Tuy4n t$p Hdi nghj Khoa hgc k^ ni0m 40 nam Vign Han lim KHCNVN Hi Ngi, ngiy 07/10/2015 NHU CAU NANG LU^QfNG VA XU HUOfNG CHE B I E N , SU^ DUNG KHI THIEN NHIEN Luru Ckm Loc* '''' Vien Cong Nghe Hoa hoc,[.]
Tuy4n t$p Hdi nghj Khoa hgc k^ ni0m 40 nam Vign Han lim KHCNVN - Hi Ngi, ngiy 07/10/2015 NHU CAU NANG LU^QfNG V A XU HUOfNG C H E B I E N , SU^ DUNG K H I THIEN NHIEN Luru Ckm Loc* ' Vien Cong Nghe Hoa hoc, Vien Khoa hoc vd Cong nghe Viet Nam 18 - Hodng Quoc Viet, Cdu Gidy, Hd Ngi Email: lcloc@ict.vast.vn Tom t i t Trong giai doan 2000 - 2010 nhu cau nang lugmg the gidi tang 1,5%/nam DSu thd la ngudn nang luong Ion nhat Tdc dp tang nhu cau dau thd nhimg nam 1980 2010 la 1,4%/nam Nhu cau san pham dau d Viet Nam tang 5-5,5 %/nam giai doan 2010-2015, 4-4,5 %/nam giai doan 2015-2020 va dudi %/nam giai dpan tidp theo Xu hudng tang distillates nhe va giam san phim tdi lam thay ddi cdng ngh? che bien diu Cung vdi tang nhanh tieu thy nang lupng, d nhiem mdi trudng cCing tang, lam cho tinh hinh nang luong tren the gioi xku di tuong lai gan Chinh nhung dieu thitc day nghien cuu mdt mat tao cac xiic tac mdi va cac cdng nghe tien tien chd bidn diu, mat khac tim cac nguyen lieu thay the nhu thien nhien, sinh khdi nhim san xuit xang dtd va nhien Ueu diesel than thien mdi tmdng, d ^ iing tieu chuan mdi cua the gidi Trong bdi canh dau thd dang can ki?t, vdi tru lupng tren the gidi hon 6040 ngan ty feet khdi thidn nhidn trd ngudn nguyen lieu tidm nang cho san xuat nhien lieu sach va cac hda chat thiet yeu khac, gdp phan van de an ninh nang lugng qudc gia Hien tdc dp tang trudng nhu cau thien nhien tren the gidi la 2,6 %/nam \'a ciia Viet Nam la 12 %/nam Cdng nghe Gas to Liquids (GTL) chuyen ddi mdt lupng dan^ ke tluen nhien sang cic san pham dang long du de dam bao nhu cau nang luong the gidi 25 - 30 nam tdi, ddng thai tao dieu kien thuan loi hon van chuyen va tdn trii Trong cdng nghe GTL thidn nhien duoc chuyen hda cac san pham va ban san pham quan trpng san xuat nhien lieu sach va cac san phan hda hpc co ban khac nhu hydro, methanol va ammoniac thdng qua cac cdng dpan chinh la san xuat tdng hgp; tdng hop Fischer- Tropsch va hoan thien san pham GlOfI T H I E U I Nbu cau nang lirQmg cua the gidi An ninh nang lugng dang la van dd ma tit ca cac qudc gia tren thd gioi phai giai quyet Ben canh do, da phat trien nhanh chdng cua cdng nghiep hidn nay, hai van de nang lugng va mdi trudrng cang lien he mat thidt vdi Trong tinh trang dau md dang cgn kiet dan truoc tdc dp khai Ihac chong m^t nham phuc vu cho nhu cau cang tang ciia ngudi, cung voi tinh hinh bat dn chinh tri cua cac qudc gia diu md vai trd cua nhien lieu thay thd cang trd nen quan va nhan dugc sy quan tam ciia cac qudc gia cong nghiep phat trien Trong nhiing nam 1980 - 1990 nhu can nang lugng tang ddu %/nam va giai do?m 2000- 2010 toe dp tang tnrcmg la 1,5%/nam Tir nam 1990 ddn 2005 tieu thy nang lugng toan can tang % va lugng CO2 phat thai cung tang % [1] Tidu thy nang lugng tang nhanh nhat ITnh vyc giao thdng van tai va dich vy (tang 37%), dan dyng - 19% Cdng nghiep la khu vyc tidu thy nhidu nang lugng nhat vcri 3 % thi phan, ridp theo la dan dung % va giao thdng van tai - 26% Ddng thdi, cdng nghiep ciing la khu vuc thai nhidu CO2 nhit - 38%, giao thdng van tai - % va dan dung % 149 Tiiu ban: Khoa hoc V$t hau LI Shu cau dau tho va thien nhien DSu tho vcri nhihig uu dijm gia ca phai chang, dl vfa chuyen, t6n trir va chuyen hoa nhien lieu van tai la nguon nang luong Ion nhat Dau tho chiem khoang 44% thi phin ttong thi tnrcmg nang luong thS gioi va 80% nhu cau nhien lieu giao thong van tai duoc san xuit t i nhien heu hoa thach- diu tho Trong nhiing nam 1994 voi su phat triSn ciia nang lugrng nguyen hi va thien nhien, thj phan dau tho nhu c3u nang luong thS gioi giam xu6ng 40% Xu hudng giam thi phan ciia dau tho thi huong nang lucmg tidp tuc va dSn nam 2010 no chiem 37% Mac du thj phan giam nhung diu tho van la ngu6n nang luong Ion nhit tren the gioi Nhu cSu dau tho nhiing nam 1980 - 2010 tang 1,4 %/nam (ngudn UOP 23200-25), muoi lam nam 1994 - 2010 tang tit 3.100 len 3.900 trieu tin/nam Voi t6c khai thac nhu hi^n va trii luong diu hien co cua thS gioi khoang 240.10' tin, chi du khai thac khoang 50 nam Trong b6i canh do, thien nhien vcri trii luong Ion la ngudn cung cap nang lugng sach va tao dieu kien giam luong CO2 phat thai la doi tupng dugc quan tam truoc tien Nhu ciu thien nhien, chit long cua thien nhien (NGL) va hoa long (LPG) tang nhanh nhat cac nguon nhien Heu 15 nam qua Trong thdi ky nay, nhu can thien nhien tang trung binh 2,6 %/nam Trong ke hoach dai han, vdi trii luong Idfn than da va thien nhien la n^dn nguyen lieu chinh san xuat nhien heu long Nam 2004 thien nhien chiem 22% tdng nang luijajg tieu thii tren thS gidi vi du doan se tang den 24% nam 2020 (xem bang 1) Theo Energy Information Administration (EIA), thien nhien duoc dtr bao la dang nhien HSu tieu th\i tang nhanh nhit sau than tren thi gidi tu 1990 dSn 2020 [2] Nam 2004 2020 Bdng /, Thi phdn cua cdc dang ndng lu0ig Khi thien nhien Dau thd Thiiy di?n Hat nhan 22 35 13 24 35 12 Than, sinh kh6i , 24 23 Vdi hii luong thS gidi hien co vao khoang 5.100 ngan ty feet khdi cdn khai thac duoc 65 nam vdi cdng suit khai thac cua nam 1994 Tuy nhien hiu hSt cic cac md Idn nam d vi tri dja ly rat xa ncri tieu thu Vung cd trii luc;mg thien nhien Idn nhat la Trung Ddng, chijm khoang 32% trii luong the gidi va chii ydu la ddnghanh, lay tir khai thac diu Do van chuyen thien nhien dit gip lin van chuyen diu [3], nen h? thdng dudng dng dan cdn chua cd, thi thien nhien vin la san pham phu, gia tri thap 1.2, Nhu cau cdc logi sdn phdm ddu Trong 15 nam gan day nhu cau san phim diu md tang 1,4%/nam Tdng cdng suit cac nha may lpc dan cua thd gidi vao nain 2010 tang ddn 780 trieu tin/nam (10 trien thung/ngay) Xu hudng chung co ciu sir dung diu cua kinh td thd gidi la giam nhu cau diu san xuat didn va nhidt nang dudi dang nhidn lieu ddt Id va tang nhidn lieu ddng co van tai va nguyen lieu hda diu Dudi day din ca ciu sir dung dau thd tren thd gidi (% khdi lufTng): 1980 2000 Giao thdng van tai, dd: 38,6 52 Oto 27,8 40 150 Tuyin tip Hot nghi Khoa hgc k^ niSm 40 nam Vi$n Hin lim KHCNVN - Ha Ngi, ngiy 07/10/2015 Dien va nhiet nang (nhidn lieu ddt Id) Hoa dau Sir dyng cho muc dich phi nang lugng (diu nhdn, nhya ducmg, parafin, cdc.) 2000 2010 51,5 5,2 35 8,0 4,7 2020 2D3D Year Source lEA/SMPSpteedshetfinodeicdcilaba Hinh L Toe tdng nhu cdu cdc dgng nhiin lieu khdc cda thi gi&i Tren toan thd gidi, distillate trung binh (bao gdm dAu hda, nhien lieu phan lyc, diesel, diesel tau thuy va diu dot Id) cd vai trd quyet dinh ve nhu cSu ciia san pham diu, tang vdi toe dp 1,7%/nam 15 nam gan day, la nhidn lieu cd nhu cau tang nhanh nhat Xang dung vi tri thii hai danh sach vdi tdc dp tang trudng nhu cau 1,6 %/nam Mac du LPG va Naphta chiem vi tri thii ba, nhung dugc dy doan la cd toe dp tang nhanh hon xang ddi chiit (1,7 %/nam) Chi co dau FO la giam nhu cau voi toe dp 0,2%/nam Xu hudng tang nhu cau san pham sang va giam nhu cau san pham n^ng (hinh 1) dan den ddi hoi phai thay ddi cong nghe chuyen hoa va cdng suat ciia cac lpc nha may lpc - chd bidn diu Su thay doi co cau nhu cau dau thd tuong iing voi sy phat trien vugt trdi cua cac phuong tien giao thong vdi dpng eg ddt so vdi sy phat tridn nhu cau nang lugng nhiing nam gSn day Hien ty phan hda diu chiem sd lugng so sanh khdng Ion- khoang 8% khdi lugng nhu cau diu thd Trong cac nude phat trien ty phan dao dong frong khoang 2^10% Hoan toan cd kha nang vao cudi the ky XXI hda dau la hudng sii dung nhat ciia diu thd Do dd, van de tim eac ngudn nhien lieu khac thay cho dau thd lai cang trd nen cap bach Vcfi uu diem la chay sach va de van chuyen duong dng den thang ngucri tieu dung nen thidn nhidn dugc uu chupng cho myc dich sudi am va san xuat nang lugng va chiing nhanh chdng thay thd diu cac nha may san xuat nang lugng LPG da chiem dugc thi trudng cdng nghiep che bidn ndng san d Hoa Ky Bdn canh san xuSt didn hien chung dugc nghien ciiu dd sir dyng lam nhien lieu van tai thay cho xang va diesel, nhung thieu he thdng phan phdi, yen can phai cai thien cdng nghe ciia dpng CO va dau tu cao phyc vy cho chuydn doi dang nhidn lieu da han chd ung dyng ciia NGL va LPG thay the cho xang va dieasel Viet Nam cd hii lugng tiem nang 0.9 ddn 1,2 ty m^ diu va tu 2.100 ddn 2.800 ty m^ Trii lugng da dugc xac minh la gin 550 trieu tin diu va trdn 610 ty m^ Trong 1/3 la co the khai thac thuong mai; diu dang khai thac; 1/3 sd dd 151 Tiiu ban: Khoa hoc Vat Iliu khoang 300 ty m^ cd chiia ndng CO2 cao Trong thdi ky diu cua nganh cdng nghiep Viet Nam khd (cd phin chu ydu la methane) dugc su dung lam nhidn lieu cho san xuit didn (chidm khoang 70-85% tdng ±i hoiong khd) Theo xu thd chung- nai doj-i 2011-2015 la mpt giai doan chuin bj quan hgng de dua cdng nghiep Viet Nam chuydn sang buac phat tridn moi manh me, voi qui md Ion (H 21 ty mVnam) va hinh dp chd bidn cao hon (chd bidn sau, sii dyng da d^g) vdi san phim la nhidn lieu long sach va hda chat Theo Dy bao nhu ciu ttong bao cao Tdng thd: cr Viet Nam ty Id nhu cau cac loai san pham diu nhu sau: Xang Kerosene Dau Diesel Dau FO 2010 0,18 1,93 -0,5 2015 0,18 2,03 0,32 Nhu vay, can ddi nhu cau cac loai san pham diu thi ty Id san pham sang cang tang Ro rang, bdn canh sy phat trien nhanh chdng cua nhu can cac dang nhien lieu thi sir can kiet cua cac ngudn nhien lieu hoa thach khidn cho van de nang lugng thd gidi rat khd khan tuong lai khdng xa Trong bdi canh do, sy dao dpng ve gi^ dau hien ciing vdi sy gia tang phat thai dioxit carbon boat dgng cua ngudi thiic diy vide nghien ciiu nhim tim ngudn nang lugng thay thd nliien lieu hda thach MOT SO KET QUA CHINH II Xu hucmg che bien va sir dung thidn nhien H.L Cong nghe chuyin hda thdnh long (GAS TO LIQUID -GTL) Cdng nghe Gas to Liquids (GTL) vdi kha nang chuyen ddi mOt lugng dang kd thidn nhidn sang cac san pham diu dang Idng dii de dam bao nhu cau nang lugng the gidi 25 - 30 nam tdi GTL cUng tao dieu kidn cho sy phat trien kinh te cua nhiing md thien nhien d cac viing xa thi trudng tieu thy San pham ciia GTL la cac dang hydrocarbon long chat lugng cao, cd the dugc su dung tryc tidp lam nhidn li?u hoac pha trdn vdi cac san pham nhien lieu ciia dau thd cd chat lugng thap hon Cdng nghe GTL khdng chi tao co hdi su dyng hidu qua ngudn thien nhien d dang nhien lieu long (tang hieu qua kinh td) ma cdn giiip giam d nhiem mdi trudng san pham cd ham lugng luu huynh thip, kha nang chay triet dd, giam lugng CO thai Them vao do, san phim ciia qua trinh GTL df dang long nen thuan loi hon van chuyen va giam chi phi dau tu xay dyng he thdng ducmg dng Do do, GTL la sy lya chpn tiem nang tuong lai nham dap iing nhu ciu tidu thy nhien lipu va yen cau nghiem ngat vd moi tnioTig Ngudn methan ddi dao (la phan chinh ciia thien nhien, chidm 87 %Vol.), nhung viec su dung nd cd mpt sd han che lien quan vdi didm chdfp chay va nhiet dp sdi ciia thap (-161,6 °C o atm) Mac dii hien thien nhien dugc su dyng lam ngudn nhien lieu san xuat nang lugng, nhung qua trinh chuydn hda methane nhidn lieu giao thdng (nhu methanol hoac hydrocarbon phan doan trung binh) cac qua trinh cd tinh canh tranh kinh td se dugc iing dung vdi tam co Ion hon Ndu qui trinh gas - to - liquid (GTL) cd the canh tranh vdi san xuat xang tir dau md thi hang ty" lit nhien lieu long se dugc san xuat tir thidn nhidn Cong nghe GTL: Nhieu he xiic tac dugc nghien cuu cho chuydn hda methane tdng hgp, alcohols va cac san pham cd gia tri khac Methane la hydrocarbon rat ben nhiet ddng ty nhien va be gay hen ket C-H phan tir methane ddi hdi 152 Tuyin tip Hoi nghj Khoa hgc kf niem 40 nim Vien Hin lam KHCNVN - Hi Ngi, ngiy 07/10/2015 lugng dang ke nang lugng Viec chuyen hda tryc tidp methane nhien lieu va san phim hda diu van cdn la mdt thach thiic Idn ddi vdi nganh cdng nghiep va khdng hip din ve kinh te, ngogi le trii reforming hgi nude (steam reforming) va oxy hoa chpn lpc (partial oxidation) [4] Do dd, cdng nghe GTL chuyen hda thien nhien phai trai qua cac cdng dgan chinh la i) San xuat tdng hgp; ii) Tdng hgp Fischer- Tropsch va iii) Hoan thien san pham (hinh 2) Dung moi Cho NMLD Nhi^D ligu truns bioli Sip/DSu nhifn Parafin mach thang Hinh Cdc phuang phdp chuyin hoa thien nhien (Chu thich: SRM: Steam Reforming; ATR (autothermal reforming): Reforming tu cdp nh POX: oxi hda mgt phdn) Do trai qua nhieu budc chuyen hda hda hgc nen san pham ciia cong nghe GTL rat da dang tii naphtha, xang, dau hda, DME, diesel, diu nang, sap cho den cac san phim hda dau nhu dung mdi, methanol, nhung san pham chu yeu la cac san pham trung bmh (xang, dau hda, diesel, diu nang) phuc vy cho nhu cau nang lugng Hidu suat san pham phu thupc nhidu vao cdng nghe dugc ap dyng, dieu kien van hanh (ap suit, nhidt dd, ty Id Hi/CO), phin xuc tac va dang thiet bi Cdng nsjie GTL dugc nhieu cdng ty nghien ciiu, thuong mai hda va iing dung nhidu noi tren the gidi nhu cac nha may dugc xay dyng d Nam Phi, Quata, Malaisia Hifu qua ciia qua trinh GTL: Vide chuyen hda tryc tiep than thanh nhidn lifu long va hda chat khong cdn dugc ap dung, cdn vide chuyen hda methane tryc tiep cac hda chat nhu methanol, ethylene hoac benzen cho ddn van cdn it cdng Tuy nhien cdng nghe chuyen hda than da va methanee tdng hgp da dugc xac lap Khi tdng hgp cd the sii dung cho san xuit dien hoac chuyen hda nhien li?u than thien mdi trudng va hda chat thdng qua qua trinh Tdng hgp FischerTropsch (FTS) San pham ciia qua trinh GTL cd thd canh tranh voi san pham san xuat tir dau thd va tuong lai ciia qua hinh phu thugc \-ao gia ciia diu thd Yeu td mau chdt de thuc 153 Tiiu ban: Khoa hgc V$t Ii0u hien qua trinh GTL la gia diu thd yen thi trucmg Vi nhidu ly do, cd sy bien ddng chinh tri cac nuoc san xuit diu, gia diu thd khd doan truoc Gia dau tho tang manh nhirng nam diu th^p nien 80 cua thd ky 20, sau giam manh nhimg nam 1985-1995 va l£ii tang nhanh ddn nam 1999 Dy an dya fi-en thi6n nhien gia thip co thd x-ugt qua dugc giai d o ^ gia diu thip va cdng ngh? GTL trd nen hip din gia diu thd la 20 S/thimg va mo rgng nganh cdng nghiep GTL se kha thi [5] Qua hinh GTL se khdng kha thi ndu gia diu tho giam xudng ddn 16 $/thung va tri thai gian dai Vdi gia diu thd hi?n cd liic tang manh den tren 100 $/thung, cd luc lai xudng thip, nhung ciing khdng diip han 50 S/thung thi nen cdng nghiep cd kha nang phat tridn manh 112 Sdn xudt nhien lifu tit oxit carbon Chuydn hda methane tdng hgp vdfi ty Id COIHT khac thdng qua vi$c kdt hgp methane vdi hoi nude hoac oxi (Reforming hoi nuac; Oxy hoa timg phan va Reforming khd) la hudng che bidn thien nhien quan trpng nhat va cd cdng suat Idn nhit, chiem 45 - 60% dSu tu cac qua trinh "hda hpc Cj" Trong san phim chira hdn hgp vdi ty Id H2/CO khac (1 :1 -3:1) va mot lugng CO2 (khdng qua 13%) LTu the quan trgng cua cac qua trinh dya tren tdng hgp la no de dang chuy^ hda san pham thuan tidn cho van chuyen nhu methanol hoac hdn hgp cac hydrocarbon long Vi ly mdi truong va kinh te hidn methane cd uu the hon than da san xuat tdng hgp Vdi nguyen lieu methane, chi phi dau tu cho nha may thap han va qua trinh cd hieu qua cao hon trudng hgp chi co 25% carbon chuydn hda CO2, tir than da cd 50% carbon chuydn hda CO2 Tu cac ngudn Idii thidn nhien, than da va sinh khdi (biomass) tdng hgp (CO +H2) dugc didu che Tir tdng hgp nhien lieu sach va cac hda chit khac se dugc san xuat (dugc minh hpa hinh 3) Alcohols l- Hinh Cdc sdn phdm tir tong hgp Trong khuon khd bai bao chiing tdi gicri thieu huong iing dyng tronp i xuat nhien lieu thay the Trong cac san pham neu hinh ben canh san xuit Ml ^HI ITnh vyc nang lugng cd the ke den methanol, alcohol, nhien lieu giao th' ^ ^ FT diesel Tuy4n l^p Hdinghi Khoa hoc ky ni$m 40 nam Vien Han lam KHCNVN - Ha Noi 07/10/2015 11.2.1 San xuit xang va nhien lieu diesel Tit cac chit chua mpt nguyen hi carbon (hop chit C,) cd thd tdng hop duoc bit ky nguyen lieu chiia hydrocarbon nao Do dd hda hgc hdn hgp CO va H2 gianh dugc su quan tam to Idn Tong hgp Fischer-Tropsch (FTS) la qua trmh chuyen hda xtic tac tdng hgp (H2 va CO) tihien lieu giao thdng sach (phan doan xang va diesel), cac hgp chat trung gian, cac chat chiia oxi va nhua nang Trong tucmg lai gin, nhu ciu nhien li?u san xuat tu than da va thien ithien tang cao Thach thiic chinh viec ap dtmg Fischer-Tropsch theo hudng siin xuat nliien lieu giao thdng la cho diu tu san xuit phai kha thi vd mat kinh te so vdi chi phi thap ttong san xuit tir diu [6] 500 ThO, AlkanphaD nhanh va alcohol, r, 400 Ni (Ru) 200 Ni ; Co Pjlrafin Olefin 100 Hinh Kite tdc vd diiu kien chuyen hoa xuc tdc di thi cua tong hgp Qua hinh Tdng hgp Fischer- Tropsh (FTS) cho san pham cudi la alkan, alken va hgp chit chiia oxi nhu rugu, aldehyd, keton, axit va eter Thay ddi phan xiic tac va dieu ki?n phan iing ta cd the thay ddi phan san pham (xem hinh 4) Trong cac xuc tac kim loai thi sat, coban, niken va ruteni cd hoat cao nhat cho tdng hgp Fischer - Tropsch Xuc tac niken d 150 -250°C va ap suat bar cho san pham chii yen la methane; xiic tac cobalt 150 -250°C va ap suat 1- 25 bar cho san pham chii yen la parafin Cf-; xiic tac sit d 250 -350°C va ap suit 20 -30 bar cho san phim parafin, olefin va aromat, cdn xiic tac Ru o -100°C va ap suat tren 100 bar cho san pham chu ydulipolyetylen Trong qua trinh tdng hgp Fischer- Tropsh, tir cac oxit carbon cd the dieu chd dugc cac nhien li?u hydrocarbon hr methane ddn wax (sap) (hinh 5) Khdi lugng phan hi trung binh ciia san pham tren cac xiic tac khac giam theo thii ty sau: Ru > Fe > Co > Rh > Ni > Ir > Pt > Pd [7] 155 TiSu tian: Khoa hoc Vat li$u San xuit nhien lieu long nhan tao theo phan ling tdng hgp Fischer- Tropsh tit tdng hop dugc thuc hien diu tien vao nam 1923 d Diic vdi nguyen lieu la hdn hgp CO va hydro ±u ttr than Su xuit hien ciia diu thd gia re tren thi trudng qudc te khien cho qua ttinh khdng phat tridn Tuy nhien ttong nhihig nam 50 cua the ky XX san xujt nhien lieu dong co tu CO va Hj tten xiic tac sit dugc thuc hien Hang Sasol da xay dimg ba td hgp vdi cdng suit tdng tten ttieu tin/nam vdi tdng hgp san xuat tii than Trong thdi gian d nha may cua hang MOSGAS ciing tdng hgp nhien lieu theo phuong phap nay, nhimg vdi tdng hgp tii thien nhien a = Khiiniljigphillnenmacn Hinh 5, Cdc sdn phdm cua qud trinh Fischer- Tropsh (FTS) tir long hgp ^^ ^ Phan Idn cdng nghe FT ttong thap nien qua deu dua tten qua triiih tdng hgip Fischer- Tropsh nhi$t thip (LTFT) (200-240°C) Ca hai xdc tac sit va cobalt djn dugc su dung frong qua frinh LTFT dd san xuat hydrocarbon wax mach dai, parafin yl diesel khdng luu huynh Do xiic tac cobalt cd dp bdn va chuydn hda mdt lin cao hon xiic tac sit [8] nen xiic tac cobalt dugc coi la su lira chgn phu hgp cho qua triul LTFT, frong xiic tac Fe phii hgp hon Co frong chuydn hda nguyen lieu biomaa cd ty le Hi/CO thap Vdi muc dich didu che nhien lieu long vdi chgn Igc cao vi phan ling d ap suat tuong ddi thap nen chung tdi chgn cac xiic tac tren co sd cobalt [9, 10, 11] thu san pham la phan doan xang cd phan chii ydu la n-parrafin vdi tri s6 octan RON dat khdang 40 Hien mdi chi cd cac nha may Fischer-Tropsch thuong mji d Nam Phi (SASOL) Tuy nhien nhieu nha may mdi cd kd hgach xay dimg d Hoa Ky frong khu vuc diu Alaskan Nhu cau cung cap nhien lieu diesel sach va hieu qua cao cho cac dgng co diesel cii tien thay cho xang hien dang dugc su dung ttong xe tai, xe the thao va cac phuang ti?ii v|n tai khac cang tang [12] Tuy nhien, lugng hat thai rSn rtr ddng co diesel cao gap mudi lan so vdi ddng co xang Do dd, nhien lieu mdi ben canh yen ciu phai co tii sd cetan cao va quan ttgng la phai dap iing tieu chuan thai mdi, dac biet giam h?t thai ran Dii lieu cho thay dua mdi 1% oxy vao nhien heu diesel bing each ttdn chit oxy hda nhu glycolether lugng hat rin thai giam 4-10% [12] Su hip dan cua qiia trinli tdng hgp Fischer-Tropsch la san xuat cac phan doan nhien lieu diesel cd ham luong luu huynh va thom rat thap, chi sd cetan cao, va dac biet ddt sach frong ddng co diesel* Du an nghien ciiu cua trudng DH Pittsburgh [12] nhSm muc dich chuydn Jida tonj hgp nhien lieu diesel sach chiia 4-10% khdi lugng oxy ttong chuoi hydrocarbon Nhien heu FT-diesel cd tri sd cetan cao, va se giam xudng cdn khoang 60 kh; K156 Tuyin tip Hgi nghi Khoa hgc kf niim 40 nam Vign Hin iim KHCNVN - Hi NOi, ngiy 07/10/2015 cac nguyen tur oxy hrong chudi hydrocarbon Nhien lieu hda tan diu diesel khoang va giam lugng hat tiiai ran hieu qua Vien Nghidn ciiu Tay Nam (SwRI) pha Xson 15% dimethyl acetal, cd 6% oxy, vao diesel khoang lugng phat thai hat ran giam 40% Nhu vay, san pham FT dugc sii dung nhu phu gia cho diu diesel diu md de giam phat thai va tang tri sd cetan Cac nha may Shell FT d Malaysia sir dung xiic tac cobalt san xuat nhidn lieu diesel vai tri sd cetan khoang 70; nhidn li?u khdng chiia cac chat tham va luu huynh Bang Califomia da nhap khiu nhien lieu diesel FT hi Shell, pha Ihdm lugng nhd nhien lieu diesel diu mo dd dap iing tidu chuin mdi trudng II.2.2 Methanol vd cdc alcohol nang Khi tdng hgp cdn la nguyen lieu cho tit ca cac nha may san xuit methanol va tdng hgp Fischer-Tropsch Hien nay, mdi nam the gidi tieu thy trdn 25 trieu tin methanol Nhieu nha may san xuat methanol dugc xay dyng a Hoa Ky va tren thd gioi Methanol va cac san pham nhidn lieu van tai chiia oxy ddng vai tro quan trpng chuang trinh CFFLSCl Tdng hgp Methanol \k mdt nhiing phan iing quan trgng hda hpc Cl Nhu can methanol tren the gidi khdng ngiing tang, nd dugc sir dyng lam dung mdi, nguyen lieu san xuSt formandehyde, acid acetic, nhien lieu ddng co hoac phu gia Loai nhien li?u van tai pha methanol hidn tai cd ten M85, la hdn hgp 85% methanol trdn vdi 15% xang khdng chi cd tri sd octane 87 Theo tinh toan ciia Hdi ddng Nang lugng Califomia (Califomia Energy Commission) '"xang" M85 giam 50% sy phat thai ddc h^i vao khdng so vai xang [13] Thdng qua qua trinh "Methanol to Gasoline" (MTG), MeOH dugc chuyen hda xang Ngay tir dau nhihig nam 1970 qua hinh MTG dugc Mobil phat tridn dd san xuat xang sit dyng giao thdng Mdt nhung nha may nhu vay dugc xay dyng a New Zealand vao nhiing nam 1980 Tuy nhien, mdt nhiing nhugc diem ciia methanol sir dung lam nhidn lieu la tinh an mdn cua nd ddi vai cac kim loai bao gdm ca nhdm Trong nhimg nam 1990, lugng Idn methanol dugc sii dung d Hoa Ky dd san xuat phy gia cho xang la methyl tertbutyl ether (MTBE) Ben canh sir dyng tryc tiep lam nhien heu, methanol (hoac ethanol, it thdng dyng ban) dugc su dung lam phan qua trinh transester hda triglycerides de thu biodiesel Vi^c san xuat cac san pham tii methanol giiip lam giam phan nao sy phu thudc vao ngudn nguyen lieu d^u md Ethanol la nhien lieu thay the hap dan vi nd la nhien lieu sinh hpc tai sinh va nd la hgp chat chiia oxy, nhd cd the giam mudi thai ddng CO diesel trdn diesel vdi ethanol Tinh chat, dac diem, su anh hudng cua hdn hop diesel - ethanol ddi vcri hgat dgng, dn dinh va thai ciia ddng co diesel, cung nhu kha nang thuong mai hda dugc nghien ciiu [14] Hdn hgp pha trdn 10% ethanol va x5ng khdng chi (ElO) da dugc thuong mai hda a Hoa Ky Sir dung diesel trpn ethanol dugc nghien ciiu nhung nam 1980 va dugc bidt den vdi tdn ggi ethanol-diesel blend, dugc chap nhan cho ddng ca diesel Do gia ethanol cao nen hon hgp dugc sir dyng tnrdng hgp khan hiem nhidn lieu Gin day, tinh kinh td san xuat ethanol diu|n Igi hon va nd cd the canh tranh vdi nhien lieu diesel tieu chuan Sy quan tiim sir dung ethanol-diesel pha trdn dugc dac biet (^uan tam d khia canh giam thai Ngudn nhien lieu hda thach cang khan hiem va su phu thudc cang tang cua Hoa Ky \'ao diu thd nhap khau da dan den quan tam md rpng su dung nang lugng sir.!- hoc Cac cam ket gan day ciia chinh phu Hoa Ky nham tang nang lugng sinh hpc 157 Tiiu tian: Khoa hgc Vgt li^u ^ ,^^^-,^_»^—^^ len ba lin frong 10 nam tao them dpng luc cho vide tim kidm cac nhidn lieu sinh hpc kha thi Lien mmh chau Au (EU) ciing da thdng qua de nghi tang cudng sir dyng nhign lieu sinh hgc it nhit la 2% thj phin ddi vdi xang va diesel vao cudi nam 2005, tang den tdi thidu la 5,75% vao cudi nam 2010 Trong hai thap nien cudi cua thd ky 20, nhimg tidn bd ldm cong "gh? apng CO, din ddn tidt kiem nhidn lieu cao hon hong van tai Viec giam lugng thai tu ddng CO trd mdt ydu td quanft-gngIrong sy phat tridn dpng co mai va cac nha san xuit dang tap trung nang lugng va ngudn luc nhim dap iing tidu chuan diai Co quan Bao vd Mdi trudng Hoa Ky (US Environ- mental Protection Agency (EPA) va EU dk Do dd viec sii dyng cac nhien lieu phi truydn thdng nhu mgt phuang tien dd dap ling lihung yeu cau dd da dugc chii y IL2.3 Phu gia cho nhien lieu Phu gia cd vai trd quan trpng ddi vdi tinh chat cua nhien lieu Mgt sd phu gia tang tri sd octan dugc biet ddn nhu tetraethyl chi, MTBE va mdt sd hgp chat thom nhu benzene, toluene Tuy nhien vi tinh ddc ndn nhiing phy gia dang hi loai bo Alcohol cung la chit tang hi sd octane ty nhien va khdng cd vin de ve mdi tmdng Hon mudi nam qua, viec tdng hgp hdn hgp alcohol dugc quan tam nhu cau sit dung chiing lam chit tang octane tang Ethanol va methanol dugc sir dyng lam phy gia cho xang Cac alcohol cao dugc uu thich han methanol vi chiing cd bay hai thap hon va kha nang hda tan hydrocarbon cao hon [15] Alcohol c6 khoang sdi thich hgp cd the dugc sii dung lam phu gia cho nhien lieu diesel Cac alcohol cao vira lam tang tri sd cetan ciia diesel, viia giam mupi thai Methanol va alcohol cao hon cd the ddng thdi san xuat tir tdng hgp b^ig each sir dung cac xiic tac khac Nhidu tai lieu da gidi thieu qua trinh tdng hop methanol tir CO va hydro sii dyng xiic tac chiia Cu-Zn [16] Hdn hgp alcohols cd the dugc san xuat tir tdng hgp vdi vipc sii dyng xiic tac molybden, ddng va tungsten [15] Bang each cai tien xiic tac va qua trinh cd the tang chgn lpc tao alcohol cao, Tir ethanol cd the san xuat diethyl carbonate (DEC), chat dugc sir dyng nhu phy gia chiia oxy cho xang va diesel de giam thai DEC dugc tdng hgp thong qua qua trinh oxi-carbonyl hda ethanol pha tten xiic tac dj thd CuCl2/PdCl2 mang tren than hpat tinh dugc nghien ciiu [17] Ether vd cdc hop chdt chira oxL Cac hgp chat chiia oxy nhu ether la phy gia cai thien mdi trudng tiem nang ddi vdi nhien lieu giao thdng van tai Them cac hgp chit chiia oxy vao xang va diesel lam tang nhidt chay, cai thien hieu suit ddng ca va tao didu kidn de nhien lieu chay sach, din den lam giam lugng CO va hydrocarbon chua chay het thai Dimethyl Ether (DME), san pham quan trgng tir tdng hgp, dugc su dung lam chat phan tan thay the cho chlorofluorocarbons, nguyen lieu cho tdng hgp hda hpc va lam nhien heu diesel Vdi yeu cau nghiem ngat vd mdi trudng nen tetra etyl chi - phu gia tang tri sd octan cho xang, hi cam sir dung MTBE la phu gia octan cao hieu qua nhat, nhien mpt nhirng nguyen lieu de san xuat MTBE bi thidu hut la isobutilen va gia cao DME dugc san xuat tir thidn nhidn, ngudn nguyen lieu re hon, dugc sir dung lam phu gia tang tri sd octan cho xang va lam nhidn lieu diesfeL La nhien lieu than thien mdi trudng DME dugc su dung lam nhien lieu diesel thav l S phii hgp cho mpi thci tiet (khdng bi ddng dac o thai tiet Ignh) Qua trinh san xuSt DME hi thien nhien gdm ba cdng dgan, san xuat tdng hgp, san xuit methanol 158 Tuyen tap H^ nghj Khoa hgc ky nigm 40 nim Vien Han lam KHCNVN - Ha Ndi, 07/10/2015 va san xuat DME hi methanol Cdng nghe ba giai dgan phiic tap va dit tidn Gin day xuat hien cdng nghe san xuat DME mgt giai dgan tir tdng hgp cua hang Hardor Topse vdi che cong nghe dn hoa va chgn Igc cao Cac hgp chat chiia oxy co the dugc san xuit tii methanol hoac olefin hoac tryc tidp tu cac alcohol san xuat tu tdng hgp bang qua trinh FTS Sii dyng cac ether cao hon lam phy gia nhidn lieu vai myc tieu them chit chiia oxy cd ap suit thip va hoa tan nuac thap han so vdi hgp chat chiia oxy phan tir lugng thip nhu MTBE, ma gin day da chju ap luc ve mdi trudng Thi dy, ether hda 2,3-dimethyl-l-butene (DMIB) va 2,3dimethyl-2-butene (DM2B) vdi methanol 11.3 Sdn xuit xang tit condensate khL Cac cdng ngh^ tien tien che bidn condensate deu nhim ddn lam tang tinh than thi?n mdi truong cua xang dtd va nhien lieu diesel de dap img tieu chuin chit lugng ciia the gioi Trong nhung nam gan day, ydu cau bao ve mdi sinh, cac chi tieu ve phan hda hpc ciia xang da trd nen rat khat khe trdn quy md toan ciu Lien minh Chau Au dat gicri han ham lugng cac hgp chit dgc hai hoac cd kha nang gay ddc hai xang cho nam 2000 la: luu huynh 150 ppm, olefin 18%, benzen 1%, cac hydrocarbon tham 42% Nam 2005 ham lugng luu huynh dugc giam xudng cdn 50 ppm va ham lugng cac hydrocarbon thom xudng 35% [18], tinh ddc hai ndn benzene va cac dan xuat bi han che dan Theo tieu chuan Euro-4 va Euro-5, ndng dp hydrocarbon thom khdng qua 25 vol% va ndng dp benzene khong vugt qua vol% Tu 2011, tieu chuan Mobile Source Air Toxics (MSAT II) cd hieu lyc, ndng dp benzene hi giai han d mite 0,62 vol.% [19] Van de cang trd nen gay gat cac hgp chat phy gia chiia chi hoan toan bi loai bd, cac phy gia tang cudng tri sd octan chiia oxi nhu MTBE hoac ETBE, dac biet la MTBE, da chirng td la nhiing chat ddc hai va dang bi cam hoac giam dan sir dyng Dieu lam giam tinh chdng kich nd cua xang va can dugc bu bang cac phan octan cao va phy gia Voi muc dich giam hydrocarbon thom xang can thay thd san pham reformat bang cac phin cd tri sd octan cao khac, ddng thdi khdng thuc hien qua trinh ttiom hda cac hydrocrbon Vi vay, thay vi tang cuong ham lugng cac hydrocarbon tham xang, nhung bien phap lam tang ham lugng cac hydrocarbon parafin m^ch nhanh xang bang cac qua trinh alkyl hda va ddng phan hda cac nparafin nhe dang tro ndn biic thiet Ddng phan hda cac n-parafin thap cang ddng vai trd quan trgng, dac biet ddi vai nhu cau tang tri sd octan ciia xang Qua trinh ddng phan hda cho phep tang tri sd octan cua xang nhcr tang ham lugng isoparafin va giam nong hydrocarbon thom Theo [20], nam 1995 d Hoa Ky ti phan ciia san pham ddng phan hda cac hgp phan cua xang da chiem 11,6%, cdn d Chau Au thi ti le dd la 5%, nhung dang tang mpt each nhanh chdng Bong phdn hda cdc n-ankan thdp: Tinh chdng kich nd cao va dp bay hcri cao cua s.^-n pham ddng phan hda cac hydrocarbon C5 -^ Ce khien cho chiing trd cac cau tu cd gia tri cho xang chat lugng cao Nhd isomer hda cd the tang tri sd octan cua phan doan xang nhe (nhidt dp sdi cudi la 62 hoac 85°C) len 15 ^ 20 dan vi Do dd cimg vai sy tang trudng san xuat xang octan cao thi cdng suat isomer hda ciing tang Trong mdt so nha may cac cym ddng phan hda va reforming dugc ket hgp mdt lien hgp didng nhat de san xuat xang octan cao Trong dd, phan doan vcri nhiet soi cudi den 85 °C dugc hydro - isomer hda cdn phan doan voi nhiet dp sdi > 85°C dugc thuc hien 159 Ti4u tian: Ktioa hoc V$t li^u reforming hda Sau qua trinh hydro - isomer hda san pham cd RON - 80 ( MON = 76) ; Ddi vdi cac n-ankan thSp, tang sd nguyen hi carbon frong phan ni too dg phan ling tang, ddng thdi can bSng cimg chuydn dich vd phia cac isoankan Chinh yi vay, frong phan ling ddng phan hda hdn hgp n-ankan, vi du hdn hgp C5 - Ce, hi^u suat chuydn hda phan hi cd sd nguyen tu carbon nhd hon tang so vdi trudng hgp ddng phan hda don le Tuy nhien, can luu y la tang sd nguyen tu carbon frong phan ti nankan thi cudng cac phan iing phu hydrocracking va cdc hda cung tang, cho nen can cd su dieu chinh nhiet do, ap suit va ti le moi hydro/nguydn lieu thich hg^ Do butane khdng bi ddng phan hda tten xiic tac zeolite, ndn nguyen lieu ly tudng can co ndng butan thap, cho phep giam cdng suat so dd Cac parafin C7+ bi cracking va hydro hda propane va butane, lam giam hidu suat san pham chinh De sa dd hoat dgng hieu qua, tao isomerat cao va it tao cdc, thi ndng C^+ttongnguyen heu khong qua 5%, cdn ty le n-Cs/iso-Cs cang cao cang tdt Ndng benzene khdng dugc cao hem 2%w., de khdng cin thuc hien hydro hda benzene Trong cdng nghidp, tten xuc tac Pt mang tten alutnino-silicat va zeolit, ddng phin hda mdt lan cho phep tang tri sd octan (ON) tii 70 len den 83 va ddng phan hda hdi luu cho phep tang RON til 70 len 92 Trong nam 2005, Hang Sued-Chemie AG da dat nhiem vu nghien ciiu de xuat cum ddng phan hoa phan dgan pentane - hexane dd thu phan octan cao vdi RON tten 86 Trong nam 2010 Nga da dua vao van hanli xudng ddng phan hda ttong lien hiep «AHXK», giai quydt ddng thdi cac vin dd nhu giam ty phin xang dtd cd tri sd octan thap ttong "xang ndn" tu 41,7 xudng 9,8 %w.; giam h t o lugng benzene ttong reformat nang xudng ddn l%w; san xuit 274,4 ngan tan/nam san pham isomerizat vdi RON = 86 va sir dung nd lam phin xang oto de tang dac tinh cua xang va san xuit xang s^ch theo tieu chuin EURO Lien hiep «BHHHHe(J)TexHM» dua hai phuong an ddng phan hda - nhiet ming binh (xiic tac HnM-02) va ddng phan hda nhift thip (xiic tac mi-06) ON thu dugc frong ddng phan hda mdt lin phu fliudc vao phan nguyen lieu, tmoc tidn la ty le parafin C5/C6 frong nguydn lieu Khi tang ty Id C5/C6 tti sd octan tang Nguyen lieu chiia -50% pentane ddng phan hda fren xuc tac HnM-02 cho san phanc6 RON = 79,5, cdn ttdn Hn-06 cd RON = 82,5 Ndu thirc hien phan tach va ttian hoan { n-pentane ttd lai nguydn heu, khdng phu fliudc vao pliin nguydn lieu cd the thu dugc san phim cd RON = 86-88 Vdi muc tang chi phi van hanh viia phai cd thd tang ON len 16 - 20 don vi Hieu suat fliu isomerat Cs dat ddn 98 - 98,5% Qua triul hydroisomer hda phan dgan 70-100 (105) °C (Cj-C,) ttdn xiic tac FHn-Od, cho phep tang ON cua xang len 10 -14 don vi, dat gia fri ttung binh RON = 72, ddng thdi giam khdng chi ndng dg benzene ma ca ndng tdng hydrocarbon thom ddn gia tri dap ling tidu chuan Chau Au Hieu suit catalizat dn dinh dat 89 - 91%w Nhu ciu Hj cho phan ! ling la 0,3%w so vdi nguyen lieu I Qua frmh ddng phan hda n-parafm thip d Viet Nam dugc quan tam nghien ciiu tii nhiing nam 1980 - 1990 bdi vi, ngoai nhimg ly bit huge phai h^n chd ham lugng cac hydrocarbon fliom phin ciia xang, hiu hdt cac ddng hanh va thien nhidii d nude ta ddu giau cac hydrocarbon n-parafm Hidn hang nam Tdng Cdng ty Diu Viet Nam cung vdi cac ddi tac nude ngoai dang khai thac khoanc IS - 19 trieu tin diu va - ti met khdi thien nhien va ddng hanh Nam 2005 cac nha may chd bien cua PefroVietnam da san xuit gan 350 ngan tin LPG ' 1?() ngan tin ngung tu (condensate) San lugng thidn nhidn dang c6 m' t" s 160 Tuyin tip Hgi nghj Khoa hgc ky nijm 40 nim Vign Hin lam KHCNVN - Ha Ngi, 07/10/2015 trudng cao va nam 2010 dat 10 ti met khdi/nam Dd la tien dd rat Idn cho viec phat tridn qua trinh dong phan hda n-ankan nhe phuc vu nhu cau xang ciing la san phim dang cd miic tang tnrdng cao De tiep can van de chiing tdi da tidn hanh mdt sd nghien ciiu sii dung zeolit ddng phan hda n-hexane va ngung ty nhim tao ca so khoa hgc cho vi?c trien khai cdng nghe dong phan hda n-ankan lihe tucmg lai Nghien cuu cua chiing tdi cho thiy xiic tac Pt [21, 22] va xuc tac Pd [23] mang hen zeolite HZSM-5 la cac xiic tac hieu qua cho qua trinh isomer hda n-hexane va hdn hgp n-parafin nhe Ngoai san xuat xang la hudng chinh, condensate ciing dugc sii dyng dd san xuat cac nhidn lieu Idng khac Nhien lieu phan lyc dugc san xuit tir phan dgan 135 230 °C cua condensate Condensat la nguyen lieu cd gia tri de san xuit nhien lieu diesel Phan dgan vdi gicri ban sdi (150-180) -^ 300 "^C dap ung tieu chuin diesel mua ddng, cdn phan dgan (190-200) -^ 310-350 ^C dap iing tieu chuin diesel mua he Nhu vay, condensate la nguyen lieu cd gia tri de san xuit xang, nhien lieu phan lyc va diesel Ngoai condensate ciing cd the trai qua che bien hda hpc dd nhan alcohol, phin octan cao, dung indi, hydrocarbon tham, cac chit kim ham KET LU.4N Nganh cdng nghiep cang cd vai trd quan trpng sy phat tridn kinh td cua cac qudc gia Ngay tren the gidi, cdng nghe su dyng thien nhien (natural gas-NG), ndn (compressed natural gas - CNG) va hda Idng (liquidfied petroleum gas - LPG) da phat trien rdng nhieu nganh cua nen kinh td qudc dan Khi hydrocarbon thu tir thien nhien la nguyen lieu cd gia tri cho san xuat cac san pham hda hpc khac Tit methane, phan chinh ciia thien nhien, thu dugc cac san pham va ban san pham quan trpng san xuat nhidn lieu va cac san phin hda hgc khac Sy phat trien ciia nganh cdng nghiep tao huong khoa hpc mdi la "Hda hpc C]" va "Ky nguyen methane" Ben canh methane, kinh nghiem cua nhieu nude cho thay, nganh cdng nghiep hda dau va hda chat phat trien dya tren cac hydrocarbon nhe nhu etane, propane, butane Thyc te, tat ca cac cdng ty hda diu tir Ion deu ling dung he che bien khi; tach etan va propan, nhiet phan cac hydrocarbon nhe, san xuat hda chat va polymer tdng hgp dya tren nguyen lieu Tai lilu tham khao Worldwide trends in energy use and efficiency The online bookshop International Energy Agency, 2008 Energy Information Administtration (EIA), Annual Energy Outlook 2002: Washington, DC, DOE/EIA-0383, 2002 Wisam Al-Shalclii, Gas to Liquids Technology (GTL) s.l.; Baghdad, 2006 L Li, R.W Borry, E Iglesia, Chem Eng Sci 57,4595 (2002) Andre Steynberg, Mark Dry, Fischer-Tropsch Technology, PubUsher: Elsevier Science & Technology Books, 2004 G P Huffinan, I Wender, Fuel Process Technol 71, (2001) M.A Vannice./Cam/ 37,449(1975) B Jager, Stus Surf Sci Catal 119 25 (1998) 161 TiSu tian: Khoa hoc V$1 ll^u Luu cim Ldc, Trin Cao Dire Tmh, Lac Kidn Tridu, Nguyen Manh Huan,_Bui Thanh Huong, Dang Thi Nggc Ydn, Nguydn Tri, Hoang Tien cudng, Hd Si Thoang, Tap chi Hoa hgc, 49(5AB), 206 (2011) 10 Luu cim Ldc, Nguydn Manh Huin, Lac Kien Tridu, Bui Thanh Huong, Dang Tij Nggc Ydn, Tap chi Hoa hpc, 49(A), 190 (2011) 11 Luu Cam Loc, Lac Kien Trieu, Ho Si Thoang, Huynh Thi My Trang, Nguyen Manh Huan, Nguyen Tri, Bui Thanh Huong, Int, J Nanotechnology, 10(3/4), 313 (2013) 12.1, Wender and J W Tiemey, Department of Chemical and Pefroleum Engineering,; 1249 Benedum Hall, University of Pittsburgh, Pittsburgh, PA 15261 13 Y Okamoto, K Fukmo, T Imanaka, S Teranishi, J Phys,Chem, 87, 3740 (1983) 14 A C Hansen, Qin Zhang , Peter W.L Lyne, Bioresource Technology 96, 277 (2005) 15 HuifangShao, E L Kugler, D B Dadyburjor, S A Rykov, andLG Chen, Applied Catalysis A: General 356, 18-22 (2009) 16 V E Osttovskii, Catal Today, (3), 141 (2002) 17 N Roh, B.C Dunn, E.M Eyring, Fuel Process Technol, 83, 27 (2003) 18 T G Kaufinan, A Kaldor, G F Stuntz, M C Kerby, L L Ansell, Catalysis Today, 62, 77 (2000) 19 E R Palmer, S H Kao, C Tong and D R Shipman, Hydrocarbon Processing, TX:Mustang Engineering L P., Houston, pp 55-66 (2008) 20 S Rassaev, Thermal and Catalytic Processes in Petroleum Refining, Marce! Dekker, Inc., New York - Basel, (2003) 21 Luu Cam Loc, Dao Thi Kim Thoa, Bui Vinh Tuong, Nguyen Tri, Giang Thanh Hung, Tap chi Hoa hoc, 50(4A), 324 (2012) 22 Dao Thi Kim Thoa, Luu Cam Loc, Nguyen Tri, Hoang Mmh Nam, Giang Thanh Hung, Ho Si Thoang, Tap chi Khoa hoc -Cong nghe, 51 (5B), 118 (2013) 23 Thi Kim Thoa Dao and Cam Loc Luu, UOP Publising, Adv Nat, Sci,: Nanosd Nanotechnol 6, doi:10.1088/2043-6262/6/3/035014 (2015) 162 ... tri thii ba, nhung dugc dy doan la cd toe dp tang nhanh hon xang ddi chiit (1,7 %/nam) Chi co dau FO la giam nhu cau voi toe dp 0,2%/nam Xu hudng tang nhu cau san pham sang va giam nhu cau san... Dy bao nhu ciu ttong bao cao Tdng thd: cr Viet Nam ty Id nhu cau cac loai san pham diu nhu sau: Xang Kerosene Dau Diesel Dau FO 2010 0,18 1,93 -0,5 2015 0,18 2,03 0,32 Nhu vay, can ddi nhu cau... giam xu6 ng 40% Xu hudng giam thi phan ciia dau tho thi huong nang lucmg tidp tuc va dSn nam 2010 no chiem 37% Mac du thj phan giam nhung diu tho van la ngu6n nang luong Ion nhit tren the gioi Nhu