Ceramic Membranes in Process Technology
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1 BASF SE Ludwigshafen Hartwig Voß, Jacek Malisz, Patrick Schmidt, Jörg Therre Ceramic Membranes in Process Technology Status, future Trends, Challenges Strategie WS Hochleistungskeramiken, Bonn
2 outline introduction / membrane processes some current applications emerging future applications challenges / need for research & development Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
3 outline introduction / membrane processes some current applications emerging future applications challenges / need for research & development Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
4 introduction some basic definitions flux = J i =L ii X i + ΣL ij X j permeance = P i = J i / X i Permselectivity = P i / P j J i J j feed (F) c F i p F T F c P i p P T P permeate (P) membrane Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
5 introduction membrane processes driving force pressure partial pressure c, electr. potential reverse osmosis RO pervaporation PV dialysis D nanofiltration NF vapor separation VS electrodialysis ED ultrafiltration UF gas separation GS microfiltration MF membrane distillation MD membranes materials (porous/dense) geometries modules polymers flat sheet plate and frame ceramics hollow fibers spiral wound metals, carbon tube multi tube Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
6 outline introduction / membrane processes some current applications emerging future applications challenges / need for research & development Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
7 Some current applications concentration and cleaning of dispersions and suspensions recycling of catalysts separation of particles from product streams fractionation of dissolved compounds with different molecular weight separation of cells (bacteria, yeast, fungi) from fermentation broths water cleaning (waste/process water recycling, drinking water) water separation from organic solvents membrane type material examples porous membranes (MF,UF,NF) α-al 2 O 3, TiO 2, ZrO 2 micro-porous membranes (PV, VS) zeolite A, amorphous SiO 2 Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
8 Some current applications concentration and cleaning of a suspended catalyst (micro filtration) 1. catalyst, product, solvent 2. washing with solvent catalyst & solvent product & solvent Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
9 Some current applications water cleaning (drinking water, waste water recycling) advantages of ceramic membranes high flux and fouling resistance easy cleaning: resistance against acids, bases, Cl 2 (NaOCl) need for cheaper membrane & module concepts membrane channel plugged Filtrate slit retentate permeate feed monolitic elements with ca. 10 m² from NGK or Violia (Ceramem) Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
10 outline introduction / membrane processes some current applications emerging future applications challenges / need for research & development Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
11 emerging future applications gas or vapor separation H 2 (from CO 2 or hydrocarbons) CO 2 from CH 4 (natural gas) molecular organic-organic separations O 2 from air nanofiltration water cleaning, molecular sieving in organic solvents membrane type micro-porous membranes non-porous membranes examples zeolites, MOF s, ZIF s, carbon oxidic or non-oxidic amorphous ceramics ionic conductors like perowskites micro-porous membranes amorphous (Ti/Zr)O 2 Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
12 emerging future applications membrane reactors dehydrogenations / water gas shift [CO+H 2 O = CO 2 +H 2 ] (H 2 separation) partial oxidations (O 2 supply from air) membrane type micro-porous membranes non-porous membranes examples zeolites, MOF s, ZIF s, carbon oxidic or non-oxidic amorphous ceramics ionic conductors like perowskites Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
13 emerging future applications n- / iso-butene separation molecular separations The separation is not possible by distillation. The state of the art process utilizes the high reactivity of iso-butene: n-c 4 iso-c 4 + HO etherification ether cleavage O 1-butene iso-butene C 4 -mixture without butadiene iso-butene iso-butanol iso-butyl-tert-butylether IBTBE Only iso-butene reacts with alcohols to an ether. The ether can be separated from the mixture by distillation and cleaved back. Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
14 emerging future applications n- / iso-butene separation by a zeolithe membrane With increasing TMP (driving force) only the flux of iso-buten increases linearly, the permeance stays nearly constant. the n-butene flux increases to a limit, the permeance decreases. the permselectivity is nearly gone at the wanted process condition. no competitive process! Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
15 emerging future applications O 2 separation from air replacement of cryogenic air separation in oxy-fuel technology (coal fired power plants with CO 2 capture) material: perowskite O 2- and e - conductance at T > 700 C air side up to 10 bar oxygen side slight vacuum status: not commercial, pilot stage (air products) oxygen membrane side pure oxygen O 2- + e - conductor O 2-2 e - air side N 2 O 2 membrane and module design extremely ambitious! Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
16 emerging future applications OCM membrane reactor 2CH 4 + O 2 C 2 H 4 + 2H 2 O set-up BCFZ hollow fiber catalyst: NaMnWO 4 feed : 20 % CH 4 in He T = 800 C, P = 1 bar Caro et al ind. eng. chem. res. 49(2010)p10230 higher ethylen yield but but comparable conversion and C 2 selectivity! Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
17 outline introduction / membrane processes some current applications emerging future applications challenges / need for research & development Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
18 challenges / need for R&D challenges permeance permselectivity (membrane material, thickness of membrane layer) (membrane material, accuracy of membrane layer) operation temperature (membrane material, module) chemical stability mechanical stability module construction (membrane material, module) (membrane material, geometry of membrane) (module material, sealing, thermal elongation) membrane performance / costs of membranes and modules! Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
19 challenges / need for R&D membrane material process operation membrane technical technical type example condition performance membrane modul zeolithe LTA PV 140 C xxxx xxxx xxxx DDR PV, GS 200 C xxxx xxxx xxxx MOF's, ZIF's ZIF 8 GS < 150 C xxxx xxxx xxxx carbon turbostratic carbon GS 300 C xxxx xxxx xxxx amorphous oxide ceramic amorphous nonoxide ceramic xxxx xxxx modified SiO 2 PV, GS 140 C xxxx xxxx xxxx (Ti/Zr)O 2 NF 200 C xxxx xxxx xxxx SiC, SiCN GS 500 C xxxx xxxx xxxx performance in technical range / developed technical concept aviable performance not sufficent / not developed Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
20 challenges / need for R&D membrane material process operation membrane technical technical type example condition performance membrane modul perowskite (O 2- - permeable) dense (H + - permeable) Ba 0,5 Sr 0,5 Co 0,8 Fe 0,2 O 3 GS 900 C xxxx xxxx xxxx membrane reactor GS 900 C xxxx xxxx xxxx CO 2 stable types GS 900 C xxxx xxxx xxxx perowskite GS 1000 C xxxx xxxx xxxx cermet Zr(Y)O 2 /Pd GS 600 C xxxx xxxx xxxx xxxx xxxx performance in technical range performance not sufficent / developed technical concept aviable / not developed Dr. Hartwig Voß, GCP/TC Process Research and Chemical Engineering 20 th January
21 R & D - demand fundamentals of transport new materials, material improvement membrane scale up technical modules
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