Hybrid membrane process for polyphenol recovery from Olive mill wastewater (725a)

Transcription

1 Hybrid membrane process for polyphenol recovery from Olive mill wastewater (725a) Jack Gilron, C. Linder, M. Waisman, J. Abramowitz, G. Neimark, L. Kagan, D. Shaked, Z.Wiesman ZIWR-BIDR, Ben-Gurion Univ. Dept. of Applied Chemistry, Ben-Gurion Univ. 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 1

2 Overview Introduction What is OMW? Why treat it? How to treat it? Our flow scheme Results from 2 seasons Economic projections 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 2

3 (Paraskeva et al., 2007; Kapellakis et al., 2008; Niaounakis and Halvadakis, 2006; on the 1 of January, 2009 ). Worldwide Production of Olive Oil Olive trees surface area (km 2 ) Olives (tons per year) Olive oil (tons per year) OMWW (m 3 ) for 3-phase extraction sys. World Wide 7 x x x x10 6 Israel x x x10 4 Israeli olive oil production industry The annual turnover of the Israeli market is estimated in 120 million INS. Olive oil consumption in Israel estimated in 3.5 million liters a year.

4 Olive Oil Production 3-Phase Centrifugation System * Percents are out of initial olive weight (Kapellakis et al., 2008). 10% added water* 40% added water* 20% added water* 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 4

5 The Environmental Impacts of OMWW Threat to aquatic life - The organic load (COD ~ g/l) causes an oxygen availability reduction, promotes algae development & might lead to eutrophication. Also, the high phenolic content ( ~4.2 g/l) might cause intoxication. Discoloring of natural waters The change in color is attributed to the oxidation and polymerization of tannins producing darkly colored polyphenols. Odors - As a result of pungent fermentation methane, hydrogen-sulphide and other gases are released to the open air and cause sever odor nuisance. 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 5

6 Treatment strategies OMW Biological aerobic (polyphenol inhibition) Anaerobic long HRT Physical adsorption pptn with alum Oxidation processes WAO WACO Fenton (H2O2) Membrane processes pressure driven Contactors Energy, Byproducts? (growth hormones, herbicides) 12/1/2014 polyphenols oil

7 Tyrosol OMW Polyphenols by- products Oleuropein Apigenin Hydroxytyrosol Luteolin 4-Hydroxybenzoic acid Caffeic acid p-cumaric acid Gallic acid Quercetin Cinnamic acid

8 OMWW Polyphenols - Health Anti-oxidant Skin protectant Anti-microbial Anti-aging Oleuropein degradation Products - Polyphenols Anti-viral Anti-atherogenic Anti-cancer Anti-imflammatory Mixed polyphenols valued at 80 Euro/kg! (Capanelli, UGE) 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 8

9 Israeli Raw OMWW Characterization Olive Oil Wastewater Characterization Olive Oil mail & Olive Species ph EC (ms/cm) COD (g/l) Total phenol (g/l) TSS (g/l) Oil Content Rahat (Oct. 2008) Barnea Rahat (Oct. 2009) Barnea B. Darom ( Oct. 2009) Mix Revivim** ( Oct. 2009) Mix % % % % Ixal (Nov. 2009) - Mix % Rahat (Dec. 2009) Barnea % Rahat (Dec. 2009) Koronieky % Average 5.12 ± ± ± ± ± ±0.9 Israeli raw OMWW ph, EC, phenol and TSS concentrations are in the upper range of the reported Mediterranean raw OMWW concentrations! **Selective filtration process/ Sinolea extraction system is used (not 3-phase system ).

10 OMW and membrane filtration (adapted from Gesan- Guiziou) OMW components Inorganic ions polyphenols COD Oil droplets Bacteria Suspended material m Microfiltration 0.1 m Ultrafiltration 10 kg.mol -1 Nanofiltration 400 g.mol -1 Reverse osmosis 100 g.mol -1 Industrial membrane operations 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 10

11 Portable membrane treatment for water purification and polyphenol recovery MARS UF-NF System Irrigation Hydroxytyrosol Food Industry Pharma/Cosmetic 12/1/2014 AIChE Fall 2014, Atlanta, Georgia OMWW 11

12 Mobile OMWW + Membrane Contractor Pilot Plant OMWW COD ~ 106g/l Phenol~ 3g/l TP/TOCx100~8% NMR~ 99% Final -HT Pure product Acidification PH 2 Preparative HPLC Ultra- Filtration Product B: Food Pharma Additive Starting Material Product A: Semi-purified H2O for Agri COD~10g/l Phenol~0.7 g/l Nano- Filtration Organic Concentrate Phenol~4.5g/l Hydroxytyrosol Enriched Product HT/TOCx100~12% Compost Organic Waste MA-HT-R (MARS -. HT Recovery Sys.) 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 12

13 Composition of OMW treated by acidification-uf-nf Source Season ph Cond. PP COD (ms) (g GAE/L) (g/l) Halutza, First Halutza, First Darausha, First Halutza, Second Rahat, Second Beit Nir, Second /1/2014 AIChE Fall 2014, Atlanta, Georgia 13

14 TMP, bar Average permeate flow rate, L/h UF treatment GE ZW-10-Submerged UF N 2 1 st season 2 nd Season ` TMP Average flow rate Elapsed time, min 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 14

15 Flux, L/m2h Flux, L/m2h Flux, L/m2h NF concentration runs (NF ) Rahat 80 Beit nir Halutza TP (g/l) - perm/conc Bet Nir : 0.21/4.2 y = x y = e x x R² = Halutza : 0.61/3.95 R² = y = x Rahat : 3.1/ R² = CONTROL TEMPERATURE! VCF VCF VCF 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 15

16 J, Flux, L/m2h Sp. Flux, L/m2-h-bar Applied P, bar J, Flux, L/m2h Applied P, bar NF concentration of OMWW (sterlitech) VCF J DP DK5 NF270 J DP VCF DK5 7.1 L/m2-h-bar 0 NF L/m2-h-bar VCF 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 16

17 Treated OMWW Characterization by HPLC & LC-MS/MS Olive Oil Wastewater Characterization Conc. quality Physico-chemical Pretreatment Membrane Treatment Permeate quality HPLC chromatographs of NF270 permeate (bleu) and concentrate (red) streams of Rahats acidic OMWW. UV detector was used at 254nm.

18 NF selectivity RAHAT OMWW after UF NF-270. Permeates much larger fraction of polyphenols would require second pass 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 18

19 NF selectivity 120.0% 100.0% 80.0% Initial rejection Final rejection RAHAT OMWW after UF DK5 passes only tyrosol and hydroxytyrosol. 60.0% 40.0% 20.0% While >99% pf polyphenols in permeate were hydroxytyrosol, there is still another7 g/l of COD from which to purify it. 0.0% 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 19

20 Phenol extraction system through membrane, Ferreira FC, et al., Membrane Science and Technology, Vol: 8, Pages: Weak acids dissociate in basic medium and associate in acidic medium. 2. Phenols diffuses through the nonporous silicon membranes in their neutral state. (Han et al., 2001)

21 Membrane Contactor Hydroxytyrosol Recovery System Dialysis cell for diffusion rate measurement 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 21

22 Polymers used in membranes preparation 1) Poly (dimethylsiloxane), hydroxy terminated, average Mn ~110,000, viscosity 50,000 cst. (PDMS-1). 2) Poly (dimethylsiloxane), hydroxy terminated, average Mn ~40,000, viscosity 22,000 cst. (PDMS-2). 3) Polytrifluoropropylmethylsiloxane, silanol terminated. (PTFS). 4) Poly (4-vinylphenol), average Mw ~25,000 5) Tetraethyl orthosilicate PDMS was used as a control for state of art MARS membranes to compare with the more stable and selective membranes from PTFS and P4VP

23 Flat sheet contactor (22 cm2) with PTFS Mass transfer coefficient increased by order of magnitude Selectivity for hydroxytyrosol Polytrifluoropropylmethylsiloxane, silanol terminated. (PTFS). Poly (4-vinylphenol), average Mw ~25,000 (PVP)

24 Total phenol, mg/l MARS of NF concentrate (#76 PDMS: P4VP=8:2) Average flux is: 1.1 g Hydroxy-tyrosol/m 2 -h Total phenol for 3 contactors with membrane #76 in MARS 45 Bio phenols, mg/l Feed 0, mg/l Feed 72 h, mg/l 250 Permeate 1, 72h mg/l Permeate 2, 72h mg/l Permeate 3, 72h mg/l Hydroxytyrosol Tyrosol Run time, hours Permeate 1 Permeate 2 Permeate 3 Linear (Permeate 1) Linear (Permeate 2) Linear (Permeate 3) 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 24

25 Mobile UF/NF Unit 180 m 3 /day x 42 days operation/season (+ 21 days transport total two months operation)= 7500 m 3 /season, 22 h on, 2 h clean 80 m m 2 Membrane Contactor (offsite) 301 m 2 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 25

26 Capital costs Capital Equipment Euro UF NF MARS Contingency (5%) 9600 Total /1/2014 AIChE Fall 2014, Atlanta, Georgia 26

27 Operating cost Operating Costs (Euro/year) Electricity (NF + UF) Chemicals (acid, base, cleaning) Membrane replacement 2000 Maintenance 2000 Labor Vehicle rental (2 months) 4000 Facility rental Insurance 800 Total /1/2014 AIChE Fall 2014, Atlanta, Georgia 27

28 Balance sheet Value of recovered polyphenols that compensates costs 150 /kg Case 1: 70% recovery from NF permeate, Case 2: 50% Recovery from NF Permeate; 70% REC 50% REC Operating costs Phenol value Net Operating Income Annual Return on Investment 41% 20% Operating costs Capital costs (Charged at 10%/year) Phenol value Net Income /1/2014 AIChE Fall 2014, Atlanta, Georgia 28

29 Conclusions A membrane hybrid can be carried out on OMW which allows removal of most of polyphenols so that OMW effluent can be used for irrigation (after ph adjust) The polyphenols can be isolated with a membrane contactor to allow their further processing for nutriceutical and pharmaceutical use A mobile UF/NF treatment with central processing for polyphenol production can provide an economic route to treating OMW and limiting its environmental impact 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 29

30 Acknowledgement ENPI-EU Regional grant (Project I-B/2.1/090) Dr. Anna Mamountova, analytical support You, the listeners! 12/1/2014 AIChE Fall 2014, Atlanta, Georgia 30