CN103755997B - The preparation of metallic cation modified sodium alginate microballoon and application thereof - Google Patents

Abstract

A preparation and application of metal cation-modified sodium alginate microspheres in the field of analysis and detection technology, using _CaCl2 solution as a crosslinking agent, dispersing sodium alginate solution in _CaCl2 solution to obtain sodium alginate microspheres; Sodium alginate microspheres were placed in GaCl ₃ solution or ZrCl ₄ solution to fully react and then transferred to acetate buffer solution to obtain metal cation-modified sodium alginate microspheres, and finally wet-packed to obtain the modified alginic acid-based A packed column of sodium microspheres. The invention can effectively analyze the existence of inorganic As(III) with definite toxic effect in actual complex sample systems such as natural water body and seawater.

Description

Preparation and application of metal cation modified sodium alginate microspheres

This application is a divisional application with the application number 201110020757.3, the filing date is 2011.1.19, and the title of the invention is "Preparation Method of Arsenic Separation and Analysis Packed Column Based on Modified Sodium Alginate Microspheres".

technical field

The invention relates to a method in the technical field of analysis and monitoring, in particular to a method for preparing a packed column for arsenic separation and analysis based on metal cation-modified sodium alginate microspheres.

Background technique

With the continuous development of modern industrial and agricultural production, arsenic pollution caused by natural and human factors has become an increasingly serious threat to human health. Recently, combined with the relevant drinking water quality standards of the US National Environmental Agency (EPA), the total arsenic content in China's water quality standards has been revised to 10ng·mL ^-1 . However, since arsenic is a metamorphic element, arsenic in natural water systems mainly exists as inorganic forms of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)), and the environmental ecotoxicological effects of inorganic As(Ⅲ) are far greater Inorganic As(Ⅴ) has a significant impact on the incidence of local arsenic poisoning and has clear carcinogenic toxicity. Therefore, it is necessary to develop a low-cost, easy-to-operate and effective inorganic arsenic separation and analysis packed column system to effectively analyze natural water bodies, seawater and other actual samples The content of inorganic As(III) in the system obviously has important practical significance for scientific early warning of arsenic pollution in the environment, improving the level of environmental monitoring in China, and effectively protecting people's health and safety. The latest literature search results show that the MustafaTuzen research group in Turkey used its After the biological culture extract in the laboratory is modified to fill the column, according to the biological solanine component in the corresponding extract as the active site, the trivalent arsenic in the natural water body is selectively enriched and separated under neutral conditions, and then combined with an atomic spectrometer to effectively separate Analyzing the presence of inorganic trivalent arsenic and pentavalent arsenic in natural water bodies, related research papers have been published in "Food and Chemical Toxicology" (Food and Chemical Toxicology, 2010, Volume 48, Pages 41–46) with the title "Selective specification and determination of organic carsenicin water, food and biological samples". It is worth pointing out that the preparation process of the corresponding biological culture extract is complex and cumbersome. At the same time, during the enrichment and separation operation, the conditions for the physical and chemical parameters of the sample solution to be analyzed are harsh.

Sodium alginate (C ₆ H ₇ O ₈ Na)n is mainly composed of sodium alginate, which is a natural polysaccharide carbohydrate with good thickening, film-forming, stability, flocculation, and chelating properties. Biosafe compatible polymer materials, using calcium chloride as a cross-linking agent, can form sodium alginate microspheres with a highly cross-linked network structure, and then through the ion exchange process, different metal cations such as Fe(III) The Ca(II)-containing sodium alginate microsphere structure is introduced to prepare metal cation-modified sodium alginate microspheres. Since metal cations such as corresponding Fe(III) can be used as active sites, they have different selective coordination and binding effects with inorganic As(III) and pentavalent As(V). Therefore, based on modified sodium alginate microspheres, The arsenic separation and analysis packed column that provides the advantages of simple preparation process, low cost, environmental friendliness and no secondary pollution in the laboratory can be further developed to effectively meet the needs of the actual analysis and monitoring technical field.

Contents of the invention

Aiming at the above-mentioned deficiencies in the prior art, the present invention provides a method for preparing a packed column for separation and analysis of arsenic based on modified sodium alginate microspheres. Coordination and bonding with arsenate chemical groups that can provide a lone pair of electronic structures to selectively adsorb and separate inorganic arsenic compounds, and then use it in conjunction with corresponding analysis and detection instruments to scientifically and effectively analyze natural water bodies, seawater, etc. Inorganic As(Ⅲ) with clear toxic effect exists in complex sample system.

The present invention is achieved through the following technical solutions. _The present invention uses CaCl solution as a crosslinking agent, disperses _sodium alginate solution in CaCl solution to obtain sodium alginate microspheres; puts sodium alginate microspheres in _FeCl solution , GaCl ₃ solution or ZrCl ₄ solution and then transferred to acetate buffer solution to obtain metal cation-modified sodium alginate microspheres, and finally the packed column based on modified sodium alginate microspheres was obtained by wet packing .

The weight percentage concentration of described sodium alginate solution is 1.0-3.0wt%;

The molar concentration of the _CaCl2 solution is 0.01-1.0mol/L;

The dispersion refers to: using a peristaltic pump, at a flow rate of 1.0-3.0mL/min, the sodium alginate solution is dropped into the CaCl ₂ solution drop by drop and left at room temperature for 3 days.

_The molar concentration of the FeCl3 solution is 0.01-0.15mol/L;

The pH of the acetate buffer solution is 4.0;

The column packing refers to: packing metal cation-modified sodium alginate microspheres into a column made of quartz glass, stainless steel or polytetrafluoroethylene through a wet method, filling both ends with arsenic-free glass wool and sealing both ends, A packed column based on modified sodium alginate microspheres was obtained.

The invention has the advantages of developing and preparing a packed column for arsenic separation and analysis based on the metal cation-modified sodium alginate microspheres as the column filling material for the first time. The packed column system has the advantages of simple preparation process, low cost, environmental friendliness and avoiding secondary pollution in the laboratory.

detailed description

The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following implementation example.

Example 1

①. Weigh 2g of arsenic-free sodium alginate powder into a 250mL beaker, add 100mL of pure water for mass spectrometry, place it in an ultrasonic oscillator (water bath temperature 60±5°C, power 100W) and shake for 6 hours to fully dissolve it, and get 2% (weight percent) sodium alginate solution;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry until the supernatant is neutral, then move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue shaking at 100r/min for 12h to obtain a diameter of 2mm. Iron content 2.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 95%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 2

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.01mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, and cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue to shake at 100r/min for 12h to prepare a diameter of 2mm. Iron content 1.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 3

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL1.0mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry until the supernatant is neutral, then move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue shaking at 100r/min for 12h to obtain a diameter of 2mm. Iron content 1.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 4

①. Weigh 1g of arsenic-free sodium alginate powder into a 250mL beaker, add 100mL of pure water for mass spectrometry, place it in an ultrasonic oscillator (water bath temperature 60±5°C, power 100W) and shake for 6 hours to fully dissolve it, and get 3% (weight percent) sodium alginate solution;

②. Let the sodium alginate solution of ① pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 3mL/min, and cross-link to obtain white sodium alginate microspheres with a diameter of 4mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, continue to shake at 100r/min for 12h, and prepare a diameter of 4mm. Iron content 1.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 5

①. Weigh 3g of arsenic-free sodium alginate powder into a 250mL beaker, add 100mL of pure water for mass spectrometry, place it in an ultrasonic oscillator (water bath temperature 60±5°C, power 100W) and shake for 6 hours to fully dissolve it, and get 3% (weight percent) sodium alginate solution;

②. Let the sodium alginate solution of ① pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 3mL/min, and cross-link to obtain white sodium alginate microspheres with a diameter of 4mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.02mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, continue to shake at 100r/min for 12h, and prepare a diameter of 4mm. Iron content 1.0% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 85%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 6

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.01mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue to shake at 100r/min for 12h to prepare a diameter of 2mm. Iron content 1.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 7

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.15mol/L FeCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Iron ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue to shake at 100r/min for 12h to prepare a diameter of 2mm. Iron content 1.5% (weight percent), reddish-brown Fe(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Fe(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 8

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L GaCl ₃ solution, and vibrate on a shaking table at 100r/min for 3 days to make the trivalent Gallium ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue to shake at 100r/min for 12h to prepare a diameter of 2mm. Iron content 1.5% (weight percent), reddish-brown Ga(III) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Ga(III) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 9

①. Configure sodium alginate solution according to step ① in Example 1;

②. Let the ① sodium alginate solution pass through the peristaltic pump, and drop it into 500mL0.1mol/LCaCl ₂ solution drop by drop at a flow rate of 2mL/min, cross-link to obtain white sodium alginate microspheres with a diameter of 2mm, which are evenly dispersed in the corresponding CaCl ₂ solution, placed at room temperature for 3 days (20°C ± 5°C);

③. Wash the sodium alginate microspheres obtained in ② repeatedly with pure water for mass spectrometry, then immerse them in a glass beaker filled with 250mL of 0.1mol/L ZrCl ₄ solution, and vibrate on a shaking table at 100r/min for 3 days to make tetravalent Zirconium ions were introduced into the structure of sodium alginate microspheres as active sites. Afterwards, wash repeatedly with pure water for mass spectrometry, until the supernatant is neutral, move the corresponding sodium alginate microspheres into 250mL pH=4 acetate buffer solution, and continue to shake at 100r/min for 12h to prepare a diameter of 2mm. Iron content 1.5% (weight percent), reddish brown Zr (IV) modified sodium alginate microspheres;

④. Weigh 5.0 g of the Zr(IV) modified sodium alginate microspheres prepared in ③, fill the column with a wet method, and load it into a polytetrafluoroethylene material with a column inner diameter of 0.8 cm and a length of 15.0 cm. In the column, fill a little arsenic-free glass wool at both ends of the column, tighten the nuts at both ends of the column, and set aside;

⑤. Connect the packed separation column obtained in ④ to the peristaltic pump. Through a peristaltic pump, make 4.0mL water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution flowing through the column, and the corresponding atomic spectrometer The analysis results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 90%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column , directly flows out of the packed separation column and is accurately analyzed and detected.

Example 10

1. According to 1.2.3.4 steps in Example 1, prepare a packed separation column based on Fe(III) modified sodium alginate microspheres;

②. Weigh 5.0 g of modified sodium alginate microspheres, pack them into a column by a wet method, and put them into a separation packing column made of glass with an inner diameter of 0.8 cm and a length of 15 cm, and fill a little arsenic-free glass wool at both ends of the column. Tighten the nuts at both ends of the column and set aside;

③. Connect the packed separation column obtained in ② to the peristaltic pump. Through a peristaltic pump, make 4.0mL mixed water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution after passing through the column, and analyze it with an atomic spectrometer The results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 95%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed column, and flows out of the column directly. body and get accurate analysis and detection.

Example 11

1. Prepare Fe(III) modified sodium alginate microspheres according to 1. 2. 3. steps in Example 1;

②. Weigh 5.0 g of modified sodium alginate microspheres, pack them into a column by a wet method, and put them into a stainless steel separation packing column with an inner diameter of 0.8 cm and a length of 15 cm, and fill a little arsenic-free glass wool at both ends of the column. Tighten the nuts at both ends of the column and set aside;

③. Connect the corresponding packed separation column with the peristaltic pump. Through a peristaltic pump, make 4.0mL mixed water sample solution containing 100μg/LAs(V) and 20μg/LAs(III) flow through the packed column at a flow rate of 1.2mL/min, collect the sample solution after passing through the column, and analyze it with an atomic spectrometer The results show that: the inorganic As(V) in the corresponding water sample solution is selectively adsorbed in the column (adsorption efficiency ≥ 95%); the inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column, and flows out directly The column is accurately analyzed and detected.

Example 12

1. According to the steps of 1.2.3 in Example 1, Fe(III) modified sodium alginate microspheres were prepared;

②. Weigh 5.0 g of modified sodium alginate microspheres, pack them into a column by a wet method, and put them into a separation-packed polytetrafluoroethylene column with an inner diameter of 0.8 cm and a length of 15 cm, and fill a small amount of arsenic-free glass at both ends of the column Cotton, tighten the nuts at both ends of the column, set aside;

③. Connect the corresponding packed separation column with the peristaltic pump. Through a peristaltic pump, make 4.0mL seawater sample solution containing 100μg/LAs(V) and 20μg/LAs(III) (with artificial seawater as background, artificial seawater formula: 26.726g/LNaCl, 2.260g/LMgCl ₂ , 3.248g/ LMgSO ₄ , 1.153g/LCaCl ₂ , 0.198g/LNaHCO ₃ , 0.721g/LKCl) flowed through the packed column at a flow rate of 1.2mL/min, collected the sample solution after passing through the column, and the subsequent atomic spectrometer analysis results showed that: the corresponding seawater sample Inorganic As(V) in the solution is selectively adsorbed in the column (adsorption efficiency ≥ 95%); Inorganic As(III) in the corresponding water sample solution is not selectively retained in the packed separation column, directly flows out of the column and can be accurately analyzed detection.

Claims (10)

1. a preparation method for metallic cation modified sodium alginate microballoon, is characterized in that, with CaCl ₂sodium alginate soln, as linking agent, is scattered in CaCl by solution ₂sodium alginate micro ball is obtained in solution; Sodium alginate micro ball is placed in GaCl ₃solution or ZrCl ₄be transferred in acetate buffer solution after fully reacting in solution, obtain metallic cation modified sodium alginate microballoon.

2. the preparation method of metallic cation modified sodium alginate microballoon according to claim 1, is characterized in that, described sodium alginate soln weight percent concentration is 1.0-3.0wt%.

3. the preparation method of metallic cation modified sodium alginate microballoon according to claim 2, is characterized in that, described CaCl ₂the volumetric molar concentration of solution is 0.01-1.0mol/L.

4. the preparation method of metallic cation modified sodium alginate microballoon according to claim 3, is characterized in that, described GaCl ₃the concentration of solution is 0.01-0.15mol/L.

5. the preparation method of metallic cation modified sodium alginate microballoon according to claim 3, is characterized in that, described ZrCl ₄the concentration of solution is 0.01-0.15mol/L.

6. the preparation method of the metallic cation modified sodium alginate microballoon according to any one of claim 1-5, is characterized in that, described dispersion globulation refers to: adopt peristaltic pump, under 1.0-3.0mL/min flow velocity, sodium alginate soln is dropwise instilled CaCl ₂also at room temperature place 3 days in solution.

7. the preparation method of metallic cation modified sodium alginate microballoon according to claim 6, is characterized in that, the pH of described acetate buffer solution is 4.0.

8. an application for metallic cation modified sodium alginate microballoon, is characterized in that: using metallic cation modified sodium alginate microballoon as column material, prepares arsenic compartment analysis packed column, and for arsenic compartment analysis;

The preparation of described metallic cation modified sodium alginate microballoon: with CaCl ₂sodium alginate soln, as linking agent, is scattered in CaCl by solution ₂sodium alginate micro ball is obtained in solution; Sodium alginate micro ball is placed in GaCl ₃solution or ZrCl ₄be transferred in acetate buffer solution after fully reacting in solution, obtain metallic cation modified sodium alginate microballoon.

9. the application of metallic cation modified sodium alginate microballoon according to claim 8, it is characterized in that, described for arsenic compartment analysis, refer to: the arsenic compartment analysis packed column obtained is connected with peristaltic pump, pass through peristaltic pump, make sample solutions flow through packed column, collect the sample solution flow through after post, adopt atomic spectrograph analysis: the inorganic As (V) in corresponding sample solutions in post by selective adsorption; Inorganic As (III) in corresponding sample solutions non-selectivity in filling separator column retains, and directly flows out arsenic compartment analysis packed column and obtains analyzing and testing exactly.

10. the application of metallic cation modified sodium alginate microballoon according to claim 8 or claim 9, it is characterized in that, described arsenic compartment analysis packed column of preparing refers to: load in the pillar of silica glass, stainless steel or tetrafluoroethylene material through wet method by metallic cation modified sodium alginate microballoon, two ends are filled with Arsenic-free glass cotton and two ends sealing, obtain the packed column based on modified sodium alginate microballoon.