Tgp chi Khoa hgc Tnrang Dgi hgc Cdn Tha Phdn A: Khoa hpc Tu-nhien. Cdng nghe vd Mdi nuang 30(2014} 26-29
Tap chl Khoa hgc Tru'dng Dai hoc Can Thd website: sj.ctu.edu.vn
TONG HOfP VA DANH GIA MOT SO DAC TINH HOA - LY CUA D A U DIESEL SINH HOC TlT DAU DU'A SAP Ong Thi MJ Hiin' va Nguyin Van Dat^
' Ldp CNSHTTK39, Viin Nghien cim & Phdt triin Cong nghi Sinh hoc, Tnrdng Dgi hoc Can Tha
^ Khoa Khoa hoc Ty nhien, Trudng Dgi hoc Cdn Tha Thdng tin chung:
Ngdy nhgn: 17/08/2013 Ngdy chdp nhdn. 25/02/2014 TUle:
The synthesis and evaluation of some physicochemical properties of biodiesel fi-om Makapuno Tir khoa:
Ddu diesel sinh hoc, Makapuno. MBDF Keywords:
Biodiesel, Makapuno, MBDF
ABSTRACT
This work considered the use of Makapuno (also known as Mgcapuno) in the Mekong River Delta for the synthesis of renewable and environmentally friendly biodiesel fuel as an alternative to conventional diesel fiiel For this purpose, biodiesel was prepared fi-om Makapuno through transesterification reaction by using 100 g Makapuno oil, 20% methanol (wt % with respect to Makapuno oil), 1% potassium hydroxide catalyst at temperature condition of60°C, reaction time of 2 hours and agitation speed of 500 rpm (revolutions per minute). The experiment was carried out for three times and the average result was evaluated. The highest yield was found to be 86 5%. Moreover, the physicochemical properties of Makapuno oil as well as Makapuno biodiesel (MBDF) were evaluated by determination of important properties such as kinematic viscosity at 40°C, acid value and fatty acid profile. The results showed that MBDF exhibited fuel properties within the limits prescribed by Ihe latest American Standards for Testing Material (ASTM). European standards (EN) and Japanese Industrial Standards. Gas Chromato^aphy Mgss Spectrometry (GC-MS) analytical result showed that methyl laurate (C12:0) and methyl myristrate (C14:0) were the rwo major components of MBDF. These obtained results demonstrated the potential of Makapuno as good feedstock for biodiesel production in the Mekong River Delta.
TOM TAT
Viic su dung dira sdp tgi vitng Bong bdng song Ciru Long (DBSCL) de long hgp ddu diesel sinh hgc, mgt logi nhiin liiu thdn thiin vdi mdi trudng dd duac thuc hiin trong nghiin cuu ndy. De dgi duac muc lieu dg de ra, ddu diesel sinh hgc tir ddu dtrg sdp duac long hop thong qua phdn Ong transester hoa 100 gam ddu dira sdp, 20% methanol (so vdi khoi luang d^), 1% potassium hydroxide (so vdi khoi luong ddu). trong 2 gid thyc hien phdn ung vdi tdc dg khudy Iron 500 rpm tgi nhiit do 60X!. Thi nghiem duac thuc hien ba ldn va lay kit qud trung hinh. Hiiu sudt phdn img transester hoa dgt dugc khd cao khodng 86.5%. Ben cgnh do, nhiing tinh chdt hoa ly cua ddu dieg sdp ding nhu MBDF da duac ddnh gig thong qua viec xdc dinh dg nhdt dgng hgc tgi 40"C vd chi so acid. Hai dgi luong ndy deu dgt duoe yeu cdu eug cdc lieu chudn hien hdnh ASTM. EN. JIS. Kit qud phdn tich GC-MS cho thdy, methyl laurate (C12:0) vd methyl myristrate (C14:0) la hai thdnh phdn chinh cua ddu diesel sinh hgc long hap tir ddu dira sdp. Tit kit qud ndy cho thdy, dira sap tgi vitng DBSCL cUng Id nguon nguyen lieu thich hgp co the xem xet di sdn xudt ddu diesel sinh hoc
26
Tgp chi Khoa lipc Tntang Dgi hgc Cdn Tha 1 B^TVANDE
Viec su dung ngudn nguygn ligu hda thach la nguygn nhdn gdy ra higu iing nhd kinh. bign ddi Wii hdu todn cda Chmh vi vdy viec tim ra n p d n nguyen lieu thdn thign mdi ttudng de thay thg cho ngudn nguyen Ueu ttuyen thdng la dilu hgt siic edn thilt. Biodiesel da dugc chiing minh la mgt ttong nhimg nguon nhien lieu cd thi thay thi nhien lieu hda th?u:h.
Dira s ^ cd xuat xii tir Philippines vd ed ten khoa hgc Makapuno (hay Macapuno), Id mdt dang dgt biln ciia dira thudng Cocos nucifera 0 Viet Nam, dira sap duge ttdng chii ylu tai huygn Cdu Ke, tinh Tra Vinh. Ndng sudt dira sdp t^i huygn Cdu Ke bmh qudn 12-24 ttai/cdy/ndm (Trdn Pham Thanh Giang-2012).
Dira sap ed gid tri dinh dudng cao nen dd cd nhilu edng trinh nghien ciiu sii dung dira sap ldm thue phdm, dugc phdm. my phdm. Tuy nhien, hdu nhu chua cd thdng tin vl n ^ g n ciiu tdng hgp dau diesel sinh hgc tir ddu dira sap Viet Nam.
Bai bdo ndy trinh bdy cdc kit qud vl (1) Tdng hgp MBDF theo phuang phdp khudy tir gia nhiet, su: dyn^ xiie tac base (KOH) (2) Ddnh gia mot sd tinb ehdt hda - ly ciia ddu dira sdp va MBDF.
2 PHU'OfNG PHAP NGHIEN c u t ; 2.1 V^tlieu
Dira sdp nguyen ligu dugc mua t^ huyen Cdu Ke, rinh Trd Vinh.
Hda ehdt ehinh dimg ttong tdng hgp vd phdn tieh bao gdm KOH (Merck), methanol (Merck), hexane (Merck).
2.2 Phinrng phap Dghign ciru 2.2.1 Ly trich ddu dira sdp
Tdn nhuyen phdn sdp dira sau do phoi nang (khoang 2 ngay) cho dgn khi phdn sap dira khd va cd mdu vang uom. Cdn 30 gam cam diia sap sau khi dugc ldm khd dudi dnh sang tg nhign va cho vdo mdt tui vdi hinh tru. sau do ddt vdo ttong thdn hg thdng ly trich Soxhiet voi dung mdi hexane. Sau khi ly trich. hexane dugc tdeh ra khdi ddu dira sdp bdng he thdng cd quay. Ham lugng ddu trong com dira sap la 60%.
2.2.2 Phuong phdp tong hgp MBDF Vi chi sd acid cua ddu dira sdp kha nhd (3.5 mgKOH/g) ngn biodiesel tir ddu dira sap dugc tdng hgp bdng phuong phap khudy tu ^ a nhiet sir dung xiie tae base (KOH). qua mgt giai doan nhu
Kliga hoc Tir nhien. Cong nghe va Mdi truang. 30 (2014): 26-29 phuong phap tdng hgp biodirael tir ma ca Tra, ca Basa (Nguyen Van Dat, 2009). Qud ttinh tdng hgp dugc tiln hanh nhu sau: cdn lugng methanol cdn thilt cho vao binh tam gidc 250 mL rdi cho vao dd xiic tdc base (KOH) de tao dung dich KOH trong methanol, ddu dugc cdn vd cho vdo binh phdn iing, sau dd, ddt len mdy khuay tu, dieu chinh nhiet d?
cdn thilt. Rdt tix tu dung djch KOH ttoi^ methanol vao binh phdn ung tten, khudy hdn hgp phdn ling va theo doi qud trinh phan iing. Sau khi phdn iing xong, hdn hgp phan iing duge de dn dinh ttong phlu chilt vd tdeh ldp. Sdn pham biodiesel dugc tinh chl bdng each riia nhilu ldn vdi nude am nhdm loai bd xdc tdc, methanol vd cu6i ciing Idm khan bdng NaiSO^.
Dua vdo kit qud phdn tich thdnh phdn tinh dugc M MBDF = r ^ ' " ' ttong dd, M,: khoi lugng phdn tii methyl ester; m,: phdn tram khdi lugng methyl ester. Tir dd. tinh dugc higu sudt tong hgp biodiesel. Hieu suit phdn iing (ki higu HMBDF) dugc tinh theo edng thiic sau: ff^j,^ = — ^ x 100. vdi
mn = M MBDF x3«dii-
2.2.3 Xdc dinh do nhdt dgng hoc tgi 40V va chi so acid
Do nhdt ddng hge (mm^/s) duge xdc dinh o 40°C, bdng each do thdi gian dg mdt thg tich chat ldng xac dinh chdy qua mdt mao qudn thiiy tinh dudi tde dung ciia ttong luc. Trong nghign cuu nay, thilt bi do dd nhdt Viscosity Measuring unit ViscoClock (Schott Instrument) cd chl do tg d§ng hien thi thdi gian dugc sir dung dg xdc djnh dp nhdt ddng hgc eiia ddu dira sap va MBDF. Dd nhdt dgng hge Id ket qud tinh dugc tir thdi gian chdy va hdng sd tuong iing cua nhdt ke Ostwald.
Chi sd acid ciia ddu nguygn lieu cdng nhu biodiesel dugc xac dinh bang phuong phap chudn dg the ti'ch.
2.2.4 Phdn tich thdnh phAi acid beo cua MBDF Sdn phdm MBDF dugc phdn tieh thanh phdn hda hgc tai phdng thi nghigm Hda Sinh thugc B§
mdn Hda hgc, Khoa Khoa hge Tu nhign - Trudng Dai hgc Cdn Tha bdng sdc ky khi ghep khdi pho GC-MS (Themio scientific) vdi cdt TG-SQC GC column 15mx0.25mmx0.25um. Khi mang la He vdi tdc do ddng 1.2 mL/phiit. Chuang ttinh nhifit do dugc Sli dung nhu sau: nhiet do ddu 60°C, toe
Tgp chi Khoa hgc Tnrang Dgi hoc Cdn Tha Phdn .A: Khoa hgc Ty nhien. Cong nghi vd Moi Int&ng- 30 (2014) - 26-29 dg gia nhigt lO^C/phiit din 260°C vd giii tai nhigt
do dd 1 phiit.
3 KET QUA VA THAO LU^^N 3.1 Tong hgp MBDF
Do ddu diia sdp cd ehi sd acid thdp (AV = 3.5 mg KOH/g) ngn qua trmh tdng hgp MBDF chi tiln hanh mdt giai doan khdng cdn phdi qua giai doan xii ly ldm hg ehi sd acid. Phdn iing tdng hgp MBDF dugc nghien cihi vdi cdc dilu kien thi nghiem nhu sau: nhigt do (60°C), tdc do khudy (500 vdng/phut), thdi gian (2 gid), khdi lugng methanol (20% khdi lucmg ddu), khdi lugng KOH (1% khdi lugng ddu). Kit qud nghien ciiu eho thdy higu sudt tdng hgp MBDF dat 86.5%.
3.2 Nhiing tinh ch^t hda Iy cua dau dira sdp va MBDF
Chi sd acid va dg nhdt dgng hge d 4 0 ^ ciia dau dira sdp dugc ttinh bdy ttong Bdng 1.
Bang 1: Tinh chat hda ly cua d^u dira sap Tinb chat hda D^u D^u diia Dau _l£ dira sap thufrng diesel
Chi sd acid, mg „ 2) KOH/g ^-^^ '^"•""
Do nhdt ddng
hge d 40''C, 24.05^> 29.463' 3.00 mm-^/s
" Thuc nghiem -' Bui Thi Buu Hue el al. 2010 * Nguyen Van Dat. 2010
Ddu dira : Coconut oil Ddu dira sdp : Makapuno oil
Do nhdt ddng hgc phu thudc vao nhilu ylu td ttong dd thdnh phdn hda hgc, thdi gian vd each bdo qudn Id dnh hudng dang ke. Tir kit qua ttgn eho thay, do nhdt ddng hgc d 40''C cua ddu dua sap nhd hon mgt it so vdi ddu dira. Su khde nhau ndy cd thg do (1) su khde nhau vg thdnli phdn hda hoc - thdnh phdn hda hgc ciia ddu chiia cdng nhidu ttiester ciia cac acid beo no thi do nhdt cang eao. (2) thdi gian va each bdo qudn ddu - thdi gian bdo qudn edng ldu cung nhu ddu cang tigp xiic nhigu vdi nhiing tde nhdn Idm tdng qua ttinh oxi hda (tilp xiic vdi khong khi, bdo qudn d nhiet dg eao,...) thj se lam tdng dg nhdt bdi vi khi ddu bi oxi hoa se xdy ra phdn ling kit hgp giira cdc gde tu do tao thanh cdc sdn phdm poluner hda lam tdng dg nhdt. Dg nhdt dgng hgc d 40°C cua ddu dira sap hay ddu dira tiiudng diu cao ban diesel khodng 8-10 ldn so vdi ddu diesel nen khdng thi diing chiing d dgng nguygn chdt cho dOng ca diesel md phdi ldm gidm dg nhdt ciia chiing trudc khi dua vdo ddng co lam nhien ligu. Trong nghien ciiu nay, qud ttinh
transester hda xiic tdc base dugc sir dung de ldm gidm dd nhdt ciia dau dira sap. Ngodi ra, ehi sd acid etia ddu diia sap kha nhd ngn chi edn tien hanh phdn iing ttansester hda qua mgt giai doan, nghia Id khdng cdn qua giai dogn Idm ha chi sd acid (ddu dira thudng ttong nghign cihi eiia Bui Thi Buu Hue vd ctv cd ehi sd acid rat cao digu nay cd the do thdi gian tdn trii ddu qua ldu).
Bang 2: Tinh chdt hda 1;^ cua MBDF
Tinh chit hda ly MBDF" CME^' Chi sd acid, mg KOH/g 0.31 Do nhdt ddng hgc d
40°C, mm-/s 4.19
0.29 3.12 '> Thuc nghiem. -> Nguyen Van Dat, 2010 Chisdacid. mgKOH/g . ASTM(0.5max.). EN(0.5 max.), JIS (0.5 max)
Bo nhat dgng hgc a 40'C. mm-Zs : ASTM (1.9-5.0). ES (3.5-5.0). JIS (3 5-5.0)
CME : Coconul Methyl Esters (dau diesel sinh hpc long hgp tir dau dira ihirdng)
ASTM : American Society for Testing and Materials EN . European Commilleefor Standardization JIS . Japanese Industrial Standard
Tix kgt qud d Bdng 2 cho thdy, chi sd acid va dg nhdt dgng hgc d 40''C ciia MBDF dgu ndm ttong gidi han ciia cac tigu chudn hien hanh ve kilm sodt chdt lugng ciia ddu diesel sinh hoc va gid ttj cua nhung dai lugng nay eiing gdn vdi gid trj ciia biodiesel tir ddu diia thudng.
3.3 Thanh phdn acid beo ciia MBDF Kit qud phdn tich GC-MS eho thdy thdnh phdn acid beo cua MBDF ehii ylu tir C8 din Cl 8. Thdnh phdn C12:0 chilm nhilu nhdt (34.95%) tilp din Id C14:0 (22.52%). Tdng ham lugng cua cdc ester no chilm 90.96%, ttong khi dd, ham lugng ester eiia acid beo ehua no C18:l chi chiem mgt phdn nhd 9.04%. So sdnh vdi kit qua nghien ciiu ciia Bui Thi Buu Hue (2010) thi thdy rdng ham lugng cdc acid beo ciia dira sap gdn gidng vdi dira thudng ma tdc gid da phdn tieh (C12:0) chilm nhigu nhdt (38.61%) tilp din Id C14:0 (19.81%). Tdng ham iugng ciia cdc ester no ehiem 85.68% va C18:I chi chilm mdt phdn nhd (10.45%).
Do ham lugng methyl ester eua acid beo no chilm ham lugng Idn ndn MBDF se cd nhimg thudn Igi vd bdt lgi nhdt dinh. Thudn lgi- MBDF se cd do ben oxi hda eao, ddy Id mdt tinh chat rat quan ttgng ddi vdi dgng ca diesel, dde bigt Id vi?c sir dimg loai nhien lieu nay d nh&ng vung cd nhigt do tnmg binh eao nhu d nude ta. Bdt lai - MBDF se cd nhigt dp ddng dac cao dilu ndy se gdy nhilu bdt lgi cho vigc sir dung loai nhign lieu nay d cac vimg cd khi hdu lanh, nhigt do ttung binh thdp.
Tap chi Khoa hpc Truang Dgi hgc Can Tha Phdn A: Khoa hgc Ty nhien. Cdng ngh^ va Moi tnidng. 30 (2014): 26-29
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vd CME, %
"'SoC:S6c=C(Cx:ii) C8:0
(b)C10:0 (c)C12:0 (d)C!4:0 (e)C16:0 (f)C18:0 (g) C20:0 (h) C22:0 (i) C24:0
""SCacid Mo hoa) (k)C18:l
""'Z(acid chiia mpt Hen kit C=C)
(1)C18:2
"^ 'S(acid chiia nhieu lien kit C=C)
Thanh ph MBDF"
6.13 9.14 34.95 22.52 14.11 4.11
90.96 9.04 9.04
In (%) CME'>
5.62 5.19 38.61 19.81 12.65 3.54 0.13 0.04 0.09 85.68 10.45 10.45 3.20 3.20
" Thyc nghiem -' Bui Thi Buu Hue el a!. 2010
"' C80 methyl capry-late. CIO 0 methyl capraie. C12.0 methyl laurate. C 14:0 methyl myrisyaie. CI6: 0 meylhylpalmitale. C18:0 methyl stearaie. C18I methyl oleaie. C18.2 methyl Unoleale. C22:0
melhyldocosanoate. C24.0 mellrylleyacosanoale
"''^acidbao hda) = C8.Q - CIO.O- C12:0 + C14 0
* CI6 0 - C18:0 + C20:0 - C22.0 - C24 0
"'" £(acid chita mpt lien kil C^C) = C18:l
"^' l(acid chua nhiiu lien kh C^C) ^CI8 2 4 KET LUAN
Dd ly ttich duge ddu diia sap tir com dira sdp bdng phuang phdp chilt Soxhiet vdi hdm lugng
ddu khodng 60% khdi lugng com diia s ^ . Ben canh dd, nghien cuu cung da tdng hgp dugc MBDF vdi hieu suat 86.5% bdng phuang phdp khuay t&
gia nhiet. Ket qud phdn tich thdnh phan acid biSo cho thdy nhimg thdnh phdn acid beo ed trong MBDF tuong tu vdi thdnh phdn acid beo cua CME.
TAX LIEU THAM KHAO 1. Bui Thi Buu Hue, Nguyen Van Dat,
Toshihiro Hirotsu and Shinichi Goto, 2011.
Oxidation stability of Coconut based biodiesel. Joumal of Applied Chemistiy, Viemam, ISSN 0866-7004, 4 (8).
2. Nguyen Van Dat, 2009. A Stiidy towards the Effect of Antioxidants on Vietnamese Catfish Fat Biodiesel. Collected Papers of Invited Research, Asia Biomass Ener©- Researchers Program 2009, New Energy Foundation, Japan.
3. NguyenVanDat, 2010. Potential of Utilizing Some Biomass Sources as a Feedstock for Biodiesel and Oxidation I Stability of Biodiesel-Diesel Blends.
Collected Papers of Invited Research, Asia Biomass Energy Researchers Program 2010, New Energy Foundation, Japan. i 4. Trdn Ph^m Thanh Giang, 2012. Danh gift
chdt lugng ttdi dira sdp (CocoSjp.) tten dia | bdn huygn Cdu Ke, tinh Trd Vinh. Tdp san Khoa hgc & Gido due, sd 2, ttang 58.
