New ED - Advanced Bipolar Membrane Processes for Remediation of Highly Saline Waste-water Streams. Thomas Melin Nano4water Workshop,

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1 New ED Advanced Bipolar Membrane Processes for Remediation of Highly Saline Wastewater Streams Thomas Melin Nano4water Workshop,

2 New ED Project 3year EU project Full title: Advanced bipolar membrane processes for highly saline wastewater streams Objective: Development of new type of bipolar membranes 6 project partners, coordinated by RWTH 5 Work packages WP1 Membrane development WP2 Module development WP3 Testing and Evaluation 2

3 Function of bipolar membranes Cathode H 3 O H 2 O Cation selective layer Anion selective layer OH H 2 O Anode SEM image of BP1 bipolar membrane of Tokoyama Soda Source: Uni Stuttgart ~2 nm Bipolar membrane 3

4 Principle of Electrodialysis using bipolar membranes (EDBM) Feed (salt solution) NaCl Recirculated acid Repeating unit Recirculated base Electrode rinse Cl H H 2 O OH H 2 O Na Acid HCl Base NaOH Threecompartment EDBM cell Diluted salt solution 4

5 EDBM undesired transport effects Base chamber Acid chamber Desired Undesired Diluate (Feed) M OH H 3 O H 2 O X H 2 O H 2 O Diluate (Feed) Bipolar salt ion transport Monopolar coion transport OH M Ion and water flux in opposite direction reduces efficiency X H High current density dehydration 5

6 Concept of the new membrane Transverse convective instead of diffusive water transport to the bipolar junction Biplolar junction Ionconductive porous layer Balster et al. Porous intermediate layer located b/n an & cation permeable layers Water transport to the inside of the BPM Conventionally: in a direction opposite to the ion transport New ED: orthogonal to the ion flux driven by pressurizing water supply side Anion permeable layer Cation permeable layer Water channel Decouple requirement of high selectivity and water permeability 6

Manufacturing approaches Four manufacturing

7 Manufacturing approaches Four manufacturing approaches: Corrugated membrane Sulfochlorination microporous PE substrate woven or nonwoven PE fibers Ion conductive fleeces Porous ion exchange resin layer Source: Balster et al. Source: NRC Canada Source: Crawford Scientific 7

Nano/Micro Adapted module design Alkaline resistant spacers Source: Fumatech Tailormade

8 Multiscale Approach Pilot scale case studies Phosphoric acid recovery Salt streams from PC production Organic acid production Economic & environmental evaluation Macro Application Nano/Micro Adapted module design Alkaline resistant spacers Source: Fumatech Tailormade membrane design Membrane layer optimization by modelling Different material mix for tailormade membrane properties 8

9 Status of the Project Status of the Project WP1 Membrane design WP2 Module Design WP3 Testing & Evaluation Sulphochlorination of Adapted module design porous films Optimized spacer design Corrugated membranes Critical review of litererature Benchmark experiments Planning of case studies WP4 Dissemination Market Study and technical contacts of interesting processes 9

10 Market study project relevance Chemical Processing Process Integration Pollution Control Resources recovery Acid and base production Theoretically largest area of application Concentration too low Isolation of organic acids Pharma / food sector Ultrapure water Promising Saline streams treatment Acid / base recovery Industrial applications available Membrane development critical Equally important current efficiency improvement Longterm data of membranes lacking EDBM as one step of a complete process solution 10

11 Industrial saline streams process evaluation PC Production emits 617 wt% NaCl brines m3 waste water/h Recovery of aqueous phosphate solutions Emits 200 tons/a Recovery as phosphoric acid Phosgene Solvent BPA NaOH Reaction Phase separation Aqueous phase Washing, Drop separation Processing polymer phase Solvent, catalyst recycling Neutralization HCl NaOH EDBM (NEW ED) Memb. Contactor (Phenol recovery) Waste water dilute salt stream Polycarbonate, Intergaration of Recyled Streams 11

12 3NaHIt 1NaHIt Fermentation (ITA Prod.) OH H ED Na HIt 1NaHIt 1Na 2 It 1NaHIt 1H 2 It Pulsed diafiltration (Enzyme retention) Fermentation: Itaconic acid H 2 It <> H HIt <> 2H It 2 3.5=pKa 1 5.5=pKa 2 1H2It Crystalisation / extraction 12

Sulphochlorination of porous films and fleeces Reaction Parameters LDPE film LDPE film Material Novatexx 2432 ND fleece Novatexx 2432 ND fleece Solupor 10P05A, HDPE fleece Thickness

13 Sulphochlorination of porous films and fleeces Reaction Parameters LDPE film LDPE film Material Novatexx 2432 ND fleece Novatexx 2432 ND fleece Solupor 10P05A, HDPE fleece Thickness (μm) Flow SO 2 /Cl 2 Temp. ( o C) Time (hr) 2: : : : : Nano4water Name Workshop, der Präsentation, New ED,

14 Properties of sulphochlorinated films Material S% Cl% Capacity (meq/dry gr) Swelling (%) Resistance (Ω*cm 2 ) LDPE film LDPE film Novatexx 2432 ND fleece Novatexx 2432 ND fleece Solupor 10P05A, HDPE fleece Solupor Porous PE film Weak and brittle after reaction Biaxially stretched film Wrong anisotropy Nano4water Name Workshop, der Präsentation, New ED,

15 Module Concept Water supply concept Four chamber module 15

16 Improving process efficiency Modified module designed Patent application Optimisation of spacer design CFD simulation Woven spacer Extruded spacer Electrical Simulation Velocity vector of fabric spacer 16

Optimisation of spacers for EDBM Electrical Simulation Current efficiency at differrent thicknesses of spacers Current efficiency at different mesh openings of spacers Current efficiency [%] 1,00

17 Optimisation of spacers for EDBM Electrical Simulation Current efficiency at differrent thicknesses of spacers Current efficiency at different mesh openings of spacers Current efficiency [%] 1,00 0,90 0,80 0,70 0,60 0,50 0,40 0,30 0,20 0,10 0, Repeat unit Current efficiency [%] 1,00 0,90 0,80 0,70 0,60 0,50 0,40 0,30 0,20 0,10 0, Repeat unit 0,417mm 0,75mm 1mm 0,3mm 0,75 mm 1 mm 0,5 mm 0,25 mm 17

18 Benchmark FuMATech BPM 300 Bipolar Membrane UIcurve Testcell = Perspex (49 cm²), 4 chamber, temperature = 25 C, 0.5 M NaCl elektrode rinsing = 0.25 M Na2SO4, fumasep FKB for electrode seperation 250 i / [A/m²] M _Messung1_0_39_ M _Messung2_0_39_ M _Messung3_0_39_ ,2 0,4 0,6 0,8 1 1,2 U/ (V) 18

Benchmark data Feed: NaCl 13wt%, typical data Membrane set Voltage Concentration Current Efficiency 67% Energy Consumption Fumasep FBM, AEM, FKB 4 V / repeat unit ca. 1.5 M HCl 4.

19 Benchmark data Feed: NaCl 13wt%, typical data Membrane set Voltage Concentration Current Efficiency 67% Energy Consumption Fumasep FBM, AEM, FKB 4 V / repeat unit ca. 1.5 M HCl 4.3 kwh / kg HCl Automated labscale plant from Fuma with 5 flowcycles, operable at max 20A 60V ED experiments including scaling and fouling evaluation ED stack with 100 cm 2 A mem Feed: Na 3 PO4 1.5N, typical data Membrane set Voltage Concentration Current Efficiency 65% Energy Consumption Fumasep FBM, FAB, FKB 4 V / repeat unit ca. 3 N H 3 PO kwh / kg H 3 PO4 19

20 Limitations Current efficiency Product Purity Na in acid [%] 12% 10% 8% 6% 4% 2% 0% Acid purity vs feed concentration Feed concentration [wt%] 20

21 Acknowledgment New ED is a Collaborative Project (Grant Agreement number ) cofunded by the Research DG of the European Commission within the joint RTD activities of the Environment and NMP Thematic Priorities

Copyright 2015 Saltworks Technologies Inc.

Copyright 2015 Saltworks Technologies Inc. EDR 201 Electrodialysis II www.saltworkstech.com Outline 1. Advanced EDR Operating Principle 2. Type of Membranes 3. EDR Stack Components 4. EDR System Components 5. Leak Test 6. Current Limit Test 7.