Bio based Waste. Lakhya Jyoti Konwar Technical Chemistry, Department of Chemistry, Umeå University Prof. J P Mikkola s group

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1 Active Carbon Catalysts from Bio based Waste Lakhya Jyoti Konwar Technical Chemistry, Department of Chemistry, Umeå University Prof. J P Mikkola s group 1

2 Adsorbents, catalysis, electrodes in batteries, electronics, structural reinforcer ACS Catal., 2014, 4 (10), pp

3 Applications of carbon/active carbon Main applications of active carbon Gas purification Waste water treatment t t Medicinal applications Mercury scrubbing Removing contaminants from food and beverage Limited applications in industrial catalysis xidation reduction Fuel gas cleaning (Dechlorination and desulfation) Halogenation Production of S 2 Cl 2, polysulfides, phosgene etc Adsorption and its Applications in Industry and Environmental Protection Vol.I: Applications in Industry, Edited by A. DąbrowskiStudies in Surface Science and Catalysis, Volume 120, Part A, Pages U.S. sales of catalyst support materials. Renew. Sustainable Energy Rev. 29 (2014)

4 Carbon materials as catalyst/supports Pros Tailorable porous structure and surface chemistry Inexpensive resistant to acids and bases High thermal stability Easy recovery of active phase (e.g. metals) Cons Low mechanical stability Susceptible to hydrogenation, gasification and oxidation reactions Lipids, cellulose, hemicellulose etc. ACS Catal., 2014, 4 (10), pp Renew. Sustainable Energy Rev. 29 (2014)

5 Some common catalytic routes for conversion of biomass components Aluminosilicate systems are not suitable for handling baimass platforms (presence of H 2 and narrow pore dimesions) 5

6 CH H H H 3 SC 6 H 4 C 6 H 4 S 3 H N NH HC N 2 H N N H 3 SC 6 H 4 C 6 H 4 S 3 H H N H HC C 6 H 4 S 3 H Carbon-S 3 H Example of carbon material as acid and RR catalyst oil seed processing protein waste (press cake) were converted to high h value porous carbon materials (N doped d carbons and sulfonated carbons) Application as inexpensive electrocatalyst and heterogeneous acid catalysts (1) Chemical (50% H 3 P 4 ) activation followed by sulfonation using different protocols: (a) 4-BDS, method 1 H 3 S (b) conc. H 2 S 4,method 2 (porous catalyst) Sulfonation (method 1 or 2) N-doped active carbon (Electrocatalyst) (2) ne pot hydrothermal carbonization and H 2 S 4 o C, method 3 (non-porous catalyst) N 2 + Cl - Sulfonic acid functionalize d carbon materials (Catalyst) (method 3, one pot route) 6 Raw material/oil seed from three different sources applied.

7 TEM micrographs and XPS of N1s and S2p peaks Typical lhigh hresolution s2p peaks (for materials obatained method 2 and 3) 2 (S2p) S as S 3 H <1 m 2 /g 93 m 2 /g, 3.9 nm intensity (a.u) i S as SH Binding energy (e.v) 468 m 2 /g, 4 nm 483 m 2 /g, 4.8 nm Typical high resolution s2p peak (materials obtained by method 1) 2 (S2p) SasPhSH 3 1 (N1s) ity (a.u) intensi Binding energy (e.v) 7

8 perational stability weight los ss % Difference between sulfated and non-sulfated forms of AC JACS PACS MACS MAC (non-sulfonated) T ( o C) Stable upto ca. 242 o C in oxygen free conditions 8

9 Wate derive active carbon upon RR in 0.1 M KH at% N, content of Pyridinic-N and pyrrolic-n> 50% cathodic peak Waste derived N doped carbons are potential metalfree electrocatalyst for RR Konwar, L.J., Sugano, Y., Chutia, R.S., Mäki Arvela, P., Kataki, R & Mikkola, J P. Materials Letters, 173, ,

10 Cellulose acetate (CA) and catalyst mixture Transparent cellulose Acetate (CA) film 1) Add acetone + As a catalyst upon 3) Decentation cellelose l valorization i 2) 4000 rpm (35 min) 1) Redissolve in CH 2 Cl 2 2) Dry in vacuo Cellulose cetate (CA) powder Sulfonated carbon (Catalyst) Cellulose acetate (CA) in acetone Add 50% aq. Ethanol 1) Filter 2) Wash with Deionized water and dry Precipitated cellulose acetate (CA) Yield upto 70% for acetone soluble cellulose diacetates corresponding to DS 2.7 in 80 o C, catalyst can be recycled Konwar, L.J., Mäki Arvela P., Salminen, E., Kumar, N, Thakur, A.J., Mikkola, J P. & Deka D. Applied Catalysis B Environmental, , 20 35, Konwar, L.J., Mäki Arvela, P., Thakur, A.J., Kumar, N. & Mikkola, J P. RSC Advances, 6, , Amorphous cellulose conversion 60%, with glucose yield upto 53% For pretreated biomass conversion upto 90%, with sugar yield of 78%, at 150 o C, 24 h 10

11 As a catalyst upon glycerol valorization triacetin synthesis H H H Propane-1,2,3-triol (Glycerol) (major product) H H H H 1,3-Dihydroxypropyl 2,3-Dihydroxypropyl acetate acetate t (2-monoacetin) (1-monoacetin) H-beta (Si/Al=25) H 1-Hydroxy-2,3-propanediyl diacetate (1,2-diacetin) H 2-Hydroxy-1,3-propanediyl diacetate (1,3-diacetin) H-Y Carbon-S 3 H black: monoacetin, red: diacetin blue: triacetin, magenta: glycerol 1,3-Diacetyloxypropan-2-yl acetate (Triacetin) The desired product is formed only if catalyst pore space > triacetin critical diameter and the catlyst has enough acid sites Shape selectivity and acidity effects in glycerol acetylation with acetic anhydride: Selective synthesis of triacetin over Y Zeolite and sulfonated mesoporous carbons, Konwar, L.J., Mäki Arvela P., Begum, P., Kumar, N., Thakur, A.J., Mikkola, J P., Deka, R.C. & Deka, D. Journal of Catalysis, 329, ,

12 As a catalyst upon glycerol valorization (cont.) Selective synthesis of monoglycerides (MG) Selectivity effected by pore size and surface hydrophilicity and fatty acid chain length Upto 80% monoglycerides selectivity Effect of fatty acid and reaction temperature in nitial rate (mmo ol/min) oleic lauric r MG (oleic) r MG (lauric) Reaction temperature ( o C) r MG ctiveity to MG (mol-%) Sele ACS3H HTS3H H-ZSM-5 20 H-Y HY H 2 S 4 blank Conversion (mol-%)

13 As a catalyst upon FAME synthesis Esterification of oleic acid oils to FAME over a mesoporous sulphonated carbon catalyst Sulfonated if R = CH Carbon 3 H CH + RH 3 + H 2 Conditions: 3 wt% catalyst, 64 C, 10 h, MeH/acid=20 leic acid Methylolate (FAME) - Large pore Carbon-S 3 H outperforms zeolites, H 2 S 4 and non porous carbon-s 3 H catalysts (higher TF) - FAME yield upto 96% Reusability 80 20:1 (MeH:A, molar ratio) Cycle 1 Cycle 2 Cycle 3 % Conversion n % Conversion n Blank JAC MAC PAC JACS MACS PACS MACH 2 S 4 MACHT H 2 S 4 H-Y ZSM-5 0 MACS PACS JACS MACH 2 S 4 MACHT Konwar, L.J., Mäki Arvela P., Salminen, E., Kumar, N, Thakur, A.J., Mikkola, J P. & Deka D. Applied Catalysis B Environmental, , 20 35,

14 As a catalyst upon FAME synthesis Simultaneous esterification and transesterification of acid oils to FAME over a mesoporous sulphonated carbon catalyst FFA + MET W + FAME where, TG + MET DG + FAME FFA= Free fatty acid, MET = Methanol, W = H 2, DG + MET MG + FAME TG = triglycerides, DG = diglycerides, MG = MG + MET GLY + FAME monoglycerides, FAME = fatty acid methyl ester FAME yield upto 120 o C, effect of FFA%, deactivation due to pore blocking blue = FFA, green = FAME, red = MG, magenta = TG, cyan = DG, black=water, yellow=gly Kinetic plots of simultaneous esterification and transesterification of feedstock oil I at temperatures of 80 (a), 100 (b) and 120 C (c e). Conditions: catalyst amount = 0.5 g and methanol to FFA in oil molar ratio = 40/1 (a c), ratio = 10/1 (d) and ratio = 20/1 (e). Symbols: blue = FFA, green = FAME, red = MG, magenta = TG, cyan = DG, black = Water, yellow = GLY, solid lines-model l and circles-experimental i l point. Konwar, L.J., Wärnå, J., Mäki Arvela, P., Kumar, N. & Mikkola, J P. Fuel, 166, 1 11,

15 Solid acids/s dopeddoped carbons from valorization of sulfur rich solid wastes into catalytic materials in ntensity (au) S/sulfate rich carbon precursor Controlled processing S 3 H/S doped carbons 1s C1s S2s S2p binding energy(ev) SH CH S H 3 S S H SH S S H S S H 3 S S S 3 H H S H HC S 3 H 15

16 122 m 2 /g, 14.5 nm nm dv/ /dlog(d)(cm³/g) m 2 /g, 7 nm Pore diameter (nm) 100 nm 16

17 Future plans Improvement of textural properties Fixed bed applications Explore additional fields of application for the S doped/sulfonated carbon materials Water purification/waste water treatment Electrochemical/energy storage applications 17

18 Thank you for your attention! 18