Available online at ScienceDirect. Procedia Environmental Sciences 23 (2015 )

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1 Aville online t ScienceDirect Procedi Environmentl Sciences 23 (2015 ) Interntionl Conference on Tropicl nd Costl Region Eco-Development 2014(ICTCRED 2014) Cellulose Isoltion from Tropicl Wter Hycinth for Memrne Preprtion Titik Istirokhtun,c)*, Nur Rokhti,c), Rich Rchmwty ), Metty Meriyni ), Slmet Priynto ), Heru Susnto,c) Environmentl Engineering Deprtment, Engineering Fculty, Diponegoro University, Semrng 50275, Indonesi Chemicl Engineering Deprtment, Engineering Fculty, Diponegoro University, Semrng 50275, Indonesi c Memrne Reserch Center(Mer-C), Center Of Reserch And Services-Diponegoro University, Semrng 50275, Indonesi *Corresponding uthor : titik.istirokhtun@undip.c.id Astrct The presence of wter hycinth (Eichhorni crssipes) s n qutic plnt in mny lkes or other sins cuses mny conservtion prolems. Mny efforts hve een devoted to overcome these prolems such s y utiliztion of wter hycinth for energy production, for wter tretment, etc. In this reserch, cellulose ws isolted from wter hycinth nd further used for memrne preprtion. Cellulose isoltion ws performed y extrction followed y cetyltion resulting cellulose dicette. The memrnes were prepred y phse seprtion methods. The resulting memrnes were then chrcterized y mesuring wter flux nd surfce chemistry (y FTIR). In ddition, the memrnes were exmined for filtering humic cid solution s model of surfce wter. The results show tht cellulose cn e isolted from wter hycinth nd cn further e processed into cellulose dicette with the yield of 5,6 %. The memrne preprtion shows tht the concentrtion of polymer nd evportion time influence the performnce of the memrne, where the greter concentrtion of the cellulose polymer nd the longer of the evportion time results in the denser nd the smller memrne pores Pulished The Authors. y Elsevier Pulished B.V. This y Elsevier is n open B.V. ccess rticle under the CC BY-NC-ND license ( Peer-review under responsiility of scientific committee of the ICTCRED Peer-review under responsiility of scientific committee of the ICTCRED 2014 Keywords: tropicl wter hycinth, cellulose, memrne preprtion, humic cid filtrtion Pulished y Elsevier B.V. This is n open ccess rticle under the CC BY-NC-ND license ( Peer-review under responsiility of scientific committee of the ICTCRED 2014 doi: /j.proenv

2 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) Introduction Wter hycinth (Eichhorni crssipes) is floting plnt species tht live in wter. Rpid reeding led to wter hycinth plnt hs turned into weed in some res in Indonesin wters such s in mny lkes or other sins. Wter hycinth is clled the world s worst qutic weed due to its ility to rpidly cover whole wterwys. The growth of wter hycinth within 6 months reches 125 tonnes wet weight in the re of 1 h [1]. It forms dense, impenetrle mts over the wter surfce, nd other specific impcts such s locking irrigtion chnnels nd rivers, restricting livestock ccess to wter, destroying nturl wetlnds, eliminting ntive qutic plnts, reducing infiltrtion of sunlight, chnging the temperture, ph nd oxygen levels of wter, reducing gs exchnge t the wter surfce, incresing wter loss through trnspirtion (greter thn evportion from n open wter ody), ltering the hitts of qutic orgnisms, restricting recretionl use of wterwys, reducing esthetic vlues of wterwys, reducing wter qulity from decomposing plnts, destroying fences, rods nd other infrstructure when lrge floting rfts ecome moile during flood events, nd destroying pstures nd crops when lrge floting rfts settle over pddocks fter flood events [2]. Rw Pening (with the re of 2,670 hectres), lke locted in Semrng district, Centrl Jv hs prolems cused y wter hycinth. It ws found tht lke sedimenttion rte due to the presence of wter hycinth reches tons/yer. As result the wter volume decresed 29.34% over the lst 22 yers [3]. Therefore, the prolems due to wter hycinth re very importnt to e overcome. Eichhorni crssipes is n excellent source of iomss s ioenergy rw mteril. Gsifiction of one ton dry mtter y ir nd stem t high tempertures (800 C) gives pproximtely 1,100 m 3 nturl gs (143 Btu/cuft) contining 16.6% H 2, 4.8% methne, 21.7% CO, 4.1% CO 2, nd 52.8% N. Nevertheless, the high moisture content of wter hycinth, cusing high hndling cost, tends to limit commercil ventures [4]. In trditionl process wter hycinths re used to mke furniture, hndgs, rope, rt pper [5], ioethnol production nd prticle ord [6]. High cellulose content in wter hycinth (i.e. 25 % cellulose, 33 % hemicellulose, nd 10 % lignin) hs potentil to e used s rw mteril for cellulose se polymers, which hve higher economic vlue compred the existing use. In previous studies, Thiripur nd Rmesh [7] hve isolted cellulose from wter hycinth. On the other hnd, production of cellulose se polimers using nother ioms mteril lso hs done (Sntoso) [8]. Sljoughi et l. [9] conducted study on the effect of pretretment vriles on the morphology structure nd flux of symmetric memrne prepred from cellulose cette. The result showed tht the polymer concentrtion vritions ffect the memrne performnce. Severl previous memrne studies more focused on the process of memrne preprtion, while the nlysis of lterntive mterils tht hve economic vlue hs not een done. Therefore, th purpose of this study is to investigte the potentil of wter hycinth for the preprtion of cellulose se polymers. Further, the resulted cellulose se polymers re used for memrne preprtion. The effects of process condition in memrne mnufcturing on memrne performnce for surfce wter filtrtion re presented. 2. Mterils nd Methodes Mterils Wter hycinth in dry fier form ws otined from the Rw Pening lke. Toluene 99.9%, ethnol 99.8%,, cetone 99.8 %, (CH3CO) 2 O (cetic nhydride) 98,5 % nd PEG (polyethylene glycol) were purchsed from Merck, Germny. While cellulose cette ws tken from Aldrich, Germny Methods Cellulose isoltion Wter hycinth fiers were extrcted using mixed toluene/ethnol solvent with rtio of 2: 1 for 3 hours t C. Furthermore, leching process using NClO 3% for 2 hours t 80 0 C ws performed. Then, hemicellulose ws removed y hydrolysis using NOH 1% t 60 0 C for 2 hours. The second leching ws performed to remove the remining lignin through cooking process using NClO 1% nd stirred t 75 0 C for 3 hours. The lst stge ws

3 276 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) hydrolysis using HCl 5% s ctlyst for 6 hours t 65 0 C. The smple ws filtered nd the otined solid ws wshed with distilled wter until free of cid Cellulose product cetyltion Cellulose cetyltion ws conducted using the following processes: initilly 10 g of cellulose from fier stlks of wter hycinth nd 24 ml glcil cetic cid were mixed nd stirred t 40 0 C for 1 hour. Furthermore, 0,1 ml sulfuric cid nd 60 ml glcil cetic cid were dded, nd stirred gin for 45 minutes t the sme temperture. The mixture ws cooled to 18 o C nd then 27 ml cetic nhydride ws dded. Therefter, 1 ml sulfuric cid nd 60 ml glcil cetic cid were dded to the mixture, nd cetyltion time of 3 hours t temperture of 40 o C. Furthermore 67% cetic cid ws dded to the mixture t 40 o C for hydrolysis process s long s 15 hours t room temperture. After doing cetyltion nd hydrolysis, cellulose cette ws precipitted y dding distilled wter drop y drop nd stirred to otin powder precipitte. The resulted powder precipitte ws wshed nd dried in n oven t 50 o C Preprtion of Cellulose Acette Memrnes Cellulose dicette solutions with concentrtion of % were prepred using ceton s solvent then stirred for 3 hours until ll the cellulose cette dissolved. Polyethylene glycole (5%) ws dded drop y drop. The homogenous polymer solution ws left without stirring until no ules were oserved. The polymer solution ws cst with thickness of 200 m using steel csting knife on glss sustrte, then left in free ir contct with time vries ie 0, 5, 10 nd 15 seconds. Therefter, the proto-memrne ws solidified y inserting into cogultion th contining wter for 1 dy t room temperture. The resulting memrnes were wshed to remove excess solvent [10] Memrne Chrcteriztion Flux nd rejection test The resulted memrnes were exmined for filtrtion of humic cid solution s model of surfce wter. Firstly, compction process ws done y filtering pure wter t pressure of 0,5 tm. After the compction process, distilled wter in filtrtion cell is replced with 25 ppm humic cid solution. The filtrtion ws performed t pressure of 0.5 tm. Flux mesurement ws performed y mesuring the volume of solution tht cn e ccumulted for 120 minutes with n intervl of 10 min. Flux vlue ws mesured y clculting volume rtio of permete per unit memrne re per unit time. While the rejection rte ws otined y mesuring the concentrtion of the solution efore nd fter pssing through the memrne y using spectrophotometer nd turidimeter FTIR (Fourier Trnsform Infr Red) The chemicl chrcteristic of wter hycinth, cellulose nd memrnes ws investigted y using Shimdzu FTIR spectrophotometer. There IR Spectr were then compred with commercil cellulose cette. 3. Result nd Discussion 3.1. Isoltion of cellulose from wter hycinth Isoltion of cellulose for hycinth ws performed y exctrction, leching nd lkline hydrolysis respectively. During extrction the mss of hycinth ws reduced out 44% of initil mss. As reported y Thiripur nd Rmesh [7] extrction process could remove extrctive compounds contined in the stlks of wter hycinth except lignin, cellulose nd hemicellulose. The resulted product from extrction hd rown color (Fig. 1), indicting other impurities such s lignin nd hemicellulose in the fier hve not een removed yet. Bleching process using NOCl could further removed lignin y reking ether ond nd incresed the whitness degree of fiers (Fig 1). Alkline hydrolysis ws performed y cutting the chin to seprte hemicellulose from the min chin, nmely cellulose (Fig. 1c). In ddition, rection with NOH solution will lso cuse degrdtion of lignin molecules due to the termintion of ryl-ether onds, cron-cron, ryl-ryl nd lkli-lkli [7]. Second leching nd hydrolisis processes were performed to remove the remining lignin nd hemicellulose. From Fig.2 it cn e oserved tht the results of the IR spectrum of wter hycinth displys peks t wvelength of cm -1, which indictes the presence of cetyl nd ester in croxyl group chin of the cid p-koumeril s well

4 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) () () (c) Fig 1. Isoltion process result () fter extrction() fter leching (c) hydrolisis s indicting the presence of lignin nd hemicellulose. This result is in greement with previous work presented y Thiripur nd Rmesh [7]. There re lso peks t wvelength of 1519 cm -1, which indictes the presence of the C=C group on the romtic ring of lignin. Hemicellulose is seen from the presence of the pek t wvelength of cm -1. All three groups showed the presence of impurities in the form of hemicellulose nd lignin. The IR spectrum of cellulose shows tht some peks hve een lost due to the purifiction process tht hs een crried out. On the other hnd, the results of the IR spectrum of cellulose mintined peks t wvelength of 3404 cm -1 nd 2920 cm -1 which indictes the presence of C-H nd O-H groups, where oth groups re the min functionl groups of cellulose. The resulted spectrum shows tht impurities contined in the wter hycinth hs een removed. Then the high purity cellulose ws produced. () () wter hycinth cellulose s o r n c e Wvelength (1/cm) Fig. 2. IR spectrum of wter hycinth nd cellulose from wter hycinth 3.2. Cellulose Acetyltion Cellulose cetyltion process produced white solid cellulose dicette (CA). To determine the functionl group chnges fter cetyltion, the cetyltion products were tested using FTIR instrument. Bsed on Fig. 3, it cn e seen tht the results of the IR spectrum of cellulose dicette hs significnt difference compred with the results of the IR spectrum of cellulose. In the IR spectrum of cellulose dicette results pper shrp peks t wvelength of cm -1 nd cm -1 which indictes the presence of cronyl group C=O nd C-O ester group. This result suggests tht cellulose cetyltion process hs successfully performed. A comprtive nlysis etween the functionl groups of the resulted CA nd commercil CA ws lso performed (Fig. 4). The result shows tht the IR spectrum of the the resulted CA nd commercil CA re similr indicting tht isoltion nd cetiltion hve een well performed. Overll, ech 100 grms of dried wter hycinth produced 5.6 grms cellulose dicette. Thus, the yield otined in the mnufcture of cellulose dicette from wter hycinth is out 5.6%.

5 278 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) s o r n c e () cellulose () cellulose dicette (CA) Wvelength (1/cm) Fig. 3. IR spectrum of cellulose nd cellulose dicette (CA) () () commercil cellulose cette synthetic cellulose dicette s o r n c e Wvelength (1/cm) Fig. 4. IR spectrum of synthetic cellulose dicette nd commercil cellulose dicette 3.3. Memrne Preprtion Effect of evportion time on flux nd rejection In this work, the effect of evportion time on flux nd rejection ws investigted. Humic cid solution ws used during rejection experiment. The results re presented in Fig. 5 nd Tle 1. It cn e seen tht flux decreses with incresing time of evportion, ecuse the longer evportion time will cuse the memrne pore size ecomes smller due to incresing polimer concentrtion on the top lyer of memrne. The interction of solvent exchnge with the mient ir is smller thn interction etween the solvent exchnge nd non solvent [11, 12]. Moreover, the top lyer will inhiit the exchnge rte etween residul solvent nd non solvent through the memrne surfce during immersion process in the cogultion th. However, the memrne with smller pores size hve higher rejection towrds humic cid. In generl, the results show tht trde off etween flux nd rejection ws found nd this is in good greement with previous results which reported memrne preprtion using non CA polymers. Good memrnes should hve high oth flux nd rejection [13, 14]. In this context, the est memrne ws otined

6 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) from the result of csting process with 10 seconds evportion time Effect of polymer concentrtion on flux nd rejection The effect of CA concentrtion on flux nd rejection ws investigted. The increse in polymer concentrtion decreses flux on the one hnd nd increses rejection on the other hnd. This phenomenon cn e explined y the higher concentrtion of cellulose cette the higher numer of polymer molecules per unit volume; consequently the numer of solvent molecules which will e replced y non-solvent into the pore decreses [15]. In ddition, the increse in polymer concentrtion lso strengthens the thermodynmic stility of the solution to e formed into films. Therey, the memrne pore sizes resulted from higher polymer concentrtion should e nrrower. Figure 5 presents mesurement dt with the vrition of evportion time nd polymer concentrtion. Flux (L/m 2.hour.r) seconds detik 5 seconds detik 10 seconds detik seconds detik Polymer Konsentrsi conc. CA polimer-sa (1=13%w;(1=13%; 2=14%w;3=15%w) 2=14% ; 3=15%) Fig.5. Memrne flux vs concentrtion of CA with vrition of evportion time (pressure 0.5 tm) 3.4. Memrne Rejection Mesurement Tle 1. Memrne Rejection on ech memrne composition nd evportion time Evportion Time Rejection (%) Polimer Concentrtion (w/w) (seconds) NTU Humic Acid FTIR Anlysis To determine the functionl groups present in the memrne, the memrnes were nlyzed using FTIR

7 280 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) spectrophotometer (Fig. 6). Bsed on the test results of FTIR nlysis cn e seen tht ll memrnes hve C=O group, CH 3 nd -COOH s shown with wvelengths contined in Tle 2. Overll no difference in chemicl structure is oserved for the memrne s prepred with different evportion time, mening tht evportion did not chnge the chemicl structure of resulted memrne. s o r n c e Wvelength (1/cm) Fig. 6. IR Spectrum of CA memrne with vrition of concentrtion nd evportion time Tle 2. Functionl Group of IR Spectrum CA memrne No Functionl group Wvelength (cm -1 ) 13% - 0 second 13% - 10 seconds 13% - 15 seconds 15% - 0 seconds 1 C=O CH COOH Conclusion Celloluse hs een successfully isolted from wter hycinth nd cn further e processed into cellulose dicette (CA). The yield otined for preprtion of CA from hycinth ws 5.6%. The resulted CA hs similr chemicl structure with commercil CA. The resulted CA ws used to prepre memrnes. Polymer concentrtion nd time of evportion ffects on flux nd rejection hve een investigted. The higher evportion time, the lower flux nd the higher rejection were resulted. The higher CA concentrtion, the lower flux nd the higher rejection were resulted. CA concentrtion of 15% nd evportion time of 10 seconds re the est operting conditions used in the mnufcture of the memrne with flux vlue of L/m2.hours nd the rejection coefficient of 64.28%. Acknowledgement The uthors thnk to Diponegoro University for the finncil support of this reserch through Non Tx Ntionl Revenue Budget excution list Nr /2014 yer References [1] Heyne, K., Useful Plnts in Indonesi 2nd edition. Bogor: Forestry Reserch nd Development Agency, Ministry of Forestry, Repulic of Indonesi; 1987(in Indonesi). [2] Bourton J, Vn OE, nd Ensey. R (2010), Wter Hycinth : Weed of Ntionl Significnce; ccessed on 28 August 2014.

8 Titik Istirokhtun et l. / Procedi Environmentl Sciences 23 ( 2015 ) [3] Amnd, Rw Pening Will Be Free From Wter Hycinth in 2030, ccessed on 25 Aug (in Indonesi) [4] Duke J. Eichhorni crssipes, in Hndook of Energy Crops. Aville only online. An excellent source of informtion on numerous plnts; [5] Psriu, G. dn Shwlit, Rehilittion of Forest Resources nd Conservtion, Pdng Indonesi; Min Ppers on Exposure Reserch Results; 2006.(in Indonesi). [6] Willy S nd Dedy D. Cross nd evn cellulose from stlk of wter hycinth s prticle ord rw mteril, Thesis; Sepuluh Novemer Institute of Technology; 2010.(in Indonesi). [7] Thiripur M, nd Rmesh A, Isoltion nd Chrctheriztion of cellulose nnofiers from the equtic weed wter hycinth - Eichhorni crssipes, Journl of Crohydrte Polymers, 2012; 87, [8] Sntoso SD, Synthesis of cellulose dicette from pinepple lef fiers (Anns Comocus), Sury: Airlngg University; undergrduted thesis. [9] Sljoughi E, Sdrzdeh M, dn Mohmmdi T, Effect of preprtion vriles on morphology nd pure wter permetion flux through symmetric cellulose cette memrnes, Journl of Memrne Science, 2009; 326, [10] Susnto H, Ulricht M. Chrcteristics, performnce nd stility of polyethersulfone ultrfiltrtion memrnes prepred y phse seprtion method using different mcromoleculr dditives, Journl of Memrne Science 2009;327, [11] Strthmnn H, Scheile RW, nd Bke, A rtionle for preprtion of Loe-Sourirjn-type cellulose cette memrnes, Journl of Polymeric Science, 1971; 15, [12] Mulder M, Bsic Principles of Memrne Technology, Netherlnd; Kluwer Acdemic, [13] Li Go et. l, An Experimentl Investigtion of Evportion Time nd The Reltive Humidity On A Novel Positively Chrge Ultrfiltrrion Memrne Vi Dry-Wet Phse Inversion, Journl of Memrne Science, 2009; 326, [14] Soroko I, Mkowski M, Spill F, nd Livingston A, The Effect of Memrne Formtion Prmeters on Performnce of Polyimide Memrne For Orgnic Solvent Nnofiltrtion (OSN). Prt B : Anlysis of Evportion Step nd The Role of Co-Solvent, Journl of Memrne Science, 2011; 381, [15] Mohn D., Thnikiveln, nd Rjendrn, M. Synthesis, chrcteriztion nd therml studies on cellulose cett memrne with dditive, Europn Polymer Journl 2004;