CN106124255B - A kind of method of phthalic acid ester in graphene/ionic liquid composite material enriched air - Google Patents
A kind of method of phthalic acid ester in graphene/ionic liquid composite material enriched air Download PDFInfo
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- CN106124255B CN106124255B CN201610431477.4A CN201610431477A CN106124255B CN 106124255 B CN106124255 B CN 106124255B CN 201610431477 A CN201610431477 A CN 201610431477A CN 106124255 B CN106124255 B CN 106124255B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Abstract
The invention discloses the methods of phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air, using graphene and the compound obtained material of poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphoric acid ionic liquid as adsorbent, phthalic acid ester in air is analyzed in conjunction with thermal desorption-gas chromatography-mass spectrography detection means, the graphene oxide using ball-milling method preparation passes through CO2After activation, the carbon material of high-ratio surface and multi-pore channel is obtained, bioaccumulation efficiency is improved；The problems such as not needing using a large amount of organic solvents, avoiding solvent volatilization, cross contamination, operating procedure is simple, high sensitivity good to the selectivity of phthalic acid ester, adsorbent recoverable, and can Sync enrichment gaseous state and graininess phthalic acid ester.
Description
Technical field
The present invention relates to a kind of methods of enrichment and detection phthalic acid ester, more particularly to a kind of to utilize stone
Black alkene/ionic liquid composite material is divided as adsorbent material in conjunction with thermal desorption-gas chromatography-mass spectrography detection means
The method for analysing phthalic acid ester in air.
Background technique
Indoor organic pollutant can be divided into volatility and half volatile, and half volatile organic contaminant refers to saturated vapor
Pressure and volatility are lower, the stronger a kind of organic pollution materials of adsorptivity, mainly include pesticide, plasticizer, fire retardant etc..Adjacent benzene
Dicarboxylic acid esters can generate interaction between the secondary molecules of polymeric chain, and then improve the elasticity of polymer material, and increase poly-
The ductility and pliability for closing object material are a kind of more satisfactory plasticizer, but phthalic acid ester shadow can ring the mankind
Endocrine system leads to reproduction, development and abnormal behavior, thus in the world to the disabling cry of phthalic acid ester increasingly
It is high.Phthalic acid ester belongs to semi-volatile organic matter pollutant, exists in air with Gas and particles, and majority is in
Trace ultra trace is horizontal.Therefore, the phthalic acid ester in enriched air is an important link of environmental analysis.Traditional adopts
Quadrat method needs largely to use organic solvent, often along with solvent volatilization, cross contamination the problems such as, handled before prolonged
It is also easy to the impurity being introduced into solvent and ambient enviroment in journey, sample is polluted, influences the accuracy of quantitative result, and not
It can Sync enrichment gas phase and particle.
Ionic liquid is forced down as a kind of novel green solvent, steam, not volatile；Stability is good, nonflammable；Dissolve energy
Power is strong；Designability is strong, recoverable.All there is good dissolubility to inorganic, organic substance and polymer.Using ion
Liquid can acquire the phthalic acid ester of gaseous state and particulate form, the structure designability of ionic liquid as enrichment material simultaneously
Also the selectivity to pollutant is considerably increased, the application of ionic liquid also simplifies complicated pretreatment process.
The two-dimensional material for the single layer atomic thickness that graphene is made of carbon atom with sp2 hydridization, thickness only have
0.335nm, has long-range pi bond conjugated structure, and theoretical specific surface area is up to 2600m2/ g, hexagonal array array structure enables it to and it
Strong interaction occurs for its molecule, and it is comparatively ideal enrichment material that this, which makes it have stronger adsorption capacity,.Graphite is dilute to be recognized
For be a kind of nonpolarity, it is hydrophobic, have the structure of very strong affinity for the ring of carbon matrix, it is available in analytical chemistry field
In reverse phase solid phase extraction, also can be used as the adsorbent material of SPE and SPME, graphene can also provide it is many can decorating site,
Possibility is provided for selective enrichment analyte, the preparation and application of graphene composite material have become the heat of scientific circles' research
Point problem.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide phthalic acid ester in a kind of enriched air
Method, the problems such as not needing using a large amount of organic solvents, avoid solvent volatilization, cross contamination, operating procedure is simple, to neighbour
The selectivity of phthalic acid ester is good, high sensitivity, and adsorbent is reusable, and can Sync enrichment gaseous state and graininess neighbour benzene two
Formic acid esters.
To achieve the above object, the present invention provides the following technical scheme that a kind of graphene/ionic liquid composite material is rich
Collect the method for phthalic acid ester in air, characterized by the following steps:
1) preparation of graphene oxide: weighing graphite oxide into ball grinder, and DMF is added, and ammonium hydrogen carbonate, ball milling is added
Product in ball grinder is added in ethyl alcohol by 10-15h, at 20-30 DEG C, is carried out ultrasound 24-36h, is obtained the glue of graphene oxide
Liquid solution, centrifugation, is successively cleaned with deionized water and ethyl alcohol, is centrifuged, dry；Dilute graphite oxide is the dilute precursor of synthetic graphite,
It has the group for being very easy to be modified by sulphation, and allows graphene compound with multiple material.
2) it the activation of graphene oxide: weighs dried graphene oxide and is placed in tube furnace, be passed through 60-80mL
min-1N230-60min；By stove with 5-20 DEG C of min-1Heating rate be raised to 750-950 DEG C；Then gas is changed into CO2,
Flow 10-60mL min-1, keep the temperature 2-5h；Change gas into N2, flow 60-80mL min-1, tube furnace is cooled to room temperature, is obtained
To activated graphene；Pass through CO2Obtained grapheme material is activated, micropore can be introduced in the material, there is graphene more
The cellular structure of grade, can reduce the reunion of graphene, keep high specific surface area, it is ensured that graphene is abundant with substance to be adsorbed
Contact, improves its accumulation ability to many chemical substances.
3) activated graphene and poly- 1- allyl -3- graphene/ionic liquid composite material sampling pipe preparation: are weighed
Ethyl benzo imidazole hexafluorophosphoric acid ionic liquid is added DMF, so that it is uniformly distributed to solution in 30-60 DEG C of sonic oscillation
In, obtain the mixture of graphene and poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphoric acid ionic liquid；Coated in white
It is dry to be coated with the white carrier infrared baking lamp of graphene/ionic liquid composite material for the surface of color carrier；Dry postposition
It in 110-120 DEG C of baking 2-5h in baking oven, is cooled to room temperature, inserts in glass tube；Activation, both ends, are put at room temperature beyond the Great Wall
It is spare in drier.Ionic liquid is compound with graphene, the hydrophily and dispersibility of graphene can be increased, obtain stability
Higher compound, while being avoided that the phenomenon that graphene is reunited due to π-pi-electron sedimentation and van der Waals interaction, energy
Obtain bioaccumulation efficiency more higher than individual graphene oxide.
4) it samples: being sampled using double gas circuit constant current atmosphere sampling instruments, sampling flow: 500-1000mL/min, sampling
Time: 90min after sampling, is sealed immediately.
5) it thermal desorption-gas chromatography-mass spectrometry analysis: is examined using automatic thermal desorption instrument-gas chromatograph-mass spectrometer (GC-MS)
Survey analysis, the condition of thermal desorption are as follows: desorption gas: helium；First stage sample cell desorption, 220-280 DEG C of desorption temperature, desorption
Flow velocity 50mL/min is desorbed in time 10-15min；0 DEG C of cold trap trapping temperature, second stage cold-trap desorption, desorption temperature 260-
280 DEG C, desorption time 5-15min, 30-40 DEG C of heating rate/s, without shunting after trap before trap；230 DEG C of six-way valve temperature, transmission
240-280 DEG C of line temperature；GC conditions: chromatographic column: DB-5MS chromatographic column is used；Specification: the μ of 30m × 0.25mm × 0.25
m；Carrier gas: high-pure helium, purity >=99.999%；Injector temperature: 250 DEG C；Sample volume: 1 μ L；Split sampling, split ratio: 20:
1；Constant current mode, flow velocity: 1.0mL/min；Mass Spectrometry Conditions: ionization mode: electron bombardment ionization source (FI)；Ionizing energy: 70eV；Transmission
Line temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；Grab type: selection ion scan+full scan
(SIM+Scan)；Solvent delay: 10min；Temperature program: 80 DEG C of initial temperature, 0.5min is kept, extremely with the rate of 30 DEG C/min
160 DEG C, 3min is kept, then with the rate of 5 DEG C/min to 300 DEG C, keeps 5min.
As a further improvement of the present invention, graphite oxide in the step 1: DMF: the mass ratio of ammonium hydrogen carbonate is 10: 1
∶6。
As a further improvement of the present invention, planetary ball mill is selected in the step 1, ball mill rotational velocity is
1200r/min, revolution speed 600r/min.
As a further improvement of the present invention, graphene in the step 3: ionic liquid: the mass ratio of DMF is 1: 2: 6.
As a further improvement of the present invention, it is activated in the step 3 and carrier gas is made with helium, in the flow velocity of 60mL/min
Under, 250-280 DEG C of activation 30-60min is down to 30 DEG C or less in the case where uninterrupted helium stream.
As a further improvement of the present invention, the standard items of selection include phthalic acid two (2- ethylhexyl)
(DEHP), dibutyl phthalate (DBP), O-phthalic acid butyl benzyl group ester (BBP), repefral (DMP),
Diethyl phthalate (DEP) and diisooctyl phthalate (DIDP) select following qualitative ion and quota ion
It is as follows:
The present invention is using graphene/ionic liquid composite material as adsorbent, in conjunction with thermal desorption-gas chromatography-mass spectrum
Associated with detection means analyze phthalic acid ester in air, the graphene oxide using ball-milling method preparation passes through CO2Activation
Afterwards, it has obtained specific surface and pore volume is respectively 1047m2g-1And 3.8cm3g-1Carbon material, improve bioaccumulation efficiency；It does not need
Using a large amount of organic solvents, the problems such as avoiding solvent volatilization, cross contamination, operating procedure is simple, to phthalic acid ester
The good, high sensitivity of selectivity, adsorbent recoverable, and can Sync enrichment gaseous state and graininess phthalic acid ester.
Detailed description of the invention
Fig. 1 is graphene Raman of the present invention figure；
Fig. 2 is graphene SEM of the present invention figure；
Fig. 3 is graphene of the present invention/ionic liquid TEM figure.
Specific embodiment
Following embodiment is given below to be described in further detail the present invention
1) thermal desorption-gas chromatography-mass spectrometry analysis: the condition of thermal desorption are as follows: desorption gas: helium；First stage sample
220-280 DEG C of desorption temperature, desorption time 10-15min, flow velocity 50mL/min is desorbed in pipe desorption；0 DEG C of cold trap trapping temperature, the
Two-stage cold-trap desorption, 260-280 DEG C of desorption temperature, desorption time 5-15min, 30-40 DEG C of heating rate/s, before trap after trap
Without shunting；230 DEG C of six-way valve temperature, 240-280 DEG C of transmission line temperature；GC conditions: chromatographic column: DB-5MS chromatography is used
Column；Specification: 30m × 0.25mm × 0.25 μm；Carrier gas: high-pure helium, purity >=99.999%；Injector temperature: 250 DEG C；Sample introduction
Amount: 1 μ L；Split sampling, split ratio: 20: 1；Constant current mode, flow velocity: 1.0mL/min；Mass Spectrometry Conditions: ionization mode: electronics bangs
Hit source (EI)；Ionizing energy: 70eV；Transmission line temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；It adopts
Collect type: selection ion scan+full scan (SIM+Scan)；Solvent delay: 10min；Temperature program: it 80 DEG C of initial temperature, protects
0.5min is held, with the rate of 30 DEG C/min to 160 DEG C, 3min is kept, then with the rate of 5 DEG C/min to 300 DEG C, keeps 5min；
The qualitative ion and quota ion that 1 mass spectral analysis of table is selected
2) preparation of standard solution: six kinds of phthalic acid ester standard items: (the 2- second of phthalic acid two are accurately weighed respectively
Base hexyl ester) (DEHP), dibutyl phthalate (DBP), O-phthalic acid butyl benzyl group ester (BBP), phthalic acid two
Methyl esters (DMP), diethyl phthalate (DEP), diisooctyl phthalate (DIDP) 500mg, with methanol dilution constant volume
Into 100ml volumetric flask, it is made into the mixed standard solution of 5mg/ml；The mixed standard solution of 5mg/ml is diluted step by step with methanol
Constant volume, obtain 0.1 μ g/mL, 0.5 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 30 μ g/mL, 50 μ g/mL concentration gradients mark
Quasi- solution.
The preparation of activated graphene A
1) preparation of graphene oxide A: weighing 10g graphite oxide into ball grinder, and 1gDMF is added, and 6g bicarbonate is added
Product in ball grinder is added in ethyl alcohol by ammonium, ball milling 13h, at 20 DEG C, is carried out ultrasound 28h, is obtained the glue of graphene oxide A
Liquid solution, centrifugation, is successively cleaned with deionized water and ethyl alcohol, is centrifuged, dry；
2) it the activation of graphene oxide A: weighs dried graphene oxide A and is placed in tube furnace, be passed through 65mL min-1
N240min；By stove with 10 DEG C of min-1Heating rate be raised to 800 DEG C；Then gas is changed into CO2, flow 20mL min-1, keep the temperature 3h；Change gas into N2, flow 60mL min-1, tube furnace is cooled to room temperature, activated graphene A is obtained；
The preparation of activated graphene B
1) preparation of graphene oxide B: weighing 10g graphite oxide B into ball grinder, and 1gDMF is added, and 6g bicarbonate is added
Product in ball grinder is added in ethyl alcohol by ammonium, ball milling 14h, at 25 DEG C, is carried out ultrasound 30h, is obtained the glue of graphene oxide B
Liquid solution, centrifugation, is successively cleaned with deionized water and ethyl alcohol, is centrifuged, dry；
2) it the activation of graphene oxide B: weighs dried graphene oxide B and is placed in tube furnace, be passed through 70mL min-1
N250min；By stove with 15 DEG C of min-1Heating rate be raised to 850 DEG C；Then gas is changed into CO2, flow 40mL min-1, keep the temperature 4h；Change gas into N2, flow 70mL min-1, tube furnace is cooled to room temperature, activated graphene B is obtained；
The preparation of graphene/ionic liquid composite material A sampling pipe
The poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphoric acid ionic liquid of 1g activated graphene A and 2g is weighed, is added
Enter 6gDMF, disperses it uniformly in 40 DEG C of sonic oscillations, obtain graphene and poly- 1- allyl -3- ethyl benzo imidazole six
The mixture of fluorophosphate ionic liquid；It weighs 45g white carrier and is added to graphene A and poly- 1- allyl -3- ethyl benzo miaow
In the mixture of azoles hexafluorophosphoric acid ionic liquid, the white carrier of graphene/ionic liquid composite material A is coated with red
Outer heat lamp is dry；Drying is placed in baking oven in 115 DEG C of baking 3h, after being down to 25 DEG C, is inserted in glass tube；It activates, beyond the Great Wall both ends,
It is put into spare in drier at room temperature.
The preparation of graphene/ionic liquid composite material B sampling pipe
The poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphoric acid ionic liquid of 2g activated graphene B and 4g is weighed, is added
Enter 12gDMF, be distributed to it uniformly in solution in 30-60 DEG C of sonic oscillation, obtains graphene B solution and ionic liquid
Mixture；Weigh 90g white carrier be added to graphene B solution and poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphate from
In the mixture of sub- liquid, it is dry to be coated with the white carrier infrared baking lamp of graphene/ionic liquid composite material B；It will
Ionic liquid/graphene composite material after drying is placed in baking oven in 120 DEG C of baking 4h, is down to 25 DEG C, is inserted in glass tube；It is living
Change, both ends, are put into spare in drier at room temperature beyond the Great Wall.
Embodiment 1
Draw 0.1 μ g/mL, 0.5 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 30 μ of 1uL respectively with microsyringe
The standard solution of g/mL, 50 μ g/mL concentration are injected in sampling pipe A, are carried out under the conditions of thermal desorption-gas chromatography-mass spectrometry analysis
Measurement, using peak area as ordinate, concentration is that abscissa draws working curve.
2 standard curve detection limit of table and quantitative limit
| Serial number | Title | Regression equation | Related coefficient | Detection limit μ g/g | Quantitative limit μ g/g |
| 1 | DBP | Y=2569x+1375.4 | 0.9991 | 0.07 | 0.36 |
| 2 | BBP | Y=2635x+1824.6 | 0.9994 | 0.01 | 0.21 |
| 3 | DEHP | Y=3761x+2015.7 | 0.9993 | 0.04 | 0.19 |
| 4 | DMP | Y=3258x+2038.4 | 0.9992 | 0.02 | 0.27 |
| 5 | DEP | Y=1983x+1164.3 | 0.9993 | 0.03 | 0.32 |
Embodiment 2
Draw 0.1 μ g/mL, 0.5 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 30 μ of 1uL respectively with microsyringe
The standard solution of g/mL, 50 μ g/mL concentration are injected in sampling pipe B, are carried out under the conditions of thermal desorption-gas chromatography-mass spectrometry analysis
Measurement, using peak area as ordinate, concentration is that abscissa draws working curve.
3 standard curve detection limit of table and quantitative limit
| Serial number | Title | Regression equation | Related coefficient | Detection limit μ g/g | Quantitative limit μ g/g |
| 1 | DBP | Y=3148x+2014.5 | 0.9990 | 0.04 | 0.25 |
| 2 | BBP | Y=2874x+2137.5 | 0.9994 | 0.03 | 0.27 |
| 3 | DEHP | Y=3637x+1962.1 | 0.9991 | 0.03 | 0.18 |
| 4 | DMP | Y=1958x+1983.6 | 0.9993 | 0.02 | 0.34 |
| 5 | DEP | Y=2536x+2036.5 | 0.9994 | 0.03 | 0.36 |
Embodiment 3
Taking concentration is respectively the standard sample of 0.1 μ g/mL, 5 μ g/mL, 50 μ g/mL, uses sampling pipe A and sampling pipe B respectively
Do precision and rate of recovery experiment
The rate of recovery and RSD of 4 three kinds of mark-on samples of table
Embodiment 4
Using double gas circuit constant current atmosphere sampling instruments, the sampling time: 90min after sampling, is sealed immediately.
The testing result of the different embodiments of table 5
Claims (6)
1. the method for phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air, it is characterised in that: including
Following steps:
Step 1: the preparation of graphene oxide: weighing graphite oxide into ball grinder, and DMF is added, and ammonium hydrogen carbonate, ball milling is added
Ball grinder product is added in ethyl alcohol by 10-15h, at 20-30 DEG C, is carried out ultrasound 24-36h, is obtained the colloid of graphene oxide
Solution, centrifugation, is successively cleaned with deionized water and ethyl alcohol, is centrifuged, dry；
Step 2: the activation of graphene oxide: weighing dried graphene oxide and be placed in tube furnace, be passed through 60-80 mL
min-1 N230-60min；By stove with 5-20 DEG C of min-1Heating rate be raised to 750-950 DEG C；Then gas is changed
At CO2, flow 10-60 mL min-1, keep the temperature 2-5h；Change gas into N2, flow 60-80 mL min-1, tube furnace is cold
But to room temperature, activated graphene is obtained；
Step 3: the preparation of graphene/ionic liquid composite material sampling pipe: weighing activated graphene and poly- 1- allyl -3-
Ethyl benzo imidazole hexafluorophosphoric acid ionic liquid is added DMF, disperses it uniformly in 30-60 DEG C of sonic oscillation, obtain
The mixture of activated graphene and poly- 1- allyl -3- ethyl benzo imidazole hexafluorophosphoric acid ionic liquid；Mixture is applied
On the surface of white carrier, it is dry to be coated with the white carrier infrared baking lamp of graphene/ionic liquid composite material；It is dry
It is placed in baking oven in 110-120 DEG C of baking 2-5h, is cooled to room temperature, insert in glass tube；Activation, both ends, are put into room beyond the Great Wall
It is spare in drier under temperature；
Step 4: sampling: being sampled using double gas circuit constant current atmosphere sampling instruments, sampling flow: 500-1000mL/min, sampling
Time: 90min after sampling, is sealed immediately；
Step 5: thermal desorption-gas chromatography-mass spectrometry analysis: being carried out using automatic thermal desorption instrument-gas-chromatography-mass spectrometer
It tests and analyzes, the condition of thermal desorption are as follows: desorption gas: helium；First stage sample cell desorption, 220-280 DEG C of desorption temperature,
Flow velocity 50mL/min is desorbed in desorption time 10-15min；0 DEG C of cold trap trapping temperature, second stage cold-trap desorption, desorption temperature
260-280 DEG C, desorption time 5-15min of degree, 30-40 DEG C of heating rate/s, without shunting after trap before trap；Six-way valve temperature
230 DEG C, 240-280 DEG C of transmission line temperature；GC conditions: chromatographic column: DB-5MS chromatographic column is used；Specification: 30m ×
0.25mm×0.25µm ；Carrier gas: high-pure helium, purity >=99.999%；Injector temperature: 250 DEG C；Sample volume: 1 μ L；Point
Sample is flowed into, split ratio: 20:1；Constant current mode, flow velocity: 1.0 mL/min；Mass Spectrometry Conditions: ionization mode: electron bombardment ionization source
(EI)；Ionizing energy: 70 eV；Transmission line temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；Acquisition
Type: selection ion scan+full scan (SIM+Scan)；Solvent delay: 10min；Temperature program: 80 DEG C of initial temperature,
0.5 min is kept, with the rate of 30 DEG C/min to 160 DEG C, keeps 3 min, then extremely with the rate of 5 DEG C/min
300 DEG C, keep 5 min.
2. phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air according to claim 1
Method, it is characterised in that: graphite oxide in the step 1: DMF: the mass ratio of ammonium hydrogen carbonate is 10:1:6.
3. phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air according to claim 2
Method, it is characterised in that: planetary ball mill is selected in the step 1, ball mill rotational velocity is 1200r/min, revolution speed
For 600r/min.
4. phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air according to claim 3
Method, it is characterised in that: graphene in the step 3: ionic liquid: the mass ratio of DMF is 1:2:6.
5. phthalic acid ester in a kind of graphene/ionic liquid composite material enriched air according to claim 4
Method, it is characterised in that: activation makees carrier gas with helium in the step 3, under 60 mL/min flow velocity, 250-280 DEG C
30-60 min is activated, is down to 30 DEG C or less in the case where uninterrupted helium stream.
6. adjacent benzene two in a kind of graphene/ionic liquid composite material enriched air according to claim 1-5
The method of formic acid esters, it is characterised in that: the standard items of selection include phthalic acid two (2- ethylhexyl) (DEHP), adjacent
Dibatyl phithalate (DBP), O-phthalic acid butyl benzyl group ester (BBP), repefral (DMP), O-phthalic
Diethyl phthalate (DEP) and diisooctyl phthalate (DIDP) select following qualitative ion and quota ion as follows:
。
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| CN108614041A (en) * | 2018-03-29 | 2018-10-02 | 南京大学 | A method of quantitatively detecting incretion interferent difference occurrence patterns content in water |
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| CN110333127B (en) * | 2019-06-24 | 2020-06-12 | 北京大学 | Online measurement system, method and application of gas-phase semi-volatile organic compounds |
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Denomination of invention: A method for enrichment of phthalates in air by graphene/ionic liquid composites Effective date of registration: 20221128 Granted publication date: 20190129 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Wenzhou Cangnan Qianku small and micro enterprise franchise sub branch Pledgor: Wenzhou Baofeng Packaging Technology Co.,Ltd. Registration number: Y2022330003241 |