EP4271515A1 - Production en continu de membranes échangeuses d'ions immobilisées sur un support en verre - Google Patents
Production en continu de membranes échangeuses d'ions immobilisées sur un support en verreInfo
- Publication number
- EP4271515A1 EP4271515A1 EP21847540.8A EP21847540A EP4271515A1 EP 4271515 A1 EP4271515 A1 EP 4271515A1 EP 21847540 A EP21847540 A EP 21847540A EP 4271515 A1 EP4271515 A1 EP 4271515A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- ion exchange
- comprised
- support material
- cross
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 53
- 239000011521 glass Substances 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 73
- 230000008569 process Effects 0.000 claims abstract description 55
- 239000003463 adsorbent Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010612 desalination reaction Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000005202 decontamination Methods 0.000 claims abstract description 9
- 230000003588 decontaminative effect Effects 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims description 62
- 239000011324 bead Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 39
- 238000004132 cross linking Methods 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 17
- 238000004873 anchoring Methods 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 12
- 229920002530 polyetherether ketone Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 239000011859 microparticle Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- ZJDGKLAPAYNDQU-UHFFFAOYSA-J [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O Chemical class [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O ZJDGKLAPAYNDQU-UHFFFAOYSA-J 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 claims 3
- 238000005112 continuous flow technique Methods 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000002440 industrial waste Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000001728 nano-filtration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 231100000824 inhalation exposure Toxicity 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- -1 poly (ether sulfone ketone Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- 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
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
Definitions
- the present invention relates to adsorbent cartridges each one comprising cross-linked ion exchange membranes anchored to a support material, a process based upon a continuous flow technique for the production of said cartridges as well as the use of the same for the desalination and/or decontamination and/or purification of water.
- the membranes based upon poly (ether ether ketone) sulfonate (“SPEEK”) are widely used in processes of nanofiltrations and inverse osmosis.
- SPEEK poly (ether ether ketone) sulfonate
- the corresponding covalently cross-linked ones are nowadays substantially unexplored in said fields (Briggs, et al. 2017 DURABLE ASYMMETRIC COMPOSITE MEMBRANE United States HYDROXSYS HOLDINGS LIMITED (Auckland, NZ) 20170086469; Craft, Lenka Benacek et al. 2017 ASYMMETRIC COMPOSITE MEMBRANE AND A METHOD OF PREPARATION THEREOF HYDROXSYS HOLDINGS LIMITED (Auckland, NZ) PCT/IB2016/055899).
- the high degree of sulfonation (DS) allows to obtain high ion exchange capabilities and the structural polarity limits problems relating the “fouling” of the membranes themselves, which influences directly the durability thereof.
- the cross-linking of covalent nature can confer on the membrane a considerable chemical stability and physical robustness apart from the capability of limiting the swelling thereof, for example in aqueous means, thus allowing to work under contained pressure conditions.
- the low-cost SPEEK-type membranes thanks to their chemical and physical features are currently used for processes of nanofiltration, inverse osmosis, for the purification of waste water coming from industrial waste and for the desalination of marine and brackish water.
- their polar nature limits the fouling thereof due to the accumulation of hydrophobic substances such as proteins and many other contaminants, thus involving a decrease in management costs and a higher durability with respect to membranes consisting of hydrophobic materials.
- Glass beads as such are used as filtering agents for processes for the removal of suspended solids, by replacing the sand filtration procedures. Their use determines the development of more effective filtration protocols, by allowing the application of better flow rates with a considerable decrease in investment costs. Moreover, they are capable of considerable hydraulic performances and they can be cleaned easily.
- the first one provides the immersion of the glass beads, at constant speed, in a tank containing the material to be put in solution, preferably by avoiding abrupt stirring; the beads then remain still and immersed - in the closed tank - to allow the coating thereof by the material and, at last, they are removed at constant speed, by leaving them to drain to remove the solution excess.
- the “casting” technique instead, provides for the use of open tanks which allow the evaporation of the solvent and the consequent formation of a film on the surface of the beads (X. D. Liu et al., Surface modification of nonporous glass beads with chitosan and their adsorption fortransition metal ions, Carbohydrates Polymers, 2002, 49, 103-108).
- the low homogeneity/reproducibility of the coating film which is obtained generally represents the greater disadvantage of such techniques.
- a coating inhomogeneity causes the impossibility of obtaining a uniform distribution of sizes of the pores of the film at issue, involving a not constant response of the system in its application.
- the not always optimum percentage of coating represents a further limit.
- Other disadvantages are the material loss and the long process time - above all with reference to the immersion technique - and the exposure to the inhalation of (typically toxic) solvent vapours.
- an oxidizing solution NaCIO, KMnC
- a second dosing pump in this way filtering systems constituted by MnOx(s) are obtained which are washed (still continuously), dried (discontinuously) and used for removing manganese from water.
- the water treatment protocols resulted to be more effective than those using the same filtering system by immersion or “casting” techniques.
- the (perforated) tubular supports first of all are immersed for 2-3 h in deionized water, then placed in a baking chamber; the coating material, dissolved in a 17% solution by weight of acetone (volatile and unsafe solvent) is made to flow through the ceramics by using an electric pump for 5 minutes. Washing and drying the adsorbent system instead are carried out discontinuously; particularly, the exceeding solution is removed from the tubular system, the coating is made to gel by immersing it in a thermostated bath and the full system is dried to allow the removal of the solvent(s).
- acetone volatile and unsafe solvent
- the present invention relates to the development of a technology for the production of crosslinked ion exchange membranes, particularly membranes of organic polymeric type, anchored to support materials such as glass beads, with variable sizes, to obtain effectively adsorption systems, non-deformable over time, to be used in fixed-bed columns useful in several industrial fields, preferably processes for the decontamination and/or purification of water.
- the authors of the present invention have devised a new process for the production of cross-linked ion exchange membranes anchored on support materials, for example glass beads, based upon a continuous flow technique.
- the use of systems in continuous mode can guarantee the formation of homogeneous “coating”, in considerably reduced process time.
- said ion exchange membranes are cross-linked membranes of poly (ether ether ketone) sulfonate (SPEEK), having a degree of sulfonation comprised between 0.60-0.95 (starting from a Degree of sulfonation, DS, equal to 1 with treatments between 2-33 hours at 180°C) and a structural polarity assisting the anchoring on glass.
- SPEEK poly (ether ether ketone) sulfonate
- the present invention relates to, is effective in the production of ready cartridges of SPEEK-type ion exchange membranes, in the specific case cross-linked, supported on glass beads with variable diameter. More specifically, the present invention provides for the implementation in continuous mode of the following processes in sequence: (i) coating of the support material with ion exchange membrane, (ii) in-situ cross-linking of the ion exchange membrane (iii) system porosity control by means of an inert gas, preferably nitrogen, (iv) washing and (v) drying.
- an inert gas preferably nitrogen
- Such “all-in-one” invention indeed, consists in the possibility of carrying out the above- mentioned steps without interruption, by reducing considerably the material loss, operation time and costs.
- the inhalation exposure to reagents and solvents is reduced to minimum.
- the present invention also provides for the incorporation, in the base material constituting the membrane, of micro- and nano-particles made of inorganic materials increasing the adsorbing capability and/or stability thereof, more specifically zirconium phosphates/phosphonates and/or metal organic framework (MOF).
- the base material constituting the membrane of micro- and nano-particles made of inorganic materials increasing the adsorbing capability and/or stability thereof, more specifically zirconium phosphates/phosphonates and/or metal organic framework (MOF).
- MOF metal organic framework
- the technology allows to implement, in a reproducible way, adsorbent systems based upon low-cost materials, and having ion exchange capability, robustness, porosity varying depending upon the application needs (“tailor-made” systems).
- An extremely important aspect in this technology is also related to the fact that the flow system, basically, can be automated with a much lower effort than the discontinuous processes (“batch”) and with a more effective control level, which is to be considered an advantage even from the safety point of view.
- DMSO is classified as “not dangerous substance” according to the current European legislation (EC Nr. 1272/2008) and this is particularly relevant in fields such as decontamination/purification of water, where traces of residual toxic solvent have to be accurately removed before using said systems.
- the present invention relates to: an adsorbent cartridge comprising a cross-linked ion exchange membrane anchored to a support material; a process for the preparation of an adsorbent cartridge comprising a cross-linked ion exchange membrane anchored to a support material, comprising the following steps: i. arranging a support material inside a reactor; ii. coating said support material by continuous flow of a solution comprising a polymeric material, so as to form a film of said polymeric material on the surface of said support material; iii. anchoring said film to the surface of said support material; iv. cross-linking said polymeric material; v. washing the adsorbent cartridge obtained in step iv; vi. drying said adsorbent cartridge; and the use of one or more adsorbent cartridges according to any one of the herein described embodiments, for the decontamination and/or purification and/or desalination of water.
- Figure 1 Scheme example of continuous flow reactor for the production of ion exchange membranes immobilized on glass support.
- a first aspect of the present invention then relates to an adsorbent cartridge comprising a crosslinked ion exchange membrane anchored to a support material.
- said support material is a material in granular form, that is characterized by a spherical shape, having a diameter of few millimetres.
- said support material is substantially constituted by glass beads, wherein substantially it shows at least 90%, preferably at least 95% still more preferably at least 99%, still more preferably said support material substantially or wholly consists of glass beads.
- said glass beads have a diameter ⁇
- ion exchange membrane also known in English as “Ion Exchange Membrane” (I EM)
- I EM Ion Exchange Membrane
- a half-permeable membrane is meant, characterized by the presence of functional groups having positive and/or negative charge inside the matrix thereof it consists; the presence of these groups confers on the above-mentioned membrane the capability of allowing the interchange and/or selective passage of some ions.
- the ion exchange membranes can consist of an organic polymeric matrix or an organic and/or inorganic composite material.
- cross-linked used in the present description with reference to said ion exchange membrane, relates to the presence of cross-linked chains inside the membrane polymeric matrix, that is chains joined therebetween by covalent bonds (also called crossed bonds) having a bond energy equal to that of the chains’ atoms.
- covalent bonds also called crossed bonds
- the degree of cross-linking (DXL) influences the chemical and mechanical stability of an ion exchange membrane: a higher degree of cross-linking can confer for example on the membrane a greater robustness and size selectivity.
- the degree of cross-linking of an ion exchange membrane can be evaluated by means of determination of the ion exchange capability (I EC) of the membrane at the beginning and at the end of the cross-linking process, through the following equation:
- an ion exchange membrane suitable to be incorporated inside an adsorbent cartridge according to the present invention is a membrane having a cross-linking degree at least equal to 10%.
- said cross-linked ion exchange membrane is a proton exchange membrane or an anionic exchange membrane.
- said cross-linked ion exchange membrane is a membrane consisting of an organic polymer, preferably an organic polymer of polar nature.
- SPEEK poly (ether ether ketone) sulfonate
- SPEK poly (ether ketone ketone) sul
- said cross-linked ion exchange membrane is a poly (ether ether ketone) sulfonate (SPEEK) membrane.
- the poly (ether ether ketone) sulfonate is an organic polymer characterized by the following structure:
- SPEEK membranes have low cost and they are characterized by a polar nature limiting “fouling” phenomena of the membrane linked to the accumulation of hydrophobic substances, for example proteins, thus involving a decrease in the management costs and a greater durability with respect to membranes consisting of hydrophobic materials.
- An additional aspect of the present invention relates to an adsorbent cartridge comprising a crosslinked ion exchange membrane anchored to a support material, wherein said membrane incorporates, inside the polymeric matrix, micro- and/or nano-particles made of inorganic materials selected from phosphates or zirconium phosphonates and/or metalorganic structures (MOF).
- the resulting adsorbent cartridge is characterized by greater adsorbent capabilities and stability.
- said ion exchange membrane has a degree of sulfonation comprised between 0.85 and 0.95%, and/or it has a polarity, expressed in terms of water content (“water uptake”, Wil), at least equal to 110% at room temperature (25°C).
- the adsorbent cartridge comprises a cross-linked ion exchange membrane, anchored to said support material so as to form a film on the surface of said support material.
- said film consisting of the ion exchange membrane has a thickness comprised between 2-30 micron.
- said support material coated with a film of said ion exchange membrane is characterized by a percentage of coating (C%) at least equal to 90%, 95%, 98%, or 99%, wherein said C % is calculated by means of the following formula: c(%): [(Mcc - Msc) - Mti] x 100, wherein Mcc is the mass of the coated support material, Msc is the mass of the uncoated support material, Mti is the mass of said solid ion exchange membrane.
- An embodiment according to the present invention relates to an adsorbent cartridge comprising a plurality of glass beads, each one coated with an ion exchange membrane consisting of an organic polymer.
- a preferred embodiment according to the present invention particularly relates to an adsorbent cartridge comprising a plurality of glass beads, each one coated with a cross-linked SPEEK ion exchange membrane.
- said glass beads are characterized by a percentage of coating C% with cross-linked SPEEK membrane at least equal to 95%, wherein said C% is calculated by means of the following formula: c %)-. [(Mcc - Msc -? Mti] x 100, wherein Mcc is the mass of a coated bead, Msc is the mass of an uncoated bead, Mti is the mass of said solid ion exchange membrane.
- said cartridge according to any one of the previously described variants comprises an ion exchange membrane characterized by a porosity comprised between 20 and 60%.
- the present invention also relates to a process for the preparation of an adsorbent cartridge comprising a cross-linked ion exchange membrane anchored to a support material, comprising the following steps:
- a support material inside a reactor; ii. coating said support material by continuous flow of a solution comprising a polymeric material, so as to form a film of said polymeric material on the surface of said support material; iii. anchoring said film to the surface of said support material; iv. cross-linking said polymeric material; v. washing the adsorbent cartridge obtained in step iv; vi. drying said adsorbent cartridge.
- said support material substantially or wholly consists of glass beads, particularly glass beads having a diameter ⁇
- the polymeric material used in step ii. of the above-described process in form of solution preferably is an organic polymer.
- said organic polymer is poly (ether ether ketone) sulfonate (SPEEK).
- said solution made of polymeric material further comprises micro- and/or nano-particles made of inorganic materials selected from phosphates or zirconium phosphonates and/or metalorganic structures (MOF), so as to increase the resulting adsorbent capability and/or the stability of the ion exchange membrane.
- inorganic materials selected from phosphates or zirconium phosphonates and/or metalorganic structures (MOF)
- the step i. of the herein described process can be carried out by inserting the support material inside any reactor suitable to operate in continuous flow mode known in the art.
- reactor suitable to operate in continuous flow mode is represented by a thermostated reactor, comprising a chamber configured to house the support material to be coated with the ion exchange membrane, and which can be connected to at least a device with pump function capable of pumping one or more reactive flows to specific flow rates inside said chamber.
- a reactor comprising polymeric material, preferably teflon, it has a length comprised between 2-3 m and a diameter ⁇
- said reactor is thermostated at a temperature comprised between 30-50°C, and it is connected to a device with pump function.
- the step i. of the process according to any one of the herein described variants is carried out by means of a flow of inert gas, for example nitrogen.
- inert gas for example nitrogen.
- the use of an inert gas flow during the reactor filling step allows to obtain a compact packaging of the support material inside the reactor chamber.
- said solution made of polymeric material is made to flow cyclically, by means of a pump system, inside said reactor said reactor.
- the solution made of polymeric material usable in step ii. of the process is a solution comprising an organic polymer dissolved in an organic solvent.
- organic solvent most suitable for the preparation of a polymer solution to be used in the process according to the invention.
- said solution made of polymeric material is a solution of poly (ether ether ketone) sulfonate in dimethyl sulfoxide (DMSO).
- Said solution is characterized by a SPEEK concentration in a range comprised between 1 :6-1 :15 mg/mL, preferably 1 :8-1 :12 mg/mL.
- said solution made of polymeric material is made to flow inside the reactor by using a flow rate comprised in the range 1-10 mL/min, preferably between 3-5 mL/min.
- said step ii., or the contact time between the solution made of polymeric material and the support material has an overall duration comprised between 100-180 minutes.
- the reactor temperature is increased so as increase the viscosity of the solution made of polymeric material (favoured by an increase in the concentration due to the effect of partial evaporation of the solvent) and then to allow the anchoring of the film made of polymeric material on the surface of the support material.
- the anchoring step iii. is carried out at a temperature at least equal to 140°C.
- the reactor is heated so as to favour the covalent cross-linking of the film based upon polymeric material which coats the support material.
- the cross-linking step iv. is carried out at a temperature comprised between 160°C and 180°C for a duration comprised between 2 and 33 hours.
- inert gas particularly nitrogen
- nitrogen is made to flow inside the reactor, at a pressure comprised between 1-2 mbar.
- the nitrogen flow allows the formation of pores inside the coating of polymeric material, with a consequent increase in the surface area thereof and, then, an increase in the contact surface between the adsorbent and adsorbed material.
- the use of the gas flow during the cross-linking step preferably allows to obtain a degree of porosity of the film made of polymeric material anchored on the surface of the support material comprised in the range 20-60%.
- the adsorbent cartridge obtained at the end of step iv. comprises a cross-linked ion exchange membrane, anchored to said support material, characterized by a degree of porosity comprised between 20-60%.
- the adsorbent cartridge obtained at the end of step iv. can be subjected to washing so as to remove possible residues.
- an aqueous solution of sulfuric acid and, subsequently, distilled water are made to flow inside said reactor with a flow rate comprised between 2-3 mL/min.
- the adsorbent cartridge can be subjected to a drying process; according to an aspect of the invention the drying step vi. is carried out by means of nitrogen flow at a temperature equal to 120°C.
- the process according to any one of the previously described embodiments can include an additional step of chemical-physical characterization of the obtained adsorbent cartridge.
- Said characterization step can be performed, for example, with the purpose of determining the percentage of coating the glass beads, as well as to evaluate the performances and/or the degree of cross-linking of the coating ion exchange membrane, based upon polymeric material.
- a characterization method commonly used to evaluate the performances of an ion exchange membrane is represented by the determination of the ion exchange capability (IEC). This quantity is defined as the amount of exchangeable ions, expressed in milliequivalents or millimoles per gram of dry polymer (meq/g or mmol/g, respectively). It represents the total of the active sites or the functional groups responsible for the ion exchange in the ion exchange membrane.
- said cartridge characterization step provides for the determination of the ion exchange capability of said coating membrane by means of acidbase titration.
- the membrane first of all is immersed in a saline solution, for example a 1.5 N solution of NaCI, under stirring at room temperature, for an overall duration equal to 24 hours.
- the so-obtained solution is titrated with a base, for example a 0.02 N solution of NaOH.
- a base for example a 0.02 N solution of NaOH.
- the ion exchange capability of the system then can be determined by multiplying the so-obtained value by the amount of membrane homogenously dispersed in the reactor.
- the present invention also relates to an adsorbent cartridge obtainable by a process according to any one of the previously described embodiments.
- adsorbent cartridges according to any one of the herein described variants can be used in water treatment processes, for example nano-filtration processes in the treatment of waste water coming from industrial waste and desalination of marine and brackish water.
- the present invention then further relates to the use of one or more cartridges according to any one of the previously described embodiments, for the decontamination and/or purification and/or desalination of water.
- one relates, in the present description, to a process for the treatment and/or filtration of water aimed at removing and/or reducing the amount of harmful substances of chemical nature and/or biological nature inside the same, such as heavy metals, dyes, or pathogen microorganisms.
- pathogen microorganisms include bacteria, viruses, protozoa, fungi.
- said water can be waste water, for example water coming from industrial waste, sewage, marine, and/or brackish water.
- An aspect of the present invention particularly relates to the use of adsorbent cartridges as previously defined, wherein said adsorbent cartridges are used inside fixed bed columns and/or adsorbers.
- fixed bed columns are tubular reactors inside thereof glass beads coated with SPEEK membrane as described previously are arranged, therethrough a fluid current containing the substance(s) to be adsorbed is made to pass.
- the glass beads coated with SPEEK membrane are packed, still, inside the fixed bed column; vice versa the liquid phase is fed continuously.
- the treated current impoverishes progressively of the unwished solute.
- the present invention also relates to a process for the decontamination and/or purification and/or desalination of water comprising at least a step of transporting the water to be treated through one or more cartridges according to any one of the previously described embodiments.
- a predetermined amount of SPEEK deriving from the described protocol, (M.L. Di Vona, et al., Front. Energ. Res., 2, 39, 2014, 1-7; R. Narducci, PhD Thesis, University of Rome Tor Vergata, Aix-Marseille University 2014) is solubilized in dimethyl sulfoxide (DMSO) at room temperature and under stirring to obtain a solution at known concentration in the range 1 :8-1 :12 mg/mL, preferably 1 :10 mg/mL.
- DMSO dimethyl sulfoxide
- the method developed for creating the continuous flow system typically comprises the steps described hereinafter:
- the flow rate is comprised in the range 1-10 mL/min, more particularly 3-5 mL/min.
- the contact time between the SPEEK solution and the glass beads is comprised in the range 100-180 min.
- the reactor temperature, in a second moment, is increased preferably up to 140°C, to make viscous the solution (the concentration increases by partial evaporation of the DMSO) and to allow the membrane anchoring on the glass.
- the reactor is then heated at temperatures comprised between 160°C and 180°C for different periods of time, from 2 to 33 hours.
- the covalent cross-linking of the SPEEK-based film coating the glass beads takes place.
- inert gas in the specific case nitrogen, is made to flow into the reactor, at a pressure comprised between 1-2 mbar for different periods of time from 2 to 33 hours.
- the nitrogen flow allows the formation of pores inside the coating, with a consequent increase in the surface area thereof and, then, an increase in the contact surface between adsorbent and adsorbed material.
- the coating porosity is comprised in the range 20-60%.
- the adsorbent system obtained according to the described procedure then is subjected to washing, to remove possible residues.
- an aqueous solution of sulfuric acid and, subsequently, distilled water is made to flow in the reactor with a rate comprised in the range 2-3 mL/min.
- the adsorbent system is then dried by making nitrogen flow to pass in the reactor, at different temperatures, preferably at a temperature of 120°C.
- the percentage of coating (C) of the glass beads was evaluated, which is given by the difference between the mass of the coated beads (Mcc) and the mass of the uncoated beads (Msc), according to the Equation 1 ;
- M t j designates the mass of the solid membrane included in the initial solution in DMSO.
- the ion exchange capability was measured by acid-base titration (B. Maranesi et al., Cross- Linking of sulfonated poly ether ether ketone by thermal treatments: how does the reaction occur?, Fuel Cells, 2013, 13, 2, 107-117).
- a known amount of membrane in proton form was then collected by the system and it was converted into Na + form by immersion in 1.5 N solution of NaCI, under stirring at room temperature (24 h).
- the resulting solution was titrated with a 0.02N solution of NaOH.
- the pH was determined by potentiometric route, so as to determine the equivalent point. BY multiplying such value by the amount of membrane homogeneously dispersed in the reactor it was possible to evaluate the IEC of the total system.
- the procedure was carried out on the initial membrane and on the membrane after the thermal treatment, in the specific case carried out at 180°C (3h), inducing (final) cross-linking.
- FIG. 3 shows by way of example the results of the analyses for (a) a sample of beads obtained by using the method the present invention relates to, compared to those for (b) a sample obtained by using a discontinuous process (“batch”) and for (c) a sample of not supported membrane. It is clear that its own signals, typical and characteristic of (c) can be recognized in (a), and the intensity of such signals is much higher in (a) than in (b).
- the water content (“water uptake”, Wil) of SPEED-type membranes is usually expressed in grams (of water) per gram of anhydrous polymer (Eq. 3): wherein m(dry) and m(wet) are the dry and humid sample weight, respectively.
- the Wil value is correlated to the ion exchange capability and then to the number of the sulphonic groups (polar groups); the greater their number is, the greater Wil will be.
- the cross-linking then allows to modulate suitably this parameter, by allowing to reach the best compromise between the water content, the mechanical resistance and the ion exchange capability. In the specific case a Wil equal to 110% (25°C) was measured.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
La présente invention concerne des cartouches adsorbantes comprenant chacune une membrane échangeuse d'ions réticulée ancrée sur un matériau de support, un procédé basé sur une technique d'écoulement continu pour la production desdites cartouches ainsi que leur utilisation pour le dessalement et/ou la décontamination et/ou la purification de l'eau.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT202000032957 | 2020-12-31 | ||
PCT/IB2021/062247 WO2022144718A1 (fr) | 2020-12-31 | 2021-12-23 | Production en continu de membranes échangeuses d'ions immobilisées sur un support en verre |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4271515A1 true EP4271515A1 (fr) | 2023-11-08 |
Family
ID=75111782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21847540.8A Pending EP4271515A1 (fr) | 2020-12-31 | 2021-12-23 | Production en continu de membranes échangeuses d'ions immobilisées sur un support en verre |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP4271515A1 (fr) |
WO (1) | WO2022144718A1 (fr) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2194900B (en) * | 1986-09-12 | 1991-01-02 | Dow Chemical Co | High performance anion-exchange chromatographic packing composition |
DK165090D0 (da) * | 1990-07-09 | 1990-07-09 | Kem En Tec As | Konglomererede partikler |
-
2021
- 2021-12-23 EP EP21847540.8A patent/EP4271515A1/fr active Pending
- 2021-12-23 WO PCT/IB2021/062247 patent/WO2022144718A1/fr unknown
Also Published As
Publication number | Publication date |
---|---|
WO2022144718A1 (fr) | 2022-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yin et al. | Ultra-fine electrospun nanofibrous membranes for multicomponent wastewater treatment: Filtration and adsorption | |
Yang et al. | A de novo sacrificial-MOF strategy to construct enhanced-flux nanofiltration membranes for efficient dye removal | |
Yun et al. | High efficient dye removal with hydrolyzed ethanolamine-Polyacrylonitrile UF membrane: Rejection of anionic dye and selective adsorption of cationic dye | |
Kheirieh et al. | Application and modification of polysulfone membranes | |
McVerry et al. | Fabrication of low-fouling ultrafiltration membranes using a hydrophilic, self-doping polyaniline additive | |
CN110314559A (zh) | 一种界面聚合复合膜的制备方法 | |
Macanás et al. | Development of polymeric hollow fiber membranes containing catalytic metal nanoparticles | |
Ng et al. | Alteration of polyethersulphone membranes through UV-induced modification using various materials: A brief review | |
Buonomenna et al. | New PVDF membranes: The effect of plasma surface modification on retention in nanofiltration of aqueous solution containing organic compounds | |
Yao et al. | High-throughput thin-film composite membrane via interfacial polymerization using monomers of ultra-low concentration on tannic acid–copper interlayer for organic solvent nanofiltration | |
Tamaddondar et al. | Self-assembled polyelectrolyte surfactant nanocomposite membranes for pervaporation separation of MeOH/MTBE | |
Weidman et al. | Nanostructured membranes from triblock polymer precursors as high capacity copper adsorbents | |
Pei et al. | In situ one-pot formation of crown ether functionalized polysulfone membranes for highly efficient lithium isotope adsorptive separation | |
Qu et al. | Preparation of chemically-tailored copolymer membranes with tunable ion transport properties | |
CN106345324B (zh) | 一种杂化离子交换膜的制备方法 | |
CN105435653A (zh) | 一种对二价离子脱除具有高选择性的复合纳滤膜及其制备方法 | |
JP5795686B2 (ja) | 多孔膜上への機能性および再使用可能電着コーティング | |
US5151182A (en) | Polyphenylene oxide-derived membranes for separation in organic solvents | |
Hoffman et al. | Dual-functional nanofiltration membranes exhibit multifaceted ion rejection and antifouling performance | |
Hoffman et al. | 100th anniversary of macromolecular science viewpoint: integrated membrane systems | |
Qi et al. | Synergetic effects of COFs interlayer regulation and surface modification on thin-film nanocomposite reverse osmosis membrane with high performance | |
Wang et al. | Polyelectrolyte interlayer assisted interfacial polymerization fabrication of a dual-charged composite nanofiltration membrane on ceramic substrate with high performance | |
JP6210925B2 (ja) | ポリケトン多孔膜 | |
EP4271515A1 (fr) | Production en continu de membranes échangeuses d'ions immobilisées sur un support en verre | |
CN111974230B (zh) | 一种用于制备高通量反渗透膜的亲水性基膜的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230627 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) |