CN117783376B - MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds - Google Patents
MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 78
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 45
- 239000013178 MIL-101(Cr) Substances 0.000 title claims abstract description 44
- 239000000945 filler Substances 0.000 title claims abstract description 24
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- 230000032683 aging Effects 0.000 claims description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 3
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- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract description 2
- 239000012494 Quartz wool Substances 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 description 7
- 239000002594 sorbent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
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- 239000012224 working solution Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- -1 dichloroethylene, trichloroethylene, toluene Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
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- 210000000987 immune system Anatomy 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 239000013076 target substance Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The application relates to the technical field of volatile organic compound adsorption detection, and discloses an MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds. One end of the adsorption tube is a gas adsorption inlet end and a thermal desorption gas outlet end, the other end of the adsorption tube is a gas adsorption outlet end and a thermal desorption purge gas inlet end, the gas adsorption and thermal desorption gas flow directions are opposite, the metal tubular shell is from the gas adsorption inlet end to the gas outlet end, and the inside filling sequence is sequentially a metal plug mesh, quartz wool, MIL-101 (Cr) filler, quartz wool, a metal plug mesh and a G-shaped buckle. The adsorption tube provided by the application creatively uses MIL-101 (Cr) as a packing adsorbent, can be applied to high-efficiency detection of benzene series and chlorinated volatile organic compounds by thermal desorption-gas chromatography mass spectrometry, expands the actual application scene of MOFs materials in the field of environment detection, and provides the research and development direction of new products of the VOCs adsorption tube.
Description
Technical Field
The application relates to the technical field of volatile organic compound adsorption detection, in particular to an MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds.
Background
Volatile Organic Compounds (VOCs) are one of the main pollutants in the ambient air, are also important precursors for inducing secondary pollutants such as fine particulate matters and ozone to generate, and are easy to cause the problems of haze, photochemical smog and other atmospheric environments. Among them, VOCs such as benzene series, halogenated hydrocarbon and the like may damage nervous system, immune system and endocrine system of human body, and even induce canceration, thus becoming a target substance for important monitoring of ambient air.
At present, VOCs in the ambient air are mainly sampled by methods such as an air bag, a soda tank, an adsorption tube and the like, and qualitative and quantitative analysis is realized by combining Gas Chromatography (GC) or a gas chromatography mass spectrometer (GC-MS). The adsorption tube sampling method has the advantages of convenience in sampling and transportation, high sensitivity, low loss rate and the like, and has good application prospects in field detection work and laboratory scientific research. The adsorbents packed by the adsorption tubes currently sold in the market mainly comprise porous organic polymers (Tenax, chromosob and the like), carbon adsorbents (activated carbon, carbon molecular sieves, graphitized carbon black and the like) and composite materials thereof. Metal Organic Frameworks (MOFs) are used as novel porous materials assembled by metal ions and organic ligands, have very high specific surface area and abundant micropore structures, and draw attention of researchers at home and abroad in the directions of gas adsorption, separation, catalysis and the like. However, no report on application of MOFs to the field of adsorption-thermal desorption detection of volatile organic compounds has been presented.
Disclosure of Invention
The invention aims to provide an adsorption tube applied to detection of benzene series and chlorinated volatile organic compounds by thermal desorption-gas chromatography mass spectrometry.
In order to achieve the above purpose, the invention adopts the following technical scheme:
An MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds, wherein one end of the MIL-101 (Cr) filler adsorption tube is a gas adsorption inlet end and a thermal desorption gas outlet end, the other end of the MIL-101 (Cr) filler adsorption tube is a gas adsorption outlet end and a thermal desorption purge gas inlet end, the gas adsorption and thermal desorption gas flow directions are opposite, a metal tubular shell sequentially comprises a metal plug mesh, quartz cotton, MIL-101 (Cr) filler, quartz cotton, a metal plug mesh and a G-shaped buckle from the gas adsorption inlet end to the gas outlet end.
Preferably, the distance between the metal plug nets fixed at the two ends inside the metal tubular shell is controlled to be 4.5-5.5 cm, and the metal plug nets at the gas adsorption inlet end are fixed to be abutted against the groove line of the shell.
Preferably, the metal tubular shell is 1/4 inch in diameter by 3.5 inch in length, and the mass of the MIL-101 (Cr) metal-organic framework filler filled in the metal tubular shell is 70-170 mg; the mass of the quartz cotton filled at one side inside is 10-20 mg.
The invention also provides a method for detecting benzene series and chlorinated volatile organic compounds, which comprises the steps of using the MIL-101 (Cr) filler adsorption tube to adsorb and thermally desorb the benzene series and chlorinated volatile organic compounds, then detecting by combining with gas chromatography-mass spectrometry, and carrying out aging pretreatment of more than 50 min on the MIL-101 (Cr) filler adsorption tube before use.
Preferably, the aging step is: high-purity nitrogen is introduced from the inlet end of the thermal desorption purge gas to carry out thermal desorption, and the thermal desorption temperature is 300 ℃.
Preferably, the adsorption step mainly comprises the steps of injecting standard working solution into an adsorption tube, and keeping the adsorption tube on a high-purity nitrogen flow purging device for 3 min to obtain the adsorption tube after adsorption.
Preferably, the thermal desorption conditions mainly comprise that the primary desorption temperature is 300 ℃ and the desorption time is 10 min; the secondary desorption temperature is 300 ℃ and the desorption time is 3 min; the cold trap temperature was-25 ℃.
Preferably, the benzene-based and chlorinated volatile organic compounds include 1, 1-dichloroethane, cis-1, 2-dichloroethylene, trichloroethylene, toluene, chlorobenzene, ethylbenzene, m, p-xylene, o-xylene, 1,3, 5-trimethylbenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1,2, 4-trichlorobenzene and hexachloroprene.
The invention has the beneficial effects that:
The VOCs adsorption sampling tube provided by the invention creatively utilizes MOFs material MIL-101 (Cr) as a packing adsorbent, can be applied to high-efficiency detection of benzene series and chlorinated volatile organic compounds including dichloroethane, dichloroethylene, trichloroethylene, toluene, chlorobenzene, ethylbenzene, dimethylbenzene, trimethylbenzene, dichlorobenzene, trichlorobenzene and the like by using thermal desorption-gas chromatography mass spectrometry, expands the practical application scene of MOFs materials in the field of environment detection, and provides the research and development direction of new products of the VOCs adsorption tube.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic packing diagram of MIL-101 (Cr) packing adsorbent tubes of example 1.
FIG. 2 shows the variation of background noise when MIL-101 (Cr) packed adsorbent tube of example 3 was aged 9 times in succession.
FIG. 3 is a total ion flow chromatogram of a 100 ng mixed standard sample of MIL-101 (Cr) packed adsorbent tube of example 4.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
The embodiment provides an MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds, wherein the preparation method of MIL-101 (Cr) comprises the following steps: adding 2.5 mmol parts of terephthalic acid, 2.5 parts of mmol parts of Cr (NO 3)2·9H2 O and 32 mu L of hydrofluoric acid) into 15-20 mL of water, stirring at room temperature, ultrasonically treating, transferring to a reaction kettle, keeping the temperature of 220 ℃ in a high-temperature oven for reacting for 8-10 hours, taking out the mixed solution after the reaction is finished, repeatedly cleaning with hot water and methanol, finally centrifugally collecting green precipitate, adding 10-15 mL of DMF into the precipitate, heating and stirring at 80 ℃ for 1h parts of DMF, centrifugally recovering the precipitate again, adding 10-15 mL of methanol into the precipitate, heating and refluxing for reacting for 1h parts, cooling, centrifugally recovering the precipitate, adding 10-15 mL of water into the precipitate, heating and refluxing for 1h parts of water, cooling, recovering the precipitate again, and finally vacuum drying the precipitate to obtain MIL-101 (Cr) green powder, and placing the precipitate at a cool and dry place for standby.
The internal assembly sequence of MILs-101 (Cr) packed sorbent tubes in this example (fig. 1). The metal plug net, the quartz cotton, the MIL-101 (Cr), the quartz cotton, the metal plug net and the G-shaped buckle are sequentially filled in the shell of the blank adsorption tube from right to left, the right end of the MIL-101 (Cr) filler adsorption tube is a gas adsorption inlet end and a thermal desorption gas outlet end, the left end is a gas adsorption outlet end and a thermal desorption purge gas inlet end, and the gas adsorption and thermal desorption gas flow directions are opposite. The specific parameters of the filling adsorption tube mainly comprise that the size of a metal tubular shell is 1/4 inch in diameter multiplied by 3.5 inches in length, the distance between two fixed metal plug meshes is controlled to be 4.5-5.5 cm, the metal plug meshes at the gas adsorption inlet end are fixed at the positions of groove lines of the shell, the mass of quartz cotton filled at one side is 10-20 mg, and the mass of MIL-101 (Cr) metal organic framework material filled at the middle part is 70-170 mg. And after the MIL-101 (Cr) filler adsorption tube is filled, carrying out gas resistance test, wherein when the gas flow is set to be 0.5L/min, the gas resistance of the MIL-101 (Cr) filler adsorption tube is 3-15 kPa, so that the adsorption tube can be ensured to have a good gas passage, and a sufficient contact area is provided for efficiently adsorbing VOCs.
Example 2:
the specific parameters of the filling adsorption tube mainly comprise that the spacing between metal plug meshes fixed at two ends is controlled to be 5.0 cm, the mass of quartz cotton filled at one side is 15 mg, and the mass of MIL-101 (Cr) metal organic framework material filled at the middle part is 100 mg. The remainder was the same as in example 1.
Example 3:
The background noise of the MIL-101 (Cr) packed adsorbent tube prepared in example 2 was investigated as a function of the aging period, and the results are shown in FIG. 2. The aging procedure of one period in the implementation process is specifically as follows: first, thermal desorption is carried out on a thermal desorption end at 10 min, the thermal desorption temperature is 300 ℃, and then the background noise value is recorded on a gas chromatography mass spectrometry end. In the 1 st aging period, the background noise of the newly packed adsorption tube is more obvious. The background noise value of the blank adsorption tube is obviously weakened along with the increase of the aging period times, and when the aging period times reach 5 times, the change of the background noise value of the adsorption tube is stable. Therefore, the MIL-101 (Cr) packing adsorption tube of the invention completes at least 5 cycles, namely 50 min aging cycles before being applied to VOCs detection.
Example 4:
15 benzene series and chlorinated VOCs were detected on a thermal desorption-gas chromatograph-mass spectrometer using MIL-101 (Cr) packing adsorption tube of example 2. 100 The total ion flow chromatogram of the ng mixed standard sample is shown in fig. 3, wherein specific VOCs targets designated by serial numbers are shown in table 1. The specific operation of VOCs adsorption acquisition mainly comprises the steps of installing a blank adsorption tube subjected to aging pretreatment on an air sampler, setting gas acquisition flow to be 0.1-0.2L/min, and acquiring time to be 10-15 min.
A standard curve for detecting 15 benzene series and chlorinated VOCs by using an MIL-101 (Cr) filler adsorption tube is established. And (3) diluting the 2000 mg/L mixed standard solution by taking methanol as a solvent to prepare standard working solutions with concentration gradients of 5, 10, 25, 50 and 100 mug/mL. And (3) mounting the blank adsorption tube subjected to aging pretreatment on a high-purity nitrogen flow purging device, respectively injecting 1 mu L of standard working fluids with different concentrations into the adsorption tube, and maintaining nitrogen purging for 3 min to obtain a series of MIL-101 (Cr) filler adsorption tubes with the concentrations of 5, 10, 25, 50 and 100 ng, wherein the standard curve adsorption tube is prepared on the same day as the loading machine. When the machine is used for detection, the thermal desorption conditions comprise that the primary desorption temperature is 300 ℃ and the desorption time is 10 min; the secondary desorption temperature is 300 ℃ and the desorption time is 3 min; the cold trap temperature was-25 ℃. The gas chromatographic conditions include that the chromatographic column adopts an Agilent DB-624 capillary column (30 m multiplied by 0.25 multiplied by mm multiplied by 0.25 mu m), the temperature of a sample inlet is 200 ℃, carrier gas is high-purity nitrogen, the flow rate of the column is 1.3 mL/min, and sample injection is not split; the temperature program was kept at an initial temperature of 30℃for 3.2 min, followed by a temperature rise of 11℃per minute to 200℃for 3 min. The mass spectrum condition comprises that the scanning mode adopts full scanning, the scanning range is 30-270 aum, the ion source is an electron bombardment ion source (EI source), the ionization energy is 70 eV, the ion source temperature is 230 ℃, and the quadrupole temperature is 150 ℃.
After the test is completed, the mass (x, ng) of VOCs targets injected into the adsorption tube is taken as an abscissa, the peak area (y) of the measurement result is taken as an ordinate, and linear fitting is carried out, so that a standard curve regression equation (table 1) of 5-100 ng of 15 VOCs single targets is obtained, wherein the standard curve regression equation specifically comprises 1, 1-dichloroethane, cis-1, 2-dichloroethylene, trichloroethylene, toluene, chlorobenzene, ethylbenzene, m-xylene, o-xylene, 1,3, 5-trimethylbenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1,2, 4-trichlorobenzene and hexachloroprene, and the correlation coefficient R 2 is more than or equal to 0.99, and the good linear relation is expressed. The detection limit of 15 VOCs in MIL-101 (Cr) packed sorbent tube was calculated by measuring 8 parallel sorbent tube samples with injection of 1 ng (Table 1). Average recovery and relative standard deviation of 15 VOCs from MILs-101 (Cr) packed sorbent tube measurements were obtained by measuring parallel sorbent tube samples with injection volumes of 5 ng, 30 ng, and 70 ng, respectively (table 2). This example illustrates that MILs-101 (Cr) packed sorbent tubes are suitable for quantitative testing of the 15 benzene series and chlorinated VOCs listed in this patent.
Table 1 example 4MIL-101 (Cr) packed sorbent tube was used to detect retention time, regression equation, quantitative ion, characteristic ion, linear correlation coefficient, and detection limit of VOCs.
Table 2 example 4MIL-101 (Cr) packed adsorbent tube was used to detect the average recovery and relative standard deviation (n=3) of VOCs.
As can be seen from tables 1 and 2, R 2, limit of detection, recovery, and relative standard deviation together confirm that the "MIL-101 (Cr) packing adsorption tube is suitable for quantitative testing of 15 benzene series and chlorinated VOCs listed in the patent. "
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The MIL-101 (Cr) filler adsorption tube for detecting benzene series and chlorinated volatile organic compounds is characterized in that one end of the MIL-101 (Cr) filler adsorption tube is a gas adsorption inlet end and a thermal desorption gas outlet end, the other end of the MIL-101 (Cr) filler adsorption tube is a gas adsorption outlet end and a thermal desorption purge gas inlet end, the gas adsorption and thermal desorption gas flow directions are opposite, a metal tubular shell sequentially comprises a metal plug mesh, quartz cotton, MIL-101 (Cr) filler, quartz cotton, a metal plug mesh and a G-shaped buckle from the gas adsorption inlet end to the gas outlet end;
The benzene series and the chlorinated volatile organic compounds are a mixture of 1, 1-dichloroethane, cis-1, 2-dichloroethylene, trichloroethylene, toluene, chlorobenzene, ethylbenzene, m, p-xylene, o-xylene, 1,3, 5-trimethylbenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1,2, 4-trichlorobenzene and hexachloroprene;
The preparation method of MIL-101 (Cr) comprises the following steps: 2.5mmol of terephthalic acid and 2.5mmol of Cr (NO 3)2·9H2 O and 32 mu L of hydrofluoric acid) are respectively taken and added into 15-20 mL of water, the mixture is stirred at room temperature and is transferred into a reaction kettle after ultrasonic treatment, the reaction is carried out for 8-10 h at 220 ℃ in a high-temperature oven, the mixed solution is taken out after the reaction is finished, hot water and methanol are used for repeatedly cleaning, finally, the green precipitate is centrifugally collected, 10-15 mL of DMF is added into the precipitate, the mixture is heated and stirred at 80 ℃ for 1h, the precipitate is centrifugally recovered again, 10-15 mL of methanol is added into the precipitate, the mixture is heated and refluxed for 1h, the precipitate is centrifugally recovered after cooling, 10-15 mL of water is added into the precipitate, the mixture is heated and refluxed for 1h, the precipitate is recovered again after cooling, and finally, the precipitate is dried in vacuum to obtain the green powder of MIL-101 (Cr).
2. The MIL-101 (Cr) packing adsorption tube for detecting benzene series and chlorinated volatile organic compounds according to claim 1, wherein the distance between the metal plug nets fixed at the two ends inside the metal tubular shell is controlled to be 4.5-5.5 cm, and the metal plug nets fixed at the gas adsorption inlet end are propped against the groove line of the shell.
3. The MIL-101 (Cr) packing adsorption tube for benzene series and chlorinated volatile organic compound detection as claimed in claim 1, wherein the metal tubular shell is 1/4 inch in diameter by 3.5 inches in length, and the mass of the internally filled MIL-101 (Cr) metal organic framework packing is 70-170 mg; the mass of the quartz cotton filled at one side inside is 10-20 mg.
4. A method for detecting benzene series and chlorinated volatile organic compounds, which is characterized in that the MIL-101 (Cr) filler adsorption tube as claimed in any one of claims 1-3 is used for carrying out adsorption and thermal desorption of benzene series and chlorinated volatile organic compounds, then the detection is carried out by combining with gas chromatography mass spectrometry, and the MIL-101 (Cr) filler adsorption tube is subjected to aging pretreatment for more than 50 minutes before use.
5. The method for detecting benzene series and chlorinated volatile organic compounds as set forth in claim 4, wherein the aging step is as follows: high-purity nitrogen is introduced from the inlet end of the thermal desorption purge gas to carry out thermal desorption, and the thermal desorption temperature is 300 ℃.
6. The method for detecting benzene series and chlorinated volatile organic compounds as set forth in claim 4, wherein the step of adsorbing mainly comprises the steps of injecting standard working fluid into the adsorption tube, and maintaining the adsorption tube on a high-purity nitrogen flow purging device for 3min to obtain the adsorbed adsorption tube.
7. The method for detecting benzene series and chlorinated volatile organic compounds as claimed in claim 4, wherein the thermal desorption conditions mainly comprise a primary desorption temperature of 300 ℃ and a desorption time of 10min; the secondary desorption temperature is 300 ℃ and the desorption time is 3min; the cold trap temperature was-25 ℃.
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