CN108079977B - Preparation method of nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material and solid phase extraction method - Google Patents

Preparation method of nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material and solid phase extraction method Download PDF

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CN108079977B
CN108079977B CN201711283321.7A CN201711283321A CN108079977B CN 108079977 B CN108079977 B CN 108079977B CN 201711283321 A CN201711283321 A CN 201711283321A CN 108079977 B CN108079977 B CN 108079977B
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silica gel
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guanidine hydrochloride
hydroxyapatite
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CN108079977A (en
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李成威
于洪梅
占美红
刘岐
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University of Science and Technology Liaoning USTL
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Abstract

The invention relates to a preparation method of a nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material, wherein the composite material is prepared by loading nano hydroxyapatite on silica gel through an adhesive polyhexamethylene guanidine hydrochloride, firstly activating the silica gel, then adding the activated silica gel into a 0.25-1.0% polymethylene guanidine hydrochloride solution according to the mass ratio of 1:5-1:30 of the nano hydroxyapatite to the activated silica gel, ultrasonically oscillating, centrifuging and drying in a vacuum drying oven to obtain a finished product. The invention is a solid phase extraction adsorption material, and avoids the defects that a single nanometer material is easy to run off and block pipelines in the use process. The enrichment effect on Cr (VI) is ideal, and the method can be used for morphological analysis of chromium in an environmental water sample. Can be reused at least 20 times.

Description

Preparation method of nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material and solid phase extraction method
Technical Field
The invention relates to a solid phase extraction material, in particular to a preparation method of a nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material and a method for extracting trace Cr (VI) in water in a solid phase manner.
Background
The accurate determination of trace heavy metal element chromium and the form thereof in water is an important index for water quality detection. The problems that the chromium element content in water is low, the matrix interference of coexisting salts exists and the like are always required to be solved in water quality detection. In this case, the separation and enrichment of the sample is an essential step. Solid phase extraction is one of the commonly used sample pretreatment techniques. Due to the wide variety of selective adsorption materials, the research has been widely conducted by researchers. At present, the search for new adsorbing materials with excellent performance or the modification and modification of the existing adsorbing materials is a hot point of the research of the solid phase extraction technology.
The nano material has large specific surface area and strong adsorption performance, and the carbon nano tube and the like are used for solid phase extraction of chromium in water. However, the problems of easy loss, easy pipeline blockage and the like exist in the solid-phase extraction due to the large flow resistance in the solid-phase extraction because the particle size of the nano material is small. To solve this problem, the nanomaterial is often supported on a carrier, such as carbon nanotubes supported on silica gel, which solves the problem of flow resistance, but the mechanical strength is not high by merely supporting the nanomaterial by physical adsorption.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material, which is environment-friendly, low in price and simple in preparation. And used for solid phase extraction of trace Cr (VI) in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material comprises the following steps:
(1) activation of silica gel
Putting the silica gel into 2.5mol/L nitric acid solution, stirring for 30-40 minutes, soaking for 14-16 hours, filtering, washing to be neutral by deionized water, drying for 4-5 hours at the temperature of 150-.
(2) Preparation of composite Material
Adding nano hydroxyapatite and activated silica gel into 0.25-1.0% polyhexamethylene guanidine hydrochloride solution according to the mass ratio of 1:5-1:30, shaking up, ultrasonically oscillating for 10-15 minutes, centrifuging for 20-25 minutes, and drying in a vacuum drying oven at the temperature of 60-65 ℃ for 14-16 hours to obtain the composite material.
The silica gel is analytically pure, and the particle size is 80-100 meshes; the particle size of the nano hydroxyapatite is 20-50 nm; polyhexamethylene biguanide hydrochloride has an average molecular weight of 1500-.
The centrifugation adopts a centrifuge with the rotation number of 8000-.
A method for extracting trace Cr (VI) in water from nano-hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material in a solid phase mode includes the steps of loading the composite material into a micro enrichment column, connecting a peristaltic pump to enrich Cr (VI) in a sample, eluting with nitric acid, measuring an eluent by an atomic absorption spectrophotometer, recording an absorbance value, and measuring the content of Cr (VI) in water by a standard curve method.
The micro enrichment column is a polytetrafluoroethylene tube with the inner diameter of 2.0mm and the length of 4.0 cm.
The enrichment conditions are as follows: 20mg of composite material, the pH value of a sample solution is 4.0, the enrichment volume is 40mL, and the sampling flow rate is 2.5-3.5 mL/min.
The elution conditions are that the concentration of nitric acid in the eluent is 8-10% (v/v), the elution volume is 1mL, and the elution flow rate is 6.5 mL/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the composite material prepared by taking silica gel as a carrier and loading nano hydroxyapatite on the silica gel through an adhesive polyhexamethylene guanidine hydrochloride has the performance of adsorbing Cr (VI).
2. The ternary composite material is novel, high in adsorption efficiency, simple and easily available in preparation method, and has no toxicity, harm and environmental pollution.
3. The invention is a solid phase extraction adsorption material, and avoids the defects that a single nanometer material is easy to run off and block pipelines in the use process. Can be reused at least 20 times.
4. The composite material has ideal enrichment effect on Cr (VI) and can be used for morphological analysis of chromium in an environmental water sample.
Drawings
FIG. 1 is a graph of the energy spectrum analysis of example 1.
Detailed Description
The following embodiments of the invention are further illustrated:
example 1
The preparation method of the nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material comprises the following specific steps:
(1) weighing 6.0g of silica gel with the particle size of 80-100 meshes, putting the silica gel into a 100mL beaker, adding 60mL of 2.5mol/L nitric acid solution, stirring for 30 minutes, sealing, soaking for 16 hours, filtering, washing with deionized water to be neutral, and drying at 150 ℃ for 4 hours.
(2) Weighing 80.0mg of activated silica gel, putting the activated silica gel into a 10mL centrifuge tube, adding 10mL of polyhexamethylene guanidine hydrochloride solution with the average molecular weight of about 2000 and the concentration of 1.0%, shaking up, ultrasonically vibrating for 10 minutes, then adding 16.0mg of nano-hydroxyapatite with the particle size of 20-50nm, namely the mass ratio of the nano-hydroxyapatite to the silica gel is 1:5, shaking up, ultrasonically vibrating for 10 minutes, centrifuging for 20 minutes (the revolution of a centrifugal machine is 10000 r/min), washing the mixture with deionized water for a plurality of times, putting the mixture into a 60 ℃ vacuum drying oven, and drying for 16 hours to obtain the composite material.
Example 2
And (2) taking 20mg of the composite material prepared in the example 1, filling the composite material into a self-made micro enrichment column, wherein a polytetrafluoroethylene tube with the inner diameter of 2.0mm and the length of 4.0cm is connected with a peristaltic pump, the pH value of a water sample is adjusted to be 4.0, 40mL of the water sample is enriched at the sampling flow rate of 3.5mL/min, then 1mL of 8% (v/v) nitric acid solution is used for eluting at the elution flow rate of 6.5mL/min, an eluent is measured by an atomic absorption spectrophotometer, and the absorbance value is recorded. And (3) measuring the content of Cr (VI) in the water by adopting a standard curve method.
The method is used for morphological analysis of chromium in 3 kinds of electroplating wastewater, and a standard recovery experiment is carried out, and the experimental result is shown in table 1.
Table 1: morphological analysis result of chromium in environmental water sample (n ═ 3, confidence coefficient 95%)
Figure BDA0001497895880000031
As can be seen from Table 1, the recovery rate by spiking was between 98.3% and 104.6%. The established method has better accuracy and practicability.
The composite material of example 1 was subjected to energy spectrum analysis as shown in FIG. 1.
As can be seen from figure 1, the composite material contains elements of C, N and Cl in polyhexamethylene guanidine hydrochloride and elements of P and Ca in nano hydroxyapatite in addition to elements of Si and O in silica gel, which proves that the composite material has been successfully prepared.
The foregoing is considered as illustrative only of the principles of the invention and is not to be in any way limiting, since all equivalent changes and modifications are intended to be included within the scope of the appended claims.

Claims (7)

1. The preparation method of the nano-hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material is characterized in that the composite material is prepared by loading nano-hydroxyapatite on silica gel through an adhesive, namely polyhexamethylene guanidine hydrochloride, and comprises the following specific steps:
(1) activation of silica gel
Putting silica gel into 2.5mol/L nitric acid solution, stirring for 30-40 minutes, soaking for 14-16 hours, filtering, washing to be neutral by deionized water, drying for 4-5 hours at the temperature of 150-;
(2) preparation of composite Material
Adding nano hydroxyapatite and activated silica gel into 0.25-1.0% polyhexamethylene guanidine hydrochloride solution according to the mass ratio of 1:5-1:30, shaking up, ultrasonically shaking for 10-15 minutes, centrifuging for 20-25 minutes, and drying in a vacuum drying oven at the temperature of 60-65 ℃ for 14-16 hours to obtain the composite material.
2. The method for preparing nano hydroxyapatite/polyhexamethylene biguanide hydrochloride/silica gel composite material according to claim 1, wherein the silica gel is analytically pure and has a particle size of 80-100 meshes; the particle size of the nano hydroxyapatite is 20-50 nm; polyhexamethylene biguanide hydrochloride has an average molecular weight of 1500-.
3. The method for preparing nano hydroxyapatite/polyhexamethylene guanidine hydrochloride/silica gel composite material according to claim 1, wherein the centrifugation is performed at 8000-.
4. The method for solid-phase extraction of trace Cr (VI) in water by using the nano-hydroxyapatite/polyhexamethylene biguanide hydrochloride/silica gel composite material prepared according to the preparation method of claim 1 is characterized in that the composite material is loaded into a micro enrichment column, a peristaltic pump is connected to the micro enrichment column to enrich Cr (VI) in a sample, nitric acid is used for elution, an eluate is measured by an atomic absorption spectrophotometer, an absorbance value is recorded, and the content of Cr (VI) in water is measured by a standard curve method.
5. The method of claim 4, wherein said micro-size enrichment column is a polytetrafluoroethylene tube.
6. The method according to claim 4, wherein the enrichment conditions are: 20mg of composite material, the pH value of a sample solution is 4.0, the enrichment volume is 40mL, and the sampling flow rate is 2.5-3.5 mL/min.
7. The method according to claim 4, wherein the elution conditions are an eluent nitric acid concentration of 8-10% v/v, an elution volume of 1mL, and an elution flow rate of 6.5 mL/min.
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WO2009101995A1 (en) * 2008-02-15 2009-08-20 Opelontex Co., Ltd. Deodorizing material
CN101658784A (en) * 2008-08-25 2010-03-03 赵瑛 Solid composite filter adsorbing sphere for disinfection and chromium removal of well water
CN103537255A (en) * 2013-07-28 2014-01-29 王泽辉 Nanometer oxide ceramic purification and adsorption material with decomposition and bactericidal performance
CN105195087A (en) * 2015-10-26 2015-12-30 王立卓 Extra-large-aperture silicon dioxide new material and preparation method thereof

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