WO2023065752A1 - 一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制法及应用 - Google Patents

一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制法及应用 Download PDF

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WO2023065752A1
WO2023065752A1 PCT/CN2022/107803 CN2022107803W WO2023065752A1 WO 2023065752 A1 WO2023065752 A1 WO 2023065752A1 CN 2022107803 W CN2022107803 W CN 2022107803W WO 2023065752 A1 WO2023065752 A1 WO 2023065752A1
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tannic acid
clay
kaolin
antibiotics
adsorption
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French (fr)
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杨琥
常慊慊
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Quanzhou Institute For Environmental Protection Industry Nanjing University
Nanjing University
Nanjing Tech University
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Quanzhou Institute For Environmental Protection Industry Nanjing University
Nanjing University
Nanjing Tech University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to an adsorbent prepared by a simple one-step reaction of clay materials, natural polymer tannic acid and metal ions to achieve the effect of efficiently adsorbing antibiotics in water bodies, and belongs to the field of water environment treatment.
  • PPCPs pharmaceuticals and personal care products
  • Antibiotics are one of the main types of PPCPs. They are widely used due to their broad-spectrum antibacterial properties and low side effects. They can be divided into sulfonamides, fluoroquinolones, tetracyclines, ⁇ -lactams and macrocyclics. Lactones. After antibiotics enter the human body or animal body, 10%-90% are excreted in the form of metabolites due to incomplete absorption and metabolism. On the one hand, due to the low removal efficiency of antibiotics in traditional sewage treatment plants, antibiotics enter the environment with the reuse of reclaimed water.
  • antibiotics used in animal husbandry and fishery will be directly discharged into the environment.
  • Antibiotics in the environment will induce the production of bacterial resistance genes, posing a threat to the ecological environment; in addition, antibiotics in the environment will accumulate in animals and plants, enter the human body through the food chain, and pose a potential threat to human health. Therefore, the environmental problems caused by excessive use of antibiotics have attracted more and more people's attention, and antibiotic pollution has become a major environmental pollution problem to be solved urgently.
  • antibiotics are mainly removed by means of advanced oxidation, membrane separation, and adsorption.
  • advanced oxidation requires high costs and may produce more toxic by-products.
  • Membrane separation is affected by temperature, organic matter, The influence of soluble salt etc. is great, it is easy to cause membrane fouling, reduce the membrane flux, and then affect the degradation performance; the adsorption method has the characteristics of simple process, low energy consumption, high removal efficiency, and no generation of toxic intermediate products, etc., but the existing adsorption method
  • disadvantages such as large dosage, high cost, and low adsorption efficiency. Therefore, it is necessary to develop a low-cost, high-capacity adsorbent to adsorb different antibiotics.
  • Tannic acid is rich in resources and widely exists in persimmon skin, grape skin, tea and other plants. The content in plants is second only to cellulose and hemifiber.
  • Lignin and lignin are water-soluble, hydroxyl-rich polyphenols with universal adhesion. The phenolic hydroxyl groups of tannins can undergo chelation reactions with metal ions to form five-membered or six-membered chelate ring compounds.
  • tannins are easily soluble in water and cannot be directly used as adsorption materials, which hinders the development of tannins as adsorbents.
  • Clay is an important part of soil particles ( ⁇ 2 ⁇ m), and it is also a common substance in our daily life. It is widely distributed in nature and has a high content.
  • the chemical composition of clay materials is aluminosilicate without definite molecules, and its physical structure is usually lamellar. Clay materials are characterized by strong plasticity, can present a specific structure without cracking, can be deformed under a small pressure when exposed to water and can maintain a specific shape for a long time. In addition, the specific surface area of clay materials is large, and the particle surface is negatively charged. It has good physical adsorption performance and surface chemical activity, and can be used as a good carrier material and react with other substances.
  • Chinese patent CN111229176A discloses a method of directly modifying tannic acid by polyethyleneimine to remove heavy metal ions such as lead ions and copper ions;
  • Chinese patent CN109078616B discloses a composite material of tannic acid/gelatin/graphene oxide , as dye adsorption material;
  • Chinese patent CN109225144A discloses a kind of method by zirconium tetrachloride, phthalic acid, cobalt sulfate synthesis metal organic framework (MOF) material, this reaction process needs 20-30h, to fluoroquinolone antibiotic hydrochloride The highest adsorption capacity of levofloxacin is 70.21mg/g (0.176mol/g).
  • the relevant patents on the modification of tannic acid have the problems of long time-consuming synthesis, complex reaction process and low adsorption capacity of the relevant patent materials that do not reduce antibiotics in water or absorb antibiotics.
  • the purpose of the present invention is to provide a kind of natural macromolecular material tannic acid and clay mineral material, metal ion to synthesize novel composite adsorbent and its preparation method with simple method, apply in sewage to reach the effect of efficient adsorption antibiotic.
  • the tannic acid is fixed on the clay material through metal ion cross-linking, and under the joint action of the three, the adsorption capacity for antibiotic pollutants is improved.
  • the technical scheme proposed is: a kind of preparation method of the clay/tannic acid/metal ion composite material that is used for efficiently adsorbing antibiotics, which is made by mixing natural polymer materials, clay mineral materials and metal ions A composite adsorbent obtained;
  • the natural polymer material is tannic acid;
  • the clay mineral material is kaolin, montmorillonite, attapulgite, bentonite or illite;
  • the metal ion is iron ion, Copper, aluminum, magnesium or titanium ions;
  • the natural polymer material tannic acid and the metal ion solution are dissolved in water respectively, after fully dissolving, the molar concentration of the tannic acid solution is 1-100mmol/L, and the concentration of the metal ion solution is 10-160mmol/L, Disperse the clay material in the buffer solution, then add the tannic acid solution and the metal ion solution to the clay dispersion, adjust the pH value to be greater than 7, stir and react at room temperature for 30 seconds to 3 minutes, filter, wash, and dry, that is The final clay/tannic acid/metal composite adsorbent is obtained.
  • the molar ratio of the natural polymer material tannic acid to the metal ion is 1:4; the clay mineral material is kaolin; the metal ion is titanium ion, and the mass ratio of the tannic acid to the kaolin is 1:1. .
  • MOPS 3-morpholine propanesulfonic acid buffer solution
  • the clay mineral material dispersion buffer solution is tris(hydroxymethyl)aminomethane buffer solution (Tris) or 3-morpholine propanesulfonic acid buffer solution (MOPS).
  • Tris tris(hydroxymethyl)aminomethane buffer solution
  • MOPS 3-morpholine propanesulfonic acid buffer solution
  • the drying method may be room temperature drying or freeze drying.
  • the antibiotics are sulfonamides, fluoroquinolones, tetracyclines, ⁇ -lactams or macrolides.
  • the present invention adopts a one-step method to prepare the clay/tannic acid/metal composite adsorbent, the preparation method and operation process are simple, the synthesis time is short, and the output is large.
  • the raw material that the present invention adopts is natural macromolecule tannic acid, and its source is extensive, nontoxic, biodegradable, no secondary pollution risk, because a large amount of phenolic hydroxyl groups are rich in the tannic acid structure, not only can be combined with metal
  • the ion undergoes chelation reaction, and also effectively adsorbs pollutants in the water body, especially after compounding with clay and metal ions, a new complex with a unique structure is formed, the surface is rougher, the adsorption active sites are increased, and the adsorption is effectively increased. Improve the adsorption performance of pollutants.
  • the clay/tannic acid/metal composite adsorbent of the present invention has a good adsorption effect on antibiotics.
  • Example 2 Compared with the adsorption capacity of the kaolin/tannic acid/iron ion composite adsorbent whose feed ratio is 1:4 in Example 1 (table 2), along with the increase of feed ratio, the kaolin/tannic acid/iron ion The adsorption capacity of the composite adsorbent for enrofloxacin antibiotics first increased and then decreased slightly, and reached the optimal effect when the feed ratio was 1:4.
  • Fig. 1 is the infrared spectrogram of kaolin, tannic acid, tannic acid/metal ion complex and kaolin/tannic acid/metal ion composite adsorbent.
  • Fig. 2 is a scanning electron microscope image of kaolin, tannic acid, tannic acid/metal ion complex and kaolin/tannic acid/metal ion composite adsorbent.
  • Fig. 3 is the adsorption capacity graph of kaolin, tannic acid, tannic acid/metal ion complex and kaolin/tannic acid/metal ion composite adsorbent to a kind of fluoroquinolone antibiotic: ofloxacin.
  • Fig. 4 is the adsorption kinetics diagram of kaolin/tannic acid/iron ion composite adsorbent to a kind of fluoroquinolone antibiotic: ofloxacin.
  • Figure 3 is a comparison chart of the adsorption effect of the simulated water sample in the laboratory using wastewater containing a fluoroquinolone antibiotic: ofloxacin.
  • Fig. 4 is the adsorption kinetics diagram of ofloxacin, which contains a fluoroquinolone antibiotic on the kaolin/tannic acid/iron ion composite adsorbent.
  • the initial concentration of ofloxacin in simulated wastewater was 0.2mmol/L, and 10mg of composite adsorbent was added to 30mL ofloxacin solution for adsorption for 12h. This process detects the adsorption capacity of ofloxacin that the product actually adsorbs by liquid chromatography.
  • the adsorption capacity of kaolin/tannic acid/iron ion composite adsorbent to ofloxacin can basically reach adsorption saturation when adsorbed for 6 hours, and the highest adsorption effect can be achieved when adsorbed for 12 hours.
  • the wastewater containing enrofloxacin antibiotics is a simulated laboratory water sample.
  • the initial concentration of enrofloxacin antibiotics in the simulated wastewater is 0.2mmol/L, and 10mg of composite adsorbent is added for adsorption for 12h.
  • This process detects the effect of the actual adsorption enrofloxacin antibiotic of product by liquid chromatography, compares (table 2) with the kaolin/tannic acid/iron ion composite adsorbent adsorption capacity of 1:4 in the embodiment 1.
  • the wastewater containing tetracycline antibiotics is a simulated laboratory water sample.
  • the initial concentration of tetracycline antibiotics in the simulated wastewater is 0.2mmol/L, and 10mg of composite adsorbent is added for adsorption for 12h. This process detects the actual adsorption effect of tetracycline antibiotics by liquid chromatography.
  • the wastewater containing sulfonamide antibiotics was simulated laboratory water samples.
  • the initial concentration of sulfa antibiotics in the simulated wastewater was 0.2mmol/L, and 10mg of composite adsorbent was added for adsorption for 12h. This process detects the actual adsorption effect of tetracycline antibiotics by liquid chromatography.
  • the wastewater containing macrolide antibiotics is a simulated laboratory water sample.
  • the initial concentration of macrolide antibiotics in the simulated wastewater is 0.2 mmol/L, and 10 mg of composite adsorbent is added for adsorption for 12 hours. This process detects the effect of actually adsorbing macrolide antibiotics by the product through liquid chromatography.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the wastewater containing ⁇ -lactam antibiotics is a simulated laboratory water sample.
  • the initial concentration of ⁇ -lactam antibiotics in the simulated wastewater is 0.2 mmol/L, and 10 mg of composite adsorbent is added for adsorption for 12 hours. This process detects the actual adsorption effect of ⁇ -lactam antibiotics by liquid chromatography.

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Abstract

本发明属于水环境处理领域，具体涉及一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制法及应用。本发明采用一步法制得粘土/单宁酸/金属复合吸附剂，制备方法和操作工艺简单，合成时间短，产量大。本发明采用的原料是天然高分子单宁酸，其来源广泛，无毒，可生物降解，无二次污染风险，由于单宁酸结构中富含大量的酚羟基，不仅能够与金属离子发生螯合反应，还有效吸附水体中污染物，特别是与粘土及金属离子复合后，形成一种独特结构的新的复合体，表面更加粗糙，吸附活性位点增加，有效增加吸附，大大提高对污染物的吸附性能。本发明的粘土/单宁酸/金属复合吸附剂对抗生素具有良好的吸附效果。

Description

一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制法及应用 技术领域
本发明涉及粘土材料、天然高分子单宁酸与金属离子经过简单一步法反应制备吸附剂，以达到高效吸附水体中抗生素的效果，属于水环境处理领域。
背景技术
近年来，PPCPs(药品及个人护理品)的广泛应用在提高人类的生活方式与水平的同时也作为一种新型污染物受到广泛关注。抗生素是PPCPs的主要种类之一，由于具有广谱的抗菌性以及较低的副作用而被人们广泛使用，其又可以分为磺胺类、氟喹诺酮类、四环素类、β-内酰胺类和大环内酯类。抗生素进入人体或动物体内后，由于不完全的吸收代谢，10％-90％以代谢产物的形式被排出体外。一方面，由于传统的污水处理厂对抗生素去除效率低，导致抗生素随着再生水的再利用进入到环境中，另一方面，畜牧业以及渔业上使用的抗生素会直接排放到环境中。环境中的抗生素会诱导细菌耐药基因的产生，对生态环境造成威胁；另外，环境中的抗生素会在动植物体内累积，通过食物链最终进入人体，对人类健康造成潜在威胁。因此，过度使用抗生素所引起的环境问题越来越得到人们的关注，抗生素污染也成为目前亟待解决的重大环境污染问题。
目前，主要通过高级氧化法、膜分离法及吸附法等手段去除抗生素药物，然而在实际应用中，高级氧化法需要高昂成本且可能产生毒性更高的 副产物，膜分离法受到温度、有机物、可溶性盐等的影响大，容易造成膜污染，降低膜通量，进而影响降解性能；吸附法具有工艺简单、能耗低、去除效率高、无有毒中间产物生成等的特点，但现有的吸附剂存在用量大，成本高，吸附效率低等的缺点。因此，需要开发一种成本低，吸附量大的吸附剂来吸附不同抗生素。
天然高分子具有成本低、绿色环保、来源广泛等特点，单宁酸资源丰富，广泛存在于柿子皮，葡萄皮，茶叶等多种植物中，在植物中的含量仅次于纤维素、半纤维素和木质素，是一种具有水溶性，富含羟基的多酚类物质，同时具有普适粘附性。单宁的酚羟基能够与金属离子发生螯合反应，形成五元或六元的螯环化合物。然而，单宁易溶于水，无法直接用作吸附材料，这种缺点阻碍了单宁作为吸附剂的发展。
粘土是土壤微粒(<2μm)的重要组成部分，也是我们日常生活中常见的一类物质，在自然界中分布广泛，含量较高。粘土材料的化学组成为无确定分子的硅铝酸盐，其物理结构通常为片层。粘土材料的特点为有很强的可塑性，可以呈现特定结构而不开裂，遇水在较小的压力下可以变形并能长久保持特定形态，另外，粘土材料比表面积大，其颗粒表面带有负电性，有较好的物理吸附性能和表面化学活性，可以用作一种良好的载体材料并且与其他物质发生反应。
中国专利CN111229176A公开了一种直接由聚乙烯亚胺改性单宁酸的方法来去除铅离子、铜离子等重金属离子；中国专利CN109078616B公开了一种单宁酸/明胶/氧化石墨烯的复合材料，作为染料吸附材料；中国专利CN109225144A公开了一种由四氯化锆，苯二甲酸，硫酸钴合成金属有机 框架(MOF)材料的方法，该反应过程需要20-30h，对氟喹诺酮类抗生素盐酸左氧氟沙星的最高吸附容量为70.21mg/g(0.176mol/g)。但对单宁酸改性的相关专利存在未消减水体中抗生素或吸附抗生素的相关专利材料合成耗时长，反应过程复杂且吸附容量过低等的问题。
发明内容
本发明的目的是提供一种天然高分子材料单宁酸与粘土矿物材料、金属离子用简单方法合成新型复合吸附剂及其制法，在污水中应用以达到高效吸附抗生素的效果。将单宁酸通过金属离子交联固定在粘土材料上，在三者共同作用下，提高对抗生素污染物的吸附容量。
为了解决本发明的技术问题，提出的技术方案为：一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制备方法，由天然高分子材料、粘土矿物材料和金属离子混合制得的一种复合吸附剂；所述的天然高分子材料是单宁酸；所述的粘土矿物材料是高岭土、蒙脱石、凹凸棒、膨润土或伊利石；所述的金属离子是铁离子、铜离子、铝离子、镁离子或钛离子；
将天然高分子材料单宁酸和金属离子溶液分别充分溶于水，将粘土材料分散在缓冲溶液中，然后将单宁酸溶液与金属离子溶液加入粘土分散液中，调节pH值大于7，在室温条件下搅拌反应，过滤，洗涤、干燥，即得到最终的粘土/单宁酸/金属复合吸附剂。
优选的，将天然高分子材料单宁酸和金属离子溶液分别溶于水，充分溶解后，单宁酸溶液的摩尔浓度为1-100mmol/L，金属离子溶液的浓度是10-160mmol/L，将粘土材料分散在缓冲溶液中，然后将单宁酸溶液与金属 离子溶液加入粘土分散液中，调节pH值大于7，在室温条件下搅拌反应30秒-3分钟，过滤，洗涤、干燥，即得到最终的粘土/单宁酸/金属复合吸附剂。
优选的，所述天然高分子材料单宁酸与金属离子的摩尔比为1:4；所述的粘土矿物材料是高岭土；所述的金属离子是钛离子，所述单宁酸与高岭土质量比为1:1。。
优选的，(1)在3-吗啉丙磺酸缓冲溶液(MOPS)缓冲溶液中加入2g高岭土，超声分散，得到高岭土分散液；
(2)将10mmol/L单宁酸溶液和40mmol/L钛离子溶液加入高岭土分散液中，调节pH＝7.5在室温条件下反应1分钟左右，过滤，水洗，干燥得到投料比为1:4的高岭土/单宁酸/钛离子复合吸附剂。
优选的，所述的粘土矿物材料分散缓冲溶液是三(羟甲基)氨基甲烷缓冲溶液(Tris)或3-吗啉丙磺酸缓冲溶液(MOPS)。
优选的，上述的复合吸附剂，所述的干燥方法可以是室温干燥或冷冻干燥。
为了解决本发明的技术问题，提出的另一技术方案为：用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的应用，污水中应用以达到高效吸附抗生素。
优选的，所述抗生素是磺胺类、氟喹诺酮类、四环素类、β-内酰胺类或大环内酯类。
相比现有技术，本发明的有益效果如下：
(1)本发明采用一步法制得粘土/单宁酸/金属复合吸附剂，制备方法和操作工艺简单，合成时间短，产量大。
(2)本发明采用的原料是天然高分子单宁酸，其来源广泛，无毒，可生物降解，无二次污染风险，由于单宁酸结构中富含大量的酚羟基，不仅能够与金属离子发生螯合反应，还有效吸附水体中污染物，特别是与粘土及金属离子复合后，形成一种独特结构的新的复合体，表面更加粗糙，吸附活性位点增加，有效增加吸附，大大提高对污染物的吸附性能。
(3)本发明的粘土/单宁酸/金属复合吸附剂对抗生素具有良好的吸附效果。
(4)高岭土/单宁酸/钛离子复合吸附剂，高岭土/单宁酸/铁离子复合吸附剂，高岭土/单宁酸/铜离子复合吸附剂的吸附量逐渐降低，这主要是由于价态更高的金属离子与氧氟沙星具有更加强的螯合作用，大大提高对氧氟沙星的吸附容量。
(5)与实施例1中投料比为1:4的高岭土/单宁酸/铁离子复合吸附剂吸附容量进行对比(表2)，随着投料比的增加，高岭土/单宁酸/铁离子复合吸附剂对恩诺沙星抗生素的吸附容量先上升后轻微下降，在投料比为1:4时达到最优效果。
附图说明
图1为高岭土、单宁酸、单宁酸/金属离子复合物及高岭土/单宁酸/金属离子复合吸附剂的红外光谱图。
图2为高岭土、单宁酸、单宁酸/金属离子复合物及高岭土/单宁酸/金属离子复合吸附剂的扫描电镜图。
图3为高岭土、单宁酸、单宁酸/金属离子复合物及高岭土/单宁酸/金属离子复合吸附剂对一种氟喹诺酮类抗生素：氧氟沙星的吸附容量图。
图4为高岭土/单宁酸/铁离子复合吸附剂对一种氟喹诺酮类抗生素：氧氟沙星的吸附动力学图。
具体实施方式
以下通过实施例进一步说明本发明。
实施例1：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在MOPS缓冲溶液中加入2g高岭土，超声分散，得到高岭土分散液；
(2)将10mmol/L单宁酸溶液和40mmol/L铁离子溶液加入高岭土分散液中，所述单宁酸与高岭土质量比为1:1，调节pH＝7.5在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到单宁酸与金属离子的摩尔投料比为1:4；的高岭土/单宁酸/铁离子复合吸附剂。图1是高岭土/单宁酸/铁离子复合吸附剂的红外光谱图，与粘土、单宁酸及单宁酸/金属离子复合物相比，高岭土/单宁酸/金属离子复合吸附剂的红外光谱包含了粘土及单宁酸的红外特征峰；此外，单宁酸在1720cm -1处的C＝O伸缩振动峰及1325cm -1处的C–O弯曲振动峰，经与高岭土复合后，分别位移到1714cm -1及1350cm -1，说明高岭土与单宁酸及金属离子复合后，说明反应中伴随着电子转移过程， 铁离子与单宁酸的酚羟基之间形成了螯合键，形成一种独特结构的新的复合体。图2电镜照片也显示，高岭土/单宁酸/铁离子复合吸附剂表面更加粗糙，比表面积更大。
将10mmol/L单宁酸溶液和40mmol/L钛离子溶液加入高岭土分散液中，调节pH＝7.5在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到高岭土/单宁酸/钛离子复合吸附剂。
将10mmol/L单宁酸溶液和40mmol/L铜离子溶液加入高岭土分散液中，调节pH＝7.5在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到高岭土/单宁酸/铜离子复合吸附剂。
图3是以含有一种氟喹诺酮类抗生素：氧氟沙星的废水为实验室模拟水样的吸附效果对比图。图4是高岭土/单宁酸/铁离子复合吸附剂吸附含有一种氟喹诺酮类抗生素：氧氟沙星的吸附动力学图。模拟废水初始氧氟沙星浓度为0.2mmol/L，在30mL的氧氟沙星溶液中加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附氧氟沙星的吸附容量，从图3中可以看出，上述三种复合吸附剂的吸附效果相比单独高岭土及单宁酸/金属离子复合物吸附效果有了显著提升，这主要是由于高岭土与单宁酸及金属离子复合后，形成一种独特结构的新的复合体，表面更加粗糙，吸附活性位点增加。同时，从表1和图3可以看出高岭土/单宁酸/钛离子复合吸附剂，高岭土/单宁酸/铁离子复合吸附剂，高岭土/单宁酸/铜离子复合吸附剂的吸附量逐渐降低，这主要是由于价态更高的金属离子与氧氟沙星具有更加强的螯合作用，大大提高对氧氟沙星的吸附容量。从图4可以看出，高岭土/单宁酸/铁离子复合吸附剂对氧氟沙星的吸附量在吸附6h时可以基 本达到吸附饱和，吸附12h时，能够达到最高吸附效果。
表1 实施例1中三种种类复合吸附剂的吸附容量对比
Figure PCTCN2022107803-appb-000001
实施例2：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在MOPS缓冲溶液中加入2g高岭土，超声分散，得到高岭土分散液；
(2)将10mmol/L单宁酸溶液分别和20、30、40、50、60mmol/L的铁离子溶液加入高岭土分散液中，所述单宁酸与高岭土质量比为1:1，调节pH＝7.5并在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到复合吸附剂，分别得到单宁酸与金属离子摩尔投料比为1:2、1:3、1:4、1:5、1:6的高岭土/单宁酸/铁离子复合吸附剂。
含有恩诺沙星抗生素的废水为实验室模拟水样，模拟废水初始恩诺沙星类抗生素浓度为0.2mmol/L，加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附恩诺沙星抗生素的效果，与实施例1中投料比为1:4的高岭土/单宁酸/铁离子复合吸附剂吸附容量进行对比(表2)，随着投料比的增加，高岭土/单宁酸/铁离子复合吸附剂对恩诺沙星抗生素的吸附容量先上升后轻微下降，在投料比为1:4时达到最优效果。
表2 实施例2中不同投料摩尔比的高岭土/单宁酸/铁离子复合吸附剂的吸附容量对比
Figure PCTCN2022107803-appb-000002
实施例3：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在Tris缓冲溶液中加入10g凹凸棒，超声分散，得到凹凸棒分散液；
(2)将1mmol/L单宁酸溶液和80mmol/L铜离子溶液加入凹凸棒分散液中，所述单宁酸与凹凸棒质量比为1:1，调节pH＝7，在室温条件下反应1分钟左右，过滤，水洗，冷冻干燥得到复合吸附剂。
含有四环素类抗生素的废水为实验室模拟水样，模拟废水初始四环素类抗生素浓度为0.2mmol/L，加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附四环素类抗生素的效果。
实施例4：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在MOPS缓冲溶液中加入1g膨润土，超声分散，得到膨润土分散液；
(2)将100mmol/L单宁酸溶液和160mmol/L钛离子溶液加入膨润土分散液中，所述单宁酸与膨润土质量比为1:1，调节pH＝6.5，在室温条件下反应1分钟左右，过滤，水洗，冷冻干燥得到复合吸附剂。
含有磺胺类抗生素的废水为实验室模拟水样，模拟废水初始磺胺类抗生素浓度为0.2mmol/L，加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附四环素类抗生素的效果。
实施例5：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在MOPS缓冲溶液中加入7g蒙脱石，超声分散，得到蒙脱石分散液；
(2)将80mmol/L单宁酸溶液和60mmol/L铝离子溶液加入蒙脱石分散液中，所述单宁酸与蒙脱石质量比为1:1，调节pH＝7，在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到复合吸附剂。
含有大环内酯类抗生素的废水为实验室模拟水样，模拟废水初始大环内酯类抗生素浓度为0.2mmol/L，加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附大环内酯类抗生素的效果。
实施例6：
一种粘土/单宁酸/金属离子复合吸附剂的制备方法
(1)在Tris缓冲溶液中加入5g伊利石，超声分散，得到伊利石分散液；
(2)将50mmol/L单宁酸溶液和120mmol/L镁离子溶液加入伊利石分散液中，所述单宁酸与伊利石质量比为1:1，调节pH＝7.5，在室温条件下反应1分钟左右，过滤，水洗，室温干燥得到复合吸附剂。
含有β-内酰胺类抗生素的废水为实验室模拟水样，模拟废水初始β-内酰胺类抗生素浓度为0.2mmol/L，加入10mg复合吸附剂吸附12h。本工艺通过液相色谱仪检测产品实际吸附β-内酰胺类抗生素的效果。

Claims (2)

  1. 一种用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制备方法，其特征在于：由天然高分子材料、粘土矿物材料和金属离子混合制得的一种复合吸附剂；所述的天然高分子材料是单宁酸；所述的粘土矿物材料是高岭土；所述的金属离子是钛离子；所述天然高分子材料单宁酸与金属离子的摩尔比为1:4；所述单宁酸与高岭土质量比为1:1，具体制备方法如下：
    (1)在三羟甲基氨基甲烷缓冲溶液Tris或3-吗啉丙磺酸缓冲溶液MOPS缓冲溶液中加入2g高岭土，超声分散，得到高岭土分散液；
    (2)将10mmol/L单宁酸溶液和40mmol/L钛离子溶液加入高岭土分散液中，调节pH＝7.5在室温条件下反应1分钟左右，过滤，水洗，干燥得到投料比为1:4的高岭土/单宁酸/钛离子复合吸附剂。
  2. 根据权利要求1所述的用于高效吸附抗生素的粘土/单宁酸/金属离子复合材料的制备方法，其特征在于：上述的复合吸附剂，所述的干燥方法可以是室温干燥或冷冻干燥。
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