WO2021112011A1 - Échantillonneur de piégeage de composés per- et poly-fluoroalkyle - Google Patents

Échantillonneur de piégeage de composés per- et poly-fluoroalkyle Download PDF

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WO2021112011A1
WO2021112011A1 PCT/JP2020/044306 JP2020044306W WO2021112011A1 WO 2021112011 A1 WO2021112011 A1 WO 2021112011A1 JP 2020044306 W JP2020044306 W JP 2020044306W WO 2021112011 A1 WO2021112011 A1 WO 2021112011A1
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polyfluoroalkyl
activated carbon
compound
volatile
pel
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PCT/JP2020/044306
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English (en)
Japanese (ja)
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山下信義
谷保佐知
▲高▼阪務
横井誠
堀千春
島村紘大
浅野拓也
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フタムラ化学株式会社
国立研究開発法人産業技術総合研究所
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Priority claimed from JP2020193453A external-priority patent/JP2021092557A/ja
Application filed by フタムラ化学株式会社, 国立研究開発法人産業技術総合研究所 filed Critical フタムラ化学株式会社
Publication of WO2021112011A1 publication Critical patent/WO2021112011A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/04—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising inertia
    • B01D45/08—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising inertia by impingement against baffle separators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • 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
    • G01N1/04—Devices for withdrawing samples in the solid state, e.g. by cutting
    • 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

Definitions

  • the present invention relates to a pel and a polyfluoroalkyl compound collection sampler that collects various forms of pel and polyfluoroalkyl compounds present in the atmosphere.
  • the perfluoroalkyl compound has a completely fluorinated linear alkyl group and is a substance represented by the chemical formula (ii).
  • PFOS perfluorooctane sulfonic acid
  • PFOA perfluorooctanoic acid
  • IUPAC name 2,2,3,3,4,5,5,6,6,7,7,8,8,8- Pentadecafluorooctanoic acid
  • a polyfluoroalkyl compound indicates a substance in which a part of hydrogen of an alkyl group is replaced with fluorine, and is a substance represented by the chemical formula (iii). For example, there is fluorotelomer alcohol and the like.
  • a method using a high volume air sampler is known for measuring pel and polyfluoroalkyl compounds in the atmosphere (see, for example, Non-Patent Document 1).
  • a filter paper made of fine fibers such as quartz fiber filter paper is mounted inside a high volume air sampler, the sampler is aerated for a certain period of time, and airborne particles are collected and contained in the airborne particles. Measure the PFOS.
  • the substances collected by aerating through the filter paper are limited to non-volatile ionic compounds such as PFOS and PFOA, which are perfluoroalkyl compounds adsorbed on airborne particles.
  • non-volatile ionic compounds such as PFOS and PFOA
  • perfluoroalkyl compounds adsorbed on airborne particles.
  • Examples of the per and polyfluoroalkyl compounds that cannot be collected by the sampler include volatile compounds. Volatile pel and polyfluoroalkyl compounds cannot be quantitatively measured because they pass through the filter paper.
  • a collection sampler capable of collecting pel and polyfluoroalkyl compounds existing in other forms, such as a volatile polyfluoroalkyl compound that is not contained in airborne particles that cannot be collected by the sampler, has been desired. ..
  • a silica gel-based collecting agent or the like is used as a collecting agent for volatile pel and polyfluoroalkyl compounds.
  • a silica gel-based collecting agent or the like is used as a collecting agent for volatile pel and polyfluoroalkyl compounds.
  • an organic fluorine-based compound adsorbent made of a cyclodextrin polymer has been proposed (Patent Document 1).
  • This adsorbent is not suitable for use as a collector used for quantitative measurement because it specializes only in adsorption and cannot desorb the compound.
  • the cyclodextrin polymer is in the form of powder or fine particles, has poor handling, has high resistance during liquid passage or aeration, and has problems such as a risk of outflow of fine powder to the secondary side.
  • the existing adsorbent cannot sufficiently collect volatile pel and polyfluoroalkyl compounds, and accurate quantitative measurement cannot be performed.
  • the present invention has been made in view of the above points, and is a sampler for collecting pel and polyfluoroalkyl compounds capable of efficiently and comprehensively collecting pel and polyfluoroalkyl compounds existing in the atmosphere in various forms. Is to provide.
  • the first invention is a sampler that collects pels and polyfluoroalkyl compounds in the sample atmosphere, and is connected to an intake portion that sucks the sample atmosphere and the intake portion, and adsorbs particles in the atmosphere.
  • a particle-adsorbing compound collection area provided with an inertial impactor for collecting sex pel and polyfluoroalkyl compounds, and a semi-volatile pel and polyfluoro in the atmosphere connected to the particle-adsorbing compound collection area.
  • a semi-volatile compound collection area provided with a urethane foam filter unit for collecting alkyl compounds and a semi-volatile compound collection area connected to the semi-volatile compound collection area to collect volatile pels and polyfluoroalkyl compounds in the atmosphere.
  • a volatile compound collection area provided with a filter portion made of adsorbed activated carbon having a BET specific surface area of 900 m 2 / g or more, and the atmosphere connected to the volatile compound collection area and ventilated in each area are exhausted.
  • the present invention relates to a pel and polyfluoroalkyl compound collecting sampler, which comprises an exhaust portion.
  • the particle-adsorbing compound collecting area sequentially captures the fine particle-like pel and the polyfluoroalkyl compound in the atmosphere for each of a plurality of particle sizes in descending order of particle size.
  • the present invention relates to a pel and a polyfluoroalkyl compound collecting sampler composed of the inertial impactor portions of a plurality of layers to be collected.
  • the third invention relates to a per and polyfluoroalkyl compound collecting sampler in which the amount of surface oxide of the adsorbed activated carbon is 0.10 meq / g or more in the first or second invention.
  • the fourth invention is the capture of pel and polyfluoroalkyl compounds in which the sum (V mic ) of the micropore volume of 1 nm or less of the adsorbed activated carbon is 0.35 cm 3 / g or more in any of the first to third inventions. Related to the collection sampler.
  • a fifth invention is a per and polyfluoroalkyl compound in which the sum (V met ) of the mesopore volumes of the adsorbed activated carbon at 2 to 60 nm is 0.02 cm 3 / g or more in any one of the first to fourth inventions. Related to the collection sampler.
  • the sixth invention is the sum of the micropore volumes (V mic ) and the mesopore volume sum (V met ) of the adsorbed activated carbon specified in the following formula (i) in the first to fifth inventions.
  • the present invention relates to a sampler for collecting pel and polyfluoroalkyl compounds having a volume difference (V s) of 0.45 or more.
  • the particle-adsorbing compound collection area is a particle of the fine particle pel and polyfluoroalkyl compound in the atmosphere. Since it is composed of the inertial impactor portions of a plurality of layers that sequentially collect each of a plurality of particle sizes in descending order of diameter, fine particle pels and polyfluoroalkyl compounds in the atmosphere are efficiently collected for each arbitrary particle size. can do.
  • the amount of surface oxide of the adsorbed activated carbon is 0.10 meq / g or more, it depends on the pores of the activated carbon. It has not only adsorption performance but also chemical adsorption capacity, and can further improve the adsorption performance of pel and polyfluoroalkyl compounds.
  • the sum (V mic ) of the micropore volumes of 1 nm or less of the adsorbed activated carbon is 0.35 cm 3. Since it is / g or more, the adsorption performance of the pel and the polyfluoroalkyl compound by the pores of the adsorbed activated carbon can be improved.
  • the sum of the mesopore volumes (V met ) of the adsorbed activated carbon at 2 to 60 nm is 0.02 cm. Since it is 3 / g or more, the adsorption performance of the pel and the polyfluoroalkyl compound by the pores of the adsorbed activated carbon can be improved.
  • the sum of the micropore volumes (V) specified in the above formula (i) of the adsorbed activated carbon Since the volume difference (V s ) between mic) and the sum of the mesopore volumes (V met ) is 0.45 or more, the adsorption performance of the pel and polyfluoroalkyl compounds by the pores of the adsorbed activated carbon should be improved. Can be done.
  • FIG. 2 is an enlarged upper view of FIG.
  • FIG. 2 is a top view which shows the shape example of an impactor plate. It is a lower enlarged view of FIG.
  • the purpose of the pel and polyfluoroalkyl compound collection sampler is to comprehensively collect pel and polyfluoroalkyl compounds existing in various forms in the atmosphere.
  • Per and polyfluoroalkyl compounds present in the atmosphere are roughly classified into three types.
  • One is a particle-adsorbing pel and a polyfluoroalkyl compound attached to the surface of fine particles suspended in the atmosphere (for example, dust such as pollen and soil particles), and most of them are ionic compounds.
  • N-EtFOSE N-ethylperfluorooctanesulfonic acid amide ethanol
  • N-MeFOSE N-methylperfluorooctanesulfonic acid amide ethanol
  • Semi-volatile pel and polyfluoroalkyl compounds A semi-volatile organic compound is defined by the World Health Organization (WHO) as a compound having a boiling point of 260 to 380 ° C. It is known that PFOS and PFOA are produced by decomposition of semi-volatile per and polyfluoroalkyl compounds.
  • WHO World Health Organization
  • PFOS and PFOA are produced by decomposition of semi-volatile per and polyfluoroalkyl compounds.
  • N-EtFOSE is a substance represented by the following chemical formula (iv)
  • N-MeFOSE is a substance represented by the chemical formula (v).
  • the third is volatile pels and polyfluoroalkyls that exist as gases in the atmosphere represented by fluorotelomer alcohols (hereinafter referred to as "FTOHs") as shown in the above chemical formula (iii). It is a compound.
  • Volatile organic compounds as defined by the World Health Organization (WHO), are compounds with a boiling point of 50-160 ° C.
  • the pel and polyfluoroalkyl compounds which are the objects of the present invention, are present in the atmosphere mainly in three forms as described above. From this, as shown in FIGS. 1 and 2, the sampler of the present invention is formed by being divided into areas for collecting pel and polyfluoroalkyl compounds for each form.
  • the sampler 10 of the present invention has a particle-adsorbing compound collecting area 20, a semi-volatile compound collecting area 30, and a volatile compound collecting area 40 from the upstream where the sample air is sucked to the downstream where the air is discharged. It is arranged and formed in order.
  • the sample atmosphere is sucked from the intake unit 12 by a suction pump or the like arranged on the downstream side of the sampler, passes through the particle-adsorbing compound collecting area 20 for collecting the particle-adsorbing pel and the polyfluoroalkyl compound, and then passes through the particle-adsorbing compound collecting area 20.
  • the particle-adsorbing compound collection area 20 includes an inertial impactor unit 21 that collects particle-adsorbing pels and polyfluoroalkyl compounds in the atmosphere.
  • the inertial impactor is used for collecting fine particles (aerosol) suspended in a gas, and the particles are passed from a nozzle toward an impactor plate (collection plate) by inertial force. The particles are made to collide with the impactor plate and collected on the impactor plate. Further, by connecting inertial impactors having different nozzle diameters in multiple stages, it becomes possible to collect particles having different particle diameters on the impactor plates of each stage.
  • the inertial impactor portion 21 is provided with a collecting filter paper 22 in the center of a disk-shaped object, and an impactor plate 23 having a plurality of through holes 24 formed on its outer peripheral edge, and a clearance on the upstream side of the impactor plate 23. A portion 25 and a connecting hole 27 on the downstream side are provided.
  • the inertial impactor unit 21 classifies and collects fine particles (aerosol) by using an inertial force. By abruptly changing the traveling direction of the airflow of the sample atmosphere that has flowed in from the upstream side, the particle size dependence of the inertial motion of the fine particles is used to collect particles of a certain size or larger and collide with the filter paper to cause the fine particles. Collect. Since the fine particles and the gas do not pass through the filter paper in the inertial impactor portion, the substance exchange between the collected particles on the filter paper and the aerated gas, which is a concern in the existing method of passing through the filter paper, is minimized.
  • the inertial impactor portions 21 are arranged in a plurality of layers.
  • the size of the fine particles that can be collected can be appropriately adjusted depending on the shape of the through hole 24 formed in the impactor plate 23, the diameter size, the distance to the lower plate, and the like.
  • the shape of the through hole 24 formed in the impactor plate 23 for example, the shape as shown in FIG. 4 can be mentioned. Therefore, it is possible to collect fine particles having different particle sizes in each layer.
  • the inertial impactor portions 21 having a plurality of layers are arranged so as to sequentially collect the fine particles in descending order of particle size from the upstream side to the downstream side, the collection efficiency is increased.
  • an acceleration nozzle 26 for accelerating the airflow formed on the taper toward the downstream side.
  • the particle-adsorbing compound collection area 20 of this embodiment is provided with a three-stage or four-stage inertial impactor 21, and has a particle size of 10 ⁇ m or more, 2.5 to 10 ⁇ m, and 1.0 to 2.5 ⁇ m from the upstream.
  • Particle-adsorbing pels and polyfluoroalkyl compounds are collected by the inertial impactor portion of each layer.
  • a collection filter paper 22 is provided on the upper surface of the disk-shaped object 28 having a plurality of through holes 24.
  • a very small particle collecting portion 29 was formed.
  • the ultra-small particle collecting unit 29 may be omitted depending on the purpose.
  • the volatile compound collecting area 40 connected to the semi-volatile compound collecting area 30 includes a filter unit 41 made of an adsorption activated carbon C that collects volatile pels and polyfluoroalkyl compounds existing in a gaseous state in the atmosphere.
  • the filter unit 41 may be arranged in a plurality of layers.
  • Pell and polyfluoroalkyl compound adsorption activated carbon consist of fibrous activated carbon or powdered activated carbon.
  • the fibrous activated carbon is an activated carbon obtained by carbonizing and activating an appropriate fiber, and examples thereof include a phenol resin type, an acrylic resin type, a cell roll type, and a coal pitch type.
  • the fiber length, cross-sectional diameter, etc. are appropriate. If the fiber cross-sectional diameter is too large, the surface area is reduced and the contact efficiency is lowered. Therefore, the fiber cross-sectional diameter is preferably 30 ⁇ m or less from the viewpoint of improving the adsorption capacity.
  • Raw materials for powdered activated carbon include wood (waste wood, thinned wood, ogako), coffee bean pomace, paddy husks, coconut husks, bark, fruit nuts, etc. These naturally derived raw materials are likely to develop pores by carbonization and activation. Moreover, since it is a secondary use of waste, it can be procured at low cost. In addition, fired products derived from synthetic resins such as tires, petroleum pitches, urethane resins, and phenol resins, and coal and the like can also be used as raw materials. When the particle size of the activated carbon is small, the density of the filter body becomes high, and the adsorption performance of the pel and the polyfluoroalkyl compound is improved.
  • the average particle size of the powdered activated carbon can be appropriately adjusted according to the conditions of use, and the adsorption performance of the pel and the polyfluoroalkyl compound can be improved while ensuring the air permeability.
  • the activated carbon raw material is carbonized by heating in a temperature range of 200 ° C. to 600 ° C. as needed to form fine pores. Subsequently, the activated carbon raw material is exposed to water vapor and carbon dioxide gas in a temperature range of 600 ° C. to 1200 ° C. and is activated. As a result, activated carbon with various pores developed is completed. In addition, at the time of activation, there is also zinc chloride activation and the like. In addition, sequential cleaning is also performed.
  • the physical properties of the activated carbon thus produced define the adsorption performance of the substance to be adsorbed.
  • the adsorption performance of activated carbon that adsorbs pel and polyfluoroalkyl compounds, which are substances to be adsorbed, is defined by the specific surface area, which is an index indicating the amount of pores formed in the activated carbon.
  • the specific surface area of each prototype is measured by the BET method (Brunauer, Emmett and Teller method).
  • Activated carbon is also defined by the pore size of the pores.
  • an adsorbent such as activated carbon
  • any of micropores, mesopores, and macropores is present.
  • the adsorption target and performance of activated carbon change depending on which range of pores are developed more.
  • the activated carbon desired in the present invention is to desorbably and effectively adsorb molecules of pel and polyfluoroalkyl compounds.
  • acidic functional groups on the surface of activated carbon there are acidic functional groups on the surface of activated carbon.
  • the acidic functional groups that increase due to the surface oxidation of activated carbon are mainly hydrophilic groups such as carboxyl groups and phenolic hydroxyl groups. Acidic functional groups on the surface of activated carbon affect the collection capacity. The amount of these acidic functional groups can be grasped as the amount of surface oxide. As the amount of surface oxide of activated carbon increases, the hydrophilicity of the surface of activated carbon increases, and it is considered that the collection performance of fluorotelomer compounds having a hydrophilic group among pel and polyfluoroalkyl compounds is improved.
  • the following methods can be mentioned as methods for increasing the surface oxide of activated carbon.
  • One is a method of promoting the oxidation of surface residues and increasing the number of acidic functional groups by going through the heating step again. That is, oxidation in air or oxygen atmosphere.
  • air having a temperature of 25 to 40 ° C. and a humidity of 60 to 90% is introduced in an air atmosphere. Therefore, activated carbon having an increased amount of surface oxide can be obtained by heating at 150 to 900 ° C. for 1 to 10 hours. It is considered that the amount of acidic functional groups increases due to the oxidation of hydrocarbon groups such as alkyl groups existing on the surface of activated carbon by heating with moist air and the introduction of hydroxyl groups of water to the surface.
  • Another method is to oxidize the surface of activated carbon with an oxidizing agent to increase the surface oxide.
  • the oxidizing agent include hypochlorous acid and hydrogen peroxide.
  • Activated carbon with an increased amount of surface oxide can be obtained by immersing the activated carbon in a liquid containing these oxidizing agents and then drying it.
  • the amount of acidic functional groups on the surface of the activated carbon can be measured as the amount of surface oxide as shown in each prototype described later.
  • the adsorption performance of activated carbon that desorbably adsorbs volatile pels and polyfluoroalkyl compounds is exhibited by setting the specific surface area to 900 m 2 / g or more, as derived from the examples described later. When the pores of the activated carbon are formed to a certain level or more, the adsorption performance of the compound is ensured.
  • the micropores refer to pores having a pore diameter of 1 nm or less, and the total pore volume (V mic ) of the micropores is 0.35 cm 3 / g or more as derived from the examples described later. Then, the adsorption performance of the volatile pel and the polyfluoroalkyl compound is improved.
  • the micropore volume of 1 nm or less in each prototype is measured by the MP method (Micropore method). It is considered that the compound is easily collected in the pores when the micropores are formed to a certain level or more.
  • the mesopores refer to pores having a pore diameter in the range of 2 to 60 nm, and the total pore volume (V met) of the mesopores is 0 as derived from the examples described later.
  • V met the total pore volume of the mesopores
  • the mesopore volume in the range of 2 to 60 nm of each prototype is measured by the DH method (Dollimore-Heal method). Since it was measured by the DH method, the measurement target was pores of 2.43 to 59.72 nm. It is considered that when the mesopores are formed to a certain level or more, the compound can easily penetrate into the micropores.
  • the difference between the pore volume of the micropores and the pore volume of the mesopores is also considered to contribute to the efficient adsorption of the per and polyfluoroalkyl compounds.
  • the volume difference (V s ) between the sum of the micropore volumes (V mic ) and the sum of the mesopore volumes (V met ) is 0.45 or more, so that the volatile pellets are volatile.
  • the polyfluoroalkyl compound can be efficiently and desorbably adsorbed.
  • the hydrophilicity of the surface of activated carbon can be enhanced, and pel and polyfluoroalkyl compounds can be efficiently adsorbed.
  • a quartz fiber filter manufactured by Shibata Scientific Technology Co., Ltd. was used for the collection filter paper in each particle-adsorbing compound collection area.
  • Urethane foam filter part Polyurethane foam (manufactured by Shibata Scientific Technology Co., Ltd.), diameter 47 mm, height 50 mm
  • Activated carbon adsorbent used The inventors used the following raw materials to prepare pel and polyfluoroalkyl compound adsorption activated carbon.
  • the specific surface area (m 2 / g) was determined by the BET method by measuring the nitrogen adsorption isotherm at 77K using the automatic specific surface area / pore distribution measuring device "BELSORP? MiniII” manufactured by Microtrac Bell Co., Ltd. (BET specific surface area).
  • Table 1 shows the physical characteristics of the adsorbed activated carbon of each prototype. From the top of Table 1, the amount of surface oxide (meq / g), BET specific surface area (m 2 / g), average pore diameter (nm), and average fiber diameter ( ⁇ m) are shown.
  • the collection filter paper of each stage was sufficiently contact-stirred with 15 ml of a mixed solvent containing dichloromethane and ethyl acetate as main components, and then centrifuged to separate the solid and liquid, and the extract was collected.
  • the extract was quantitatively measured in MRM mode using GC-MS / MS (QuatrimicroGC manufactured by Waters), and the collection performance was confirmed.
  • Table 3 shows the recovered amount (pg / m 3 ) of PFOS and PFOA adhering to the fine particles for each particle size (each stage). Quantitative measurement was performed 4 times.
  • FTOHs and ethyl perfluorooctane sulfoamide (IUPAC name: N-ethyl-1,1,2,2,3,3,4,5,5,6,6,7 , 7,8,8,8-Heptadecafluorooctane-1-sulfoamide) (hereinafter referred to as "N-EtFOSA") was used for evaluation.
  • N-EtFOSA ethyl perfluorooctane sulfoamide
  • N-EtFOSA is a substance represented by the following chemical formula (vii).
  • Each standard substance (4: 2FTOH (IUPAC name: 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol), 6: 2FTOH (IUPAC name: 3,3,4,4) , 5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol), 8: 2FTOH, 10: 2FTOH (IUPAC name: 3,3,4,5,5) , 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluoro-1-dodecanol), N-EtFOSA and N-EtFOSE) 100 ⁇ l of the solution diluted with methanol to 100 ppb was added to the urethane foam filter portion of the semivolatile compound collection area. Subsequently, air at 22 to 24 ° C. was aerated at a rate of 20 l / min to the semi-volatile compound collecting area and the volatile compound collecting area for 48 hours.
  • the urethane foam filter part and the filter part made of activated carbon of each prototype are taken out, and after sufficient contact stirring with 15 ml of a mixed solvent containing dichloromethane and ethyl acetate as main components, centrifugation is performed to solid-liquid. Separated and the extract was collected.
  • the extract was quantitatively measured in MRM mode using GC-MS / MS (QuatrimicroGC manufactured by Waters), and the collection performance was confirmed.
  • Table 4 shows the recovery rate (%) for each target substance in the urethane foam filter section. Quantitative measurement was performed 4 times. In the table, "ND" indicates that it is equal to or less than the lower limit of quantification.
  • Table 5 shows the recovery rate (%) for each target substance in the filter section made of activated carbon of each prototype. Quantitative measurement was performed 4 times.
  • Prototype Example 1 does not have the pores and specific surface area required for collecting the target substance, it is presumed that the collection performance was not sufficiently exhibited. Further, in Prototype Example 2, although it is possible that the specific surface area was sufficient, it is presumed that various hydrophilic FTOHs could not be sufficiently collected because the surface was hydrophobic.
  • the collection rates of 4: 2 FTOH, 6: 2 FTOH, 8: 2 FTOH, and 10: 2 FTOH all have a high collection rate of 70% or more, and the best collection performance is achieved. confirmed.
  • Prototype Example 4 which has the same surface area as Prototype Example 2, suggests that the collection performance is significantly improved by oxidizing the surface of the activated carbon. That is, for N-EtFOSA, the specific surface area of Prototype Example 3 is required, and the number of acidic groups on the surface of the activated carbon is increased, so that sufficient collection performance can be provided.
  • the semi-volatile pel and N-EtFOSA which is a polyfluoroalkyl compound
  • the recovery rate of the compound was almost 100%. Since the compound was not detected in the filter section of the volatile compound collection area, the semi-volatile pel and polyfluoroalkyl compound and the volatile pel and polyfluoroalkyl compound were separated in each collection area. It turned out that it is possible to collect it efficiently.
  • Semi-volatile pels and polyfluoroalkyl compounds are segregated and collected in the semi-volatile compound collection area located in front of the volatile compound collection area, so that the adsorbed activated carbon in the filter section of the volatile compound collection area It is expected that the clogging of the micropores will be prevented and the deterioration of adsorption performance will be reduced. Further, by separating and collecting, it is possible to prevent the co-elution phenomenon at the time of measurement, reduce the analysis error in the measuring device, and improve the measurement accuracy.
  • the pel and polyfluoroalkyl compounds adsorbed on the particles, the semi-volatile pel and polyfluoroalkyl compound, and the volatile pel and polyfluoroalkyl compound are collected in different collection areas, respectively. It has been found that the compounds can be segregated and collected, and all forms of pel and polyfluoroalkyl compounds can be satisfactorily measured.
  • the volume difference (V s ) of Prototype Examples 6 to 21 is the value obtained by subtracting the sum of mesopore volumes (V met ) (cm 3 / g) from the sum of micropore volumes (V mic ) (cm 3 / g). Therefore, it was calculated from the above equation (i).
  • the activated carbon of the prototype was transferred to a PP centrifuge tube (capacity: 15 ml), and 10 ml of a mixed solvent containing dichloromethane and ethyl acetate as main components was added.
  • the centrifuge tube was shaken at 225 rpm for 10 minutes, and then the extract was collected. The process of collecting the extract was repeated twice in succession, and a total of 30 ml of the extract was collected.
  • the collected extract is concentrated to 1 ml by a nitrogen spray concentrator, and then the extract is quantitatively measured in MRM mode using GC-MS / MS (“GCMS-TQ8050”, manufactured by Shimadzu Corporation) and captured. Confirmed the collection performance.
  • Tables 9 to 11 show the recovery rate (%) of fluorotelomer alcohols (FTOHs) for each target substance for the activated carbons of Prototype Examples 6 to 21.
  • the target substances are 4: 2FTOH (IUPAC name: 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol), 6: 2FTOH (IUPAC name: 3,3,4,4). , 5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol), 8: 2FTOH, 10: 2FTOH (IUPAC name: 3,3,4,5,5) , 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluoro-1-dodecanol).
  • Prototype Examples 10 to 21 the pore volumes of both the micropores and the mesopores are large, and it is considered that both pores are sufficiently developed, so that the FTOH molecule is smoothly introduced into the pores of the activated carbon. It can be inferred that excellent adsorption performance was shown.
  • Prototype Examples 12 to 19 showed particularly excellent FTOH recovery performance. All of Prototype Examples 12 to 19 are characterized in that the pore volume of the micropores is large and the pore volume of the mesopores is not so large although the pores of the mesopores are developed. After adsorbing the FTOH molecule in the micropores, it is easy to be smoothly desorbed out of the pores during the extraction operation, so it is considered that a particularly good recovery rate was shown.
  • Prototype Examples 20 and 21 can be said to be activated carbons having pores that are complicatedly developed from large pores to small pores because the pore volumes of both the micropores and the mesopores are large. It is presumed that the FTOH molecules adsorbed in the complicatedly developed pores were difficult to be smoothly desorbed during the extraction operation, and the recovery rate of FTOH was slightly inferior to that of Prototype Examples 12 to 19. Will be done. In view of these results, the sum of the pore volumes of the micropores of the activated carbon (V mic ), the sum of the pore volumes of the mesopores (V met ), and the volume difference (V s ), which is the difference between them, are the recovery of FTOH. It is understood that the rate is affected.
  • PFCAs perfluorocarboxylic acids
  • 6 2 FTUCA (IUPAC name: 3, 4, 4, 5, 5,).
  • PFSAs perfluoroacids
  • FTI fluorotelomer iodines
  • the urethane foam filter part of the semi-volatile compound collection area is packed in a PP syringe, and 18 ml of a mixed solvent of dichloromethane and ethyl acetate is passed through the solution at a rate of 1 drop / second (1 drop / second) to a PP test tube. Extract A-1 was obtained. Further, 15 ml of methanol was passed through the solution at a rate of 1 drop / second (1 drop / second) to obtain Extract B in a PP test tube. The extracts A-1 and B were concentrated by spraying nitrogen, and the volume was adjusted to 1 ml.
  • the filter part made of adsorbed activated carbon in the volatile compound collection area into a PP test tube, add 10 ml of a mixed solvent of dichloromethane and ethyl acetate, shake for 10 minutes, and then transfer the permeate to another PP test tube. The work was repeated twice and the extract was collected. The extract was concentrated by spraying nitrogen to a volume of 1 ml, and quantitative analysis of pel and polyfluoroalkyl compounds collected in the volatile compound collection area was performed in MEM mode using GS-MS / MS.
  • the concentrations of pel and polyfluoroalkyl compounds with respect to the atmosphere (pg / m 3 ) are shown, and Tables 15 and 19 show the concentrations of volatile pel and polyfluoroalkyl compounds with respect to the sample atmosphere in the volatile compound collection area (pg / m 3). ) Is shown.
  • Tables 12, 14 to 16, 18 and 19 show the concentrations of per and polyfluoroalkyl compounds (pg / m 3 ) with respect to the sample atmosphere.
  • concentration of pel and polyfluoroalkyl compounds divide the collection amount (pg) of pel and polyfluoroalkyl compound (target substance) collected in each collection area by the integrated flow rate (m 3 ) through the sampler. It is a value obtained by the following formula (ix).
  • BLANK is a numerical value detected by performing the same measurement on the collection filter paper, the urethane foam filter part, and the filter part before the experiment
  • LOQ is the quantification of each substance of the measuring device. Indicates the lower limit that can be measured. “-” Indicates that the value is below the lower limit of quantification.
  • Tables 13 and 17 show the particles collected in the particle-adsorbing compound collection area and the particle-adsorbing pel and polyfluoroalkyl compounds.
  • the particle collection amount (mg) was calculated as the difference between the filter weight after the experiment and the filter weight before the collection experiment.
  • the weight of the filter is weighed up to 1 ⁇ g in a space adjusted to a temperature of 25 ⁇ 1 ° C and a humidity of 35 to 40% using a precision balance (A & D Co., Ltd., microelectronic balance “BM-20”). did.
  • the particle concentration ( ⁇ g / m 3 ) is a value obtained by dividing the above-mentioned collected amount (mg) by the integrated flow rate (m 3 ) in which the sampler is aerated, and is obtained from the following mathematical formula (x).
  • the concentrations of pel and polyfluoroalkyl compounds adhering to the collected particles are referred to as PFAS concentrations in Tables 13 and 17.
  • the PFAS concentration ( ⁇ g / g) is a value indicating the ratio of the detected pel and polyfluoroalkyl compound (PFAS) to the amount of collected particles. It is a value obtained by dividing the total concentration (pg / m 3 ) of the pel and polyfluoroalkyl compounds in the particle-adsorbing compound collection area by the particle concentration ( ⁇ g / m 3 ), and is the following formula (xi). ).
  • particle-adsorbing compound collection areas shown in Tables 12, 13, 16 and 17 particle-adsorbing pels and polyfluoroalkyl compounds were detected, and it can be said that good collection was realized.
  • the types of particle-adsorbing pels and polyfluoroalkyl compounds detected had similar tendencies in their respective regions, different types of particle-adsorbing pels and polyfluoroalkyl compounds were collected, or pels and polyfluoroalkyl compounds were collected.
  • the semi-volatile pels and polyfluoroalkyl compounds were well collected in the semi-volatile compound collection areas shown in Tables 14 and 18. Since the particle-adsorbing pel and the polyfluoroalkyl compound are also detected in the semi-volatile compound collection area in each area, particles having a smaller particle size can be collected in the particle-adsorbing compound collection area. It is considered that the accuracy of collecting pel and polyfluoroalkyl compounds for each form can be further improved by setting a particle-adsorbing compound collection area.
  • Volatile pels and polyfluoroalkyl compounds were also successfully collected in the volatile compound collection areas shown in Tables 15 and 19. Similar to the other forms of pel and polyfluoroalkyl compounds mentioned above, there are regional differences in the collected pel and polyfluoroalkyl compounds, as a sampler used for quantitative measurement of volatile pel and polyfluoroalkyl compounds. Was shown to be significant. Since the recovery of FTOHs used as surrogate is also good, it is also shown that the accuracy of volatile pel and polyfluoroalkyl compounds as samplers is high.
  • the per and polyfluoroalkyl compound collection sampler according to the present invention can efficiently and comprehensively collect per and polyfluoroalkyl compounds existing in the atmosphere, and further, separate them by form. It was shown that it is possible to collect and perform quantitative measurement with high accuracy.
  • the per and polyfluoroalkyl compound collection sampler of the present invention can comprehensively collect per and polyfluoroalkyl compounds existing in the atmosphere in various forms for each form of the compound.
  • the per and polyfluoroalkyl compound collection sampler of the present invention can comprehensively collect per and polyfluoroalkyl compounds existing in the atmosphere in various forms for each form of the compound.
  • Sampler 20 Particle-adsorbing compound collection area 21 Inertial impactor part 22 Collection filter paper 23 Impactor plate 24 Through hole 25 Clearance part 26 Acceleration nozzle 27 Connecting hole 28 Disc-shaped object 29 Micro particle collection part 30 Semi-volatile Compound collection area 31 Urethane foam filter section 32 Urethane foam 40 Volatile compound collection area 41 Filter section C Adsorption activated carbon

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Abstract

Le problème Décrit par la présente invention est de fournir un échantillonneur de piégeage de composés per-et poly-fluoroalkyle qui peut piéger de manière très efficace et complète des composés per-et poly-fluoroalkyle se produisant dans l'air atmosphérique sous diverses formes. La solution selon l'invention porte sur l'échantillonneur de piégeage de composés per-et poly-fluoroalkyle : une zone de piégeage de composé adsorbant les particules qui est pourvue d'une section d'aspiration de gaz capable d'aspirer un échantillon d'air atmosphérique et d'une section d'impacteur inertiel reliée à la section d'aspiration de gaz et capable de piéger des composés per-et poly-fluoroalkyle adsorbant les particules ; une zone de piégeage de composé semi-volatil qui est reliée à la zone de piégeage de composé adsorbant les particules et est pourvue d'une section de filtre en mousse d'uréthane capable de piéger des composés semi-volatils per-et poly-fluoroalkyle ; une zone de piégeage de composés volatils qui est reliée à la zone de piégeage de composés semi-volatils et est pourvue d'une section de filtre comprenant du charbon actif adsorbant Capable de piéger des composés volatils per-et poly-fluoroalkyle et ayant une surface spécifique BET de 900 m2/g ; et une section de décharge de gaz qui est reliée à la zone de piégeage de composé volatil et à travers laquelle l'air atmosphérique passant à travers chacune des zones est déchargé.
PCT/JP2020/044306 2019-12-05 2020-11-27 Échantillonneur de piégeage de composés per- et poly-fluoroalkyle WO2021112011A1 (fr)

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JP2019-220421 2019-12-05
JP2020193453A JP2021092557A (ja) 2019-12-05 2020-11-20 ペル及びポリフルオロアルキル化合物捕集サンプラー
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6431014B1 (en) * 1999-07-23 2002-08-13 Msp Corporation High accuracy aerosol impactor and monitor
JP2005189025A (ja) * 2003-12-25 2005-07-14 Miura Co Ltd 残留性有機汚染物質の採取方法および採取器
WO2009031562A1 (fr) * 2007-09-04 2009-03-12 Daikin Industries, Ltd. Procédé d'adsorption et procédé de récupération de composé contenant du fluor
CN105445061A (zh) * 2016-02-01 2016-03-30 南京工业职业技术学院 一种大气中持久性有机污染物PAHs主动式采样系统
JP2017538568A (ja) * 2014-10-14 2017-12-28 サウジ アラビアン オイル カンパニー 化学蒸着による規則性微孔性カーボンの合成
CN107843463A (zh) * 2017-10-27 2018-03-27 中国科学院生态环境研究中心 大气中持久性有机污染物主动采样套筒
JP2019064869A (ja) * 2017-09-29 2019-04-25 株式会社Ｌｉｘｉｌ 造粒活性炭及びその製造方法
JP2019107642A (ja) * 2017-12-18 2019-07-04 フタムラ化学株式会社 吸着剤の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6431014B1 (en) * 1999-07-23 2002-08-13 Msp Corporation High accuracy aerosol impactor and monitor
JP2005189025A (ja) * 2003-12-25 2005-07-14 Miura Co Ltd 残留性有機汚染物質の採取方法および採取器
WO2009031562A1 (fr) * 2007-09-04 2009-03-12 Daikin Industries, Ltd. Procédé d'adsorption et procédé de récupération de composé contenant du fluor
JP2017538568A (ja) * 2014-10-14 2017-12-28 サウジ アラビアン オイル カンパニー 化学蒸着による規則性微孔性カーボンの合成
CN105445061A (zh) * 2016-02-01 2016-03-30 南京工业职业技术学院 一种大气中持久性有机污染物PAHs主动式采样系统
JP2019064869A (ja) * 2017-09-29 2019-04-25 株式会社Ｌｉｘｉｌ 造粒活性炭及びその製造方法
CN107843463A (zh) * 2017-10-27 2018-03-27 中国科学院生态环境研究中心 大气中持久性有机污染物主动采样套筒
JP2019107642A (ja) * 2017-12-18 2019-07-04 フタムラ化学株式会社 吸着剤の製造方法

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