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WO2022122931A1 - Purifying polar liquids - Google Patents

Purifying polar liquids Download PDF

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Publication number
WO2022122931A1
WO2022122931A1 PCT/EP2021/085016 EP2021085016W WO2022122931A1 WO 2022122931 A1 WO2022122931 A1 WO 2022122931A1 EP 2021085016 W EP2021085016 W EP 2021085016W WO 2022122931 A1 WO2022122931 A1 WO 2022122931A1
Authority
WO
WIPO (PCT)
Prior art keywords
aems
cems
feed liquid
organic compound
inorganic salt
Prior art date
Application number
PCT/EP2021/085016
Other languages
French (fr)
Inventor
Bernardus Gerardus Johannes GOOSSENS
Eduard Jozef VAN DER BURG
Original Assignee
Fujifilm Manufacturing Europe Bv
Fujifilm Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujifilm Manufacturing Europe Bv, Fujifilm Corporation filed Critical Fujifilm Manufacturing Europe Bv
Publication of WO2022122931A1 publication Critical patent/WO2022122931A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2287—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention is related to a process for purifying a polar liquid, especially an aqueous feed liquid, using electrodialysis (ED) units.
  • ED electrodialysis
  • the first commercially available ED units were developed in the 1950's to demineralize brackish water. Since then, improvements in ion exchange membranes have lead to significant advances in ED.
  • ED units typically comprise one or more membrane stack. Each stack typically comprises an anode, a cathode and a number of cell pairs through which fluids pass. A cell pair comprises an ion diluting compartment and an ion concentrating compartment.
  • Each cell comprises a wall made from a negatively charged cation exchange membrane (CEM) and a wall made from a positively charged anion exchange membrane (AEM).
  • CEM negatively charged cation exchange membrane
  • AEM positively charged anion exchange membrane
  • ED units are therefore useful for converting a feed liquid comprising dissolved inorganic salts into a stream having a much lower content of such salts.
  • a typical ED unit is schematically illustrated in Fig.1.
  • the feed liquid is separated into streams (i) and (ii) (not shown): stream (i) (concentrate stream or concentrate): a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid; and stream (ii) (diluate stream or diluate): a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid, also referred to as product stream.
  • the focus is generally on cost effective removal of unwanted charged species such as dissolved inorganic salts.
  • the main intrinsic properties are the permselectivity (PS) and the electrical resistance (ER) of the AEMs and CEMs.
  • PS permselectivity
  • ER electrical resistance
  • the AEMs and CEMs have a PS as high as possible and an ER is low as possible to achieve an efficiency as high as possible.
  • the present invention may be used to remove inorganic salts from a feed liquid comprising an organic compound and inorganic salts, with a low loss of organic compound, using membranes having a high ER.
  • a process for purifying e.g.
  • an electrodialysis (ED) unit comprising a stack of cation exchange membranes (CEMs) and anion exchange membranes (AEMs), wherein at least one of the CEMs and the AEMs has a water permeability of less than 7.5*10 -12 m 3 /m 2 .s.kPa and an electrical resistance of at least 6.0 ohm.cm 2 .
  • ED electrodialysis
  • CEMs cation exchange membranes
  • AEMs anion exchange membranes
  • the economical benefit of this invention can be found in reduction of losses of the organic liquids during purification.
  • Typical costs for organic liquid purification range from € 200,000.- to € 2,500,000.- per year using evaporation techniques.
  • a decrease in loss of organic liquids during purification has a significant impact on the yearly cost of systems for purification of a feed liquid comprising an inorganic salt and an organic compound. It is estimated that this invention can reduce yearly cost of purification of feed liquids comprising an inorganic salt and an organic compound by reducing the loss of organic liquid to less than 700 kg loss of organic liquid per ton salt removal. This equals to € 92,000.- to € 1,100,000.- per year.
  • the verb "comprise” and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
  • Fig.1 depicting an ED unit according to the present invention and its use
  • the feed liquid enters ion diluting compartment (D1), whereupon inorganic anions pass through the anion exchange membrane (AEM1) and into a first ion concentrating compartment (C1) and inorganic cations pass through the cation exchange membrane (CEM2) and into a second ion concentrating compartment (C2).
  • Organic compounds to be purified remain in the ion diluting compartment (D1).
  • the anode (+) provides the attractive force which pulls the inorganic anions through the AEM
  • the cathode (-) provides the attractive force which pulls the inorganic cations through the CEM.
  • Electrolyte is passed through the anode compartment and the cathode compartment.
  • the principle repeating unit of [AEM - ion diluting compartment - CEM - ion concentrating compartment] is also shown in Fig.1.
  • the inventors have surprisingly found that a high ER of the ion exchange membranes helps in reducing the loss of organic compound during the desalination.
  • Water permeability is a parameter that indicates how much water is transported through the membranes during desalination as a result of osmosis. It was found that a low water permeability also helps in reducing the loss of organic compounds. Although not expected apparently also organic compounds are transported through the membrane together with the water molecules although the size of the organic molecules is generally much larger.
  • Specific water permeability is the water permeability independent of thickness and is also an intrinsic property of the membrane material.
  • the electrical resistance (ER) is measured at 25°C, e.g. using 0.5N NaCl solution.
  • a suitable method for measuring ER is described below in more detail.
  • at least half of the CEMs and/or the AEMs (more preferably at least 90% of the CEMs and the AEMs) have an ER of at least 6.0 ohm.cm 2 .
  • Preferably at least half of the CEMs and/or the AEMs have an ER of less than 10 ohm.cm 2 .
  • At least one, more preferably at least half of the CEMs and/or the AEMs has an electrical resistivity of at least 3 ohm.m, more preferably at least 4 ohm.m, especially at least 5 ohm.m.
  • at least one, more preferably at least half of the CEMs and/or the AEMs has an electrical resistivity of less than 10 ohm.m.
  • the water permeability (WP) of the AEM and CEM may be measured by the general technique described in more detail below.
  • At least half of the CEMs and the AEMs have a WP of less than 7.5*10 -12 m 3 /m 2 .s.kPa, more preferably less than 7.0*10 -12 m 3 /m 2 .s.kPa.
  • the WP of the CEMs and the AEMs will be at least 0.5*10 -12 m 3 /m 2 .s.kPa, especially at least 1.0*10 -12 m 3 /m 2 .s.kPa for membranes having an electrical resistance of less than 10 ohm.cm 2 which is preferred.
  • the specific water permeability of a membrane is the water permeability per unit thickness thus this value is independent of the membrane thickness.
  • the specific water permeability of the CEMs and the AEMs will be at least 0.1*10 -16 m 3 /m.s.kPa, especially at least 0.5*10 -16 m 3 /m.s.kPa for membranes having an electrical resistivity of less than 10 ohm.m which is preferred. Not all AEMs and CEMs need to have the specified electrical resistance and water permeability. For instance the membranes facing the electrode compartments may have different properties since these have a different function.
  • a feed liquid e.g.
  • the removal of an inorganic salt) comprising an inorganic salt and an organic compound comprises passing the feed liquid through an electrodialysis (ED) unit such that the feed liquid is separated into streams (i) and (ii): stream (i): a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid; and stream (ii): a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid; wherein the organic compound comprises a hydroxy group and/or an amine group.
  • ED electrodialysis
  • the feed liquid is passed through diluting chambers of the stack and the inorganic compounds (i.e.
  • a second liquid e.g. water or a diluted salt solution
  • a stream (ii) exits the diluting chamber and comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid and a stream (i) exits the concentrating chambers which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid.
  • the organic compound present in the feed liquid is a polar organic compound which comprises one or more polar groups selected from hydroxy groups and amine groups.
  • the process according to the present invention is particularly suitable for purifying organic compounds that have a solubility in water at 25°C of at least 100g/L, more preferably at least 400g/L, especially compounds that are fully miscible with water.
  • the organic compound comprises a hydroxy group and/or an amine group (e.g. –NH2).
  • the organic compound present in the feed liquid is dissolved in the feed liquid.
  • the feed liquid comprises 10 to 90 wt%, specifically 20 to 80 wt%, e.g.30 to 70 wt% of the organic compound(s).
  • the feed liquid comprises 0.1 to 10 wt%, specifically 1 to 8 wt%, e.g.2.5 to 7 wt% of the inorganic salt. In a specific embodiment at least 50 wt% of the inorganic salts present in the feed liquid is NaCl.
  • the feed liquid may comprise more than one organic compound.
  • the feed liquid may comprise more than inorganic salt.
  • inorganic salts include sodium, potassium and/or lithium cations, e.g. with halide (e.g. chloride or bromide), sulphate, sulphite, carbonate etc. anions and mixtures thereof.
  • the inorganic salts may arise from the manufacturing process used to make the organic compound or from a process wherein the organic compound is used and the process according to the first aspect of the present invention is aimed at removing these unwanted inorganic salts.
  • the process according to the present invention is especially useful for purifying organic compounds comprising a hydroxy group and/or an amine group.
  • organic compounds comprising a hydroxyl and/or amino group include alcohols (especially glycols), amines (especially alkylamines) and alcoholamines, in each case preferably containing less than 10 carbon atoms.
  • glycols include include alkylene glycols (e.g. as monoethylene glycol, diethylene glycol, triethylene glycol and propylene glycol.
  • Examples of alcohols include ethanol, i-propanol, n-butanol.
  • Examples of alcoholamines include monoethanolamine, diethanolamine, isopropanol amine, di-isopropanol amine and N-methyl diethanol amine.
  • Preferably at least half, more preferably at least 75% and most preferably at least 90% of the CEMs have the specified water permeability an electrical resistance.
  • Preferably at least half, more preferably at least 75% and most preferably at least 90% of the AEMs have the specified water permeability an electrical resistance.
  • the ED unit further comprises an anode compartment and a cathode compartment and the stack of CEMs and AEMs is preferably located between the anode compartment and the cathode compartment.
  • the AEM and CEM are in alternating order in the stack, thereby creating alternating dilution chambers and concentration chambers, each chamber including an AEM wall and CEM wall.
  • the AEM and CEM are each independently obtainable by a process comprising curing a curable composition comprising: (a) 0 to 60 wt% of a curable compound having one ethylenically unsaturated group and an ionic group; (b) 1 to 88 wt% of a curable compound comprising at least two ethylenically unsaturated groups and optionally an ionic group; (c) 0 to 10 wt% of radical initiator; and (d) 0 to 55 wt% of solvent; wherein at least one component of the curable composition comprises an ionic group which is for the AEM a cationic group and for the CEM an anionic group.
  • the amount of component (a) is more preferably 0 to 40wt%, especially 5 to 40wt%.
  • the amount of components (b) is more preferably 5 to 80wt%, especially 20 to 70wt%.
  • the combined amount of components (a) and (b) is preferably 40 to 85wt%, more preferably 50 to 75wt%.
  • the ethylenically unsaturated group is preferably a vinyl group or a (meth)acrylic group, more preferred a styryl group or an acrylamide group.
  • the ionic group is preferably a quaternary ammonium group for an AEM and a sulfonic acid group or a salt thereof for a CEM.
  • curable compounds having an ethylenically unsaturated group and an anionic group or cationic group include the following compounds of Formula (A), (B), (CL), (SM), (MA), (MB- ⁇ ), (C), (ACL-A), (ACL-B), (ACL-C), and/or (AM-B): wherein in Formulas (A) and (B), R A1 to R A3 each independently represent a hydrogen atom or an alkyl group; R B1 to R B7 each independently represent an alkyl group or an aryl group; Z A1 to Z A3 each independently represent –O– or –NRa-, wherein Ra represents a hydrogen atom or an alkyl group; L A1 to L A3 each independently represent an alkylene group, an arylene group or a divalent linking group of a combination thereof; R X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a divalent linking group of a combination thereof;
  • L 1 represents an alkylene group or an alkenylene group
  • R a , R b , R c , and R d each independently represent a linear or branched alkyl group or an aryl group, R a and R b , and/or R c and R d may form a ring by being bonded to each other
  • R 1 , R 2 , and R 3 each independently represent a linear or branched alkyl group or an aryl group, R 1 and R 2 , or R 1 , R 2 and R 3 may form an aliphatic heterocycle by being bonded to each other
  • n1, n2 and n3 each independently represent an integer of 1 to 10
  • X1-, X2- and X3- each independently represent an organic or inorganic anion.
  • formula (CL) and (SM) include: Synthesis methods can be found in EP3184558 and US2016/0001238.
  • R A1 represents a hydrogen atom or an alkyl group
  • Z 1 represents –O– or –NRa–, wherein Ra represents a hydrogen atom or an alkyl group
  • M + represents an organic or inorganic cation, preferably a hydrogen ion or an alkali metal ion
  • R A2 represents a hydrogen atom or an alkyl group
  • R A4 represents an organic group comprising a sulphonic acid group and having no ethylenically unsaturated group
  • Z 2 represents –NRa–, wherein Ra represents a hydrogen atom or an alkyl group preferably a hydrogen atom.
  • formula (MA) and (MB- ⁇ ) include:
  • L 1 represents an alkylene group
  • n represents an integer of 1 to 3, preferably 1 or 2
  • m represents an integer of 1 or 2
  • L 2 represents an n-valent linking group
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents -SO 3 -M + or -SO 3 R 3 ; in case of plural R 2 's, each R 2 independently represents -SO 3 M + or -SO 3 R 3
  • M + represents a hydrogen ion, an inorganic ion, or an organic ion
  • R 3 represents an alkyl group or an aryl group.
  • Examples of formula (C) include: Synthesis methods can be found in EP3187516. wherein in Formulas (ACL-A), (ACL-B), (ACL-C) and (AM-B), each of R and R' independently represents a hydrogen atom or an alkyl group; LL represents a single bond or a bivalent linking group; each of LL 1 , LL 1' , LL 2 , and LL 2 ' independently represents a single bond or a bivalent linking group; and each of A and A' independently represents a sulfo group in free acid or salt form; and m represents 1 or 2.
  • Examples of formula (ACL-A), (ACL-B), (ACL-C) and (AM-B) include: Synthesis methods can be found in US2016/0362526. Other suitable monomers include:
  • compositions may be cured by any suitable process, including thermal curing, photocuring, electron beam (EB) radiation, gamma radiation, and combinations of the foregoing.
  • EB electron beam
  • compositions are preferably cured by photocuring, e.g. by irradiating the compositions by ultraviolet of visible light and thereby causing the curable components present in the compositions to polymerise.
  • thermal initiators examples include 2,2'-azobis(2-methylpropionitrile) (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'- azobis(2,4-dimethyl valeronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'- azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethyl valeronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis[N-(2-propenyl)-2- methylpropionamide, 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-Azobis(N-butyl-2- methylpropionamide), 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-Azobis(2- methylpropionamidine) dihydrochloride
  • Suitable photoinitiators which may be included in the compositions include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and an alkyl amine compounds.
  • Preferred examples of the aromatic ketones, the acylphosphine oxide compound, and the thio-compound include compounds having a benzophenone skeleton or a thioxanthone skeleton described in "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY", pp.77-117 (1993).
  • More preferred examples thereof include an alpha- thiobenzophenone compound described in JP1972-6416B (JP-S47-6416B), a benzoin ether compound described in JP1972-3981B (JP-S47-3981B), an alpha-substituted benzoin compound described in JP1972-22326B (JP-S47-22326B), a benzoin derivative described in JP1972-23664B (JP-S47-23664B), an aroylphosphonic acid ester described in JP1982- 30704A (JP-S57-30704A), dialkoxybenzophenone described in JP1985-26483B (JP-S60- 26483B), benzoin ethers described in JP1985-26403B (JP-S60-26403B) and JP1987- 81345A (JPS62-81345A), alpha-amino benzophenones described in JP1989-34242B (JP H0
  • the photoinitiators described in JP2008-105379A and JP2009-114290A are also preferable.
  • photoinitiators described in pp. 65 to 148 of "Ultraviolet Curing System” written by Kato Kiyomi may be used.
  • the composition comprises 0.0 to 5 wt%, more preferably 0.005 to 2 wt%, especially 0.01 to 0.9 wt% of radical initiator if curing is performed by thermal or photo-curing.
  • the AEM and/or the CEM comprise a porous support. The porous support can be useful to strengthen the AEM and/or CEM.
  • porous supports there may be mentioned woven and non-woven synthetic fabrics and extruded films.
  • examples include wetlaid and drylaid non-woven material, spunbond and meltblown fabrics and nanofiber webs made from, e.g. polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyphenylenesulfide, polyester, polyamide, polyaryletherketones such as polyether ether ketone and copolymers thereof.
  • Porous supports may also be porous membranes, e.g.
  • the porous support preferably has an average thickness of between 10 and 200 ⁇ m, more preferably between 20 and 150 ⁇ m. Preferably the porous support has a porosity of 30 and 95%.
  • the porosity of the support may be determined by a porometer, e.g. a PoroluxTM 1000 from IB-FT GmbH, Germany.
  • the porous support when present, may be treated to modify its surface energy, e.g. to values above 45 mN/m, preferably above 55mN/m. Suitable treatments include corona discharge treatment, plasma glow discharge treatment, flame treatment, ultraviolet light irradiation treatment, chemical treatment or the like, e.g. for the purpose of improving the wettability of and the adhesiveness to the porous support.
  • Commercially available porous supports are available from a number of sources, e.g.
  • the porous support is a polymeric support.
  • the porous support is a woven or non-woven synthetic fabric or an extruded film without covalently bound ionic groups.
  • the ED unit comprises a manifold comprising an inlet for the feed liquid and an outlet for a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid.
  • the manifold further comprises an outlet for a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid.
  • the invention will now be illustrated with reference to the following non-limiting Examples in which all parts and percentages are by weight unless specified otherwise. The following measurement techniques were used in the Examples: Electrical resistance (ER) The ER of the AEMs and CEMs in ohm.cm 2 was measured by the method described by Dlugolecki et al, J.
  • WP Water-permeability
  • WP u is the uncorrected water-permeability of the membrane in m 3 /m 2 .s.kPa, calculated using Formula (2) below
  • CF is the correction factor in m 3 /m 2 .s.kPa to take account of electro-osmosis and ion transportation through the membrane, calculated using Formula (3) below.
  • the correction factor CF was calculated using Formula (3) as follows: wherein: M H is the change in molar concentration of NaCl in the concentrate respectively in mol/L; V H is the change in volume of the concentrate in litres (“L”); M L is the change in molar concentration of NaCl in the diluate in mol/L; VL is the change in volume of the diluate in L; MW NaCl is the molecular weight of the salt being removed (i.e.58.44 in the case of NaCl); MW 8H2O is the molecular weight of water being removed with the salt (i.e.
  • the membrane was clamped between two spacers (PE netting/PES gasket, 290 ⁇ m thick, strand distance 0.8 mm, 310 x 110 mm, effective area 280 x 80 mm) on either side supported by a PMMA plate each having a cavity of 3 mm deep creating chambers having a volume of 280 x 80 x 3 mm on each side of the membrane.
  • the two chambers, together with the membrane separating them, constituted a test cell.
  • the spacer minimized the formation of an electrical double layer.
  • the plates were greased to prevent leakage and fastened to each other by 12 bolts and nuts using a torque of 10 N/m. Prior to the actual measurement, the chambers were washed with the relevant concentrate and diluate.
  • the concentrate and diluate were then pumped into the chambers either side of the membrane under test via Masterflex PharmaPure tubing using a Masterflex console drive (77521-47) with Easy Load II model 77200-62 gear pumps at a rate of 0.31L/min.
  • the chamber contained 0.7M NaCl (40.91 g/L, i.e. the concentrate) and the chamber on the other side of the membrane contained 0.1 M NaCl (i.e. the diluate).
  • Air was removed by placing the cell in a vertical position. After 5 minutes the pumps are switched in reverse direction and the chambers were emptied.
  • the measurements required to calculate water-permeability of the membrane began by filling the chambers with the concentrate and diluate at a speed of 0.26L/min, corresponding with about 0.9 cm/s.
  • the concentrate and diluate were circulated through their respective chambers via storage containers for at least 16 hours after which the chambers were emptied again.
  • the start weights (WC1 and WD1), start densities (D C1 + D D1 ), end weights (W C2 and W D2 ) and end densities (D C2 + D D2 ), of the concentrate and diluate were measured as well as their absolute temperatures and the exact duration of the experiment in hours.
  • the van’t Hoff factor (i) is 2 because each molecule of NaCl dissociates completely into two ions (Na + and Cl-).
  • R is 0.008314 kPa m 3 K -1 .
  • Ingredients used in the examples The AEMs and CEMs were prepared as follows: Each of the curable compositions described in Table 1 was applied by hand to an aluminum underground carrier using a 100 ⁇ m wire wound bar, at a speed of approximately 5 m/min, followed by application of a non-woven support.
  • a production scale path length test was simulated by transporting a fixed volume (80 L) of feed solution through the stack five times. Nr. of Cellpairs 20 Membranes see Table 2 Spacers Silicone, thickness 600 ⁇ m, woven netting at 45° Membrane length 30 cm Membrane width 6 cm Membrane area 0.018 m 2 Current 7 A (389 A/m 2 ) Flow velocity 14 cm/s Solutions: Electrolyte was 0.5M Na 2 SO 4 . Feed liquid (fed to the diluting chambers) was 80L of a solution according to the composition in Table 3 below, also referred to as diluate. Liquid fed to the concentrating chambers was 80L of 5 g/L NaCl in pure water, also referred to as concentrate.
  • TDS IN (kg/h) Flow (L/h) * Salt content at Feed Start (kg/L)
  • TDS OUT (kg/h) Flow (L/h) * Salt content at Feed End (kg/L)
  • TDS Transport (kg/h) TDS IN – TDS OUT

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Abstract

A process for the removal of an inorganic salt from a feed liquid comprising an inorganic salt and an organic compound comprising a hydroxy group and/or an amine group, comprising passing the feed liquid through an electrodialysis (ED) unit comprising a stack of cation exchange membranes (CEMs) and anion exchange membranes (AEMs), wherein at least one of the CEMs and the AEMs has a water permeability of less than 7.5*10-12 m3/m2.s.kPa and an electrical resistance of at least 6.0 ohm.cm2.

Description

PURIFYING POLAR LIQUIDS The present invention is related to a process for purifying a polar liquid, especially an aqueous feed liquid, using electrodialysis (ED) units. The first commercially available ED units were developed in the 1950's to demineralize brackish water. Since then, improvements in ion exchange membranes have lead to significant advances in ED. ED units typically comprise one or more membrane stack. Each stack typically comprises an anode, a cathode and a number of cell pairs through which fluids pass. A cell pair comprises an ion diluting compartment and an ion concentrating compartment. Each cell comprises a wall made from a negatively charged cation exchange membrane (CEM) and a wall made from a positively charged anion exchange membrane (AEM). When a feed liquid passes through the cells and a DC voltage is applied across the electrodes, dissolved inorganic cations pass through the CEM and towards the cathode, whereas dissolved inorganic anions pass through the AEM and towards the anode. Typically the cathode and anode are washed with a rinse fluid during the deionisation process. In this way, the inorganic cations and anions (e.g. Ca2+, Na+, SO4 2+ and CI-) originally present in the feed liquid permeate through the membranes, to leave behind a stream of desalinated liquid (having a lower inorganic ionic content than the original feed liquid) and a stream of liquid containing elevated levels of inorganic ions is created. ED units are therefore useful for converting a feed liquid comprising dissolved inorganic salts into a stream having a much lower content of such salts. A typical ED unit is schematically illustrated in Fig.1. As a consequence of passing through an ED unit, the feed liquid is separated into streams (i) and (ii) (not shown): stream (i) (concentrate stream or concentrate): a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid; and stream (ii) (diluate stream or diluate): a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid, also referred to as product stream. In purification processes relying on ED, the focus is generally on cost effective removal of unwanted charged species such as dissolved inorganic salts. Much attention goes to the AEMs and CEMs that form a crucial part of any ED unit. These membranes largely determine the quality of the desalination process. Apart from robustness and chemical stability, the intrinsic properties of the AEMs and CEMs are the main parameters which influence the efficiency of the ED unit to perform desalination or purification. The main intrinsic properties are the permselectivity (PS) and the electrical resistance (ER) of the AEMs and CEMs. Generally it is preferred that the AEMs and CEMs have a PS as high as possible and an ER is low as possible to achieve an efficiency as high as possible. Surprisingly the present invention may be used to remove inorganic salts from a feed liquid comprising an organic compound and inorganic salts, with a low loss of organic compound, using membranes having a high ER. According to a first aspect of the present invention there is provided a process for purifying, e.g. for the removal of an inorganic salt from a feed liquid comprising an inorganic salt and an organic compound comprising a hydroxy group and/or an amine group, comprising passing the feeding feed liquid through an electrodialysis (ED) unit comprising a stack of cation exchange membranes (CEMs) and anion exchange membranes (AEMs), wherein at least one of the CEMs and the AEMs has a water permeability of less than 7.5*10-12 m3/m2.s.kPa and an electrical resistance of at least 6.0 ohm.cm2. The economical benefit of this invention can be found in reduction of losses of the organic liquids during purification. Typical costs for organic liquid purification range from € 200,000.- to € 2,500,000.- per year using evaporation techniques. A decrease in loss of organic liquids during purification has a significant impact on the yearly cost of systems for purification of a feed liquid comprising an inorganic salt and an organic compound. It is estimated that this invention can reduce yearly cost of purification of feed liquids comprising an inorganic salt and an organic compound by reducing the loss of organic liquid to less than 700 kg loss of organic liquid per ton salt removal. This equals to € 92,000.- to € 1,100,000.- per year. In this document (including its claims), the verb "comprise" and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. In addition, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article "a" or "an" thus usually mean "at least one". Brief Description of the Drawings Fig.1 schematically depicts an ED unit according to the present invention. In Fig.1 depicting an ED unit according to the present invention and its use, the feed liquid enters ion diluting compartment (D1), whereupon inorganic anions pass through the anion exchange membrane (AEM1) and into a first ion concentrating compartment (C1) and inorganic cations pass through the cation exchange membrane (CEM2) and into a second ion concentrating compartment (C2). Organic compounds to be purified remain in the ion diluting compartment (D1). The anode (+) provides the attractive force which pulls the inorganic anions through the AEM and the cathode (-) provides the attractive force which pulls the inorganic cations through the CEM. Electrolyte is passed through the anode compartment and the cathode compartment. The principle repeating unit of [AEM - ion diluting compartment - CEM - ion concentrating compartment] is also shown in Fig.1. The inventors have surprisingly found that a high ER of the ion exchange membranes helps in reducing the loss of organic compound during the desalination. An even better parameter appears to be the electrical resistivity which is independent of the thickness of the membranes. Water permeability is a parameter that indicates how much water is transported through the membranes during desalination as a result of osmosis. It was found that a low water permeability also helps in reducing the loss of organic compounds. Although not expected apparently also organic compounds are transported through the membrane together with the water molecules although the size of the organic molecules is generally much larger. Specific water permeability is the water permeability independent of thickness and is also an intrinsic property of the membrane material. Preferably the electrical resistance (ER) is measured at 25°C, e.g. using 0.5N NaCl solution. A suitable method for measuring ER is described below in more detail. Preferably at least half of the CEMs and/or the AEMs (more preferably at least 90% of the CEMs and the AEMs) have an ER of at least 6.0 ohm.cm2. Preferably at least half of the CEMs and/or the AEMs (more preferably at least 90% of the CEMs and the AEMs) have an ER of less than 10 ohm.cm2. Preferably at least one, more preferably at least half of the CEMs and/or the AEMs (especially at least 90% of the CEMs and the AEMs) has an electrical resistivity of at least 3 ohm.m, more preferably at least 4 ohm.m, especially at least 5 ohm.m. Preferably at least one, more preferably at least half of the CEMs and/or the AEMs (especially at least 90% of the CEMs and the AEMs) has an electrical resistivity of less than 10 ohm.m. The water permeability (WP) of the AEM and CEM may be measured by the general technique described in more detail below. Preferably at least half of the CEMs and the AEMs (more preferably at least 90% of the CEMs and the AEMs) have a WP of less than 7.5*10-12 m3/m2.s.kPa, more preferably less than 7.0*10-12 m3/m2.s.kPa. Practically the WP of the CEMs and the AEMs will be at least 0.5*10-12 m3/m2.s.kPa, especially at least 1.0*10-12 m3/m2.s.kPa for membranes having an electrical resistance of less than 10 ohm.cm2 which is preferred. The specific water permeability of a membrane is the water permeability per unit thickness thus this value is independent of the membrane thickness. Preferably at least half of the CEMs and/or the AEMs (more preferably at least 90% of the CEMs and the AEMs) have a specific water permeability of less than 1.0*10-15 m3/m.s.kPa, more preferably less than 0.9*10-15 m3/m.s.kPa. Practically the specific water permeability of the CEMs and the AEMs will be at least 0.1*10-16 m3/m.s.kPa, especially at least 0.5*10-16 m3/m.s.kPa for membranes having an electrical resistivity of less than 10 ohm.m which is preferred. Not all AEMs and CEMs need to have the specified electrical resistance and water permeability. For instance the membranes facing the electrode compartments may have different properties since these have a different function. In accordance with the first aspect of the present invention the process for purifying a feed liquid (e.g. the removal of an inorganic salt) comprising an inorganic salt and an organic compound comprises passing the feed liquid through an electrodialysis (ED) unit such that the feed liquid is separated into streams (i) and (ii): stream (i): a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid; and stream (ii): a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid; wherein the organic compound comprises a hydroxy group and/or an amine group. Typically the feed liquid is passed through diluting chambers of the stack and the inorganic compounds (i.e. inorganic salts) pass through the AEM wall and the CEM wall of the diluting chambers whereas the organic compound is largely or wholly retained within the diluting chambers. A second liquid (e.g. water or a diluted salt solution) is passed through concentrating chambers of the stack. As a consequence of applying a charge across the anode and cathode of the ED Unit, a stream (ii) exits the diluting chamber and comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid and a stream (i) exits the concentrating chambers which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid. Preferably the organic compound present in the feed liquid is a polar organic compound which comprises one or more polar groups selected from hydroxy groups and amine groups. The process according to the present invention is particularly suitable for purifying organic compounds that have a solubility in water at 25°C of at least 100g/L, more preferably at least 400g/L, especially compounds that are fully miscible with water. Preferably the organic compound comprises a hydroxy group and/or an amine group (e.g. –NH2). Preferably the organic compound present in the feed liquid is dissolved in the feed liquid. Typically, the feed liquid comprises 10 to 90 wt%, specifically 20 to 80 wt%, e.g.30 to 70 wt% of the organic compound(s). Typically, the feed liquid comprises 0.1 to 10 wt%, specifically 1 to 8 wt%, e.g.2.5 to 7 wt% of the inorganic salt. In a specific embodiment at least 50 wt% of the inorganic salts present in the feed liquid is NaCl. Of course, the feed liquid may comprise more than one organic compound. Similarly, the feed liquid may comprise more than inorganic salt. Examples of inorganic salts include sodium, potassium and/or lithium cations, e.g. with halide (e.g. chloride or bromide), sulphate, sulphite, carbonate etc. anions and mixtures thereof. The inorganic salts may arise from the manufacturing process used to make the organic compound or from a process wherein the organic compound is used and the process according to the first aspect of the present invention is aimed at removing these unwanted inorganic salts. The process according to the present invention is especially useful for purifying organic compounds comprising a hydroxy group and/or an amine group. Examples of organic compounds comprising a hydroxyl and/or amino group include alcohols (especially glycols), amines (especially alkylamines) and alcoholamines, in each case preferably containing less than 10 carbon atoms. Examples of glycols include include alkylene glycols (e.g. as monoethylene glycol, diethylene glycol, triethylene glycol and propylene glycol. Examples of alcohols include ethanol, i-propanol, n-butanol. Examples of alcoholamines include monoethanolamine, diethanolamine, isopropanol amine, di-isopropanol amine and N-methyl diethanol amine. Preferably at least half, more preferably at least 75% and most preferably at least 90% of the CEMs have the specified water permeability an electrical resistance. Preferably at least half, more preferably at least 75% and most preferably at least 90% of the AEMs have the specified water permeability an electrical resistance. Preferably the ED unit further comprises an anode compartment and a cathode compartment and the stack of CEMs and AEMs is preferably located between the anode compartment and the cathode compartment. Typically the AEM and CEM are in alternating order in the stack, thereby creating alternating dilution chambers and concentration chambers, each chamber including an AEM wall and CEM wall. Preferably the AEM and CEM are each independently obtainable by a process comprising curing a curable composition comprising: (a) 0 to 60 wt% of a curable compound having one ethylenically unsaturated group and an ionic group; (b) 1 to 88 wt% of a curable compound comprising at least two ethylenically unsaturated groups and optionally an ionic group; (c) 0 to 10 wt% of radical initiator; and (d) 0 to 55 wt% of solvent; wherein at least one component of the curable composition comprises an ionic group which is for the AEM a cationic group and for the CEM an anionic group. The amount of component (a) is more preferably 0 to 40wt%, especially 5 to 40wt%. The amount of components (b) is more preferably 5 to 80wt%, especially 20 to 70wt%. The combined amount of components (a) and (b) is preferably 40 to 85wt%, more preferably 50 to 75wt%. The ethylenically unsaturated group is preferably a vinyl group or a (meth)acrylic group, more preferred a styryl group or an acrylamide group. The ionic group is preferably a quaternary ammonium group for an AEM and a sulfonic acid group or a salt thereof for a CEM. Examples of curable compounds having an ethylenically unsaturated group and an anionic group or cationic group include the following compounds of Formula (A), (B), (CL), (SM), (MA), (MB-α), (C), (ACL-A), (ACL-B), (ACL-C), and/or (AM-B):
Figure imgf000008_0001
Figure imgf000008_0002
wherein in Formulas (A) and (B), RA1 to RA3 each independently represent a hydrogen atom or an alkyl group; RB1 to RB7 each independently represent an alkyl group or an aryl group; ZA1 to ZA3 each independently represent –O– or –NRa-, wherein Ra represents a hydrogen atom or an alkyl group; LA1 to LA3 each independently represent an alkylene group, an arylene group or a divalent linking group of a combination thereof; RX represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a divalent linking group of a combination thereof; and XA1 to XA3 each independently represent an organic or inorganic anion, preferably a halogen ion or an aliphatic or aromatic carboxylic acid ion. Examples of compounds of Formula (A) or (B) include:
Figure imgf000009_0001
Figure imgf000010_0001
Synthesis methods can be found in e.g. US2015/0353721, US2016/0367980 and US2014/0378561.
Figure imgf000010_0002
wherein in Formulas (CL) and (SM), L1 represents an alkylene group or an alkenylene group; Ra, Rb, Rc, and Rd each independently represent a linear or branched alkyl group or an aryl group, Ra and Rb, and/or Rc and Rd may form a ring by being bonded to each other; R1, R2, and R3 each independently represent a linear or branched alkyl group or an aryl group, R1 and R2, or R1, R2 and R3 may form an aliphatic heterocycle by being bonded to each other; n1, n2 and n3 each independently represent an integer of 1 to 10; and X1-, X2- and X3- each independently represent an organic or inorganic anion. Examples of formula (CL) and (SM) include:
Figure imgf000011_0001
Synthesis methods can be found in EP3184558 and US2016/0001238.
Figure imgf000012_0001
wherein in formula (MA) and (MB-α), RA1 represents a hydrogen atom or an alkyl group; Z1 represents –O– or –NRa–, wherein Ra represents a hydrogen atom or an alkyl group; M+ represents an organic or inorganic cation, preferably a hydrogen ion or an alkali metal ion; RA2 represents a hydrogen atom or an alkyl group, RA4 represents an organic group comprising a sulphonic acid group and having no ethylenically unsaturated group; and Z2 represents –NRa–, wherein Ra represents a hydrogen atom or an alkyl group preferably a hydrogen atom. Examples of formula (MA) and (MB-α) include:
Figure imgf000012_0002
Figure imgf000013_0001
Synthesis methods can be found in e.g. US2015/0353696.
Figure imgf000013_0002
Synthesis methods can be found in e.g. US2016/0369017.
Figure imgf000013_0003
wherein in Formula (C), L1 represents an alkylene group; n represents an integer of 1 to 3, preferably 1 or 2; m represents an integer of 1 or 2; L2 represents an n-valent linking group; R1 represents a hydrogen atom or an alkyl group; R2 represents -SO3-M+ or -SO3R3; in case of plural R2's, each R2 independently represents -SO3M+ or -SO3R3; M+ represents a hydrogen ion, an inorganic ion, or an organic ion; and R3 represents an alkyl group or an aryl group. Examples of formula (C) include:
Figure imgf000014_0001
Synthesis methods can be found in EP3187516.
Figure imgf000014_0002
Figure imgf000014_0003
wherein in Formulas (ACL-A), (ACL-B), (ACL-C) and (AM-B), each of R and R' independently represents a hydrogen atom or an alkyl group; LL represents a single bond or a bivalent linking group; each of LL1, LL1', LL2, and LL2' independently represents a single bond or a bivalent linking group; and each of A and A' independently represents a sulfo group in free acid or salt form; and m represents 1 or 2. Examples of formula (ACL-A), (ACL-B), (ACL-C) and (AM-B) include:
Figure imgf000015_0001
Synthesis methods can be found in US2016/0362526. Other suitable monomers include:
Figure imgf000016_0001
The compositions may be cured by any suitable process, including thermal curing, photocuring, electron beam (EB) radiation, gamma radiation, and combinations of the foregoing. However the compositions are preferably cured by photocuring, e.g. by irradiating the compositions by ultraviolet of visible light and thereby causing the curable components present in the compositions to polymerise. Examples of suitable thermal initiators which may be included in the compositions include 2,2'-azobis(2-methylpropionitrile) (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'- azobis(2,4-dimethyl valeronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'- azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethyl valeronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis[N-(2-propenyl)-2- methylpropionamide, 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-Azobis(N-butyl-2- methylpropionamide), 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-Azobis(2- methylpropionamidine) dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-Azobis{2-[1-(2- hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane], 2,2'-Azobis(1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, 2,2'- Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethl]propionamide} and 2,2'-Azobis[2- methyl-N-(2-hydroxyethyl)propionamide]. Examples of suitable photoinitiators which may be included in the compositions include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and an alkyl amine compounds. Preferred examples of the aromatic ketones, the acylphosphine oxide compound, and the thio-compound include compounds having a benzophenone skeleton or a thioxanthone skeleton described in "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY", pp.77-117 (1993). More preferred examples thereof include an alpha- thiobenzophenone compound described in JP1972-6416B (JP-S47-6416B), a benzoin ether compound described in JP1972-3981B (JP-S47-3981B), an alpha-substituted benzoin compound described in JP1972-22326B (JP-S47-22326B), a benzoin derivative described in JP1972-23664B (JP-S47-23664B), an aroylphosphonic acid ester described in JP1982- 30704A (JP-S57-30704A), dialkoxybenzophenone described in JP1985-26483B (JP-S60- 26483B), benzoin ethers described in JP1985-26403B (JP-S60-26403B) and JP1987- 81345A (JPS62-81345A), alpha-amino benzophenones described in JP1989-34242B (JP H01-34242B), U.S. Pat. No. 4,318,791A, and EP0284561A1, p-di(dimethylaminobenzoyl) benzene described in JP1990-211452A (JP-H02- 211452A), a thio-substituted aromatic ketone described in JP1986-194062A (JPS61-194062A), an acylphosphine sulfide described in JP1990-9597B (JP-H02- 9597B), an acylphosphine described in JP1990- 9596B (JP-H02-9596B), thioxanthones described in JP1988-61950B (JP-S63-61950B), and coumarins described in JP1984-42864B (JP-S59-42864B). In addition, the photoinitiators described in JP2008-105379A and JP2009-114290A are also preferable. In addition, photoinitiators described in pp. 65 to 148 of "Ultraviolet Curing System" written by Kato Kiyomi (published by Research Center Co., Ltd., 1989) may be used. Preferably the composition comprises 0.0 to 5 wt%, more preferably 0.005 to 2 wt%, especially 0.01 to 0.9 wt% of radical initiator if curing is performed by thermal or photo-curing. In a preferred embodiment the AEM and/or the CEM comprise a porous support. The porous support can be useful to strengthen the AEM and/or CEM. As examples of porous supports there may be mentioned woven and non-woven synthetic fabrics and extruded films. Examples include wetlaid and drylaid non-woven material, spunbond and meltblown fabrics and nanofiber webs made from, e.g. polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyphenylenesulfide, polyester, polyamide, polyaryletherketones such as polyether ether ketone and copolymers thereof. Porous supports may also be porous membranes, e.g. polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide, polyimide, polyethermide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly(4-methyl 1-pentene), polyinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene and polychlorotrifluoroethylene membranes and derivatives thereof. The porous support preferably has an average thickness of between 10 and 200µm, more preferably between 20 and 150µm. Preferably the porous support has a porosity of 30 and 95%. The porosity of the support may be determined by a porometer, e.g. a Porolux™ 1000 from IB-FT GmbH, Germany. The porous support, when present, may be treated to modify its surface energy, e.g. to values above 45 mN/m, preferably above 55mN/m. Suitable treatments include corona discharge treatment, plasma glow discharge treatment, flame treatment, ultraviolet light irradiation treatment, chemical treatment or the like, e.g. for the purpose of improving the wettability of and the adhesiveness to the porous support. Commercially available porous supports are available from a number of sources, e.g. from Freudenberg Filtration Technologies (Novatexx materials), Lydall Performance Materials, Celgard LLC, APorous Inc., SWM (Conwed Plastics, DelStar Technologies), Teijin, Hirose, Mitsubishi Paper Mills Ltd and Sefar AG. Preferably the porous support is a polymeric support. Preferably the porous support is a woven or non-woven synthetic fabric or an extruded film without covalently bound ionic groups. Preferably the ED unit comprises a manifold comprising an inlet for the feed liquid and an outlet for a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid. Typically the manifold further comprises an outlet for a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid. The invention will now be illustrated with reference to the following non-limiting Examples in which all parts and percentages are by weight unless specified otherwise. The following measurement techniques were used in the Examples: Electrical resistance (ER) The ER of the AEMs and CEMs in ohm.cm2 was measured by the method described by Dlugolecki et al, J. of Membrane Science, 319 (2008) on page 217-218 with the following modifications: • the auxiliary membranes were CMX and AMX from Astom, Japan; • the capillaries as well as the Ag/AgCl references electrodes (Metrohm type 6.0750.100) contained 3M KCl; • the calibration liquid and the liquid in compartment 2, 3, 4 and 5 was 0.5 M NaCl solution at 25°C; • the effective membrane area was 9.62 cm2; • the distance between the capillaries was 5.0 mm; • the measuring temperature was 25°C; • a Cole Parmer Masterflex console drive (77521-47) with easy load II model 77200- 62 gear pumps was used for all compartments; • the flowrate of each stream was 475 ml/min controlled by Porter Instrument flowmeters (type 150AV-B250-4RVS) and Cole Parmer flowmeters (type G-30217-90). Electrical Resistivity ρ: (ER (ohm*cm2) * 10-4) / (thickness (µm) * 10-6) ohm.m. The formula is based on ρ = R * A / L in which R * A is ER and L is thickness of the membrane. The Water-permeability (WP) The WP of the AEMs and CEMs was determined by performing the calculation described below in Formula (1) below: WP = WPu + CF Formula (1) wherein: WPu is the uncorrected water-permeability of the membrane in m3/m2.s.kPa, calculated using Formula (2) below; and CF is the correction factor in m3/m2.s.kPa to take account of electro-osmosis and ion transportation through the membrane, calculated using Formula (3) below. WPu was calculated using Formula (2) as follows: WPu = (ΔW/(SA x Time x DH2O x Pos)) Formula (2) wherein: ΔW is the average change in weight in Mg (n.b. Mg means 1000Kg) according to the calculation ΔW = [(WC2-WC1) + (WD2-WD1)] x 10-6/2; WC1 is the start weight of the concentrate in g; WC2 is the end weight of the concentrate in g; WD1 is the start weight of the diluate in g; WD2 is the end weight of the diluate in g; and SA is the surface area of the membrane under test in m2; Time is the duration of the measurement in seconds; and DH2O is the density of water in Mg/m3 (i.e.1) Pos is the osmotic pressure in kPa, calculated using Formula (4) below. The correction factor CF was calculated using Formula (3) as follows:
Figure imgf000020_0001
wherein: MH is the change in molar concentration of NaCl in the concentrate respectively in mol/L; VH is the change in volume of the concentrate in litres (“L”); ML is the change in molar concentration of NaCl in the diluate in mol/L; VL is the change in volume of the diluate in L; MWNaCl is the molecular weight of the salt being removed (i.e.58.44 in the case of NaCl); MW8H2O is the molecular weight of water being removed with the salt (i.e. 8 x (1+1+16) in the case of NaCl = 144); and SA, Time, DH2O and Pos are as hereinbefore defined in relation to Formula (2). Several of the integers used above were measured as follows: Measurement of Osmotic Pressure (Pos) A membrane sample at least 30cm x 9cm in size was conditioned for 16 hours in a 0.1 M NaCl (5.843 g/L) solution. The membrane was clamped between two spacers (PE netting/PES gasket, 290 µm thick, strand distance 0.8 mm, 310 x 110 mm, effective area 280 x 80 mm) on either side supported by a PMMA plate each having a cavity of 3 mm deep creating chambers having a volume of 280 x 80 x 3 mm on each side of the membrane. The two chambers, together with the membrane separating them, constituted a test cell. The spacer minimized the formation of an electrical double layer. The plates were greased to prevent leakage and fastened to each other by 12 bolts and nuts using a torque of 10 N/m. Prior to the actual measurement, the chambers were washed with the relevant concentrate and diluate. The concentrate and diluate were then pumped into the chambers either side of the membrane under test via Masterflex PharmaPure tubing using a Masterflex console drive (77521-47) with Easy Load II model 77200-62 gear pumps at a rate of 0.31L/min. On one side of the membrane the chamber contained 0.7M NaCl (40.91 g/L, i.e. the concentrate) and the chamber on the other side of the membrane contained 0.1 M NaCl (i.e. the diluate). Air was removed by placing the cell in a vertical position. After 5 minutes the pumps are switched in reverse direction and the chambers were emptied. The measurements required to calculate water-permeability of the membrane began by filling the chambers with the concentrate and diluate at a speed of 0.26L/min, corresponding with about 0.9 cm/s. The concentrate and diluate were circulated through their respective chambers via storage containers for at least 16 hours after which the chambers were emptied again. The start weights (WC1 and WD1), start densities (DC1 + DD1), end weights (WC2 and WD2) and end densities (DC2 + DD2), of the concentrate and diluate were measured as well as their absolute temperatures and the exact duration of the experiment in hours. From the densities, the molar concentrations of NaCl were calculated according formula: Molar concentration = (density – 0.9985)/0.0403 The osmotic pressure (Pos) in kPa was then calculated using Formula (4): Pos = i x [((MC1 + MC2) - (MD1 + MD2))/2] x R x Temp Formula (4) wherein: i is the van't Hoff factor; MC1 is the starting molar concentration of the concentrate in mol/m3; MC2 is the end molar concentration of the concentrate in mol/m3; MD1 is the starting molar concentration of the diluate in mol/m3; MD2 is the end molar concentration of the diluate in mol/m3; R is the gas constant in kPa m3 K-1 mol-1; and Temp is the average temperature of the concentrate and diluate in Kelvin during the test. When the membrane is being used to remove NaCl from water containing NaCl, the van’t Hoff factor (i) is 2 because each molecule of NaCl dissociates completely into two ions (Na+ and Cl-). R is 0.008314 kPa m3 K-1. Ingredients used in the examples
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000023_0001
The AEMs and CEMs were prepared as follows: Each of the curable compositions described in Table 1 was applied by hand to an aluminum underground carrier using a 100 µm wire wound bar, at a speed of approximately 5 m/min, followed by application of a non-woven support. Excess composition was scraped- off using a wire bar (Standard K bar No.0 with 0.05mm diameter wire, by RK Print Coat Instruments Ltd) and the impregnated support was cured by irradiation with UV light with a dose of 0.21J/cm2 at one side using a Light Hammer LH6 from Fusion UV Systems fitted with a D-bulb working at 100% intensity with a speed of 30 m/min (single pass) resulting in a composite membrane. The resultant AEMs and CEMs had the properties shown in Table 2 below. Comparative examples are the commercially available membranes Fujifilm Type 10 and Astom Neosepta. Table 2
Figure imgf000023_0002
Figure imgf000024_0001
Laboratory scale tests Small ED stacks comprising the AEM and CEM described in Table 2 were prepared. A production scale path length test was simulated by transporting a fixed volume (80 L) of feed solution through the stack five times. Nr. of Cellpairs 20 Membranes see Table 2 Spacers Silicone, thickness 600 µm, woven netting at 45° Membrane length 30 cm Membrane width 6 cm Membrane area 0.018 m2 Current 7 A (389 A/m2) Flow velocity 14 cm/s Solutions: Electrolyte was 0.5M Na2SO4. Feed liquid (fed to the diluting chambers) was 80L of a solution according to the composition in Table 3 below, also referred to as diluate. Liquid fed to the concentrating chambers was 80L of 5 g/L NaCl in pure water, also referred to as concentrate. Table 3
Figure imgf000024_0002
Diluate and concentrate flow rates were 280 L/h. Electrolyte was circulated at 400 L/h. Analyses The content of MEG was determined by Gas Chromatography. The content of inorganic ions was determined using Ion Chromatography for anions and ICP-MS for cations. Method for determination of MEG content Sample preparation: Samples are diluted 50x and 100x in MeOH. Calibration standards of 5~10000 mg/L are used to quantify the amount by external standard calibration. Method: Instrument: : HP 7890A Injector: : Agilent 7683B series injector Injection volume : 1 µl Syringe size : 10 µl Washes Sample : PreInj=5 Solvent A : PreInj + PostInj = 5 Solvent B : PreInj + PostInj = 0 Pump : 5 Inlet Mode : Split Gas type : Helium Initial temp. : 200 °C Split Ratio : 71.4: 1 Split Flow : 50.0 ml/min Gas Saver : On Saver flow : 20.0 ml/min Saver time : 5.00 min Column 1 Model Number : Varian CP-Wax 52CB CP-7792i, 25 x 0.15mm, df = 0.25 µm. Max Temperature : 250 °C Mode : Constant Flow Ambient Initial Flow : 0.7 ml/min Oven Initial temp : 50 °C Initial time : 1.5 min Maximum temp : 265 °C Equilibration time : 0.10 min Ramps: Rate (°C/min) 35 Final Temp (°C) 250 Final Time (min) 1 Post temp : 50 °C Post time : 0.1 min. Runt time : 8.21 min Detector Temperature : 250 °C Hydrogen flow : 40.0 ml/min Air flow : 450.0 ml/min Mode : Constant makeup flow Makeup flow : 45.0 ml/min Makeup gas type : Helium Flame : On Electrometer : On Lit offset : 2.0 Signal 1 (Det.) Data rate : 10 Hz The salt content was calculated as follows: Salt content = Ca2+ content (mg/L) + Mg2+ Content (mg/L) + K+ Content (mg/L) + Na+ Content (mg/L) + Cl- content (mg/L) + SO4 2- Content (mg/L) The MEG loss from the diluting chambers through the membranes to the concentrating chambers of the ED unit was calculated as follows: MEG IN (kg/h) = Flow (L/h) * MEG content at Feed Start (kg/L) MEG OUT (kg/h) = Flow (L/h) * MEG content at Feed End (kg/L) MEG Loss (kg/h) = MEG IN – MEG OUT. The transport of salt (i.e. the inorganic ions) through the membranes was calculated as follows: TDS IN (kg/h) = Flow (L/h) * Salt content at Feed Start (kg/L) TDS OUT (kg/h) = Flow (L/h) * Salt content at Feed End (kg/L) TDS Transport (kg/h) = TDS IN – TDS OUT The MEG Loss is expressed as kg per ton Salt Transport as follows: MEG Loss (kg/ton Salt Transport) = MEG Loss (kg/h) / TDS Transport (kg/h) * 1000 The results of the experiments are summarized in Table 4. Table 4
Figure imgf000027_0001

Claims

CLAIMS 1. A process for the removal of an inorganic salt from a feed liquid comprising an inorganic salt and an organic compound comprising a hydroxy group and/or an amine group, comprising passing the feed liquid through an electrodialysis (ED) unit comprising a stack of cation exchange membranes (CEMs) and anion exchange membranes (AEMs), wherein at least one of the CEMs and the AEMs has a water permeability of less than 7.5*10-12 m3/m2.s.kPa and an electrical resistance of at least 6.0 ohm.cm2.
2. The process according to claim 1 wherein the feed liquid is separated into streams (i) and (ii): stream (i): a stream which comprises a higher mass ratio of the inorganic salt to organic compound than the feed liquid; and stream (ii): a stream which comprises a lower mass ratio of the inorganic salt to organic compound than the feed liquid.
3. The process according to any of the preceding claims wherein at least one of the CEMs and at least one of the AEMs have an electrical resistance of less than 10 ohm.cm2.
4. The process according to any of the preceding claims wherein at least one of the CEMs and/or the AEMs has an electrical resistivity of at least 3 ohm.m.
5. The process according to any of the preceding claims wherein at least one of the CEMs and/or at least one of the AEMs has a specific water permeability of less than 1.0*10- 15 m3/m.s.kPa.
6. The process according to any of the preceding claims wherein at least half of the CEMs and at least half of the AEMs have the specified water permeability and electrical resistance.
7. The process according to any of the preceding claims wherein the feed liquid comprises at least 10wt% and at most 90 wt% of the organic compound.
8. The process according to any of the preceding claims wherein the inorganic salt comprises at least 50wt% of NaCl.
9. The process according to any of the preceding claims wherein the organic compound comprises an alcohol and/or an alcoholamine.
10. The process according to any of the preceding claims wherein the organic compound comprises an alkylene glycol or an alcoholamine.
11. Use of an ED unit comprising a stack of cation exchange membranes (CEMs) and anion exchange membranes (AEMs), wherein at least one of the CEMs and the AEMs has a water permeability of less than 7.5*10-12 m3/m2.s.kPa and an electrical resistance of at least 6.0 ohm.cm2 for the the removal of an inorganic salt from a feed liquid comprising an inorganic salt and an organic compound comprising a hydroxy group and/or an amine group.
12. Use of an ED unit according to claim 12 wherein the organic compound comprises an alcohol and/or an alcoholamine.
13. Use of an ED unit according to claim 11 wherein the organic compound comprises an alkylene glycol or an alcoholamine.
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