Hoi nghi Khoa hoc ky'''' niim 35 ndm I''''ien Khoa hoc vd Cong nghi Viet Nam Hd Noi 10 2010 NHLTNG KET QUA NGHIEN ClTU THlTC NGHIEM CONG NGHE KHONG BA THAI TRONG SAN XUAT BIODIESEL Tir D A U THl/C V A T VIE[.]
Hoi nghi Khoa hoc ky' niim 35 ndm I'ien Khoa hoc vd Cong nghi Viet Nam - Hd Noi 10 2010 NHLTNG KET QUA NGHIEN ClTU THlTC NGHIEM CONG NGHE KHONG BA THAI TRONG SAN XUAT BIODIESEL Tir D A U THl/C V A T VIET NAM • • • Ho Son Lam Viin Khoa hgc vdt lieu itng dung (lAMS) Sabll, Mgc Dinh CM, Qudn I Thdnh phd Hd Chi Minh sanlamho05(d),vahoo com Tom tat: Bdi viit giai thiiu sa luge vi cdng nghi khdng bd thdi sdn xudt biodiesel tit ddu thue vdt Viet nam Ndi dung gdm nhirng kit qud thue nghiem thu dugc qud trinh nghiin citu sdn xudt biodiesel a qui md phdng thi nghiim vd qui md pilot Nhung kit qud vi vdn ep bin nude di tir vd hgt ddu ihirc vdt, cdc chdt ed hogt linh sinh hgc trich ly tir hgt diing ldm thude trit sdu sinh hgc, thuc dn gia siic vd chdt tdng trgng tu bd hgt Trong qud trinh sdn xudt biodiesel, ngodi sdn phdm chinh Id B-IOO dgt lieu chudn, cdn cd Glyxerin dugc nghiin cuu di sdn xudt polyme ttr phdn hiiy sinh hgc Abstract: This pgper describes recent develgpment on investigation from using Vietnamese Vegetable Seed oil as bio-diesel In the Process of Biodiesel producdon, non-waste technological was study and development The result show thai, some byproduct war beginning to take shape and has good chance to use like composite material from husk of seed; bioaclive substance like saponyl agent from process extraction bad of seed lo use as insecticide; animal food from bait of seed and glycerin as raw material to synthesis ofbiopolymer I.Dat van de: a/Sff luge Ijch su phdt triin biodiesel: Nghien ciin sir dyng diu thuc vat lam nhien lieu da dugc Rudolf Diesel tiln hanh each day tren 100 nam Nam 1895, dng da sir dyng diu Lac cho viec thu nghiem cac ddng co dit ciia minh, vin dugc su dyng loai diu cd phan doan nang tir dau md Cdng trinh dugc cdng bl nam 1900 tai Paris Exposition Nam 1916, ddng ca diesel dau tien dugc xuit sang Argentina, Gutien-ez, da dimg diu Thiu diu dl thir nghiem lai nbirng y tudng ciia R.Diesel, nhung nhirng khd khan vl ty trong, nhdt qua trinh phun nhien lieu da lam cho nhung nghien cim khdng phat triln duac Diu Cp Cling dugc sir dyng cho myc dich nhien lieu thay diu diesel tir nam 1920 Mdt nhirng cdng b6 sdm nhat ve viec img dyng ester ciia diu Cp dugc cdng b l vao nam 1942 Din 1944, cung mdt ngudi Argentina khac, Martinez de Vedia da tiln hanh lin diu tien viec pha trdn (bleding) dau diesel vdi dau thyc vat vdi ham lugng diu thyc vat tir 30-70% Tac gia da su dung nhieu loai dau khac nhu Bdng, Hudng duong Lac ' va chay thir ddng ca 420 gid Cac thdng sd va ket qua dugc ghi nhan, cho thiy cdn nhilu vin dl chua thi giai quyet tren dpng co dd Tir nam 1920 den nam 1947 ngudi ta ghi nhan din 99 cdng trinh sir dung dau thyc vat lam nhien lieu diesel Han nira, vao thdi dilm dd, diu md dang kha dii dao dau thuc vat chua du cung cip cho viec san xuit diu an, cac nghien cim cua Rudolf Diesel bj roi vao quen lang Cac cupc khung hoang nhien lieu xiy nhirng nam 70-80 da thiic day cac nha khoa hpc trd lai vdi y tudng ban diu ciia Rudolf Diesel va cac nha khoa hpc tien bdi, ket qua la mpt loat cac nghien cim vl sir dung diu thuc vat duac tiln hanh I hang gieng nam 1991, chuang trinh nghien cim sir dyng Biodiesel ciia CHLB Dire bit diu 75 Tieu ban: Khoa hoc Vdt liiu ISBN: 978-604-913-011-3 chinh thirc boat dpng, the ma 10 nam sau san lugng Biodiesel ciia dire da dat tren trieu tin/nam Chi thdi gian tuong ddi ngan hang loat cac nha ma}' san xuat nliien lipu biodiesel d qui md cdng nghiep vdi cdng suat vai tram ngan tan/nam da ddi, tap trung nhieu nhit d Dire, Italia, Ao, Phap, Thyy Dien, Tay Ban Nha Tdng cdng suit hien cua chau au la trieu tin Trong tai chau A, viec nghien cim va img dyng BDF cung phat trien manh, tieu bilu nhu: An Dp, Trung Qu6c, Nhat Ban, H6ng Kong Ngoai ra, cac nude Chau Phi va Chau Uc ciing dang budc diu trien khai nghien cim nhieu ve BDF Trong thyc te, tren thi gidi, nude sir dyng rdng rai BDF nhat hien la Hoa Ky vdi nliieu chinh sach un dai b/Tdc dung cua Biodiesel doi v&i nhu cdu ndng luffng, bdo ve moi trudng vd xda ddi gidm ngheo: Sir dyng nhien lieu cd nguIn glc sinh hpc khdng chi cd tac dyng ve mat kinh te va nang lugng, ma cdn cd lgi vl mdi trudng Cac nha Idioa hpc da chi rang neu sir dyng 1kg biodiesel se giam 3kg CO2 thai, so vdi diesel diu md Cac nghien cim ciia chiing tdi cho thiy ' niu pha 5-15% BIO-/IAMS (mdu chimg ldi sdn xudt) vdi diesel, hdm litgn^ hydrocarbon thdi cita mdy phdt diin gidm, vd gidm han V: niu pha 10% Cdc chdt gdy ung thu nhu NO, NOx gidm theo thdi gian ldm viic cita ddng ca, cdng Idu cdng gidm.[\'\ C6 thi neu nhiing tac dyng quan trpng cua viec sir dyng biodiesel: l.Gdp phan giai quyet nguyen lieu cho viec san sinh nang lupng:van de da dugc nhilu nude tren the gidi img dyng Chi rieng khdi ASIAN, cac mrdc nhu Thailand, Philippines, Indonexia, Malaixia deu cd chuong trinh nghien ciin va sir dung dau thyc vat lam nhien lieu Biodiesel Chau Au da pha 5% Biodiesel vao diesel dau md ke tir 1/1/2005 va tdng cdng suat san xuat Biodiesel hien dat khdang trieu tan/nam 2.Bao ve moi trudng: sir dyng dau thyc vat lam nhien lieu gdp phan bao ve mdi tmdng tren hai khia canh: -i-Nbiing cay cho dau cd the la than thao, cd the la than gd dugc trdng d nhieu dja hinh khac nhau, khdng ken chpn, cd the phii xanh dat trdng ddi trpc, chdng xdi mdn va bac mau dat, tao mdt lugng oxy Idn va hap thy mpt lugng CO2 dang ke, lam sach bau quyen Trong chu ky sdng ciia minh, thdi gian cay xanh hap thy CO2 va giai ph6ng Oxy nhieu hon thdi gian san sinh CO2 -i-Nhien lieu Biodiesel tao lugng thai cd it chat dpc hai hon nhien lieu diesel dau md: sir dung 1kg biodiesel cd the giam kg CO2 so vdi diesel dau md cac chat ddc hai khac cung giam 3.Biodiesel ( Dau thyc vat) gan lien vdi dai bp phan dan cu va dien tich dat viing sau , viing xa Vi vay, phat trien va ii'ng dyng biodiesel la ca hdi cho ngudi dan d nhirng viing cd the ty minh xda ddi, giam ngheo, cd the lam giau tren chinh manh dat can edi ciia minh c/Tmh hinh nghien cuu & Viet nam: Ci Viet Nam vdng 20 nam trd lai day da bat dau cd nhirng cdng trinh nghien cim ve biodiesel, nhien cdn mpt sl han cbl ket qua nghien cim ciing nhu chua cd nhiing chinh sach khuyin khich tir phia Nha nude nen biodiesel chua dugc img dyng rdng rai Nhin chung, cac cdng trinh tap trung chu ylu vao nghien cim ca ban, ca che phan ung, xiic tac, cracking hai nude Viec dilu ehl va thir nghiem BDF tir dau thyc vat tai nude ta bit diu dugc quan tam tir nhiing nam 1980 Trong khoang nam gan day cac nghien cim ve dieu cbl BDF dugc chu y nhilu, chii ylu theo phuang phap este hda vdi ngudn nguyen lieu tir diu dau nanh, diu dira, dau an phi thai Mpt s6 cong trinh nghien ciin phan img transeste hoa bing sdng sieu am [2,3] d/Xu the thai dgi: Sir dyng BDF gdp phin giai quyet an ninh nang lugng, thay thi ngudn nhien lieu hda thach dang can dan, gdp phan da dang hda va tao ngudn nang lugng sach Trong tuong lai, cac ngudn nang lugng tmyln thdng can dan thi kha nang sir dyng ngudn nhien lieu mdi se cd nhilu triln vpng ban Do dd, dang nhien lieu mdi dugc tao tir 76 Hoi nghi Khoa hoc ky niim 35 ndm Vien Khoa hoc vd Cong nghi Viet Nam - Hd Not 10/2010 dau thyc vat cd the se la tiln dl cho viec djnh hudng phat trien cay thyc vat cd dau \ a md rdng nganh cdng-ndng nghiep san xuit va tinh che dau thuc vat Iam nhien lieu d qui md Idn Tuy nhiin, niu chi sdn xudt biodiesel thi gid thdnh sdn phdm se dnh hudng din khdng nhitngkhd ndng ung dung md cdn dnh hudng din ngudi trdng nguyin liiii-ld nhirng viing kinh li khd khdn, thu nhdp thdp Do dd, cdn thiit phdi cd mdt cdng nghi hodn chinh, tgo rg ciing liic nhiiu sdn phdm khdc nhgu trin mdt dan vi nguyen lieu, de hg gid thdnh sdn phdm ciing nhu dn dinh gid thu mua nguyin lieu, bdg ddm ngudi trdng cd thi song dugc vdi sdn phdm ldm rg ciig minh Dd chinh Id cdng nghi khdng bd thdi sdn xudt biodiesel tir ddu thuc vgt ciig Viin Khoa hgc Vdt lieu lfng ditng H.Nhiing ket qua nghien ciru thuc nghiem De phyc vy cho rnyc dich san xuit nhien lieu sinh hpc, chiing t6i da tiln hanh nghien cim d6ng bp nhieu van de lien quan nhu sau: - Nghien cuu t6ng the cac loai hat cd diu beo dang cd tai Viet nam - Nghien ciin cac san pham phy dong hanh vdi qua trinh san xuit biodiesel - San xuat thir nghiem B-lOO dat tieu chuin va thir nghiem tren dpng ca - Nghien ciin sy anh hudng ciia cac mach hydroeacbon B-lOO len phan thai ILL Cac loai dau beo o Viet nam co thi lam nguyen lieu cho Biodiesel Viet nam, nam 1924 CREVOST va LEMARIE da thing ke dugc 70 loai cay cd diu Nam 1970, PHAN KE LQC da suu tim dugc 474 loai thupc 330 chi ciia 96 hp thyc vat Din nhihig nam gan day V.N.TU va cac ddng nghiep d Vien khoa hpc Viet nam da thing ke dugc tren 564 loai ciia hon 100 hp cay cd diu Dac dilm vj tri dja ly da tao cho nude ta dilu kien trdng va thich nghi nhilu loai cay cd diu ban dja cung nhu nhap ngoai, lam cho danh sach cay cd_dau cang dai them va phong phii ca vl s l lugng va chit lugng Nhirng cay cd diu phi bien d nude ta dugc cac nha khoa hpc ciia Vien khoa hpc Viet nam xip 51 loai 19 hp [4,5,6,7] day chiing tdi chi gidi thieu mpt sl diu cd thi sir dyng lam nguyen lieu cho san xuat Biodiesel: Bdng I B-IOO ciia mdt sd logi ddu beo Viet ngm; Diesel dau mo Cetan n-parafin 77,02 n-CetanCioH34 100 Napten 48,85 C10H20 Diu bdng vai Ninh thuan (18% C12-C16 ; 80% 47 C18-C20) Diu hat Sd Ha Giang (35%C8-C16 ; 64% C18- 49 C20) Diu hat Cao su Binh phudc (10% C14-C16, 88% 47 C18-C20) 46 Diu hat Cai Ha giang (57% C18 va 40% C20) Diu gdn Tiln giang (16% C12-C16, 83% C18) MetyldipropylDecalylmetan Cetan Diu t h y c vat Viet nam n-DecanCioH22 Decalen B-lOO 20,98 48 Diu dira Tiln giang (20% C9-C10, 50% C 16,25% CI8) 49 77 ISBN: 978-604-913-01 !-3 Tiiu ban: Khoa hoc Vdt lieu CioHn-CgHn Hydrocarbon thffm: Metylnaptalen C10H7CH3 Dau Cam gao Tien giang (25% C8-C16, 70%> C18) Diu lac ( dau phong) Ddng nai (10%o C12-C16 85%C18) Dau diesel thuffng pham 47 Diu dau nanh DlngNai(12% C14-C16 85%C18) Diu Cp niii Ha giang (Cui qua)(37% C6-C16-60% 47 C18) Octylnaphtalen CioHyCgHiv 49 18,12 52-55 Diu cp niii Ha giang( 13%C18) nhan)(85% C6-C16, 49 49 Diu cp Malaixia nhap khiu (35%) CI2-C16, 63% 49 C18) Dau thirc vat Chau Au • • Diu hat Hudng duang(12% C14-C16, 87% C18) 47 Cai diu (rape) (6% C14, 81% C18, 12% C20 48 Qua bang 1, cd the thay rang cac loai dau beo Viet nam deu cd the dimg de san xuat B100 vdi chat lugng khdng thua kem cac loai dau ciia Chau Au hay Bac My Ngoai cdn mpt s6 loai dau khac hien dang dugc dau tu trdng nhu jatropha II.2 Nghien cihi san pham phu qua trinh san xuat biodiesel Nhu da trinh bay d tren, viec san xuat biodiesel lu6n gap phai van de trg gia C5 Due, ngudi ta phai trg gia cho nong nghiep de san xuat dau hat cai ( diu Rape) Khi Nha nude khdng the tiep tyc trg gia, van de gia nguyen lieu da lam cho nganh c6ng nghiep san xuit Biodiesel gap nhieu kho khan.Viet nam tuang lai ciing se gap phai tinh hinh tuong ty, neu viing nguyen lieu tap tmng vao mpt so it nha diu tu D I kh6ng bj phy thupc, chung t6i da nghien cim su da dang nguyen lieu nhu da trinh bay d tren Hinh 2; Sa dd cdng nghi khdng bd thdi; Hat dau TV —• Vo Nhan Ep dau Van ep ben DUO'C Ba sau ep Chiet xuat Dau Dau Cac chat co HTSH Ba Thuc an gia siic Thuoc trir sau SH SX biodiesel Glyxerin thucng pham Biodiesel 78 NC tong hop Polyme tu phan huy tu glyxerin Hoi nghi Khoa hgc ky niim 35 ndm Viin Khoa hoc vd Cong nghi Viet Nam - Hd Ngi 10/2010 III.Co cau san pham ciia cong nghe -i-Van ep composite ben nude tir vd +Thu6c trir sau +Thuc an gia siic +Glyxerin va Biopolyme tir glyxerin +Biodiesel III.l Van ep ben nuuc [8] Cac loai vd hat Trau, Sd Cao su, Jatropha, dugc xay nhd, sau dd trdn vdi phy gia va phdi lieu, ep d viing nhiet dp 220-230 °C, vdi luc ep la 30Kg/cm^ San phim la van ep bin nude, cd cac cac uu diem ban han van dang ban tren thj tmdng PPinh ; Sdn xudt thu nghiim vdn ep bin nude + Dien tich tim ep: 0,5m x 0,5m x 0,01m; Trpng lugng sgi thien nhien (xa dira, ram, ra): 0,5 kg; Trpng lugng Phi thai: 0,8 kg; Trpng lugng phy gia: 1,2 kg; Luc ep: 30 kg/cm2 Bdng 2; Kit qud xdc dinh cdc tinh chdt vdt ly ciia tdm ep composite vd so sdnh vdi vdn ddm thi trudng nhu sau; Ten mau Dp ben Dp ben u6n MPa keo MPa TCVN TCVN 365.1970 364.1970 1-A 7,69 2-B Dp ben ngam Dp ben ngam nudclanh 27-29 °C nude sdi va tilp tyc gid, siy 60 °C dun sdi 3h TC 04-90 45 ph TC 04-90 2,60 Kh6ng thay ddi Khong thay ddi 2,40 0,87 Khdng thay doi Khdng thay ddi 3-C 9,35 4,20 Kh6ng thay d6i Kh6ng thay ddi 4-D 3,40 1,96 Khong thay ddi Khdng thay doi 1,32 0,83 Van thj trudng Ghi Chu A,B,C,D la phan ciia mau Ra Ra 79 Tiiu ban: Khoa hoc Vgl lieu ISBN: 978-604-913-0 ! III.2 Nghien ciin trich ly Saponin ba DTV di lam thulc trii' sau sinh hoc [9] Sau trich diu tir nhan hat, ba cdn khoang tir 35-53% so \'di nhan , vdi nha may san xuit 30 tin hat /ngay, lugng ba thai ciing khoang tren dudi 15 tan ba /ngay Trong ba chira mpt lugng Idn protein khoang 50%, cao ban khd dau nanh nhung cd chira mpt lugng saponin dang kl la dpc t l dii vdi dpng vat do khdng the lam thirc an gia siic chua loai saponin D I loai saponin kh6i ba , chiing t6i diing Methanol hoac Ethanol cd dp cdn 5080%, d nhiet dp tir 50 °C din 65 °C Sau dd loai cin khdi hgp chat chira Saponin Cdng doan tren dugc tiln hanh lai vdi dung mdi la Butanol Sau loai Butanol hgp chat tren dugc boa tan bing mpt lugng Ethanol rli kit tinh Saponin bing hon hgp ether-aceton( 1:4).Saponyl dugc diing lam thulc trir sau sinh bpclTng dyng cy the la cac loai tbudc diet bp dau den d miln Ddng Nam bp dang dugc thir nghiem vdi ket qua tdt: Hinh 4; Sdn phdm Iu Saponyl III.3 Thuc an gia sue va chat tang tir ba Dau thuc vat [10] So sanh san pham len men ba DTV tir chiing nam moc Aspergillus niger K84 va vi khuan Bacillus sublilis vdi san pham nhap tir nude ngoai nhu Kemzym va Termamyl : Kemzym la san pham thirc an bd sung dung chan nudi san xuat d Singapore dang sir dyng rong rai d Viet Nam Kemzym ciing la mpt che pham sinh hpc dugc san xuat tii' viec len men bdi chiing Aspergillus, san pham giau enzym, myc dich bd sung enzym cho thirc an chan nu6i, chiing giiip gia sue, gia cam tang trpng nhanh, tieu hao thirc an it, phong benh dudng mpt Gia ban d thj trudng Viet nam ( gia ciia nam 2005) la 40.000 ddng/kg Termamyl la san pham ( amylase ciia hang Novo, Dan Mach dugc sir dyng de thiiy phan tinh hot diing cong nghe san xuat dudng glucose, mach nha hoac san xuat cdn tir tinh hot Lieu diing lg Termamyl thiiy phan 1kg tinh bpt Gia ban hien d Viet Nam( gia ciia nam 2005) la 120.000 dIng/kg Chiing tdi so sanh boat lyc enzym ( amylase, protease, cellulase va dam tdng so ciia san pham A (ba DTV : ba khoai mi 8:2) len men tir nim mIc A.niger K84 va san phim B (ba DTV: bdt bap 1:2) len men tir chiing Bacillus sublilis vdi san pham kemzym va Termamyl ciia nude ngoai Ket qua nhan dugc: Bang 3; So sdnh sarI phdm len men ciia qui trinh (A,B)vdi sdr phdm nhdp; Chi tieu/ Mau a amylasa(UI/g) 80 A Kemzym B Termamyl 384,6 16,2 366,7 12362 Hoi nghi Khoa hoc ky niem 35 ndm I 'iin Khoa hoc vd Cong nghi Viet Nam - Hd Ngi 10 2010 Protease(UI/g) 0,98 0,72 Cellulase(UI/g) 616,3 230,5 Dam t6ng(%g/Kg) 65 1,17 8,6 52 Qua bang nhan thiy san phim A cd boat lyc enzym ( amylase cap gap hon 20 lan va cellulase cao gip ban 2.5 lin va dam ting s l cao hon gip 55 lin ciia kemzym, nhu vay cd the thay thi kemzym bing san phim A san xuit tir ba DTV Ien men vdi nam moc Aspergillus niger K84 San phim B c6 boat luc ( amylase thip hon Termamyl gan 3.5 lan, dieu cho thiy CO thi thay thi Termamyl bing san phim B san xuit tir ba DTV len men vdi vi khuan Bgcillus sublilis III.4.Glyxerin va Biopolyme tir glyxerin [11] Thanh phin chinh diing dl san xuit loai vat lieu la tinh bpt, glyxerin (san pham phy ciia qua trinh san xuit biodiesel tir diu thuc vat) va mpt sd chat phy gia can thiet khdng gay dpc hai cho m6i trudng va sire khoe ciia ngudi Loai Polyme cd the ty buy hoan toan sau 30 (khi chdn dat) Hinh 5; Sdn phdm biapolyme lit glyxerin ciig qui trinh ni.5 Biodiesel[12] Mpt so mau B-lOO dugc san xuat tir dau thyc vat Viet nam d qui m6 pilot 100 kg/ de xac djnh che dp c6ng nghe ciing nhu hieu suat ciia phan iing dugc t6ng ket bang sau: Bdng 5: Tiiu chudn Biodiesel ciia cdc mdu; STT Chi so Hoa ly Et>ieste Dau Cao su Et>'leste Etyleste Etyleste Etyleste Dau Bong Diu Gon Dau Dieu Dau Dira Ty trpng( g/ml) 0,895 0,897 0,896 0,894 0,864 Dp nhdt DH(mm^/s) 3,838 3,790 2,477 3,467 3,273 Ham lugng nude 0,245 0,173 0,206 0.187 0.165 81 ISBN: 978-604-913-01 Tiiu ban: Khoa hoc Vdt lieu (mg/Kg) Chi sd axit 0,621 0,907 0,291 0,655 0,20 (mg KOH/g) Chisdlod(gl2/100g) 115 112 110 105 90 Tdng glyxerit(%)m/m) 0 0 Glyxerit ty do(%)m/m) 0 0 Ham lugng Etyleste (%) 99,80 99,96 99,88 99,59 99,97 Bdng 6; So sdnh cdc mdu Bio-I,2,3/IAMS vdi RME vd EDIN 51606 STT Dan vi Chi sd Ty trpng RME Bio-I Bio-2 Bio-3 EDIN lAMS lAMS lAMS 51606 g/ml 0,876 0,886 0,890 0,90 0,8750,900 (15°C) Dp nhdt DH mm / s 4,24 4,98 5,02 5,35 3,5-5,5 Ham lugng nude mg/kg 300 165 187 245