 Comparative Example 1 Adhesion Force (mN / m) 2.9153 3.2022 3.9758 7.7084
[0067] As can be seen from Table 2, the adhesion force between the anti-sticking structure provided in the embodiments of the present invention and the CO2 hydrate is significantly lower than the adhesion force between the untreated pipe wall structure of the comparative example and the CO2 hydrate, indicating that the anti-sticking structure provided by the present invention has excellent anti-sticking performance.
[0068] In summary, the anti-sticking structure provided by the present invention has excellent hydrophobic performance and anti-sticking performance.
[0069] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.
Claims
1. An anti-sticking structure, characterized in that, It includes a substrate and grooves provided on the surface of the substrate; the grooves are arranged in a two-dimensional lattice on the substrate surface; the projected shape of the grooves on the substrate surface is a regular hexagon, a square or a circle.
2. The anti-sticking structure according to claim 1, characterized in that, When the projected shape of the grooves on the substrate surface is a regular hexagon, the grooves are arranged in a honeycomb lattice.
3. The anti-sticking structure according to claim 1 or 2, characterized in that When the projected shape of the grooves on the substrate surface is a regular hexagon, the side length of the grooves is 80 - 120 μm, the depth is 40 - 60 μm, and the spacing is 40 - 60 μm.
4. The anti-sticking structure according to claim 1, wherein When the projected shape of the grooves on the substrate surface is a square or a circle, the grooves are arranged in a square lattice.
5. The anti-sticking structure according to claim 1 or 4, characterized in that, When the projected shape of the grooves on the substrate surface is a square, the side length of the grooves is 130 - 170 μm, the depth is 40 - 60 μm, and the spacing is 40 - 60 μm.
6. The anti-sticking structure according to claim 1 or 4, characterized in that, When the projected shape of the grooves on the substrate surface is a circle, the diameter of the grooves is 130 - 170 μm, the depth is 40 - 60 μm, and both the horizontal spacing and the vertical spacing are 40 - 60 μm.
7. The preparation method of the anti-sticking structure according to any one of claims 1 to 6, characterized in that, It includes: Processing the surface of the substrate with femtosecond laser to obtain an anti - sticking structure.
8. The preparation method according to claim 7, characterized in that, The laser wavelength of the femtosecond laser is 1030 - 1050 nm, the pulse width is 400 - 900 fs, the repetition frequency is 400 - 1000 kHz, and the scanning speed is 0.01 - 0.1 m / s.
9. Application of the anti - sticking structure according to any one of claims 1 - 6 or the anti - sticking structure obtained by the preparation method according to claim 7 or 8 in a pipeline for CO2 hydrate transportation.
10. The application according to claim 9, wherein The inner wall of the pipeline is the anti - sticking structure according to any one of claims 1 - 6 or the anti - sticking structure obtained by the preparation method according to claim 7 or 8.