HOA - CHE B | 6 N D A U KHl
Nghien cau tong hop phu gia chong an mon kim logi cho nhien lieu sinh hpc pha etanol tu nguon
dau thac vgt phi thac phdm
ThS. VO An, ThS. L I Thii Stfn, ThS. Phan Trpng HIJu, KS. Trin Thanh PhiTohg ThS. Nguyin Thj Thu Hiln, KS. Cao Huy Hilp, KS. LUcmg Vin ThUPng Vl^n Ddu khi Vlit Nam
KS. BOi Ngpc DUOng Tdp dodn Ddu khi Vlft Nam
Tdm tit
Trong nghiin cdu ndy, cdc ddn xudt imidazolin cda cde logi ddu thUe vdt phi thUc phdm bao gdm: ddu cpc rdo, ddu hgt cao su, ddu bdng vd ddu dn thdi... dd duac tdng hap vd chf rd suphdn bdmgch carbon eung nhUthdnhphAi cua chung trong sdn phdm tdng hap. Od Id ddng hap chdt imidazolin vdi 5 thdnh phdn ehfnh ed mach carbon phdn b6 trong khodng tu'C,^ - C,,. Sdn phdm tdng hap duac ddc trUng bdng cdc phuang phdp phd hdng ngoai (IR), phi cdng hudng tCfhat nhdn NMR IH. Ode biit, phd sdc ky Idng hiiu ndng cao (HPLC-UV) eho thdy vdng hdp rfiu UVdgctrtAtg cua ddn xudt imidazolin d230nm.
Khd ndng chdng dn mdn kim loai cda phu gia tong hap duac ddnh gid bdng cdc phuang phdp diin hda vd hda hpc. Cdc ddn xudt imidazolin thu dUac tU cdc loai ddu khdo sdt diu cd tinh ndng M o v l cdc chi tiit kim loai thulotq gap trong cdc hi thdng ton cbUa, sCfdung vd van chuyin nhlin Iliu sinh hpc pha etanol {Fe, Cu), trong dd Imulazolio thu duac tU dau cpc rdo cho hiiu qud bdo vi cao nhdt. Anh hudng eda phu gia tong hap lin ede tfnh chdt cda nhOn lieu sinh hpc pha etanol dUac tien hdnh ddnh gid theo cdc tiiu chudn quy dinh vi tinh tuang thfch eda phu gia doi nd cdc vdt lieu vd nhiin lieu khdo sdt. Kit qud thu dUOc cho thdy phu gia chdng dn mdn kim loaf tdng hop tif cdc hgi dau tht/c vdt phi thUc phdm ed khd nang ddp dng duac cdc yiu cdu ky thudt d6i vdi nhiin liiu sinh hpc pha etanrd theo QCVN 1:2009/BKHCN.
1. GiPi thieu
Phu gia cho n h i i n l i i u npi chung va n h i i n l i l u sinh hpc pha etanol (bio-etanol) nPi rilng, dPng vai trp r l t quan trong trong v i i c d i m b i o tinh nang I i m viec eda dpng CO. Mdt trong cic phu gia tfnh n i n g r l t quan trpng cho nhien lieu pha etanol l i phu gia chdng I n mdn kim loai. Do etanol cd tfnh hut I m manh n i n nguy cd nude x i m nhap vao h i thdng nhien lieu n i y k h i eao. Td dd, h i i n tuong i n mdn cle v i t lieu kim loai trong he thdng thudng xay ra trong q u i trinh sCrdung, tdn chda ddi vdi h i nhien lieu nly, d i n den cle sy cd nghiem trpng nhu:
c h l y nd do ro ri nhiin lieu, t i e nghen luu thdng do tfch ty ri set. V) the, phu gia chdng i n mon daac sCf dung nham n g i n ngda cie hien tupng I n mon x l y ra khi sd dung bio-etanol. Phu gia chong an mdn cho bio-etanol thuPng dupc sd dung la cie dan xuat imdfazolin dupe
d i l u e h l t d axit b l o cd mach hydrocarbon trong khoing C,j - C,g, cho h i | u q u i b l o ve kim loai trong h i thdng n h i i n l i l u k h i eao (hdn 90% d ndng dp trong khoang 10-50ppm)t4,S,12,13].
D i n nay, c i c cdng trinh n g h i i n cdu dUpc dang ky b i n q u y l n tai My v l t r i n eie tap chi eda cie nha xuat b i n ACS Publications, SpringerLink, ScienceDired tdng hpp d i n x u l t imidazolin t d d e axit b l o rieng I I nhu axit oleic, axit stearic, axit palmitic, axit lauric metyl este mP dpng v i t h o i c hdn hpp axit t i e h ra tddSu oilu, d l u dda, d l u ngd lam phu gia de ehe an mdn ctro n h i i n l i l u bio-etanol h o i c cho dUPng dng dan, b l chiJa.
Chua cd cdng trinh n i o d l c i p den q u i trinh tdng htfp d i n x u l t imidazolin cung nhy d i n h g i l hieu q u i \W v i kim loai cda td hpp e h l t dc che I n mon imidazolffi cP m^eh carbon phan bd t d C,^ - C,^ trong mdi t r i ( ^
[ 42 DAUKHI-SP4/2012
io-etanol t d d c loai d l u bdng, d l u cpc r i o , d i u hat cao u va dau I n phe t h i i [5,8,12].
Hiln nay, ehua ed n h i l u nghien cdu tdng hpp cic loai ihu gia cho n h i i n l i l u gde khoing pha etanol. Cic nghien du chd yeu t i p ehung v i o q u i trinh lua chpn nhdng phy lia sin cd t r i n thj trudng sau dd pha c h l v i o nhien lieu ihim muc dich dat dUdc cic chl tieu ky t h u l t cho nhien l u gdc khoang pha etanol. Oi t i i "Nghien cdu lya chon ac ehlt phu gia pha trdn nhiin li^u sinh hpc vdi n h l i n li|u
|dc khoang n h l m d i m b l o yeu elu v l ehit lupng nhiin eu trong q u i trinh b i o q u i n v l sd dung, ddng thdi d i m )io tinh an t o i n mpi trudng cda n h i i n lilu"eda nhdm t i c
|il Vien D l u khi\fiit Nam.Trong d l t i i t r i n , nhdm t i c g i l ia td hpp dupe gdi phy gia tinh nang cho n h i i n lieu sinh ipe phdi trpn nhiin lieu khoing t d d e t h i n h p h l n don I I , ac d l t i i ehl h o i n t h i n h pha ehe td hpp gdi phy gia t d :ac phy gia ddn I I cP s i n t r i n thj trUpng. Ngoii ra, mdt sd :dng trinh nghien cdu tdng hpp hoac lya chpn phy gia dc :hl an mPn phye vu n g i n h cdng nghiep d l u khi. Trong iP CO cdng trinh nghiin edu td hpp phu gia de e h l i n non cho dung djch packer (dung djch gdc nuPc) hay cPng rinh nghiin cdu tdng hpp chat de c h l i n mon imidazolin d nguyin l i l u d l u dda n h i m b l o v i elc dudng dng dan lau cua nhdm t i c gia Trung t i m Nghien edu Cfng dyng v i iihuyin giao edng n g h i (CTAT) - V i i n Dlu khf Viet Nam.
uy nhiin, co t h i nhan t h i y d i l m khlc nhau gida mye ffeh sddung va ngudn nguyen lieu trong eie ePng trinh ighiln cdu. Do vly, vile lUa ehon ngudn nguyin lieu phi hyc p h l m sSn ed trong nUPe vPi gia thanh thap nhu dau )dng, d l u cpc rlo, d l u hat cao su, dau an t h i i d l tdng hpp )hy gia ehdng i n mdn kim loai eho nhiin lieu sinh hoe
>ha etanol s l dem lai h i i u q u i kinh t l ky t h u i t .
'.. Thuc nghiem
\1. Tong hap phu gia '. /. /. Diiu chi axit bio tii dau thuc vat
Phin dng x i phdng hda: Cln 700g dau thye v l t vao dc chju n h i l t 21 d i t l l n b I p d i l u nhiet. Hda tan 196g KOH i o 650ml nude elt, khuay cho tan h i t . Nhd t d t d dung Ijeh nay vao c6c ehju nhiet 21 cd ehda dau, khuly deu va leu chinh n h i l t dp khdi chat Idng trong cde khoing 90 - 00°C. Sau khi nhd h i t dung djch KOH, khuly them 2 gid ho p h l n dng x i phdng hda x i y ra hoan toan. Tien h i n h 'Sa sin p h l m b l n g dung djeh NaCI bao hda dun ndng hoIng 80°C ba l l n . Sau do rda tiep sin p h l m b l n g nude dng 80°C d i n khi pH cda nUdc rda trung tfnh.
Phin dng axit hda: Cin 50g x i phong vao binh c l u 250ml cd g i n sinh h i n hdi luu. Tien hanh gia n h i i t cd khuly d i n nhiet dp khoing dCC. Pha loing 12.5ml dung djeh HjSO^ d i m die b i n g 62.5ml nude eat de thu dUpe dung dieh H^SO^ 20%. Nhd t d t d dung djch n l y vao binh elu ba cd. Sau khi nhd h i t dung djeh gia n h i i t cho hdn hpp p h l n dng d i n n h i l t dd 100''C v i gid n h i l t dd n i y trong mpt gid.
2.12 Tong hpp imidazolin
Cin 1,04g dietylentriamin v i 50ml xylen v i o binh elu ba cd 250ml ehju nhiet. T i l p theo, d n 6,02g axit b l o v i o ede 100ml. Oat binh d u len may khuay t d eP gia nhiet, I l p sinh h i n hdi lUu, nhiet ke, pheu nhd giot v i o h i thdng p h l n dng. Tiln h i n h gia nhiet cd khuay, khi nhiet dp dat d i n n h i i t dp 150''C, nhd gipt hdn hpp axit beo v i o he thdng p h l n dng den h i t v i gid nhiet do trong sudt thdi gian p h i n dng. Sau 8 gid p h i n dng, tien h i n h ehin khdng 2 gid d nhiit dp 1SCC va dieu kiln chan khong 3mm Hg.
Sin pham p h l n dng dupe ket tinh lai trong dung mdi n-hexan ndng d nhiit dp 80°C.
Qua trinh ket tinh nhu sau: Tat c i sin pham cOa phan dng dupc dUa vao binh tam giae 250ml, dun ndng n-hexan den SO^C trong mdt binh tam giac khie. Nhd t d t d mpt lupng nhat djnh dung djeh n-hexan vao binh tam giac ed chda sin pham phan dng. Moi lan dUa dung mPi v i o lac deu hdn hpp sao cho luong dung moi dUa vao coi nhu vda dd hPa tan mpt lupng nhat dmh sin pham. Thyc h i i n qua trinh den khi lupng n-hexan vda du de h o i tan h i t hdn hpp phan dng. Lam lanh t d hdn hpp t r i n d i n khi cP x u l t h i i n chat ket tua mau trang. Lpc de loai bd p h l n dung mdi va thu lai phan ket tua tren giay Ipe. Phan ehlt r l n thu dupe dem ket tinh lai den khi chat ran thu dupc co m i u trIng trong sudt [3,4,8,10,11,12,13].
2.1.3. Cdc phuang phdp dac trOng sdn phdm 11}
Phuong phap sic ky khi khdi phd (GC-MS): mau dupc phan tieh t r i n t h i l t bj GC-6890A ket ndi MS-5975C tai Phong thi nghiim trpng ctiem, Viin Hoa hpc v i Cdng nghiip Viet Nam. Dieu k i i n do: cdt sic ky HP-5ms 30m X 0,25mm x 0,25ym, the tfch bdm mau Ipl (chia dPng80:l).
Phuong p h i p phd hdng ngoai (IR): xle djnh d e dao dpng cda nhdm chdc trong p h i n t d d vung t i n sd sdng t d 4.000em"' - 400cm"', sd dung cuvet chda mau Idng, thiet bj do FTIR IMPACT 410 tai Vien HPa hoc - Vien Khoa hpc va Cdng nghe Viet Nam.
DfiUKBl-60 4/2012 43 i
HOA - CHg' BIEN D A U KHI
Phuang phap phd sic ky Idng hi§u n l n g eao (HPLC- UV); sd dung pha dpng 7V metanol/3V nUde, cpt C18, the tich bom m l u 20tjl, p h l n m I m Empower softw/are, p h i n tieh tai V i i n HPa hpc - Vi§n Khoa hpe v l Cdng n g h | Viet Nam,
2.1.4. Cdc phuang phdp ddnh gid khd ndng ifc chi an mdn cua phu gia Oc chi dn mdn [2]
D i n h g i l k h i n i n g dc c h l i n mPn b l n g phUdng p h i p d i l n hda: sddung t h i l t bj do Parstat 2273 Advanced Electrochemical System t^i Phdng thf n g h i | m ehdng I n mdn - CTAT. Cie thPng sd do: t h i m^eh hd (E,,) v i h i | u q u i b i o ve theo g i i trj m i t dp dPng i n mdn (HQBV).
D l p h i n loai v i lya ehon duoe s i n p h l m imidazolin cP tinh nang b l o v l tdt n h l t , cie sin p h l m tdng hpp thu dupe t d cic lo^i d i u n g h i i n cdu dupc d i n h g i l so bp qua d c p h i p do i n mPn d i i n hPa t r i n cic v i t l i | u kim loai nghien cdu (Fe, Cu, Al). Cic p h i p do dupe t i l n h l n h bao gdm:
-I- Do the mach hd EO: nghien edu n h i i t ddng q u i trinh an mdn de d i n h g i i k h i n i n g xly ra h i i n tUdng an mon kim loai trong mdi trudng nghiin cdu.
+ Do tdc dp i n mon icorr ( m i t do dPng an mPn):
nghien edu ddng hpe q u i trinh i n mPn d l xie djnh mde dp an mon kim loai trong mdi trUdng n g h l i n edu, t d dd xac dinh h i i u q u i b i o v l kim loai. H i i u q u i b i o v l duoe xie dinh theo gia trj m i t dd ddng i n mon (icorr) eda kim loai trong mau dung djeh do SO vdi mau dung dieh ehuan ban d i u (mau khdng sd dung de che) theo edng thde:
(1) K i t q u i xac dinh m i t dp ddng i n mPn (i^.^^^^) qua cic dudng cong p h i n cue cua d c kim loai n g h i i n edu (Fe, Cu, Al) trong eac dung djch nuPe ehilt t d cie mau NLSH pha etanol (EIO). DPng an mPn dUdc xic djnh b l n g phuong phap d i l n trd p h i n eye vdi k h o i n g dien the AE = I E-E^^, I = lOmV va tdc dp q u i t v = 0,5mV/s. Cic duPng cong p h i n eUc thu daac dCing de xle djnh mat dp ddng an mPn i^^^_ [8].
D i n h g i i i n mon t h i p theo tieu chuan ASTM D665:
danh g i i k h i nang chdng rl thep trong mdi truPng n h i i n lieu khi eP nude (hdn hpp nUdc nhiin lieu). Hdn hdp 300ml nhien lieu va 30ml nuPe d t hole nudc bien n h i n tao Quae khuly d n h i l t dp 60 + 1°C, mpt dng thep hlnh try dupc nhdng v i o dung djch t r i n . Q u i trinh thd nghiem
t i l n h l n h trong 4 gid. Sau t h d n g h l | m xiiC djnh mded^r cda v l l n d ^ n .
D i n h g i l I n mPn ddng theo t i l u chuIn ASTIi/
D130: sd dyng t h i l t bj do Italy S,D.M Model 1440 ta Phdng U'ng dyng v i Phit t r i l n s i n p h l m mPi-CTATDi&
ki§n do: lupng m l u 30ml, n h i l t dp do 100°C trong 2 gift Sau khi thCr nghl|m, so sinh mdc dd b l l n ddi m i u cda tin ddng so vdi b i n g m l u t i l u chuln.
2.1.5. Cdc phuang phdp ddnh gid tfnh chdt nhiin liiu khi pha php gia Cfc chidn mdn
Khi n l n g p h i n huy sinh hpc: k h i ning phln ra sinh hpe h i l u khi eda phu gia dupe xAc djnh theo phuong p h i p BODIS Marine da dupc sda ddi t d t i l u chuln ISO TC/147, SC5/WG4-N141 BOD-test I p dyng cho d e ehlt khdng (hoic it) hda tan trong nude (1995) v i t i i lieu H|
thdng Q u i n 1^ ehlt lupng theo tieu chuln ISO 9001-200(h PII-75-02 "Hudng d i n xlc djnh k h i n i n g phln ra sinh hpc"-Trung t i m Nghiin cufu v i Phit t r i l n An t o l n vIMoi trudng D l u k h f - V i i n D l u khi V i l t Nam.
Khi n i n g tUOng hpp cua phu gia vdi cie vat lieu phi kim loai bao gdm:
Dp gian d i i tPi h^n xic dinh theo t i l u chuan: ISO 527-2 (1993) t r i n m i y Housfield eua Anh. Tdc dp keo 5mm/phut, nhiet dp 25°C dp am 75%.T3t e i d c mauA) ed kich thude theo tieu chuan hinh m l i chIo, kich thudc 20 X 150 x 4mm, khoing gida 12 x 80 x 4mm.
+ Dp b i n k l o xic djnh theo t i l u ehuan ISO 527- 2 (1993) t r i n m i y Housfield cua Anh. Tde dp keo 5mm/
phut, n h i l t dp 25''C dp am 75%. T i t c l d c mau do ed kidi thudc theo t i l u c h u l n hinh m i i cheo, kich thUde 20 x 150 x 4mm, khoing gida 12 x 80 x 4mm.
+ Od edng cua v | t lieu dupe do theo TCVN 1595-07, m l u do cP kfch thUdc thfch hpp, m i t I p p h l i ed diln tich tdi t h i l u SOOmm^ vdi mdt Id t i m 5,4mm ± 0,2mm.
+ Su thay ddi t h i tieh xie djnh theo phuong phap nhdng ehim chinh l i hieu sd suthay ddi the tich cua mJc nudc khi tien h i n h nhdng ehim m l u trudc v i sau khi tier h l n h hdi lUu trong n h l i n lieu xang. DO cd v i khdng |S pha phy gia.
Anh hudng eda phy gia den tinh ehlt nhien l i ^ xic dinh tinh e h l t cda nhien lieu khi cd va khdng cd g | gia theo QCVN 1:2009/BKHCN.
44 DAUKHf-Sp4/2012
3 . K € t q u l t h l o l u S n
3.1. Tinh chdt cda cdc loai ddu tht/c vdt Ngudn nguyin l i l u d l u thyc v i t phi thyc pham dupe lya ehpn de tdng hpp phu gia chdng an mdn kim loai cho nhien lieu sinh hpc pha etanol bao gdm: d l u bdng thd, d l u cpc rao, dau hat cao su v i d l u an p h i t h i i . Thanh phan chd y i u eda cic loai d l u thye v l t nay la d c triglyxerit cda cie axit b l o eo mach hydrocarbon trong khoing C,j- C,^. Cie nguyin lieu t r i n sau khi tinh e h l dupe t i l n hanh p h l n tich d c d i e tfnh hPa ly cho ele k i t q u i trong Bing 1.
Td bang p h l n tfch eie ehl t i l u hPa ly eda d c mau dau, co the so s i n h tUdng ddi chfnh xie tinh chat cua d c mau d l u . Chl sd lot cua cac loai dau thuc v l t cho b i l t sd lupng l i l n k i t n CO trong mpt loai d l u ; dp b i n oxy hda khae nhau cda cie loai d l u ; dp nhdt v i do kho hay khong khd. Dau hat cao su cd ehi sd iot cao nhat, kem b i n oxy hda nhat. Dau cpc rao CO chl sd lot t h i p n h l t , dp ben oxy hPa tdt nhlt. Ham lupng nUPe t y n h i i n cd trong dau thuc vat cung I I mpt chl t i i u danh g i i chat lupng cua d l u . D l u chda lUpng nUde eing thap thi cdng doan tinh ehe s i n pham d n g de d i n g . Cic chi tieu khlc cda d l u cung p h l n i n h tinh chat hda ly d i e trung cho tdng loai dau va l i chl sd quan trpng de d i n h gia k h i nang sddung cua tdng loai dau trong mpt mue dfnh n h l t djnh. De xac djnh mach hydrocarbon trong p h i n t d dau thuc v i t , nhom t i e gia da t i l n hanh p h l n este hoa cheo dau thyc vat b l n g metanol d l ehuyin cae phan t d triglyxerit t h i n h metyleste va p h i n tich t h i n h p h l n metyleste b l n g t h i l t bj GC-MS. Ket q u i dupe dUa ra trong Blng 2.
Cac loai d l u d l u cd maeh cacbon p h l n bd chu y i u la C^^ v i C,g. Cu t h i nhu sau: d l u bPng 73,33%V C,g, 23,81 %V C,^; d l u cpc r l o 84,36%V C,g, 15,65%V C,^; d I u hat eao su 88,03%V C,g, 10,21%V C,^; dau i n p h i t h i i 75,37%V C,g, 2,03%V C^^. SU p h i n bd maeh cacbon tuong dng vdi ehl sd xa phdng hda va chl sd iot eda eie loai d l u .
Qua trinh p h i n dng chuyen h o i t d dau
Tinh chit Miu sic
Bdng 1. Tinh chdt hda ly cua cdc ddu thUc vdt sau khi tinh che T«n d i u
Chl s6 axit, mg KOH/g ChisPxiphPng, mg KOH/g
\ Chls6lot,gl2/100g NUPc, % khdi lupng 06 nhdt dpng hpc
• 40''C, est Oilm chdp chiy, "C
^ Dilm dPng d i e "C Dlu bdng niu sdng
0,925
0,03 ; 39,0 !
Dlu cpc r i o
Dlu hat caosu ving- ndu sing
15,4 189 116 0,05 30.7 210 !
0,3 I 33,4 ' 260 I
Dlu an p h ^ t h i i
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0,16 I 35,3 I
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14,97 0,68 9,15
Dlu hat cao su
0,69 10,21
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10,27Dau an phe t h i i 0,66 2,03 5,76 46,24^
32,52 41,58 28,03 3.2. Pho IR cda ddu thuc vdt, axit beo ddu thUc vdt vd sdn pham imidazolin tong hap
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HOA - C H i ' BIEN DAU KHl
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• imidazolin t h u o n g p h l m (D,C)
D a o Triglyxerit
- C = 0 (RCOOR')
1741,38 1742 1743.33 1747,88
doc tnmg cue nguyin li^u vd sdn phdm ddng cCia n l i 6 m d i e t r U n g
A x i t b ^ o -c=o (RCOOH) 1705,99 1712,77 1710,74 1710,66
c m ' i m i d a z o l i n t d n g h ^ -CON- - C = N - (am(t) 1648.90 1638.33 1647.63 1634.91 1652,62
[Imidazolin) 1553.73 1561,72 1552,43 1548.06 1555.55
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I8£4i1j_11.72 2V» a&tS 2Ut is A 4 • ' • • ThM gim, (phOQ
Hinh 5. Pho HPLC-UV cCia phu gia thuang mgl hda
thye v | t - » axit b l o - • imidazolin dupcthS hl$n bdi sy x u l t h i | n cAc nhdm chdc flSc trung t h i h l | n t r i n phd IR cda tCftig loai h ^ c h i t (Hlnh 1-3).
Phd HPLC-UV cda m l u phu gia tdng h^p (Hlnh 4) v l phu gia thUPng m^i (Hlnh 5) d^u cd d e dinh h i p thy UV d 230nm. D l y 11 v ^ h i p thy d|c trdng cda vdng imidazolin. Cu thi nhusau:
Odi vdi phd HPLC-UV phy gia tdng hop:
+ Oinh (peak) cd thdi gian lUu 13,95: hip thy UV = 230nm, d(|n tich dinh (peak) 27,82%
tUPng dng vdi C,,^
-f Oinh cd thdi gian It/u 14,655: hip thu UV = 230nm, d i | n tich dinh (peak) 14,96%
tuong Lfng vdi C,g_
+ Dinh cd thdi gian lUu 15,175: hap thu UV = 230nm, d i l n tich dinh (peak) 8,77%uing vdi C „
+ Dinh cd thdi gian lUu 20,265: hip thu UV = 230nm, dien tich dinh (peak) 13,96%
tuong dng vdi C,^
-I- Oinh cd thdi gian luu 20,635: hap thu UV = 230nm, dien tich dinh (peak) 28,79%
tUdng ufng vdi C,^.
Odi vdi phd HPLC-UV phu gia thucmg m^i hda:
+ Oinh cd thPi gian lUu 2,73: h i p thu UV
= 230nm
+ Oinh cd thdi gian Idu 4,28: hip thu UV=230nm
+ Oinh cd thdi gian Idu 7,90: h i p thu UV
= 230nm
-I- Oinh cd thdi gian luu 10,56: hip thu UV=230nm.
Trong hon hdp sin pham ed tdn t^i 5 s i n pham ehinh: 2 - h e p t a d e c ^ ^ 1 - [ ( 2 - o e t a d e c e n o y l a m i n o ) e t h y l ] : 2 - imidazoline(C,gJ; 2-heptadediee^^
1 -[(2-octadedieenoylamino) ethyII-^
imidazoline(C,gJ; 2 - h e p t a d e c ^ - l ^ | oetadeeanoylamino)ethyl]-2-imidazo»ff' {C,B); 2-pentadeeeyl-1-[{2-
hexadeeenoylamino)ethyl]-2-imidazoline ( C , J ; 2 - p e n t a d e e y l - l - [ ( 2 - h e x a d e c a n o y l a m i n o ) e t h y l ] - 2 - imidazoline (C^.). Cie hpp c h i t n i y cd p h l n bd mach cacbon II Cj^ v i C,gVi ty l i gida d c c h i t trong sin p h l m da dupe chl ra trong phd HPLC.
NhUvly, b l n g phuong phap hdng ngoai, phd NMR IH v l phd HPLC-UV ed the d y d o l n edng thde d u tao cCia sin p h l m ehinh tdn tai trong hdn hpp sin p h l m hp imidazolin nhusau:
Sin p h l m imidazolin t d axit oleic cd cong thdc d u tao:
C17H33 , H
Tin gpi: 2-heptadecenyi-1-[{2-octadecenoylamino) ethyl]-2-imidazoline
Sin pham imidazolin t d axit stearic ed edng thdc
C17H35 , H
Ten gpi: 2-heptadecyl-i-[(2-octadecanoylamino}ethyl]- 2-imidazoline
- Sin pham imidazolin t d axit palmitic cd cdng thdc d u tao:
C15H3, , H
Tin gpi: 2-pentadecyl-1-[(2--hexadecanoytamino}ethyl]- 2-imidazoline
Nhu viy, di tai da tong hpp dupc phy gia dc che i n mPn dong imidazolin t r i n co sd d c axit beo t i e h ra t d 4 loai d l u thyc vat. Phan tich cu the ddi vdi dau cpc r i o cho thiy, phu gia la td hpp eda 5 thanh phan ehinh tUOng dng vdi phan bd maeh carbon C,g va C,^. Sy phan bd maeh carbon nay se t i n g eudng k h i nang phan t i n cua phu gia trong mdi trudng nhiin l i i u ddng thdi tang cUdng k h i nlng dc c h l an mdn kim loai trong mdi truPng nhien l i l u cung nhu k h i n i n g khang khuan eho nhiin lieu sinh hpc.
Blng b i i n luan trong phan tdng quan, nhPm t i e g i l d i ehi ra ddi vdi phy gia dc che an mdn thuong mai p h i i l i td hdp cda nhilu t h i n h p h l n vdi mach carbon p h i n bd chd yeu t d C,j - C,g. Oieu n i y dupc chdng minh cu the qua
p h i n tich phd HPLC-UV eda m l u imidazolin daac thuong mai hPa.Td hpp nhilu t h i n h phan vdi maeh cacbon phan bd rpng khong nhdng t i n g cudng k h i n i n g tUOng thich vdi mdi trudng p h i n tan m i cPn tang cddng k h i nang dc c h l i n mdn cda sin pham.
3.3. Khdo sdt cdc yiu td dnh hUdng din hiiu sudt phdn ijfng tdng hgp
Cic y i u td ehfnh i n h huPng d i n hliu suit p h l n dng tdng hpp imidazolin t d c i c axit beo d l u thyc v l t khlo sit bao gdm: nhiit dd t i l n h i n h phin dng; t^ l i moi eie c h i t tham gia p h i n dng: axit blo/DETA; thpi gian tien hanh phln dng. Cic thdng sd tren dupe t l l n hinh khio sit d dieu kien p h i n dng: dd ehin khong 3mmHg, thdi gian chin khdng 2 gid, dung mdi xylen, tde dp khuay 400 - 500 vPng/phdt.
Anh hvdng cua nhl^t d$ c6 5i> d^ng dung mSI vi chin khAng
Hinh 6. Anh hudng cua nhiet do den hiiu sudt tgo imidazolin
i » j
E
"
A n h hLFiTng
T y l f A > n
cua t y 11 m o i axH b 6 o f D E T A
- ^ C H u c c c r t e - • - D b caosu - * ~ [ ] i u A n p n i i r A -•-D4ubfin9>iHy
Hinh 7. Anh hudng cOa ty li axit beo/DETA den hieu sudt tao imidazolin
i 100
*
1 BO 9 60
1"
• ZO
A n h hiFong cua th64 gfan phSn Crng
^ ^ ' ' - ^
ni* glsn phan ling. gUr
- a - D i u cao su - * - D & u d n p h i l h a i
—•—Oiu bflpg X* ly
tfmh 8. Anh hudng cua th^ gian den hiiu sudt phdn itng tao imidazolin
HOA - cne' BII'N DAU KHI
Kit q u i khlo sit d c y i u td i n h hUdng d i n p h l n dng tao imidazolin eua eie d l u thyc v i t nghiin cdu eho t h i y h i i u suit p h l n dng cue dai dng vPI d c d i l u ki|n p h i n dng nhusau:
+ Nhiet dp: 130-170-C
^ T ^ l ^ axit blo/DETA; 1 -3 -•- Thdi gian p h l n dng: 4 - 1 0 gid.
Cie k i t q u i so bd d i n h g i l tinh n i n g ehdng I n mdn kim loai trong h i thdng nhiin li^u sinh hpc eda elc phy gia tdng hpp t d 4 loai d l u k h l o sit trong p h l n "Dinh g i i tinh nang s i n p h l m imidazolin tdng hpp" cho t h i y imidazolin tdng hpp t d d l u epe r i o eho k i t q u i tdt n h l t . Vl viy, p h l n dng tdng hop imidazolin t d d l u cpc r l o dUpc lya chpn de thyc h i i n cic nghiin edu tdi uu hda d i l u k i | n p h l n dng.
3.4. Tdi UU hda cdc diiu kiin phdn Ung 3.4.1. Chpn cdc yiu to dnh hudng
Trong qua trinh p h l n dng tdng hpp imidazolin t d d l u cpc rao, h i i u suit p h l n dng phu thupc vao nhieu y i u td.
Tuy nhiin, cac yeu td duoe chdng tdi chpn lya d l lam b i i toan quy hoach tdi Uu hda d i l u k i l n p h l n dng la cac y i u td dupe lya ehpn trong q u i trlnh k h l o s i t bao gdm:
Z,: Nhiit dp phan dng, t Zy Ty I I moi eua axit beo/DETA, moi Z^: Thdi gian p h l n dng, gid Y: Hilu suit p h i n dng, %KL
Td eie k i t q u i nghiin edu, nhdm t i e g i i lya ehpn vung k h l o s i t thieh hpp ddi vdi cie y i u td n i y nhu sau:
Nhiltdp:130-170°C Ty l i axit blo/DETA: 1 - 3 ThPi gian p h i n dng: 4 - 1 0 gid
Phuong trinh bleu dien mdi quan h i gid h i l u s u i t hlnh thanh s i n pham vdi eie y i u td d l u v i o nhu sau:
Y = f(Z,, Zj, Zj). Bii t o i n dat ra I I tim d i l u kien eua c i c b l l n Z,, Zj, Zj de Y dat eye trj IPn n h l t .
3.4.2. Chon phuang dn quy hooch
Quy hoaeh thUc nghilm b l n g h i m trye giao e l p I vdi thye nghiem yeu td t o i n p h l n 2 mdc, k y i u td i n h hUdng.
Phuong trlnh hdi quy ed dang:
Y = b„ + b,x, -I- bjXj + b,x, + b.^x/^ + b,3X,x, + b^x^Xji
b,j3X,x^X3 (2)
3.4.3. Thi nghiem trpc giao cdp I
Sd thi nghiem c l n x l c djnh trong phUdng i n 1^
2" = 2' = 8, d i l u k i | n thf nghiem dUpc chl trong Bing 4. • Bdng 4. Diiu kl4n tb! nghiim
CIc mOrc Mdc trin (+1) MyecOsP(O) MdcdUdM-l) Khoing biln thiln
Cic yiu X6 i n h htfAng Zv-C Z „ m o l
170 3
ML.i
150 20
T i l n h l n h thi nghiem theo ma t r i n v i x i y duhg ma t r i n thuc nghiem, tim c i c h | sd trong phuemg trlnh hdi quy t u y l n tinh, k i l m djnh mdc y nghia trong phUOig trlnh hdi quy. K i t q u i phUdng trlnh hdi quy cd d^ng:
Y^^ = 67,288 ^ l,7B8x, -l,263x, + 2,363x, (3) 3.4.4. Tdi Uu hda thuc nghiem dithu dUpc hiiu sudt imid- azolin tdn nhdt
Tinh budc chuyen ddng 5. TCr mdc cd sd v l phUong trlnh hdi quy t u y l n tinh ddi vdi h i m muc tieu, t i l n hlnh tinh bude chuyin ddng 5 cho mdi yeu t d sau do tien h i n h c i c thi n g h i l m leo dde d l tim eUc tri. Kit q u i dcthi n g h i l m leo dde t h i hi^n qua B l n g 5.
Thi n g h l ^
1 2 3 4
Bdng 5 Cicy
»c 150 160 170 180
Thi nghi$m leo ddc didm cUC tri 6u td I n
moi 2 1.6 1.2 0.8
huimg
7 9 11 13
H l t u s u i l t ^ Imidazolin (HI, W L
7 « e 76.8 73,2 70,9 Nhu vly, d i l u k i l n p h l n dng cho h i l u suit tao sSn
.
p h l m imidazolin tdi Uu I I 76,8%.Tai d c d i l u kien nhUsau:
N h i l t dp p h l n dng 160°, t? I I moi axit beo/DETA I I IA thdi gian p h l n dng 9 gid.
3.5. Ddnh gid tinh ndng sdn phdm Imidazolin ting hdp 3.5.1. Tinh chong dn mdn kim logi
- Nhiet dpng q u i trlnh i n mdn eda n h i i n l i l u pha phij gia: K i t q u i do t h i mgeh hd E^ cda dung djch nUdc chiA
•, 48 Dlu KHi-sd 4/2012
chda phu gia tdng hpp (50ppm) t d d l u cpc rlo, d l u h?t eao su, d l u bdng v i d l u i n t h i i dupe t h i h i | n qua Hlnh 9,10,11.
ts
i t .
h'
• O S
Diln Mli in|chha>ciki F« tnmg EIO
1 3 5 10
A
- ^ ^ ^ ^ ^ ^ = = 1 j : r ^ ^ - ^ ^ ^ f r > ^ ^ ^
• m
ThM )Un ngkn m k . n a l i '
- ^ O h i U n g - ^ O l u v h t M l -•-Diuoocrlo
Hlnh 9.Jhi mach hd cda Fe trong EIO
B i ^ f i i m|Gh Mcdi Cu twis EIO
HJnh TO. Thimgch hdcda Cu trong EIO
0
>
•ai^ • a 2
| 4 L 3
r
•as
H f n l i i Mfdi ha-cOi M «nig EIO
1 3 K «
'tf'—-—ft
—--'''iJiiC——r •
^ -^ k
1IM^mta^mlm.wttf
- « - D k b A i i t - • - D b i i l i t M
-B-DluhvlCM n
HJnh 11. Thi mach hdcOaAl trong EW Dien t h i mach hd cua cie dung djch nude c h i l t cda I nhiin lieu sinh hpe EIO pha elc imidazolin tdng hpp t d , d c dau khio s i t cd xu hUdng t i n g theo thdi gian. D i l u I niy cho thay viec pha imidazolin v i o nhien lieu sinh
hpc EIO I i m cho dien the d n b l n g cua cic kim loai djch
! ehuyin theo chilu dUdng hay c h i t dc e h l cd k h i n l n g dc I c h l an mon. Trong vdng 3 n g l y d l u , q u i trinh hap phy
; cda imidazolin len b l mat kim loai co t i e dung c l n trd q u i , trlnh i n mdn x l y ra tuy vPi mdc dd khie nhau d t d n g c h i t
de ehl. Ldc d l u Idp m i n g ehlt dc che hap phu t r i n b l m$t kim loai chUa kin xit n i n ed sy tang g i l m v l k h i nang b i o v l kim logi. TCi ngiy thd 5 trd di, khi IPp m i n g dc c h l p h i t t r i l n d l u khIp b l m i t kim lo?i thi k h i n i n g b i o v l kim loai b i t d l u dn djnh. Trong sd 4 loai imidazolin khlo sit, d thdi d i l m t d n g l y thd 5 trd di, ed t h i t h i y imidazolin t d d l u epe r l o cd k h i n i n g b i o v | eie kim loai nghiin edu (Fe, Cu, Al) tdt n h l t (dp djch ehuyin d i i n t h i ein cIng theo ehilu duong nhilu nhat). Hi|u q u i b i o v | kim loai theo ndng dp phy gia t h i hi^n qua Hlnh 12,13,14.
H l f u q u i b l o v f t h t p thao nAng d ^ phw g i i
Ning at phv gin, ivn>
Hinh 12. Hiiu qud bdo vi thip theo ndng do phu gio trong EIO
110
* 100 f 90 1 SO
• g 7 0
Z eo f so 40
00 00 00 00 00 00 DO
Hifu qud bSo vf h^p Mm ddng theo n&ng df phg gia
/ ^
r
5 10 20 so 70 100NAngdfphvgl'.Ppni
-m-tAiiniiitaii -W-Okbeng -*-l>tivgia(k:
Hinh 13. Hi4u qud bdo vi dSng theo ndng ddphij gia trong EW
^ 100 f eo
3 -
| e o X 50
40 00 00 DO 00 00 00
Hlf u qui bio vf hpp kim nhfm theo n&ng df phy gia
/ ^ "
r
5 ID 20 so 70 100Ning d ( phV glB, ppm
- • - D i u an phi Ih^
-K-DiubSng
~ « - P h v gia d6i ctii^ng
Hinh 14. Hliu qud bdo ve nhdm theo nong do phu gia trong EIO
Hieu q u i b i o v i khi sd dung phu gia dc che i n mPn tdng hpp t d nguyin lieu d l u cpc rao tUdng ducffig vPi phy gia ddi chdng v i cao hon so vdi phy gia dc che tdng hdp t d ngudn nguyen lieu d i u cao su, dau an phe t h i i v i
HOA-CHE'BI^NDAUKH!
d l u bdng. Kit q u i d i n h g i i h i | u q u i b i o v | cung eho thay ndng dd phy gia de c h l I n mdn hi§u q u i khi pha v i o nhiin li|u I I SOppm. Hi|u q u i b l o v | cic kim lo?i (Fe, Cu, Al) trong d c nhiin li|u sinh hpc El 0, D5 theo thdi gian v l ndng dp dupe t h i hi|n qua d e Hlnh t d 15 - 23.
Hlf u qui bio vf thf p thao thM giin
Hlnh 15. Hiiu qud bdo vi thip theo thPI gian trong E10
i 90,00 1 80,00
•g 7 0 , 0 0
i " "
i 50,00
Htf u q u f b l o v f h 9 p kim dAng theo t h M gian
1 3 S 7 to IS ThM glin. ngiy
- • - o i u an pnt ihti - w - O a u M n g -•—PtiU gta iJc
Hinh 16. Hiiu qud bdo vidong theo thdi gian trong EIO
11000
* 90,00 1 00.00
? 70,00 3 60,00 5 sooo
H l f u q u i b f 0 v f h g p him n h f m theo t h M gian
1 3 S 7 10 15 ThM glin, ngiy
- • - • k i c g c r t a - A - D h i c K d i - • - D k f e i p h t l U I
- • - P h g g H *
Hinft 17. Hi^u qud bdo v$ nhdm theo thdi gian trong EW
i M,MI
^ 50,00
H l f u q u i b i o v f t h f p theo n i n g d f phv gie
• - - " ^ ^ ^ ^ ^
/Lf^"^
y//^
w/
f
S 10 20 so 70 100 Ning Of phv gil, ppm
- - - D t u c v c r t a - • - D k i an ph( tn*i
Hinft 18. Hiiu qud bdo vi thip theo nong dd phu gia trong D5
i 50 OAU KHl-sd 4/2012
I M
g OD
J '•
} "z
00 00 00 DO 00H l f u q u f b f 0 v f t i g p klrndftng theo n i n g d f p h g gia
n ^ B P i a
'
B 10 2D 00 TO too Nfnptff pNv gil, ppm
- • - O k w r l o -^Okiaeu - • - D t u l m M U i
- ^ P h d O U *
Hinft T9. Hl^u qud bdo vi ding theo ndng dd phu gia trong DS
H l f u q u f b f 0 v f h ? p kkn n h f m Iheo ndng d f phg gia no 00
/ 100,00
•* <«no 1 »0,00
—-___>'^r^J^l^jl ^ l — / MT"
^//
W/
\
S 0 20 so 70 too - • - O l u c w r i a - * - D t u c > i H
- • - C f u M v - » - P T « v d ( M B
2*
N » n e a » p ) « e M . w «
HJnh 20. Hliu qud bdo vi nhdm theo ndng dPphugia trongDS
£ SOOO
H l f u q u f b i o v f t h i p Iheo I h M gian
fcf . * « * _ ^
•"-T-J ' V "t^i. m I
^^^^F^w^TfL t. 1
1 1 t 7 10 TS T 1 t M ^ n . n g * y
- A - D l u a o u - • - O b t o p l f M -u-OkibUe - • - n i u M f t
Mnfi 21. Hiiu qud bdo vi thip theo tftpf gian trong 05
110 00 I t 100,00 f 90,00 a sooo 1 70,00 1 600Q g 50,00 Z 40,00 30,00
H l f u q u i b f o v f h v p U n d&ng thM> t h M gian
fc^ -%z.—z
^tS-^ "{""^*"^
^~*^-^"r=^4-
' ^ D h i w e i f c i "
- ^ D f c i a o w
^ • - • t u t i M g
1 3 5 7 10 15
ThM gian, ngiy J
Hinft 22. Hiiu qud bdo vi dSng theo tftPi gianpong DS
11000
•f 90,00 e 00,00 2 70,00 1 0 0 , 0 0 2 90,00 I 40,00
H l f u q u f b f 0 v f h 9 p Kkn n h f n i I h e o I h M gian
1 3 S 7 10 IS ThM gian. ngiy
J L p m ^ * "^
^as
Hinh 23. Hiiu qud bdo vi nhdm theo thdi gian trong D5 ^^
Theo thPI gian hieu qui bio v l cda phu gia dc chl I n mPn tdng hpp td dau cpc rlo v l phu gia ddi ehdng tuong ty nhau va deu dn dmh sau 7 ngiy. Hi^u qui bio v l theo thdi gian eda phu gia de ehl an mdn tii dlu cpc rao IPn eao hon so vdi phu gia tdng hpp td cie loai dlu cPn lai.
Qua cle ket qui do the maeh hP E^ v l xlc djnh hieu qui blo v l theo thdi gian v l theo ndng dd phu gia cho thiy, phu gia tdng hpp tCr dlu coe rio ed hilu qui blo v l tuong
duong vdi phu gia thuong mai d ndng dp SOppm. Do viy, phu gia tdng hop td dlu coc rio dupe sd dung de dinh gii khi nang ehdng rl thip theo tilu chuln ASTM D665, an mdn ddng theo tilu chuan ASTM Dl 30, tUOng hpp vat lilu phi kim loai va dinh gii mdc dd thay ddi tfnh chat nhiin lilu. Kit qui chdng ri thip theo tiiu chuln ASTM D665 v l an mdn ddng theo ASTM Dl 30 eda phu gia tdng hpp dapc minh hpa blng cac Hinh ty24 - 26, Nhien lieu EIO
E10 + Nuoc Ctit k l i o n g p l u i tjiii
An mdn thep trong hon hop tE 10 * nuoi j l CO phu qiii t o n g h o p
EIO * N u o c n i u o i khong phu gia
i o n ihep Irong hon Itap (EW + nuoc nuioi) EIO + Nadc muoi c6 phu qia t o n g h o p Hinh 24. An mon tiiep trong moi tradng nhien lieuEW (ASTM D665)
Nhien lieu D5
D5 + Nuoc cat k h o n g p h u gia An mon thep trong hon hap fD5 + nuac cdt)
D5 !• Nudc cat co phu gia t o n g hgp
D5 + NUdc m u o j k h d n g p h u gia
An mon thep trong hon hap fD5 + nUac muoi) D5 + Nudc muoi co phu gia t o n g hop Hinh 25. An mon thep trong moi trUdng nhien iieu DS lASTM D665)
Nhan xer;Tac dung dc che cua phu gia tong hpp dUpc the hien rd qua phep thd ASTM D665. Mau thep trong nhien lieu EIO, D5 cd sddung phu gia cd hmh thai be mat sang deu va hau nhU khdng xuat hien vet ri.Trong khi, cac mau thep trong cac nhien lieu khong phu gia co be mat bi ri vdi cac mdc dp khac nhau (td nhe (EIO) cho tdi ri nang {D5)
E10 khdng phu gia An mon ddng trong hon hap EW
E10 + phu gia tong hgp
D5 khong phu gia An mdn Pong trong hon iiap DS
Hinh 26. An mdn dong trong cdc nhiin iliu bio-etanol (ASTIVID130) 5 + i^liLi gia Edng hop
HOA - C H ^ BI^N D A U K H I
Nhdn xit: K i t q u i cho thiy, m l u El 0, D5 cd e l p dd I n mdn l b , trong khi dP m l u EIO, D5 ehda phy gia tdng hpp cd e l p dp la (tdt hon).
3.5.2. Khd ndng chdng dn mdn ddng trong nhiin liiu (ASTM 0130)
Tic dyng de c h l eua phy gia tdng hpp dupc t h i hl$n ro qua p h i p t h d ASTM D66S. M l u t h i p trong n h i i n ll^u EIO cd sddung phy gia cd hinh t h i l b l m i t sing d l u v l h l u nhu khPng x u l t hl^n v l t rl. Trong khi, ele m l u t h i p trong cic n h i i n l i i u khPng phy gia ed b l m i t bj rl vPi
eie mde dd k h l c nhau. Theo b l n g m l u t i l u chuln AS1M D130, n h i i n l l | u EIO khdng cd phy gia dc c h l I n m ^ d thang l b , n h l i n li^u EIO cd phy gia dc e h i l n mdnd thang la.
3.5.3. Khd ndng tUPng thich vdt Iliu vd nhiin Iliu ^
• Cie v l t li$u phi kim lo^i sd dyng d l d i n h gil tfnh tuong thfch v i t ll$u gdm Vltton A, Polyurethane v l caosu buna - N. CIc chl t l l u d i n h g t l bao gdm: mCilc d d t i t h i tieh, thay ddl dd cdng v l thay ddl dd d i n d l i t ^ | _ Kich thudc m l u t h d dupc quy djnh theo t i l u chuln ISO 527-2:1993, k i t q u i do trong Blng 6,7,8,9.
Bdng6. Thay ddi thi tich cdo vdt Iliu
T l n v S t l i ^ U P h u o n g p h a p t h u
% t h a y d o i t h e t i c h
A92 EIO E10 + PG Die
2 Polyurethane 3 Cao su b u n a - N
1 V l t t o n A 2 Polyurethane 3 C a o s u buna-N
Bang 7. Thay doi do cu'ng cua vat lieu
P h u o n g p h a p thCr
% t h a y d o i d o c U n g
A92 EIO E10 + PG D i e s e l D5 DS + PG
•1^,5 12,0 ),;,D 1 0 , ; - 9 3 -9,2 18,3 -20,0 -19,3 -39,4 -46,7 -45,3 26,7 -30,2 -28,6 -45,1 -48.7 -48,3
B d n g 8. Thuy ddi do ddn ddi toi han
Vitton A Polyurethane Cao su buna-N
T i n vat l i l u I Vltton A
Polyurethane I Cao su buna-N
P h u o n g p h a p t h u
ISO 527-2 A92
14,8 -2,9 4,5
EIO '-1,4 -3,5 -4,3
%
t h a y d o E10-4-9.2 -3,7 -8,9
d o d a
=G n d a i t o
D i e s e l 4,0 -3.5 -6,3
h a n D5 -4,2 -3,9 -8,7
DS-t-PG -4,3 -4,0 -8,5
Bang 9. Thay doi do i}en keo dut
ang p h a p t h U
SO 527-2 A 9 2
-26,5 -7,4 -5,8
EIO
•29,4 -13,5 -10,2
°'o t h a y d o i d o b e n k e o dUt E I O - H P G
-29,7 -14,8 -9,5
D i e s e l -13,8
-4,3 -4,5
0 5 -12,6
-6.5 -4,7
DS-i-PG -11,3
-6,8 -4,3
52 D<IIIM-s04/2ai2
SUbienddicotrnh:thlt(ch,dpcyng,dddandaitPihan, dd b i n keo eda ele v l t l i l u phi kim thd nghilm trong cic nhiin lieu xang A92,E10vlD5(edvl khdng pha phy gia tdng hpp) chinh lech khdng nhilu (< 10%) v l d l u n l m trong glPi han cho phip. Vivly.nhien lilu EIO, D5 pha phy gia d c c h l i n mon tdng hpp d i p dng dUpe tieu chuln v l k h i n i n g tuong tich v^t lieu phi kim theo TCVN 1595-88, ASTM D 641 -04 v i ISO 527-2.
-I- Kit q u i do tinh ehlt cua n h i i n lieu EIO, EIO chda phu gia tdng hpp dupe t h i h i l n qua Bing 10,11,
Kit q u i phan tfeh c l e c h l t i l u hda ly cua n h i i n lieu sinh hpc pha etanol trUPe v l sau khi bd sung phu gia chdng i n mdn tdng hpp cho t h i y I n h
hudng eda phy gia tdng hpp den elc tinh c h i t cda nhien lieu sinh hpe l i khdng d i n g ke v i d l u nam trong gidi han eho phep theo elc tieu chuan quy dinh.
- Tinh an todn moi trUdng
loai d l u thye v l t phi thye pham {dlu cpc rao, hat cao su, bdng v i d i u i n thii) eho thiy:
+ Phu gia de c h l i n mdn tdng hpp dupc t d 4 loai d l u khio sit l i d i n xuat cda Imidazolin dya t r i n 5 thanh phln chinh vdi p h i n bd mach carbon Cl 6 v l Cl 8 d l u cd tinh b l o v l kim loai trong cic loai nhiin liiu sinh hpc pha etanol (EIO, D5) tuong dUOng hoic hon phy gia nhip ngoai;
+ Hieu suit p h i n dng tdng hpp Imidazolin ddi vdi cic loai dau thye v i t phi thyc p h l m khio sat n l m trong khoing 65 - 75%. Phln dng tdng hpp phu gia t d d l u cpc r i o eho h i l u suit cao nhat khoing 75% v i h i l u q u i b l o v i cao n h l t (96%) d ndng dp SOppm.
Tinh an toan moi trudng eda phu gia tdng hpp dupc danh g i l qua k h i nang p h l n hCiy sinh hpc cua phy gia theo tieu chuan quy djnh (Hlnh 27).
Theo t i i u chuan OECD (1992), m l u thd nghiem dUpc xem la eo k h i nang phan r i sinh hpe d l d i n g trong mdi truPng nude bien neu tjf I I phan ra sinh hpc sau 28 ngay dat 60%. Mau phu gia t h d nghiem cP k i t q u i kha nang phan ra sinh hpc dat 52%, dupc xem la c h i t cP k h i nang phan hdy sinh hpc nhung khong daac x i p vao loai p h l n ra sinh hpc de d i n g trong moi trudng nude b i l n . 4. Ket luan
Cac k i t q u i nghiin cdu tdng hpp v i d i n h gia tinh ning phu gia chdng I n mdn kim loai (imidazolin) t d elc
ThPI gian
EIO (ASTM D525), phdt ,
Bdng 10. Dd 6n dmh oxy hda EIO, EW*phugia theo thpigian 28 ngiy Ongiy ' 7 ngiy 14 ngiy
!
>480 E10-f50ppmPG
(ASTM D52S), phut
>480 >480
Bdng 11. Cdc tinh chdt cua nhien liiu EiO. EW + phu PhUcmg phap thd E' Thinh phan cit
10% V j 50%V ' 90% V
Hhmjapng lUu huynh (ASTM D2622),%kl C Ham luong oxy (ASTM D4815), %kl
Him lupng nUPc, %kl
El 0 -f phu gia (SOppm)
T;^ trong, 15°C (kg/I) _^
Ap suat hoi bao hPa, 37,8''C, kPa (ASTM D5191)
0,7574 60 An mon ddng (ASTM 130)
Kha nang phan buy sinh hoc
^^»-niiJ gia tc
Tbiri gian, ngiy
HJnh 27. Gidn do bieu dien qud trinh phdn huy sinh hoc
D^H KHl - SP 4/2012 53 ,
H O A - C H E BIEN D A U KHl
-I- Cic loai nhiin l i l u sinh hpc pha etanol v i sd dyng phu gia Imidzolin dupe tdng hpp t d d l u cpc r l o cP cic d i e tinh ky t h u l t d^t y i u c l u theo QCVN v i TCVN (ehdng an mPn, b i n oxy hda, tuong thich v | t li|u, an t o i n mdi trudng).
Thinh edng cda n g h i i n edu n i y d i md ra mdt hUPng nghiin edu mPi n h l m da dang hPa ngudn nguyin li|u tdng hop phu gia de c h l i n mdn. TrUdc diy, cie nghiin cdu tdng hpp phy gia dc c h l I n mdn imidazolin eho n h i i n l i l u sinh hpc t r i n t h i gidi chu y i u di t d c i c axit rilng I I hoac cic td hpp t h i n h p h l n vPi m^ch carbon C18. Phy gia tdng hop I I d i n xult eda imidazolin vdi m^ch carbon p h i n bd t d C,^ - C,, cd k h i n i n g p h i n t i n tdt trong n h i l u mPi trudng d l u khi kh^c nhau, Vi viy, phu gia tdng hpp cp t h i dng dyng I i m chit chdng i n mPn trong cic dUPng dng dan dau, eie lo^i dung dich nUPe bom I p , bdn b l chda nhien l i l u .
T l i l i l u tham khlo
1. Nguyen Hdu DTnh, Trin Thj O i , 1999, (/ng di^ng mpt s6phuang phdp phd nghiin edu cdu true phdn tCf. Nhi xuat b i n Giao dye.
2. Truong Ngpc Lien, 2004. An mdn vd bdo ve kim loai.
Nha x u l t b i n Khoa hpe ky t h u l t Ha NPi.
3. Achyuta N. Acharya, 2011. A novel approach for solid-phase synthesis of substituted imidazolines and bls- imidazollnes J org.chem. Vol 06(25), p 8673-8676
4 A Noda, Shiseido, 2006. Fotiy imidazoline chemistry. Synthesis. Properties and Then Industrial Applications. Journal or oleo science, Vol 55, No 7, p 319-329.
„ 5, Gordon G. Knapp, Banlon R^in}!, ! ! * £ . Coirosion t fihibitors for alcohol containing ii^ot»i /^/I'/'UniteS St«tp' Patent. Patent number 4, i y , p. 367, ^ . ^^^
6. IraJ Mohammadpoor-Baltork, Majid Moghadam, 2008. Supported 12-tungstophosphorlc acid as heterogeneous and recoverable catalysts for the synthesist^
oxazoline, imidazolines and thlazolines under solvent-free conditions. Polyhedron, Vol 27, Iss 2, p. 750 - 758.
7. Ismail Abdelrhman Aiad, A.A. Hafiz, 2010. Sortie imidazoline derivatives as corrosion inhibitors. J. Surfacr.
Deterg,Vol13,p.247-2S4.
8. Jin Zhang, Xiao Wang, Melpan Yang, Kerou Wan, Bing Yin, Yinxia Wang, Jianii 11, Zhen Shi, 2011.
Copper-cataliyzed synthesis of 2-imidazollne5 and theit N-hydroxyethyl derivatives under various conditions.
Tetrahedron Letters, Vol 52, Iss 14, p.l578 -1582.
9. J. Cruz, R.Martinez, J. Genesca, E. Garcia-Ochoa, 2004.Experimentalandtheoreticalstudyof 1 -(2-ethylamino)- 2-methylimldazoiine as an inhibitor of carbon steel corrosm in acid media. Journal of Electroanalytical chemistry, VoL 566,p. I l l - 1 2 1 .
10. Kraig Worrall, Boran Xu, Sebastien Bontemps, and Bruce A. Arndtsen, 2011. A palladium-catalyzed multicomponent synthesis of imidazolinium salts and imidazolines from imines, acid chlorides, and cadxtn monox/de.J.org.chem,Vol76(l), p.170-180.
11. Qiang Zhu and Yixin Lu, 2010.fi3c//esyntfieiBrf bicycllc amldines and imidazolines from 1,2 -diamines. Org.
Lett, Vol 12(181, p 4156-4159
12 Rashnii Ty.igi, VK. Tyagi and S.K Pandey, 2007, Imidazoline and Its derivatives An ove/'v/eiv-JournalofOieo Stience, Vol56. No5, p 211 -222
13, Ray, pmd G.Bistline, JR„ James W,Hampson and W,ir5#r M,Linfield, 1 9 8 3 . i ^ / i e s / s and properties of fottj
%^rj$dqzoline and their N-(2^^oethyl) derivatives. JAO^
• f H a j , No t ^ p . 823 - 828,
DflUKHI-S0 4,'2012