NGHIEN CUU PHAN UNG TONG HOP BIODIESEL BANG PHUONG PHAP SI£U TOI HAN VA THU GLYXERINE DO TINH KHIET CAO SUMMARY VO THI THU HAt LE DANG KHOA?, NGUYEN DINH LAM? 1 Vign Hoa hoe Cong nghigp ?Khoa Héa hoc - Dai hoc Bach Khoa - Dai hoc Ba Ndng Biodiesel have been investigated and used as an alternative fuel for traditional diesel. There were some initial researches of biodiesel synthesis in Vietnam. This article presents the results of our inves- tigation on the new method, transesterification in supercritical metanol. Keywords: Supercritical metanol, Biodiesel, Transesterification, Alkyl esters. 1. DAT VAN DE Biodiesel 1a foai nhién ligu thay thé diesel c6 nguin g6c sinh hoc. Biodiesel duge sin xuft nh’ qué trinh este hod chéo cla déu thye vat hog md dong vat véi rugu. Qué trinh sén xudt biodiesel truyén théng la qué trinh sit dung xtc téc bazo-déng thé [1-5]. Tuy nhién, phan img sis dyng xic t4c dng thé ddi hdi nguyén ligu phdi cé ham lugng nude va axit béo ty do thiip, déng thai, qué trinh sén xugt thudng t6n nhigu thoi gian va ning lugng do déu thyc vat khéng tan trong rugu va sin phdm cia qué trinh cin phai lim sach kndi cdc tap chét. Vi ty do dé, gid thanh cia biodiesel thutng cao hon gid thanh nhién ligu dieset [6]. Ngoai ra, sin phdm phy c6 gié tri cao 1& glyxerin khéng sach do c6 in nhigu tap chat tir qua trinh téng hop. Qué trinh sin xuét biodiesel trong diéu kién siéu toi han cia metanol khde phys dupe nhimg nhugo diém ké trén cla qui trinh sin xudt truyén théng [7]. Trong diéu kign thutng, rugu khong tan trong d&u thye vat. Tuy nihign, & trang thai siéu t6i han, tuy thud vao dp suft va nhigt d® ma lién két hydro lién phan tit gia cdc phan ‘tit rugu cling nhu d6 phan cue cia ching bj yéu di cho phép déu thye vat hoa tan mgt phén hoc hoan toan vao methanol. Lic nay, metanol tré thanh mgt monome ty do true tigp tac dung lén nguyén tir cacbon cia nhém cacbony! cia triglyxerit dé thyc hign phan img este hod chéo nén thai gian phan ing rét ngdn (8). Nubc va axit béo ty do la céc tée nhan 06 hai trong phuong phép xic ‘tac truyén théng nhung trong phuong phdp sidu téi han ching [a cdc téc nhan nh huding tich cyc dén thoi gian phan cing va higu suit biodiesel. Phuong phdp mdi nay ccho higu sugt biodiesel cao hon déng thai qué trinh xis i san phém don gin hon va dc bigt glyxerin thu duge 66 dO tinh khiét cao hon rét nhiéu so voi phuong phdp truyén théng. Nhi 46, biodiesel thu duge ti phuong phap nay 06 gié thanh ré hon so v6i phuong phdp truyén thing [9]. Trong bai béo nay, ching t6i tién hanh nghién cau phan img este hod chéo ddu thyc vat trong mdi trudng siéu tdi han, khao sét céc yéu tf anh hung dén qué trinh va so sénh qué trinh nay véi qué trinh este hod chéo kin dign, sit dung xic téc déng thé KOH. I, THYC NGHIEM Noguyén figu ddu dita tinh luyén duge cung cp béi Céng ty déu Tudng An. Metanol va cdc hod chat khdc duge cung c&p bai Sigma Aldrich. San padm phan ting duoc phan tich trén s&e ki long higu n&ng cao HPLC MERCK HITACHI 07000 va duge danh gid 49 nhét theo phucng ph4p ASTM 0445-04, Qué trinh este hod chéo si dung xiic tie d6ng thé KOH dugc tign hanh nhu da mé ta trong 40 tai ligu [10]. Qué trinh este ‘hod cho trong méi trudng siéu téi han duge tién hanh trong thiét bj phan dng chiu 4p & 200 bars va 280°C (cdc gid tri t6i han cla metanol !4 Pc = 80,9 bars, Tc = 239,40C). Sau khi két thc phan tng, hdn hop san phdm trong thiét bj phan Ung duge lam nguoi aén nhigt dQ thuéng r6i dua vao ph&u chiét dé tach hai pha biodiesel va glyxerin. 54868 Héa hoe & Ung dyng -2&8(68)KET QuA VA THAO LUAN rong qué trinh este hod chéo trong mdi trutng si8u 16 han, dé xéc inh chinh xée ung chét phan tng trong thigt bi phan tng dé bao dim cdc gia tri nhigt dp va dp sult cin hai of tr tren (diéu Kién dng tich), ching toi 6a sit ding m6 hinh nigt dng SRK 8 tinh todn, Bang 1 dia ra thanh phan hén hgp phan dng ti cdc ty @ MeOH/ddu kde nau vét thé teh thigt bi phan dng 1a 143,5 m3. Bang 1: Thanh phin hén hgp phan thg tai cdc t7 1e MeOH/déu khée nhau 1. Anh huéng cia ty 16 MeOH/ddu Ching t6i da tién hanh Khao sat Anh hung cla ty lg MeOH/du #8n higu suit metyl este va d6 nhét cia san phd trong'diéu kign c6 mat 5% trong lugng nude va thdi gian phn dng la 3h. Két qua dupe trinh bay trong fink 7. Trong pham vi ty gié tri 10/1 dén 25/1, ty 18 MeOH/dau anh hudng manh dén 46 chuyén hoa cling nhu 46 nhét cla san phdm. Vugt qua gid tr 25/1 Anh hung cia ty 1 MeOH/dau tré nén khéng ding é. Do ty 1@ MeOH/déu quyét dinh dén cOng sudt cla thiét bj déng théi, qué trinh thyc nghiém da chimg 1 ring khi ty 1@ nay tang len, qué trinh phan tach pha tré nén kno khan hon nén ching t6i chon ty 1 toi wu 1a 25/1. 2. Anh huéng ciia ham lugng nue Qué trinh khdo sét Anh huting ciia ham luong nude duge tign hanh 8 ty 18 MeOH/déu = 15/t v6i thdi gian phan ting 1a 3 gid. Cac két qui nghién cdu duge trinh bay trén hlnh 2. Sy c6 mat ciia nudc trong nguyén ligu 3 tang cudng phan ting thiy phan céc triglyxerit tao thanh cdc axit béo ma cde axit béo nay sau dé igi tham gia vao phan img este hod tao ra cc metyl este tusng ing. Biéu nay lam ting higu suét cla qua trinh va gidm d6 nhét cla sdn phdm biodiesel thu duge. 3. Anh huéng cia thi gian phan img Qué trinh khdo sat 2nh hudng cia thai gian phan Ging lén higu sudt metyl este va dO nhét cia sin phdm duge thyc hién trong digu kign cé mat 5% trong lugng nubc, ty I@ MeOH/ddu bing 25/1. Két qua thu duge cia qué trinh nay duge trinh bay 6 Ainh 3. Sau 1 gid déu tién, phan dng x4y ra khOng ding ké, céc pic chinh Sé 8(68) 5007 ~ Hoa hoc & Ung dung trong nguyén ligu van cdn xuét hign trén sfc ky d6 v6i cutng do khé lon. Két qua thu duge ti hinh 3 cho thay ‘8 d9 chuyén h6a cdc triglyxerit din ra chi: yéu trong 2 gid déu tien va do d6 46 nhét cia sin phém gidm ahanh. Day chil yBu 1a cdc triglyxerit c6 sf eacbon thép, chigm da s6 trong nguyén ligu, c6 kha nang phan ing tt. Sau 2 gid phn ing, higu sudt phan dng thay déi khong dang 46 trong khi 46 nhét sin phém van con gidm khé manh ching 18 rng cdc triglyxerit c6 s6 nguyén tir cacbon cao hon cdi c6 théi gian dai hon dé 06 thé chuyén hoa hét vé céc dang metyl este tuong ing. (by 2 2 a Hoku alt 0) Hinh 1: (a): Sic ky d6 cia déu dia va chc miu metyl este thu duge (b): Sy phy thuge cia higu sudt metyl este va dé nhét vao ty 18 mol MeOH/ddu 4. So sanh hai phuong phép san xust biodiesel Két qua nghién céu cho thdy cd hai phuong phap iéu ch€ biodiesel déu cho 46 chuyén hod hoan toan, Tuy nhién, phuong phap truyén théng tgo ra biodiesel 66 dé nhét bs hon so vi phuong phdp siéu toi han (2,62 cSt so véi 3,1 cSt) - khdng trinh bay két qua & Gy. Hién tugng nay due gidi thich ld do kh& nang tly rita cao cla KOH, pha glyxerine thd cla phuong phép xe te ddng thé hod tan KOH do d6 sé hap thy toan bO céc tap chat gay mau vén c6 trong lugng phan ti cao, d6 nhét cao cd trong hin hgp sn phdm. Bigu nay cing gidi thich sy khéc bigt vé mau sic cia clyxerin ‘thu duc tix hai phudng phdp: trong suét déi véi phuong TE MeOH: Die 41phén sidu t6i han metanol va ving slim doi voi phuong Pheip xic tac déng thé. RO ring, glyxerin thu dupe ti phuong phdp siéu t6i han metanol c6 chat lugng t6t hon so v6i glyxerin trong phyong phép xiic tac kiém. @) 3 oe hens © yates 0189 Sac ky dé ciia dau dita va céc mau biodiesel eo0 70 60 9500 co apo 9200 10%H 20 (b): Sy phy thudc cia higu suat va d9 nhot vao cae ty Ie khdi lugng Hy0/MeOH ace 0 o 99.00 0 96.00 95,00 9400 93.00 92,90 ° 3 10 %9H20 Bieri €9 © Daaluesaa%c uso : (a): Sic ky dé ciia déu dita va cc mau metyl este thu duye (b): Sy thay déi cia hidu sudt metyl este va d@ nhot sdn phdm theo thai gian phan tng Iv. KET LUAN x Cae nghién cit trén day cho phép hiéu duyc ban chat cia phan tng este hod chéo céc triglyxerit 4 diéu kign siéu téi han metanol. 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