CN106944005B

CN106944005B - Resin-based nano composite adsorbent for deeply removing trace fluorine in water and preparation method and application thereof

Info

Publication number: CN106944005B
Application number: CN201710286632.2A
Authority: CN
Inventors: 潘丙才; 张璐; 蒋朝; 张孝林; 黎智贤; 郑琪; 林斌
Original assignee: Nanjing University
Current assignee: Nanjing University
Priority date: 2017-04-27
Filing date: 2017-04-27
Publication date: 2020-05-22
Anticipated expiration: 2037-04-27
Also published as: CN106944005A

Abstract

本发明公开了一种深度去除水中微量氟的树脂基纳米复合吸附剂及其制备方法和应用，属于水处理技术领域。本发明的树脂基纳米复合吸附剂以叔胺化超高交联聚苯乙烯‑二乙烯苯为骨架，叔胺基含量为0.2‑1.5mmol/g，有机骨架内负载氧化锆纳米颗粒，负载量以锆元素计为10‑30wt％，纳米颗粒尺寸为10‑80nm；复合材料中2nm以下的孔占总孔容的比例≥90％。本发明的纳米复合材料微孔结构丰富，可通过尺寸排除作用减少天然有机物对复合材料除氟的影响，在高有机物背景下依然可实现对水中微量氟的深度净化。The invention discloses a resin-based nano-composite adsorbent capable of deeply removing trace fluorine in water, a preparation method and application thereof, and belongs to the technical field of water treatment. The resin-based nanocomposite adsorbent of the present invention takes tertiary aminated ultra-high cross-linked polystyrene-divinylbenzene as a skeleton, the content of tertiary amine groups is 0.2-1.5 mmol/g, and the organic skeleton is loaded with zirconia nanoparticles, and the loading amount is 0.2-1.5 mmol/g. Calculated as zirconium element, it is 10-30wt%, and the nanoparticle size is 10-80nm; the proportion of pores below 2nm in the total pore volume in the composite material is ≥90%. The nanocomposite material of the present invention has rich microporous structure, can reduce the influence of natural organic matter on fluorine removal of the composite material through size exclusion, and can still achieve deep purification of trace fluorine in water under the background of high organic matter.

Description

Resin-based nano composite adsorbent for deeply removing trace fluorine in water and preparation method and application thereof

Technical Field

The invention belongs to the technical field of water treatment, and particularly relates to a resin-based nano composite adsorbent for deeply removing trace fluorine in water, and a preparation method and application thereof.

Background

Fluorine is an essential element of human body, and a proper amount of fluorine has important effects on teeth and bones; however, if the fluorine intake is excessive, the method will have many adverse effects on human body, such as: resulting in dental fluorosis and fluorosis, and destroying normal calcium and phosphorus metabolism. At present, the abnormal fluorine content of natural water is a major problem worldwide, and when the fluorine content in drinking water exceeds the standard, the endemic fluorosis can be caused. Fluorosis is one of the most serious endemic diseases in China, strict regulations are made on the fluorine content of drinking water at home and abroad, and the development of an efficient water body fluorine pollution control technology is urgently needed.

In the past two decades, the adsorption method has become one of the best methods for removing fluorine due to the advantages of simple operation, stable effect, economy, feasibility and the like. Among them, the nano hydrous zirconia becomes one of the ideal fluorine adsorbents because of its characteristics of high adsorption selectivity, large adsorption capacity, strong material stability, etc. The nano hydrous zirconia has extremely high specific surface area and reaction activity, and a large number of hydroxyl groups on the surface can generate specific adsorption on fluorine through ligand exchange. However, the nanometer hydrous zirconia has the defects of difficult recycling, easy agglomeration and inactivation, large pressure drop, high energy consumption, easy loss and the like in the using process, and the method is also a main technical problem for limiting the defluorination process of the nanometer hydrous zirconia. In order to overcome the defects, the development of the nano-loaded hydrous zirconia composite material is a common treatment means for solving the problem of industrial application.

Through retrieval, a great deal of patent reports about the preparation of the composite defluorinating material by loading the nano hydrous zirconia on the matrix material are disclosed. For example, chinese patent 201210524428.7 discloses that polystyrene resin with a nano-pore structure is used as a carrier, nano-hydrous zirconia particles are loaded in the pore channels of a polymer carrier through an in-situ precipitation technology, so as to successfully develop an organic-inorganic nano composite adsorbing material, treat micro-fluorine pollution in water to a dosage harmless to human bodies, and successfully solve the problem that fluorine is difficult to deeply treat. The nano composite adsorption material has the characteristics of high selectivity, excellent fluid mechanical property, high mechanical strength and the like. More importantly, the organic carrier surface contains abundant charged groups, so that the fluorine ions can be pre-enriched by the Donnan effect, and the fluorine removal performance of the nano composite adsorption material is obviously improved.

However, the pores of the nanocomposite material referred to in the above application are mainly of a macroporous structure, and most of the nano hydrous zirconia is distributed in the pores of 30nm or more. Due to the characteristics of the pore structure, Natural Organic Matters (NOM) widely existing in natural water bodies are very easy to diffuse into pores and interact with nanoparticles to occupy active sites, so that the defluorination process is influenced. Research shows that under the condition that the concentration of natural organic matters in water is 10-500mg/L, the removal rate and the adsorption capacity of fluorine can be reduced by more than 90% at most by adopting the nano composite material in the application (Environ Sci Technol, 2013, 47, 9347). In addition, the porous resin is generally prepared by a suspension copolymerization method, and a pore-forming agent is required to be additionally added; the pore-forming agent is mostly liquid, and in the suspension copolymerization liquid-solid phase conversion process, the pore-forming agent forms nano liquid drops to occupy the solid phase space so as to form pores. As the pore-forming agent is not easy to disperse into uniform small-size nano liquid drops in the reaction process, almost all porous resins have rich macroporous structures, and the load type nano zirconia material prepared by taking the material as a carrier is difficult to theoretically eliminate the adverse effect of NOM on the defluorination process.

Disclosure of Invention

1. Technical problem to be solved by the invention

The invention aims to overcome the defect that the removal effect of fluorine is influenced due to the fact that the fluorine is greatly influenced by natural organic matters in water when the conventional resin-based nano zirconia composite material is used for removing fluorine in natural water, and provides a resin-based nano composite adsorbent for deeply removing trace fluorine in water and a preparation method and application thereof. The invention effectively reduces the adverse effect of natural organic matters on the fluorine removal of the zirconia nano-particles by utilizing the size removal effect, and can still efficiently remove trace fluorine in water with higher natural organic matter content.

2. Technical scheme

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

the resin-based nano composite adsorbent for deeply removing trace fluorine in water takes ultrahigh crosslinked polystyrene-divinylbenzene as an organic framework, zirconium oxide nano particles are loaded in the organic framework, and the pore volume of the nano composite adsorbent is 0.3-0.9cm³(g) specific surface area of 600-1500m²The ratio of pores with the diameter of less than 2nm to the total pore volume is more than or equal to 90 percent.

Furthermore, the loading amount of the zirconium oxide in the composite adsorbent is 10-30 wt% calculated by zirconium element, and the size of the zirconium oxide nano-particles is 10-80 nm.

Furthermore, the organic framework is covalently combined with tertiary amine groups, the content of the tertiary amine groups is 0.2-1.5mmol/g, and the pore volume is 0.5-1.2cm³(g) specific surface area of 400-²/g。

Secondly, the preparation method of the resin-based nano composite adsorbent comprises the following steps: immersing the tertiary aminated ultrahigh crosslinked polystyrene resin after drying treatment into ZrOCl₂·8H₂O, HCl and ethanol, and evaporating to dryness under stirring; and then adding NaOH and NaCl aqueous solution, and carrying out transformation, water washing, alcohol washing and drying to obtain the resin-based nano zirconia composite material.

Further, ZrOCl₂·8H₂O, HCl and ethanol, ZrOCl₂·8H₂O, HCl and ethanol in the mass ratio of (2.5-8) to 1: 6.

Furthermore, the mass concentration of the NaOH solution and the NaCl aqueous solution is 3-6%.

Thirdly, the resin-based nano composite adsorbent for deeply removing trace fluorine in water is applied to adsorbing the fluorine in the water, and the concentration of the fluorine after treatment can be reduced to below 1 mg/L.

Furthermore, when the nano composite adsorbent is used for treating fluorine-containing water, the adsorbent-loaded zirconium oxide nano particles can adsorb 40-120mg of fluorine per gram on average in terms of zirconium.

Furthermore, the adsorbed nano composite adsorbent is desorbed and regenerated by an alkali salt mixed solution, the desorption rate of fluorine is more than 90%, wherein the alkali in the alkali salt mixed solution is NaOH or KOH, the salt is NaCl or KCl, and the mass concentrations of the alkali and the salt are both 3-6%.

3. Advantageous effects

Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:

(1) the invention relates to a resin-based nano composite adsorbent for deeply removing trace fluorine in water, which is prepared byThe ultrahigh crosslinked polystyrene-divinylbenzene is taken as an organic framework, zirconia nano-particles are loaded in the organic framework, and the pore volume of the nano-composite adsorbent is 0.3-0.9cm³(g) specific surface area of 600-1500m²The ratio of pores with the diameter of less than 2nm to the total pore volume is more than or equal to 90 percent. The pore structure of the nano composite material is mainly distributed in the micropore range, so that the influence of natural organic matters on fluorine removal can be reduced through the size removal effect, the fluorine removal effect is hardly influenced when the concentration of organic matters in water is high, and the deep treatment and safety control of trace fluorine in water can be realized.

(2) According to the resin-based nano composite adsorbent for deeply removing trace fluorine in water, the loading capacity of zirconium oxide in the adsorbent is 10-30 wt% calculated by zirconium element, the size of zirconium oxide nano particles is 10-80nm, compared with the prior art, the zirconium oxide nano particles are high in loading amount and fine in size, the adsorption area is greatly increased, and therefore the fluorine adsorption amount is effectively increased.

(3) According to the preparation method of the resin-based nano composite adsorbent, the size of micropores on the adsorbent carrier can be effectively reduced, and the loading capacity of zirconium oxide particles is improved, so that the deep removal effect of the prepared adsorbent on trace fluorine in water is ensured.

(4) The resin-based nano-composite adsorbent for deeply removing trace fluorine in water is used for adsorbing fluorine in water, the concentration of fluorine in water can be effectively reduced to be below 1mg/L, the adsorbent subjected to adsorption treatment can be subjected to desorption regeneration by adopting an alkali salt mixed solution, and the desorption rate of fluorine is up to 90%.

Detailed Description

The resin-based nano composite adsorbent for deeply removing trace fluorine in water takes tertiary aminated ultrahigh crosslinked polystyrene-divinylbenzene as an organic framework, the content of tertiary amino groups is 0.2-1.5mmol/g, and the pore volume of the organic framework is 0.5-1.2cm³(g) specific surface area of 400-²And the pores on the organic framework comprise two types of macropores and micropores,the diameter of the large hole is more than 30nm, the diameter of the small hole is less than 2nm, and the proportion of the two holes is 40-60%. The organic framework is loaded with zirconia nanoparticles, the loading amount of zirconia is 10-30 wt% calculated by zirconium element, the size of the zirconia nanoparticles is 10-80nm, the zirconia nanoparticles are mainly loaded in macropores on the organic framework, and the pore volume of the composite adsorbent obtained after loading is 0.3-0.9cm³(g) specific surface area of 600-1500m²The ratio of pores with the diameter of less than 2nm to the total pore volume is more than or equal to 90 percent.

The preparation method of the resin-based nano composite adsorbent comprises the following steps: immersing the tertiary aminated ultrahigh crosslinked polystyrene resin after drying treatment into ZrOCl₂·8H₂O, HCl and ethanol, and evaporating to dryness under stirring to obtain ZrOCl₂·8H₂O, HCl and ethanol in the mass ratio of (2.5-8) to 1: 6; and sequentially adding NaOH and NaCl aqueous solutions with the mass concentration of 3-6%, and carrying out transformation, washing, alcohol washing and drying to obtain the resin-based nano-zirconia composite material.

When the resin-based nano composite adsorbent prepared by the invention is used for adsorbing fluorine in water, the pore structure of the loaded nano composite material is mainly distributed in the micropore range, so that the influence of natural organic matters on fluorine removal can be reduced through the size removal effect, the fluorine removal effect is hardly influenced when the concentration of organic matters in water is high, and the deep treatment and safety control of trace fluorine in water can still be realized. The zirconium oxide nano particles loaded in the adsorbent can adsorb 40-120mg of fluorine per gram on average in terms of zirconium, the adsorption rate is high, and the concentration of fluorine in water can be effectively reduced to be below 1 mg/L. Meanwhile, the adsorbed nano composite adsorbent can be desorbed and regenerated through the alkali salt mixed solution, the desorption rate of fluorine is more than 90%, the alkali in the alkali salt mixed solution is NaOH or KOH, the salt is NaCl or KCl, and the mass concentrations of the alkali and the salt are both 3-6%.

For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention.

Example 1

Will be driedThen 10g of tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amino group content 0.8mmol/g, organic skeleton pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 30gZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then sequentially adding NaOH with the mass concentration of 5% and NaCl solution with the mass concentration of 5% for transformation, washing with alcohol, and drying to obtain the resin-based nano zirconia composite material (nano composite adsorbent).

After acidification and digestion, the zirconium content in the composite material is measured to be 12 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.6cm³Per g, specific surface area 900m²(ii)/g, pores having a diameter of 2nm or less account for 95% of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) was passed through the resin bed at a flow rate of 20mL/h, at a throughput of 160BV (BV being the volume of the resin bed) the concentration of fluorine in the effluent was effectively reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 2

Drying 10g of tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, organic skeleton pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 30g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. Then sequentially adding NaOH with the mass concentration of 5% and NaCl with the mass concentration of 5% for transformation, washing with alcohol, and drying to obtain the resin-based nano-zirconia compositeAnd (5) synthesizing the materials.

After acidification and digestion, the zirconium content in the composite material is measured to be 12 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.6cm³Per g, specific surface area 900m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 3

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.2mmol/g, pore volume 1.2 cm)³Per g, specific surface area 1200m²/g) immersion in 25g ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then sequentially adding NaOH with the mass concentration of 3% and NaCl with the mass concentration of 3% for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano zirconia composite material.

After acidification and digestion, the zirconium content in the composite material is measured to be 10 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1500m²In terms of the volume ratio of pores/g, pores of 2nm or less account for 96% of the total pore volume.

Will be describedLoading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading the simulated fluorine micro-polluted water (pH of water is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (3%) -NaCl (3%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 4

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 1.5mmol/g, pore volume 0.5 cm)³Per g, specific surface area 400m²/g) immersion in 80g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then sequentially adding 6% of NaOH and 6% of NaCl for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

After acidification and digestion, the zirconium content in the composite material is measured to be 30 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.3cm³Per g, specific surface area of 600m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 160BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with NaOH (6%) -NaCl 6%) was used to flow through the tree at a rate of 4mL/hThe lipid bed layer is desorbed, the desorption rate of fluorine is more than 90 percent, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 5

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.6mmol/g, pore volume 0.8 cm)³Per g, specific surface area 1000m²/g) immersion in 65g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

After acidification and digestion, the zirconium content in the composite material is measured to be 25 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.5cm³Per g, specific surface area 800m²The pores with the diameter of less than 2nm account for 93 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 6

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.g mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 30g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. Then adding 5% ofTransforming NaOH and 5 percent NaCl, washing with alcohol, and drying to obtain the resin-based nano zirconia composite material.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 7

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 30g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

After acidification and digestion, the zirconium content in the composite material is measured to be 12 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.6cm³Per g, specific surface area 900m²Pores of 2nm or less per gAccounting for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 160BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 8

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. Using 200ml of NThe mixed solution of aOH (5%) -NaCl (5%) is concurrently passed through the resin bed layer at the flow rate of 4mL/h to make desorption, the fluorine desorption rate is greater than 90%, and the desorbed nano composite material can be continuously used for next cyclic adsorption.

Example 9

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 10

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 30g of ZrOCl₂·8H₂Mixing of O, 10g HCl, 60g ethanolThe solution was 200mL and evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 160BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 11

After acidification and digestion, the zirconium content in the composite material is measured to be 12 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium oxide nanoparticles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nanoparticles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by the adsorption and desorption test was 0.6cm³Per g, specific surface area 900m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L. 200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 12

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) was passed through the resin bed at a flow rate of 20mL/hThe theoretical amount is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

200mL of mixed solution with the concentration of NaOH (5%) -NaCl (5%) flows through the resin bed layer at the flow rate of 4mL/h for desorption, the desorption rate of fluorine is more than 90%, and the desorbed nano composite material can be continuously used for next cycle adsorption.

Example 13

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 160BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 14

Drying 10g of tertiary aminated ultrahigh cross-linked polystyrene resin (tertiary amine content 0.8 mmo)l/g, pore volume 1.0cm³Per g, specific surface area 800m²/g) immersion in 30g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 15

The zirconium content in the composite material is measured to be 12 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES) after acidification digestion,the particle size of the zirconia nano-particles in the composite material is 10-80nm as observed by a transmission electron microscope. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.6cm³Per g, specific surface area 900m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 16

The obtained nanocomposite (4mL) was loaded into a jacketed glass adsorption column (. PHI.12X 240mm), and a simulated fluorine micro-contaminated water body (water body pH about 6.5, fluorine concentration 5 mg)The concentration of humic acid is 10mg/L (DOC), and the background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 160BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 17

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 140BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 18

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 80BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 19

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. Then adding 5% NaOH and 5% NaCl for transformation and washingAnd washing with alcohol and drying to obtain the resin-based nano zirconium oxide composite material.

The zirconium content in the composite material is measured to be 22 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES) after acidification and digestion, and the zirconium oxide nano particles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nano particles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1200m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 20

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

The zirconium content in the composite material is measured to be 22 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES) after acidification and digestion, and the zirconium oxide nano particles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nano particles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1200m²G, 2nm andthe pores below account for 95% of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 21

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through a resin bed layer at a flow rate of 20mL/h, the treatment capacity is 230BV, and effluent is dischargedThe fluorine concentration is reduced to below 1 mg/L.

Example 22

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 23

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 24

After acidification digestion, the zirconium content in the composite material is measured to be 22 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES), and the zirconium content is displayed through transmission electronThe particle size of the zirconia nano-particles in the composite material is 10-80nm as observed by a microscope. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1200m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 230BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 25

Loading the obtained nanocomposite (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and treating the water body (pH of water body is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is concentrated) with simulated fluorine micro-pollutionDegree of 10mg/L (DOC), background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 26

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 27

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 250mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 230BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 28

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. Then adding 5 percent NaOH and 5 percent NaCl for transformation, washing with alcohol and dryingAnd obtaining the resin-based nano zirconia composite material.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 29

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.5mmol/g, pore volume 0.7 cm)³Per g, specific surface area of 700m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then sequentially adding 4% of NaOH and 4% of NaCl for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

The zirconium content in the composite material is measured to be 22 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES) after acidification and digestion, and the zirconium oxide nano particles in the composite material can be observed by a transmission electron microscope, wherein the particle size of the zirconium oxide nano particles is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1200m²(g) pores of 2nm or less account for the total poresAnd 94% of the volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 30

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 2.5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at a flow rate of 20mL/h, the treatment capacity is 230BV, and the concentration of the fluorine in the effluent is reduced to1mg/L or less.

Example 31

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 5mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 32

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.8mmol/g, pore volume 1.0 cm)³Ratio of/gSurface area of 800m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 33

10g of the dried tertiary aminated ultrahigh crosslinked polystyrene resin (tertiary amine content 0.g mmol/g, pore volume 1.0 cm)³Per g, specific surface area 800m²/g) immersion in 60g of ZrOCl₂·8H₂200mL of a mixed solution of O, 10g of HCl and 60g of ethanol is evaporated to dryness with stirring. And then adding 5% of NaOH and 5% of NaCl in sequence for transformation, washing with water, washing with alcohol, and drying to obtain the resin-based nano-zirconia composite material.

The zirconium content in the composite material is measured to be 22 wt% by utilizing inductively coupled plasma emission spectroscopy (ICP-AES) after acidification digestion, and the zirconium content can be obtained by observing through a transmission electron microscopeThe particle size of the zirconia nano-particles in the composite material is 10-80 nm. By N₂The pore volume of the nanocomposite measured by an adsorption-desorption test was 0.9cm³Per g, specific surface area 1200m²The pores with the diameter of less than 2nm account for 95 percent of the total pore volume.

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 5mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 230BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 34

The obtained nanocomposite (4mL) was loaded into a jacketed glass adsorption column (. PHI.12X 240mm), and a simulated fluorine micro-contaminated water body (water pH of about 6.5, fluorine concentration of 5mg/L, humic acid concentration of 10mg/L (DOC) was treated) Background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 300BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 35

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 10mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 270BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Example 36

Loading the obtained nano composite material (4mL) into a jacketed glass adsorption column (phi 12X 240mm), and loading simulated fluorine micro-polluted water (water pH is about 6.5, fluorine concentration is 20mg/L, humic acid concentration is 10mg/L (DOC)), and background ion Cl^-、SO₄ ^2-、NO₃ ^-、SiO₃ ^2-All 500mg/L) is passed through the resin bed layer at the flow rate of 20mL/h, the treatment capacity is 230BV, and the concentration of the fluorine in the effluent is reduced to below 1 mg/L.

Claims

1. a resin-based nano-composite adsorbent for deep removal of trace fluorine in water, is characterized in that: this adsorbent is an organic framework with ultra-high cross-linked polystyrene-divinylbenzene, and is loaded with zirconia nanoparticles in the organic framework, The loading of zirconia is 10-30wt% in terms of zirconium element, and the size of zirconia nanoparticles is 10-80nm; the pore volume of the nanocomposite adsorbent is 0.3-0.9cm ³ /g, and the specific surface area is 600-1500m ² /g, and the proportion of pores with diameters below 2 nm in the total pore volume is ≥90%.

2. a kind of resin-based nanocomposite adsorbent for deeply removing trace fluorine in water according to claim 1, is characterized in that: described organic skeleton is covalently bound with tertiary amine group, and the content of tertiary amine group is 0.2-1.5mmol /g, and the pore volume of the organic framework before loading is 0.5-1.2 cm ³ /g, the specific surface area is 400-1200 m ² /g, the pores on the organic framework include macropores with a diameter of more than 30 nm and small pores with a diameter of less than 2 nm, Both types of pores account for 40-60% of the total pore volume.

3. a preparation method of resin-based nanocomposite adsorbent as claimed in claim 1 or 2, is characterized in that, its process is as follows: the tertiary aminated ultra-high cross-linked polystyrene resin after drying treatment is immersed in ZrOCl ₂ 8H ₂ O, HCl and ethanol mixed solution, and evaporated to dryness under stirring conditions; then added NaOH and NaCl aqueous solution, transformed, washed with water, washed with alcohol, and dried to obtain resin-based nano-zirconia composite material.

4. the preparation method of a kind of resin-based nanocomposite adsorbent according to claim 3 is characterized in that: in the mixed solution of ZrOCl ₂ .8H ₂ O, HCl and ethanol, ZrOCl ₂ .8H ₂ O, HCl and ethanol The mass ratio is 2.5-8:1:6.

5. The preparation method of a resin-based nanocomposite adsorbent according to claim 3 or 4, wherein the mass concentration of the NaOH solution and the NaCl aqueous solution is both 3-6%.

6. the application of a resin-based nanocomposite adsorbent for deep removal of trace fluorine in water, characterized in that: adopt the resin-based nanocomposite adsorbent according to claim 1 or 2 to carry out adsorption treatment to the fluorine in water, and after the treatment, the fluorine The concentration dropped below 1 mg/L.

7. The application of a resin-based nanocomposite adsorbent for deep removal of trace fluorine in water according to claim 6, wherein: when the nanocomposite adsorbent is used to treat fluorine-containing water, the adsorbent-loaded oxidation The zirconium nanoparticles adsorb 40-120 mg of fluorine per gram on average in terms of zirconium.

8. The application of a resin-based nanocomposite adsorbent for deep removal of trace fluorine in water according to claim 6 or 7, characterized in that: the nanocomposite adsorbent after adsorption is desorbed and regenerated by alkali-salt mixed solution , the desorption rate of fluorine is >90%, wherein the alkali in the alkali-salt mixed solution is NaOH or KOH, the salt is NaCl or KCl, and the mass concentration of the alkali and the salt are both 3-6%.