CN107621511A - BPS method in magnetic bamboo charcoal SPE liquid chromatographic detection water - Google Patents
BPS method in magnetic bamboo charcoal SPE liquid chromatographic detection water Download PDFInfo
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Abstract
The invention discloses the method for BPS in magnetic bamboo charcoal SPE liquid chromatographic detection water：The activation of step 1, bamboo charcoal；Step 2, the carboxylated of bamboo charcoal；Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethylene glycol mixing, magnetic bamboo charcoal is prepared after reacted；Step 4, utilize the magnetic bamboo charcoal progress disperse matrix SPE obtained through step 3, magnetic bamboo charcoal is adsorbed on container inner wall with alnico magnets afterwards, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, with high performance liquid chromatography detection, the time of its appearance and the situation of area are observed, BPS in water is completed and detects.The method of the present invention, synthesizing magnetic bamboo charcoal, using disperse matrix SPE as preconditioning technique, using high performance liquid chromatography as analysis means, establish the analysis method of BPS in water as adsorbent.
Description
Technical field
The invention belongs to detection method technical field, and in particular to a kind of magnetic bamboo charcoal SPE-liquid chromatographic detection
BPS method in water.
Background technology
Bisphenol S (4,4'- dihydroxydiphenylsulisomers, Bisphenol S, BPS, CAS Registry Number 80-90-1), as bisphenol-A
One of the substitute of (Bisphenol A, BPA), it is a kind of material more stable than BPA, mainly makes an addition to plastic products.
Solubility (1.1g Ls of the BPS in water-1, 20 DEG C) be BPA (<0.1g L-1, 20 DEG C) more than 10 times, accordingly, with respect to BPA
For, BPS more easily enters environment water.
BPS has certain physiological-toxicity, and such as Ji researchs show, BPS can influence the devices such as biological young hypophysis cerebri
The development of official.Female zebra fish is exposed to 10 μ g L by Naderi-1Water in, find thyroxine and the triiodo first shape in blood
Gland propylhomoserin level is decreased obviously.BPS also has stronger toxicity to mammal, and Kuruto-Niwa even has found, BPS have with
Endocrine about the same BPA.Physiological-toxicity research shows, should also cause enough even if trace BPS presence
Attention, therefore the analysis method for establishing trace BPS in environment water is highly important.
So far, the document report of BPS analysis methods is few in water body, and reported analysis method mainly utilizes liquid phase
Chromatogram is detected.Diao etc. reports a kind of BPS being vortexed in auxiliary liquid-phase micro-extraction combination liquid-phase chromatographic analysis water；Zhou
Etc. a kind of on-line solid phase extraction is reported, the method for BPS in liquid chromatographic detection water is utilized.For trace organic pollutant in water
Analysis, preprocessing process expend more time.Disperse matrix SPE is a kind of potential enrichment water pollutant
Preconditioning technique.But in disperse matrix SPE, the separation of adsorbent and aqueous phase needs centrifugation step, relatively complicated,
And adsorbent and being completely separated for aqueous phase have difficulties.
The content of the invention
It is an object of the invention to provide the method for BPS in magnetic bamboo charcoal SPE-liquid chromatographic detection water a kind of, synthesis
Magnetic bamboo charcoal is as adsorbent, using disperse matrix SPE as preconditioning technique, using high performance liquid chromatography as analysis means,
Establish the analysis method of BPS in water.
The technical solution adopted in the present invention is BPS method in magnetic bamboo charcoal SPE-liquid chromatographic detection water,
Specifically implement according to following steps：
The activation of step 1, bamboo charcoal；
Step 2, the carboxylated of bamboo charcoal；
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, sees the time of its appearance and the situation of area, completes BPS in water and detects.
The features of the present invention also resides in：
Step 1 is specifically implemented according to following steps：
Step 1.1, weigh 4g~6g bamboo charcoals and be put into reactor, then 18g~22g KOH are added into reactor, then
Water is added, is advisable immersion bamboo charcoal 22h~26h with submerging bamboo charcoal；
Step 1.2, after step 1.1, all materials in reactor are placed under oxygen free condition, using micro-wave oven to bamboo charcoal
Activation process 8min~12min；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal.
Reactor in step 1.1 is ptfe autoclave.
Step 2 is specifically implemented according to following steps：
Step 2.1, the bamboo charcoal after 1.5g~2.5g activation is taken, be added in 100mL nitric acid；
Step 2.2, by the bamboo charcoal in step 2.1 together with nitric acid transfer vessel, in 70 DEG C~90 DEG C oil bath pans
Back flow reaction 2.5h~3.5h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal.
Step 3 is specifically implemented according to following steps：
Step 3.1, the bamboo charcoal 0.1g~0.3g for taking carboxylated, by itself and 1.5g~1.9g PAAs, 1.5g~1.9g
Sodium acetate, 1g~1.4g FeCl3·6H2O, 15mL~19mL ethylene glycol, the mixing of 5mL~7mL diethylene glycols, obtain mixture
Material, 1.5h~2.5h is then sonicated after being stirred to mixed material；
Step 3.2, mixed material will be obtained through step 3.1 it is added in reactor, 9h is heated at 180 DEG C~220 DEG C
~10h, is cooled to room temperature afterwards；
Step 3.3, the bamboo charcoal after step 3.2 is handled used into ethanol and water washing respectively, be finally putting into 60 DEG C~70 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal.
Reactor in step 3.2 is tetrafluoroethene reactor.
In step 3.3：Washed 4~6 times, be washed with water 4~6 times with ethanol.
Step 4 is specifically implemented according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 28mg~32mg to be obtained through step 3 are added in the conical flask containing 100mL water,
Vibrated with turbula shaker and accelerate absorption, after the completion of to be adsorbed, attract magnetic bamboo charcoal being fixed on conical flask with alnico magnets
Inwall on, abandon aqueous phase；
Step 4.2, after step 4.1,0.5mL eluant, eluents, vortex oscillation, then with alnico magnets are added into conical flask
Magnetic bamboo charcoal is fixed on the inwall of conical flask by attraction, draws 10 μ L eluant, eluents with liquid chromatogram micro-sampling pin and is divided
Analysis, specific analytical method are as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is cleaned 2 times with 2.0mL eluant, eluents, then with 5.0mL
Deionized water is cleaned 3 times, is reused after removing impurity.
Eluant, eluent is methanol.
The beneficial effects of the present invention are：
In water body in the detection process of contaminant trace species, pretreatment occupies most of workload, synthesizing magnetic bamboo charcoal
As the adsorbent of disperse matrix SPE, the use of magnetic bamboo charcoal, traditional disperse matrix solid phase extraction procedure had both been avoided
In the tedious steps that centrifuge of two steps, also achieve being kept completely separate for solid-phase adsorbent and liquid phase aqueous phase and organic solvent phase, quickening
Speed, substantially reduces preprocessing process, improves pretreatment efficiency.
Brief description of the drawings
Fig. 1 is the XRD phenograms of the magnetic bamboo charcoal prepared in the inventive method；
Fig. 2 is the BET analysis result schematic diagrames of bamboo charcoal, Activated Bamboo, carboxylated bamboo charcoal and magnetic bamboo charcoal；
Fig. 3 is the M-H phenograms of magnetic bamboo charcoal in the inventive method；
Fig. 4 is the graph of a relation of absorbance and time.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
BPS method in magnetic bamboo charcoal SPE-liquid chromatographic detection water of the present invention, it is specifically real in accordance with the following methods
Apply：
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 4g~6g bamboo charcoals and be put into ptfe autoclave, then add into ptfe autoclave
Add 18g~22g KOH, then add water, be advisable with submerging bamboo charcoal, immersion bamboo charcoal 22h~26h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
8min~12min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal.
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 1.5g~2.5g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 70 DEG C~90 DEG C oil
Back flow reaction 2.5h~3.5h in bath, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing, until washings pH value is 7, places into vacuum and do
Dried in dry case, complete the carboxylated of bamboo charcoal.
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.1g~0.3g for taking carboxylated, by itself and 1.5g~1.9g PAAs, 1.5g~1.9g
Sodium acetate, 1g~1.4g FeCl3·6H2O, 15mL~19mL ethylene glycol, 5mL~7mL diethylene glycols are added in beaker together,
Mixed material is formed in beaker, 1.5h~2.5h is then sonicated after being stirred to mixed material；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, in 180 DEG C~220
9h~10h is heated at DEG C, is cooled to room temperature afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 4~6 times, be finally putting into
Dried in 60 DEG C~70 DEG C vacuum drying chambers, obtain magnetic bamboo charcoal.
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, sees the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 28mg~32mg to be obtained through step 3 are added in the conical flask containing 100mL water,
Vibrated with turbula shaker and accelerate absorption, after the completion of to be adsorbed, attract magnetic bamboo charcoal being fixed on conical flask with alnico magnets
Inwall on, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (wherein, eluant, eluent uses methanol), whirlpool
Rotation vibration accelerates desorption, then attracts magnetic bamboo charcoal being fixed on the inwall of conical flask with alnico magnets, micro- with liquid chromatogram
Amount sample introduction needle is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, by the magnetic bamboo charcoal after desorption, with 2.0mL eluant, eluents, (wherein, eluant, eluent uses first
Alcohol) clean 2 times, then cleaned 3 times with 5.0mL deionized waters, reused after removing impurity that may be present；
Wherein, it is understood that there may be impurity mainly have：Some bamboo charcoals to lose magnetism (main), some particles and reality in air
Test the organic matter of process absorption.
Embodiment 1
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 4g bamboo charcoals and be put into ptfe autoclave, then added into ptfe autoclave
18g KOH, then add water, are advisable with submerging bamboo charcoal, immersion bamboo charcoal 22h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
8min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal；
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 1.5g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 70 DEG C of oil bath pans
Back flow reaction 2.5h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal；
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.1g for taking carboxylated, by itself and 1.5g PAAs, 1.5g sodium acetates, 1g FeCl3·
6H2O, 15mL ethylene glycol, 5mL diethylene glycols are added in beaker together, obtain mixed material, surpass again after being stirred to mixed material
Sonication 1.5h；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, is heated at 180 DEG C
9h, room temperature is cooled to afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 4 times, be finally putting into 60 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, observes the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 28mg to be obtained through step 3 are added in the conical flask containing 100mL water, to be vortexed
Oscillator vibration accelerates absorption, after the completion of to be adsorbed, attracts for magnetic bamboo charcoal to be fixed on the inwall of conical flask with alnico magnets
On, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (eluant, eluent uses methanol), vortex shakes
Swing acceleration desorption, then with alnico magnets attract magnetic bamboo charcoal is fixed on the inwall of conical flask, with liquid chromatogram it is micro enter
Sample pin is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is clear with 2.0mL eluant, eluents (eluant, eluent uses methanol)
Wash 2 times, then cleaned 3 times with 5.0mL deionized waters, reused after removing impurity that may be present.
Embodiment 2
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 4.5g bamboo charcoals and be put into ptfe autoclave, then added into ptfe autoclave
19g KOH, then add water, are advisable with submerging bamboo charcoal, immersion bamboo charcoal 23h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
9min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal；
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 1.8g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 75 DEG C of oil bath pans
Back flow reaction 2.5h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal；
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.15g for taking carboxylated, by itself and 1.6g PAAs, 1.6g sodium acetates, 1.1g
FeCl3·6H2O, 16mL ethylene glycol, 5.5mL diethylene glycols are added in beaker together, obtain mixed material, mixed material is stirred
2h is then sonicated after mixing；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, is heated at 190 DEG C
9.5h, room temperature is cooled to afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 4 times, be finally putting into 60 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, observes the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 29mg to be obtained through step 3 are added in the conical flask containing 100mL water, to be vortexed
Oscillator vibration accelerates absorption, after the completion of to be adsorbed, attracts for magnetic bamboo charcoal to be fixed on the inwall of conical flask with alnico magnets
On, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (eluant, eluent uses methanol), vortex shakes
Swing acceleration desorption, then with alnico magnets attract magnetic bamboo charcoal is fixed on the inwall of conical flask, with liquid chromatogram it is micro enter
Sample pin is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is clear with 2.0mL eluant, eluents (eluant, eluent uses methanol)
Wash 2 times, then cleaned 3 times with 5mL deionized waters, reused after removing impurity that may be present.
Embodiment 3
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 5g bamboo charcoals and be put into ptfe autoclave, then added into ptfe autoclave
20g KOH, then add water, are advisable with submerging bamboo charcoal, immersion bamboo charcoal 24h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
10min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal；
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 2g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 80 DEG C of oil bath pans
Back flow reaction 3h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal.
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.2g for taking carboxylated, by itself and 1.7g PAAs, 1.7g sodium acetates, 1.2g FeCl3·
6H2O, 17mL ethylene glycol, 6mL diethylene glycols are added in beaker together, obtain mixed material, surpass again after being stirred to mixed material
Sonication 2h；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, is heated at 200 DEG C
9.5h, room temperature is cooled to afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 5 times, be finally putting into 65 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, observes the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 30mg to be obtained through step 3 are added in the conical flask containing 100mL water, to be vortexed
Oscillator vibration accelerates absorption, after the completion of to be adsorbed, attracts for magnetic bamboo charcoal to be fixed on the inwall of conical flask with alnico magnets
On, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (eluant, eluent uses methanol), vortex shakes
Swing acceleration desorption, then with alnico magnets attract magnetic bamboo charcoal is fixed on the inwall of conical flask, with liquid chromatogram it is micro enter
Sample pin is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is clear with 2.0mL eluant, eluents (eluant, eluent uses methanol)
Wash 2 times, then cleaned 3 times with 5.0mL deionized waters, reused after removing impurity that may be present.
Embodiment 4
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 5.5g bamboo charcoals and be put into ptfe autoclave, then added into ptfe autoclave
21g KOH, then add water, are advisable with submerging bamboo charcoal, immersion bamboo charcoal 25h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
11min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal；
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 2.3g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 85 DEG C of oil bath pans
Back flow reaction 3.5h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal.
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.25g for taking carboxylated, by itself and 1.8g PAAs, 1.8g sodium acetates, 1.3g
FeCl3·6H2O, 18mL ethylene glycol, 6.5mL diethylene glycols are added in beaker together, obtain mixed material, mixed material is stirred
2.5h is then sonicated after mixing；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, is heated at 210 DEG C
9.5h, room temperature is cooled to afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 6 times, be finally putting into 68 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, observes the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 31mg to be obtained through step 3 are added in the conical flask containing 100mL water, to be vortexed
Oscillator vibration accelerates absorption, after the completion of to be adsorbed, attracts for magnetic bamboo charcoal to be fixed on the inwall of conical flask with alnico magnets
On, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (eluant, eluent uses methanol), vortex shakes
Swing acceleration desorption, then with alnico magnets attract magnetic bamboo charcoal is fixed on the inwall of conical flask, with liquid chromatogram it is micro enter
Sample pin is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is clear with 2.0mL eluant, eluents (eluant, eluent uses methanol)
Wash 2 times, then cleaned 3 times with 5mL deionized waters, reused after removing impurity that may be present.
Embodiment 5
The activation of step 1, bamboo charcoal, specifically implements according to following steps：
Step 1.1, weigh 6g bamboo charcoals and be put into ptfe autoclave, then added into ptfe autoclave
22g KOH, then add water, are advisable with submerging bamboo charcoal, immersion bamboo charcoal 26h；
Step 1.2, after step 1.1, all materials in ptfe autoclave are transferred in round-bottomed flask, in nothing
12min is handled to bamboo charcoal activation using micro-wave oven under the conditions of oxygen；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo
The activation of charcoal；
Step 2, the carboxylated of bamboo charcoal, specifically implement according to following steps：
Step 2.1, the bamboo charcoal after 2.5g activation is taken, be added in 100mL nitric acid；
Step 2.2, the bamboo charcoal in step 2.1 is transferred in round-bottomed flask together with nitric acid, in 90 DEG C of oil bath pans
Back flow reaction 3.5h, cool down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, placed into true
Dried in empty drying box, complete the carboxylated of bamboo charcoal.
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethyl two
Alcohol mixes, and magnetic bamboo charcoal is prepared after reacted, specifically implements according to following steps：
Step 3.1, the bamboo charcoal 0.3g for taking carboxylated, by itself and 1.9g PAAs, 1.9g sodium acetates, 1.4g FeCl3·
6H2O, 19mL ethylene glycol, 7mL diethylene glycols are added in beaker together, obtain mixed material, surpass again after being stirred to mixed material
Sonication 2.5h；
Step 3.2, mixed material will be obtained through step 3.1 it is added in ptfe autoclave, is heated at 220 DEG C
10h, room temperature is cooled to afterwards；
Step 3.3, by the bamboo charcoal after step 3.2 is handled respectively with ethanol and washing it is each washing 5 times, be finally putting into 70 DEG C
Dried in vacuum drying chamber, obtain magnetic bamboo charcoal；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, use alnico magnets afterwards
Magnetic bamboo charcoal is adsorbed on container inner wall, the sample after extraction is drawn with liquid chromatogram micro-sampling pin, uses high-efficient liquid phase color
Spectrum detection, observes the time of its appearance and the situation of area, completes BPS in water and detects, specifically implements according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 32mg to be obtained through step 3 are added in the conical flask containing 100mL water, to be vortexed
Oscillator vibration accelerates absorption, after the completion of to be adsorbed, attracts for magnetic bamboo charcoal to be fixed on the inwall of conical flask with alnico magnets
On, abandon aqueous phase；
Step 4.2, after step 4.1, into conical flask add 0.5mL eluant, eluents (eluant, eluent uses methanol), vortex shakes
Swing acceleration desorption, then with alnico magnets attract magnetic bamboo charcoal is fixed on the inwall of conical flask, with liquid chromatogram it is micro enter
Sample pin is drawn 10 μ L eluant, eluents and analyzed；
Specific analytical method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through
The time and area for observing appearance analyze BPS absorption situation；
Step 4.3, after step 4.2, the magnetic bamboo charcoal after desorption is clear with 2.0mL eluant, eluents (eluant, eluent uses methanol)
Wash 2 times, then cleaned 3 times with 5.0mL deionized waters, reused after removing impurity that may be present.
Specific surface area analysis (BET) is carried out respectively to bamboo charcoal, Activated Bamboo, carboxylated bamboo charcoal and magnetic bamboo charcoal, with this
Judge the situation of change of specific surface area in magnetic bamboo charcoal preparation process；Powder diffraction analysis (XRD) are carried out to magnetic bamboo charcoal, through dividing
Analysis, which understands to be magnetic, introduces material；Magnetometric analysis (M-H curves) is carried out to magnetic bamboo charcoal, judges MAC magnetic intensities.Such as Fig. 1 institutes
Show, be the XRD phenograms of magnetic bamboo charcoal, wherein 2 θ=30.12 °, 35.56 °, 42.82 °, 54.04 °, 56.74 °, 62.34 ° and
73.45 ° of characteristic peak, corresponds to Fe respectively3O4(220) crystal face, (311) crystal face, (400) crystal face, (422) crystal face, (511) it is brilliant
Face, (440) crystal face and (533) crystal face, the result show that magnetic comes from paramagnetic Fe3O4Crystal.Bamboo charcoal, Activated Bamboo, carboxylic
The BET analysis results of base bamboo charcoal and magnetic bamboo charcoal are as shown in Fig. 2 bamboo charcoal, Activated Bamboo, carboxylated bamboo charcoal and magnetic bamboo charcoal
Specific surface area is respectively 119.5,1054.4,338.6 and 93.5m2/g.The M-H of magnetic bamboo charcoal is characterized as shown in figure 3, saturation magnetic
Change degree is 23.3emu/g, has stronger magnetic.
Disperse matrix SPE condition optimizes：
Using acetone, methanol and acetonitrile as eluant, eluent, obtained through research：The elution effect of methanol is best, therefore uses first
Alcohol is as eluant, eluent.The volume of eluant, eluent can influence concentration of the BPS in eluant, eluent, and then influence the sensitivity of method.Grind
Studied carefully influence of the different methanol volumes (0.5mL, 1.0mL, 1.5mL, 2.0mL and 3.0mL) to the inventive method, peak area with
The reduction of eluant, eluent volume and increase, use eluant, eluent volume as 0.5mL.
Vortex time can influence adsorb completeness, consider different vortex times (1min, 4min, 8min, 10min,
15min and 20min) influence, peak area does not increase with the extension of time substantially after 8min.It has studied different elution times
The influence of (0.5min, 1min, 2min, 4min and 6min), when elution time is more than 2min, peak area change is little.
Investigated different pH (2,4,6,8 and influence 10), as a result peak area increase with pH reduction；But pH is
When 2, magnetic bamboo charcoal easily loses magnetism, and uses pH as 4.NaCl (0,2.5,5.0,7.5 Hes of different content are added into sample
10.0%, m/v), when finding NaCl contents more than 2.5%, peak area is basically unchanged.
The performance indications of the inventive method：With means discussion the inventive method detection limit of continuous working solution, it is
0.05μg/L；The range of linearity is the μ g/L of 0.1 μ g/L~20, relative coefficient 0.9991；To the standard liquid that concentration is 1 μ g/L
Parallel determination 7 times, relative standard deviation 5.6%.
Actual environment water sample analysis：
Water sample is derived from draining outside certain sewage treatment plant of enterprise, is filtered before being analyzed with 0.45 μm of filter membrane；Analysis
As a result find, BPS is found in the outer draining, but be lower than 0.10 μ g/L.In order to investigate influence of the water sample matrix to this method,
The μ g/LBPS of mark-on 1.0 into the water sample respectively, relative recovery are respectively 88.7 and 90.6%, as a result satisfactory.Water sample and
For the liquid chromatogram of mark-on water sample as shown in figure 4, Fig. 4 is absorbance and the graph of a relation of time, curve a is the outer draining after filtering
Water sample carries out absorbance and the relation of time after liquid chromatogram measuring, and as can be seen from the figure a water samples occur one in 3~4min
Individual raised small peak, illustrates to contain BPS in water sample, (BPS standard samples carry out liquid chromatographic detection, peak occur in 3~4min)
But peak value is smaller and unobvious, therefore into water sample, the μ g/LBPS of mark-on 1 are b again, then survey its mark-on water sample with liquid chromatogram
Absorbance, similarly find at the peak that same trend occurs in 3~4min and obvious, and the time at peak occur with a water samples
It is consistent, shows to contain BPS in the water sample, the analysis that this method is used in actual environment water sample is as a result satisfactory.
The inventive method and other methods are compared, its result is as shown in table 1；The inventive method has and vortex
Liquid-phase micro-extraction-liquid chromatogram, on-line solid phase extraction-liquid chromatogram and the suitable inspection of dispersive liquid-liquid microextraction-liquid chromatogram
Rising limit and the range of linearity, better than fluorescent method.
This method of table 1 and other method comparative results
Disperse matrix solid phase extraction techniques of the inventive method using magnetic bamboo charcoal as adsorbent, examined with reference to high performance liquid chromatography
Survey, establish the analysis method of BPS in water, institute's method for building up detection is limited to 0.05 μ g/L, and the range of linearity is 0.1~20 μ g/L.
Analyzed for actual water sample, it is as a result satisfactory.
Claims (9)
1. BPS method in magnetic bamboo charcoal SPE-liquid chromatographic detection water, it is characterised in that specifically according to following steps
Implement：
The activation of step 1, bamboo charcoal；
Step 2, the carboxylated of bamboo charcoal；
Step 3, will be through the hydroxylated bamboo charcoal of step 2 and PAA, sodium acetate, FeCl3·6H2O, ethylene glycol, diethylene glycol mix
Close, magnetic bamboo charcoal is prepared after reacted；
Step 4, using the magnetic bamboo charcoal that is obtained through step 3 disperse matrix SPE is carried out, afterwards with alnico magnets by magnetic
Property bamboo Charcoal Adsorption on container inner wall, draw the sample after extraction with liquid chromatogram micro-sampling pin, examined with high performance liquid chromatography
Survey, see the time of its appearance and the situation of area, complete BPS in water and detect.
2. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 1
In the step 1 is specifically implemented according to following steps：
Step 1.1, weigh 4g~6g bamboo charcoals and be put into reactor, then 18g~22g KOH are added into reactor, then add
Water, it is advisable immersion bamboo charcoal 22h~26h with submerging bamboo charcoal；
Step 1.2, after step 1.1, all materials in reactor are placed under oxygen free condition, using micro-wave oven to bamboo charcoal activation
Handle 8min~12min；
Step 1.3, the bamboo charcoal obtained through step 1.2 is washed with water to neutrality, dried in vacuum drying chamber, complete bamboo charcoal
Activation.
3. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 2
In the reactor in the step 1.1 is ptfe autoclave.
4. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 1
In the step 2 is specifically implemented according to following steps：
Step 2.1, the bamboo charcoal after 1.5g~2.5g activation is taken, be added in 100mL nitric acid；
Step 2.2, by the bamboo charcoal in step 2.1 together with nitric acid transfer vessel, flowed back in 70 DEG C~90 DEG C oil bath pans
2.5h~3.5h is reacted, cools down, centrifuge after bamboo charcoal is taken out；
Step 2.3, the bamboo charcoal obtained through step 2.2 added into water washing repeatedly, until washings pH value is 7, places into vacuum and do
Dried in dry case, complete the carboxylated of bamboo charcoal.
5. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 1
In the step 3 is specifically implemented according to following steps：
Step 3.1, the bamboo charcoal 0.1g~0.3g for taking carboxylated, by itself and 1.5g~1.9g PAAs, 1.5g~1.9g acetic acid
Sodium, 1g~1.4g FeCl3·6H2O, 15mL~19mL ethylene glycol, the mixing of 5mL~7mL diethylene glycols, obtain mixed material, right
1.5h~2.5h is then sonicated after mixed material stirring；
Step 3.2, mixed material will be obtained through step 3.1 be added in reactor, heated at 180 DEG C~220 DEG C 9h~
10h, room temperature is cooled to afterwards；
Step 3.3, the bamboo charcoal after step 3.2 is handled used into ethanol and water washing respectively, be finally putting into 60 DEG C~70 DEG C vacuum
Dried in drying box, obtain magnetic bamboo charcoal.
6. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 5
In the reactor in the step 3.2 is tetrafluoroethene reactor.
7. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 5
In in the step 3.3：Washed 4~6 times, be washed with water 4~6 times with ethanol.
8. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 1
In the step 4 is specifically implemented according to following steps：
Step 4.1, the magnetic bamboo charcoal for taking 28mg~32mg to be obtained through step 3 are added in the conical flask containing 100mL water, with whirlpool
Revolve oscillator vibration and accelerate absorption, after the completion of to be adsorbed, attract magnetic bamboo charcoal being fixed in conical flask with alnico magnets
On wall, aqueous phase is abandoned；
Step 4.2, after step 4.1,0.5mL eluant, eluents, vortex oscillation, then attract with alnico magnets are added into conical flask
Magnetic bamboo charcoal is fixed on the inwall of conical flask, 10 μ L eluant, eluents are drawn with liquid chromatogram micro-sampling pin and analyzed, are had
Body analysis method is as follows：
10 μ L sample liquid chromatographic detections of absorption, the graph of a relation of absorbance and time occur on computer, passes through observation
Time of appearance and area analyze BPS absorption situation；
Step 4.3, after step 4.2, by the magnetic bamboo charcoal after desorption with 2.0mL eluant, eluents clean 2 times, then with 5.0mL go from
Sub- water cleans 3 times, is reused after removing impurity.
9. BPS method, its feature exist in magnetic bamboo charcoal SPE-liquid chromatographic detection water according to claim 8
In the eluant, eluent is methanol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109507333A (en) * | 2018-12-26 | 2019-03-22 | 江苏赫尔斯检测技术有限公司 | A kind of method of bisphenol-A in detection water |
| CN112881552A (en) * | 2021-01-14 | 2021-06-01 | 广东省科学院生物工程研究所 | Application of bagasse-based magnetic activated carbon in detection of triazine herbicide in brown sugar |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104749277A (en) * | 2015-03-26 | 2015-07-01 | 聊城大学 | Method for detecting polychlorinated biphenyl based on magnetic bamboo charcoal disperse substrate solid-phase extraction |
-
2017
- 2017-10-18 CN CN201710971360.XA patent/CN107621511A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104749277A (en) * | 2015-03-26 | 2015-07-01 | 聊城大学 | Method for detecting polychlorinated biphenyl based on magnetic bamboo charcoal disperse substrate solid-phase extraction |
Non-Patent Citations (4)
| Title |
|---|
| AL-MASHHADANI,SUHAIB ABDULSATTAR: "ADSORPTION OF BISPHENOL-S(BPS) FROM WATER USING ACTIVATED CARBON", 《OHIOLINK》 * |
| LINGLIGN WANG,ET AL.: "Magnetic solid phase extraction using nanoporous three dimensional graphene hybrid materials for high capacity enrichment and simultaneous detection of nine bisphenol analogs from water sample", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| ZHENZHEN ZHANG，ET AL: "Controlled synthesis or hollow porous carbon spheres for enrichment and simultaneous determination of nine bisphenols from real samples", 《TALANTA》 * |
| 杨肖: "基于高效富集技术的水中痕量有机污染物检测的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109507333A (en) * | 2018-12-26 | 2019-03-22 | 江苏赫尔斯检测技术有限公司 | A kind of method of bisphenol-A in detection water |
| CN112881552A (en) * | 2021-01-14 | 2021-06-01 | 广东省科学院生物工程研究所 | Application of bagasse-based magnetic activated carbon in detection of triazine herbicide in brown sugar |
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