CN107560926B - Underwater VOCs purging and trapping device and purging and trapping method using same - Google Patents
Underwater VOCs purging and trapping device and purging and trapping method using same Download PDFInfo
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Abstract
The invention discloses a device for sweeping and trapping VOCs (volatile organic compounds) in water and a sweeping and trapping method using the device, wherein the device comprises a mixed carrier gas inlet, a sweeping pipe, a pure carrier gas inlet, a dehydration device, a cyclone separator and an enrichment separation device; the mixed carrier gas inlet is connected with one end of the purging pipe, and the other end of the purging pipe is connected with the water sample inlet and outlet and the purging gas outlet and is connected with the pure carrier gas inlet and the dehydration device through the three-way valve; the cyclone separator is arranged between the dehydration device and the enrichment separation device, and the tail end of the enrichment separation device is connected with a detector. The purging and trapping device can improve the purging and trapping efficiency, reduce the consumption of carrier gas and shorten the time. Purging is performed through the mixed gas, so that the mass transfer speed of the VOCs between liquid and gas is increased, the purging and trapping rate of the VOCs in water is increased, the detection limit of the VOCs is improved, the evaporation capacity of water vapor can be reduced, and the water removal, the trapping and the detection in the next step are facilitated.
Description
Technical Field
The invention belongs to the field of analytical instruments, and particularly relates to a device for sweeping and trapping VOCs in water and a sweeping and trapping method using the device.
Background
Pollution from Volatile Organic Compounds (VOCs) in the environment has attracted increasing attention, and in fact, many of these VOCs are toxic or carcinogenic and pose a significant hazard to the ecosystem and even to humans. The major sources of pollution of VOCs in water are widespread, such as industrial emissions, municipal water, and accidental leaks, and VOCs are present in many products and processes (e.g., paints, fuels, petroleum products, raw materials, solvents, etc.), which makes it difficult to control such pollution. The pollution of VOCs in groundwater is particularly serious due to the influence of discharge and leakage of sewage treatment plants. The content of volatile organic compounds in the environmental water is low, direct measurement of the volatile organic compounds is extremely difficult, and a proper sample pretreatment method needs to be selected for separation and enrichment, so that the detection limit of an analytical instrument is reached.
The purging and trapping technology is widely applied, and is commonly used for measuring volatile and semi-volatile organic compounds in water, soil and atmosphere after being combined with chromatographic separation and mass spectrometry detection. The purging and trapping method has the advantages of high enrichment efficiency, small pollution, simplicity and convenience in operation and the like, is widely applied to analysis of VOCs in environmental water bodies, is a recommended standard method of the United states environmental protection agency (US-EPA), but most of the purging and trapping instruments are imported abroad at present, and mature instruments are not available at home. The instruments imported from foreign countries are expensive and the use cost is high.
The principle of the purging and trapping method is that a water sample or a soil sample in a chamber is purged by using high-purity nitrogen or helium gas, volatile gas dissolved in the soil or the water is purged out and is enriched into a trapping pipe filled with active filler, and trapping can be carried out at normal temperature or low temperature. After purging is finished, the collecting pipe is heated instantly, and the collected gas sample to be analyzed is analyzed and enters an instrument and a detector for measurement.
In the prior art, pure carrier gas is used for sweeping and trapping, such as nitrogen, helium and the like, and is influenced by the properties of the gas, so that the mass transfer rate of bubbles and liquid is influenced, and the difficulty is increased for later-stage dehydration.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a device for sweeping and trapping VOCs in water. The mixed carrier gas is used for sweeping and trapping, so that the mass transfer speed between gas and liquid can be effectively improved, the sweeping and trapping time and the consumption of the carrier gas are reduced, and the sweeping and trapping rate of VOCs in water is increased.
The invention also provides a sweeping and trapping method using the device for sweeping and trapping the VOCs in the water.
The technical scheme is as follows: in order to achieve the purpose, the device for sweeping and trapping the VOCs in the water comprises a mixed carrier gas inlet, a sweeping pipe, a pure carrier gas inlet, a dehydration device, a cyclone separator and an enrichment separation device; the mixed carrier gas inlet is connected with one end of the purging pipe, and the other end of the purging pipe is connected with the water sample inlet and outlet and the purging gas outlet and is connected with the pure carrier gas inlet and the dehydration device through the three-way valve; the cyclone separator is arranged between the dehydration device and the enrichment separation device, and the tail end of the enrichment separation device is connected with a detector.
Wherein, the mixed carrier gas inlet is connected with the purging pipe through a first two-way valve. The gas inlet section of the purging pipe is connected with a first two-way valve, and the purging pipe can be switched to pure inert carrier gas through the valve.
Wherein the mixed carrier gas is the mixture of inorganic inert gas and water-insoluble nonpolar organic gas; the melting point of the nonpolar organic gas is-5-20 ℃, and the nonpolar organic gas accounts for 0.01-1% of the volume of the mixed gas. Such as nitrogen or helium, and non-polar organic gas such as tetradecane, pentadecane, cyclohexane, etc., which are insoluble in water; and the mass transfer speed of the VOCs between the liquid and the gas is improved through the mixed gas.
Preferably, the purging pipe is provided with a purging section, and the outer wall of the purging section is fixed with an ultrasonic generator. The frequency range of the ultrasonic sounder is 20 Khz-500 MHz.
Further, the ultrasonic generator is vertically fixed on the outer wall of the blowing section and does not exceed one third of the circumference of the blowing section. And the space between the ultrasonic generator and the outer wall of the blowing section is filled with silica gel. The outer wall of the purging section can vertically fix a plurality of ultrasonic generators, but the outer wall does not exceed one third of the circumference of the purging section, so that the phenomenon that the ultrasonic generators are not tightly attached to the purging section is avoided, and the ultrasonic transmission efficiency is reduced.
Wherein the purge section and ultrasonic sound generator are encased by a heater. The heating temperature does not exceed 60 c and is as low as possible so that the amount of water evaporated is not too great. An ultrasonic device is added on one side of the purging section, and the mass transfer speed between bubbles and liquid is increased through the ultrasonic effect, so that the consumption of carrier gas is reduced, meanwhile, the heating device can achieve a good auxiliary purging effect without high heating temperature, and the evaporation capacity of water vapor can be reduced under the same purging efficiency.
Preferably, the purging pipe is a U-shaped pipe, the bubble generator is arranged in the U-shaped pipe and located at the bottom end of the purging section, and the bubble generator comprises a porous glass plate. The bubble generator comprises a porous material, preferably a glass porous plate, bubbles with certain characteristic diameters are generated through the porous material, the characteristic diameters of the bubbles are adjusted by adjusting the ventilation flow rate of the purging pipe, the smaller the bubbles are, the larger the relative gas-liquid surface area is, and the mass transfer effect can be improved.
And the cyclone separator is connected with the enrichment separation device through a second two-way valve and a third two-way valve.
Preferably, a semiconductor refrigerator is arranged outside the cyclone separator.
The invention discloses a sweeping and trapping method by using a device for sweeping and trapping VOCs (volatile organic compounds) in water, which comprises the following steps of:
(1) adding a water sample to be detected through a water sample inlet and a water sample outlet, heating by using a purging pipe, purging the water sample by introducing mixed carrier gas, and performing ultrasonic assisted purging;
(2) drying the mixed water vapor after purging, feeding the dried carrier gas into a cyclone separator for cyclone low-temperature separation, and then feeding the carrier gas into an enrichment separation device;
(3) after purging is finished, introducing pure inorganic carrier gas to push all gas in a system pipeline to enter an enrichment separation device and carry out detection;
(4) heating the cyclone separator to vaporize, introducing pure inorganic carrier gas, pushing the vaporized gas into an enrichment separation device to perform enrichment separation and detect.
Further, the cyclone low-temperature separation in the step (2) needs to be cooled to a temperature below the liquefaction temperature of the organic gas in the mixed carrier gas, so that the organic gas is condensed into liquid and solid.
The working principle is as follows: a water sample to be detected is added through a water sample inlet and a water sample outlet, the purging pipe is heated to a preset temperature through the heater, the first two-way valve is opened, organic and inorganic mixed gas is introduced into the mixed carrier gas inlet, such as nitrogen or helium and water-insoluble non-polar organic gas such as tetradecane, pentadecane and cyclohexane is mixed, the melting point of the non-polar organic gas is-5-20 ℃, and the non-polar organic gas accounts for 0.01-1% of the volume of the mixed gas. Purging a water sample, adjusting the flow rate, enabling mixed gas to pass through a porous glass plate bubble generator to generate proper bubbles and bubble quantity, simultaneously opening an ultrasonic generator to start ultrasonic assisted purging, sending the mixed water vapor to a dehydration device for drying through a three-way valve after purging, opening a second two-way valve, closing a third two-way valve, enabling the dried carrier gas to enter a carrier gas inlet of a cyclone separator for cyclone low-temperature separation, cooling the cyclone separator to be below the liquefaction temperature of organic gas through a semiconductor refrigerator arranged on the outer side, enabling the organic gas to be condensed into liquid and solid, realizing separation in the cyclone separator, and enabling the gas to pass through a first gas outlet of the separator and then enter an enrichment separation device. And after purging is finished, stopping purging, switching the three-way valve to a pure carrier gas inlet to introduce pure inorganic carrier gas, such as nitrogen or helium, and pushing all gas in a system pipeline to enter the enrichment separation device for detection. And then closing the second two-way valve, opening the third two-way valve, heating the cyclone separator to 20 ℃, so that the condensed organic matters are completely vaporized, switching to a pure carrier gas inlet through a three-way valve, introducing pure inorganic carrier gas, pushing the vaporized gas into an enrichment separation device through a second gas outlet of the separator, carrying out enrichment separation, and detecting through a detector.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the volatile organic compound purging and trapping device is reasonable in structure and simple in arrangement, purging and trapping efficiency can be effectively improved, instrument sensitivity is improved, consumption of carrier gas is reduced, and time is shortened. Purging is carried out through the mixed gas, so that the mass transfer speed of the VOCs between liquid and gas is improved; increase the entrapment rate that sweeps to aquatic VOCs, improve VOCs's detection limit, reduce the consumption of carrier gas, shorten and sweep the entrapment time, later isolate the organic matter that adds through low temperature cyclone separator, remaining gas is getting into the collection pipe to realize high-efficient entrapment. Meanwhile, the ultrasonic device is arranged on the purging pipe, the heating device can achieve a good auxiliary purging effect without high heating temperature, the evaporation capacity of water vapor can be reduced under the same purging efficiency, and the next step of dehydration, trapping and detection is facilitated.
Drawings
FIG. 1 is a schematic diagram of the configuration of an in-water VOCs purging and trapping device according to the present invention;
FIG. 2 is a schematic structural diagram of a cyclone separation device in the purging and trapping device of the present invention;
fig. 3 is a top view of fig. 2.
Detailed Description
The invention is further illustrated by the following figures and examples.
Examples
As shown in fig. 1-3, a device for purging and trapping VOCs in water comprises a mixed carrier gas inlet 1, a purging pipe 2, a pure carrier gas inlet 3, a dehydration device 4, a cyclone separator 5, and an enrichment and separation device 6; the mixed carrier gas inlet 1 is connected with one end of the purging pipe 2 through a first two-way valve 11, and the other end of the purging pipe 2 is connected with a water sample inlet and outlet 7 and a purging gas outlet 8 and is connected with the pure carrier gas inlet 3 and the dehydration device 4 through a three-way valve 9; the purging pipe 2 is a U-shaped pipe, a purging section 12 is arranged on the U-shaped pipe, an ultrasonic generator 13 is fixed on the outer wall of the purging section 12, the ultrasonic generator 13 can be vertically attached to one side of the outer wall of the purging section 12 in a row or a plurality of rows side by side, and the circumference of the purging section 12 is not more than one third, so that an effective sound field is formed, and the ultrasonic generator 13 and the glass wall of the outer wall of the purging section 12 are tightly filled, such as silica gel and the like, so that air space cannot exist; the frequency and intensity of the ultrasonic generator 13 can be adjusted by the circuit, and the frequency range of the ultrasonic generator 13 is 20 Khz-500 MHz. The purging section 12 and the ultrasonic sound generator 13 are wrapped by the heater 14; the heater 14 also includes a corresponding electrical circuit to heat the water to a temperature not exceeding 60 c to prevent excessive evaporation of the water. A bubble generator 15 is also arranged in the purging pipe 2 and is positioned at the bottom end of the purging section 12, the bubble generator 15 generates bubbles with certain characteristic diameter, and corresponding sound wave frequency is adopted corresponding to the characteristic diameter; the bubble generator 15 includes a porous material such as a porous glass plate or the like, and adjusts the diameter of bubbles and the amount of bubbles by adjusting the flow rate of aeration. The cyclone separator 5 is arranged between the dehydration device 4 and the enrichment separation device 6, the cyclone separator 5 and the enrichment separation device 6 are connected through a second two-way valve 16 and a third two-way valve 17, and a semiconductor refrigerator 18 is arranged on the outer side of the cyclone separator 5; the tail end of the enrichment and separation device 6 is connected with a detector 10.
When the purging and trapping device is used, a water sample to be detected is added through the water sample inlet and outlet 7, the volume of the water sample to be detected is 5ml, and the water sample is 5ug/L o-xylene standard solution; a heater 14 is added to 20 ℃, a first two-way valve 11 is opened, and nitrogen and tetradecane mixed carrier gas accounting for 0.1 percent of the volume of the mixed gas are added into a mixed carrier gas inlet 1, or other inorganic inert gases such as helium and nonpolar organic gases accounting for 0.01 to 1 percent of the volume of the mixed gas such as pentadecane and cyclohexane; adjusting the flow rate to set the gas flow rate at 30ml/min, so that the mixed gas and water sample pass through the porous glass plate of the bubble generator 15 to generate proper bubbles and bubble amount, and simultaneously turning on the ultrasonic generator 13 to start ultrasonic auxiliary purging, ultrasonic frequency combination: 20-50-100kHz, sending the mixed water vapor into the dehydration device 4 for drying through the three-way valve 9 after purging, opening the second two-way valve 16 at the moment, closing the third two-way valve 17, enabling the dried carrier gas to enter a carrier gas inlet 19 of the cyclone separator for cyclone low-temperature separation, and cooling the cyclone separator to be below the liquefaction temperature of the organic gas through a semiconductor refrigerator arranged on the outer side, so that the organic gas is condensed into liquid and solid, and the separation is realized in the cyclone separator. And then enters the enrichment and separation device through a first gas outlet 20 of the separator. And the purging time is 8min, after purging is finished, purging is stopped, the three-way valve 9 is switched to the pure carrier gas inlet 3 to introduce pure inorganic carrier gas such as nitrogen or helium, nitrogen is introduced for 5min, and the flow rate of the carrier gas is 20ml/min, so that all the gas in the system pipeline is pushed to enter the enrichment separation device and is detected. And then closing the second two-way valve 16, opening the third two-way valve 17, heating the cyclone separator to 20 ℃, so that the condensed organic matters are completely vaporized, then passing through the carrier gas of the three-way valve 9, passing through the pure carrier gas inlet 3 and nitrogen for 5min, and passing through the carrier gas flow rate of 20ml/min, pushing the vaporized gas into an enrichment separation device through the second gas outlet 21 of the separator for enrichment separation, and detecting through a detector. The result was a normalized recovery of 95% with a relative standard deviation of 5%.
Claims (6)
1. A device for sweeping and trapping VOCs in water is characterized by comprising a mixed carrier gas inlet (1), a sweeping pipe (2), a pure carrier gas inlet (3), a dehydration device (4), a cyclone separator (5) and an enrichment separation device (6); the mixed carrier gas inlet (1) is connected with one end of the purging pipe (2), and the other end of the purging pipe (2) is connected with a water sample inlet and outlet (7) and a purging gas outlet (8) and is connected with the pure carrier gas inlet (3) and the dewatering device (4) through a three-way valve (9); the cyclone separator (5) is arranged between the dehydration device (4) and the enrichment separation device (6), and the tail end of the enrichment separation device (6) is connected with a detector (10); a section of purging section (12) is arranged on the purging pipe (2), and an ultrasonic generator (13) is fixed on the outer wall of the purging section (12); the purging section (12) and the ultrasonic generator (13) are wrapped by a heater (14); the heating temperature of the heater (14) is not more than 60 ℃; the purging pipe (2) is a U-shaped pipe, a bubble generator (15) is arranged in the U-shaped pipe and is positioned at the bottom end of the purging section (12), and the bubble generator (15) comprises a porous glass plate; the cyclone separator (5) is connected with the enrichment separation device (6) through a second two-way valve (16) and a third two-way valve (17), and a semiconductor refrigerator (18) is arranged on the outer side of the cyclone separator (5).
2. An in-water VOCs purging and trapping device according to claim 1, wherein the mixed carrier gas inlet (1) is connected to the purging pipe (2) through a first two-way valve (11).
3. The in-water VOCs purging and trapping device of claim 1, wherein the mixed carrier gas is an inorganic inert gas mixed with a water-insoluble nonpolar organic gas.
4. The device for sweeping and trapping the VOCs in the water according to claim 3, wherein the non-polar organic gas has a melting point of-5 ℃ to 20 ℃ and accounts for 0.01% to 1% of the volume of the mixed carrier gas.
5. A method for purging and trapping VOCs in water using the apparatus for purging and trapping VOCs in water of claim 1, comprising the steps of:
(1) adding a water sample to be detected through a water sample inlet and a water sample outlet, heating by using a purging pipe, purging the water sample by introducing mixed carrier gas, and performing ultrasonic assisted purging;
(2) drying the mixed water vapor after purging, feeding the dried carrier gas into a cyclone separator for cyclone low-temperature separation, and then feeding the carrier gas into an enrichment separation device;
(3) after purging is finished, introducing pure inorganic carrier gas to push all gas in a system pipeline to enter an enrichment separation device and carry out detection;
(4) heating the cyclone separator to vaporize, introducing pure inorganic carrier gas, pushing the vaporized gas into an enrichment separation device to perform enrichment separation and detect.
6. The purging and trapping method according to claim 5, wherein the cyclone cryogenic separation in step (2) is performed to reduce the temperature below the liquefaction temperature of the organic gas in the mixed carrier gas, so that the organic gas is condensed into liquid and solid.
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| CN108402513A (en) * | 2018-04-26 | 2018-08-17 | 河北中烟工业有限责任公司 | A kind of scavenging conduit for the detection of cigarette purge and trap |
| CN109443893B (en) * | 2018-11-28 | 2021-10-15 | 佛山科学技术学院 | Solid-liquid separation device for treating volatile organic pollutants through photocatalysis |
| CN115343403B (en) * | 2022-08-16 | 2023-05-26 | 生态环境部南京环境科学研究所 | Detection device for benzene series in underground water of typical pesticide contaminated site |
| CN116116035B (en) * | 2023-02-14 | 2023-11-14 | 湖北省智云冷锋环保科技有限公司 | Industrial low-temperature cold trap and temperature control method |
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| CN2601245Y (en) * | 2002-12-09 | 2004-01-28 | 南京大学环境学院 | Means for eliminating volatile pollutant in sewage by supersonic blowing |
| CN1271398C (en) * | 2004-09-24 | 2006-08-23 | 浙江大学 | Concentration method and its device for micro test sample |
| CN101893613B (en) * | 2009-05-20 | 2014-01-08 | 北京东西分析仪器有限公司 | Purge and trap device |
| DE102009045529A1 (en) * | 2009-10-09 | 2011-04-21 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Method and apparatus for removing chloride from volatile organic carbon-containing samples |
| RU2589055C2 (en) * | 2010-12-17 | 2016-07-10 | Юнивейшн Текнолоджиз, Ллк | Systems and methods of extracting hydrocarbons from polyolefin-containing gaseous blowing product |
| CN202061532U (en) * | 2011-03-03 | 2011-12-07 | 国家海洋局第一海洋研究所 | Automatic dehydration separation device |
| CN105758976A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | On-line sample concentrating device and use method thereof |
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