CN106153776B - A kind of method of LC-MS analysis water sulfolan - Google Patents
A kind of method of LC-MS analysis water sulfolan Download PDFInfo
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Abstract
The invention belongs to analysis technical fields, and in particular to a kind of method of LC-MS analysis water sulfolan.Water sample of the present invention is directly directly analyzed after 0.22 μm of membrane filtration, liquid chromatogram separation is using methanol acetic acid aqueous ammonium system as mobile phase, gradient elution, quadrupole rod _ flight time mass spectrum device detection, using external standard method, quantitative detection is carried out with the peak area of Objective extraction ion.Precision is good, the rate of recovery is high, detection limit is low, it is particularly suitable for micro, even trace sulfolane in industrial wastewater, industrial cycle water, drinking water to detect, to the discharge of Fast Evaluation industrial wastewater whether there is or not being polluted to water resource, the industrial cycle excellent quality of the water water quality and processing for such industrial wastewater and cycling use of water, utilization and reference sanitary of water sources safeguard procedures play effective directive function.
Description
Technical field
The invention belongs to analysis technical fields, and in particular to a kind of method of LC-MS analysis water sulfolan.
Background technology
Sulfolane, chemical name thiophane -1,1- dihydride, molecular formula C4H8O2S is a kind of liquid of water white transparency,
Density 1.26-1.27g/mL, 285 DEG C of boiling point, can be dissolved each other with arbitrary proportion with water, while dissolve in methanol, acetone, toluene etc. has
It is a kind of industrial solvent highly stable to proton in solvent.In petroleum chemical industry, sulfolane is used as aromatic hydrocarbon extraction solvent
Has more than 40 years history.
On the one hand, since sulfolane price is more expensive, if a large amount of sulfolane remains in industrial wastewater, not only can
Cause the loss of sulfolane, it is often more important that the waste water containing sulfolane is discharged into water source, water quality sensory properties can be caused to decline, oxygen consumption
Amount increases, although China there is no its related sanitary standard in the surface water, with some researches show that sulfolane can lead to human body
Distortion, the residence time is longer in brain tissue, leads to the symptoms such as twitch, clonic spasm, it is proposed that surface water sulfolan is most
High acceptable concentration is 5mg/L；If in addition, containing a large amount of sulfolane in industrial cycle water, the corrosion of equipment but will be caused, it is past
Toward that can cause device that the usage time of design is much not achieved it is necessary to carry out checking maintenance in advance, the warp of whole device is seriously affected
Ji benefit.Therefore, a kind of simple, quick sulfolane content detected in water is established, it is each using sulfolane for Fast Evaluation
Whether there is or not being polluted to water resource, the industrial cycle excellent quality of water water quality, valuator device corrodes for the discharge of industry industrial wastewater
The reason and processing for such industrial wastewater and cycling use of water, utilization and reference sanitary of water sources safeguard procedures play effective guidance
Effect.
Currently, generally being contained both at home and abroad come the sulfolane analyzed in water using AP Oil incorporated business of U.S. standard UOP660
Amount, and in particular to gas chromatography.Gas chromatography has many advantages, such as that separation and quantitative ability is strong, only needs to utilize various solvents
Water sulfolan is extracted, single extraction efficiency is low, need to extract repeatedly, and extractant dosage is big, and time-consuming, the rate of recovery compared with
It is low, it is difficult to which that realization is automatically brought into operation, and follow-up the problems such as there are the processing of extractant.
In consideration of it, it is necessary to study one kind without carrying out pre-treatment to sample, can quickly, it is simple qualitative and quantitatively detect water
The new detection method of sulfolan.LC-MS（HPLC-MS）Technology is using high performance liquid chromatography as separation means, with mass spectrum
For a kind of separate analytical technique of Identification Tools.Currently, there is no using HPLC-MS analysis means for water sulfolan content point
The report of analysis.
Invention content
The shortcomings that in order to overcome the prior art, the present invention provides a kind of LC-MS analyze water sulfolan method,
It is not necessarily to carry out pre-treatment, direct injection analysis, to which realization is simple, fast and accurately contains the sulfolane in water to sample
Amount is analyzed, and precision is good, and the rate of recovery is high, and detection limit is low.
The technical scheme adopted by the invention to solve the technical problem is that：Include the following steps：
（One）Chromatography and Mass Spectrometry Conditions
（1）Instrument is Agilent high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer, chromatographic column Shim
Pack VP-ODS liquid-phase chromatographic columns（15cm×4.6mm×5μm）；
（2）Liquid-phase condition：Mobile phase：A：Methanol；B:The water of the ammonium acetate containing 5mmol/L；Flow velocity：0.4mL/min, gradient are washed
De- program：0-5min：Containing A：40%, remaining group is divided into B；5.1-8min：Containing A：90%, remaining group is divided into B；8.1-10min：Contain
A：90%, remaining group is divided into B；10.1-14min ：Containing A 40%, remaining group is divided into B；Column temperature is 25 DEG C, 20 μ L of sample size；
（3）Mass Spectrometry Conditions：Electron spray ionisation source, positive ion detection pattern, 300 DEG C of ion source temperature, dry gas stream amount
10L/min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 120V, orifice potential 65V, eight
Pole bar radio-frequency voltage 750V, quota ion m/z=138.0578（M+NH4）, qualitative ion m/z=121.0336（M+H）, m/z=
143.0146（M+Na）.
（Two）The drafting of standard curve
Weigh sulfolane（Mass fraction ＞ 99.8%）501mg is added deionized water, waits for that sample fills in 100ml volumetric flasks
Point dissolving after, constant volume obtains the standard solution of a concentration of 5000mg/L of sulfolane, respectively draw 40,100,200,300,
400,500,600,800,1000 μ L above-mentioned standards use liquid, and 100mL is settled to respectively with pure water, obtain 2,5,10,15,20,
25, the series standard liquid of 30,40,50mg/L carries out the titer of various concentration using under above-mentioned chromatography and Mass Spectrometry Conditions
It measures, record quota ion m/z=138.0578（M+NH4）Peak area, draw peak area-concentration standard curve；According to quantitative
Ion m/z=138.0578（M+NH4）Corresponding extraction ion peak areas carries out regression analysis with sulfolane concentration, obtains linear
Equation：Y=791004.1678x-249521.1958, R2=0.9996（X is sulfolane concentration, mg/L）.
（Three）Water sample detection to be measured
It takes the water sample to be measured of certain mass in 100ml volumetric flasks, deionized water is added, after mixing well, constant volume is adopted
Eluent is obtained after being 0.22 μm of membrane filtration with specification, using being surveyed to eluent under above-mentioned chromatography and Mass Spectrometry Conditions
It is fixed, record the peak area of quota ion；Bring step into（Two）In peak area-concentration standard curve, checked in by standard curve
Sulfolane concentration C in eluent, unit mg/L, using formula X=100*C/m, you can obtain containing for water sample sulfolan to be measured
Amount；In formula：
X --- the content of water sample sulfolan to be measured, unit mg/kg；
C --- standard curve checks in the sulfolane concentration C in eluent, unit mg/L；
M --- water sample quality to be measured, unit g.
Step（Four）Described in a kind of water sample to be measured include industrial wastewater, industrial cycle water, drinking water etc..
Beneficial effects of the present invention：
（One）Without carrying out pre-treatment, direct injection analysis, to realize simply, quickly to the sulfolane in water to sample
Content is analyzed；
（Two）It is involved in the present invention to molten sample solvent all be deionized water, it is at low cost, it is pollution-free；
（Three）The present invention has precision good, and the rate of recovery is high, and detection limit is no more than 0.2 μ g/L.
（Four）The present invention uses high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer for the first time, coordinates dedicated liquid phase color
Spectrum, mass spectrometry parameters, can be efficient, accurately realizes the measurement to the sulfolane content in water.
Description of the drawings
Fig. 1 is that 50mg/L sulfolane standard solution of the present invention extracts ion stream（m/z=138.0578）；
Fig. 2 is that 2 sample to be tested sulfolan standard of the embodiment of the present invention extracts ion stream（m/z=138.0578）；
Fig. 3 is the equation of linear regression of ion peak areas of the present invention and sulfolane concentration.
Specific implementation mode
Embodiment one
（One）Laboratory apparatus and reagent
（1）Laboratory apparatus：Agilent high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer, chromatographic column Shim
Pack VP-ODS liquid-phase chromatographic columns（15cm×4.6mm×5μm）；The organic filter membrane of syringe type micro-hole（0.22μm）；
（2）Experiment reagent：Methanol, ultra-pure water, ammonium acetate, sulfolane standard items
（Two）Chromatography and Mass Spectrometry Conditions
（1）Liquid-phase condition：Mobile phase：A：Methanol；B:The water of the ammonium acetate containing 5mmol/L；Flow velocity：0.4mL/min, gradient are washed
De- program：0-5min：Containing A：40%, remaining group is divided into B；5.1-8min：Containing A：90%, remaining group is divided into B；8.1-10min：Contain
A：90%, remaining group is divided into B；10.1-14min ：Containing A 40%, remaining group is divided into B；Column temperature is 25 DEG C, 20 μ L of sample size；
（2）Mass Spectrometry Conditions：Electron spray ionisation source, positive ion detection pattern, 300 DEG C of ion source temperature, dry gas stream amount
10L/min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 120V, orifice potential 65V, eight
Pole bar radio-frequency voltage 750V, quota ion m/z=138.0578（M+NH4）, qualitative ion m/z=121.0336（M+H）, m/z=
143.0146（M+Na）.
（Three）The drafting of standard curve
Weigh sulfolane（Mass fraction ＞ 99.8%）501mg is added deionized water, waits for that sample fills in 100ml volumetric flasks
Point dissolving after, constant volume obtains the standard solution of a concentration of 5000mg/L of sulfolane, respectively draw 40,100,200,300,
400,500,600,800,1000 μ L above-mentioned standards use liquid, and 100mL is settled to respectively with pure water, obtain 2,5,10,15,20,
25, the series standard liquid of 30,40,50mg/L records quota ion m/ using being measured under above-mentioned chromatography and Mass Spectrometry Conditions
z=138.0578（M+NH4）Peak area, draw peak area-concentration standard curve；According to quota ion m/z=138.0578（M+
NH4）Corresponding extraction ion peak areas carries out regression analysis with sulfolane concentration, obtains linear equation：y=791004.1678x-
249521.1958 R2=0.9996（X is sulfolane concentration, mg/L）.
（Four）Water sample detection to be measured
It takes certain company's industrial wastewater of certain mass in 100ml volumetric flasks, deionized water is added, after mixing well,
Constant volume, use specification for 0.22 μm of membrane filtration after obtain eluent, using under above-mentioned chromatography and Mass Spectrometry Conditions to eluent
It is measured, records the peak area of quota ion；Bring step into（Three）In peak area-concentration standard curve, by standard curve
Check in the sulfolane concentration C in eluent, unit mg/L, using formula X=100*C/m, you can obtain water sample middle ring fourth to be measured
The content of sulfone is 920mg/kg.
Embodiment two
（One）Laboratory apparatus and reagent
（1）Laboratory apparatus：Agilent high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer, chromatographic column Shim
Pack VP-ODS liquid-phase chromatographic columns（15cm×4.6mm×5μm）；The organic filter membrane of syringe type micro-hole（0.22μm）；
（2）Experiment reagent：Methanol, ultra-pure water, ammonium acetate, sulfolane standard items
（Two）Chromatography and Mass Spectrometry Conditions
（1）Liquid-phase condition：Mobile phase：A：Methanol；B:The water of the ammonium acetate containing 5mmol/L；Flow velocity：0.4mL/min, gradient are washed
De- program：0-5min：Containing A：40%, remaining group is divided into B；5.1-8min：Containing A：90%, remaining group is divided into B；8.1-10min：Contain
A：90%, remaining group is divided into B；10.1-14min ：Containing A 40%, remaining group is divided into B；Column temperature is 25 DEG C, 20 μ L of sample size；
（2）Mass Spectrometry Conditions：Electron spray ionisation source, positive ion detection pattern, 300 DEG C of ion source temperature, dry gas stream amount
10L/min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 120V, orifice potential 65V, eight
Pole bar radio-frequency voltage 750V, quota ion m/z=138.0578（M+NH4）, qualitative ion m/z=121.0336（M+H）, m/z=
143.0146（M+Na）.
（Three）The drafting of standard curve
Weigh sulfolane（Mass fraction ＞ 99.8%）501mg is added deionized water, waits for that sample fills in 100ml volumetric flasks
Point dissolving after, constant volume obtains the standard solution of a concentration of 5000mg/L of sulfolane, respectively draw 40,100,200,300,
400,500,600,800,1000 μ L above-mentioned standards use liquid, and 100mL is settled to respectively with pure water, obtain 2,5,10,15,20,
25, the series standard liquid of 30,40,50mg/L records quota ion m/ using being measured under above-mentioned chromatography and Mass Spectrometry Conditions
z=138.0578（M+NH4）Peak area, draw peak area-concentration standard curve；According to quota ion m/z=138.0578（M+
NH4）Corresponding extraction ion peak areas carries out regression analysis with sulfolane concentration, obtains linear equation：y=791004.1678x-
249521.1958 R2=0.9996（X is sulfolane concentration, mg/L）.
（Four）Water sample detection to be measured
It takes certain company's industrial cycle water of certain mass in 100ml volumetric flasks, deionized water is added, waits mixing well
Afterwards, constant volume, use specification for 0.22 μm of membrane filtration after obtain eluent, using under above-mentioned chromatography and Mass Spectrometry Conditions to elution
Liquid is measured, and records the peak area of quota ion；Bring step into（Three）In peak area-concentration standard curve, by standard song
Line checks in the sulfolane concentration C in eluent, unit mg/L, using formula X=100*C/m, you can obtains water sample middle ring to be measured
The content of fourth sulfone is 932mg/kg.
Embodiment three
（One）Laboratory apparatus and reagent
（1）Laboratory apparatus：Agilent high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer, chromatographic column Shim
Pack VP-ODS liquid-phase chromatographic columns（15cm×4.6mm×5μm）；The organic filter membrane of syringe type micro-hole（0.22μm）；
（2）Experiment reagent：Methanol, ultra-pure water, ammonium acetate, sulfolane standard items
（Two）Chromatography and Mass Spectrometry Conditions
（1）Liquid-phase condition：Mobile phase：A：Methanol；B:The water of the ammonium acetate containing 5mmol/L；Flow velocity：0.4mL/min, gradient are washed
De- program：0-5min：Containing A：40%, remaining group is divided into B；5.1-8min：Containing A：90%, remaining group is divided into B；8.1-10min：Contain
A：90%, remaining group is divided into B；10.1-14min ：Containing A 40%, remaining group is divided into B；Column temperature is 25 DEG C, 20 μ L of sample size；
（2）Mass Spectrometry Conditions：Electron spray ionisation source, positive ion detection pattern, 300 DEG C of ion source temperature, dry gas stream amount
10L/min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 120V, orifice potential 65V, eight
Pole bar radio-frequency voltage 750V, quota ion m/z=138.0578（M+NH4）, qualitative ion m/z=121.0336（M+H）, m/z=
143.0146（M+Na）.
（Three）The drafting of standard curve
Weigh sulfolane（Mass fraction ＞ 99.8%）501mg is added deionized water, waits for that sample fills in 100ml volumetric flasks
Point dissolving after, constant volume obtains the standard solution of a concentration of 5000mg/L of sulfolane, respectively draw 40,100,200,300,
400,500,600,800,1000 μ L above-mentioned standards use liquid, and 100mL is settled to respectively with pure water, obtain 2,5,10,15,20,
25, the series standard liquid of 30,40,50mg/L records quota ion m/ using being measured under above-mentioned chromatography and Mass Spectrometry Conditions
z=138.0578（M+NH4）Peak area, draw peak area-concentration standard curve；According to quota ion m/z=138.0578（M+
NH4）Corresponding extraction ion peak areas carries out regression analysis with sulfolane concentration, obtains linear equation：y=791004.1678x-
249521.1958 R2=0.9996（X is sulfolane concentration, mg/L）.
（Four）Water sample detection to be measured
It takes certain village drinking water of certain mass in 100ml volumetric flasks, deionized water is added, it is fixed after mixing well
Hold, use specification for 0.22 μm of membrane filtration after obtain eluent, using under above-mentioned chromatography and Mass Spectrometry Conditions to eluent into
Row measures, and records the peak area of quota ion；Bring step into（Three）In peak area-concentration standard curve, looked by standard curve
Obtain the sulfolane concentration C in eluent, unit mg/L, using formula X=100*C/m, you can obtain water sample sulfolan to be measured
Content be 0.03mg/kg.
Control experiment：
1, the precision of method measures
Same a collection of each 7 parts of certain the company's industrial wastewater for weighing different quality respectively, is added separately to 7 100ml volumetric flasks
In, be added deionized water, after mixing well, constant volume, use specification for 0.22 μm of membrane filtration after, using above-mentioned chromatography with
It is measured under Mass Spectrometry Conditions, records the peak area of quota ion；It brings peak area-concentration standard curve into, is looked by standard curve
The sulfolane concentration C in eluent is obtained, unit mg/L, using formula X=100*C/m, result of calculation is as shown in the table：
| Tested number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | RSD% |
| Content | 920 | 921 | 918 | 925 | 920 | 919 | 918 | 0.26 |
From the data in the table, the experimental result repeatability of this method is good.
2, the accuracy determination of method
Same a collection of each 5 parts of certain the company's industrial wastewater for weighing different quality respectively, is added separately to 5 100ml volumetric flasks
In, it is then separately added into 40,100,200,300,400 μ L above-mentioned standards into this 5 volumetric flasks and uses liquid, it is fixed with deionized water
Hold, using being measured under above-mentioned chromatography and Mass Spectrometry Conditions, records the peak area of quota ion；Bring peak area-concentration mark into
Directrix curve checks in the sulfolane concentration C in eluent by standard curve, and unit mg/L is calculated using formula X=100*C/m
The results are shown in table below：
3, the detection limit of method measures
According to the detection limit that the ratio of the response of instrument and noise is 3 computational methods, the detection of sulfolane is limited to 0.002
μg/L。
As described above, a kind of method of LC-MS analysis water sulfolan of the present invention, it be not necessarily to sample into
Row pre-treatment, direct injection analysis, precision is good, and the rate of recovery is high, detection limit it is low, it can be achieved that it is simple, fast and accurately in water
Sulfolane content analyzed.
Claims (2)
1. a kind of method of LC-MS analysis water sulfolan, it is characterised in that：Include the following steps：
It takes the water sample to be measured of certain mass in 100ml volumetric flasks, deionized water, after mixing well, constant volume, using rule is added
Lattice, using being measured to eluent under dedicated chromatography and Mass Spectrometry Conditions, are remembered to obtain eluent after 0.22 μm of membrane filtration
Record the peak area of quota ion；According to peak area-concentration standard curve, by standard curve y=791004.1678x-
249521.1958 R2=0.9996；Wherein x is sulfolane concentration；Check in the sulfolane concentration C in eluent, unit mg/L,
Using formula X=100*C/m, you can obtain the content of water sample sulfolan to be measured；In formula：
X --- the content of water sample sulfolan to be measured, unit mg/kg；
C --- standard curve checks in the sulfolane concentration C in eluent, unit mg/L；
M --- water sample quality to be measured, unit g；
Chromatography and Mass Spectrometry Conditions：
（1）Instrument is Agilent high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer, and chromatographic column is Shim pack
VP-ODS liquid-phase chromatographic columns 15cm × 4.6mm × 5 μm；
（2）Liquid-phase condition：Mobile phase：A：Methanol；B:The water of the ammonium acetate containing 5mmol/L；Flow velocity：0.4mL/min, gradient elution journey
Sequence：0-5min：Containing A：40vt%, remaining group are divided into B；5.1-8min：Containing A：90%, remaining group is divided into B；8.1-10min：Containing A：
90%, remaining group is divided into B；10.1-14min ：Containing A 40%, remaining group is divided into B；Column temperature is 25 DEG C, 20 μ L of sample size；
（3）Mass Spectrometry Conditions：Electron spray ionisation source, positive ion detection pattern, 300 DEG C of ion source temperature, dry gas stream amount 10L/
Min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 120V, orifice potential 65V, octupole bar
Radio-frequency voltage 750V, quota ion m/z=138.0578 M+NH4, the qualitative M+H of ion m/z=121.0336, m/z=143.0146
M+Na。
2. the method for LC-MS analysis water sulfolan according to claim 1, it is characterised in that：The water to be measured
Sample is industrial wastewater or industrial cycle water or drinking water.
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