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Definitions

• the present invention relates to pel and polyfluoroalkyl compound adsorption activated carbon that collects pel and polyfluoroalkyl compounds contained in an atmospheric sample.
• Pell and polyfluoroalkyl compounds are fluorine-substituted aliphatic compounds having high thermal stability, high chemical stability, and high surface modification activity. Pell and polyfluoroalkyl compounds are widely used in industrial and chemical applications such as surface treatment agents, packaging materials, and liquid fire extinguishing agents by taking advantage of the above characteristics.
• 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.
• Patent Document 1 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.
• pel and polyfluoroalkyl compounds remain in the environment in various forms with a wide range of physicochemical properties, and there is a problem that existing adsorbents do not have sufficient collection performance and accurate quantitative measurement cannot be performed. there were.
• the present invention has been made in view of the above points, and in particular, a pel and polyfluoroalkyl compound adsorbed activated carbon capable of desorbably collecting pel and polyfluoroalkyl compounds in an atmospheric sample, and activated carbon thereof.
• the filter body used is provided.
• the first invention is the adsorption of pel and polyfluoroalkyl compounds for desorbably adsorbing pel and polyfluoroalkyl compounds in an atmospheric sample made of an activated carbon adsorbent having a BET specific surface area of 900 m 2 / g or more.
• activated carbon adsorbent having a BET specific surface area of 900 m 2 / g or more.
• the second invention relates to the per and polyfluoroalkyl compound adsorbing activated carbon in which the sum (V mic ) of the micropore volume of 1 nm or less of the activated carbon adsorbent is 0.35 cm 3 / g or more in the first invention.
• the third invention is the adsorption of pel and polyfluoroalkyl compounds in which the sum (V met ) of the mesopore volumes of the activated carbon adsorbent of 2 to 60 nm or less is 0.02 cm 3 / g or more in the first or second invention.
• V met the sum of the mesopore volumes of the activated carbon adsorbent of 2 to 60 nm or less is 0.02 cm 3 / g or more in the first or second invention.
• the fourth invention is the sum of the micropore volumes (V mic ) and the mesopore volume (V) specified in the following formula (i) of the activated carbon adsorbent in any of the first to third inventions. It relates to pel and polyfluoroalkyl compound adsorption activated carbon having a volume difference (V s) of 0.45 or more from met).
• the fifth invention relates to pel and polyfluoroalkyl compound adsorbing activated carbon in which the surface oxide amount of the activated carbon adsorbent is 0.10 meq / g or more in any one of the first to fourth inventions.
• the sixth invention relates to pel and polyfluoroalkyl compound adsorbed activated carbon in which the activated carbon adsorbent is a fibrous activated carbon in any one of the first to fifth inventions.
• the seventh invention relates to a pel and polyfluoroalkyl compound adsorption filter body, which retains the adsorption activated carbon according to any one of the first to sixth inventions.
• the pel and polyfluoroalkyl compounds in an atmospheric sample made of an activated carbon adsorbent having a BET specific surface area of 900 m 2 / g or more can be desorbably adsorbed. Because it is a per and polyfluoroalkyl compound adsorption activated carbon for this purpose, the compound, which has been considered difficult to quantitatively measure, can be desorbably collected.
• the sum (V mic ) of the micropore volume of 1 nm or less of the activated carbon adsorbent is 0.35 cm 3 / g or more. Therefore, the pel and the polyfluoroalkyl compound can be efficiently and detachably collected.
• the sum (V met ) of the mesopore volumes of the activated carbon adsorbent having a mesopore volume of 2 to 60 nm or less is 0.02 cm 3 /. Since it is g or more, the pel and polyfluoroalkyl compounds can be efficiently and desorbably collected.
• the sum of the micropore volumes (V) specified in the following formula (i) of the activated carbon adsorbent is 0.45 or more, the pel and polyfluoroalkyl compounds can be efficiently and desorbably collected. ..
• the amount of surface oxide of the activated carbon adsorbent is 0.10 meq / g or more. It has not only adsorption performance by pores but also chemical adsorption ability, and can further improve the adsorption performance of pel and polyfluoroalkyl compounds.
• the activated carbon adsorbent is a fibrous activated carbon, contact with the pel and the polyfluoroalkyl compound. The efficiency can be increased and the adsorption performance can be improved.
• the pel and polyfluoroalkyl compound adsorption filter body according to the seventh invention since the adsorption activated carbon according to any one of the first to sixth inventions is retained, the collection efficiency of the pel and polyfluoroalkyl compounds is improved. At the same time, it can be provided with good handleability.
• the pel and polyfluoroalkyl compound adsorption activated carbon of the present invention is composed of fibrous activated carbon or granular 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 cellulose type, and a coal pitch type.
• the fiber length, cross-sectional diameter, etc. are appropriate.
• Raw materials for granular activated carbon include wood (waste wood, thinned wood, ogako), coffee bean pomace, rice husks, coconut husks, bark, and fruit nuts. 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.
• 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. When the amount of surface oxide of activated carbon is increased, the hydrophilicity of the surface of activated carbon is increased, and it is considered that the collection performance of fluorotelomer alcohols 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 oxidation of hydrocarbon groups such as alkyl groups existing on the surface of activated carbon by heating with moist air and 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 pel and polyfluoroalkyl compounds in an atmospheric sample 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 pel and the polyfluoroalkyl compound in the atmospheric sample 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 when the micropores are formed to a certain level or more, the compound is easily collected in the pores.
• the mesopore refers to a pore having a pore diameter in the range of 2 to 60 nm, and the total pore volume (V met) of the mesopore is 0 as derived from the examples described later.
• V met the total pore volume of the mesopore
• 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 in the atmospheric sample.
• Per and polyfluoroalkyl compounds can be efficiently and desorbably adsorbed.
• the adsorption performance of the pel and polyfluoroalkyl compounds is improved, and the compounds are smoothed during the subsequent extraction operation. It is considered that quantitative measurement can be performed satisfactorily by making it desorbable.
• the hydrophilicity of the surface of activated carbon can be enhanced, and the per and polyfluoroalkyl compounds in the atmospheric sample can be efficiently adsorbed.
• 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).
• the average pore diameter (nm) was calculated by a mathematical formula (iv) using the values of the pore volume (cm 3 / g) and the specific surface area (m 2 / g), assuming that the shape of the pores is cylindrical. ..
• Table 1 shows the physical characteristics of the activated carbons of Prototype Examples 1 to 5. 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.
• FTOHs fluorotelomer alcohol
• N-EtFOSA ethyl perfluorooctanosulfonamide
• N-EtFOSA is a substance represented by the following chemical formula (v).
• Each standard substance was diluted to 100 ppb with methanol, and 100 ⁇ l was added to flexible polyurethane foam (PUF), which was set in the first stage. Subsequently, 1.2 g of the adsorption activated carbon of the prototype example was filled in the case of 45 mm ⁇ in the second stage, and air at 22 to 24 ° C. was applied to the PUF of the first stage and the fibrous activated carbon of the second stage at a speed of 20 l / min. Ventilated for 48 hours.
• PUF flexible polyurethane foam
• the activated carbon adsorbent of the prototype example was sufficiently contact-stirred with 15 ml of a mixed solvent containing dichloromethane and ethyl acetate as main components, followed by centrifugation, solid-liquid separation, and an 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 2 shows the recovery rate (%) of fluorotelomer alcohol (FTOH) for each target substance for the activated carbons of Prototype Examples 1 to 5.
• 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), N-EtFOSA.
• ND indicates that it is below the lower limit of quantification.
• recovery rate was 150% or more due to the co-elution phenomenon in which the mass number affected the same fragment.
• ⁇ Prototype example 9 10 g of Futamura Chemical's fibrous activated carbon "FE3010" (C2) was immersed in 500 ml of a hydrogen peroxide concentration 4.2% solution, allowed to stand for 150 hours, then taken out and dried to obtain the activated carbon of Prototype Example 9.
• the pore volume was measured by nitrogen adsorption using an automatic specific surface area / pore distribution measuring device (“BELSORP-miniII”, manufactured by Microtrac Bell Co., Ltd.).
• 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 physical characteristics of the activated carbons of Prototype Examples 6 to 21 are shown in Tables 3 and 4. From the top of Table 3, the amount of surface oxide (meq / g), BET specific surface area (m 2 / g), average pore diameter (nm), micropore volume (V mic ) (cm 3 / g), mesopores. The volume (V met ) (cm 3 / g) and the volume difference (V s ) (cm 3 / g).
• Each standard substance was diluted to 100 ng / ml (100 ppb) with methanol, 100 ⁇ l was added to flexible polyurethane foam (PUF), and the mixture was set in the first stage.
• the activated carbon of the prototype example was filled in the case of 47 mm ⁇ in the second stage so that the thickness at the time of filling was about 2 mm, and air at 22 to 24 ° C. was applied to the PUF in the first stage and the second stage at a speed of 20 l / min.
• the fibrous activated carbon of the eyes was aerated for 48 hours.
• 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.
• Tables 6 to 8 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 were recoverable for any of the FTOHs. It was shown that the target substance can be adsorbed when the BET specific surface area is 900 m 2 / g or more. It is inferred that the parameter of the specific surface area of activated carbon has a certain effect on the adsorption performance of each FTOH. In particular, Prototype Examples 10 to 19, which are fibrous activated carbons, had good results of 50% or more in any FTOH recovery rate. From the viewpoint of the contact efficiency between the target substance and the activated carbon, it is considered that the fibrous activated carbon can adsorb FTOH more efficiently.
• 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.
• 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 from 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 both the micropores and the mesopores have large pore volumes. 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.
• the pel and polyfluoroalkyl compound adsorption activated carbon of the present invention can desorbably adsorb the pel and polyfluoroalkyl compound in the atmospheric sample, the quantification of the compound, which was not possible with the existing collection material. The measurement was made possible. This enabled effective quantitative evaluation of persistent organic pollutants.

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