Preparation and application of marine biomass composite Ti-O nanocluster microspheres
By preparing marine biomass composite Ti-O nanocluster microspheres as adsorbents, the problems of high cost and difficult separation of traditional adsorbents were solved, and efficient and environmentally friendly dye wastewater treatment effects were achieved.
Patent Information
- Application Number
- CN202511016162.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-23
- Publication Date
- 2025-09-16
AI Technical Summary
Existing technologies make it difficult to efficiently remove pollutants from direct dye wastewater. Traditional adsorbents are expensive and difficult to separate, and are prone to secondary pollution.
Marine biomass composite Ti-O nanocluster microspheres were used as adsorbents, and nanocluster microspheres with rigidity and microporous structure were prepared by ionic crosslinking to remove pollutants from dye wastewater.
It achieves efficient adsorption of direct dyes, has a stable structure and is easy to separate, is environmentally friendly and reusable, and avoids the shortcomings of traditional methods.
Smart Images
Figure FT_1 
Figure FT_2 
Figure SMS_1
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of preparation of marine biomass hybrid nanocluster microspheres and dye wastewater treatment application, and particularly relates to preparation and application of marine biomass composite Ti-O nanocluster microspheres. Background Art
[0002] Direct dyes are a widely used class of water-soluble anionic dyes. Due to their simple dyeing methods, comprehensive color spectrum, and low cost, they play an important role in the dyeing of cellulose fibers such as cotton, linen, viscose, silk, and their blended fabrics. However, it is precisely their good water solubility (their molecular structure often contains hydrophilic groups such as sulfonic acid groups) and high chroma that lead to extremely high chroma, chemical oxygen demand (COD), and biological oxygen demand (BOD) in wastewater containing undyed dyes. Discharge of untreated direct dye wastewater into water bodies not only causes serious visual pollution, disrupts the ecological balance of water bodies, inhibits photosynthesis in aquatic plants, but also accumulates through the food chain, endangers human health, and may contaminate groundwater sources. According to statistics, the textile printing and dyeing industry is the second largest source of industrial wastewater pollution in the world, of which dye wastewater is one of the main pollution loads. Therefore, it is crucial to seek efficient, economical, and environmentally friendly direct dye wastewater treatment technologies. At present, the treatment technologies for dye wastewater (including direct dyes) are mainly divided into physical, chemical and biological methods. However, direct dyes are highly water-soluble, have large molecular weights and stable structures. Traditional physical, chemical and biological treatment methods are often difficult to remove efficiently and may even easily cause secondary pollution (large amounts of chemical sludge, difficult-to-treat concentrated water, toxic by-products, etc.).
[0003] Adsorption methods have attracted widespread attention in dye wastewater treatment due to their advantages such as ease of operation, high efficiency, flexible design, no production of toxic byproducts, and recyclable adsorbents. Activated carbon is the most widely used adsorbent and has a strong adsorption capacity for a variety of dyes. However, its high cost and the difficulty in solid-liquid separation of powdered activated carbon limit its large-scale industrial application. Therefore, the development of new adsorbent materials that are efficient, inexpensive, easy to separate and recycle, and reusable has become a current research hotspot. Ideal adsorbents should have the following characteristics: high adsorption capacity and rapid adsorption kinetics, good physicochemical stability, easy separation from the treatment system, environmental friendliness, a wide range of raw material sources, and low cost.
[0004] Against this backdrop, a new type of adsorption sphere has emerged. This technology aims to design and manufacture a functionalized adsorption material with a specific physical form (e.g., spherical) specifically for the efficient adsorption and removal of pollutants from direct dye wastewater. Such adsorption spheres generally offer the following potential advantages: Morphological advantages: The regular spherical structure facilitates controlled bulk or fixed-bed filling in adsorption columns, enabling continuous flow operation. It also facilitates rapid and thorough solid-liquid separation in stirred reactors through simple filtration or sieving, resolving the bottleneck problem of powdered adsorbent separation. Material advantages: Polymers with abundant functional groups (e.g., amino, carboxyl, hydroxyl, quaternary ammonium salt groups), modified natural polymers, and inorganic / organic composite materials can be selected or synthesized as matrices. Through physical or chemical modification, they are endowed with high selectivity and high adsorption capacity for direct dyes (anionic properties). The operating process is simple and easy to control. Patent 202210913377.0 reports that gel spheres prepared by combining sepiolite with a regular octahedral structure with the natural polymer chitosan exhibit unique removal properties for cationic dyes. Based on this, the present invention proposes a novel method for preparing marine biomass composite Ti-O nanocluster microspheres, and uses the method for separating direct dye wastewater. Summary of the Invention
[0005] In order to achieve the above object, the present invention adopts the following technical solutions: A method for preparing marine biomass composite Ti-O nanocluster microspheres comprises the following steps: (1) Precursor Ti(OBu)4 and complex monocarboxylic acids (propionic acid, methacrylic acid, and valproic acid) are dispersed in ethylene glycol, sealed in a reactor, heated for a certain period of time, and then naturally cooled. The mixture is then filtered, washed, and dried to obtain Ti-O nanoclusters. (2) dissolving marine biomass sodium alginate (SA) in deionized water at room temperature, dissolving sodium carboxymethyl cellulose in deionized water at room temperature, and then mixing the two and mechanically stirring to obtain a mixed solution 1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), uniformly dispersing by ultrasonication and defoaming, to obtain a mixed solution 3; (5) The mixed solution 3 of step (4) is dropped into an FeCl3 aqueous solution for ion cross-linking to form balls. After aging, washing, filtering and drying, marine biomass composite Ti-O nanocluster microspheres are obtained.
[0006] Furthermore: in step (1), the amount of precursor Ti(OBu)4 is recorded as n(Ti(OBu)4) (unit: mmol); the monocarboxylic acid is selected from one of propionic acid, methacrylic acid, and valproic acid, and the amount is recorded as n(monocarboxylic acid) (unit: mmol); the amount of ethylene glycol is recorded as V(ethylene glycol) (unit: ml); the amount ratio is: n(Ti(OBu)4):n(monocarboxylic acid)=1:1~1:2, [n(Ti(OBu)4)+n(monocarboxylic acid)] / V(ethylene glycol)=1:1.5~1:2.4 (mmol / ml); the temperature of the heating reaction is 100~150℃, and the time of the heating reaction is 20~28h.
[0007] Furthermore: in step (2), the mass ratio of marine biomass sodium alginate (SA): sodium carboxymethyl cellulose is 1:1 to 1:4, and the total mass concentration of the mixed solution 1 is 2wt% to 4.0wt%; the stirring speed is 1000 to 3000 rpm, and the stirring time is 60 to 120 min.
[0008] Furthermore: in step (3), the mass concentration of Ti-O nanoclusters in the mixed solution 2 is 0.5wt% to 2.0wt%.
[0009] Furthermore, in step (4), the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt% to 4.0 wt%; the frequency of ultrasound is 50 to 100 Hz, and the time of ultrasound is 20 to 60 min.
[0010] Furthermore: in step (5), the concentration of the FeCl3 aqueous solution is 10-15 g / L; the aging time is 2-5 h; and the drying temperature is 40-90°C.
[0011] The marine biomass composite Ti-O nanocluster microspheres are obtained by the above preparation method.
[0012] Application of the above-mentioned marine biomass composite Ti-O nanocluster microspheres in dye wastewater treatment; Furthermore, the marine biomass composite Ti-O nanocluster microspheres are added as an adsorbent into wastewater containing dyes to adsorb and remove the dyes in the wastewater.
[0013] The Ti-O nanoclusters formed by the present invention use different monocarboxylic acids to form different carboxyl ligands on the surface, but the Ti-O skeleton structures are similar. The cyclic {Ti 32 O 16The skeleton is an overall donut-shaped structure with an outer diameter of 26.9A and a height of 10.4A. The sixteen oxygen groups on the inner wall of the donut form an internal cavity with a diameter of approximately 8.3A. This rigid and microporous structure further lays the structural foundation for efficient adsorption. The present invention uses the obtained rigid and microporous structured Ti-O nanoclusters as additives and disperses them in a marine biomass sodium alginate (SA) solution. Since the carboxyl groups in the SA molecular chain can cross-link with high-valent cations to form gel balls with an "egg-box" structure, various fillers dispersed in the SA solution can be evenly filled in the formed gel microspheres. The marine biomass composite Ti-O nanocluster microspheres formed by the present invention are uniform in size and simple in preparation method. The rigidity and microporous structure of the Ti-O nanoclusters further increase the specific surface area and stability of the marine biomass composite Ti-O nanocluster microspheres, and the carboxyl ligands on the surface of the Ti-O nanoclusters further increase the number of carboxyl groups in the SA molecules, thereby increasing the ability of the SA molecules to cross-link with high-valent cations. Therefore, the formed marine biomass composite Ti-O nanocluster microspheres can be better used for dye adsorption.
[0014] Compared with the prior art, the present invention has the following advantages: (1) Compared with traditional nanofillers, the Ti-O nanoclusters obtained in the present invention have a rigid and microporous structure, which can avoid the agglomeration problem caused by excessive dosage during the addition process. The structure of the obtained marine biomass composite Ti-O nanocluster microspheres is uniform.
[0015] (2) The aqueous ionic cross-linking gelation process used in the present invention is simple to operate, has a mild and thorough reaction, and can effectively avoid the material loss problem caused by traditional methods. In addition, the uniform spherical structure formed facilitates separation after adsorption.
[0016] (3) The Ti-O nanoclusters in the present invention have rigidity and microporous properties, which can give the marine biomass composite Ti-O nanocluster microspheres a certain compressive strength and can be recycled multiple times while still ensuring the structural integrity of the microspheres.
[0017] (4) Compared with traditional substrates, the present invention uses marine biomass shell sodium alginate, which is green and environmentally friendly. Introducing it into the field of adsorbent preparation can increase the space for value-added utilization. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1: a is an optical image of the marine biomass composite Ti-O nanocluster microspheres prepared in Example 14; b is a 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5; c is an SEM scanning image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5; d is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5; e is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5 after adsorbing direct red 23; f is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5 after adsorbing direct black 19.
[0019] Figure 2 The crystal structure of the Ti-O nanoclusters prepared in Example 14 was determined by single crystal diffractometry. This is a top view of a ball-and-stick model drawn using Diamond software. Color coding: teal represents carbon atoms; dark gray represents hydrogen atoms; yellow represents oxygen atoms; and light gray represents titanium atoms. DETAILED DESCRIPTION
[0020] In order to make the purpose and technical solution of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiment of the present invention.
[0021] The magnetic ferrosoferric oxide used in the examples was purchased from Tianjin Kemeiou Chemical Reagent Co., Ltd. (http: / / www.chemreagent.com / search.html?typeid=xz&title=%E5%9B%9B%E6%B0%A7%E5%8C%96%E4%B8%89%E9%93%81&button2.x=27&button2.y=18).
[0022] Example 1 (1) Precursor Ti(OBu)4 and complex propionic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:1, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:1.5 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 20 h, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0023] Example 2 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(methacrylic acid)=1:1, [n(Ti(OBu)4)+n(methacrylic acid)] / V(ethylene glycol)=1:1.5 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 20 h, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0024] Example 3 (1) Precursor Ti(OBu)4 and complex valproic acid were dispersed in ethylene glycol solvent at a ratio of n(Ti(OBu)4):n(valproic acid) = 1:1, [n(Ti(OBu)4) + n(valproic acid)] / V(ethylene glycol) = 1:1.5 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 20 h, then naturally cooled, filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0025] Example 4 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:1.5, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:1.8 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 22 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0026] Example 5 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0027] Example 6 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2.3 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 h, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0028] Example 7 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 min to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 3 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0029] Example 8 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a mechanical speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 4 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 0.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0030] Example 9 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0031] Example 10 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.5 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0032] Example 11 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 2.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 50 Hz and an ultrasonic time of 20 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0033] Example 12 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 60 Hz and an ultrasonic time of 30 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 2 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 40°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0034] Example 13 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 80 Hz and an ultrasonic time of 40 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 3 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 60°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0035] Example 14 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 80 Hz and an ultrasonic time of 40 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 3 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1), and the concentration of the FeCl3 aqueous solution was 10 g / L. After aging at room temperature for 2 h, washing with deionized water, filtering, and drying at 70°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0036] Example 15 (1) Precursor Ti(OBu)4 and complex methacrylic acid were dispersed in ethylene glycol solvent in a ratio of n(Ti(OBu)4):n(propionic acid)=1:2, [n(Ti(OBu)4)+n(propionic acid)] / V(ethylene glycol)=1:2 (mmol / ml). The mixture was sealed in a reactor and heated at 100°C for 24 hours, then naturally cooled. The mixture was then filtered, washed with anhydrous ethanol, and dried at 40°C to obtain Ti-O nanoclusters. (2) Dissolving marine biomass sodium alginate (SA) in deionized water at room temperature to obtain an SA solution, and dissolving sodium carboxymethyl cellulose (CMC-Na) in deionized water at room temperature to obtain a CMC-Na solution, and then mixing the two, mechanically stirring at a stirring speed of 1500 rpm for 60 minutes to obtain a mixed solution 1; the total mass concentration of the mixed solution 1 is 2 wt%, wherein the mass ratio of SA to CMC-Na is 1:1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; the mass concentration of the Ti-O nanoclusters in the mixed solution 2 is 1.0 wt%; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), and subjecting the mixture to ultrasonic treatment at room temperature for uniform dispersion and defoaming, with an ultrasonic frequency of 80 Hz and an ultrasonic time of 40 min, to obtain a mixed solution 3; the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 3 wt%; (5) The mixed solution 3 of step (4) was dropped into an FeCl3 aqueous solution for ion crosslinking to form spheres (the volume ratio of the mixed solution 3 to the FeCl3 aqueous solution was 1:1). The concentration of the FeCl3 aqueous solution was 12.5 g / L. After aging at room temperature for 3 h, washing with deionized water, filtering, and drying at 90°C, marine biomass composite Ti-O nanocluster microspheres were obtained.
[0037] Dye wastewater treatment: About 0.1 to 0.3 g of the uniform marine biomass composite Ti-O nanocluster microspheres prepared in Examples 1 to 14 were added to a series of 150 ml conical flasks, which were filled with 25 ml of a 200 mg / L aqueous solution of Direct Black 19 and a 300 mg / L aqueous solution of Direct Red 23, respectively. After shaking at room temperature for 60 min to 180 min, the absorbance of the original solution and the filtrate was measured by a 0.45 μm water filter membrane using an ultraviolet spectrophotometer (Direct Black 19: λ max =662nm, Direct Red 23:λ max =507nm), the standard curves of the two dyes were tested in advance by ultraviolet spectrophotometer to obtain the concentrations of the dyes before and after adsorption, and the adsorption amount Q was calculated by the following formula e (mg·g -1 ) and removal rate η (%), which are calculated as follows: Among them, C0 and C e are the initial concentration of the dye solution and the concentration of the dye solution remaining in the filtrate after equilibrium adsorption, mg / L; V is the volume of the dye solution, L; m is the added mass of Fe3O4@SA / CMC-Fe magnetic microspheres, g; η is the removal rate, %.
[0038] The test results are shown in the following table: Example <![CDATA[Direct red 23 removal rate η1(%)]]> <![CDATA[Removal rate η2(%) of Direct Black 19]]> Example 1 70～96 73～96 Example 2 71～95 72～96 Example 3 71～96 73～95 Example 4 71～96 72～96 Example 5 72～97 72～97 Example 6 72～95 73～97 Example 7 68～93 74～92 Example 8 69～92 73～92 Example 9 83～98 86～97 Example 10 81～98 81～96 Example 11 76～95 79～94 Example 12 78～97 79～97 Example 13 73～97 73～97 Example 14 83～98 86～97 Figure 1 a is an optical image of the marine biomass composite Ti-O nanocluster microspheres prepared in Example 14. It can be seen that the obtained microspheres are uniform in size and complete in spherical shape. Figure 1 b is a 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5. It can be seen that the enlarged image of a single microsphere still has a complete spherical structure. Figure 1 c is a SEM scanning image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5. It can be seen that the SEM image of the single microsphere still has a complete spherical structure. Figure 1 d is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5. It can be seen that the obtained microsphere has abundant spine folds, which further gives it a high specific surface area and adsorption performance. Figure 1 e is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5 after adsorption of Direct Red 23. It can be seen that the wrinkles of the microsphere have been filled with Direct Red 23. Figure 1 f is a local 3D microscope image of a single marine biomass composite Ti-O nanocluster microsphere obtained in Example 5 after adsorption of direct black 19. It can be seen that the folds of the microsphere have been filled with direct black 19. Obviously, the adsorption methods of direct red 23 and direct black 19 are different, so the pictures after adsorption are different.
[0039] Figure 2 A top view of a ball-and-stick model of the Ti-O nanoclusters prepared in Example 14. Color coding: teal blue represents carbon atoms; dark gray represents hydrogen atoms; yellow represents oxygen atoms; and light gray represents titanium atoms. The image shows that the nanoclusters are crystals with a "doughnut" structure, with an inner diameter of approximately 0.83 nm and an outer diameter of approximately 2.69 nm. This large specific surface area provides the structural foundation for the production of marine biomass-composite Ti-O nanocluster microspheres for efficient adsorption.
Claims
1. A method for preparing marine biomass composite Ti-O nanocluster microspheres, characterized by: The steps include: (1) Precursor Ti(OBu)4 and complex monocarboxylic acid are dispersed in solvent ethylene glycol, sealed in a reactor, heated for a certain period of time, and then naturally cooled. The mixture is then filtered, washed, and dried to obtain Ti-O nanoclusters. (2) dissolving marine biomass sodium alginate in deionized water at room temperature, dissolving sodium carboxymethyl cellulose in deionized water at room temperature, and then mixing the two and mechanically stirring to obtain a mixed solution 1; (3) adding Ti-O nanoclusters to the mixed solution 1 of step (2) to obtain a mixed solution 2; (4) adding magnetic ferroferric oxide to the mixed solution 2 of step (3), uniformly dispersing by ultrasonication and defoaming, to obtain a mixed solution 3; (5) The mixed solution 3 of step (4) is dropped into an FeCl3 aqueous solution for ion cross-linking to form spheres. After aging, washing, filtering and drying, marine biomass composite Ti-O nanocluster microspheres are obtained.
2. The method for preparing marine biomass composite Ti-O nanocluster microspheres according to claim 1, characterized in that: In step (1), the monocarboxylic acid is selected from propionic acid, methacrylic acid, and valproic acid; the molar ratio of Ti(OBu)4:monocarboxylic acid is 1:1-1:2, and the molar volume ratio of Ti(OBu)4) + monocarboxylic acid:ethylene glycol is 1:1.5-1:2.4 in mmol / ml; the heating reaction temperature is 100-150°C, and the heating reaction time is 20-28 h.
3. The method for preparing marine biomass composite Ti-O nanocluster microspheres according to claim 1, characterized in that: In step (2), the mass ratio of sodium alginate: sodium carboxymethyl cellulose is 1:1~1:4; the total mass concentration of the mixed solution 1 is 2wt%~4.0wt%; the stirring speed is 1000~3000 rpm, and the stirring time is 60~120 min.
4. The method for preparing marine biomass composite Ti-O nanocluster microspheres according to claim 1, characterized in that: In step (3), the mass concentration of Ti-O nanoclusters in the mixed solution 2 is 0.5 wt% to 2.0 wt%.
5. The method for preparing marine biomass composite Ti-O nanocluster microspheres according to claim 1, characterized in that: In step (4), the mass concentration of magnetic ferroferric oxide in the mixed solution 3 is 1 wt% to 4.0 wt%; the frequency of ultrasound is 50 to 100 Hz, and the time of ultrasound is 20 to 60 min.
6. The method for preparing marine biomass composite Ti-O nanocluster microspheres according to claim 1, characterized in that: In step (5), the concentration of the FeCl3 aqueous solution is 10-15 g / L; the aging time is 2-5 h; and the drying temperature is 40-90°C.
7. Marine biomass composite Ti-O nanocluster microspheres obtained by the preparation method according to any one of claims 1 to 6.
8. Use of the marine biomass composite Ti-O nanocluster microspheres according to claim 7 in dye wastewater treatment.
9. The use according to claim 8, characterized in that: Marine biomass composite Ti-O nanocluster microspheres are added as adsorbents into wastewater containing dyes to adsorb and remove the dyes in the wastewater.
Citation Information
Patent Citations
Preparation method of magnetic bentonite gelatin composite microspheres for removing Cu ions in water body bottom mud
CN115254044A