Tp ch Khoa hc HQGHN, Khoa hc T nhin v Cng ngh 26 (2010) 211-216

Nghin cu kh nng thy phn bng axt long v bc u nh gi hiu qu sn xut etanol sinh hc t thn cy ng
Nguyn Xun C*
Khoa Mi trng, Trng i hc Khoa hc T nhin, HQGHN, 334 Nguyn Tri, H Ni, Vit Nam
Nhn ngy 19 thng 11 nm 2010 Tm tt. Nghin cu ny tp trung vo nh gi hiu qu sn xut etanol sinh hc t thn cy ng vi phng php thy phn bng axt long cc nng axit v thi gian thy phn khc nhau. Kt qu nghin cu cho thy thn cy ng sau thu hoch c thnh phn chnh gm 37,2% cellulose; 24,1% hemicellulose v 17,8% lignin. Qu trnh thy phn thn cy ng bng H2SO 4 2% 121 0C trong 60 pht c hm lng ng kh hnh thnh kh cao (4,2 g/l) trong dung dch c t l nguyn liu/dung dch l 1/10 (w/v). y c xem l iu kin thch hp cho qu trnh thy phn thn cy ng bng axt long. S dng Saccharomyces Cerevisiae ln men c th chuyn ha khong 70% lng ng kh trong dung dch thnh etanol vi nng t ti 2,7% theo th tch. Tnh s b, mun sn xut 1 lt etanol sinh hc cn khong 3,24 kg thn cy ng. T kha: thy phn, axit long, etanol sinh hc, cy ng.

1. t vn n nh v m bo an ninh nng lng p ng nhu cu ngy cng tng ca con ngi cng nh cc ngnh cng nghip, cc nh khoa hc ang tp trung nghin cu tm ra nhng ngun nng lng mi, trong nghin cu v pht trin nhin liu sinh hc c ngun gc t sinh khi ng, thc vt l mt hng i y trin vng thay th mt phn ngun nhin liu ha thch ang dn cn kit. S dng nhin liu sinh hc mang li nhiu li ch nh gim thiu nhim mi trng, v nhin liu sinh hc khng cha cc hp cht thm, hm lng lu hunh thp, khng cha

cht c hi. Hn na, nhin liu sinh hc khi thi vo t c tc phn hy cao gp 4 ln so vi nhin liu du m nn gim kh nng gy nhim mi trng. [1] Mt s cng trnh nghin cu trn th gii cho thy cc loi ph phm nng nghip giu hp cht hydratcacbon u c th s dng lm nguyn liu sn xut etanol sinh hc [2-4]. Thnh phn ca rm r, thn cy ng bao gm phn ln l cellulose, hemicelluloses, lignin nn duocj xem l ngun nguyn liu tim nng sn xut etanol sinh hc. Vic nghin cu s dng ph phm nng nghip giu hp cht lignocellulose sn xut etanol sinh hc c thc hin vi 2 qu trnh c bn: (1) thy phn cc hp cht lignocellulose thnh ng; v (2) ln men ng thnh etanol. Trong bo co ny 211

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T: 84-4-38584995. E-mail: cunx@vnu.edu.vn

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Lng ng kh (g/l)

ch yu tp trung vo qu trnh s dng vi sinh vt ln men cc hp cht ng trong dung dch thy phn thn cy ng bng axit long thnh etanol [3]. 2. i tng v phng php nghin cu Qu trnh chuyn ha cc hp cht lignocellulosse thnh etanol i hi phi x l nguyn liu thnh ng n trc khi thc hin qu trnh ln men. Thn cy ng c nghin nh ri thy phn bng dung dch axt long H2SO4 0,5 - 1 v 2% 1210 C trong thi gian 15-30-60 v 120 pht. T l nguyn liu v dung dch l 1/10 (w/v). Dung dch sau thy phn c trung ha bng KOH long cho qu trnh ln men. Chng nm men s dng l Saccharomyces Cerevisiae do Vin Vi sinh vt v Cng ngh sinh hc, i hc Quc gia H Ni cung cp. iu kin ln men nhit 30 0 C; pH= 5,5 v thi gian trong 4 ngy.

2.5 2 1.5 1 0.5 0 0 30 60 90 120 150 Thi gian (pht) Hnh 1. nh hng ca thi gian thy phn n lng ng kh

3. Kt qu nghin cu v tho lun 3.1. nh hng ca thi gian n phn ng thy phn Nghin cu nh hng ca thi gian n qu trnh thy phn c thc hin iu kin nng H2SO4 0,5%, nhit 1210C v thi gian 30-60-90 pht. Kt qu nghin cu v nh hng ca thi gian n phn ng thy phn cc hp cht lignocellulosse c trnh by hnh 1. Hm lng ng kh trong dch thy phn tng ln khi thi gian thy phn tng v t gi tr cao nht (2,3 mg/l) sau 120 pht x l mu. Tuy nhin phn ng thy phn xy ra mnh 60 pht u tin, ng vi lng ng kh to thnh l 2,0 g/l, sau hm lng ng kh tng ln khng ng k. Do vy, c th thy rng iu kin cho qu trnh x l s b vi H2SO4 0,5% iu kin 1210C trong 60 pht l c hiu qu nht.

Nh vy phn ng thy phn cc hp cht lignocellulosse xy ra mnh trong thi gian khong 60 pht u tin ca qu trnh x l mu. t hiu sut cao ca qu trnh thy phn c th duy tr phn ng trong thi gian di hn. Tuy nhin s tiu tn nhiu thi gian cho qu trnh x l mu, nn lm gim hiu qu ca qu trnh sn xut. Do vy tt nht c th la chn thi gian x l mu trong 60 pht c th t c hiu sut v hiu qu cao mc hp l. 3.2. nh hng ca nng axt n qu trnh thu phn Phn ng thy phn cc nng axit H2SO4 long 1-2 v 4% trong thi gian 60 pht v nhit 1210C. Kt qu cho thy nng axt c nh hng rt mnh n phn ng thy phn cc hp cht lignocellulose, th hin lng ng kh c to thnh tng nhanh theo nng axit (Hnh 2). Sau 60 pht thy phn, lng ng kh c gi tr cao nht (4,2 g/l) nng axt H2SO4 4%, tip n (4,0g/l) nng H2SO4 2% v thp nht (2,4 g/l) nng H2SO4 1%. Hm lng ng kh tng nhanh khi nng axt tng t 1% ln 2%, sau tng chm.

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Vic la chn nng axit thch hp cho qu trnh thy phn c ngha ln v nh hng n hiu qu sn xut etanol t thn cy ng. nng axit thp 0,5%, hiu qu thy phn t thp. Ngc li nng axit cao 4%, qu trnh thy phn din ra mnh nhng s tiu tn ha cht v gy kh khn cho qu trnh trung ha ln men etanol sua ny. Do vy nng axit 2% c xem l thch hp cho qu trnh thy phn cc hp cht hydratcacbon trong thn cy ng. Vi kt qu th nghim cho thy iu kin nng axt H2SO4 2% 121 0 C v thi gian 60 pht l thch hp cho qu trnh thy phn cc hp cht lignocellulose. Kt qu ny cng ph hp vi cc nghin cu c cng b bi Mandels v nnk. (1996), Cheng shung gong v nnk. (1981). [3,5]
Lng ng kh (g/l) 4.5 4 3.5 3 2.5 2 0 1 2 3 4 Nng axt (%) 5

3.3. Hiu qu thy phn hp cht lignicellulose trong thn cy ng Kh nng chuyn ha cc hp cht lignocellulose trong thn cy ng c nh gi thng qua kt qu phn tch hm lng cellulose, hemicellulose v lignin c trong mu nguyn liu trc v sau khi thy phn. Kt qu bng 1 cho thy trong iu kin axt long 0,5% H2SO4 c khong 55,6% hm lng hemicellulose b thy phn. Trong khi lng lignin v cellulose b thy phn t hn nhiu, tng ng l 25,3 v 26,1%. Kt qu ny cng ch r kh nng d b thy phn ca hemicellulose so vi cc hp cht lignocellulose khc. Xt v tng th, trong iu kin axt long H2SO4 0,5% ch c mt phn cc cht trong nguyn liu ban u b thy phn, tng ng vi 32,3% lng cht kh ca nguyn liu ban u

Hnh 2. nh hng ca axt n lng ng kh

Bng 1. Kh nng chuyn ha cc cht lignocellulosse trong qu trnh thy phn Hp cht Cellulose Hemicellulose Lignin Cht khc Tng Nguyn liu ban u (gam) 37,2 24,1 17,8 20,9 100,0 Sau thy phn bng H2SO4 0,5% 27,5 10,7 13,3 16,2 67,7 Mc chuyn ha gam % 9,7 26,1 13,4 4,5 4,7 32,3 55,6 25,3 22,5 32,3

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Qu trnh thy phn cc cht lignocellulose xy ra mnh hn nng axt 2%. Lc ny Qu trnh x l mu trong iu kin ny c 73,4% hm lng hemicellulose b thy phn, tip n lignin l 43,3%. Tuy nhin qu trnh ny cng ch thy phn c khong 39,5%

lng cellulose ban u trong cy ng (Bng 2). Cng t kt qu bng 2 cho thy qu trnh thy phn mu trong iu kin axit H2SO4 2% v thi gian 60 pht c th chuyn ha c 51,4% cc cht trong nguyn liu ban u.

Bng 2. Hiu qu chuyn ha cc hp cht lignocellulosse t cy ng trong qu trnh thy phn Hp cht Cellulose Hemicellulose Lignin Cht khc Tng Nguyn liu ban u (gam) 37,2 24,1 17,8 20,9 100,0 Sau thy phn bng H2SO 4 2% 22,5 6,4 10,1 9,6 48,6 Mc chuyn ha gam % 14,7 39,5 17,7 73,4 7,7 43,3 11,3 54,1 51,4 51,4

3.4. Hiu sut ca qu trnh ln men nh gi kh nng ln men etanol, nghin cu s dng chng nm men Saccharomyces Cerevisiae, 30 0C v pH= 5,5 trong thi gian 4 ngy. Cc dch ln men c k hiu nh sau: Dch ln men 1 (LM1): ln men t dch thy phn bng H2SO4 0,5%. Dch ln men 2 (LM2): ln men t dch thy phn bng H2SO4 2% Dch ln men 3 (LM3): ln men t hn hp dung dch thu c t qu trnh x l mu bng H2SO4 0,5% v H2SO4 2%, theo t l 1:1 (v/v).

Kt qu nghin cu cho thy gi tr pH gim dn t 5,5 xung cn 4,4 sau 4 ngy u k t khi b sung chng nm men vo dung dch. Trong phm vi pH nh vy, nm men pht trin kh tt. Tuy nhin t thi gian ny, do pH ca cc dch ln men thp hn ch s pht trin ca nm men. Khng c s khc nhau ng k no v hiu sut ln men trong dung dich LM2 v LM3 vi hm lng ng kh l 4,2 v 3,1 g/l. Tuy nhin hiu sut ln men dch LM1 ch l 48,5%, thp hn nhiu so vi 2 dch ln men LM2 v LM3 (Bng 3). Nguyn nhn c th l do hm lng ng thp nn hn ch s sinh trng ca cc vi sinh vt ln men.

Bng 3. Hiu sut chuyn ha ng kh trong qu trnh ln men (4 ngy) Tn cng thc ln men LM1 LM2 LM3 Hm lng ng kh (g/l) Trong dch trc khi Trong dch sau ln men (a) khi ln men 2,0 1,03 4,2 1,16 3,1 0,86 Hiu sut chuyn ha ng kh (%) (b/a)*100 48,5 72,4 72,3

Chuyn ha (b) 0,97 3,04 2,24

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3.5. Hm lng etanol trong dch sau ln men Hm lng etanol to thnh trong dch sau ln men c xc nh bng phng php im si v phng php t trng k. Kt qu c trnh by bng 4. Lng etanol trong dch sau ln men vo khong 1,9- 4,2 % v th tch. Nu so vi sn xut etanol t nguyn liu tinh bt c th t ti 6-9,5% v th tch. Nh vy, lng etanol sn xut t nguyn liu thn cy ng l khng cao (ch vo khong gn 50% so vi sn

xut t tinh bt). Tuy nhin kt qu ny cng ch ra tim nng ln cho vic sn xut etanol sinh hc t thn cy ng v y l ngun nguyn liu rt di do v khng nh hng n cung cp lng thc cho con ngi. T cc kt qu trnh by trn v hiu sut ca qu trnh thy phn v qu trnh ln men c th tnh s b nhu cu nguyn liu sn xut etanol sinh hc t thn cy ng vo khong 12 kg nguyn liu th/1lit etanol tinh khit.

Bng 4. Hm lng etanol trong dch sau ln men TT 1 2 3 Tn cng thc LM1 LM2 LM3 Hm lng etanol (%V) Phng php im si 2,1 2,8 2,7

Phng php t trng k 1,7 2,4 2,2

Trung bnh 1,9 2,6 2,5

4. Kt lun Thn cy ng sau thu hoch c thnh phn chnh gm 37,2% cellulose; 24,1% hemicellulose v 17,8% lignin. Qu trnh thy phn thn cy ng bng H2SO4 2 % 1210C trong 60 pht c hm lng ng kh hnh thnh kh cao (4,2 g/l) khi t l nguyn liu/dung dch l 1/10 (w/v). y c xem l iu kin thch hp cho qu trnh thy phn thn cy ng bng axit long. S dng Saccharomyces Cerevisiae ln men c th chuyn ha khong 70% lng ng kh trong dung dch v lng etanol to thnh c nng 2,5% th tch. Da trn cc kt qu nghin cu ny, c th tnh s b sn xut 1 lt etanol sinh hc cn khong 3,24 kg nguyn liu t thn cy ng. Li cm n Cc tc gi by t lng bit n i hc Quc gia H Ni ti tr cho nghin cu ny

trong phm vi ti Nghin cu khoa hc trng im QGT 09-06.

Ti liu tham kho

[1] P.C. Badger, Trends in new crops and new uses, Etanol from cellulose: A general review, 2002, p. 1721. [2] Berg, Jeremy M.; Tymoczko, L. John, Stryer, Lubert, Biotechnology for Fuels and ChemicalsApplied Biochemistry and Biotechnology, Biochemistry, Spinger, 2002. [3] Cheng-shung gong, li-fu chen, Michael C. Flickinger, Ling- Chang Chiang, and George T. Tsao, Applied and environmental microbiology: Production of Etanol from D-Xylose by Using D-Xylose Isomerase and Yeasts, 1981, p. 430436 [4] D. James Kerstetter, Ph.D.John Kim Lyons, Wheat straw for etanol, Production in Washington: A Resource, Technical, and Economic Assessment, 2001, p.18. [5] R. Mandels Andreotii, Rochee, Enzymatic conversion of cellulose matterials, New York, p.79-85.

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The research on hydrolytic ability by dilute acid and initial evaluation of bioethanol production from corn stover
Nguyen Xuan Cu
Faculty of Environmental Sciences, Hanoi University of Science, VNU, 334 Nguyen Trai, Hanoi, Vietnam

This research focus on evaluating the effects of time-consuming and acid concentration on hydrolysis of corn stover and the effectiveness of fermentation process to ethanol production from hydrolyzed solutions. The results shows that corn stover contains about 37.2% of cellulose; 24.1% of hemicellulose and 17.8% of lignin. The suitable conditions for hydrolysis of corn stover is at concentration of H2SO4 2 %, temperature of 1210C and consuming time of 60 minutes. The total reducing sugar concentration in the hydrolyzed solution is about 4.2 g/l in the treatment of corn stover/solution of 1/10 (w/v). The Saccharomyces Cerevisiae can convert about 70% of total reducing sugar to produce ethanol with the concentration of 2.7% in volume. Theoretically, 3.24 kg of dry matter of corn stover can produce 1 litter of ethanol by this processes. Keywords: hydrolysis, dilute acid, bioethanol, corn stover.