CN109030683B - A method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid - Google Patents
A method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid Download PDFInfo
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Abstract
The present invention relates to chemical analysis technology fields, and in particular to a method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid.2,2'- bipyridyl and 4,4'- bipyridyl can be totally separated from by the present invention using liquid chromatogram-triplex tandem quadrupole rod mass spectrography, have the characteristics that detection limit is low, analysis speed is fast (total detection time is 3min or so)；1- methyl chloropyridine is measured, high sensitivity, selectivity and good separating effect using high performance liquid chromatography (matching UV detector), analysis speed is fast (total detection time is 10min or so).Embodiment the experimental results showed that, method provided by the invention is easy to operate, it is stable and reproducible, it can be realized the content for accurately and rapidly measuring bipyridyl and 1- methyl chloropyridine in paraquat waste liquid, it is practical, have a wide range of application, the measurement of bipyridyl and 1- methyl chloropyridine content in paraquat waste liquid in industry can be instructed.
Description
Technical field
The present invention relates to chemical analysis technology fields, and in particular to bipyridyl and 1- methyl in a kind of measurement paraquat waste liquid
The method of pyridinium chloride content.
Background technique
Bipyridyl (bipyridine) is one kind product as made from association response as pyridine, is in synthesis paraquat
Mesosome, mainly include 2,2'- bipyridyl and 4, two kinds of 4'- bipyridyl.2,2'- bipyridyl and 4,4'- bipyridyl analysis detection hand
Section is also very rich, including high performance liquid chromatography, gas chromatography, ultraviolet spectrophotometer method, nuclear magnetic resonance spectroscopy internal standard
Method etc., wherein nuclear magnetic resonance spectroscopy internal standard method and high performance liquid chromatography are most widely used, but due to nuclear magnetic resonance internal standard method
It can only measure 2,2'- bipyridyl, and bad searching (Wang Limin, Zhuan Wangwei, the Chen Tong etc. of the internal standard compound of 4,4'- bipyridyls；Not Tongfang
Method measures 2,2'- bipyridyl comparision contents [J]；Guangdong chemical industry；21 phases in 2015).High effective liquid chromatography for measuring 2,2'- joins pyrrole
Peak shape is bad when pyridine, there is serious hangover, and has stronger interference (Hu Min, Hu Changqin, Liu Wenying；Nuclear magnetic resonance spectroscopy is surveyed
Determine the absolute content [J] of drug primary standard substance；Analytical chemistry；04 phase in 2004).
Methyl chloropyridine is the by-product for synthesizing paraquat, at present not for the analysis method of 1- methyl chloropyridine
It is common.
In order to facilitate the content of analysis bipyridyl and 1- methyl chloropyridine, and then have to the synthesis purity of paraquat
Effect detection, it is necessary to develop a kind of new side suitable for measuring bipyridyl and 1- methyl chloropyridine content paraquat waste liquid
Method.
Summary of the invention
The purpose of the present invention is to provide bipyridyl and 1- methyl chloropyridine contents in a kind of measurement paraquat waste liquid
Method, method provided by the invention is easy to operate, stable and reproducible, and it is useless to can be realized accurately and rapidly measurement paraquat
The content of bipyridyl and 1- methyl chloropyridine in liquid.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of methods of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid, including
Following steps:
Paraquat waste liquid is extracted using organic solvent, obtains extract liquor；
The extract liquor is subjected to liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis, according to the standard of bipyridyl content
Curve and gained chromatogram, obtain the content of bipyridyl in paraquat waste liquid；The bipyridyl includes 2,2'- bipyridyl and 4,
4'- bipyridyl；
The extract liquor is subjected to efficient liquid phase chromatographic analysis, according to the standard curve of 1- methyl chloropyridine content and institute
Chromatogram is obtained, the content of 1- methyl chloropyridine in paraquat waste liquid is obtained.
Preferably, the mass spectrographic liquid chromatogram operating condition of the liquid chromatogram-triplex tandem quadrupole rod includes:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A is the water that pH value is 4.5, Mobile phase B
For methanol, the volume ratio of the mobile phase A and Mobile phase B is 7:3；Flow velocity is 0.4mL/min；
Sample volume: 1 μ L.
Preferably, carrying out chromatographic column used by the liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis is C18Column, rule
Lattice are 2.1 × 50mm, and packing material size is 1.8 μm；Column temperature is 30 DEG C.
Preferably, the mass spectrographic mass spectrum operation condition of the liquid chromatogram-triplex tandem quadrupole rod includes:
Ion source: the source ESI；Scanning mode: cation；Detection mode: multiple-reaction monitoring, atomization gas, gas curtain gas, auxiliary add
Hot gas and collision gas are high pure nitrogen；Collision cell high speed voltage is 4, and fragmentation voltage is 135, collision energy 15.
Preferably, the quantitative daughter ion of 2, the 2'- bipyridyl is 131.0, the quantitative daughter ion of 4, the 4'- bipyridyl
It is 131.3.
Preferably, the operating condition of the high performance liquid chromatography includes:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A be pH value be 4, concentration is
The ammonium acetate solution of 0.02mmol/L, Mobile phase B are methanol, and the volume ratio of the mobile phase A and Mobile phase B is 8:2；Flow velocity
For 1mL/min；
Sample volume: 5 μ L；
Detector: VWD detector；Detection wavelength is 259nm.
Preferably, carrying out used chromatographic column when the efficient liquid phase chromatographic analysis is C18Column, specification be 4.6 ×
250mm, packing material size are 5 μm；Column temperature is 30 DEG C.
Preferably, the extraction is Solid Phase Extraction.
Preferably, the organic solvent includes methanol and toluene, and the volume ratio of the methanol and toluene is (2.5~3.5):
1。
Preferably, the volume ratio of the organic solvent and paraquat waste liquid is 1:(1.8~2.2).
The present invention provides a kind of methods of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid, including
Following steps: paraquat waste liquid is extracted using organic solvent, obtains extract liquor；The extract liquor is subjected to liquid phase color
Spectrum-triplex tandem quadrupole rod mass spectral analysis obtains paraquat waste liquid according to the standard curve of bipyridyl content and gained chromatogram
The content of middle bipyridyl；The bipyridyl includes 2,2'- bipyridyl and 4,4'- bipyridyl；The extract liquor is subjected to efficient liquid
Analysis of hplc obtains 1- first in paraquat waste liquid according to the standard curve of 1- methyl chloropyridine content and gained chromatogram
The content of base pyridinium chloride.The present invention using liquid chromatogram-triplex tandem quadrupole rod mass spectrography can by 2,2'- bipyridyl and 4,
4'- bipyridyl is totally separated from, and has the characteristics that detection limit is low, analysis speed is fast (total detection time is 3min or so)；Using
High performance liquid chromatography (matching UV detector) is measured 1- methyl chloropyridine, high sensitivity, selectivity and separation effect
Fruit is good, and analysis speed is fast (total detection time is 10min or so).Embodiment the experimental results showed that, method provided by the invention
It is easy to operate, it is stable and reproducible, it can be realized and accurately and rapidly measure bipyridyl and 1- methyl chloride in paraquat waste liquid
The content of pyridine, it is practical, have a wide range of application, bipyridyl and 1- methyl chloride pyrrole in paraquat waste liquid can be instructed in industry
The measurement of pyridine content.
Detailed description of the invention
Fig. 1 is the chromatogram of 2,2'- bipyridyl standard sample；
Fig. 2 is the chromatogram of 4,4'- bipyridyl standard sample；
Fig. 3 is the chromatogram of 2,2'- bipyridyl and 4,4'- bipyridyl in paraquat waste liquid sample；
Fig. 4 is the chromatogram of 1- methyl chloropyridine standard sample；
Fig. 5 is the chromatogram of 1- methyl chloropyridine in paraquat waste liquid sample；
Fig. 6 is to be tested using high performance liquid chromatography 1- methyl chloropyridine under the conditions of mobile phase A is ultrapure water
Chromatogram；
Fig. 7 is using high performance liquid chromatography under the conditions of mobile phase A is not adjust the ammonium acetate solution of pH value to 1- first
The chromatogram that base pyridinium chloride is tested；
Fig. 8 be mobile phase A be pH value be 4 ammonium acetate solution under the conditions of using high performance liquid chromatography to 1- methyl chloride
Change the chromatogram that pyridine is tested.
Specific embodiment
The present invention provides a kind of methods of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid, including
Following steps:
Paraquat waste liquid is extracted using organic solvent, obtains extract liquor；
The extract liquor is subjected to liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis, according to the standard of bipyridyl content
Curve and gained chromatogram, obtain the content of bipyridyl in paraquat waste liquid；The bipyridyl includes 2,2'- bipyridyl and 4,
4'- bipyridyl；
The extract liquor is subjected to efficient liquid phase chromatographic analysis, according to the standard curve of 1- methyl chloropyridine content and institute
Chromatogram is obtained, the content of 1- methyl chloropyridine in paraquat waste liquid is obtained.
The present invention extracts paraquat waste liquid using organic solvent, obtains extract liquor.In the present invention, hundred grass
Withered waste liquid is preferably the waste liquid generated during paraquat pesticide producing.
The present invention preferably first pre-processes the paraquat waste liquid, before carrying out the Solid Phase Extraction to described
Paraquat waste liquid is tentatively extracted, and solid impurity therein etc. is removed；In the present invention, the pretreated method is preferably wrapped
Include following steps:
100mL paraquat waste liquid is taken to be placed in 5 50mL centrifuge tubes and (have 20mL paraquat waste liquid in i.e. each centrifuge tube),
Then 10mL water, 2g sodium chloride and 20mL methanol are added into each centrifuge tube, 5min is centrifuged under the conditions of 5000r/min, it will
Supernatant liquor is transferred to another centrifuge tube；Said extracted process is repeated with 20mL methanol again, combined extract carries out subsequent extraction
Take processing.
After obtaining extracting solution, the present invention extracts the extracting solution using organic solvent, obtains extract liquor.In this hair
In bright, the organic solvent preferably includes methanol and toluene, and the volume ratio of the methanol and toluene is preferably (2.5~3.5): 1,
More preferably 3:1.The present invention, as extractant, can be realized the abundant extraction of target determinand using methanol and toluene, subject to
It really detects its content and basis is provided.In the present invention, the volume ratio of the organic solvent and paraquat waste liquid is preferably 1:(1.8
~2.2), more preferably 1:2.In the present invention, the extraction is preferably Solid Phase Extraction；The present invention is for the Solid Phase Extraction
Specific steps do not have special restriction, using the technical solution of Solid Phase Extraction well known to those skilled in the art.In this hair
In bright embodiment, the Solid Phase Extraction preferably includes following steps:
In solid phase extraction column (C18Column, specification 500mg, 3mL) upper end be packed into 1cm high anhydrous sodium sulfate (play
Desiccation), first with extractant, (volume ratio of methanol-toluene mixed solution, methanol and toluene is (2.5~3.5): 1) pre-leaching
The solid phase extraction column is washed, leacheate is discarded；Then the extracting solution is crossed into column, and is eluted with extractant, coutroi velocity is
0.5mL/min gained eluent is concentrated with Rotary Evaporators later, residue methanol constant volume, and it is micro- to cross 0.45 μm of organic phase
After the filter membrane of hole, obtains extract liquor and detected for subsequent chromatography.
After obtaining extract liquor, the extract liquor is carried out liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis, root by the present invention
According to the standard curve and gained chromatogram of bipyridyl content, the content of bipyridyl in paraquat waste liquid is obtained；The bipyridyl packet
Include 2,2'- bipyridyl and 4,4'- bipyridyl.In the present invention, the mass spectrographic liquid phase color of the liquid chromatogram-triplex tandem quadrupole rod
Spectrum operating condition preferably includes:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A is the water that pH value is 4.5, Mobile phase B
For methanol, the volume ratio of the mobile phase A and Mobile phase B is 7:3；Flow velocity is 0.4mL/min；
Sample volume: 1 μ L.
In the present invention, it is preferred to carry out chromatographic column used by the liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis
For C18Column, specification are preferably 2.1 × 50mm, and packing material size is preferably 1.8 μm；Column temperature is preferably 30 DEG C.
In the present invention, the mass spectrographic mass spectrum operation condition of the liquid chromatogram-triplex tandem quadrupole rod preferably includes:
Ion source: the source ESI；Scanning mode: cation；Detection mode: multiple-reaction monitoring, atomization gas, gas curtain gas, auxiliary add
Hot gas and collision gas are high pure nitrogen；Collision cell high speed voltage is 4, and fragmentation voltage is 135, collision energy 15.
In the present invention, the quantitative daughter ion of 2, the 2'- bipyridyl is preferably 131.0, and 4, the 4'- bipyridyl is determined
Quantum ion is preferably 131.3.
After the extract liquor is carried out liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis, the present invention contains according to bipyridyl
The standard curve and gained chromatogram of amount, obtain the content of bipyridyl in paraquat waste liquid；The bipyridyl includes 2,2'- connection pyrrole
Pyridine and 4,4'- bipyridyl.In the present invention, the standard curve of the bipyridyl content is preferably the mass concentration and color of bipyridyl
The equation of linear regression of spectral peak area specifically includes the standard curve and 4 of 2,2'- bipyridyl content, the mark of 4'- bipyridyl content
Directrix curve.
In the present invention, the method for establishing the standard curve of 2, the 2'- bipyridyl content preferably includes following steps:
The 2,2'- bipyridyl standard solution of series of concentrations is provided；
The 2,2'- bipyridyl standard solution of the series of concentrations is subjected to liquid chromatogram-triplex tandem quadrupole rod matter respectively
Spectrum analysis, using peak area as ordinate, concentration is abscissa, and peak area makees linear equation to concentration, obtains 2,2'- bipyridyl and contains
The standard curve of amount.
Present invention firstly provides the 2,2'- bipyridyl standard solution of series of concentrations.In the present invention, 2, the 2'- joins pyrrole
The concentration range of pyridine standard solution is preferably 10~100mg/L.Preparation of the present invention for the 2,2'- bipyridyl standard solution
Method does not have special restriction, using the preparation method of standard solution well known to those skilled in the art.Of the invention
In embodiment, standard items 2 are specifically weighed, 2'- bipyridyl 100mg is accurate to 0.1mg, is transferred to after being dissolved with proper amount of methanol
100mL volumetric flask and constant volume, oscillation shake up, acquired solution 2,2'- bipyridyl standard reserving solution；2,2'- is accurately pipetted respectively
Bipyridyl standard reserving solution 1mL, 2mL, 4mL, 6mL, 10mL, with methanol constant volume, obtains the system in 5 100mL volumetric flasks
The 2,2'- bipyridyl standard solution of column concentration.
After obtaining 2, the 2'- bipyridyl standard solution of series of concentrations, the present invention is by 2, the 2'- bipyridyl of the series of concentrations
Standard solution carries out liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis respectively, and using peak area as ordinate, concentration is horizontal seat
Mark, peak area make linear equation to concentration, obtain the standard curve of 2,2'- bipyridyl content.In the present invention, the liquid phase color
Spectrum-triplex tandem quadrupole rod mass spectral analysis condition preferably with the liquid phase color that uses when measuring extract liquor in above-mentioned technical proposal
Spectrum-triplex tandem quadrupole rod mass spectral analysis is consistent, is no longer repeated herein.In the present invention, 2, the 2'- joins pyrrole
The standard curve and related coefficient of pyridine content are respectively y=0.0007x-11.698, R2=0.9997 (y is peak area；X is matter
Measure concentration, mg/L；R2For related coefficient).
In the present invention, establish the method for the standard curve of 4, the 4'- bipyridyl content preferably with establish described 2,2'-
The method of the standard curve of bipyridyl content is consistent, the difference is that, the concentration range of 4,4'- bipyridyl standard solution is preferred
For 10~500mg/L；The standard curve and related coefficient of 4, the 4'- bipyridyl content are respectively y=0.0011x-0.0749,
R2=0.9972 (y is peak area；X is mass concentration, mg/L；R2For related coefficient).
In the present invention, according to the chromatogram of the standard curve of bipyridyl content and extract liquor, in available extract liquor
The content of bipyridyl, and then obtain the content of bipyridyl in paraquat waste liquid.
After obtaining the extract liquor, the extract liquor is carried out efficient liquid phase chromatographic analysis by the present invention, according to 1- methyl chloride
The standard curve and gained chromatogram for changing pyridine content, obtain the content of 1- methyl chloropyridine in paraquat waste liquid.In this hair
In bright, the operating condition of the high performance liquid chromatography is preferably included:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A be pH value be 4, concentration is
The ammonium acetate solution of 0.02mmol/L, Mobile phase B are methanol, and the volume ratio of the mobile phase A and Mobile phase B is 8:2；Flow velocity
For 1mL/min；
Sample volume: 5 μ L；
Detector: VWD detector；Detection wavelength is 259nm.
In the present invention, carrying out used chromatographic column when the efficient liquid phase chromatographic analysis is preferably C18Column, specification are excellent
It is selected as 4.6 × 250mm, packing material size is preferably 5 μm；Column temperature is preferably 30 DEG C.
After the extract liquor is carried out efficient liquid phase chromatographic analysis, the present invention is according to the standard of 1- methyl chloropyridine content
Curve and gained chromatogram, obtain the content of 1- methyl chloropyridine in paraquat waste liquid.In the present invention, the 1- methyl chloride
The standard curve for changing pyridine content is preferably the mass concentration of 1- methyl chloropyridine and the equation of linear regression of chromatographic peak area.
In the present invention, the method for establishing the standard curve of the 1- methyl chloropyridine content preferably includes following step
It is rapid:
The 1- methyl chloropyridine standard solution of series of concentrations is provided；
The 1- methyl chloropyridine standard solution of the series of concentrations is subjected to efficient liquid phase chromatographic analysis respectively, with peak face
Product is ordinate, and concentration is abscissa, and peak area makees linear equation to concentration, and the standard for obtaining 1- methyl chloropyridine content is bent
Line.
Present invention firstly provides the 1- methyl chloropyridine standard solution of series of concentrations.In the present invention, the 1- methyl
The concentration range of pyridinium chloride standard solution is preferably 5~100mg/L.The present invention is molten for the 1- methyl chloropyridine standard
The preparation method of liquid does not have special restriction, referring to the preparation method of above-mentioned 2,2'- bipyridyl standard solution.
After obtaining the 1- methyl chloropyridine standard solution of series of concentrations, the present invention is by the 1- methyl chloride of the series of concentrations
Change pyridine standard solution and carry out efficient liquid phase chromatographic analysis respectively, using peak area as ordinate, concentration is abscissa, peak area pair
Concentration makees linear equation, obtains the standard curve of 1- methyl chloropyridine content.In the present invention, the high performance liquid chromatography point
The condition of analysis preferably in above-mentioned technical proposal measure extract liquor when use efficient liquid phase chromatographic analysis it is consistent, herein
No longer repeated.In the present invention, the standard curve and related coefficient of the 1- methyl chloropyridine content are respectively y=
0.0154x-1.9093, R2=0.9998 (y is peak area；X is mass concentration, mg/L；R2For related coefficient).
In the present invention, available according to the chromatogram of the standard curve of 1- methyl chloropyridine content and extract liquor
The content of 1- methyl chloropyridine in extract liquor, and then obtain the content of 1- methyl chloropyridine in paraquat waste liquid.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
1. materials and methods
1.1 reagents and instrument
Methanol: chromatographic grade；Toluene: analysis is pure；Acetic acid: chromatographically pure；Sodium chloride: analysis is pure；Anhydrous sodium sulfate, analysis is pure,
Through 650 DEG C of calcination 4h, it is placed in spare in drier；Ammonium acetate is analyzed pure；2,2'- bipyridyls are analyzed pure；4,4'- bipyridyls,
It analyzes pure；1- methyl chloropyridine is analyzed pure.
Solid phase extraction column is C18Column, specification 500mg, 3mL；Assay balance, sensibility reciprocal 0.1mg；Centrifuge；
Agilent1260 high performance liquid chromatograph is matched UV detector (VWD), and performance liquid chromatographic column is POROSHELL 120EC
C18Column, specification are 4.6 × 250mm, and packing material size is 5 μm；Agilent6460 liquid matter matter is combined (triplex tandem quadrupole rod matter
Spectrum), match the source ESI, liquid matter matter coupled HPLC column is ZORBAX ECLIPSE PLUS C18Column, specification are 2.1 × 50mm, filler grain
Diameter is 1.8 μm.
1.2 the preparation of standard solution
Standard items 2 are weighed respectively, and 2'- bipyridyl, 4,4'- bipyridyl, 1- methyl chloropyridine 100mg are accurate to
0.1mg is transferred to three 100mL volumetric flasks and constant volume respectively after being dissolved with proper amount of methanol, oscillation shakes up, and acquired solution is as mark
Quasi- stock solution；
Standard reserving solution 1mL, 2mL, 4mL, 6mL, 10mL of 2,2'- bipyridyl are accurately pipetted respectively in 5 100mL capacity
Bottle, with methanol constant volume, obtains 2, the 2'- bipyridyl titer of series of concentrations, and 2,2'- joins in 2, the 2'- bipyridyl titer
The concentration range of pyridine is 10~100mg/L；
Standard reserving solution 1mL, 2mL, 3mL, 4mL, 5mL of 4,4'- bipyridyl are accurately pipetted respectively in 5 100mL capacity
Bottle, with methanol constant volume, obtains 4, the 4'- bipyridyl titer of series of concentrations, and 4,4'- joins in 4, the 4'- bipyridyl titer
The concentration range of pyridine is 10~50mg/L；
Standard reserving solution 0.5mL, 1mL, 2mL, 5mL, 10mL of 1- methyl chloropyridine are accurately pipetted respectively in 5
100mL volumetric flask obtains the 1- methyl chloropyridine titer of series of concentrations, the 1- methyl chloropyridine with methanol constant volume
The concentration range of 1- methyl chloropyridine is 5~100mg/L in titer；
The condition of 1.3 liquid chromatograies-triplex tandem quadrupole rod Mass Spectrometer Method bipyridyl
Use acetic acid adjust water pH value be 4.5, after degassing be used as mobile phase A it is spare；As flowing after methanol is deaerated
Phase B is spare；
Chromatographic column is C18Column (ZORBAX ECLIPSE PLUS C18Column, specification are 2.1 × 50mm, and packing material size is 1.8 μ
M), column temperature is 30 DEG C, and the volume ratio of mobile phase A and Mobile phase B is 7:3, and flow velocity 0.4mL/min, sample volume is 1 μ L；
Ion source: the source ESI；Scanning mode: cation；Detection mode: multiple-reaction monitoring (MRM)；Atomization gas, gas curtain gas,
Auxiliary heating gas and collision gas are high pure nitrogen；Collision cell high speed voltage is 4, and fragmentation voltage is 135, collision energy 15；
By daughter ion scan 2,2'- bipyridyl quantitative daughter ion be 131.0,4,4'- bipyridyls it is quantitative son from
Son is 131.3.
The condition of 1.4 high performance liquid chromatographs detection 1- methyl chloropyridine
Ammonium acetate is mixed with water, it is 4 that acetic acid tune pH value, which is then added dropwise, obtains the ammonium acetate water that concentration is 0.02mmol/L
Solution, it is spare as mobile phase A after degassing；It is spare as Mobile phase B after methanol is deaerated；
Chromatographic column is C18Column (POROSHELL 120EC C18Column, specification are 4.6 × 250mm, and packing material size is 5 μm), column
Temperature is 30 DEG C, and the volume ratio of mobile phase A and Mobile phase B is 8:2, and flow velocity 1mL/min, sample volume is 5 μ L, VWD detectors, inspection
Survey wavelength is 259nm.
The foundation of 1.5 standard curves
2,2'- bipyridyl standard solution and 4,4'- bipyridyl standard solution are subjected to liquid chromatogram-triplex tandem quadrupole rod
1- methyl chloropyridine is carried out efficient liquid phase chromatographic analysis by mass spectral analysis, respectively obtains corresponding chromatogram (Fig. 12,2'- connection
Chromatogram, Fig. 2 of pyridine standard sample are the chromatogram of 4,4'- bipyridyl standard sample, Fig. 4 is 1- methyl chloropyridine standard
The chromatogram of sample), using peak area as ordinate, concentration is abscissa, and peak area makees linear equation to concentration, 2 are respectively obtained,
The standard curve of 2'- bipyridyl, 4,4'- bipyridyl and 1- methyl chloropyridine.The results show that concentration of standard solution and peak area
Between linear relationship it is relatively good, the standard curve and related coefficient of 2,2'- bipyridyls are respectively y=0.0007x-
11.698 R2The standard curve and related coefficient of=0.9997,4,4'- bipyridyls are respectively y=0.0011x-0.0749, R2=
The standard curve and related coefficient of 0.9972,1- methyl chloropyridine are respectively y=0.0154x-1.9093, R2=0.9998；
Wherein, y is peak area；X is mass concentration, mg/L；R2For related coefficient.
1.6 samples (paraquat waste liquid) extraction
100mL paraquat waste liquid is taken to be placed in 5 50mL centrifuge tubes and (have 20mL paraquat waste liquid in i.e. each centrifuge tube),
Then 10mL water, 2g sodium chloride and 20mL methanol are added into each centrifuge tube, 5min is centrifuged under the conditions of 5000r/min, it will
Supernatant liquor is transferred to another centrifuge tube；Said extracted process, combined extract are repeated with 20mL methanol again；
In solid phase extraction column (C18Column, specification 500mg, 3mL) upper end be packed into 1cm high anhydrous sodium sulfate, first use
5mL extractant (volume ratio of the mixed solvent of methanol and toluene, the methanol and toluene is 3:1) elutes the Solid Phase Extraction in advance
Pillar discards leacheate；Then above-mentioned gained extracting solution is crossed into column, and is eluted with 50mL extractant, coutroi velocity 0.5mL/
Gained eluent is concentrated into 5mL or so with Rotary Evaporators later by min, with methanol constant volume to 10mL, crosses 0.45 μm of organic phase
After miillpore filter, obtains extract liquor and detected for subsequent chromatography.
2. sample detection
Liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis is carried out to the extract liquor, according to the standard of bipyridyl content
Curve and gained chromatogram, obtain the content of bipyridyl in paraquat waste liquid；Carry out high-efficient liquid phase color is carried out to the extract liquor
Spectrum analysis, according to the standard curve of 1- methyl chloropyridine content and gained chromatogram (Fig. 3 is 2 in paraquat waste liquid sample,
2'- bipyridyl and 4, the chromatogram of 4'- bipyridyl, Fig. 5 are the chromatogram of 1- methyl chloropyridine in paraquat waste liquid sample),
Obtain the content of 1- methyl chloropyridine in paraquat waste liquid；Take the average value for the content being measured in parallel twice as final
Test result, the results are shown in Table 1.
The content of 2,2'- bipyridyl, 4,4'- bipyridyl and 1- methyl chloropyridine in 1 paraquat waste liquid of table
| Classes of compounds | Content (mg/L) |
| 2,2'- bipyridyl | 15.18 |
| 4,4'- bipyridyl | 15.80 |
| 1- methyl chloropyridine | 48.30 |
3. the research of sample recovery rate and precision
3.1 recovery of standard addition
It is returned using the sample of standard substance additive process measurement 2,2'- bipyridyl, 4,4'- bipyridyl and 1- methyl chloropyridine
Yield, the average value to measure 6 times add the standard specimen of different quality, are tested according to the above method as the original value of sample
Measurement calculates the rate of recovery.The results are shown in Table 2.From table 2 it can be seen that sample recovery rate between 98%~105%, is analyzed
Error is smaller, and operating process loss is less, and method is accurate and reliable.
The sample recovery rate of 2 2,2'- bipyridyl of table, 4,4'- bipyridyl and 1- methyl chloropyridine
3.2 precision
Experiment has carried out method repetitive research in this laboratory first, and 2,2'- connection is determined under the conditions of repeatability
The average value and the coefficient of variation of pyridine, 4,4'- bipyridyl and 1- methyl chloropyridine, each sample are measured in parallel 6 times daily, into
The repetition of row 6 days, each sample totally 36 repeated data.The results are shown in Table 3.As can be seen from Table 3, the repeated coefficient of variation
1.04~2.78%, precision is preferable.
The average value and the coefficient of variation of 3 2,2'- bipyridyl of table, 4,4'- bipyridyl and 1- methyl chloropyridine
4. influence of the different extractants to testing result
To guarantee the extraction of paraquat waste liquid completely, suitable extractant is selected to be very important.It is mixed using methanol-toluene
It closes solution (volume ratio of methanol and toluene is 3:1), methanol, acetonitrile to be extracted as extractant, testing result such as 4 institute of table
Show.From table 4, it can be seen that several extractants are obvious to the effect of extracting difference of bipyridyl and 1- methyl chloropyridine, methanol-first
Benzene mixed solution effect of extracting is preferable, can headed by select extractant.
Influence of the different extractants of table 4 to testing result
| Content (mg/L) | Methanol-toluene mixed solution (methanol and volume of toluene ratio 3:1) | Methanol | Acetonitrile |
| 2,2'- bipyridyl | 15.18 | 12.34 | 12.98 |
| 4,4'- bipyridyl | 15.80 | 11.78 | 14.23 |
| 1- methyl chloropyridine | 48.30 | 31.78 | 28.76 |
5. influence of the different extractant volumes to testing result
Paraquat waste liquid sample toluene-methanol mixed solution (volume ratio of methanol and toluene is 3:1) is respectively with difference
Extraction volume is extracted, and adds extractant volume step by step, to sample detection after the extract liquor extraction of addition different volumes, detection
The results are shown in Table 5.As can be seen from Table 5, extractant volume change is to the effect of extracting of paraquat waste liquid sample without conspicuousness
Difference.Consider from economizing on resources with effect of extracting angle, 50mL can be chosen, i.e. 50mL extractant can extract the sample of 100mL or so
Product.
Influence of the different extractant volumes of table 5 to testing result
6. high performance liquid chromatography is under the conditions of different mobile phases to the separating effect of 1- methyl chloropyridine
Respectively under the conditions of different mobile phases, 1- methyl chloropyridine is tested using high performance liquid chromatography, respectively
The solution of ammonium acetate and acetic acid is added for (1) mobile phase A；(2) ammonium acetate is only added in mobile phase A, does not use acetic acid tune pH value,
(3) mobile phase A is ultrapure water.Three kinds of method mobile phase As and the volume ratio of Mobile phase B methanol are 8:2.Mobile phase as the result is shown
A is only that the separating effect of ultrapure water is very poor, and hangover is very serious (shown in Fig. 6), and ammonium acetate is added, and does not adjust pH value, point
It makes moderate progress from effect, but still has hangover (shown in Fig. 7), the appearance effect of only adjusting solution ph to 4 is best, does not trail
There is (shown in Fig. 8) in phenomenon.It so ammonium acetate is added in mobile phase A, and is 4 with acetic acid tune pH value.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of method of bipyridyl and 1- methyl chloropyridine content in measurement paraquat waste liquid, comprising the following steps:
Paraquat waste liquid is extracted using organic solvent, obtains extract liquor；
The extract liquor is subjected to liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis, according to the standard curve of bipyridyl content
With gained chromatogram, the content of bipyridyl in paraquat waste liquid is obtained；The bipyridyl includes 2,2'- bipyridyl and 4,4'- connection
Pyridine；
The extract liquor is subjected to efficient liquid phase chromatographic analysis, according to the standard curve of 1- methyl chloropyridine content and gained color
Spectrogram obtains the content of 1- methyl chloropyridine in paraquat waste liquid；
Wherein, the mass spectrographic liquid chromatogram operating condition of the liquid chromatogram-triplex tandem quadrupole rod includes:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A is the water that pH value is 4.5, and Mobile phase B is first
The volume ratio of alcohol, the mobile phase A and Mobile phase B is 7:3；Flow velocity is 0.4mL/min；
Sample volume: 1 μ L；
Carrying out chromatographic column used by the liquid chromatogram-triplex tandem quadrupole rod mass spectral analysis is C18Column, specification be 2.1 ×
50mm, packing material size are 1.8 μm；Column temperature is 30 DEG C；
The mass spectrographic mass spectrum operation condition of the liquid chromatogram-triplex tandem quadrupole rod includes:
Ion source: the source ESI；Scanning mode: cation；Detection mode: multiple-reaction monitoring, atomization gas, gas curtain gas, auxiliary heating gas
It is high pure nitrogen with collision gas；Collision cell high speed voltage is 4, and fragmentation voltage is 135, collision energy 15；
The quantitative daughter ion of 2, the 2'- bipyridyl is 131.0, and the quantitative daughter ion of 4, the 4'- bipyridyl is 131.3；
The operating condition of the high performance liquid chromatography includes:
Mobile phase: mobile phase includes mobile phase A and Mobile phase B, wherein mobile phase A be pH value be 4, concentration 0.02mmol/L
Ammonium acetate solution, Mobile phase B is methanol, and the volume ratio of the mobile phase A and Mobile phase B is 8:2；Flow velocity is 1mL/min；
Sample volume: 5 μ L；
Detector: VWD detector；Detection wavelength is 259nm；
Carrying out used chromatographic column when the efficient liquid phase chromatographic analysis is C18Column, specification are 4.6 × 250mm, packing material size
It is 5 μm；Column temperature is 30 DEG C.
2. the method according to claim 1, wherein the extraction is Solid Phase Extraction.
3. method according to claim 1 or 2, which is characterized in that the organic solvent includes methanol and toluene, the first
The volume ratio of pure and mild toluene is (2.5~3.5): 1.
4. according to the method described in claim 3, it is characterized in that, the volume ratio of the organic solvent and paraquat waste liquid is 1:
(1.8~2.2).
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