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TNG HP DIESEL SINH HC T B C PH

Nguyn Vn t, Bi Th Bu Hu, V Anh Khoa, L Th Bch, Ng Kim Lin, Phm B Nh, H Th Kim Quy v Hong Th Mai Lan1

ABSTRACT
Objective of the current work is to study the potential of utilizing waste coffee ground as a feedstock to produce biodiesel. For this purpose, acid-catalyzed pretreatment of highly acidic coffee oil (IA = 21.19 mgKOH/g) followed by a standard transesterification procedure with methanol and potassium methoxide as a catalyst was used to produce coffee oil methyl esters. The transesterification reaction parameters such as methanol to oil molar ratio, catalyst concentration, temperature and time have been investigated. The optimized yield was found to be 74.5%. The quality of the produced biodiesel was evaluated by the determinations of important properties such as density, kinematic viscosity, acid value, iodine value, fatty acid composition and the oxidation stability. The results showed that the produced biodiesel exhibited fuel properties within the limits prescribed by the latest American Standards for Testing Material (ASTM), European standards (EN) and Japanese Industrial Standard (JIS). These obtained results demonstrated the potential of waste coffee ground as an excellent feedstock for biodiesel production. Keywords: biodiesel, coffee oil, oxidation stability Title: Biodiesel from waste coffee ground

TM TT
Mc tiu ca nghin cu ny l nh gi tim nng tn dng b c ph lm nguyn liu tng hp diesel sinh hc. t c mc ch ny, qu trnh hai giai on gm este ha xc tc acid v sau l transester xc tc base, c thc hin tng hp diesel sinh hc t du c ph c ch s acid cao (IA = 21,19 mgKOH/g). Nhng thng s cho phn ng transester ha nh t l mol methanol/du, hm lng xc tc v nhit phn ng c ti u ha. Hiu sut phn ng iu ch biodiesel di nhng iu kin ti u ny l 74,5%. Cht lng ca diesel sinh hc tng hp c c nh gi thng qua vic xc nh nhng thng s quan trng nh t trng, nht ng hc, ch s acid, ch s iod, thnh phn acid bo v bn oxi ha. Kt qu cho thy, diesel sinh hc tng hp c tha mn cc tiu chun cht lng ca M (ASTM), Chu u (EN) v Nht Bn (JIS). Nhng kt qu ny cho thy rng b c ph l ngun nguyn liu y tim nng sn xut diesel sinh hc. T kha: diesel sinh hc, du c ph, bn oxi ha 1 T VN

Biodiesel hay diesel sinh hc l thut ng dng ch loi nhin liu dng cho ng c diesel c sn xut t du thc vt hay m ng vt. Thnh phn chnh ca biodiesel l cc alkyl ester, thng dng nht l methyl ester. Trong nhng nm gn y, c rt nhiu nc trn th gii nghin cu, s dng v pht trin sn xut biodiesel gp phn gii quyt an ninh nng lng, thay th ngun nhin liu ha thch ang cn dn, gp phn a dng ha v to ra ngun nng lng sch lm
1

Khoa KHTN, Trng i hc Cn Th

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gim nhim mi trng. Nhiu phng php iu ch biodiesel t du m ng thc vt c a ra nh: sy nng, pha long, cracking, nh tng ha, transester ha,... trong s thng dng nht l phn ng transester ha do qu trnh phn ng tng i n gin v to ra sn phm ester c tnh cht ha l gn ging nhin liu diesel. Hn na, cc este c th c t chy trc tip trong bung t ca ng c v kh nng hnh thnh cn thp. Phn ng transester ha l phn ng gia triglyceride (thnh phn chnh trong du thc vt hay m ng vt) v alcohol (Hnh 1). S hin din ca xc tc (acid, base,...) s thc y qu trnh phn ng. t h s chuyn i cao phi dng lng d alcohol do phn ng transester ha l qu trnh thun nghch (Demirbas, Ayhan, 2009).
H2C HC H2C OCOR1 OCOR2 OCOR3 Methanol + 3CH3OH KOH R1COOCH3 R2COOCH3 R3COOCH3 Biodiesel + H2C HC H2C OH OH OH

Triglyceride

Glycerin

Hnh 1: Phn ng transester ha tng hp biodiesel

Mt trong nhng bt li ln nht ca vic dng biodiesel l tnh bn oxi ha ca loi nhin liu ny km hn nhiu so vi du diesel. Chng rt nhy i vi cc tc nhn oxi ha nh: khng kh, nh sng, nhit , vt kim loi,... do bn cht biodiesel l nhng este ca nhng acid bo, trong , acid bo cha no chim a s, chng d b tc ng bi nhng tc nhn oxi ha hnh thnh gc t do v tip n l hnh thnh cc peroxide, aldehyde v cui cng acid (ch yu l nhng acid mch ngn). Vic hnh thnh cc acid ny l nguyn nhn chnh gy ra nhng tc ng n mn ng c (Dunn Robert O, 2008). Theo nghin cu c thc hin nm 2005, c khong 75% quc gia sn xut c ph trn th gii, trong Vit Nam c xp hng th hai v lnh vc ny ch sau Brazil (D. Dhaeze, J. Deckers, D. Raes, T.A. Phong, H.V. Loi, 2005). Vit Nam, hng ngy, mt lng ln b c ph t cc gia nh, nh hng, qun c ph,... thi ra mi trng v c rt t cng trnh nghin cu tn dng ngun sinh khi rt di do ny. Vic nghin cu tn dng ngun du bo t b c ph khng nhng gp phn pht trin kinh t m cn gp phn bo m an ninh nng lng, bo v mi trng. Trong cng trnh ny cc kt qu nghin cu tng hp du diesel sinh hc t du b c ph (CBDF) quy m phng th nghim bng phng php hai giai on: ester ha xc tc acid v transester ha xc tc base. CBDF c nh gi cht lng thng qua vic xc nh cc c tnh ha l nh: t trng 15C, nht ng hc 40C, ch s acid, ch s iod, bn oxi ha (theo hai phng php Rancimat v PetroOXY) v phn tch thnh phn methyl ester ca acid bo c trong CBDF.

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2 VT LIU V PHNG PHP NGHIN CU 2.1 Vt liu - B c ph c thu gom ti cn tin khoa Khoa hc T nhin Trng i hc Cn Th v du c ph c ly trch bng h thng Soxhlet vi dung mi hexan. - Tt c cc ha cht c s dng l cc ha cht tinh khit thng mi. 2.2 Phng php nghin cu 2.2.1 Ly trch du c ph t b c ph 20 g b c ph sau khi c lm kh di nh sng t nhin c cho vo mt ti giy hnh tr (cylindrical filter paper) v t vo vo h thng ly trch Soxhlet vi dung mi hexan. Sau khi ly trch, hexan c tch ra khi du c ph bng h thng c quay. Hiu sut du c ph t b c ph ph thi l 12,01%. 2.2.2 Phng php hai giai on tng hp CBDF t du c ph Cc phn ng tng hp c thc hin theo phng php khuy t kt hp gia nhit c in. Do du c ph c ch s acid cao (IA = 21,19 mgKOH/g) nn qu trnh tng hp biodiesel phi tin hnh qua hai giai on: giai on ester ha xc tc acid nhm lm gim ch s acid n mt gi tr thch hp, giai on transester ha xc tc base nhm chuyn cht bo v dng methyl ester (biodiesel). Trong giai on ester ha xc tc acid, cc iu kin phn ng c c nh nh sau: nhit 60oC, thi gian phn ng l 2 gi, phn trm th tch methanol so vi du l 35%, phn trm khi lng acid sulfuric so vi du l 1%, tc khuy l 500 vng/pht. Kt qu thu c du c ph ch s acid l 1,5 mgKOH/g, thch hp tin hnh giai on transester ha xc tc base. Trong giai on transester ha xc tc base, khi lng du c ph (IA=1,5 mgKOH/g) mi th nghim c dng khng i l 100 g, khi lng methanol ly theo t l mol methanol: du t 4:1 n 8:1, hm lng xc tc thay i t 0,5 n 1,5% (tnh theo khi lng du). Xc tc KOH ha tan trong methanol bng my khuy t nhit phng trc khi cho vo bnh phn ng cha du c gia nhit trc n nhit th nghim. Hn hp phn ng c n nh trong phu chit v tch lp. Sn phm CBDF c tinh ch bng cch ra hai ln bng nc m nhm loi b xc tc, methanol. Lm khan bng Na2SO4, cn sn phm v xc nh hiu sut phn ng. 2.2.3 Phn tch tnh cht ha l ca du c ph v CBDF T trng (g/cm3) c xc nh bng my o t trng DMA 4100A, Anton Paar GmbH Austria. nht ng hc (mm2/s) c xc nh 40oC, bng cch o thi gian mt th tch cht lng xc nh chy qua mt mao qun thy tinh di tc dng ca trng lc nht ng hc l kt qu tnh c t thi gian chy v hng s tng ng ca nht k. Hm lng nc (mg/kg) c xc nh bng cch dng thit b 831 KF coulometer (Metrohm) theo tiu chun BS EN ISO 12937:2001.
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bn oxi ha (gi) c xc nh bng c hai phng php Rancimat v PetroOXY. bn oxi ha c o bng h thng Rancimat (Type 743, Metrohm) theo tiu chun Chu u EN 14112:2003 v kt qu c so snh vi kt qu o t h thng PetroOXY (Petrotest Gmh& Co. KG, Germany). Ch s acid (mg KOH/g) c xc nh bng cch dng thit b chun th t ng GT-100 lin kt vi h thng bm mu t ng GT-07 (Mitsubishi Chemical Analytech Co., Ltd., Japan) theo chun JIS K 0070-1992. Ch s iod (g I2 /100g) c xc nh bng phng php chun th tch dung dch phn ng ca du hoc nhin liu sinh hc vi dung dch Wijs (Cl3I/I2 trong dung dch acid acetic) theo tiu chun JIS K0070-1992. Ch s peroxide (meq/kg) c xc nh bng cch dng thit b chun th (Titrado 809, Metrohm) theo tiu chun BS ISO 27107:2008. 2.2.4 Phn tch thnh phn acid bo ca CBDF Phn tch sn phm CBDF sch trn my sc k ghp khi ph (GC-MS 2010, Shimadzu, Co., Nht Bn) vi ct wax (30 m 250 m 0,25 m). Lng mu 1 L c bm t ng (OAL-20i, Shimadzu); nhit bm mu 250oC; tc dng kh mang (He) 2 mL/pht, theo chng trnh nhit phn tch mu du bo. 3 KT QU V THO LUN 3.1 Nhng tnh cht l - ha ca du c ph
Bng 1: Tnh cht ha l ca du c ph dng tng hp CBDF

Thng s T trng ti 15oC (g/cm3) nht ng hc 40oC (mm2/s) Hm lng nc (mg/kg) Ch s acid (mg KOH/g) Ch s iod (g I2/100g)

Gi tr 0,92 39,40 1360,00 21,19 59,54

Du b c ph sau khi trch ly c tin hnh nh gi cht lng thng qua mt s ch tiu ha l c bn. Kt qu c trnh by trong bng 1. T y cho thy nht ng hc ca du c ph cao hn rt nhiu ln so vi du diesel. y l mt trong nhng l do chnh lm cho du c ph ni ring hay du thc vt v m ng vt ni chung khng th dng trc tip nh du diesel. nht khng t chun s nh hng n kh nng bm v phun nhin liu vo bung t. Do , qu trnh chuyn chng thnh dng ester c nhng tnh cht tng t du diesel l cn thit. Phn ng ester ha v phn ng transester ha u l nhng phn ng cn bng, v nc l mt trong nhng yu t nh hng bt li n s dch chuyn cn bng ca cc phn ng ny. T kt qu phn tch trn cho thy, hm lng nc trong du c ph kh ln (1360 mg/kg), nn trc khi tin hnh phn ng vic lm khan nc l cn thit gip phn ng t hiu sut cao. Bn cnh , ch s acid ca du c ph rt cao. Ch s acid ny ph thuc vo nhiu yu t nh thi gian v cch bo qun v du rt d b oxi ha cng nh qu trnh thy phn xy ra do s hin din ca cc phn t nc trong du. Ch s acid
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cng cao th phn ng transester ha cng kh thc hin v acid bo t do s phn ng vi xc tc kim hnh thnh x phng v nh vy khng tch c CBDF ra khi glyxerin. Do , qu trnh tng hp CBDF phi qua hai giai on: (1) ester ha xc tc acid nhm chuyn acid bo t do v dng ester lm gim ch s acid v (2) phn ng transester ha xc tc kim. Trong nghin cu ny, cc iu kin giai on ester ha xc tc acid c c nh nh sau: nhit phn ng 60oC, tc khuy l 500 vng/pht, thi gian phn ng l 2 gi, phn trm th tch methanol so vi du l 35%. Kt qu thu c du c ph c ch s acid l 1,5 mgKOH/g, thch hp tin hnh giai on 2. 3.2 Nhng yu t nh hng n hiu sut phn ng transester ha 3.2.1 nh hng ca hm lng xc tc KOH n qu trnh iu ch CBDF kho st nh hng ca lng xc tc, cc th nghim c tin hnh vi nng xc tc KOH thay i t 0,5 n 1,5% (so vi khi lng du) v c nh cc yu t cn li nh sau: t l mol methanol/du l 6:1, nhit l 60oC, tc khuy l 500 vng/pht, thi gian phn ng l 2 gi.
80 70 61.8 60 50.2 50 40 74.5 73.3 71.9

Kt qu c biu din bng th Hnh 0.4 0.6 0.8 1.0 1.2 1.4 1.6 N ng KOH, % 2. Hiu sut phn ng cao nht khi hm lng xc tc KOH l 1%. nng KOH nh hn 1%, lng xc tc khng Hnh 2: nh hng ca KOH n hiu sut Biodiesel phn ng hon tt. Ngc li, khi nng KOH ln hn 1%, hiu sut phn ng c khuynh hng gim bi v khi tng lng xc tc th lm tng lng x phng to thnh, t hiu sut thu sn phm gim. 3.2.2 nh hng ca t l mol methanol/du n hiu sut iu ch biodiesel T l mol methanol/du l mt trong nhng yu t quan trng nht nh hng n hiu sut phn ng. Trong nghin cu ny, mt chui cc th nghim c thc hin vi t l mol methanol/du thay i t 4:1 n 8:1. Hnh 3 cho thy nh hng ca t l methanol/du n hiu sut to CBDF. Theo chiu hng tng t l mol th hiu sut cng tng. T l mol cng cao hn t l mol trong phn ng transester ha gia methanol v du (3:1) th tc hnh thnh ester cng nhanh (Hideki Fukuda, Akihiko Kondo and Hideo Noda, 2001). Khi t l mol l 6:1 th hiu sut t cao nht. Tuy nhin, nu t l mol cao hn 6:1 th hiu sut c khuynh hng gim, iu ny do methanol c nhm OH phn cc ng vai tr nh mt cht nh ha (Umer Rashid, Farooq Anwar, 2008), lm tng kh nng ha tan ca glycerin trong dung dch phn ng. Khi glycerin cn li trong dung dch phn ng s lm cho cn bng chuyn dch theo chiu ngc li vi hng to mono ester, hiu sut s gim. Mt l nguyn nhn khc na l do methanol ha tan c c glycerin v alkyl ester, nn mt lng alkyl ester s theo methanol vo trong pha glecerin v do lm gim hiu sut.
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80 74.5 Hiu sut, % 70 69.9 72.4 71.35

80.0 75.0 Hiu sut, % 70.0 65.0 60.0 55.0

3 4 5 6 7 8 T l mol (methanol/du) 9

74.5 69.5 62.0

73.9

60

56.2

50

45.0

50.0

55.0

60.0
o

65.0

70.0

Nhi t , C

Hnh 3: nh hng ca t l mol (methanol/du) hiu sut biodiesel

Hnh 4: nh hng ca nhit n hiu sut biodiesel

3.2.3 nh hng ca nhit phn ng n hiu sut iu ch biodiesel Phn ng transester ha xc tc thng c nghin cu trong khong nhit gn vi nhit si ca methanol (Srivastava A, Prasad R, 2000). V vy, cc th nghim c tin hnh bn nhit khc nhau 45, 55, 60 v 65oC vi vic c nh cc yu t nh: nng xc tc KOH l 1% (theo khi lng du), t l mol methanol/du l 6:1, tc khuy l 500 vng/pht, thi gian phn ng l 2 gi. Hiu sut phn ng ti cc nhit khc nhau c trnh by th Hnh 4. Hiu sut cao nht t ti 60oC. Khi tng nhit hiu sut phn ng to CBDF tng. Tuy nhin, khi nhit tng cao hn 60oC, th hiu sut phn ng c khuynh hng gim, iu ny c th do phn ng x phng ha du xy ra trc khi hon tt phn ng transester ha. Mt khc, nhit cao dn n tht thot methanol mt phn lm gim hiu sut. Vy iu kin ti u cho phn ng transester ha nh sau: - Hm lng xc tc KOH: 1% (so vi khi lng du) - T l mol (metanol/du): 6:1 - Nhit phn ng: 60 C 3.3 Nhng tnh cht l ha ca biodiesel iu ch t du c ph Bng 2 trnh by nhng tnh cht ha l ca CBDF c so snh vi biodiesel iu ch c t m c tra, c basa (FBDF) v du ht cao su (RBDF). Nhng tnh cht nh: t trng 15oC, nht ng hc 40oC, ch s acid, ch s iod v bn oxi ha (theo phng php Rancimat) ca CBDF u t yu cu ca cc tiu chun M, Chu u v Nht Bn. Hu ht biodiesel iu ch c t du thc vt v m ng vt u khng tha c tiu chun v bn oxi ha. Tuy nhin, mt iu bt ng th v l CBDF c bn oxi ha theo phng php Rancimat (10,31 gi) tha c yu cu ca tt c cc tiu chun, bn ny li rt cao so vi biodiesel iu ch t m c Tra Basa (5,4 gi) hay so vi biodiesel iu ch t du ht cao su (2,74 gi). iu ny c th do trong thnh phn ca du c ph c mt hm lng ln nhng cht khng oxi ha t nhin.

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Bng 2: Nhng tch cht ha l ca CBDF

Cc tiu chun

Cc tnh cht ha l Rancimat (gi) PetroOXY (gi) Ch s acid (mg KOH/g) Ch s peroxide (meq/kg) Ch s iod (g I2/100g) nht ng hc 40oC (mm2/s)

JIS

EN

ASTM

CBDF

FBDF1)

RBDF2)

10 min. 0.5 max. 130 max. 3.55.0

6 min. 3 min. 0.5 max 0.50 max 130 max. 130 max. 3.5 5.0 1.9 5.0

10,31 2,15 0,12 6,20 61,12 4,64

5,40 2,74 0,90 0,33 0,10 0,06 10,20 38,40 34,00 126,13 4,62 4,75

Ngun: 1) Nguyen Van Dat, 2010, 2) Nguyen Van Dat, 2011

Ch s iod (IV) ph thuc vo thnh phn methyl ester ca cc acid bo (FAME), FAME cha no cng nhiu th tr s IV cng cao v FAME cng km bn oxi ha. Tr s IV ca CBDF (61,12 g I2/100g) v RBDF (126,13 g I2/100g) cao hn nhiu so vi FBDF (34 g I2/100g). T y cho thy, biodiesel iu ch t m c c tra, c basa c cha hm lng cc methyl ester ca cc acid bo ha cao nht. Tuy nhin, bn oxi ha ca FBFD km hn so vi du c ph c th do trong thnh phn ca du c ph c hin din mt hm lng ln nhng cht khng oxi ha t nhin (Belay, Ture, Redi and Asfaw, 2008). Mc d ch s peroxide (PV) khng c trong cc tiu chun hin hnh, nhng y cng l mt trong nhng thng s rt c quan tm. S d nh vy l v PV c lin quan n ch s cetane, mt thng s quan trng c lin quan n tiu chun ca nhin liu (Dunn RO, 2005). Nhin liu cng km bn oxi ha th ch s PV cng cao. T kt qu nghin cu cho thy gi tr PV ca CBDF l nh nht. iu ny, mt ln na khng nh bn oxi ha ca CBDF. 3.4 Thnh phn acid bo ca du c ph Thnh phn axt bo (FAME) ca CBDF c phn tch bng sc k kh ghp khi ph. Kt qu c tm tt trong Bng 3.
Bng 3: Thnh phn acid bo ca CBDF

Tn acid Acid capric (C10:0) Acid lauric (C12:0) Acid myristic (C14:0) Acid palmitic (C16:0) Acid margaric (C17:0) Acid arachidic (C20:0) Acid oleic (C18:1) Acid linoleic (C18:2) Acid eicosedienoic (20:2) Acid eicosatrienoic (20:3) Acid bo bo ha Acid bo cha mt mi i C=C Acid bo cha nhiu mi i C=C

Hm lng, % 0,49 3,62 3,29 28,44 0,33 0,08 58,21 1,06 0,15 1,12 36,30 58,95 2,36

Thnh phn FAME ca CBDF ch yu l C10 n C20. Thnh phn C18:1 chim nhiu nht (58,21%) tip n l C16:0 (28,44%). Tng hai thnh phn ny chim
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n 86% v nhng thnh phn cn li ch tn ti dng lng vt. Hm lng ca a ni i ch chim mt phn rt nh 2,36%. Tm li, du CBDF tng hp c p ng tt yu cu v cht lng theo cc tiu chun hin hnh, c bit l ch tiu v bn oxy ha. iu ny khc vi a s cc loi diesel sinh hc tng hp t du thc vt khc hoc m ng vt vn rt km bn oxi ha. iu ny c th do hm lng ca a ni i ch chim mt phn rt nh (2,36%) nhng cng c th do s c mt ca cc cht khng oxi ha t nhin c trong thnh phn ca du c ph. 4 KT LUN ly trch c du c ph t b c ph ph thi vi hiu sut 12,01% v tng hp c CBDF t du c ph ny vi hiu sut 74,5% quy m phng th nghim. Sn phm CBDF t c yu cu v cht lng theo tiu chun ca ASTM, EN v JIS, c bit l ch tiu v bn oxi ha. iu ny gp phn khng nh CBDF l ngun nguyn liu y tim nng cho vic sn xut diesel sinh hc trong tng lai. TI LIU THAM KHO
Belay, A., Ture, K., Redi, M., and Asfaw, (2008). Measurement of caffeine in coffee beans with UV/vis spectrometer. Food Chemistry 108: 310315. D. Dhaeze, J. Deckers, D. Raes, T.A. Phong, H.V. Loi, (2005). Environmental and socioeconomic impacts of institutional reforms on the agricultural sector of Vietnam Land suitability assessment for Robusta coffee in the Dak Gan region. Agriculture, Ecosystems and Environment 105: 5976. Demirbas, Ayhan. (2009). Biofuels: Securing the Planet's Future Energy Needs. Springer Dunn Robert O. Effect of temperature on the oil stability index (OSI) of biodiesel, (2008). Energy & Fuels 22(1):65762. Dunn RO. Effect of antioxidants on the oxidative stability of methyl soyate (biodiesel), (2005). Fuel Process Technol 86: 1071. 85 Hideki Fukuda, Akihiko Kondo and Hideo Noda, (2001). Biodiesel fuel production by transesterification of oils: review. Bioscience and Bioengineering 92(5): 40516. Nguyen Van Dat, (2010). A Study towards the Effect of Antioxidants on Vietnamese Catfish Fat Biodiesel, Collected Papers of Invited Research, Asia Biomass Energy Researchers Program 2009, New Energy Foundation, Japan. Nguyen Van Dat, (2011). Potential of Utilizing Some Biomass Sources as a Feedstock for Biodiesel and Oxidation Stability of Biodiesel-Diesel Blends. Asia Biomass Energy Researchers Program 2010, New Energy Foundation, Japan. Srivastava A, Prasad R, (2000). Triglycerides-based diesel fuels. Renewable & Sustainable Energy Reviews 4: 11 -33. Umer Rashid, Farooq Anwar, (2008). Production of biodiesel through optimized alkaline catalyzed transesteification of rapeseed oil. Fuel 87: 265-273

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