Filler for gas-liquid reactor and application thereof

Abstract

The invention belongs to the technical field of gas pollutant treatment, and particularly relates to filler for a gas-liquid reactor and application of the filler. The filler comprises a high-wettability corrosion-resistant polymer layer and a corrugated partition plate layer used for providing a channel for gas. The polymer layers and the corrugated partition plate layers in the filler are arranged at intervals, and the two polymer layers are arranged on the two sides of each corrugated partition plate layer in an attached mode respectively; the filler provided by the invention is formed by coupling the high-wettability polymer layer and the corrugated partition plate layer, the high wettability of the polymer layer can ensure that liquid is uniformly distributed on the polymer layer, and a layer of uniform water film is formed, so that the reaction efficiency of reaction gas and the liquid is improved, and a product after the reaction can be taken out by the liquid on the water film in time; the air resistance is reduced and the reaction efficiency is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of gas pollutant treatment, and particularly relates to a filler for a gas-liquid reactor and its application. Background Art

[0002] As a key process equipment in the modern industrial system, the gas-liquid separator has a wide range of applications covering core fields such as energy, chemical industry, environmental protection, and medical treatment, and deeply affects production efficiency and the sustainable development process. In the energy industry, it ensures the efficient separation of gas-liquid mixtures in oil and gas extraction, improves the development economy of unconventional resources (such as shale gas and coalbed methane), and ensures the medium purity in biomass energy purification and the hydrogen energy industrial chain; in the chemical industry, the process stability is optimized by removing reaction by-products and recovering solvents; in environmental protection, the droplet interception after flue gas desulfurization and the gas-liquid treatment of geothermal fluids contribute to the realization of ultra-low emission standards; the medical and food industries rely on its aseptic separation function to ensure process safety.

[0003] Currently, there are more and more types of harmful gases contained in the waste gas generated industrially, and people have tried various methods to remove the harmful gases in the waste gas to meet the emission requirements, so as to carry out safe emission.

[0004] Currently, most of them use traditional scrubbers or spray towers. However, there are still many drawbacks in the currently most used spray towers and scrubbers. In the existing scrubbers / spray towers, problems such as the inability of the spray liquid to be evenly distributed on the filler, large gas resistance during operation, and poor corrosion resistance of the filler have not been solved for a long time. The washing liquid is sprayed out from the spray nozzles of the spray tower, and it is impossible to ensure its even distribution on the filler, resulting in some fillers not being attached with the washing liquid. When the gas passes through this part, it cannot achieve a purification effect. These traditional packed towers have poor removal efficiency for acidic (HF and hydrochloric acid) and alkaline (ammonia) gases when the inlet concentration is lower than 1 ppmv and 3 ppmv, and cannot meet the emission standards. For composite pollutants (such as dust + acid mist + VOCs), multi-stage series treatment is required, and a single spray tower is difficult to take into account. For example, an alkaline spray liquid can neutralize acidic gases, but will saponify with some VOCs to form viscous by-products, exacerbating blockage.

[0005] The gas enters the inside of the scrubber from below and flows upward, and the washing liquid is sprayed downward, which will also form a certain pressure resistance, thus preventing the washing liquid from flowing out and causing a reduction in washing efficiency. In order to achieve the required effect, the gas-liquid ratio needs to be increased, and the system needs to maintain a high liquid-gas ratio (usually 3 - 10 L / m³) to ensure mass transfer efficiency, resulting in the energy consumption of the circulation pump and the fan accounting for 60% - 80% of the total energy consumption of the equipment. This also greatly increases the energy consumption in this process.

[0006] From the aspect of durability, the relationship between cost and output needs to be considered. Some of the substances to be removed currently contain certain corrosiveness. In this regard, if the packing is frequently replaced or the equipment is frequently repaired, it will not only delay the process but also increase the cost. Therefore, careful selection should be made in terms of the materials selected, and materials that are better adapted to this environment should be chosen. High-speed air flow causes droplets to be entrained to the outlet, and a demister needs to be added. However, the traditional baffle demister has low separation efficiency for ultra-fine droplets (<10μm) and is prone to causing corrosion or secondary pollution of downstream equipment. In an acidic (such as H2S, HCl) or alkaline (such as NH3) environment, the corrosion rate of a carbon steel tower body can reach 0.5 - 2 mm / year. Even when using fiberglass (FRP) or PP materials, creep deformation is still likely to occur under long-term high temperature.

[0007] In summary, the traditional scrubbing tower and spray tower have the following technical problems: (1) The nozzles of the traditional scrubbing tower and spray tower will be blocked by the substances generated by the reaction.

[0008] (2) The spray liquid of the traditional scrubbing tower / spray tower is sprayed onto the packing from above, and the distribution on the packing is uneven.

[0009] (3) The packing of the current scrubbing tower / spray tower has poor corrosion resistance and a high replacement frequency. Summary of the Invention

[0010] In view of the above technical problems, the present invention provides a packing for a gas-liquid reactor and a novel gas-liquid reactor.

[0011] In order to achieve the above technical objectives, the present invention provides the following technical solutions: A packing for a gas-liquid reactor, the packing includes a polymer layer with high wettability and corrosion resistance and a corrugated baffle layer for providing channels for gas; in the packing, the polymer layer and the corrugated baffle layer are arranged at intervals, and a polymer layer is respectively attached to both sides of each corrugated baffle layer; The polymer layer is composed of ultra-fine fibers, and the ultra-fine fibers are prepared from any one or all of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), isophthalic acid (IPA); The corrugated baffle layer is made of any one or more of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), polysulfone (PSU), and the corrugated baffle layer includes a number of corrugated units connected in sequence.

[0012] Further, in the polymer layer, the length of the ultrafine fiber is 5 mm - 20 mm, and the diameter is 5 μm - 40 μm; the preparation method of the polymer layer is as follows: When any one of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA) is used to prepare the ultrafine fiber, after the surface of the obtained ultrafine fiber is hydrophilized, the polymer layer is prepared by using the hydrophilized ultrafine fiber; or, when all types of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA) are used to prepare the ultrafine fiber, the mixed hydrophilized ultrafine fiber is prepared according to the ratio of 5 - 20 wt% of polypropylene (PP), 10 - 25 wt% of polyethylene (PE), 10 - 20 wt% of polyethylene terephthalate (PET), 10 - 30 wt% of polyvinyl chloride (PVC), 5 - 20 wt% of polytetrafluoroethylene (PTFE), 10 - 15 wt% of polycarbonate (PC), 2 - 10 wt% of polyamide (PA), and 5 - 20 wt% of isophthalic acid (IPA), and then the polymer layer is prepared by using the mixed hydrophilized ultrafine fiber.

[0013] Further, the surface hydrophilization treatment of the obtained ultrafine fiber is specifically as follows: treating the ultrafine fiber with polyether modified silicone oil and sodium alginate or subjecting the ultrafine fiber to ozone oxidation treatment; among them, the ether modified silicone oil can introduce hydrophilic polyether segments (such as PEG) to endow the fiber with hygroscopicity. Sodium alginate is a natural polysaccharide with good hydrophilicity; by forming a gel through ion exchange between sodium alginate and calcium ions in the fiber and coating it on the fiber surface, the hydrophilicity of the fiber can be significantly enhanced. Ozone treatment can increase the oxygen-containing groups on the fiber surface and thus enhance the hydrophilicity.

[0014] The specific method for preparing the mixed hydrophilized ultrafine fiber is as follows: mixing polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA) according to the ratio, heating and melting them, and adjusting the temperature to 220°C - 300°C to obtain the mixed hydrophilized ultrafine fiber with a diameter of 5 μm - 40 μm.

[0015] In this step, by defining the specific ratio of the raw materials for the preparation of ultrafine fibers or hydrophilizing the ultrafine fibers, the stiffness of the fibers is improved, and the corrosion resistance of the fibers is enhanced; it also enables the liquid to better wet the polymer layer; the ultrafine fibers in the polymer layer contain a large number of hydrophilic groups -OH or oxygen-containing groups. When the polymer layer comes into contact with the liquid, under the guidance of the hydrophilic groups or oxygen-containing groups, liquid molecules can quickly enter the interior of the polymer layer material, and then spread downward under the action of their own gravity. The liquid molecules above are still continuously entering the material interior, and then driven by capillary force, the liquid can spread more evenly. Finally, with the cooperation of Brownian diffusion, the entire material is completely wetted, forming a uniform water film on the surface of the polymer layer, and the reaction rate is increased.

[0016] Furthermore, the method for preparing the polymer layer by using ultrafine fibers with surface hydrophilic modification or by using mixed hydrophilic ultrafine fibers is as follows: Perform a web-forming operation on the ultrafine fibers with surface hydrophilic modification or the mixed hydrophilic ultrafine fibers, set the web-laying speed at 100 - 500 m / min, and set the roll gap at 0.05 - 0.3 mm to form a uniform network structure of ultrafine fiber web; Repeatedly puncture the ultrafine fiber web with barbed needles or impact the ultrafine fiber web with high-pressure micro water jets to entangle the fibers in the ultrafine fiber web and obtain a polymer layer with high wettability and corrosion resistance.

[0017] Furthermore, the thickness of the polymer layer is 0.5 mm - 3 mm; the contact angle of the polymer layer is less than 80°; among them, the size of the thickness of the polymer layer plays an important role in the effect of the polymer layer. When the thickness is too thick, the effective contact area between the polymer and the reactor in the same volume will decrease, and the reaction effect will be reduced. When it is too thin, a uniform water film cannot be formed, and the reaction effect will also be reduced.

[0018] The grammage of the polymer layer is above 150 g / m 2 Above, each gram of the polymer layer absorbs more than 1.5 g of liquid; the corrosion rate of the polymer layer is less than or equal to 0.01 mm / year.

[0019] Furthermore, the width of each corrugated unit in the corrugated partition layer is 1 mm - 6 mm, the thickness is 0.3 mm - 2 mm, and the height is 1 mm - 20 mm.

[0020] Furthermore, the preparation method of the corrugated partition layer includes: Any one or more of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), and polysulfone (PSU) particles are dried to remove moisture, melt-extruded, and then enter a cooling water tank with a water temperature of 10 - 25°C for shaping to form a corrugated corrugated separator; specifically, the melt-extruded melt passes through the corrugated layer structure, and the corrugated layer is pressed into a wavy shape by a designed corrugated roller and is compounded with the upper and lower planar layers in a mold. Then it enters a cooling water tank with a water temperature of 10 - 25°C for shaping to form a corrugated corrugated separator. Among them, when using any multiple of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), and polysulfone (PSU) particles, they can be mixed in any proportion.

[0021] The conditions for drying are 80 - 100°C for 2 - 4 hours; the barrel temperature of the screw extruder is 190 - 260°C, and the die head temperature is 210 - 280°C.

[0022] Furthermore, the filler as a whole is in a roll-type cylindrical structure or a stacked cube structure.

[0023] An application of a filler for a gas-liquid reactor, using the filler to prepare a gas-liquid reactor.

[0024] Furthermore, the gas-liquid reactor prepared using the filler is used for the separation of crude oil and natural gas, for removing liquid hydrocarbons and H2S in natural gas, for the separation of the drug solution and the reaction-generated gas during antibiotic production, for removing moisture and oil mist generated during food processing, for removing SO2 and dust in the fields of steel, non-ferrous metals, cement or glass, or for removing HF, HNO3, HNO2, CH3COOH, HCN, H2SO4 in the semiconductor field.

[0025] The beneficial effects of the present invention are: The filler provided by the present invention is composed of a highly wettable polymer layer and a corrugated separator layer coupled together. The high wettability of the polymer layer can ensure the uniform distribution of liquid on the polymer layer and form a uniform water film, which improves the reaction efficiency of the reaction gas and the liquid. The reaction product can be promptly carried out by the liquid on the water film, reducing the gas resistance and improving the reaction efficiency; moreover, the combination of the corrugated separator layer and the polymer layer provides a specific channel for the reaction gas, avoiding the tortuous reaction path of the gas and improving the reaction efficiency. Description of the Drawings

[0026] Figure 1Electron micrograph of the superfine fibers with hydrophilic treatment in the embodiments of the present invention; Figure 2 Schematic diagram of the corrugated partition layer in the embodiments of the present invention; Figure 3 Thermogravimetric analysis curve in Example 9; Figure 4 Thermogravimetric analysis curve in Example 10; Figure 5 Physical diagram of the cubic structure filler in the embodiments of the present invention; Figure 6 Mechanism diagram of the high wettability of the polymer layer material in the embodiments of the present invention; Reference numerals: 1. Polymer layer; 2. Corrugated partition layer. Detailed implementation manners

[0027] The technical solutions of the present invention will be further described below in conjunction with specific embodiments and the accompanying drawings.

[0028] The technical solutions of the present invention will be clearly and completely described below in a specific implementation manner. However, those skilled in the art will understand that the following described embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can be obtained as conventional products through commercial purchase.

[0029] The filler includes a polymer layer with high wettability and corrosion resistance and a corrugated partition layer for providing a channel for gas; in the filler, the polymer layer and the corrugated partition layer are arranged at intervals, and a polymer layer is respectively attached to both sides of each corrugated partition layer; The polymer layer is composed of superfine fibers, and the superfine fibers are prepared from any one or all of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), isophthalic acid (IPA); The corrugated partition layer is made of any one or more of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), polysulfone (PSU), and the corrugated partition layer includes a number of corrugated units connected in sequence.

[0030] In this embodiment, in the polymer layer, the length of the ultrafine fibers is 5 mm - 20 mm, and the diameter is 5 μm - 40 μm; the preparation method of the polymer layer is as follows: When preparing ultrafine fibers using any one of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA), after surface hydrophilization treatment of the obtained ultrafine fibers, the polymer layer is prepared using the surface-hydrophilic modified ultrafine fibers; or, when preparing ultrafine fibers using all types of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA), mixed hydrophilic ultrafine fibers are prepared according to the ratio of polypropylene (PP) 5 - 20 wt%, polyethylene (PE) 10 - 25 wt%, polyethylene terephthalate (PET) 10 - 20 wt%, polyvinyl chloride (PVC) 10 - 30 wt%, polytetrafluoroethylene (PTFE) 5 - 20 wt%, polycarbonate (PC) 10 - 15 wt%, polyamide (PA) 2 - 10 wt%, and isophthalic acid (IPA) 5 - 20 wt%, and then the polymer layer is prepared using the mixed hydrophilic ultrafine fibers; In this embodiment, the surface hydrophilization treatment of the obtained ultrafine fibers is specifically: treating the ultrafine fibers with polyether-modified silicone oil and sodium alginate or performing ozone oxidation treatment on the ultrafine fibers; The specific method for preparing the mixed hydrophilic ultrafine fibers is: mixing polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), and isophthalic acid (IPA) according to the ratio, heating and melting them, adjusting the temperature to 220°C - 300°C, setting the spinneret hole diameter to 0.2 - 0.5 mm, and preparing the mixed hydrophilic ultrafine fibers with a diameter of 5 μm - 40 μm.

[0031] In this embodiment, the method for preparing the polymer layer using the surface-hydrophilic modified ultrafine fibers or the mixed hydrophilic ultrafine fibers is as follows: The surface-hydrophilic modified ultrafine fibers or the mixed hydrophilic ultrafine fibers are subjected to a web-forming operation, setting the laying speed at 100 - 500 m / min, and setting the roll gap at 0.05 - 0.3 mm to form a uniform web-like structure of ultrafine fiber web; The ultrafine fiber web is repeatedly punctured with barbed needles or impacted with high-pressure micro water jets, so that the fibers in the ultrafine fiber web are entangled to obtain a polymer layer with high wettability and corrosion resistance.

[0032] In this embodiment, the thickness of the polymer layer is 0.5 mm - 3 mm; the contact angle of the polymer layer is less than 80°; The grammage of the polymer layer is above 150 g / m 2 Above, each gram of the polymer layer absorbs more than 1.5 g of liquid; the corrosion rate of the polymer layer is less than or equal to 0.01 mm / year.

[0033] In this embodiment, the width of each corrugated unit in the corrugated separator layer is 1 mm - 6 mm, the thickness is 0.3 mm - 2 mm, and the height is 1 mm - 20 mm.

[0034] In this embodiment, the preparation method of the corrugated separator layer includes: Any one or more of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), and polysulfone (PSU) particles are dried to remove moisture and then melt-extruded. The melt passes through the corrugated layer structure, and the corrugated layer is pressed into a wavy shape by a specially designed corrugated roller and then compounded with the upper and lower plane layers in a mold. Then it enters a cooling water tank with a water temperature of 10 - 25 °C for shaping to form a corrugated corrugated separator. In the present invention, the production of the corrugated plastic separator is based on bionic structure strengthening and polymer material forming technology. The geometric shape of the corrugation (such as the arch mechanical principle) is used to disperse stress, significantly improving the compressive and flexural strength of the separator (3 - 5 times higher than that of a flat plate).

[0035] In this embodiment, the drying conditions are 80 - 100 °C for 2 - 4 hours; the barrel temperature of the screw extruder is 190 - 260 °C, and the die head temperature is 210 - 280 °C.

[0036] In this embodiment, the filler as a whole is in a roll-type cylinder structure or a stacked cube structure.

[0037] The operating conditions of traditional packed bed scrubbers meet the requirements (for example, the pH value is greater than 7, the wetting coefficient is greater than 0.1 cubic meters per hour, the empty tower residence time is greater than 0.5 seconds, the specific surface area is greater than 90 square meters per cubic meter, etc.), but the removal efficiency for acidic and alkaline gases is also much lower than the value required by the emission standard (for example, 95% required in the semiconductor industry). The polymer layer and the corrugated separator layer selected in the present invention form a roll-type cylinder structure through a slitting and rewinding machine, which not only ensures that the washing liquid is evenly distributed on the filler but also provides a dedicated channel for the gas. When the gas passes through the pores in the corrugated separator layer, it can fully contact the washing liquid on the surface of the polymer layer, greatly improving the efficiency.

[0038] In addition to the roll-type cylinder structure, the polymer layer and the corrugated separator layer are combined into a stacked cube structure by being arranged at intervals (such asFigure 5 As shown in the figure, the height is 10 cm - 100 cm. Because the water absorption of the material is extremely good, after liquid molecules enter the interior of the material, they continuously diffuse. Also, due to the action of its own gravity, they diffuse downward. Liquid molecules above are still continuously entering the material interior. A water film is continuously formed under the action of the high wettability of the material in a cycle. This ensures that when gas flows through the straight through holes of the corrugated baffle layer, it fully contacts the water film under the Brown diffusion mechanism and further reacts with the components in the water film. At the same time, the substances generated by the reaction are on the water film. Since the liquid in the water film is continuously flowing from top to bottom, under the action of the gravity of the substances generated by the reaction, the products can be washed away in time to avoid blockage.

[0039] In order to study the influence of the components of the polymer layer on wettability, study the thermal stability and corrosion resistance of the polymer layer, the influence of the size of the corrugated baffle on the removal effect, and to study the removal effect corresponding to the filler provided by the present invention, the present invention provides the following implementation cases.

[0040] Implementation Case 1: A preparation method of a polymer layer includes: According to the mass ratio, polypropylene PP 15 wt%, polyethylene PE 17 wt%, polyethylene terephthalate PET 15%, polyvinyl chloride PVC 15 wt%, polytetrafluoroethylene PTFE 10 wt%, polycarbonate PC 10 wt%, polyamide PA 2 wt%, isophthalic acid IPA 16 wt% are used. The fiber bundle is dispersed into single fiber state by a carding machine to reduce agglomeration. Then, the broken fibers are melted by a screw extruder, and extruded into filaments through a melt pump and a spinneret so that the diameter of the obtained ultrafine fibers is in the range of 5 - 40 μm and the fiber length is in the range of 5 mm - 20 mm. Finally, it is solidified by cooling air; the laying speed is set at 100 - 500 m / min, and the roll gap is set at 0.05 - 0.3 mm to form a uniform network structure of ultrafine fibers; the ultrafine fiber web is repeatedly punctured with barbed needles to entangle the fibers in the ultrafine fiber web to obtain a polymer layer.

[0041] Take 100 g of the prepared polymer layer material and soak it in a beaker filled with water for 10 min. Take out the material and dry the water on the surface, and then measure its weight to be 487.8 g.

[0042] Implementation Case 2: The other operation steps in this embodiment are the same as those in Embodiment 1. The difference is that the raw material ratio selected in this embodiment is polypropylene PP 15wt%, polyethylene PE 18wt%, polyethylene terephthalate PET 11%, polyvinyl chloride PVC 16wt%, polytetrafluoroethylene PTFE 14wt%, polycarbonate PC 10wt%, polyamide PA 3wt%, isophthalic acid IPA 13wt%. Take 100g of the polymer layer material prepared in this embodiment and soak it in a beaker filled with water for 10 minutes. Then take out the material, dry the water on the surface, and measure its weight again, which is 443.1g.

[0043] Implementation Case 3: The other operation steps in this embodiment are the same as those in Embodiment 1. The difference is that the raw material ratio selected in this embodiment is polypropylene PP 15wt%, polyethylene PE 16wt%, polyethylene terephthalate PET 15%, polyvinyl chloride PVC 14wt%, polytetrafluoroethylene PTFE 12wt%, polycarbonate PC 10wt%, polyamide PA 5wt%, isophthalic acid IPA 13wt%. Take 100g of the polymer layer material prepared in this embodiment and soak it in a beaker filled with water for 10 minutes. Then take out the material, dry the water on the surface, and measure its weight again, which is 452.8g.

[0044] Implementation Case 4: The other operation steps in this embodiment are the same as those in Embodiment 1. The difference is that the raw material ratio selected in this embodiment is polypropylene PP 10wt%, polyethylene PE 20wt%, polyethylene terephthalate PET 10%, polyvinyl chloride PVC 18wt%, polytetrafluoroethylene PTFE 16wt%, polycarbonate PC 6wt%, polyamide PA 12wt%, isophthalic acid IPA 8wt%. Take 100g of the polymer layer material prepared in this embodiment and soak it in a beaker filled with water for 10 minutes. Then take out the material, dry the water on the surface, and measure its weight again, which is 247.6g.

[0045] Implementation Case 5: The other operation steps in this embodiment are the same as those in Embodiment 1. The difference is that the raw material ratio selected in this embodiment is polypropylene PP 15wt%, polyethylene PE 14wt%, polyethylene terephthalate (PET 14%, polyvinyl chloride PVC 14wt%, polytetrafluoroethylene PTFE 12wt%, polycarbonate PC 10wt%, polyamide PA 6wt%, isophthalic acid IPA 13wt%. Take 100g of the polymer layer material prepared in this embodiment and soak it in a beaker filled with water for 10 minutes. Then take out the material, dry the water on the surface, and measure its weight again, which is 465.4g.

[0046] Implementation Case 6: In this embodiment, other operation steps are the same as those in Embodiment 1, except that only one kind of fiber, polypropylene (PP), is selected to prepare ultrafine fibers, and the surface of the prepared ultrafine fibers is subjected to hydrophilization treatment, and the hydrophilization treatment is spraying polyether modified silicone oil; 100 g of the prepared polymer material is taken and immersed in a beaker filled with water, waiting for 10 min, then the material is fished out and the water on the surface is wiped dry, and then its weight is measured to be 468.1 g.

[0047] Implementation Case 7: In this embodiment, other operation steps are the same as those in Embodiment 1, except that only one kind of fiber, polyethylene (PE), is selected to prepare ultrafine fibers, and the surface of the prepared ultrafine fibers is subjected to hydrophilization treatment, and the hydrophilization treatment is spraying sodium alginate on the surface of the ultrafine fibers. 100 g of the prepared material is taken and immersed in a beaker filled with water, waiting for 10 min, then the material is fished out and the water on the surface is wiped dry, and then its weight is measured to be 472.3 g. As Figure 1 shown, it is the fiber after hydrophilization treatment. Implementation Case 8: In this embodiment, other operation steps are the same as those in Embodiment 1, except that only one kind of fiber, isophthalic acid (IPA), is selected to prepare ultrafine fibers, and the surface of the prepared ultrafine fibers is subjected to hydrophilization treatment. The hydrophilization treatment specifically is to carry out ozone oxidation treatment on the surface of the ultrafine fibers, controlling the ozone concentration at 50 - 220 g / m³, the temperature at 20 - 50 °C, and the oxidation time at 2 h to increase the oxygen-containing groups on the fibers. 100 g of the prepared material is taken and immersed in a beaker filled with water, waiting for 10 min, then the material is fished out and the water on the surface is wiped dry, and then its weight is measured to be 484.6 g.

[0048] Table 1 Immersion experiment results of Embodiments 1 - 8:

[0049] Through comparison of a large number of experiments, 13 - 18 wt% of polypropylene (PP), 14 - 18 wt% of polyethylene (PE), 11 - 16 t% of polyethylene terephthalate (PET), 14 - 16 wt% of polyvinyl chloride (PVC), 10 - 14 wt% of polytetrafluoroethylene (PTFE), 10 - 12 wt% of polycarbonate (PC), 2 - 6 wt% of polyamide (PA), 10 - 16 wt% of isophthalic acid (IPA), this proportion combination is the optimal one, and the wetting performance of the material is the best; and using any one of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), isophthalic acid (IPA) to prepare ultrafine fibers, and carrying out surface hydrophilization treatment on the obtained ultrafine fibers, the polymer layer prepared can also achieve the same effect.

[0050] Example 9: Take 3.9 mg of the material in Example 7 for thermogravimetric analysis, and set the heating rate to 10 °C / min. As Figure 3 shown, it can be seen from the thermogravimetric analysis curve that before 350 °C, the mass of the polymer layer did not decrease, and the mass loss rate reached the maximum at 450 °C. Therefore, the polymer layer of the present invention has high thermal stability before 350 °C.

[0051] Example 10: The other operation steps in this example are the same as those in Example 9, except that the heating rate is set to 20 °C / min; Figure 4 The results of the thermogravimetric analysis experiment for Example 10 are as follows: It can be seen from the thermogravimetric analysis curve that when the heating rate is increased to 20 °C / min, the mass of the polymer layer of the present invention begins to decrease at 400 °C, and the mass loss rate reaches the maximum at 450 °C.

[0052] Example 11: Take the material in Example 7, weigh the initial mass of 1.530 g after cleaning and drying, then soak it completely in 37% hydrochloric acid solution (room temperature), keep the temperature constant. After soaking for seven days, remove the surface corrosion products of the sample, and then dry and weigh it to get 1.527 g; the corrosion rate is 0.008.

[0053] Example 12: The other operation steps in this example are the same as those in Example 11, except that take 1.530 g of the common packing Raschig ring in the washing tower, after cleaning and drying, soak it completely in 37% hydrochloric acid solution (room temperature), keep the temperature constant. After soaking for seven days, remove the surface corrosion products of the sample, and then dry and weigh it to get 1.524 g, and the corrosion rate is 0.016. Compared with the traditional Raschig ring packing, the corrosion rate of the polymer layer of the present invention is reduced by half, and the corrosion resistance is greatly improved.

[0054] Example 13: Mix the polymer particles of polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyamide (PA), polyacrylonitrile (PAN), and polysulfone (PSU), and dry them in an oven to remove moisture (80 - 100 °C, 2 - 4 hours). Then carry out melt extrusion, with the barrel temperature of 190 - 260 °C and the die head temperature of 210 - 280 °C. Finally, enter the cooling water tank (water temperature 10 - 25 °C) for shaping, and process it into regular corrugated shapes to obtain a corrugated partition layer. As Figure 2 shown, the aperture of each corrugated unit in the corrugated partition layer is 1 mm - 6 mm, the thickness is 0.3 mm - 2 mm, and the height is 1 mm - 20 mm.

[0055] The corrugated partition layer obtained in this example was combined with the material obtained in Example 7 to form a honeycomb filler, which was placed in the reaction chamber of the gas-liquid reactor. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, no SO2 was detected in the tail gas, and the removal efficiency of SO2 was 100%.

[0056] Example 14: Other operating steps in this example were the same as those in Example 13, except that the pore diameter of each corrugation unit in the corrugated partition layer was increased to 8 mm. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, the SO2 concentration of 35 ppm was detected in the tail gas section.

[0057] Example 15: Other operating steps in this example were the same as those in Example 13, except that the pore diameter of each corrugation unit in the corrugated partition layer was increased to 10 mm. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, the SO2 concentration of 46 ppm was detected in the tail gas section.

[0058] Example 16: Other operating steps in this example were the same as those in Example 13, except that the pore diameter of each corrugation unit in the corrugated partition layer was increased to 12 mm. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, the SO2 concentration of 76 ppm was detected in the tail gas section.

[0059] Table 2 Experimental results of Examples 13 - 16:

[0060] It can be seen that the pore diameter size of the corrugation unit in the corrugated partition layer has an important influence on the removal effect. When the corrugated partition layer is combined with the polymer layer, the corrugated partition layer provides a specific channel for the gas. The gas contacts the polymer layer material through the channel of the corrugated partition layer and reacts. When the pore diameter of the corrugation unit in the corrugated partition layer is too large, the contact time between the gas flowing through and the material decreases, resulting in insufficient reaction. It has been experimentally proven that when the pore diameter of the corrugated partition is set at 1 - 6 mm, the removal effect is the best.

[0061] Example 17: Other operating steps in this example were the same as those in Example 13, except that the thickness of the corrugation unit in the corrugated partition layer was increased to 4 mm. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, the SO2 concentration of 12 ppm was detected in the tail gas section.

[0062] Example 18: Other operating steps in this example were the same as those in Example 13, except that the thickness of the corrugation unit in the corrugated partition layer was increased to 5 mm. SO2 with a concentration of 1000 ppm was introduced. After 2 hours of reaction, the SO2 concentration of 21 ppm was detected in the tail gas section.

[0063] Example 19: In this example, other operation steps are the same as those in Example 13, except that the thickness of the corrugated unit in the corrugated partition layer is increased to 6 mm, SO2 with a concentration of 1000 ppm is introduced, and after 2 hours of reaction, the SO2 concentration of 29 ppm is detected in the tail gas section.

[0064] Table 3 Experimental results of Examples 13, 16 - 19:

[0065] It can be seen that the thickness of the corrugated unit in the corrugated partition layer has an important influence on the removal effect. When the volume flowing through the corrugated partition layer is the same, too thick a partition thickness will block the polymer layer material, resulting in a reduction in the polymer layer material reacting with the gas and insufficient reaction. Experiments have proved that when the thickness of the corrugated partition is set at 0.3 - 2 mm, the removal effect is the best.

[0066] Example 20: In this example, the polymer layer material of Example 7 and the corrugated partition layer in Example 13 are combined into a structured packing in the form of a spiral cylinder structure and filled into a reactor with a tower height of 8 m. SO2 gas with a concentration of 2000 ppm is introduced, and after a period of reaction, the SO2 removal rate of 97% and a pressure drop of 1.5 kPa are obtained.

[0067] Example 21: In this example, the polymer layer material of Example 7 and the corrugated partition layer in Example 13 are combined into a structured packing in the form of a stacked cube and filled into a reactor with a tower height of 8 m. SO2 gas with a concentration of 2000 ppm is introduced, and after a period of reaction, the SO2 removal rate of 98% and a pressure drop of 1.47 kPa are obtained.

[0068] Example 22: In this example, other operation steps are the same as those in Example 20, except that the packing is replaced with Raschig rings, and the SO2 removal rate of 85% and a pressure drop of 4.2 kPa are obtained.

[0069] Table 4 Experimental results of Examples 20 - 22:

[0070] It can be seen that the annular structure will cause the gas path to be tortuous, resulting in an increase in pressure drop, the smooth surface makes the liquid film distribution uneven, and dust or crystals are likely to deposit, leading to a decrease in the removal rate.

[0071] Example 23: In this example, other operation steps are the same as those in Example 13, except that the height of the corrugated unit in the corrugated partition layer is set to 8 mm, SO2 with a concentration of 1000 ppm is introduced, and after 2 hours of reaction, the SO2 concentration of 0 ppm is detected in the tail gas section.

[0072] Example 24: The other operation steps in this example are the same as those in Example 13. The difference is that the height of the corrugated unit in the corrugated partition layer is set to 12 mm, and SO2 with a concentration of 1000 ppm is introduced. After 2 h of reaction, the SO2 concentration of 0 ppm is detected in the tail gas section.

[0073] Example 25: The other operation steps in this example are the same as those in Example 13. The difference is that the height of the corrugated unit in the corrugated partition layer is set to 16 mm, and SO2 with a concentration of 1000 ppm is introduced. After 2 h of reaction, the SO2 concentration of 0 ppm is detected in the tail gas section.

[0074] Example 26: The other operation steps in this example are the same as those in Example 13. The difference is that the height of the corrugated unit in the corrugated partition layer is set to 22 mm, and SO2 with a concentration of 1000 ppm is introduced. After 2 h of reaction, the SO2 concentration of 46 ppm is detected in the tail gas section.

[0075] Example 27: The other operation steps in this example are the same as those in Example 13. The difference is that the height of the corrugated unit in the corrugated partition layer is set to 24 mm, and SO2 with a concentration of 1000 ppm is introduced. After 2 h of reaction, the SO2 concentration of 62 ppm is detected in the tail gas section.

[0076] Table 5 Experimental results of Examples 23 - 27:

[0077] It can be seen that the height of the corrugated unit in the corrugated partition layer has an important influence on the removal effect. When the volume flowing through the corrugated partition layer is the same, if the height of the partition is too high, the mass transfer efficiency of the reaction with the gas will decrease, and the effect will weaken. It is proved by experiments that when the height of the corrugated partition is set at 1 - 20 mm, the removal effect is the best.

[0078] Example 28: The application of a packing for a gas - liquid reactor, using the packings described in Examples 20 and 21 to prepare a gas - liquid reactor.

[0079] Specifically, the gas-liquid reactor is used to separate crude oil and natural gas, to remove liquid hydrocarbons and H2S in natural gas, to separate drug solutions from reaction gases during antibiotic production, to remove moisture and oil mist produced during food processing, to remove SO2 and dust in the fields of steel, non-ferrous metals, cement or glass, or to remove HF, HNO3, HNO2, CH3COOH, HCN, H2SO4 in the semiconductor field. At the wellhead of an oil well, a gas-liquid separator uses the principles of gravity sedimentation and centrifugal separation to perform a preliminary separation of crude oil and natural gas; in a natural gas purification plant, a gas-liquid separator removes liquid hydrocarbons and free water from natural gas to ensure that the natural gas meets the quality standards for pipeline transportation; in the production of antibiotics, a gas-liquid separator separates the drug solution from the gas produced by the reaction to facilitate subsequent drug refining; in food processing, it is used to remove moisture, oil mist, etc. produced during the processing to ensure product hygiene and quality; this gas-liquid reactor can be used to remove SO2 in the fields of steel, cement, etc., and to remove acid gases such as H2S, HF, HNO3, HNO2, CH3COOH, HCN, and H2SO4 in the semiconductor field.

[0080] The core of this invention is the fabrication of a highly wettable and corrosion-resistant polymer layer and the optimization of the corrugated separator layer. During operation, the filler provided by this invention undergoes a dynamic process of liquid diffusion and wetting on the polymer layer, driven by surface chemical properties (such as hydrophilic groups on the fibers), microporous structure (porosity and pore size distribution), and liquid physical properties (viscosity and surface tension). Initially, hydrophilic groups trigger rapid droplet spreading by reducing the contact angle (θ), forming a precursor film that pre-wets the fiber surface. Subsequently, capillary forces (following the Lucas-Washburn equation) direct liquid penetration along the interfiber pores, with a rate proportional to the pore radius (r) and inversely proportional to the liquid viscosity (μ). During longitudinal diffusion, gravity and capillary forces compete to determine the direction of penetration, while fiber expansion upon absorption (e.g., cotton fibers) reduces pore size and accelerates capillary rise. Ultimately, viscous resistance and interfacial anchoring effects (such as chemical adsorption) bring the system into dynamic equilibrium. The entire process is essentially a synergistic effect of interfacial energy minimization and fluid transport within the porous medium.

[0081] Figure 6 This is a manifestation of the mechanism of high wettability of the polymer layer material. The bottom layer is the material of the polymer layer, and the material of the polymer layer is a water film formed by wetting and evenly distribution. The small balls on the water film are substances generated by the reaction and attached to the surface of the water film. Because the liquid on the surface of the water film is constantly flowing from top to bottom, and then through the action of its own gravity, the product can be washed away by the liquid in time, avoiding blockage and increased air resistance.

[0082] When the gas flows through the honeycomb channels, it first forms turbulent or laminar flow in the regular channels with a high specific surface area (200 - 1200 m² / m³), and contacts the liquid film (with a thickness of 10 - 200 μm) attached to the inner wall of the channels through the convection-diffusion mechanism; the active components in the gas diffuse from the gas-phase bulk to the gas-liquid interface (following Fick's law), dissolve in the liquid phase, and then undergo interfacial reactions with the reactants in the liquid. The reaction products leave the interface through the liquid film; during this process, the geometric structure of the channels (such as pore diameter and wall thickness) optimizes the gas-liquid contact area and residence time, while the surface wettability and liquid renewal rate jointly ensure the continuous and efficient progress of the reaction.

[0083] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those of ordinary skill in the art, they can still modify or improve the previously described technical solutions, and all of these fall within the protection scope of the present invention.

Claims

1. A packing for a gas-liquid reactor, characterized in that, The packing material includes a polymer layer with high wettability and corrosion resistance and a corrugated separator layer for providing channels for gas; in the packing material, the polymer layer and the corrugated separator layer are arranged at intervals, and a polymer layer is respectively attached to both sides of each corrugated separator layer; The polymer layer is composed of ultrafine fibers, and the ultrafine fibers are prepared from any one or all of polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, and isophthalic acid; The corrugated separator layer is prepared from any one or more of polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, polyacrylonitrile, and polysulfone, and the corrugated separator layer includes a number of corrugated units connected in sequence.

2. The packing for a gas-liquid reactor according to claim 1, characterized in that, In the polymer layer, the length of the ultrafine fibers is 5 mm - 20 mm, and the diameter is 5 μm - 40 μm; the preparation method of the polymer layer is: When preparing ultrafine fibers from any one of polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, and isophthalic acid, after surface hydrophilization treatment of the obtained ultrafine fibers, the polymer layer is prepared from the surface-hydrophilic modified ultrafine fibers; or, when preparing ultrafine fibers from all of polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, and isophthalic acid, mixed hydrophilic ultrafine fibers are prepared according to the ratio of 5 - 20 wt% of polypropylene, 10 - 25 wt% of polyethylene, 10 - 20 wt% of polyethylene terephthalate, 10 - 30 wt% of polyvinyl chloride, 5 - 20 wt% of polytetrafluoroethylene, 10 - 15 wt% of polycarbonate, 2 - 10 wt% of polyamide, and 5 - 20 wt% of isophthalic acid, and then the polymer layer is prepared from the mixed hydrophilic ultrafine fibers.

3. The packing for a gas-liquid reactor according to claim 2, characterized in that, The surface hydrophilization treatment of the obtained ultrafine fibers is specifically: treating the ultrafine fibers with polyether-modified silicone oil and sodium alginate or performing ozone oxidation treatment on the ultrafine fibers; The specific method for preparing the mixed hydrophilic ultrafine fibers is: mixing polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, and isophthalic acid according to the ratio, heating and melting them, and adjusting the temperature to 220°C - 300°C to prepare mixed hydrophilic ultrafine fibers with a diameter of 5 μm - 40 μm.

4. The packing for a gas-liquid reactor according to claim 3, characterized in that, The method for preparing the polymer layer from the surface-hydrophilic modified ultrafine fibers or the mixed hydrophilic ultrafine fibers is: Performing a web-forming operation on the surface-hydrophilic modified ultrafine fibers or the mixed hydrophilic ultrafine fibers, setting the laying speed at 100 - 500 m / min, and setting the roll gap at 0.05 - 0.3 mm to form a uniform web-like structure of ultrafine fiber web; Repeatedly puncturing the ultrafine fiber web with barbed needles or impacting the ultrafine fiber web with high-pressure micro water jets to entangle the fibers in the ultrafine fiber web to obtain a polymer layer with high wettability and corrosion resistance.

5. The packing for a gas-liquid reactor according to claim 1, characterized in that, The thickness of the polymer layer is 0.5 mm - 3 mm; the contact angle of the polymer layer is less than 80°; The grammage of the polymer layer is above 150 g / m 2 ², and each gram of the polymer layer absorbs more than 1.5 g of liquid; the corrosion rate of the polymer layer is less than or equal to 0.01 mm / year.

6. The packing for a gas-liquid reactor according to claim 1, characterized in that, In the corrugated separator layer, the width of each corrugated unit is 1 mm - 6 mm, the thickness is 0.3 mm - 2 mm, and the height is 1 mm - 20 mm.

7. The packing for a gas-liquid reactor according to claim 1, characterized in that, The preparation method of the corrugated separator layer includes: Taking any one or more of polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyamide, polyacrylonitrile, and polysulfone particles, drying to remove moisture, performing melt extrusion, and entering a cooling water tank with a water temperature of 10 - 25°C for shaping to form a corrugated separator; The drying conditions are 80 - 100°C for 2 - 4 hours; the barrel temperature of the screw extruder is 190 - 260°C, and the die head temperature is 210 - 280°C.

8. The packing for a gas-liquid reactor according to claim 1, characterized in that, The filler as a whole is in a coiled cylindrical structure or a stacked cubic structure.

9. Application of a packing for a gas-liquid reactor, characterized in that, The filler according to any one of claims 1 - 8 is used for preparing a gas - liquid reactor.

10. The application of a packing for a gas-liquid reactor according to claim 9, characterized in that, The gas - liquid reactor prepared by using the filler according to any one of claims 1 - 8 is used for the separation of crude oil and natural gas, for removing liquid hydrocarbons and H2S in natural gas, for the separation of the drug solution and the reaction - generated gas during the production of antibiotics, for removing moisture and oil mist generated during food processing, for removing SO2 and dust in the fields of steel, non - ferrous metals, cement, or glass, or for removing HF, HNO3, HNO2, CH3COOH, HCN, H2SO4 in the semiconductor field.

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