CN115479880A - Method for measuring permeability coefficient of high-density polyethylene film in process of blocking volatile organic compounds - Google Patents
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 96
- 229920006262 high density polyethylene film Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000035699 permeability Effects 0.000 title claims abstract description 39
- 230000000903 blocking effect Effects 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title abstract description 5
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 18
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 15
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 230000000149 penetrating effect Effects 0.000 claims description 10
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- 238000001514 detection method Methods 0.000 claims description 2
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Abstract
The invention provides a method for measuring a permeability coefficient of a high-density polyethylene (HDPE) film in the process of blocking volatile organic compounds, belonging to the technical field of risk management and control evaluation of organic pollution sites. The invention provides a method for measuring the permeability coefficient of a high-density polyethylene film blocking volatile organic compound based on a high-density polyethylene film blocking simulation device and a GC-MS test, which is based on the fact that the existing method for measuring the permeability coefficient and the permeability of the high-density polyethylene film is only suitable for measuring water vapor or single volatile organic compound and cannot simultaneously measure various volatile organic compounds. The method is high in innovation and wide in application, can be used for simultaneously measuring the permeability coefficient of various volatile organic compounds permeating the high-density polyethylene film, and provides technical reference for screening and evaluating the HDPE film barrier repair technology of the organic pollution site.
Description
Technical Field
The invention belongs to the technical field of risk management and control evaluation of organic pollution sites, and particularly relates to a method for determining a permeability coefficient of a high-density polyethylene film for blocking volatile organic compounds in an organic pollution site.
Background
Volatile Organic Compounds (VOCs) are easily inhaled by the human body through the air, and when reaching a certain amount, serious consequences such as damage to the liver, kidney, brain and nervous system of the human body can be caused. Therefore, blocking the volatile organic exposure pathway by risk management techniques is critical. The barrier landfill technology is one of main risk management and control technologies, wherein a way of blocking migration and diffusion of pollutants in soil is achieved by laying a barrier layer, so that the polluted soil is isolated from the surrounding environment, the pollutants are prevented from contacting with a human body and being harmful to the human body and the surrounding environment along with precipitation or underground water migration. The barrier landfill technology has been developed for over ten years and applied to nearly thousands of projects in China due to the advantages of short treatment period and low treatment cost. Methods of blocking volatile organic exposure pathways include laying a barrier layer, foam covering, and the like.
High Density Polyethylene (HDPE) films are a common barrier material. The HDPE film and the soil cushion layer form a composite liner which is commonly used in organic pollution sites and organic and heavy metal composite pollution sites. However, the literature (Edil T. B. A review of aqueous-phase VOC transport in modified fiber lines [ J ]. Waste Management,2003,23 (7): 561-571. And Von Shih, pengming, chen long, et al. One-dimensional transient diffusion-convection transport laws of contaminants in composite gaskets [ J ]. Report on geotechnical engineering, 2022,44 (5): 799-809.) suggests that VOCs can pass through HDPE membranes at a faster rate. Therefore, it is important to study the effect of VOCs on permeating HDPE films.
The method for testing the permeability of the plastic film and the sheet comprises a cup weight increasing and decreasing method, an electrolytic sensor method, an infrared detector method, a humidity sensor method and a pressure difference method. The cup weight increasing and reducing method utilizes the water vapor pressure difference at two sides of the membrane to test the mass of water vapor penetrating through the sample in the moisture permeable cup for a certain time, so as to calculate the water vapor transmission amount and the water vapor transmission coefficient. Wherein, the weight increasing method, namely the whole mass of the moisture permeable cup is gradually increased, and the weight decreasing method, namely the whole mass of the moisture permeable cup is gradually decreased. In the electrolytic sensor method, water vapor penetrates through a sample from a wet cavity to enter a dry cavity, is carried into an electrolytic cell by carrier gas, is quantitatively absorbed by phosphorus pentoxide on the surface of an electrode and is electrolyzed into oxygen and hydrogen, and the water vapor transmission rate is calculated according to the numerical value of electrolytic current. In the infrared detector method, water vapor penetrates through a sample from a high-humidity cavity to enter a low-humidity cavity, is carried to an infrared detector by carrier gas to generate an electric signal, and the water vapor transmission rate of the sample is calculated according to the output electric signal. In the humidity sensor method, water vapor permeates a sample from a high humidity chamber having saturated water vapor into a low humidity chamber, the relative humidity and permeation time of the low humidity chamber are measured by a humidity sensor, and the water vapor transmittance of the sample is calculated. At present, a cup-type weight increasing and reducing method, an electrolytic sensor method, an infrared detector method and a humidity sensor method are only suitable for measuring and calculating the permeability coefficient or the transmittance of water vapor penetrating through an HDPE film, and the permeability coefficient of volatile organic compounds penetrating through the HDPE film cannot be measured.
In the differential pressure method, the sample divides the reaction chamber into two parts, one of which is filled with 10 5 pa as high pressure chamber, and vacuum pump to pump the other part of air to near zero value as low pressure chamber. The pressure change is respectively measured by pressure measuring devices connected with the two sides of the high-pressure chamber and the low-pressure chamber, and the permeation time is recorded, so that the gas permeation amount and the gas permeation coefficient can be calculated. The pressure difference method is used for measuring the gas permeability and the gas permeability coefficient of the test gas by utilizing the pressure difference between a high-pressure chamber and a low-pressure chamber filled with the test gas, and can be used for volatile organic compounds. However, the differential pressure method requires a professional permeameter for testing, and the method has strong specialization and narrow adaptability, and each test is only suitable for measuring the gas permeability and the permeability coefficient of one gas.
The invention provides a method for measuring the permeability coefficient of volatile organic compounds blocked by a high-density polyethylene film based on a high-density polyethylene film blocking simulation device and a GC-MS test. The determination method comprises a high-density polyethylene film barrier simulation device and GC-MS test equipment. The high-density polyethylene film barrier simulation device is composed of two reactors, volatile organic compound mixed solution is added into a No. 1 reactor and sealed by an HDPE film, the sealed No. 1 reactor is placed into a No. 2 reactor to be kept at a constant temperature, so that volatile organic compounds are vaporized and permeate the HDPE film through molecular diffusion to enter the No. 2 reactor. And measuring the mass of the volatile organic compounds in the reactor by adopting gas chromatography-mass spectrometry, and calculating the permeability coefficient. The method is strong in innovation and wide in application, can be used for simultaneously measuring the permeability coefficient of various volatile organic compounds permeating the HDPE film, and provides technical reference for screening and evaluating the HDPE film barrier repair technology of the organic pollution site.
Disclosure of Invention
The invention aims to provide a method for measuring the permeability coefficient of a high-density polyethylene film in the process of blocking volatile organic compounds.
The technical scheme of the invention is as follows:
a method for measuring the permeability coefficient of a high-density polyethylene film in the process of blocking volatile organic compounds comprises the steps of adding a volatile organic compound mixed solution into a reactor No. 1, sealing the reactor No. 1 with an HDPE film blocking layer, placing the sealed reactor No. 2 into a reactor No. 2 for standing at a constant temperature, gasifying the volatile organic compounds, penetrating the HDPE film into the reactor No. 2 through molecular diffusion, measuring the mass of the volatile organic compounds in the reactor No. 2 through gas chromatography-mass spectrometry, and calculating the permeability coefficient; the method comprises the following specific steps:
s1: establishing a device for permeating the HDPE film with the volatile organic compounds;
s11: selecting a No. 1 reactor, adding an HDPE film barrier layer to the No. 1 reactor, adding a proper amount of volatile organic solution into the No. 1 reactor, and sealing;
s12: selecting a No. 2 reactor, vertically placing a No. 1 reactor into a No. 2 reactor, sealing the No. 2 reactor, and standing for a period of time to measure the quality of volatile organic compounds in the No. 2 reactor;
during the standing period, the volatile organic compounds in the reactor No. 1 are converted into gas from liquid, and finally reach a gas-liquid equilibrium state in the reactor No. 1; meanwhile, volatile organic compounds in the air of the reactor No. 1 enter the reactor No. 2 through the HDPE membrane by molecular diffusion and permeation; selecting a time period for uniformly increasing the mass of the volatile organic compounds in the No. 2 reactor after the volatile organic compounds in the No. 1 reactor reach a gas-liquid equilibrium state in the No. 2 reactor measuring time period;
s2: measuring the quality of the barrier layer of the volatile organic matter permeation HDPE film;
s21: measuring the mass of volatile organic compounds entering the No. 2 reactor through the HDPE membrane barrier layer of the No. 1 reactor by gas chromatography-mass spectrometry;
s211: setting test parameters according to a chromatographic-mass spectrum related detection standard of the volatile organic phase;
s212: measuring the mass delta m of the volatile organic compounds which penetrate through the HDPE film barrier layer and enter the No. 2 reactor in different time periods according to the determined test parameters and the standard curve;
s3: calculating the permeability coefficient of the volatile organic compound permeating the HDPE film barrier layer;
s31: measuring and calculating the area A of the HDPE membrane barrier layer for penetrating organic matters, and recording the penetration time t;
s32: respectively calculating the partial pressure of pollutants in the reactor No. 1 and the reactor No. 2 according to the mass of the volatile organic compounds penetrating the HDPE film barrier layer and entering the reactor No. 2, and calculating the pressure difference delta p;
s321: partial pressure p of volatile organic compounds in reactor No. 1 1 Measurement and calculation: replacing an HDPE film barrier layer in the bottle cap of the No. 1 reactor with an impermeable silica gel gasket with excellent sealability to ensure that volatile organic compounds in the No. 1 reactor reach gas-liquid balance, namely the concentration in a gas phase is not increased any more; measuring the amount of volatile organic substances in the gas phase of the reactor No. 1 after the balance, and calculating the partial pressure p of various volatile organic substances 1 ；
S322: partial pressure p of volatile organic compounds in reactor No. 2 2 Measurement and calculation: according to the amount of the volatile organic compounds in the reactor No. 2, calculating the partial pressure p of various volatile organic compounds in the reactor No. 2 according to the formula (2) 2 ；
Calculating the formula: P.V = n.R.T (2)
Wherein, P is the partial pressure P of the volatile organic compounds in the No. 2 reactor 2 Unit pa; v is the volume of the No. 2 reactor minus the No. 1 reactor in m 3 (ii) a n is the amount of volatile organic compounds in the reactor No. 2 and the unit mol; r is the molar gas constant, unit JV (mol. K); t is the temperature during standing in K;
s33: according to the mass of the volatile organic compounds, delta m, unit g, the area A of the HDPE film permeating the organic compounds, unit m 2 The reaction time t, the unit h, the pressure difference Δ p, the unit pa, the permeability coefficient Pv, the unit g/(m) is calculated according to the formula (1) 2 ·h·pa)；
Calculating the formula:
selecting a glass bottle with the volume of 1-5mL and an open cover from the reactor No. 1, and cutting the HDPE film into a size suitable for the bottle cover; and (3) plugging the cut HDPE film into the bottle cap of the No. 1 reactor, and enhancing the sealing property of the HDPE film through a silica gel ring.
The No. 2 reactor is a glass bottle with a 20-40mL capacity and a cover, and the sealed No. 1 reactor is vertically placed upwards in the No. 2 reactor.
The invention has the beneficial effects that: adding a volatile organic compound mixed solution into a reactor No. 1, sealing the reactor No. 1 by using an HDPE (high-density polyethylene) membrane, placing the sealed reactor No. 1 into a reactor No. 2, standing the reactor at a constant temperature to vaporize volatile organic compounds, penetrating the HDPE membrane into the reactor No. 2 through molecular diffusion, and calculating the permeability coefficient by using a method for measuring the mass of the volatile organic compounds in the reactor through gas chromatography-mass spectrometry. The method is widely applicable, and can be used for simultaneously measuring the permeability coefficients of the HDPE films permeated by various volatile organic compounds. The permeability coefficient of the volatile organic compounds determined by the method can provide reference for the barrier effect of an organic pollution site when a high-density polyethylene film is used as a barrier material.
Drawings
FIG. 1 is a schematic diagram of an experiment.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Determination of permeability coefficients of 23 volatile organic compounds in basic project of soil environment quality construction land soil pollution risk control standard
S1: establishing a device for permeating the HDPE film with the volatile organic compounds;
in step S1, the method for establishing the device for penetrating the HDPE film with the volatile organic compound includes the following steps:
s11: selecting a reactor No. 1, adding a high-density polyethylene film barrier layer to the reactor No. 1, adding a volatile organic solution into the reactor No. 1, and sealing;
s111, selecting a chromatographic vial with the volume of 1.5mL as a No. 1 reactor, and cutting a high-density polyethylene film with the thickness of 0.5mm into a size suitable for a bottle cap. Measuring the inner diameter of the bottle cap of the chromatographic vial to be 0.88cm and the diameter of the opening of the bottle cap to be 0.66cm by using a vernier caliper;
and S112, plugging the cut high-density polyethylene film into the bottle cap of the No. 1 reactor, enhancing the sealing property of the bottle cap through a silica gel pad, and sequentially arranging the bottle cap, the silica gel ring and the high-density polyethylene film from top to bottom. Wherein, the thickness of the annular silica gel pad is 0.5mm, the diameter of the outer ring is 0.88cm, and the diameter of the inner ring is 0.66cm;
s113, selecting 23 volatile organic compounds in the basic project of soil environment quality construction land soil pollution risk control standard GB 36600-2018. Preparing a volatile organic compound standard mixed solution with the concentration of 200 mu g/mL and the solvent of methanol. 100 μ L of the standard mix solution was added to a 1.5mL chromatography vial.
S12: selecting a No. 2 reactor, putting a No. 1 reactor into the No. 2 reactor, sealing the No. 2 reactor, and standing for a period of time;
s121, selecting a purging trap bottle with the volume of 40mL as a No. 2 reactor, vertically and upwards placing the sealed No. 1 reactor into the No. 2 reactor, sealing, and placing the reactor in a 30 ℃ artificial climate box for standing.
S2: measuring the quality of the HDPE film permeated by the volatile organic compounds;
s21: the mass of volatile organic compounds that penetrated through the HDPE membrane barrier layer of reactor No. 1 into reactor No. 2 was determined by gas chromatography-mass spectrometry.
S211: setting test parameters according to the characteristics of the 23 volatile organic compounds and headspace/gas chromatography-mass spectrometry HJ 642-2013 for measuring the volatile organic compounds of the soil and the sediments;
s212: and measuring the mass delta m of the volatile organic compounds which penetrate through the HDPE membrane barrier layer and enter the No. 2 reactor within the penetration time of 1h-188h according to the determined test parameters, wherein the unit g is 8 time points between 21h-188 h.
In this experiment, Δ m is the interval in which the mass increases uniformly. After standing for 21h, the gas phase-liquid phase in the reactor No. 1 reaches the equilibrium, and the mass of volatile organic compounds in the reactor No. 2 does not increase uniformly any more at 188 h. A linear fit was made to the 8 time points sampled to ensure a uniform increase in quality across this interval.
And S3, calculating the permeability coefficient of the volatile organic compound permeating the HDPE film.
S31 measurement and calculation of the organic permeation area A of the HDPE Membrane to 3.42 x 10 -5 m 2 (ii) a Recording the reaction time t in units of h;
s32, respectively calculating the pressure of pollutants in the reactor No. 1 and the reactor No. 2 according to the mass of the volatile organic compounds entering the reactor No. 2 through the permeation HDPE film barrier layer, and calculating the pressure difference delta p, unit pa;
s321, pressure p in membrane 1 Measurement and calculation: replacing a high-density polyethylene film and a silica gel ring in the bottle cap of the No. 1 reactor with an impermeable silica gel gasket with excellent sealability, and balancing for a period of time at 30 ℃ to ensure that volatile organic compounds in a chromatographic small bottle reach gas-liquid phase balance. In the experiment, an equilibrium state was reached already at 21 h. And (3) quickly injecting 200 mul of gas into a sample inlet of the gas chromatograph by using a 250 mul manual sample injection needle to measure the quality of the volatile organic compounds. The partial pressure p of various volatile organic compounds in the No. 1 reactor is calculated according to the formula (2) and the mass 1 。
Calculating the formula: P.V = n.R.T (2)
Wherein, P is the partial pressure P of the volatile organic compounds in the No. 1 reactor 1 (unit: pa), V is the volume of reactor No. 1, 0.0015m 3 N is the amount of volatile organic compounds in reactor No. 1 (unit: mol), R is the molar gas constant, 8.31J/(mol. K), T is the temperature during standing, 303.15K.
S322: pressure p outside the membrane 2 And (3) calculating: calculating the partial pressure p of various volatile organic compounds in the No. 2 reactor according to the formula (2) according to the mass of the volatile organic compounds in the No. 2 reactor 2 。
S33, calculating a permeability coefficient Pv according to the formula (1) according to the mass Deltam of the volatile organic compounds, the area A of the HDPE membrane permeating the organic compounds, the reaction time t and the pressure difference Deltap, wherein the unit is g/(m) 2 ·h·pa)。
Calculating the formula:
and calculating the permeability coefficient Pv. The product of the area A of the high-density polyethylene film for permeating organic matters, permeation time t and pressure difference delta p between the inside and the outside of the film is used as an abscissa, the mass m is used as an ordinate, origin is used for linear fitting, and the intercept is set to be 0. And the slope obtained by fitting is the permeability coefficient Pv. Permeability coefficient and R of 23 kinds of VOCs 2 The values are given in table 1 below.
TABLE 1 permeability coefficients (in g/(m) for 23 VOCs 2 H pa)) and R 2 Value of
Claims (3)
1. A method for measuring the permeability coefficient of a high-density polyethylene film when volatile organic compounds are blocked is characterized in that a volatile organic compound mixed solution is added into a No. 1 reactor and sealed by a high-density polyethylene HDPE film blocking layer, the sealed No. 1 reactor is placed into a No. 2 reactor to be kept at a constant temperature, the volatile organic compounds are gasified and permeate the HDPE film through molecular diffusion to enter the No. 2 reactor, and the permeability coefficient is calculated through a method for measuring the amount of the volatile organic compounds in the No. 2 reactor through gas chromatography-mass spectrometry; the method comprises the following specific steps:
s1: establishing a device for permeating the HDPE film with the volatile organic compounds;
s11: selecting a reactor No. 1, adding an HDPE film barrier layer to the reactor No. 1, adding a proper amount of volatile organic solution into the reactor No. 1, and sealing;
s12: selecting a No. 2 reactor, vertically placing a No. 1 reactor into a No. 2 reactor, sealing the No. 2 reactor, and standing for a period of time to measure the quality of volatile organic compounds in the No. 2 reactor;
during the standing period, the volatile organic compounds in the reactor No. 1 are converted into gas from liquid, and finally reach a gas-liquid equilibrium state in the reactor No. 1; meanwhile, volatile organic compounds in the air of the No. 1 reactor enter the No. 2 reactor through the HDPE membrane by molecular diffusion and permeation; selecting a time period for uniformly increasing the mass of the volatile organic compounds in the No. 2 reactor after the volatile organic compounds in the No. 1 reactor reach a gas-liquid equilibrium state in the No. 2 reactor measuring time period;
s2: measuring the quality of the barrier layer of the volatile organic matter permeating HDPE film;
s21: measuring the mass of volatile organic compounds entering the No. 2 reactor through the HDPE film barrier layer of the No. 1 reactor by gas chromatography-mass spectrometry;
s211: setting testing parameters according to a gas chromatography-mass spectrometry detection standard of the volatile organic compounds;
s212: measuring the mass delta m of the volatile organic compounds which penetrate through the HDPE film barrier layer and enter the No. 2 reactor in different time periods according to the determined test parameters and the standard curve;
s3: calculating the permeability coefficient of the volatile organic matter permeation HDPE film barrier layer;
s31: measuring and calculating the area A of the HDPE membrane barrier layer for penetrating organic matters, and recording the penetration time t;
s32: respectively calculating the partial pressure of pollutants in the reactor No. 1 and the reactor No. 2 according to the mass of the volatile organic compounds penetrating the HDPE film barrier layer and entering the reactor No. 2, and calculating the pressure difference delta p;
s321: partial pressure p of volatile organic compounds in reactor No. 1 1 Measurement and calculation: replacing an HDPE film barrier layer in the bottle cap of the No. 1 reactor with an impermeable silica gel-polytetrafluoroethylene composite gasket with excellent sealability, so that volatile organic compounds in the No. 1 reactor reach gas-liquid balance, namely the concentration in a gas phase is not increased any more; measuring the amount of volatile organic compounds in the gas phase of the reactor No. 1 after the balance, and calculating the components of various volatile organic compoundsPressure p 1 ；
S322: partial pressure p of volatile organic compounds in No. 2 reactor 2 Measurement and calculation: according to the amount of the volatile organic compounds in the No. 2 reactor, the partial pressure p of various volatile organic compounds in the No. 2 reactor is calculated according to the formula (2) 2 ；
Calculating the formula: P.V = n.R.T (2)
Wherein, P is the partial pressure P of the volatile organic compounds in the No. 2 reactor 2 The unit pa; v is the volume of the No. 2 reactor minus the No. 1 reactor in m 3 (ii) a n is the amount of volatile organic compounds in the No. 2 reactor and the unit mol is; r is a molar gas constant and has the unit J/(mol.K); t is the temperature during standing in K;
s33: according to the mass Delta m of the volatile organic compounds, unit g, the area A of the HDPE film permeating the organic compounds, unit m 2 The permeability coefficient Pv is calculated according to the formula (1) by the reaction time t, the unit h, the pressure difference delta p and the unit pa, and the unit g/(m) is 2 ·h·pa)；
Calculating the formula:
2. the method for determining the permeability coefficient of the high-density polyethylene film for blocking volatile organic compounds according to claim 1, wherein the No. 1 reactor is a glass bottle with a volume of 1-5mL and an open cover, and the HDPE film is cut into a size suitable for a bottle cap; and (3) putting the cut HDPE film into the open bottle cap of the No. 1 reactor, and enhancing the sealing property of the HDPE film through a silica gel ring.
3. The method for determining the permeability coefficient of the high-density polyethylene film for blocking the volatile organic compounds according to claim 1, wherein the No. 2 reactor is a glass bottle with a capacity of 20-40mL and a good-sealing cover, and the sealed No. 1 reactor is vertically placed upwards in the No. 2 reactor.
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