TRNG I HC CNG NGHIP TP. H CH MINH

KHOA CNG NGH HA HC

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N TT NGHIP

M PHNG QUY TRNH SN XUT DIMETYL ETE T KH TNG HP BNG PHN MM HYSYS

CHUYN NGNH: CNG NGH HO DU

Sinh vin thc hin: Nguyn Minh Tr

MSSV: 07704171 Lp: HHD3Kha: 2007-2011Ngi hng dn: Ts Nguyn Mnh HunTp. H Ch Minh, nm 2011TRNG I HC CNG NGHIP TP. H CH MINH

KHOA CNG NGH HA HC

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N TT NGHIP

M PHNG QUY TRNH SN XUT DIMETYL ETE T KH TNG HP BNG PHN MM HYSYS

CHUYN NGNH: CNG NGH HO DU

Sinh vin thc hin: Nguyn Minh Tr

MSSV: 07704171

Lp: HHD3Kha: 2007-2011Ngi hng dn: Ts Nguyn Mnh HunTp. H Ch Minh, nm 2011

TRNG H CNG NGHIP T/P HCM

KHOA CNG NGH HA HC

----- // -----CNG HO X HI CH NGHA VIT NAM

c lp T do - Hnh phc

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NHIM V N TT NGHIP

H v tn sinh vin: Nguyn Minh Tr

MSSV: 07704171

Ngnh: Cng ngh Ha Du

Lp: HHD3

1. Tn n tt nghip:

M phng quy trnh sn xut Dimetyl ete t kh tng hp bng phn mm Hysys.

2. Nhim vXy dng quy trnh iu ch DME thch hp vi cc iu kin v nhu cu thc t ca Vit Nam, bng phng php m phng trong mi trng o da trn phn mm Hysys.3. Ngy giao n tt nghip: thng 3 nm 20114. Ngy hon thnh n tt nghip: ngy 30 thng 6 nm 20115. H tn ngi hng dn:Ts Nguyn Mnh Hun

Tp H Ch Minh ngy thng nm 2011BCN KHOA CNG NGH HO HC NGI HNG DN

TRNG KHOA

(K v ghi r h tn)

(K v ghi r h tn)

I. NHN XT CA GIO VIN HNG DN

Phn nh gi:

thc thc hin:

Ni dng thc hin:

Hnh thc trnh by:

Tng hp kt qu:

im bng s:

im bng ch:

Tp. H Ch Minh, ngy thng nm 2011 NGI HNG DN (Ghi r h, tn)

LI CM N

Sau hn 3 thng thc hin ti, tuy khng phi l mt khong thi gian di nhng em rt vui mng v nhng kt qu t c cng nh nhng kin thc, k nng hu ch m em tch ly c trong qu trnh nghin cu.C c kt qu l nh s quan tm, hng dn tn tnh ca Ts Nguyn Mnh Hun t nh hng ti, n ti liu tham kho, phng php nghin cu trong sut qu trnh thc hin ti, em c th hon thnh tt cng vic. Em xin t lng bit n su sc i vi thy!Bn cnh em cng xin gi li cm n i vi qu thy c trong khoa Cng Ngh Ha ni chung, v trong t b mn Du Kh ni ring l nhng ngi trong sut 4 nm qua gip em trang b nhiu kin thc b ch v l thuyt cng nh thc t i sng, v nay li cn dnh thi gian phn bin gip bi lun vn ny c hon thin hn.

Ngoi ra, em xin gi li cm n ti gia nh v cc bn trong nhm, trong lp l nhng ngi lun bn cnh, ng h, ng vin em trong qu trnh thc hin ti ny.

Em xin chn thnh cm n!

MC LCLI NI U1PHN I 2TNG QUAN V TI

2Chng 1: C S L THUYT V DME V QU TRNH IU CH

21.1 Tng quan v Dimethyl ether

21.1.1 Tnh cht ca DME

31.1.2 ng dng ca DME

51.1.3 nh gi kh nng thay th ca DME vi mt s loi nhin liu thng dng

51.1.3.1 LPG

61.1.3.1 Diesel

71.2 Tng hp DME

71.2.1 Ngun nguyn liu: kh tng hp

101.2.2 Phn ng tng hp DME

101.2.2.1 Nhit ng phn ng:

111.2.2.2 C ch v ng hc phn ng

141.2.3 Quy trnh tng hp DME

141.2.3.1 Cc loi thit b phn ng

141.2.3.1.1 Thit b dng tng c nh (Fixed Bed)

151.2.3.1.2 Thit b dng huyn ph

171.2.3.2 Cc thng s ca qu trnh

171.2.3.2.1 T l nhp liu

181.2.3.2.2 nh hng ca p sut

181.2.3.2.3 nh hng ca nhit

191.3 Xc tc tng hp DME

191.3.1 Xc tc cho phn ng tng hp trc tip DME t kh tng hp

201.3.2 Phng php iu ch xc tc

201.3.2.1 iu ch cht mang

211.3.2.2 iu ch xc tc trn cht mang

221.4 La chn cng ngh sn xut DME

PHN II 25NI DUNG NGHIN CU V KT QU

25Chng 2: M PHNG CNG NGH SN XUT DME BNG PHN MM HYSYS

252.1 Tng quan v m phng v phn mm Hysys

252.1.1 Tm quan trng ca cc phn mm m phng

262.1.2. Gii thiu v phn mm Hysys

262.1.3 ng dng ca Hysys

272.2 M phng quy trnh cng ngh

272.2.1 Cc bc chun b

292.2.2 Nhng d liu ban u

302.2.3 Tnh ton cc gi tr ban u cho qu trnh m phng

332.2.4 Tin hnh m phng

332.2.4.1 Xy dng c s m phng

362.2.4.2 Tin hnh m phng

462.2.3 Kt qu thu c t qu trnh m phng

PHN III 49KT LUN V KIN NGH

49Chng 3: KT LUN V KIN NGH

493.1 Kt lun

493.2 Kin ngh

DANH MC CC HNH MINH HAHnh 1.1 S ph thuc p sut hi ca DME vo nhit 3Hnh 1.2 Cc phng php iu ch kh tng hp 8Hnh 1.3 Thit b phn ng tng c nh15Hnh 1.4 Thit b phn ng huyn ph16Hinh 1.5: chuyn ha CO theo thnh phn nhp liu, lu lng 3000 ml/gxt/h, P=3 Mpa, T =260oC17Hinh 1.6: chuyn ha CO theo thnh phn p sut18Hinh 1.7: chuyn ha CO theo nhit 19Hinh 1.8 nh hng ca nhit n s phn phi sn phm19Hinh 1.9 S l thuyt iu ch - Al2O3 t qung Boxit20Hnh 1.10 Quy trnh sn xut DME ca JFE23Hnh 2.1 chuyn ha CO di nh hng nhit trong phn ng tng hp DME v MeOH di p sut 3-5Mpa30Hnh 2.2 Giao din Simulation Basic Manager33Hnh 2.3 La chn cc cu t tham gia vo m phng34Hnh 2.4 La chn m hnh nhit ng34Hnh 2.5 Giao din reaction tab35Hnh 2.6 Ca s thit lp phng trnh phn ng35Hnh 2.7 Ca s khai bo cc tham s ca dng37Hnh 2.8 Thit lp my trn38Hnh 2.9 Ci t cho thit b gia nhit39Hnh 2.10 Ci t cho my nn40Hnh 2.11 Xy dng dng vo- ra v cc thuc tnh cho thit b phn ng40Hnh 2.12 Xc lp iu kin phn ng trong thit b phn ng41Hnh 2.13 Giao din thit k thp chng luyn42Hnh 2.14 Giao din thit k thit b trao i nhit43Hnh 2.15 Tng quan s m phng cng ngh sn xut DME45DANH MC CC BNG BIU

Bng 1.1 Tnh cht ha l tiu biu ca DME2Bng 1.2 So snh tnh cht ca DME vi cc nhin liu khc4Bng 1.3 nh hng ca nhit ti chuyn ha CO2, CH4 v t l H2/CO ca phn ng tri-reforming vi CH4:CO2:H2O:O2 = 1:0,475:0,475:0,1 ti 1atm9Bng 2.1 M t v cch la chn cc m hnh nhit ng trong Hysys28Bng 2.2 chuyn ha- cc phn ng xy ra trong cc thit b phn ng31Bng 2.3 Thng s ca cc dng nguyn liu37Bng 2.4 Cn bng vt cht trong cc thit b46Bng 2.5 Tng kt dng vo, ra ca cc thit b phn ng48DANH MC CC T VIT TT

DME: Dimethyl ether

LPG: Kh du m ha lng

MeOH: Methanol

MDR: Methanol Dehydrat Reaction

MSR: Methanol Synthesis Reaction

SynGas: Kh tng hpSynthetic LPG: LPG tng hpWGS: Water Gas Shift

LI NI U

Trong thi im hin nay, nn cng nghip th gii trong c Vit Nam ngy cng pht trin nhanh chng, i km theo l nhu cu to ln v nng lng. Vic tm ra ngun nhin liu mi thay th cho nhin liu ha thch truyn thng hin ang l mt nhu cu cp thit ca th gii.Trong s cc loi nhin liu thay th c ang pht trin hin nay DME (dimethyl ether) l mt loi nhin liu sch v kinh t. DME khng mu, d ho lng v vn chuyn. Trn th gii, DME c s dng thay th cho nhiu ngun nng lng ho thch ngy cng tr nn khan him. DME t gy nh hng n mi trng v c th thay th c cho nhiu cht ang s dng hin nay. DME c th s dng nh nhin liu cho my du diesel, my xng du v ng c dng kh t, hoc dng di dng gas nh LPG. DME cn c tnh nng tng t kh t nhin khi dng trong ngnh sn xut in v c cng nhn bi cc nh sn xut nh General Electric, Hitachi, Mitsubishi

Ngoi ra, nguyn liu sn xut DME cng phong ph, c th i t kh thin nhin, than , hoc biomass... thng qua cc qu trnh khc nhau.Vit Nam cng khng nm ngoi xu th chung ca vic nghin cu, trin khai quy trnh sn xut cc loi nhin liu thay th, v vi vic nghin cu iu ch DME t kh tng hp c th c xem l mt hng i ng hin nay ca chng ta n u s thay i v cung cu nng lng trong mt tng lai gn. Vi nh hng chung , mc tiu ca ti ny l tm ra mt quy trnh sn xut DME thch hp vi iu kin thc t thng qua vic m phng bng phn mm Hysys.Tuy nhin do thi gian tip cn cc phn mm cn t, kin thc thc t cn hn ch do chc chn khng th trnh khi nhng thiu st. Em rt mong nhn c s ch bo, gp ca thy c v cc bn ti hon thin hn.PHN I

TNG QUAN V TIChng 1: C S L THUYT V DME V QU TRNH IU CH1.1 Tng quan v Dimethyl ether 1.1.1 Tnh cht ca DME

Dimethyl ether (DME) l mt ete mch thng n gin c cng phn t l CH3-O-CH3 (C2H6O). DME l mt cht kh khng mu, hi c v ngt ti nhit phng v p sut kh quyn. Tnh cht vt l ca DME cng ging nh nhng kh ha lng khc nn c th phn phi, bo qun nh i vi kh ha lng. DME tan trong hu ht cc dung mi hu c phn cc v khng phn cc. DME cng tan mt phn trong nc (76g trong 1 lt nc ti 180oC).

Bng 1.1 Tnh cht ha l tiu biu ca DME [4] Tnh chtGi tr

Khi lng phn t46,7

Nhit si ti 1 bar-24,8oC

Nhit nng chy-141oC

p sut v nhit ti hn5,28 Mpa; 400,29 K (127,1oC)

Khi lng ring ti hn269,9 kg/m3

Nhit chy (kh)31,75 MJ/kg

Nhit to thnh-183 kJ/mol

Nhit dung ring (ti -24oC)2,26 kJ kg-1 K-1

Nhit bay hi (ti -20oC)410,2 kJ/kg

Nhit t bc chy235oC

Gii hn n3 17 tt % trong khng kh

im chp chy-41oC

T trng tng i (kh)1,59

Khi lng ring668,3 kg/m3 (ti 20oC)615,0 kg/m3 (ti 50oC)

tan trong nc5,7 wt % (ti 20oC, 1 bar)36 wt % (ti 20oC, 4,8 bar)

Sc cng b mt (lng)0,0125 N/m

V trng thi pha, DME ch tn ti dng kh v lng, ty theo p sut hoc nhit . Gin pha ca DME nh sau:

Hnh 1.1 S ph thuc p sut hi ca DME vo nhit [1]1.1.2 ng dng ca DMEDME c xem nh l mt ngun nhin liu thay th trong tng lai gn bi cc l do sau:

Theo nh cc tnh cht ca DME trong bng 1.2, th c th thy nhit tr ca DME thp hn LPG v Methane khng nhiu, li d ha lng hn LPG, nn DME c th c s dng thay th cho kh thin nhin hay LPG trong cc mc ch dn dng cng nh trong cng nghip nh chy my, turbine kh.... Ngoi ra, nh c mt nguyn t O trong phn t nn DME chy trit , sch, to t to cn Cacbon v sn phm ph c hi nh CO. Do khng c S, khng c lin kt trc tip C-C, gii hn chy ca DME li cao hn LPG, nn s dng DME s an ton hn LPG

Vi ch s Cetane cao hn nhin liu Diesel (55- 60 so vi 40- 55), li d ha lng iu kin thng, nn n c th thay th nhin liu Diesel. Tuy cn mt s vn khi s dng DME trong ng c Diesel nh nht thp, nhit tr thp hn Diesel, nhng hng s dng DME thay th Diesel l mt hng i y trin vng, v c th xem l ng dng quan trng nht ca DME hin nay. Ngoi ra ng dng khc ca DME nh lm cht y cho cc bnh xt tcc th s dng trong pin nhin liu (Fuel Cell), v n d dng chuyn ha thnh methanol.

Bng 1.2 So snh tnh cht ca DME vi cc nhin liu khc Tnh chtDMEMetanPropanButanMetanolDiesel

Nhit si (oC)-25,1-161,5-42,0-0,564,6180-360

p sut hi (atm 25oC)6,1-9,32,4--

T trng (so vi khng kh)1,590,551,522,00--

Khi lng ring lng (g/cm3, 20oC)0,67-0,490,570,790,84

im kch n (oC)235650470430450250

Gii hn chy (%)3,4-175-152,1-9,41,9-8,45,5-3,60,6-7,5

Ch s Cetan55-600510540-55

Nhit lng theo khi lng (kcal/kg)6,90012,00011,10010,9304,80010,200

Nhit lng theo th tch (kcal/m3)14,2008,60021,80028,300--

1.1.3 nh gi kh nng thay th ca DME vi mt s nhin liu thng dng[4]1.1.3.1 LPGDME c th c phi trn vi LPG (vi t l trn 20%) dng cho vic nu n v si m. Hn hp LPG/DME cn c gi l LPG tng hp (synthetic LPG). Gn y, ti mt s tnh ca Trung Quc nh Qung ng, An Huy ngi ta s dng hn hp 20-30% DME vi LPG dng cho mc ch sinh hot v cho kt qu rt kh quan (theo bo co ti hi ngh Coal-To-Liquids th gii 2008). Theo mt nghin cu mi y ca cc nh khoa hc . v vic s dng DME thay th cho LPG trong cc thit b sinh hot gia nh, hn hp (15- 20% th tch) DME/LPG l ti u v an ton v tng thch so vi s dng mt mnh DME. Vn c th s dng 100% DME, tuy nhin cn phi c mt s hiu chnh v thit b so vi trng hp dng LPG nh hiu chnh ng knh vi t t c hiu sut nhit tt nht. Hn na t l ha trn gia nhin liu vi khng kh cng phi thay i ci thin s n nh ca ngn la.

Tm li khi a DME vo thay th LPG s c mt s thun li nh:

V mt th trng: Kh thi do nhu cu LPG cao V mt cng ngh: Kh thi do c th dng LPG vi cc t l nh sau:

+ Trong dn dng, cng nghip: khng cn ci to thit b, ng c khi t l phi trn di 20% DME. Trong trng hp s dng t 20-100% DME, s cn hiu chnh v thit b vi t v t l ha trn vi khng kh. Tuy nhin, vic hiu chnh ny kh n gin.

+ Trong ng c giao thng vn ti, t l ti a cho php ca DME l 30% trong hn hp vi LPG. V mt mi trng: DME l loi nhin liu sch, khng c cho ngi s dng, gim pht thi CO, cc hp cht mch vng v so vi LPG. T l s dng trn quan im pht thi l 15-20% DME trong LPG.

V mt kinh t: vic s dng nhin liu DME thay th LPG s kh thi v mt kinh t khi gi du mc trung bnh v cao. y c l l u th ln nht ca DME so vi LPG trc tnh hnh gi du th gii tng cao trong thi gian gn y.

1.1.3.1 DieselDME l nhin liu c th thay th cho Diesel trong ng c nn t bt chy v n khng c lin kt carbon-carbon nh hn ch s to thnh b hng, tr s cetane cao 55-60 v kh nng t bt chy cao. Do DME d bt chy hn nn khi dng n trong ng c Diesel th cn phi c b phn d bo an ton hn ch ti thiu trng hp chy n c th xy ra.Tuy nhin, tnh cht vt l ca DME li khc hon ton so vi nhin liu Diesel nh nht thp, tnh nhn hu nh khng c v p sut hi bo ha cao hn. V p sut hi bo ha ca DME cao nn h thng cha nhin liu cn phi c iu p duy tr trng thi lng v cn ch tnh cht khng tng thch vi cc vt liu n hi (gy trng n).

V mt s tnh cht ca DME khc vi ca Diesel nn dng DME thay th th cn phi iu chnh mt s chi tit trong ng c. Nu mun s dng DME trong ng c Diesel mt cch tt nht m khng phi thay i cu trc ng c th vic phi trn l cn thit. Khi phi trn DME vi Diesel c th thu c mt loi nhin liu va m bo tnh cht vt l nh khi s dng Diesel va m bo s chy sch v thn thin vi mi trng hn. nht ca hn hp nhin liu DME/Diesel s c ci thin hn so vi khi s dng DME ring bit. Do c th s dng h thng bm v phun nhin liu ca Diesel m t cn chnh sa li. Tuy nhin, nht ca hn hp nhin liu DME/Diesel vn gy kh khn trong qu trnh s dng v ch mt lng va phi DME thm vo cng s gim mnh nht ca hn hp. Qua kho st[4], ngi ta thy rng nu thm 25% (khi lng) DME vo Diesel th nht ca nhin liu thu c s b gim xung di mc tiu chun ASTM ca Diesel. Vic nghin cu v thm ph gia vo DME hoc hn hp DME/Diesel m bo nht v tnh bi trn ca hn hp nhin liu DME/Diesel khi s dng trong ng c Diesel l cn thit.

Sau y l mt vi nh gi v kh nng thay th Diesel ca DME trong thc t:

V mt th trng: kh thi do nhu cu Diesel cao. V mt cng ngh: T l s dng ti a DME trong Diesel l 25% v phi c nhng hiu chnh thit b do s khc bit v nht v p sut hi bo ha V mt mi trng: L nhin liu sch, gim pht thi CO (43%), CO2 (7,4%), NOx (6%) v mui than (75%);

V mt kinh t: Vic s dng nhin liu DME thay th Diesel s kh thi v mt kinh t khi gi du trung bnh v cao. Ngoi ra, gi nhp khu ca DME thp hn 64% so vi gi nhp khu Diesel s mang li hiu qu kinh t cao hn cho d n sn xut DME.

1.2 Tng hp DME 1.2.1 Ngun nguyn liu: kh tng hp

DME c th i t methanol bng phn ng dehydrat ha. Ngun nguyn liu chnh hin nay iu ch DME l kh tng hp. Kh tng hp l hn hp ca CO v H2. T l H2 so vi CO trong hn hp ph thuc vo loi nguyn liu tng hp ra n, phng php iu ch v mc ch s dng cui cng. Kh tng hp c iu ch t nhiu ngun khc nhau nh kh thin nhin, cc phn on du m, than , hay t sinh khi (biomass), g. Hai qu trnh chnh iu ch l steam reforming v oxi ha khng hon ton (partial oxidation). Hnh sau minh ha phng php iu ch DME t kh tng hp:

Hnh 1.2 Cc phng php iu ch kh tng hp

Phng php steam reforming v oxi ho khng hon tonPhng php steam reforming c th p dng cho cc phn on hydrocacbon, nhit , p sut cao v c mt xc tc Ni. Tuy nhin, mch cacbon cng di, th cng kh thc hin phn ng, v hiu qu khng cao. Do , steam reforming p dng kinh t nht l i vi kh thin nhin. Mt khc, kh thin nhin c tr lng ln, nn l mt ngun cung cp di do cho vic tng hp kh tng hp cng nh cc giai on sau . Phn ng steam reforming i vi kh thin nhin:

CH4 + H2O CO + 3H2

(1.1)

CH4 + 2H2O CO2 + 5H2 (Phn ng ph) (1.2)T l H2/CO ph thuc vo mch cacbon, nhng ni chung s gim dn kh tng mch Cacbon (gim t l H/C)

Phng php oxi ha khng hon ton thc hin khng cn xc tc, nhng iu kin phn ng khc nghit:

CH4 + O2 CO + 2H2

(1.3) Phng php tri-ReformingTrong phn m phng tip sau sn xut kh tng hp cho qu trnh iu ch DME s s dng phng php tri-Reforming kh thin nhin ca tc gi Chunshan Song v Wei Pan[9], y c th xem l s kt hp ca cc phng php steam reforming, oxi ha khng hon ton v thm vo l CO2 reforming. Cc nghin cu ch ra rng ngoi vic tng hp syngas (t l H2/CO khong 1,52,0), phng php ny cn gp phn loi tr CO2 nh phn ng CO2 reforming .Phn ng tin hnh p sut mi trng, nhit phn ng 700-800oC vi s c mt ca xc tc Ni. Tri-reforming gm cc phn ng:H2O + CH4 CO + 3H2

(1.4)1/2O2+ CH4 CO + 2H2

(1.5)CO2 + CH4 2CO + 2H2

(1.6)Theo cc nghin cu[9] t l nguyn liu thch hp cho phn ng tri-reforming l CH4:CO2:H2O:O2 = 1:0,475:0,475:0,1 ti 1atm.Bng 1.3 nh hng ca nhit ti chuyn ha CO2, CH4 v t l H2/CO ca phn ng tri-reforming vi CH4:CO2:H2O:O2 = 1:0,475:0,475:0,1 ti 1atm.[9]Nhit phn ng (oC) chuyn ha CH4 (%) chuyn ha CO2 (%)T l mol H2/CO

85097,9 87,01,67

80096,0 81,11,72

75090,7 73,31,77

70086,0 55,62,14

1.2.2 Phn ng tng hp DME 1.2.2.1 Nhit ng phn ng: DME c th c tng hp t kh tng hp qua 2 con ng:

Gin tip, vi vic s dng hai thit b phn ng khc nhau.

Trc tip, vi h xc tc lng tnh, trong cng mt thit b phn ng:

Tuy i bng con ng no, th bn cht, to ra DME t kh tng hp, cn phi i qua cc giai on sau:

Tng hp methanol

CO + 2H2 CH3OH

(1.7)

G0 =- 29 kJ/molH0 = -90,7 kJ/mol

Dehydrat methanol

2CH3OH CH3OCH3 + H2O

(1.8)

G0 =- 4,5 kJ/mol

H0 = -23,5 kJ/mol

Phn ng tng

2CO + 4H2 CH3OCH3 + H2O

(1.9)

G0 = -62,5 kJ/mol

H0 = -205,7 kJ/mol

Trong trng hp c phn ng WGS xy ra

CO + H2O CO2 + H2O

(1.10)

G0 = -28,6 kJ/mol

H0 = -41,2 kJ/mol

Th phn ng tng s l

3CO + 3H2 CH3OCH3 + CO2

(1.11)

G0 = -91,1 kJ/mol

H0 = -246,9 kJ/mol

CO2 + 3H2 CH3OCH3 + H2O

(1.12)

H0 = -49,4 kJ/mol

Nhn chung, v iu kin nhit ng ca phn ng, ta c th rt ra mt s nhn xt sau:y l cc phn ng ta nhit, c bit l giai on phn ng tng hp Methanol, nn nhit phn ng cn phi c kim sot tt, v y cng l yu t nhit ng cn c ch nhiu nht khi kho st phn ng. Phn ng lm gim s mol kh, ta u thy, tng s phn t kh nguyn liu u vo cho 2 phn ng (1.9) v (1.11) u l 6 mol, s mol sau phn ng l 2. Do , p sut ca h phi cao, thc hin phn ng. p sut, ni chung c duy tr khong 3-7 MPa, v p sut ti u l 5 MPa[12]. Phn ng tng xy ra ph thuc rt ln vo vai tr ca phn ng Water-Gas-Shift (WGS). Do ta phi phn tch iu kin nhit ng trong s nh hng ca phn ng WGS.

1.2.2.2 C ch v ng hc phn ng: Nh cp phn trn, c th tng hp DME theo phng php gin tip nh hai giai on ring r. Song gn y phng php truyn thng ny dn c thay th bng m hnh trc tip nh xc tc lng tnh, s cho hiu qu cao c v chuyn ha v hiu sut. Phng php mi ny cho php gim gi thnh sn xut DME v kh nng s dng DME thay th cho nhin liu truyn thng tr thnh hin thc[5]. Do , cc phn tip theo s da trn m hnh trc tip ny. C ch v ng hc phn ng tng hp DME trn xc tc lng tnh c nhiu nghin cu v tng hp DME, song ch yu l trn lnh vc xc tc v qu trnh, cn ng hc phn ng th mi ch c mt s t nghin cu. Cc d liu ng hc thu c, ch yu l da trn m hnh ca phn ng to methanol (Methanol Synthesis Reaction), dehydrat ha (Methanol Dehydration Reaction) v nh hng ca phn ng WGS. V c ch[1]

Giai on tng hp Methanol:

CO + s1 COs1

(1.13)

H2 + s2 2Hs2

(1.14)

COs1 + Hs2 HCOs1 + s2

(1.15)

HCOs1 + Hs2 H2COs1

(1.16)

H2COs1 + Hs2 H3COs1

(1.17)

H3COs1 + Hs2 CH3OH + s1 + s2

(1.18)

Vi s1, s2 l 2 tm hot ng khc nhau

Giai on Dehydrat ha:

CH3OH(g) CH3OH

(1.19)

O + CH3OH(a) CH3O(a)+ OH

(1.20)

CH3OH(a) + CH3O(a) CH3OCH3(g) + OH

(1.21)

CH3O(a) + CH3O(a) CH3OCH3(g) + O

(1.22)

2OH H2O(g) + O (1.27)

Vi O l oxt b mt c cho l che ph b mt xc tc v a c th l tm axt hay kim. Mt s phn tch nhit ng ca qu trnh:

Ta c hai m hnh nghin cu v mt ng hc trong tng hp DME, v s la chn xc tc hay cc iu kin cng ngh l cng da trn vic la chn 2 m hnh nyM hnh A, l h phn ng thun nghch gm phn ng tng hp Methanol (Methanol Synthesis Reaction - MSR) v phn ng Dehydrate ha Methanol (Methanol Dehydration reaction - MDR):

CO + 2H2 CH3OH

(1.23)2CH3OH CH3OCH3 + H2O

(1.24)Phn ng tng:

2CO + 4H2 CH3OCH3 + H2O

(1.25)M hnh B: l h phn ng thun nghch gm phn ng tng hp Methanol (Methanol Synthesis Reaction - MSR), phn ng Dehydrate ha Methanol (Methanol Dehydration reaction -MDR), v phn ng Water Gas Shift Reaction:

CO + 2H2 CH3OH

(1.26)2CH3OH CH3OCH3 + H2O

(1.27)CO + H2O CO2 + H2O

(1.28)Phn ng tng s l:

3CO + 3H2 CH3OCH3 + CO2

(1.29)Chnh cc phn ng Dehydrat ha v WGS xy ra trn xc tc lng tnh ph gii hn cn bng ca phn ng Methanol ha, loi lng nc sinh ra to H2, chuyn dch cn bng ca phn ng chnh v pha phi. Trong , phn ng MDR ng vai tr chnh ph v hng ro cn bng ca phn ng MSR. Vai tr ca phn ng WGS l phc tp hn. N gip tng cng phn ng MSR v mt ng hc bng vic gi lng nc trong h mc thp. N cng ti iu chnh t l H2/CO trong qu trnh phn ng. Trong vng giu CO, n s cung cp tc cht gii hn l H2 qua phn ng ca H2O vi CO, iu ny tng cng c v mt nhit ng v ng hc ca phn ng MSR. Trong vng giu H2, phn ng WGS s tiu th tc cht gii hn l CO, lm km hm v mt nhit ng v ng hc ca phn ng MSR.

chn lc ca DME trong m hnh B l 0,79 v hu nh t thay i theo t l nhp liu.

M hnh B t c chuyn ha CO v hiu sut DME cao nht, c bit l khi nng CO trong nhp liu t 0,5 n 0,66. M hnh B t hiu sut tng (DME + MeOH) cao hn m hnh kia[1].

M hnh B c nhc im cn khc phc: hiu qu s dng cacbon. M hnh B c chuyn ha CO cao nht trong khi hiu qu s dng cacbon ch t 66,7%. Mt lng ln CO2 sinh ra (t phn ng WGS) song song vi s hnh thnh DME v iu ny s lm tng chi ph tch cng nh phc tp ca qu trnh bi v DME ha lng ha tan CO2 rt tt.V nhng u im ca m hnh B nn trong nhng phn tnh ton tip theo s s dng m hnh ny.1.2.3 Quy trnh tng hp DME 1.2.3.1 Cc loi thit b phn ng C 3 loi thit b thng c dng trong tng hp DME l dng huyn ph, tng c nh Fixed Bed, v tng si Fluidized Bed. Hai loi thit b u c ng dng v nghin cu t lu, trong khi loi th ba, ch c nghin cu gn y. Do c im ca vic tng hp DME l ta nhiu nhit, nn vic gii nhit v kim sot nhit cho h thng l cn thit, c bit khi xc tc c s dng c nhiu thnh phn v cng kh nhy vi nhit . Ngoi ra, cn c yu t khc cn kim sot nh gradient nhit v nng , s khuch tn tc cht v sn phm, hnh dng v tnh cht ca xc tc s dng Vic la chn loi thit b phn ng va ph thuc vo nhng yu t trn, nhng cng ty vo quy m thc hin vic iu ch, sn xut DME. Trong thc t sn xut quy m cng nghip thit b phn ng dng huyn ph t ra thch hp nht nn thng c u tin s dng. 1.2.3.1.1 Thit b dng tng c nh (Fixed Bed) L thit b on nhit, c s dng u tin v rng ri cho cc phn ng xc tc d th. Tuy nhin, n ch yu dng trong nghin cu quy m phng th nghim vi kch thc bnh phn ng nh. Lp xc tc c t trn mt lp m (l cc cht n nh thy tinh, s. Alumia) c kch thc ln hn kch thc ht xc tc. Bn trn lp xc tc, ngi ta cng thng t thm mt lp m nh na.

Hnh 1.3 Thit b phn ng tng c nh[1]Qua c im cu to nh trn, ta c th thy u im ca n l d ch to, thao tc s dng v chi ph thp; s tip xc pha kh - rn tt, nn c th nhn c chuyn ha cao. Tuy nhin, vi loi thit b ny, nhit phn ng ch c th trao i qua thnh thit b. Do , vi dng ny vic ti nhit kh hiu qu, do xc tc s dng trong thit b dng ny phi p ng nhiu yu cu hn v bn nhit. Ngoi ra, kch thc xc tc c s dng cn phi c xem xt, nu s dng ht xc tc qu nh s gy gim p ln khi kh i qua, t lm gim chuyn ha, c bit l vi cc phn ng nhanh.

1.2.3.1.2 Thit b dng huyn ph: Cc thit b phn ng c qui m Pilot tr ln, u dng dng huyn ph ny. Cu to ca thit b kh n gin, gm c bnh phn ng, ng truyn nhit i bn trong. Dung mi tr c nhit dung ln c s dng lm mi trng ti nhit. Cc ht xc tc dng bt mn s c phn tn vo h dung mi. Kh SynGas c sc t di ln vi vn tc th tch thch hp.

L phn ng dng huyn ph c ng dng rt nhiu trong cng ngh ha hc, ch yu trong lnh vc xc tc d th. Vi l phn ng dng huyn ph, vn quan trng nht chnh l s tip xc pha gia cc cu t trong pha kh cng nh s phn tn cc ht rn trong pha lng. Kch c ht xc tc thng nh hn 200 m v c gi l lng nh vo dng chy ri ca pha lng. i vi cc phn ng xy ra nhanh v qu trnh khuch tn nh hng n chn lc sn phm th kch c ht xc tc c gi cng nh cng tt. Nhng kh nng phn tch cc ht xc tc sau phn ng gii hn kch thc ca ht khng nh hn 10 m.

i vi nhng qu trnh, trong xc tc b u c nhanh chng v nhit cc b cng nh cc qu trnh cn c truyn nhit hiu qu th l phn ng dng huyn ph l s la chn thch hp nht. N c th thay th tt thit b phn ng nhiu ng dng tng c nh, c bit khi cn khng ch nhit trong cc phn ng lin quan n mt lng ln nhit c thi ra hay thu vo.

.Hnh 1.4 Thit b phn ng huyn ph[13]

Vi nhng c im nu trn, ta thy thit b phn ng dng huyn ph l mt la chn thch hp trong nhiu qu trnh xc tc d th. Vi cc qu trnh c s hin din pha lng cng nh kch tht ht xc tc cng nh khc phc hn ch ca khuch tn th thit b phn ng huyn ph l u tin s mt v gim p sut nm trong khong cho php. Bn cnh , vi cc phn ng lm gim hot tnh xc tc nhanh chng hay cn trnh ti a cc im qu nhit cc b cng nh nng cao hiu qu truyn nhit, thit b phn ng huyn ph l mt la chn thch hp.

c im phn ng tng hp trc tip DME:

Ta nhit mnh, (H0 = -246,9 kJ/mol nn cn loi thit b phn ng c kh nng cp nhit v gii nhit tt.

L phn ng hydro ha kh CO trn xc tc d th nn cn s truyn khi hiu qu gia cc pha.

Qua , ta nhn thy thit b phn ng dng huyn ph l thit b thch hp nht cho qu trnh tng hp DME trc tip vi nhiu u im cng ngh vt tri so vi dng tng c nh hay dng tng si.

1.2.3.2 Cc thng s ca qu trnh Nh chng ta bit, phn ng tng hp DME trn xc tc lng tnh l mt qu trnh xc tc d th gm nhiu giai on. c im chung l phn ng ta nhit mnh v lm gim s mol kh. Do phn ng i hi xy ra nhit va phi, nhng p sut phi ln, v tng p sut s tng hiu qu qu trnh. Vn tc th tch tng, cng lm gim hiu qu qu trnh. C nhiu nghin cu, cho thy nhng qui lut chung ca phn ng tng hp DME. Mc d nhng iu kin phn ng khc nhau, nhng kt qu kh ph hp nhau.

1.2.3.2.1 T l nhp liu T l H2/CO thch hp l 1-2. th sau cng cho ta thy iu ny:

Hinh 1.5: chuyn ha CO theo thnh phn nhp liu, lu lng 3000ml/gxt/h, P=3 Mpa, T =260oC[11]

Mt nhn xt c rt ra l: nu tng t l H2/CO qu cao th chuyn ha CO s tng, nhng chn lc s gim. iu ny l do tng t l H2/CO th tc phn ng Methanol ha tng, nhng tc phn ng WGS gim, lm H2O to ra trong phn ng Dehydrate ha khng c tiu th bi WGSR nn lm gim chn lc.

1.2.3.2.2 nh hng ca p sut: S ph thuc ca chuyn ha v chn lc vo p sut c th hin qua th sau:

Hinh 1.6: chuyn ha CO theo thnh phn p sut[11]Ni chung, chuyn ha CO tng theo s tng ca p sut. Ta thy c chuyn ha CO t cao nht khong 2600C v 5 Mpa[13].

1.2.3.2.3 nh hng ca nhit : S ph thuc ca chuyn ha v chn lc vo nhit c th hin qua th sau:

Hinh 1.7: chuyn ha CO theo nhit [11]Nhit tng th chuyn ha v chn lc tng do tng tc phn ng Dehydrat ha Methanol. Tuy nhin, s tng theo nhit b gii hn v mt nhit ng ca cc phn ng, c bit l phn ng Methanol ha do y l cc phn ng ta nhit. Ngoi ra, cn l do s gim hot tnh xc tc, nn ta c khong nhit ti u cho phn ng l 230 3000C[13].

Hinh 1.8 nh hng ca nhit n s phn phi sn phm[11]1.3 Xc tc tng hp DME[1],[12] 1.3.1 Xc tc cho phn ng tng hp trc tip DME t kh tng hp i vi qu trnh tng hp DME trc tip hin nay, th v mt bn cht, xc tc s dng c xem l xc tc lng tnh gm hai thnh phn c bn l xc tc cho phn ng methanol ha v phn ng dehydrat ha methanol thnh DME. Nu phng php iu ch lm cho thnh phn tng hp methanol che ph thnh phn Dehydrat ha, th cng lm hot tnh xc tc tr nn rt thp. Nh vy, mt xc tc lng tnh iu ch DME phi bo m c hai thnh phn l pha tng hp Methanol (Cu/Zn, Zn/Cr, Cu/Zn/Al) v tm Dehydrat ha (-Al2O3 hoc Zeolite). H xc tc c bn c nghin cu nhiu l h CuO-ZnO mang trn -Al2O3 hoc H-ZSM-5. Tnh cht cc h xc tc ny khc nhau ch yu qua phng php iu ch v loi cht mang s dng.1.3.2 Phng php iu ch xc tc[1],[12]1.3.2.1 iu ch cht mang -Al2O3:

Al2O3 c nhiu dng th hnh nh , , -Al2O3 Dng hnh th thu c l ty thuc vo nhit , iu kin nung Al(OH)3. Quy trnh chung iu ch Al2O3 ni chung v - Al2O3 ni ring l i t mui Al Al(OH)3 - Al2O3: Trong cng nghip, ngi ta c th i t qung Boxit hay t phn Al2(SO4)3. Quy trnh sau y l i t qung Boxit Al:

Hinh 1.9 S l thuyt iu ch - Al2O3 t qung Boxit[1]V mt l thuyt, -Al2O3 thu c phi t mt s tnh cht nh th tch l xp: 50-70 %) c cu trc ry phn t, ht nhuyn v mn; b mt ring kh ln: 200-450 m2/g. Kch thc mao qun khong 25Ao; khi lng ring cht ng: 0,6-0,9 g/cm3; xp: 0,4-0,7 cm3/g Zeolite:

Zeolite, v mt bn cht cng l mt Aluminosilicat, c th c trong t nhin hoc c th iu ch c. Cc Zeolite tng hp c th thu c bng phng php tng hp thy nhit dng cc tinh th vi kch thc micromet.

1.3.2.2 iu ch xc tc trn cht mang

to xc tc trn cht mang, c nhiu phng php nh tm pha hot ng ln cht mang, kt ta, trn c hc cc thnh phn hot ng, Sol- Gel, Quy trnh chung l to t nguyn liu ban u, qua cc qu trnh to lin kt cc thnh phn ca xc tc ty tng phng php, s to h xc tc dng dung dch hay huyn ph, gel. Tip , ta s em h i lm kh, sy v nung. Xc tc sau khi nung c em i p, to ht, v c kh a v dng hot ng ca n. ba giai on nh hng ln hiu qu ca phn ng nh xc tc l phng php iu ch, iu kin nung v iu kin kh. Trong , phng php iu ch l quan trng nht. C hai phng php c s dng rng ri l tm v kt ta.

Phng php tm:

Khi tip xc thu c trn c s cho cc cu t hot ng dnh ln cht mang c nhiu l xp bng vic ngm hay phun dung dch mui ca thnh phn hot ng vi anion d phn hy nhit nh nitrat, cacbonat ln cht mang rn. Sau thi gian bay hi, xc tc c em i sy, nung thu c xc tc cui cng vi thnh phn oxt bm ln cht mang. Phng php ny l n gin nht, nhng xc tc thu c s c hot tnh khng cao do ta khng kim sot c cc cu t hot ng c th bm ln cht mang hon ton hay khng v s phn b cc thnh phn . iu kin thng, p sut mao qun trong cht mang rt ln, thnh phn hot ng ch c th c tm b mt bn ngoi cht mang m thi. khc phc iu ny, ngi ta tm kt hp vi ht chn khng cht mang; tuy nhin, n i hi k thut cao v tn km.

Phng php kt ta:

L phng php c s dng rng ri nht, v n cho php thc hin c trong gii hn rng bin i cu trc xp v b mt trong ca cht xc tc v cht mang. C nhiu phng php da trn k thut ta. Nu vic ta ch xy ra trn hai cht, th ta c phng php ta thng thng. Phng php ng kt ta c thc hin di s kt ta ng thi ca hai hay nhiu mui. Ngoi ra, ta c th kt hp vic ta pha hot ng v lng ng pha ta ln cht mang rn, c gi l phng php ng kt ta lng ng. Dng kt ta thu c phi dng cc mui d phn hy nhit nh Cacbonat Trong phng php ny, giai on quan trng nht l kt ta vi hai giai on quan trng l to mm ta v pht trin tinh th ta. Ta sau khi to ra, cn phi c gi ha tinh th ta tr nn bn vng hn, to dng tinh th u. Cc yu t nh hng n qu trnh kt ta, t nh hng ti tnh cht xc tc sau ny l nhit ta, pH, thnh phn ban u ca dung dch, nng ca dung dch, cng khuy trn, th t dung dch vo nhau 1.4 La chn cng ngh sn xut DME Nhu cu th trng:Nh trnh by nhng phn trc vic s dng DME nhin liu thay th, c bit l cho LPG l mt hng i ha hn nhiu tim nng i vi iu kin thc t ti nc ta. Do DME gi thnh thp, d dng vn chuyn, tn cha v nht l c th trn chung thnh hn hp vi LPG trong cc thit b s dng cho LPG m khng cn thay i nhiu v thit b s dng.

Theo thng k ca PV Gas[6], nhu cu s dng LPG ca nc ta trong nhng nm qua l kh cao, vi sn lng tiu th ban u ca PV Gas ch t trn 100 ngn tn, sau tng ln 350 ngn tn vo nm 2005 v trong nm 2010 t mc 810 ngn tn. D bo nhu cu tiu th kh ha lng LPG nc ta s vt mc 1 triu tn vo nm 2013. Lng LPG sn xut trong nc ch yu ngun cung t nh my x l kh Dinh C (khong 230 ngn tn nm 2010), v t nm 2009 tr li y c thm ngun cung mi t nh my lc du Dung Qut (khong 340 ngn tn nm 2010), p ng khong 52% nhu cu th ni a.

Trong khun kh ti ny, xin ly mc 570 ngn tn LPG/nm l tng lng LPG sn xut trong nc nm 2010 lm mc chun lm c s cho cc bc tnh ton tip theo.

Theo mt nghin cu v vic s dng DME thay th cho LPG trong cc thit b[4], hn hp c t l khong 20% th tch DME/LPG l ti u v an ton v tng thch hn so vi s dng DME c lp. V vy ti s ly mc 20% v th tch lm t l phi trn DME vo LPG. Cng ngh: phng theo quy trnh trc tip ca JFE (Nht Bn)Nh trnh by trn DME c tng hp theo 2 phng php gin tip v trc tip. Phng php tng hp trc tip mi ch c nghin cu trong vng hn mi nm tr li y, n cho php iu ch DME trc tip t cacbon monoxit v hydro trn nhng loi cht xc tc c bit. Hin ti, 2 hng Air Product and Topsoe Haldor (EU) v JFE (Nht Bn) vi quy trnh phn ng v nhng b quyt ring ca mnh ang i u trong phng php tng hp mi ny.

Hnh 1.10 Cng ngh sn xut DME ca JFE[13]Quy trnh cng ngh gm 3 cm chnh:

1. Reforming kh thin nhin sinh kh tng hp: cng ngh Tri-Reforming[9]. Bao gm cc phn ng CO2 reforming, steam reforming v oxi ha khng hon ton.

2. Tng hp trc tip DME: bao gm phn ng hydro ha CO to methanol, dehydrate methanol to DME v phn ng WGS.3. Cm phn tch sn phm: hn hp sau phn ng s i qua cc thit b hp th v chng ct tch ri DME, MeOH v nc. Hn hp cha phn ng s c hon lu tr li tng hiu sut ca qu trnh. Xc tc:Cht xc tc s dng cho qu trnh tng hp DME dng cht mang -Al2O3, ng kt ta 3 mui Cu, Zn, Al vi t l l CuO:ZnO:Al2O3 = 2:1:6[1]. Xc tc s dng thch hp nht cho tng hp DME iu kin 275oC. Nguyn liu:Nguyn liu chn sn xut DME l methane v Flue gas t nh my in c x l loi b Nit v cc kh c NOx, SOx[9]:

- Kh t nhin Bch H s l ngun cung cp methane s dng cho qu trnh.

- Flue gas t cc nh my nng lng sau qu trnh x l loi b cc thnh phn khng thch hp hoc gy u c xc tc s c thnh phn chnh gm CO2, H2O, O2. y l cc thnh phn ph hp cho qu trnh tng hp Syngas[9].

Khi c c nhng d kin cn bn nh trn, bc tip theo s tin hnh m phng quy trnh cng ngh vi s tr gip ca phn mm Hysys vi mc ch ti u ho cc qu trnh, tm ra mt quy trnh cng ngh ph hp c th s dng trong thc t.PHN II

NI DUNG NGHIN CU V KT QUChng 2: M PHNG CNG NGH SN XUT DME BNG PHN MM HYSYS2.1 Tng quan v m phng v phn mm Hysys[2]2.1.1 Tm quan trng ca cc phn mm m phng p ng nhu cu ngy cng ln cc sn phm du m c v s lng v cht lng, chng ta phi khng ngng ci tin v cng ngh v phng php sn xut. V vy, cc cng trnh nghin cu khoa hc, cc d n thit k c tin hnh, v cng vi s pht trin vt bc ca ngnh cng ngh thng tin, vi nhng my tnh tc cao, cc h iu hnh siu vit, cc lp trnh vin gp phn to ln cho s ra i ca cc phn mm m phng.

Trc y ln k hoch cho mt d n i hi rt nhiu thi gian, v kh nng thc hin d n l kh c th bit trc c. Nhng khi cc phn mm m phng ra i, th cng vic tr nn nh nhng i rt nhiu, chng ta c th m phng hot ng ca cc nh my trong cc ch vn hnh khc nhau, thay i cc thng s lm vic ca bt k n v hot ng no m khng nh hng n qu trnh hot ng chung ca nh my. Ngoi ra, vi nhng tnh nng ca cc phn mm m phng ta c th thit k c cc d n khc nhau, tm c phng n ti u, nhanh chng, cho kt qu kh quan v t hiu qu kinh t, quan trng hn na l p dng c cho hu ht cc lnh vc ca ngnh du kh v cc ngnh cng ngh ho hc, m bo c tnh kh thi cho nhng k hoch ln s c thc hin trong tng lai.

Mt s phn mm m phng:

- Simsci (PRO/II).

- Hyprotech (HYSIM, HYSYS, HTFS, STX/ACX, BDK).

- Bryan research & engineering (PROSIM, TSWEET).

- Winsim (DESIGN II for Windows).

- IDEAS Simulation.

- Simulator 42.

- RSI.

- ChemstationsTrong ph bin nht l PRO/II, DYNSIM v HYSYS

2.1.2. Gii thiu v phn mm Hysys Hysys l phn mm chuyn dng dng tnh ton v m phng cng ngh c dng cho ch bin du v kh, trong cc qu trnh x l v ch bin kh c s dng nhiu nht.

Hysys chy trn Windows l phin bn mi ca Hysim, phn mm ny trc y dng trn h iu hnh MS Dos.

Hysys l sn phm ca cng ty Hyprotech - Canada thuc cng ty AEA Technologie Engineering Software - Hyprotech Ltd. L mt phn mm c kh nng tnh ton a dng, cho kt qu c chnh xc cao, ng thi cung cp nhiu thut ton s dng, tr gip trong qu trnh tnh ton cng ngh, kho st cc thng s trong qu trnh thit k nh my ch bin kh. Ngoi th vin c sn, Hysys cho php ngi s dng to cc th vin ring rt thun tin cho vic s dng. Ngoi ra Hysys cn c kh nng t ng tnh ton cc thng s cn li nu thit lp thng tin. y chnh l im mnh ca Hysys gip ngi s dng trnh nhng sai st v ng thi c th s dng nhng d liu ban u khc nhau.

2.1.3 ng dng ca HysysNh c c s nhit ng hc vng chc v y , kh nng thit k linh hot vi chnh xc cao v tnh thit thc ca cc h nhit ng cho php thc hin cc m hnh tnh ton rt gn vi thc t.Hysys l cng c m phng cng ngh mnh phc v cho nghin cu, tnh ton thit k cng ngh ca cc k s trn c s hiu bit v cc qu trnh cng ngh ha hc. Hysys p ng cc yu cu cng ngh nn tng c bncho m hnh ha v m phng cc qu trnh cng ngh t khai thc ti ch bin trong nh my x l kh v nh my lm lnh su, cho n cc qu trnh cng ngh lc ha du v cng ngh ha hc.S dng Hysys gip gim chi ph chi qui trnh cng ngh do c th ti u cc thit b trong dy chuyn m vn m bo yu cu v cht lng sn phm. Hysys cho php tnh ton vn v tn dng nhit, ti u c vn nng lng trong qu trnh sn xut, tun hon nguyn liu nhm tng hiu sut qu trnh.

2.2 M phng quy trnh cng ngh

2.2.1 Cc bc chun b: Chun b s qui trnh cng ngh: Chun b sn s cng ngh v cc thng s u vo, u ra cn thit (tn gi, lu lng, p sut) cc dng chy cng nh cc thng s vn hnh ca thit b (nhit , p sut, dng chy vo, ra)

Cc khai bo ban u:

Hysys l chng trnh tnh ton rt a nng v thng minh tuy nhin gip chng trnh chy chun xc th phi khai bo v phng php tnh ton nhit ng, cc cht, cc cu t. Hai khai bo trn l bt buc, ngoi ra chng ta cn c th c cc khai bo khc nh khai bo v h n v s dng, khai bo tnh cht (khi cn s dng cu t mi) v.v... Trong nhng trng hp ny chng ta nn khai bo li h n v s dng l SI nu chng trnh ang mc nh h n v khc. La chn m hnh nhit ng:La chn m hnh nhit ng thch hp cho mt ng dng c th ng mt vai tr rt quan trng, nh hng ln n chnh xc ca kt qu m phng.

Mi phng php nhit ng cho php tnh cc thng s sau :

- Hng s cn bng pha K: th hin s phn b cu t gia cc pha iu kin cn bng.

- Enthalpy ca cc pha lng v pha hi: xc nh nng lng cn thit chuyn mt h t trng thi nhit ng ny sang trng thi khc.

- Enthalpy ca cc pha lng v pha hi: nhm phc v vic tnh ton cc my nn, thit b gin n v nng lng t do ti thiu cc thit b phn ng.

- T trng ca pha lng v pha hi: tnh ton qu trnh truyn nhit, tr lc v xc nh kch thc thp chng ct.Ngoi ra la chn m hnh nhit ng thch hp cn da vo mt s yu t sau:

- Bn cht ca cc c trng nhit ng ca h nh: Hng s cn bng lng- hi (VLE: Vapor Liquid Equilibrium) ca cc qu trnh chng ct, c c hoc bc hi, qu trnh trch ly, ...

- Thnh phn ca hn hp.

- Phm vi nhit v p sut.

- Tnh sn c ca cc thng s hot ng ca cc thit b.

Trong bi m phng ny s s dng m hnh PRSV l m hnh nhit ng thch hp nht.Bng 2.1 M t v cch la chn cc m hnh nhit ng trong Hysys[7]

2.2.2 Nhng d liu ban uNh trnh by trong nhng phn trc mc 570 ngn tn LPG/nm l tng lng LPG s dng trong mt nm v, hn hp synthetic LPG c t l khong 20% l mc s dng tnh ton trong nhng phn k tip. Khi lng ring ca LPG v DME (tn/m3, 200C):

= 0,53

= 0,67

Th tch LPG sn xut mt nm:VLPG = = 1075471 (m3/nm)

DME cn thit phi trn vi LPG: (m3/nm)

Sn lng DME ca nh my l:

x 0,67 = 180141 (tn/nm)

Gi s nh my hot ng 50 tun/nm (2 tun d phng s c hoc sa cha bo tr thit b)c tnh v iu kin ca nguyn liu c ch ra di y: Methane:- p sut: 1atm

- Nhit : mi trng

- Trng thi: kh

- Thnh phn: Methane

Flue Gas:

- p sut: 1atm

- Nhit : mi trng

- Trng thi: kh

- Thnh phn: CO2, H2O, O2

2.2.3 Tnh ton cc gi tr ban u cho qu trnh m phngDa theo cc nghin cu[12] th iu kin thun li nht tin hnh phn ng tng hp trc tip DME l nhit t 230-300oC v p sut ti u l khong 5Mpa.

Hnh 2.1 chuyn ha CO di nh hng nhit trong phn ng tng hp DME v MeOH di p sut 3-5Mpa[12]Bng 2.2 chuyn ha v cc phn ng din ra trong tng thit b phn ng[9],[13]Thit bPhn ngChuyn ha

Tri-ReformingCO2 reformingCO2 + CH4 = 2CO + 2H2CO2: 87%

Steam reformingH2O + CH4 = CO + 3H2H2O: 77%

Oxi ha mt phn1/2O2 + CH4 = CO + 2H2O2: 100%

DME synthesisTng hp MeOHCO + 2H2 = CH3OHCO: 60%

Dehydrat MeOH2CH3OH = (CH3)2O + H2OMeOH: 85%

WGSWGSCO + H2O = CO2 + H2-

Sn lng DME ca nh my l

F = 180141 tn/nmLu lng khi lng sn phm:

Gi:

X1: lu lng CH4 u vo qu trnh (kgmol/h)X2: lu lng CO2 u vo qu trnh (kgmol/h)X3: lu lng H2O u vo qu trnh (kgmol/h)X4: lu lng O2 u vo qu trnh (kgmol/h)Gi thit rng t l thch hp nht cho phn ng[9] l:

X1:X2:X3:X4 = 1:0,475:0,475:0,1

Xt phn ng dedydrat ha methanol:

2CH3OH=(CH3)2O+H2O64,08

46,07

29829

21445

Vi DME to ra l 21445 kg/h, tnh c MeOH tham gia vo phn ng Dehydrat l: 29836 kg/h

Do chuyn ha methanol l 85% nn tng MeOH to ra trong phn ng tng hp MeOH l: 35092 kg/h Xt phn ng tng hp MeOH:

CO + 2H2 = CH3OH

28,01

32,430678,35

35092Tnh c CO tham gia phn ng tng hp MeOH l: 30678,35 kg/h, do chuyn ha CO l 60% nn lng CO cn thit l: 51130,6 kg/h

Xt phn ng to kh tng hp (tri-reforming):

CO2 + CH4 = 2CO + 2H244,01

56,020,87*44,01*X2

48,737*X2

H2O + CH4 = CO + 3H218,02

28,010,77*18,02*X3

21,567*X31/2O2 + CH4 = CO + 2H216

28,0132*X4

56,02*X4Tng CO to ra t 3 phn ng trn l:

48,7374*X2 + 21,5677*X3 + 56,02*X4 = 51130,6 kg/h

Do X1:X2:X3:X4 = 1:0,475:0,475:0,1 nn thay X1 vo phng trnh trn ta s c:

38,996X1 = 51130,6

T tnh c cc n s ban u:

y l cc thng s u vo cn thit c th bt u tin hnh qu trnh m phng.2.2.4 Tin hnh m phng2.2.4.1 Xy dng c s m phng

Khi ng Hysys, bt u m phng ta chn File/new/case, hoc s dng phm tt ctrl+N.Giao din Simulation Basic Manager s xut hin, y l giao din chnh thit lp cc gi tr cn bn nh cu t c mt trong qu trnh, la chn m hnh nhit ng, thit lp cc phn ng

Hnh 2.2 Giao din Simulation Basic Manager

Thit lp cc cu t:

Ti th Components tin hnh nhp cc cu t s c mt trong qu trnh m phng, bao gm: H2, CO, CO2, O2, H2O, CH3OH, CH4, DME

Hnh 2.3 La chn cc cu t tham gia vo m phng La chn m hnh nhit ng tin hnh theo cc bc:

Vo th Fluid Pkgs trong giao din Simulation Basic Manager, click chn view. Hysis cung cp rt nhiu h nhit ng ng dng cho cc qu trnh tnh ton khc nhau, chn h nhit ng PRSV.

Hnh 2.4 La chn m hnh nhit ng Thit lp cc phn ng:Cc phn ng trong Hysys c khi to tng t nh thm cu t khi bt u xy dng c s m phng.Chn th Reaction trong Simulation Basic Manager, danh sch cc cu t s hin th trong Rnx Components.

Hnh 2.5 Giao din reaction tab

Bm phm Add Rnx, chn loi phn ng Conversion t danh sch, v nhp cc thng tin cn thit nh cc cu t tham gia vo phn ng, t l cu t trong phng trnh, chuyn ha.

Hnh 2.6 Ca s thit lp phng trnh phn ng

Hnh trn l v d v thit lp phng trnh phn ng CO2 Reforming, phn ng ny c chuyn ha l 87%CO2 + CH4 = 2CO + 2H2

Tin hnh cc bc tng t vi cc phn ng chuyn ha cn li l ta thit lp xong c s d liu v cc phn ng s s dng khi tin hnh qu trnh m phng.

Ring i vi phn ng WGS v y l phn ng cn bng. Nn khi thit lp loi phn ng ta chn Equilibrium v ch cn nhp h s t lng ca phng trnh phn ng. Hysys s t tnh ton chuyn ha, hng s cn bng v cc thng s khc cho phn ng ny da trn nhng thng tin c cung cp khi thit lp Reaction set. Thit lp nhm phn ng:

V quy trnh cng ngh c tin hnh trn nhiu thit b phn ng khc nhau, trong mi thit b s din ra mt hoc mt nhm phn ng nht nh, nn ta cn phi a cc phn ng xy ra trong cng mt thit b vo chung mt nhm phn ng d dng add vo thit b khi tin hnh m phng.Tm li sau khi thit lp cc phn ng v gom nhm ta s c tt c 6 phn ng v 3 nhm phn ng tng ng vi 3 thit b nh trong bng 2.12.2.4.2 Tin hnh m phng

Sau khi hon thnh cc bc chun b cn thit trong giao din Simulation Basic Manager, bm vo phm Enter Simulation Enviroment vo mi trng m phng. Hysys cung cp rt nhiu cng c phc v cho vic xy dng lu trnh m phng gi l Object Palette. T cc cng c trong bng ny c th nhp dng hoc cc thit b cn thit khc cho qu trnh m phng. Sau y trnh t m phng: Khi to dng vt cht:Dng vt cht l mt yu t cn bn khng th thiu trong qu trnh m phng khi to dng vt cht bng cch bm phm F11 hoc chn trong thanh cng c Case (main) v ko ra PFD.

Khai bo cc thng s cho dng bng cch nhp p vo dng. Trong mi trng Hysys dng nguyn liu lun c bn bc t do, tc l Hysys c th tnh ton cn phi cung cp y bn thng tin yu cu. Bn tham s cn thit ny bao gm: Composition (thnh phn), flow rate (lu lng dng), temperature (nhit ), pressure (p sut). Khi xc nh bn thng s th thit lp c mt dng vt cht, v Hysys s t ng tnh ton cc thng s khc ca dng.Thit lp hai dng nguyn liu u vo l Metan v Flue Gas vi cc thng tin nh sau:Bng 2.3 Thng s ca cc dng nguyn liuNameMetan

Temperature25oC

Pressure1 atm

Molar Flow1311,17 kgmol/h

Component Mole Fraction

C11

NameFlue Gas

Temperature25oC

Pressure1 atm

Molar Flows

CO2622.81 kgmol/h

H2O622.81 kgmol/h

O2131,117 kgmol/h

Hnh 2.7 Ca s khai bo cc tham s ca dng

Thit lp cc thit b h tr:Trong quy trnh cng ngh ngoi cc dng vt cht v thit b phn ng l nhng thnh phn chnh, th cc thit b ph tr khc nh my trn, thit b gia nhit, my nn, cng l nhng thnh phn khng th thiu. Chng c vai tr quan trng trong iu tit lu lng; khng ch p sut, nhit ti iu kin mong mun; cng nh nh hng ti ng u khi phi trn cc dng vt cht. My trn (Mixer): s dng trn ln hai dng nguyn liu ban u, m bo s ng u ca hn hp nguyn liu sau khi ha trn.Thit lp Mixer bng cch nhp chn m hnh mixer trong Object Palette. Kt ni u vo ca Mixer vi hai dng nguyn liu Metan v Flue gas, t tn cho dng ra l Mixer Outlet nh trong hnh 2.8

Hnh 2.8 Thit lp my trn

Cc thit b lm lnh, gia nhit, my nn, u cn thit lp dng ra, vo tng t nh my trn nhng cn phi c thm bc ci t p sut hoc nhit , trong tab Work sheet cho dng i ra ty theo iu kin s dng:- Thit b gia nhit dng a dng vt cht c nhit thp ln nhit thch hp cho phn ng. Nh trong giai on trc khi a nguyn liu vo Tri-reforming Reactor cn gia nhit ti Heater cho hn hp nguyn liu ln ti nhit phn ng l 850oC.- Thit b lm ngui c tc dng gim nhit cho dng vt cht c nhit cao xung nhit thp hn. Tu theo yu cu ca tng phn trong s cng ngh m ta c cc thit b lm ngui khc nhau: cooler 1 dng gim nhit dng sn phm i ra t cm thit b tng hp DME xung nhit phn tch; cooler 2 dng lm lnh dng sn phm DME sau khi phn tch, cooler 3 c tc dng h nhit dng MeOH-H2O trc khi vo thit b chng ct.- My nn (compressor) c dng tng p sut cho mt dng kh ti p sut ph hp cho phn ng, ty thuc thng tin c cung cp, compressor s tnh ton cc tnh cht ca dng (nhit hoc p sut), hay cng sut ca my.

Hnh 2.9 Ci t cho thit b gia nhit

Hnh 2.10 Ci t cho my nn

Xy dng thit b phn ng:Trn thanh cng c Case (Main) Click vo General Reactor, chn Conversion Reactor. Double click vo thit b nhp tn cho dng nguyn liu vo, dng sn phm ra, dng nhit - trong phn Connections, th tab Design.

Hnh 2.11 Xy dng dng vo- ra v cc thuc tnh cho thit b phn ngTip tc vo th Reaction, xc lp loi phn ng v nhm phn ng tin hnh trong thiy b. bHnh 2.12 Xc lp iu kin phn ng trong thit b phn ng

n y, v c bn cung cp d kin cn thit cho mt thit b phn ng Hysys c th t ng tnh ton cc gi tr khc. Ngoi ra, trong phn rating Hysys cn c th gip ngi s dng xc lp hnh dng v kch thc ca thit b phn ng.

Trong quy trnh cng ngh sn xut DME c 3 thit b phn ng v cc bc xc lp cc thit b kia tin hnh tng t nh trn, ch khc im i vi phn ng Water Gas Shift th s dng thit b Equilibrium Reactor. Xy dng cm phn tch sn phm:Hon thnh c tt c cc phn trn l ta c mt quy trnh sn xut DME, tuy nhin DME to ra l dng th do cn ln vi hu nh ton b cc sn phm ph v cc tc cht cha phn ng ht. Do sn phm ra cn c a qua mt lot cc thit b phn tch nng cao tinh khit cho DME thnh phm trc khi a vo s dng, cng nh thu li cc sn phm ph c gi tr nh MeOH hoc lng d ca CO, H2 tin hnh hi lu nh tn dng ht hiu qu ca nguyn liu tng tnh hiu qu v kinh t cho dy chuyn cng ngh.Cc thit b chnh s dng trong cm phn tch bao gm: cc thp chng luyn c hi lu nh v un si y thp: thp th nht dng tch dung dch MeOH- H2O l cc cu t nng ra khi hn hp kh; thp th hai c tc dng tch DME khi hn hp kh; thit b tch Component Splitter dng tch CO2 trit ra khi hn hp CO-H2. Ngoi ra tn dng sn phm ph l MeOH cn cn c thm thp chng ct MeOH tch nc, thu hi MeOH cn thit.Quy trnh thit lp cho thp chng luyn gm cc bc chnh sau: chn biu tng Distillation Column trn Oject Pallete, xc lp cc dng vt cht v nng lng vo ra trong thp; nhp s a, v tr nhp liu, c ch hi lu sn phm nh. Tip ci t p sut v nhit cn thit cho cc thit b un si v ngng t, t l hi lu, lu lng sn phn nh. Bm phm Run Hysys tnh ton, nu qu trnh hi t s c thng bo Converged mu xanh l pha di nh trong hnh 2.13, bng khng cn phi tnh ton li cc thng s cung cp cho thp.Ta cng cng c cch tip cn khc khai bo thng tin cho thp m khng cn bit lu lng sn phm nh l khai bo thnh phn cu t hoc l thnh phn cc dng sn phm ca thp.

Hnh 2.13 Giao din thit k thp chng luyn

Ti u ha s dng nhit: Nhn thy rng dng nguyn liu Mixer outlet i ra t my trn trc khi i vo thit b phn ng tri-reforming cn c gia nhit ln ti nhit phn ng l 850oC, mt khc dng SynGas i ra t thit b tri-reforming ang nhit cao li cn phi lm lnh ti nhit phn ng l tng hp DME 275oC. V vy thay v s dng hai thit b gia nhit v lm ngui ring bit, ta c th tin hnh cho hai dng vt cht trao i nhit cho nhau, nh vy s tit kim c chi ph sn xut.

Chn thit b trao i nhit t Object Palette, kt ni dng vo v ra nh hnh 2.14, c th ti u dng thit b trao i nhit, gim p, h s truyn nhit trong phn Parameters. Sau chn nhit dng ra thch hp, Hysys s tnh ton cc thng s cn li.

Hnh 2.14 Giao din thit k thit b trao i nhit Sau khi thit lp, kt ni cc dng v thit b li vi nhau Hysys s tin hnh tnh ton, nu ci t cho cc thit b ph hp th s cng ngh s chuyn thnh mu xanh m, nhng phn no Hysys pht hin c vn s c thng bo li v v tr trn s cng ngh s chuyn thnh mu xanh nht. Cn phi tnh ton li cc thng s ci t xem thch hp hoc c mu thun g vi cc phn khc khng, sau d ci t li thng s mi v active li qu trnh tnh ton Hysys tin hnh kim tra, qu trnh lp i lp li cho ti khi loi b hon ton cc li thit k v s cng ngh chuyn ht thnh mu xanh m.Thc hin xong cc thao tc xy dng trn, ta c mt s m phng chung cho dy chuyn sn xut ca nh my DME nh hnh sau.

Hnh 2.15 Tng quan s m phng dy chuyn cng ngh sn xut DME2.2.3 Kt qu thu c t qu trnh m phngSau khi chy m phng, thu c kt qu cn bng vt cht ca qu trnh nh sau:Bng 2.4 Cn bng vt cht trong cc thit bTri- Reforming Reactor

Vo (Kg/h)Ra (Kg/h)

T l mol H2/CO = 1,68

CO051133,42

H206142,43

CO227409,593563,24

H2O11219,942580,58

O24195,760

CH421035,05441,74

Tng6386063860

DME Synthesis Reactor

Vo (Kg/h)Ra (Kg/h)

CO51133,4220453,36

H26142,431726,22

CO23563,243563,24

MeOH05264,27

DME021445,03

H2O2580,5810966,58

CH4441,74441,74

Tng6386063860

WGS

Vo (Kg/h)Ra (Kg/h)

CO20453,368247,00

H21726,222604,74

CO23563,2422741,44

MeOH5264,275264,27

DME21445,0321445,03

H2O10966,583116,10

CH4441,74411,74

Tng6386063860

T-100

Vo (Kg/h)Ra (Kg/h)

CO8247,008247,000

H22604,742604,740

CO222741,4422741,400

MeOH5264,270,4715263,80

DME21445,0321367,0777,95

H2O3116,107,853108,25

CH4441,74441,740

Tng6386063860

T-101

Vo (Kg/h)Ra (Kg/h)

CO8247,008246,800,197

H22604,742604,720,0144

CO222741,4022540,69200,71

MeOH0,47100,4715

DME21367,0758,8021308,27

H2O7,8507,85

CH4441,74441,580,1501

Tng5541055410

T-102

Vo (Kg/h)Ra (Kg/h)

CO000

H2000

CO2000

MeOH5263,805210,9452,86

DME77,9577,950

H2O3108.25165.652942,59

CH4000

Tng8450,058450,05

Bng 2.5 Tng kt dng vo, ra ca cc thit b phn ng

Nhit (oC)p sut (Kpa)Lu lng (kgmol/h)Nhit lng (kJ/h)

Tri- Reforming ReactorVo850101,32688-3,85*108

Ra850101,35124-1,39*108

DME Synthesis ReactorVo27550005124-2.32*108

Ra27550002933-3,52*108

WGSVo27550002933-3,52*108

Ra394.250002933-3,52*108

Da theo kt qu cc bng trn nhn thy lng DME thu c qua qu trnh m phng l 21308,27 kg/h, xp x vi lng l thuyt ra; ngoi ra cc thit lp cho Hysys u chy n nh m khng bo li. C th kt lun cc kt qu tnh ton ban u l tng i ph hp, v s cng ngh xy dng c c c s ng dng trong thc t.PHN III

KT LUN V KIN NGHChng 3: KT LUN V KIN NGH

3.1 Kt lun

Sau thi gian thc hin, ti thu c mt s kt qu sau: - xy dng c mt m hnh sn xut DME trn quy m cng nghip t kh tng hp bng phng php m phng vi nng sut DME p ng c nhu cu sn xut LPG tng hp s dng trong nc. - Dy chuyn s dng nguyn liu u vo l Flue Gas v Methane c ngun gc t kh thin nhin. - Nguyn liu trc khi cho ra DME sn phm s i qua 3 cm thit b chnh l: tri-reforming to kh tng hp, cm tng hp trc tip DME v cm phn tch sn phm. - Xc tc s dng cho qu trnh tng hp DME dng cht mang -Al2O3, ng kt ta 3 mui Cu, Zn, Al vi t l l CuO:ZnO:Al2O3 = 2:1:6[1].3.2 Kin nghDo l nghin cu qu trnh sn xut DME trn m phng l thuyt, nn cc kt qu thu c l bc nn tng cho cc bc ci tin v sau. Thc t, cn rt nhiu hn ch trong qu trnh thc hin ti nh cha khai thc ht c tnh nng ca phn mm cho mc ch ti u ha qu trnh, cng nh cn rt nhiu vn trong lnh vc tng hp DME cn phi gii quyt. Sau y l mt s xut cc nghin cu tip theo cho kt qu tt hn:- M hnh xy dng vi s h tr ca Hysys l mt phn mm m phng mnh nhng cng cn phi kim chng li bng cch xy dng m hnh pilot.

- ng dng vo thc t cn nghin cu thm v ng hc, bn v thi gian s dng xc tc.

- Do qu thi gian c hn v vic tip cn vi phn mm cha c nhiu nn trong khun kh ti ny ch dng li phn thit lp m hnh sn xut DME m khng tnh ton xy dng h thng iu khin cho qu trnh. iu ny hon ton c th thc hin c nh Hysys, v cn phi c thit lp trong cc bc pht trin tip theo ca ti.- Qu trnh cc s liu tnh ton c da trn bi ton tnh ngc ra nguyn liu t nhu cu LPG ca th trng trong nc l 21445kg/h tc khong 515 tn/ngy. Tuy nhin trong thc t ti cc nc c b dy pht trin DME, thng th nh my c cng sut t 2600-10000 tn/ngy s cho hiu qu cao nht[13].

TI LIU THAM KHO1. Lng Quc Bo (2008), Tng hp Dimethyl Ether t kh tng hp trn xc tc cht mang Al2O3, H Bch Khoa tp.HCM.2. Nguyn Th Minh Hin (2010), Hysys trong m phng cng ngh ha hc, NXB khoa hc v k thut, H Ni.

3. Trn Vnh Lc (2009), Nghin cu kh nng sn xut v s dng Dimethyl ether t kh, Du Kh (8/2009), tr.88.

4. Trn Vnh Lc, H Th M Hnh, Phan Cm Tun Huy, Nguyn Hu Lng, L Cng Tnh, Ng Kim Thanh, Nguyn Th Thu Trang (2009), nh gi kh nng s dng DME lm nhin liu thay th LPG v Diesel, Du Kh (11/2009), tr.20-27.

5. Phm Cng Tc (2004), Nht Bn v chng trnh nhin liu mi DME, Tp ch CN Ha Cht (09/2004).6. Tng Cng ty Kh Vit Nam (2009), Kh ha lng, www.pvgas.com.vn7. Aspen Technology, lnc (2002), Simulation Basic Hysys 3.1, Hyprotech, Canada.8. Aspen Technology, lnc (2002), Operations Guide Hysys 3.1, Hyprotech, Canada.9. Chunshan Song, Wei Pan (2004), Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios, Catalysis Today (98/2004), p. 463-484.10. Japanese DME Forum (2006), DME Handbook, JDF, Japan.11. Javier Eren a, Raul Garona, Jose M.Arandes, Andres T.Aguayo, Javier Bilbao (2005), Effect of operating conditions on the synthesis of dimethyl ether over a CuO-ZnO-Al2O3/NaHZSM-5 bifunctional catalyst, Catalysis Today (107-108/ 2005), p.467-473.

12. Javier Eren a, Raul Garona, Jose M.Arandes, Andres T.Aguayo, Javier Bilbao (2005), Direct Synthesis of Dimethyl Ether from (H2+CO) and (H2+CO2) Feeds. Effect of Feed Composition, International journal of chemical reactor engineering (3/2005), Article A44.13. Yotaro Ohno (2007), New Clean Fuel DME, DeWitt Global Methanol & MTBE Conferenc (12-2007).PH LC

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