Composite adsorption material with high volume efficiency, preparation method of composite adsorption material, ordered structure body and rapid circulation assembly system

Abstract

The invention belongs to the crossing field of adsorption separation, membrane technologies and functional textile materials, and particularly discloses a composite adsorbent for water or gas purification, a precise coating method of the composite adsorbent, an ordered adsorption structural body and a matched efficient adsorption separation assembly system. Aiming at the defects that the existing adsorption technology is difficult to separate and recycle, large in bed pressure drop and low in mass transfer efficiency, the traditional membrane separation technology is insufficient in selectivity, and the conventional adsorption assembly is unreasonable in hydrodynamic design, easy to generate dead zones inside, difficult to empty accumulated liquid, easy to breed microorganisms, low in equipment volume efficiency, incapable of high-frequency cyclic regeneration and the like. According to the invention, the special composite adsorbent is prepared and accurately coated on the surface of the carrier, then the regular and ordered adsorption structural body is formed by a textile process, and meanwhile, the shell structure is optimized, so that the assembly is endowed with the functions of gas-driven emptying and dynamic cleaning. Various defects in the prior art are effectively overcome, high adsorption capacity and rapid mass transfer dynamics are achieved in a compact space, meanwhile, the maintainability of equipment is improved, high-frequency cyclic regeneration can be achieved, and the device is suitable for various water purification and gas separation and purification scenes and has wide application prospects.

Description

Technical Field

[0001] This invention belongs to the interdisciplinary field of adsorption separation, membrane technology and functional textile materials. Specifically, it relates to a composite adsorbent for water or gas purification, a method for precisely coating it onto a carrier, an ordered adsorption structure formed by textile processes, and a high-efficiency adsorption separation component system with optimized shell design and support for gas-driven evacuation and dynamic cleaning functions. Background Technology

[0002] Existing adsorption technologies (such as powdered adsorbents, activated carbon, and granular beds) suffer from limitations such as difficulty in separation and recovery, large bed pressure drop, and low mass transfer efficiency. Traditional membrane separation technologies mainly rely on pore size sieving, which has insufficient selective adsorption capacity for specific ions; moreover, the design of existing adsorption components often neglects hydrodynamic optimization, easily leading to laminar flow or dead zones inside, making it difficult to drain the liquid after shutdown, and easily fostering microbial growth, resulting in low volumetric efficiency and the inability to achieve high-frequency cycle regeneration in compact equipment. Therefore, there is an urgent need for a composite technology solution that combines high capacity, fast kinetics, and ease of maintenance within a compact space. Summary of the Invention

[0003] Purpose of the invention The present invention aims to provide an adsorption system with high volumetric efficiency and rapid regeneration, which significantly improves the daily processing capacity per unit volume by synergistically optimizing material activity, coating thickness, component specific surface area and fluid dynamics.

[0004] Technical solution: Core adsorbents: Based on the oxide / hydroxide or mixed crystal structure of aluminum (Al), manganese (Mn), and titanium (Ti), the surface charge, pore size and selectivity are controlled by doping with elements such as magnesium (Mg), silicon (Si) and zirconium (Zr).

[0005] Precision coating technology: The carriers include organic flat sheet membranes / non-woven fabrics, organic hollow / solid fibers, inorganic ceramic membranes, etc. The adsorbent is fixed onto the carrier surface using wet coating, chemical vapor deposition (CVD / ALD), or dry powder coating (electrostatic spraying, hot-press bonding). The thickness of the functional layer is strictly controlled between 5-500 μm, preferably 20-50 μm, to shorten the diffusion path and improve the kinetic rate.

[0006] Multi-level ordered structure: Grade 1: Functional fibers with an adsorption coating.

[0007] Secondary: Through weaving, knitting, woven or nonwoven processes, a mesh / fabric ordered structure with three-dimensional through holes, static mirror symmetry or axial gradient arrangement is produced.

[0008] Level 3: The orderly winding integration is adopted, and the fiber spacing is 1.5 to 10 times the diameter, so as to induce turbulence in the fluid and generate fiber micro-vibration, thereby enhancing mass transfer.

[0009] Components and Engineering Systems: Shell design: Constructed of stainless steel or engineering plastics, with an internal cavity volume to adsorbent volume ratio of less than 2:1. Features a gas blowing port and vent, supporting air-driven venting (air-top water) for near-zero residue. The sanitary shell design minimizes cleaning dead zones and liquid residue.

[0010] Dynamic operation: The curtain-type component supports gas shaking cleaning and lifting detachment cleaning (lifting the component out of the liquid surface to cooperate with air scrubbing) to physically remove the attached substances.

[0011] Beneficial effects High volumetric efficiency: The adsorption capacity per unit volume is several times higher than that of traditional beds, the kinetics are improved by more than an order of magnitude, and the adsorption rate is more than 5 times that of a powder-filled bed of the same mass.

[0012] Rapid cycle: A single component can complete no less than 3 adsorption-regeneration cycles within 24 hours, significantly improving daily processing capacity.

[0013] Easy to maintain: Air-driven venting eliminates dead corners and microbial growth, extending service life.

[0014] The amount of water used for cleaning adsorbent per unit volume is greatly reduced. Attached Figure Description

[0015] Figure 1 Flowchart of composite adsorbent synthesis and coating process.

[0016] Figure 2 3,4,5,6: Comparison of the microstructure of fibrous adsorption filaments and the streamline simulation of the ordered wound filter element of the present invention.

[0017] Figure 7 : Curve comparing the adsorption capacity of the adsorption membrane with that of powdered materials and particulate adsorbents.

[0018] Figure 8 9,10: Exploded view of sanitary-grade spiral-wound assembly, low dead zone flow channel design and schematic diagram of air-driven venting of horizontal / vertical shell.

[0019] Figure 11 : Schematic diagram of the "shaking / lifting" cleaning status of the immersion curtain assembly. Detailed Implementation

[0020] 1. Adsorbent preparation (Example 1-1): Micro-interface modification of polymetallic composite oxides In this embodiment, a titanium-manganese composite oxide matrix with high ion selectivity is synthesized by hydrothermal method, and a surface impregnation technique is used to introduce modifying components to enhance its chemical stability in acidic / high-salt environments.

[0021] Step 1 (Hydrothermal Synthesis): Dissolve a titanium source (such as tetrabutyl titanate) and a manganese source (such as manganese nitrate) in a mixed solvent of ethanol and water at a metal molar ratio of Ti:Mn = 3:1. Add a precipitant to adjust the pH to 10.5, transfer to a high-pressure reactor, and react at 160°C for 18 hours.

[0022] Step 2 (washing and drying): The product is washed with deionized water until neutral, dried at 80°C and then ground to obtain multi-metal composite oxide powder.

[0023] Step 3 (Impregation): Place the powder in a salt solution containing at least one of magnesium, silicon, and zirconium (such as a 2% zirconium oxychloride solution), and ultrasonically disperse for 20 minutes. The modification element is then adsorbed onto the matrix pores and surface through equal-volume impregnation.

[0024] Step 4 (High-temperature calcination): Calcining at 550°C in air for 5 hours. Modifying elements (such as Zr) form a nanoscale oxide protective layer on the oxide lattice surface, yielding modified multi-metal composite oxide adsorbent particles.

[0025] 2. Preparation of coated fibers (Example 2-1): Precision wet coating process To ensure a high loading and bonding strength of the adsorbent on the fiber surface, this embodiment employs a modified wet coating method.

[0026] Slurry preparation: The adsorbent, binder (such as polyvinylidene fluoride PVDF) and dispersant prepared in step 1 are dissolved in N-methylpyrrolidone (NMP) at a mass ratio of 85:10:5, and then mixed with a high-shear mixer to form a uniform coating with a solid content of 25%~40%.

[0027] Coating process: Hollow fibers are passed through a coating tank using a precision coating machine, with the traction speed controlled at 5~10m / min. The thickness of the slurry on the outer surface of the hollow fibers is controlled by extrusion through a die.

[0028] Stabilization treatment: After coating, the fibers enter the hot air drying tunnel and are stabilized by hot air using gradient temperature control (60°~120°) to remove solvent. The final thickness of the adsorption coating is precisely controlled at 30±2um, and the coating is free of cracks and does not peel off.

[0029] 3. Ordered Structure Construction (Example 3-1): Hydrodynamic Optimization of Spiral Wound Components This embodiment constructs an ordered adsorption structure with low resistance and high flux through mechanical weaving and radial winding processes.

[0030] Weaving process: The coated fibers are used as warp or weft threads and woven with high-strength polyester yarns to form a plain weave absorbent fabric. The plain weave structure ensures a uniform distribution of pores between the fibers, which is conducive to fluid penetration.

[0031] Component assembly: The absorbent cloth is continuously wound radially along the porous central tube. During the winding process, a diamond-shaped mesh is inserted between each layer of absorbent cloth to form fluid channels.

[0032] Structural control: The winding body is installed into a cylindrical shell. Key parameter control: The effective width-to-height ratio (width-to-height ratio) of the shell cavity is limited to 1.5:1~1.9:1 (i.e., <2:1). This ratio can significantly reduce the radial flow deviation effect under high flow rate and ensure uniform flow field distribution.

[0033] 4. Performance Comparison Test: High-Frequency Cyclic Performance Evaluation To verify the advantages of the "ordered spiral structure" of this invention over the traditional "fixed bed particle filling structure", a comparative experiment was conducted under the same active ingredient loading.

[0034] Test conditions: High-salt brine from the oilfield with the same composition (lithium content 150 mg / L) was used, and the feed flow rate was fixed.

[0035] Experimental results: Mass transfer rate: Due to the use of an ultra-thin 30µm coating and ordered flow channels in this invention, the ion diffusion path is greatly shortened. Within an 8-hour test cycle, the component of this invention can complete 4 complete adsorption-desorption cycles; while the control group (fixed bed particles, particle size 0.5~1mm) can only complete 1.5 cycles due to high internal diffusion resistance.

[0036] Increased capacity: Calculations show that the total lithium removal per unit time of this invention is 320% higher than that of traditional fixed beds.

[0037] Pressure drop: The operating pressure of this component is only 1 / 3 of that of a fixed bed, which significantly reduces energy consumption for industrial operation.

Claims

1. A composite metal adsorbent, characterized in that, The active ingredient contains oxides or hydroxides of at least two of the elements aluminum, manganese, and titanium, and contains at least one modifying element selected from magnesium, silicon, and zirconium.

2. A method for preparing an adsorption functional layer on the surface of a carrier, characterized in that, Functional layers with a thickness of 20-50 μm are formed on fiber or flat sheet membrane carriers through wet coating, vapor deposition, thermoforming extrusion, or dry powder coating.

3. An ordered structure adsorbent material, characterized in that, The fiber described in claim 2 is formed into an ordered structure with three-dimensional through holes by a textile process, and the fiber spacing is 1.5 to 10 times the fiber diameter.

4. An adsorption separation component, characterized in that, The material comprises the material of claim 3, the housing is provided with a gas injection port and an vent, and the ratio of the volume of the housing cavity to the volume of the adsorbent material is less than 2:

1.

5. The component according to claim 4, characterized in that, This component is an immersion curtain-type component, and the system includes a mechanism capable of performing gas agitation or lifting for detachment cleaning.

6. A high volumetric efficiency adsorption method, characterized in that, Utilizing the high kinetic properties of the thin coating as described in claim 2, a single component can perform at least three adsorption-regeneration cycles within 24 hours.

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