Polymeric bodies with amine or ammonium activation for water treatment and water treatment processes using same

Abstract

Generally, the present invention relates to a method for reducing the content of halogenated organic compounds or complexes with radionuclides in a liquid. The present invention further relates to the use of water treatment plants and bodies for treating water and aqueous radioactive waste. The present invention relates to a treatment method for preparing a treatment liquid, the treatment process comprising: a. mixing water with a content of at least 70% by weight and at least 10 -10 % total content by weight of one or more X components; b. providing a plurality of solid M bodies comprising R forms of one or more R components in a total dry weight content of at least 80% by weight, a first N component and optionally further N components, and optionally water in a content of up to 90% by weight based on the total weight of the M bodies; and c. contacting the feed liquid with the plurality of M bodies to obtain a treatment liquid, the treatment liquid having a lower total content of X components than the feed liquid.

Description

[Technical field]

[0001] Generally, the present invention relates to a method for reducing the content of halogenated organic compounds or complexes with radionuclides in a liquid. The present invention further relates to the use of water treatment plants and bodies for treating water and aqueous radioactive waste. [Background technology]

[0002] Removal of halogenated organic compounds from water is necessary because they are difficult to decompose and can have adverse effects on the environment. Some specific classes are perchloroalkyl and perfluoroalkyl substances (PFAS, also known as PFCs), which are synthetic compounds. Some suitable methods are summarized in "Water-Related Chemical Substances and Their Applications" (2009) (1999).

[0003] One method for removing PFAS by adsorption onto porous particulate anion exchangers and adsorption resins is disclosed in Non-Patent Document 2. Another approach based on porous activated carbon is presented in Patent Document 1.

[0004] The adsorbent and ion exchange materials are contained by a housing such as a column, tubular reactor or tank. The housings and hardware used to host the adsorbent resins or activated carbon and carry out water treatment processes have been known for decades.

[0005] Furthermore, ion exchange resins were developed already in the 1940s based on the copolymerization of styrene crosslinked with divinylbenzene. These resins are very stable and have a much larger exchange capacity than their predecessors. Polystyrene-divinylbenzene based anion exchangers are able to remove all anions, including silicic acid and carbonate. Thus, complete desalination of water is possible.

[0006] Polystyrene-divinylbenzene resins are still used in the majority of ion exchange applications. Although the basic resin components are the same, the resins have been modified in many ways to meet the requirements of specific applications and to provide longer resin life. One of the most important changes has been the development of macroreticular or macroporous resin structures.

[0007] Standard gel resins have a permeable membrane structure. This structure meets the chemical and physical requirements of most applications. In addition to polystyrene-divinylbenzene resins, there are newer resins with acrylic structures that increase resistance to organic contamination.

[0008] In addition to the plastic matrix, ion exchange resins contain ionizable functional groups. These functional groups consist of both positively charged cationic and negatively charged anionic elements. However, only one of the ionic species is mobile. The other ionic group is attached to the bead structure. Ion exchange occurs when liquid diffuses into the bead structure and exchanges with the mobile parts of the functional groups. Ions that are displaced from the beads diffuse back into the aqueous solution.

[0009] Despite all the achievements in the field of wastewater treatment, the removal of halogenated organic compounds from water remains a challenge due to their low adsorption capacity.

[0010] Another difficult problem is the removal of radionuclides from aqueous liquids, such as in the treatment of groundwater for drinking water, or in the treatment of aqueous radioactive waste from nuclear power plants, reprocessing plants, nuclear enrichment plants, or medical facilities. For example, the use of anion exchange media can remove radionuclides from UO2(CO3)2 2- , UO2(CO3)3 4- , CaUO2(CO3)3 2-etc. from groundwater. (Non-Patent Document 3). The application of ion exchange processes for the treatment of radioactive waste is also established (Non-Patent Document 4, chapter 3.3.2). The concept of application and construction of suitable devices is also known (see Non-Patent Document 4, chapter 4.3, above).

[0011] Despite all the achievements in the field of treating aqueous radioactive waste, the removal of these compounds from the aqueous phase remains a challenge due to their low adsorption capacity. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2020 / 037061 [Non-patent literature]

[0013] [Non-Patent Document 1] I.Ross et.al. Remediation J., 28(2), 1-26 [Non-Patent Document 2] A. Zaggia, Water Research 91 (2016) 137-146 [Non-Patent Document 3] Schlussbericht Zum Verbundprojekt Uranentfernung in der Trinkwasseraufbereitung, December 2009 https: / / www.dvgw.de / medien / dvgw / wasser / qualitaet / w4_02_04.pdf [Non-Patent Document 4] INTERNATIONAL ATOMIC ENERGY AGENCY, Application of Ion Exchange Processes for Treatment of Radioactive Waste and Management of Spent Ion Exchangers, Technical Reports Series, 2002. http: / / www-pub.iaea.org / MTCD / Publications / PDF / TRS408_scr.pdf Summary of the Invention [Problem to be solved by the invention]

[0014] It is an object of the present invention to provide an improved method for reducing the content of halogenated organic compounds in a liquid, preferably water.

[0015] It is an object of the present invention to provide an improved method for reducing the content of radionuclides and radionuclide complexes in liquids, preferably water.

[0016] It is an object of the present invention to provide an improved water treatment plant.

[0017] The objective is to provide an improved process for the recovery and disposal of fire extinguishing fluids, foams and the like.

[0018] The object is to provide an improved process for the recovery and treatment of liquids resulting from textile manufacturing and textile impregnation.

[0019] The objective is to provide an improved process for the recovery and treatment of liquids from the coating and impregnation of paper and carton.

[0020] The objective is to provide an improved process for the recovery and treatment of lubricant derived liquids.

[0021] The objective is to provide an improved process for the recovery and treatment of liquids derived from consumer products that contain perfluoroalkyl substances (PFAS), such as ski wax, wood glue and cleaning agents.

[0022] The object is to provide an improved process for the recovery and treatment of sewage sludge and liquids derived from sewage sludge.

[0023] The objective is to provide an improved process for the recovery and treatment of liquid radioactive waste (radwaste).

[0024] It is an object of the present invention to provide an improved ion exchange medium for treating liquids, preferably for reducing the content of halogenated organic compounds.

[0025] The objective is to provide an improved ion exchange medium for the collection and disposal of firefighting fluids, foams and the like.

[0026] The objective is to provide an improved ion exchange medium for the recovery and treatment of liquids resulting from textile manufacture and textile impregnation.

[0027] The objective is to provide an improved ion exchange medium for the recovery and treatment of liquids from the coating and impregnation of paper and cardboard.

[0028] The objective is to provide an improved ion exchange medium for the recovery and treatment of lubricant derived liquids.

[0029] The objective is to provide an improved ion exchange medium for the recovery and treatment of liquid radioactive waste (radwaste).

[0030] The objective is to provide an improved ion exchange medium for the recovery and treatment of liquids from consumer products that contain perfluoroalkyl substances (PFAS), such as ski wax, wood glue, and cleaning agents.

[0031] The objective is to provide an improved ion exchange medium for the recovery and treatment of sewage sludge and liquids derived from sewage sludge. [Brief description of the drawings]

[0032] [Figure 1] FIG. 1 shows a schematic diagram of the process of the present invention. [Diagram 2] 1 shows a schematic sample experimental setup. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] Halogenated organic compounds (X components) The method of the present invention reduces the content of halogenated organic compounds in the liquid. Halogenated organic compounds having two or more halogen atoms (herein referred to as X-constituents) are preferred. The halogens may be selected from the group consisting of F, Cl, Br and I, preferably selected from F and Cl. In one embodiment, the X-constituents contain F atoms, preferably two or more F atoms. In one embodiment, the X-constituents contain Cl atoms, preferably two or more Cl atoms. In one embodiment, the X-constituents contain Br atoms, preferably two or more Br atoms. In one embodiment, the X-constituents contain I atoms, preferably two or more I atoms. In one embodiment, the X-constituents contain two different halogen atoms, preferably two or more, for example one or more F atoms and one or more Cl atoms, or one or more Cl atoms and one or more Br atoms.

[0034] Preferred types of X moieties include perhalogenate moieties, perfluorate or perchlorate moieties. Perhalogenate moieties are preferably carbon atoms fully substituted with halogen atoms. The perhalogenate moieties can be substituted with the same or different halogen atoms.

[0035] Some preferred X moieties are perfluoroalkyl substances (PFAS). One particularly preferred category of X moieties is X * It is an ingredient. X* The moiety has 20 or less carbon atoms. * The component preferably has from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, more preferably from 1 to 7 carbon atoms, and more preferably still from 1 to 4 carbon atoms.

[0036] Complex ions containing radioactive nuclides (X components) The method of the present invention reduces the content of radionuclide organic compounds in the liquid. Examples of radionuclide compounds that can be removed from aqueous media by the method of the present invention are UO2(CO3)2 2- , UO2(CO3)3 4- and CaUO2(CO3)3 2- and dissolved uranium complexes such as

[0037] B component In one embodiment, the process of the present invention includes a pretreatment to reduce the content of B components, which are natural organic matter (NOM) and their substances (NOM derivatives) formed in the decomposition or fermentation process from NOM in the liquid, before reducing the halogenated organic compounds in the liquid. By selecting a two-step process including pretreatment and treatment, the overall efficiency of X component removal is dramatically improved. In addition, the process design of this embodiment makes it possible to dump the solids of the pretreatment step when discharged without specific measures, while the solids discharged in the treatment step require special attention to the load of X components. The B components are different from the X components.

[0038] Natural organic matter (NOM) includes a wide range of structurally complex matrices derived from land erosion and plant or animal tissue decomposition. NOM present in all surface waters contributes the majority of dissolved organic carbon (DOC) in water. As the dominant factor influencing the aesthetic quality of water resources (color, taste and odor, etc.), NOM is the precursor of disinfection by-products (DBPs), which are the reason for bacterial regrowth in distribution systems, and is involved in the complexation or solubilization of trace metals and pesticides in the aqueous environment.

[0039] M body (exchange medium) The M-bodies of the present invention are preferably adapted and arranged to adsorb an X moiety. The M-bodies comprise a solid structure (R-bodies) of a polymer (R-moiety) having an activated species (N-moiety) adjacent to the R-bodies.

[0040] The N moiety may be attached to the R body via a covalent or non-covalent bond. When the N moiety is covalently attached to the R body, it is adjacent to the R body as a terminal species. An N moiety that is non-covalently attached to an R body is adjacent to the R body as a discrete molecule or ion, and is preferably attached to the R body by a hydrophobic bond.

[0041] The M bodies may be dry or wet. The dry weight content of the M bodies is assessed without regard to water. The moisture content of the M bodies is determined as a percentage of the total weight of the wet M bodies.

[0042] The dry weight content of the R component in the M bodies is preferably at least 80% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight.

[0043] R bodies and R components (polymers) One or more polymeric R entities (R moieties) preferably provide the solid framework of the M entities. The R entities are activated by the addition, preferably by impregnation or covalent bonding, of one or more N entities, i.e. a first N entity and optionally further N entities.

[0044] The R entity may itself contain nitrogen atoms within its polymer structure. Such nitrogen atoms are not adjacent to the R entity. Such nitrogen atoms are within the R entity. Such nitrogen atoms do not belong to the N component. Some preferred nitrogen atoms that are part of the R entity are amide and cyanide.

[0045] The polymer may be a polymer of a single monomer or a copolymer of several different monomers. One preferred polymer is polystyrene, preferably polystyrene divinylbenzene copolymer (polystyrene DVB). Another preferred polymer is an acrylate and a copolymer of an acrylate polymer, such as polyacrylonitrile. Another preferred polymer is a methacrylate. Another preferred polymer is a phenol formaldehyde resin. The preferred polymer is hydrophobic.

[0046] The R body is preferably porous. The R body is preferably penetrable by liquid. Preferred R bodies have a maximum capacity to soak up up to 10 times their own mass in water.

[0047] The R-body may have a combination of two or more selected from micropores, mesopores and macropores. Preferred pores are micropores, mesopores or macropores. The R-body may have a combination of two or more selected from micropores, mesopores and macropores. Micropores have a pore size of less than 2 nm, mesopores of 2 to 50 nm, and macropores of more than 50 nm, as defined by the IUPAC Recommendation (Pure Appl. Chem. 57, (1985)).

[0048] One preferred type of R body is a bead. Beads can be prepared by aggregation of smaller particles. The diameter d of the R body, or equivalently the M body, is 50 The preferred range of diameter d is 10 μm to 10 mm, preferably 50 μm to 5 mm, and more preferably 100 μm to 1 mm. 50 Another preferable range is 0.05 to 1.5 mm.

[0049] One preferred type of R-body is a powder. The powder can be prepared by grinding larger particles, preferably by grinding beads. The diameter d of the R-body or equivalently the M-body is 50The preferred range is 1 to 200 μm, preferably 10 to 100 μm, and more preferably 40 to 60 μm or 40 to 80 μm.

[0050] The preferred grinding process is dry grinding and wet grinding, preferably wet grinding. Grinding can be carried out under atmospheric conditions. Grinding can be carried out at high or low temperatures. The preferred grinding is freeze grinding, preferably using liquid nitrogen. One method of reducing the diameter of R-body is homogenization, preferably by hammer mill or jet mill.

[0051] N component The N moiety is used to activate the R form. Preferred N moieties according to the present invention are amines or ammonium.

[0052] Preferred N moieties according to the invention have one or more moieties with a carbon chain, here an L chain, of at least 5 in length. A chain is an array of atoms linked by covalent bonds. The length of a chain is the number of atoms linked by covalent bonds. A chain can be linear or branched. Furthermore, a chain can be saturated or unsaturated. Saturation defines that all bonds between the chain-forming atoms are single bonds. A single bond is a chemical bond between two atoms that contains two electrons. Unsaturation defines that at least one bond between any two of the chain-forming atoms contains more than two bond electrons, for example four or six bond electrons. An unsaturated chain may have two or more bonds, each containing more than two electrons. A bond with four electrons is usually called a double bond and a bond with six electrons is called a triple bond. A preferred N moiety may have one such L chain moiety, or two such L chain moieties, or three such L chain moieties. Some preferred L chain moieties are linear or branched, saturated or unsaturated. Some preferred light chain moieties are linear and saturated.

[0053] Some preferred L chain moieties may further comprise a functional group. Functional group in this context refers to a chemical group within the L chain that is different from the atoms that form the chain. Some preferred functional groups are selected from the group consisting of alkoxy, ester, ketone, aldehyde and carboxylic acid.

[0054] Some preferred moieties on the N component are one or more selected from the group consisting of alkyl, alkene, alkyne, alkoxy, ester, ketone, aldehyde, and carboxylic acid.

[0055] The N component is preferably present in the M body in a content ranging from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight, more preferably from 1 to 5% by weight.

[0056] Some preferred L chain moieties having a carbon chain length of at least 5 are pentaalkyl, hexaalkyl, heptaalkyl, octacycloalkyl, nonaalkyl, decaalkyl or higher alkyl. Preferred L chains have 5 to 20 carbon atoms, or 5 to 15 carbon atoms, or 5 to 10 carbon atoms. One preferred N moiety having a carbon chain length of at least 5 is n-octylamine. Another preferred N moiety of this type is cetrimonium chloride.

[0057] Multiple types of N components may be used in the present invention, in which case reference is made to a first N component and a further N component, the first N component being defined as above.

[0058] Some preferred further N moieties are as defined above but differ from the first N moiety in their chemical constitution and / or structure.

[0059] Preferred combinations of the first N component and the further N component include tri(n-pentyl)amine / tri(n-hexyl)amine, tri(n-pentyl)amine / tri(n-heptyl)amine, tri(n-pentyl)amine / tri(n-octyl)amine, tri(n-pentyl)amine / tri(n-nonyl)amine, tri(n-pentyl)amine / tri(n-decyl)amine, etc.; tri(n-hexyl)amine / tri(n-heptyl)amine, tri(n-hexyl)amine / tri(n-octyl)amine, tri(n-hexyl)amine / tri(n-nonyl)amine, tri(n-hexyl)amine / tri(n-decyl)amine, tri(n-hexyl)amine / tri(n-dodecyl)amine, tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-decyl)amine, tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-decyl)amine, tri(n-hexyl)amine / tri(dodecyl)amine, tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-hexyl)amine / tri(n-decyl)amine, tri ...hexyl)amine / tri(n-hexyl)amine / tri(n- tri(n-heptyl)amine / tri(n-octyl)amine, tri(n-heptyl)amine / tri(n-nonyl)amine, tri(n-heptyl)amine / tri(n-decyl)amine, tri(n-heptyl)amine / tridodecylamine, tri(n-heptyl)amine / trioctadecylamine, etc.; tri(n-octyl)amine / tri(n-nonyl)amine, tri(n-octyl)amine / tri(n-decyl)amine, tri(n-octyl)amine / tridodecylamine, tri(n-octyl)amine / trioctadecylamine, etc., and similarly, instead of n-alkylamines, combinations with iso- and branched alkylamines are preferred.

[0060] Some preferred further N moieties are as defined above but have one or more moieties having a carbon chain, here an L chain, of length 4 or less.

[0061] Some further preferred L chain moieties are alkyl, such as butyl, propyl and ethyl. Preferred L chains have up to 4 carbon atoms, such as 1 to 4 carbon atoms, i.e. 1, 2, 3 or 4 carbon atoms. One preferred further N moiety is trimethylamine. One preferred further N moiety is triethylamine. One preferred further N moiety is tri(n-propyl)amine. One preferred further N moiety is tri(n-butyl)amine.

[0062] Preferred combinations of the first component with further N components include trimethylamine / tri(n-pentyl)amine, trimethylamine / tri(n-hexyl)amine, trimethylamine / tri(n-heptyl)amine, trimethylamine / tri(n-octyl)amine, trimethylamine / tri(n-nonyl)amine, trimethylamine / tri(n-decyl)amine, etc.; triethylamine / tri(n-pentyl)amine, triethylamine / tri(n-hexyl)amine, triethylamine / tri(n-heptyl)amine, triethylamine / tri(n-octyl)amine, triethylamine / tri(n-nonyl)amine, triethylamine / tri(n-decyl)amine, etc.; tri(n-propyl)amine / tri(n-pentyl)amine, tri(n-propyl tri(n-butyl)amine / tri(n-pentyl)amine, tri(n-butyl)amine / tri(n-hexyl)amine, tri(n-butyl)amine / tri(n-heptyl)amine, tri(n-propyl)amine / tri(n-octyl)amine, tri(n-propyl)amine / tri(n-nonyl)amine, tri(n-propyl)amine / tri(n-decyl)amine, etc.; tri(n-butyl)amine / tri(n-pentyl)amine, tri(n-butyl)amine / tri(n-hexyl)amine, tri(n-butyl)amine / tri(n-heptyl)amine, tri(n-butyl)amine / tri(n-octyl)amine, tri(n-butyl)amine / tri(n-nonyl)amine, tri(n-butyl)amine / tri(n-decyl)amine, etc., and similarly, instead of n-alkylamines, combinations with isoalkylamines are preferred.

[0063] A-body The A bodies may be selected from the group consisting of activated carbon, graphite, carbon molecular sieves, iron hydroxide, and one or more polymers.

[0064] The A-body comprises one or more polymers. It may be a polymer of a single monomer or a copolymer of several different monomers. One preferred polymer is polystyrene, preferably polystyrene divinylbenzene copolymer (polystyrene DVB), polystyrene DVB acrylate, acrylate DVB copolymer, styrene ethylvinylbenzene (EVB) copolymer or mixed styrene DVB / EVB polymer. Another preferred polymer is acrylate and copolymer of acrylate polymer, such as polyacrylonitrile. Another preferred polymer is methacrylate. Another preferred polymer is phenol formaldehyde resin. The preferred polymer is hydrophobic.

[0065] A preferred embodiment is an A-body, which is activated by the addition of one or more N components, i.e. a first N component and optionally further N components, preferably by impregnation or covalent bonding. Preferably, the A-body can be defined as the M-body described in relation to the processing step. Preferably, the N-component of the A-body has one or more moieties with a carbon chain of length 4 or less, here an L-chain. Preferably, the carbon chain length is 1 or 2.

[0066] Some further preferred L chain moieties are alkyl, such as butyl, propyl and ethyl. Preferred L chains have up to 4 carbon atoms, such as 1 to 4 carbon atoms, i.e. 1, 2, 3 or 4 carbon atoms. One preferred further N moiety is trimethylamine. One preferred further N moiety is triethylamine. One preferred further N moiety is tri(n-propyl)amine. One preferred further N moiety is tri(n-butyl)amine.

[0067] The multiple A entities used in the pretreatment step can include two or more different A entities, as described above.

[0068] The A body is preferably porous. The A body is preferably penetrable by liquids. Preferred A bodies have a maximum capacity to soak up up to 10 times their own mass in water.

[0069] Body A may have pores. Preferred pores are micropores, mesopores or macropores. Body A may have a combination of two or more selected from micropores, mesopores and macropores.

[0070] One preferred type of A body is a bead. Beads can be prepared by aggregation of smaller particles. The diameter d of A body is 50 The preferred range of diameter d is 10 μm to 10 mm, preferably 50 μm to 5 mm, and more preferably 100 μm to 1 mm. 50 Another preferable range is 0.05 to 1.5 mm.

[0071] One preferred type of A-body is a powder. The powder can be prepared by grinding larger particles, preferably by grinding beads. The diameter d of A-body is 50 The preferred range is 1 to 200 μm, preferably 10 to 100 μm, and more preferably 40 to 60 μm or 40 to 80 μm.

[0072] The preferred grinding process is dry grinding and wet grinding, preferably wet grinding. Grinding can be carried out under atmospheric conditions. Grinding can be carried out at high or low temperatures. The preferred grinding is freeze grinding, preferably using liquid nitrogen. One method of reducing the diameter of A-body is homogenization, preferably by hammer mill or jet mill.

[0073] One preferred type A body has a tensile strength of 300 mm, as measured according to DIN ISO 9277:2003-05. 2 / g or more, for example, 400m 2 / g or more, 600m 2 / g or more, 800m 2 / g or more, or 1000m 2 / g or more. The BET of A-type is 2000m 2 / g or less, 1600m 2 / g or less, 1400m 2 / g or less or 1200m 2 / g or less.

[0074] Combinations of bodies used in pretreatment and treatment A preferred embodiment comprises bodies A in powder form in the pretreatment step and bodies M in bead form in the treatment step. For example, 80%, 90% or more by weight of bodies A are powders in the pretreatment step and 80%, 90% or more by weight of bodies M are beads in the treatment step. Often, less than 5%, or less than 2%, or less than 1% by weight of bodies A are not powders. Often, less than 5%, or less than 2%, or less than 1% by weight of bodies M are not beads.

[0075] In a preferred process design, both the pre-treatment and treatment steps are operated in two or more separate treatment vessels. The two or more treatment vessels can be fluidly connected. The vessel containing A bodies is placed upstream of the vessel containing M bodies. Each vessel has at least a fluid inlet and a fluid outlet. This process design can be beneficial when separate disposal of exhausted A bodies and M bodies is planned. A membrane for retaining A bodies in the treatment vessel can be placed between A bodies and the outlet of the vessel containing A bodies.

[0076] In another preferred process design, both pretreatment and treatment steps are operated in a single vessel. In this case, the M bodies are placed in the vessel and the A bodies are placed upstream of the M bodies in the flow direction. This process design can be beneficial if combined disposal of the exhausted A and M bodies is planned.

[0077] Furthermore, a separation membrane may be placed between a spatial section in the vessel containing M bodies and another spatial section in the vessel containing A bodies. The purpose of such a membrane may be to keep the A antibodies separated from the M bodies. This process design may be beneficial if separate disposal of the exhausted A bodies and M bodies is planned.

[0078] A preferred embodiment includes one or more membranes, i.e., membrane arrangements, for retaining the A and / or M bodies. Examples of suitable membranes are filters, fibrous sheets, perforated sheets, plastic sheets with holes, etc. Combinations of the foregoing can also be used. In a further preferred variation, the one or more containers containing the A and M bodies, or combinations thereof, have perforations incorporated therein, for example between the interior of the container and an outlet to the container.

[0079] In any case, the perforations, hole diameter or fineness of the filter should be selected to be the same size as or slightly smaller than the size of the respective A and M bodies to be retained. The membranes may be part of single use and multi-use and / or self-cleaning systems.

[0080] In any case, if a pre-treatment step is included in the process, the precursor liquid is fed to the pre-treatment step, at the end of which a source liquid is obtained, which then enters a treatment step, at the end of which a treatment liquid is obtained.

[0081] In a preferred embodiment, the precursor liquid is aqueous and includes one or more halogenated organic compounds as X components and B components such as NOM and NOM derivatives, and the resulting process liquid can be selected from drinking water, process wastewater, etc.

[0082] In another preferred embodiment, the precursor liquid is aqueous and contains one or more radionuclides as the X component, and the resulting treated liquid is of sufficient purity to allow the treated liquid to be discharged into a river or stream.

[0083] Preparation of culture medium Here, various methods for preparation of the medium, M bodies, are described.

[0084] A. Impregnation One preferred process for preparing the M body is impregnation. The impregnation is preferably carried out by immersing the R body in a fluid containing the N component. The preferred fluid medium for the N component may be water or an organic solvent. The preferred fluid medium is selected by those skilled in the art to suit the R body and the N component. Some preferred fluid media are one or more selected from the group consisting of water, hexane, acetone, dimethylformamide and methylformamide.

[0085] Impregnation may be carried out at ambient temperature or at an elevated temperature. The temperature is preferably appropriate for the fluid medium. Impregnation is preferably carried out with stirring or shaking or both. Impregnation is preferably carried out for a period of time ranging from 10 minutes to 2 days, preferably from 1 hour to 1 day, more preferably from 3 hours to 8 hours.

[0086] In the case of Powder R bodies, impregnation can take place before or after the grinding step, preferably before.

[0087] If the impregnation is carried out in a non-aqueous fluid medium, a solvent exchange is preferably carried out to replace the fluid medium with water.

[0088] If the N component is a gas in the temperature range of 20-100° C., impregnation can be carried out at lower temperatures, at superatmospheric pressure, or both. Autoclaves are usually well suited to employ these conditions.

[0089] B. Covalent bond Another preferred process for preparing M entities is covalent bonding, preferably halogen substitution. The formation of the covalent bond between the N moiety and the R entity preferably starts from a halogen-activated R entity, more preferably from a chlorine-activated R entity. A preferred chlorination is the Blanc reaction, preferably using formaldehyde and HCl. Another route to covalent bonding is via an oxirane-activated acrylic.

[0090] The substitution of the N component is preferably carried out at an elevated temperature, preferably above 80°C, more preferably above 90°C, more preferably above 100°C. A preferred liquid medium for the substitution reaction is dimethylformamide. A preferred concentration of the N component in the liquid medium is 10-70% by weight, preferably 20-60% by weight, more preferably 30-50% by weight. The substitution is preferably carried out for 3-24 hours, more preferably 5-20 hours, more preferably 8-15 hours. The substitution is preferably carried out with stirring or shaking or both.

[0091] If the N component is a gas in the temperature range of 20-100 °C, the chemical reaction to form the covalent bond can be carried out at lower temperatures, overpressure, or both. Autoclaves are usually well suited to employing these conditions.

[0092] C. Preparation of mixed amine media by impregnation A preferred process for preparing M bodies is a two-step repeated impregnation, the first impregnation being carried out as described in Method A.

[0093] After the first impregnation is completed, the M body containing the R body soaked in the N component is contacted with a specific amount of an acidic liquid to adjust the pH of the M body.

[0094] The acidic liquid may be any aqueous acidic solution. A preferred acidic solution is a solution containing HCl. A preferred solution containing HCl has a concentration of 5-30% by weight HCl, or about 25% by weight HCl, or about 10% by weight HCl, with the remainder to 100% by weight always being water. The M bodies are then washed with water.

[0095] Further impregnation is carried out with these M bodies by contacting them with a further specific amount of fluid containing a further N component. The embodiment of this further impregnation is the same as that described above for the first impregnation. Again, the M bodies can be contacted with a specific amount of an acidic liquid to adjust the pH of the M bodies. The same as the previous embodiment.

[0096] A preferred choice for the first impregnation is an N moiety with a carbon chain length of at least 5 and, as described above, with one or more moieties having an L chain here.

[0097] A preferred choice for the further impregnation is an N component with a carbon chain length of at least 5, as described above, now having an L chain, and having one or more moieties different from the carbon chain used in the first impregnation.

[0098] Another preferred choice for the further impregnation is an N component with a carbon chain length of 4 or less, e.g. 3, 2 or 1, as described above, now having an L chain, and one or more moieties different from the carbon chain used in the first impregnation.

[0099] If the N component is a gas in the temperature range of 20-100° C., impregnation can be carried out at lower temperatures, at superatmospheric pressure, or both. Autoclaves are usually well suited to employ these conditions.

[0100] D. Preparation of mixed amine media by covalent coupling in two steps Another preferred process for preparing M entities is covalent bonding, preferably halogen substitution. The formation of the covalent bond between the N moiety and the R entity preferably starts from a halogen-activated R entity, more preferably from a chlorine-activated R entity. A preferred chlorination is the Brann reaction, preferably using formaldehyde and HCl. Another route to covalent bonding is via an oxirane-activated acrylic.

[0101] In this embodiment, the substitution with two different N components is carried out. This can be carried out simultaneously using a mixture of two or more N components. Another more preferred option is to carry out two or more substitution reactions in succession. pH adjustment and washing steps can be intermediate.

[0102] The substitution of the first N component is preferably carried out at elevated temperatures, preferably above 80°C, more preferably above 90°C, more preferably above 100°C. A preferred liquid medium for the substitution reaction is dimethylformamide. A preferred concentration of the first N component in the liquid medium is 10-70% by weight, preferably 20-60% by weight, more preferably 30-50% by weight. The substitution is preferably carried out for 3-24 hours, more preferably 5-20 hours, more preferably 8-15 hours. The substitution is preferably carried out with stirring or shaking or both.

[0103] If the N component is a gas in the temperature range of 20-100 °C, the chemical reaction to form the covalent bond can be carried out at lower temperatures, overpressure, or both. Autoclaves are usually well suited to employing these conditions.

[0104] After the first replacement, the M body including the R body immersed in the N component is contacted with a specific amount of an acidic liquid to adjust the pH of the M body. The acidic liquid may be any acidic aqueous solution.

[0105] A preferred acidic solution is a solution containing HCl. A preferred solution containing HCl has a concentration of 5-30% by weight HCl, or about 25% by weight HCl, or about 10% by weight HCl, with the remainder to 100% by weight always being water. The M body is then washed with water.

[0106] The substitution of the further N component different from the first N component is preferably carried out at elevated temperature, preferably above 80° C., more preferably above 90° C., more preferably above 100° C. The preferred liquid medium for the substitution reaction is dimethylformamide.

[0107] If the N component is a gas in the temperature range of 20-100 °C, the chemical reaction to form the covalent bond can be carried out at lower temperatures, overpressure, or both. Autoclaves are usually well suited to employing these conditions.

[0108] The preferred concentration of the further N component in the liquid medium is 10-70% by weight, preferably 20-60% by weight, more preferably 30-50% by weight. The replacement is preferably carried out for 3-24 hours, more preferably 5-20 hours, more preferably 8-15 hours. The replacement is preferably carried out with stirring or shaking or both.

[0109] A preferred choice for the first impregnation is an N moiety with a carbon chain length of at least 5 and, as described above, with one or more moieties having an L chain here.

[0110] A preferred choice for the further impregnation is an N component with a carbon chain length of at least 5, as described above, now having an L chain, and having one or more moieties different from the carbon chain used in the first impregnation.

[0111] Another preferred choice for the further impregnation is an N component with a carbon chain length of 4 or less, e.g. 3, 2 or 1, as described above, now having an L chain, and one or more moieties different from the carbon chain used in the first impregnation.

[0112] Preferred M entities may have a first moiety and a further N moiety in a ratio of 1:20 to 20:1, such as 1:15 to 15:1, or 1:10 to 10:1, or 1:4 to 4:1, or 2:3 to 3:2, or about 1:1.

[0113] E. Preparation of Mixtures of Different Amine Media Combinations of different species of M bodies, combinations of a first species and a further species of M bodies are provided. Each species of M body comprises at least one N moiety and can be obtained according to methods A to D. Preferred species of M bodies are as follows: [Table 1]

[0114] Preferred mixtures of species of the M form are, inter alia, S1S1*, S1S2, S1S3, S1S4, S1S5, S1S6, S3S3*, S3S4, S3S5, S3S6, S5S5* and S5S6. A species marked with an asterix (*) in this list explains that this species of the M form belongs to the same class of species but is different from species not marked with an asterix (*).

[0115] In preferred mixtures of the first and further species of M bodies, the ratio may be from 1:20 to 20:1, for example from 1:15 to 15:1, or from 1:10 to 10:1, or from 1:4 to 4:1, or from 2:3 to 3:2, or about 1:1.

[0116] More preferred mixtures of M bodies contain three or more different species of M bodies.

[0117] With respect to all further steps and uses such as drying, solvent exchange and housing, the mixture of different M bodies is also referred to as "M bodies".

[0118] III. Drying In one embodiment of the present invention, the M bodies are dried to reduce their water content. One preferred drying method is infrared drying. Another preferred drying method is under reduced pressure.

[0119] IV. Solvent Exchange In one preferred preparation, a solvent exchange step is performed, which may be particularly preferred when the N moiety is introduced into the R configuration in a non-aqueous solvent such as an organic solvent.

[0120] housing The housing is the device that hosts the exchange medium (M body) and through which the liquid is flushed. The housing may have one or more inlets, one or more outlets, and possibly further connections for liquid exchange and / or sensors. The housing can be made of various materials such as glass, plastic and / or metal. The housing may also include parts made of different materials, e.g. parts of glass and other parts of metal.

[0121] drawing 1 shows a schematic diagram of a process for preparing a treated liquid. The treatment process includes at least the steps of providing a feed liquid at 101, providing a plurality of solid ion exchange media, e.g., M bodies, at 102, and contacting the feed liquid with the plurality of solid ion exchange media at 103.

[0122] A schematic sample experimental setup is shown in Figure 2. A feed liquid 111 is fed into a column 112, in which are stacked beads 113 of ion exchange media. A treated liquid 114 exits the column 112. EXAMPLES

[0123] I. Impregnation 1. Preparation of CTAC-activated ion exchange media 5 g of porous polystyrene polymer (Treverlite 510IXA in chloride form available from Chemra GmbH) was shaken for 8 hours in 50 ml of a 25 wt % aqueous solution of cetyltrimethylammonium chloride. It was then washed with water. The preparation process was repeated, except that a 25 wt % aqueous solution of tri(n-octyl)amine was used.

[0124] 2. Preparation of tri(n-octyl)amine-activated ion exchange resin 1 g of porous polystyrene polymer (Treversorb ADS 500 available from Chemra GmbH) was washed with water, acetone and n-hexane. The gel was shaken with a 30% solution of tri(n-octyl)amine in hexane for 8 hours. It was then washed with acetone and water. Successful adsorption of the amine was demonstrated by elemental analysis. [Table 2]

[0125] 3. Determination of adsorption capacity of nonafluorobutanesulfonic acid (PFAS) 1 g of medium dried to constant mass was shaken in 25 ml of 0.2 M aqueous nonafluorobutanesulfonic acid (Aldrich, MW = 300 g / mol) for 8 h. The residual concentration of nonafluorobutanesulfonic acid in the aqueous solution was then determined by titration with 0.1 M NaOH. The amount of PFAS adsorbed was determined by difference.

[0126] 4. Results In both cases, the capacity for PFAS adsorption was significantly increased compared to the non-activated ion exchange resin.

[0127] In both cases, the activated polymer resins had significantly greater capacity than similar activated porous carbon species prepared according to the method disclosed in US Pat. No. 5,399,323.

[0128] II. Covalent bond 1. Chloromethylation of PS-DVB Copolymer with 2 Weight Percent DVB A mixture of paraformaldehyde (20 g) and 1,4-butanediol (30 g) in a flask was cooled to about 7° C. in a cold water bath and hydrogen chloride gas was passed through the flask for 7 hours. The mixture was then cooled to 0° C. overnight and separated into two layers. The upper layer was collected, dried over magnesium sulfate, and distilled in vacuo to give 1,4-bis(chloromethoxy)butane.

[0129] To a stirred suspension of 1.04 g (0.01) of polystyrene-2% divinylbenzene (Supelco 434442, Merck KgAA) and 3.74 g (0.02 mol) of 1,4-bis(chloromethoxy)butane in 20 ml of dichloromethane, 0.05 ml (0.004 mol) of tin chloride was added slowly at 0° C. The reaction mixture was stirred at room temperature for 18 hours. The mixture was then cooled to 0° C. and treated with 15 ml of 1N hydrochloric acid. The polymer beads were collected by filtration and washed with water-dioxane, dioxane, methanol and dichloromethane. The beads were dried overnight in vacuum at room temperature.

[0130] 2. Amination with tertiary amines (NR3), e.g., trioctylamine The reaction was carried out in a double-walled, three-necked round-bottom flask (500 ml) equipped with a powerful condenser in the middle tube. The condenser was attached to a water cooler and the top outlet to an argon supply. The side tube was fitted with a dropping funnel with gas compensation. A third tube was used to insert a thermometer into the medium and record the temperature. The double wall of the round-bottom flask was connected to a thermostat, and oil was purged through the thermostat to regulate the temperature in the round-bottom flask. A Teflon-coated magnet was placed in the round-bottom flask, which was placed on a magnetic stirrer. The apparatus was flushed with argon before use.

[0131] 100 g of chlorinated polymeric ion exchange material from step 1 and 200 ml of dichloromethane were placed in a round bottom flask and cooled to a temperature of 10-15°C. 150 ml of a 1:2 (volume / volume) mixture of tri(n-octyl)amine (CAS number 1116-76-3) and dichloromethane were added dropwise with stirring over a period of 1 hour using a dropping funnel while maintaining a temperature of 10-15°C, and the resulting mixture was stirred and refluxed overnight. The contents of the round bottom flask were then poured onto a glass frit (type MN85 / 90, 0.45 μm, Macherey & Nagel) and the modified ion exchange material was separated from the liquid phase. The modified ion exchange material (solid residue in the frit) was washed three times with 300 ml of 2 mol / l HCl and further washed three times with 300 ml of aqua dest. The modified ion exchange material was then washed with 200 ml each of i-propanol, methanol and acetone and dried in a dry box at 50° C. under vacuum for 12 hours.

[0132] 3. Determining exchange capacity The separation column is filled with 60 ml of 0.2 mol / kg HCl solution, washed with 60 ml of aqua dest, chloride is eluted with 60 ml of 0.2 mol / kg NaNO3 solution, and 1 ml of 6 Mol / kg HNO3 is added to the eluate. Potentiometric titration of Cl with 0.05 mol / kg AgNO3 against a calomel electrode (Ag / AgCl electrode); each capacity is measured in triplicate. Capacity is given in μmol / column and μmol / mL of the column volume.

[0133] 4. Mixed amination First, the amination was carried out as in 2 above. Then, the second amination was carried out as above, but a 1:2 (volume / volume) mixture of tri(n-propyl)amine (CAS number 102-69-2) and dichloromethane was applied as above. The further procedure remained unchanged.

[0134] 5. Results In all cases, the capacity for PFAS adsorption was significantly increased compared to the non-activated ion exchange resin.

[0135] In all cases, the activated polymer resins had significantly greater capacity than similar activated porous carbon species prepared according to the method disclosed in US Pat. No. 5,399,323.

Claims

1. 1. A treatment process for preparing a treatment solution, the treatment process comprising the following treatment steps: a. providing a feedstock solution, the feedstock solution comprising: i. water in a content of at least 70% by weight; ii. at least 10 －１０ one or more X components in a total content of % by weight, each X component being a halogenated organic compound having two or more halogen atoms per molecular unit, or each X component being a complex ion containing at least one radionuclide; and b. Providing a plurality of solid M bodies, each M body comprising: i. R forms of one or more R moieties in a total dry weight content of at least 80 wt %, wherein each R moiety is a polymer; ii. a first N component and optionally further N components adjacent to said R entities in a total dry weight content ranging from 0.1 to 10 wt %, wherein each N component comprises an N atom present as an amine or ammonium; iii. Optionally, water in an amount of up to 90% by weight based on the total weight of the M bodies; and c) contacting the raw material liquid with the plurality of M bodies to obtain the treatment liquid, wherein the treatment liquid has a lower total content of X components than the raw material liquid; Including, A process wherein at least said first N component has one or more L chains linked to said N atom, each L chain having a C chain of length 5 or more.

2. The process of claim 1 , wherein there are one or more covalent bonds between the R entity and the N moiety.

3. 3. The process of claim 1 or 2, wherein there are one or more non-covalent bonds between the R entity and the N moiety.

4. One or more of the X components is X ＊ component, and each X ＊ The component has 20 or less carbon atoms per molecular unit, and X in the treatment solution ＊ The total content of the components is ＊ 3. The process of claim 1 or 2, wherein the total content of the components is less than the total content of the components.

5. 3. The process of claim 1 or 2, wherein one or more of the R forms is a gel form.

6. One or more of the R isomers is a. one or more micropores; b. one or more mesopores; c. one or more macropores; 3. The process of claim 1 or 2, comprising one or more of:

7. 3. The process of claim 1 or 2, wherein one or more of the X moieties comprises one or more F atoms per molecule.

8. 3. The process of claim 1 or 2, wherein one or more of the X moieties comprises one or more Cl atoms.

9. 3. The process of claim 1 or 2, wherein one or more of the X components comprises one or more perhalogen moieties.

10. 3. The process of claim 1 or 2, wherein one or more of the X components comprises a chemical complex containing a radionuclide.

11. The plurality of M bodies meets the following criteria: a. M body diameter d in the range of 10 μm to 10 mm ５０ and, b. 1 nm to 10 ４ Pore ​​diameter d in the nm range ５０ and, c. a moisturizing capacity in the range of 20-90%, the maximum water content based on the total weight of the wet body; The process according to claim 1 or 2, wherein one or more of the following conditions are satisfied:

12. The plurality of M bodies meets the following criteria: a. M body diameter d in the range of 1 to 200 μm ５０ and, b. 1 nm to 10 ４ Pore ​​diameter d in the nm range ５０ and, c. a moisturizing capacity in the range of 20-90%, the maximum water content based on the total weight of the wet body; The process according to claim 1 or 2, wherein one or more of the following conditions are satisfied:

13. One or more of the plurality of M entities may be prepared by the following preparation process steps: a. providing a plurality of R-isomers; b. Providing a fluid containing one or more N components; c) contacting the plurality of R bodies with the fluid to obtain the plurality of M bodies; and 3. The process of claim 1 or 2, wherein the plurality of M isomers has a total content of N moieties greater than that of the plurality of R isomers.

14. One or more of the plurality of M entities may be prepared by the following preparation process steps: a. providing a plurality of R entities, each R entity being functionalized at least once with one or more halogens; b. Providing a fluid containing one or more N components; c) contacting said plurality of R entities with said fluid to obtain said plurality of M entities by replacing one or more of said halogen functionalities with an N moiety; 3. The process according to claim 1 or 2, which is obtainable by a preparation process comprising:

15. The process according to claim 1 or 2, wherein the treatment process includes a step of adding the plurality of M bodies to the raw material liquid.

16. The plurality of M-bodies are contained in modules, and the processing process comprises the following steps: a. introducing the feedstock liquid into the module prior to the contacting step; b. after the contacting step, the processing liquid exits the module; 3. The process of claim 1 or 2, comprising:

17. The process of claim 1 , wherein the further N moiety has one or more L chains linked to the N atom, and the further N moiety is different from the first N moiety.

18. 18. The process of claim 17, wherein each L chain of the further N components has a C chain of length 5 or more.

19. 18. The process of claim 17, wherein each L chain of the further N components has a C chain of length 4 or less.

20. 19. The process of claim 17 or 18, wherein the first N component and the further N component are present in a ratio of 1:20 to 20:

1.

21. 3. The process of claim 1 or 2, wherein the plurality of solid M bodies comprises at least two species of M bodies, a first species and an additional species, and the M bodies of the first species and the M bodies of the additional species are different from each other.

22. 22. The process of claim 21, wherein the M bodies of the first species and the M bodies of the further species are present in a ratio of 1:20 to 20:

1.

23. Before step a, a pre-processing is performed, and the pre-processing includes at least the following steps: A) providing a precursor liquid, said precursor liquid comprising: I) water; II) one or more X components, each X component being a halogenated organic compound having two or more halogen atoms per molecular unit, or each X component being a complex ion containing at least one radionuclide; III) one or more B components; and and B) providing a plurality of solid A entities, each A entity being an element selected from the group consisting of activated carbon, graphite, carbon molecular sieves, iron hydroxide, and polymers; C) contacting the precursor liquid with the plurality of A bodies to obtain the raw material liquid, wherein the raw material liquid has a smaller amount of B component than the precursor liquid; 2. The process of claim 1, comprising:

24. The plurality of A entities are determined based on the following criteria: a) Diameter d of body A ５０ is in the range of 1 to 200 μm; b) At least 50% of the A-form is 300 to 2000 m ２ / g; and c) At least 50% of the A isomers are 1 to 10 ４ having pore sizes in the nm range; 24. The process of claim 23, wherein one or more of the following conditions are satisfied:

25. 25. The process of claim 23 or 24, wherein the B component is selected from the group consisting of humic substances and natural organic matter.

26. A water treatment plant comprising a plurality of M bodies, the M bodies comprising a first M body and optionally further a. at least 80 wt. % total dry weight content of the R forms of one or more R components, wherein each R component is a polymer; b. a first N component and optionally further N components adjacent to said R entities in a total dry weight content ranging from 0.1 to 10 wt %, wherein each N component comprises an N atom present as an amine or ammonium; and c. optionally, water in an amount of up to 90% by weight based on the total weight of the M bodies; Including, A water treatment plant, wherein at least said first N component has one or more L chains linked to an amino nitrogen, each L chain having a C chain of length 5 or more.

27. 27. The water treatment plant of claim 26, further comprising a plurality of A-bodies, each A-body comprising at least one element from the group consisting of activated carbon, graphite, carbon molecular sieves, iron hydroxide, and one or more polymers.

28. The plurality of A entities are determined based on the following criteria: a) Diameter d of body A ５０ is in the range of 1 to 200 μm; b) At least 50% of the A-form is 300 to 2000 m ２ / g; and c) At least 50% of the A isomers are 1 to 10 ４ having pore sizes in the nm range; 28. The water treatment plant of claim 27, wherein the water treatment plant satisfies one or more of the following conditions:

29. 29. The water treatment plant according to claim 27 or 28, wherein the A body is located upstream of the M body in relation to the direction of fluid flow in the water treatment plant.

30. Use of a plurality of M entities for water treatment, each M entity comprising: a. at least 80 wt. % total dry weight content of the R forms of one or more R components, wherein each R component is a polymer; b. a first N component and optionally further N components adjacent to said R entities in a total dry weight content ranging from 0.1 to 10 wt %, wherein each N component comprises an N atom present as an amine or ammonium; and c. optionally, water in an amount of up to 90% by weight based on the total weight of the M bodies; Including, The use wherein at least the first N component has one or more L chains linked to the amino nitrogen, each L chain having a C chain of 5 or more in length.

31. Use of a plurality of M entities for reducing the total content of X component in a liquid, each M entity comprising: a. at least 80 wt. % total dry weight content of the R forms of one or more R components, wherein each R component is a polymer; b. a first N component and optionally further N components adjacent to said R entities in a total dry weight content ranging from 0.1 to 10 wt %, wherein each N component comprises an N atom present as an amine or ammonium; and c. optionally, water in an amount of up to 90% by weight based on the total weight of the M bodies; Including, The use wherein at least the first N component has one or more L chains linked to the amino nitrogen, each L chain having a C chain of 5 or more in length.

32. 1. Use of a plurality of M bodies to reduce the total radionuclide content in a liquid, each M body comprising: a. at least 80 wt. % total dry weight content of the R forms of one or more R components, wherein each R component is a polymer; b. a first N component and optionally further N components adjacent to said R entities in a total dry weight content ranging from 0.1 to 10 wt %, wherein each N component comprises an N atom present as an amine or ammonium; and c. optionally, water in an amount of up to 90% by weight based on the total weight of the M bodies; Including, The use wherein at least the first N component has one or more L chains linked to the amino nitrogen, each L chain having a C chain of 5 or more in length.

33. 33. The use according to any one of claims 30 to 32 in combination with a plurality of A entities, said A entities being upstream of said M entities, each A entity being an element selected from the group consisting of activated carbon, graphite, carbon molecular sieves, iron hydroxide, and one or more polymers.

34. The plurality of A entities are determined based on the following criteria: a) Diameter d of body A ５０ is in the range of 1 to 200 μm; b) At least 50% of the A-form is 300 to 2000 m ２ / g; and c) At least 50% of the A isomers are 1 to 10 ４ having pore sizes in the nm range; 34. The use according to claim 33, wherein one or more of the following conditions are satisfied:

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