Chueng 4 SAN XUAT H,, CO VA KHi TONG HOP 4.1, GIGI THIEU CHUNG Khi téng hop 1 hén hop khf ciia CO va H,. Ty 1é Hp/CO thay déi tuy thude vio nguén nguyen lieu, phuong phép sin xuit va myc dich mg dung, Trong chi¢n tranh Thé gidi thi I, khi téng hep duoc sin xuat bing phuong phép khi hod than va duoc ding 4 Dute dé sin xuat hén hyp hydrocachon léng theo cong nghé Fischer-Tropsch dimg cho xéng. Cong nghé khi hod than hign nay hau nhw khong duge tng dung vi gid thanh sin phim cao, tuy nhidn né vin duge duy ui é MOt sé nude c6é nguén than dé déi dao va ré (Nam Phi). Qué tinh steam reforming khi tu nhién duce dp dung 6 nhing nude c6 nguén khé lon nhu My, Arap Xéut, trong khi d6 chau Au thudng sit dung qué wink steam reforming phan doan naphta (chtfa cde hydrocacbon ti C5 = C10). Khi khéi luong phan tir cia hydrocacbon ting (ti 1é H/C cita nguyen Jigu gidm) thi ti 1 Hy/CO trong sin phdm gidm. Ti lé nay La 3 khi sir dung nguyén itu metan; 2,5 déi vdi etan; 2,1 doi véi heptan va nhé hon 2 d6i véi cde hydrocacbon nang hon, Qué trinh oxy hod khong hoan toin khéng sir dung xiic tde cting cé thé duge sit dung dé san xuat khi téng hop, nhung ti 1é H,/CO thap hon so vi qué trinh steam reforming. Khi téng hop 1a sin phim trung gian quan trong. Hén hop CO va Hy 6 thé duge sit dyng dé sin xuat metanol, téng hop hydrocacbon theo cong ughé Fischer- ‘Tropsch. tng hop andchit va rugu theo cong nghé Oxo, Khi téng hop 1a nguén chinh dé sin xuat Hy ding cho sin xut amoniac. Amoniac lai 1a nguyén ligu du quan tong dé téng hop ure, nitrat amon va hydrazin, Qué tinh téng hop metanol va amoniac 1a ciie qué trinh xe tie ditu tign duge ap dung véi quy mo lén vao dau thé ky 20, . Nha may amoniac déu tign duge hing BASF xay dyng vao nam 1913 véi ning suat chi c6 10 ngin tdn/ndm, dén nim 1995 sin kong amoniac da tng lén 100 trigu tn/nim, Hign nay hon 600 nha may sin xudt amoniac dang hoat dong én thé gidi, mdi nha may ¢6 nang suat 1000 + £500 tan/ngiy. Nha may san xudt metanol du tigm duoe xAy dmg vao nam 1923 da dénh dau bude khéi déu cho nén cong nghiép hos hoc hign dai. Metanol 1A nguén nguyén ligu 97quan trong dé sin xudt cée hoa chat nhu formaldehit, din xuat clo, MTBE... 40% Jugng metanol duge ding dé san xuat formaldehit. 4.2, CAC PHUONG PHAP SAN XUAT H,, CO VA KHi TONG HOP Cac phuong php chinh sin xuait Hz, CO va khi téng hop bao gém: * Steam reforming ki ty nhién va céc sin phim diu mé + Oxy hod khong hoan ton khi tr nhién va ede sin phim déu md, * Khi hod than 4.2.1. Sin xuat hydro va khf tng hop bang phuong phip reforming hoi nude (steam reforming) 4.2.11. Nguyen ligu dau va phuong phép xi ly nguyén liéu du Nguyen ligu dau sit dung cho qué tinh reforming hoi nuée c6 thé 1a khi tw nhién hoac phan doan naptha. * Khine nhien ‘Trong khi ny nhién, ngoai thinh phin chinh 14 metan cdn cé mat Iueng nhd cée hgp chat hydrocacbon phan tir lugng thap, No, CO., cdc hgp chait chifa Luu huynh..., ngoai ra trong khf tw mhién con c6 thé ¢6 vét cia hop chat chia Cl phat sinh trong qué trinh bio quan. Trude khi da vio qué tinh reforming hoi nude, than phan ‘condensat phai duzge tach loai dé dim bio thanh phiin khi én dinh, cae hop chat chita Juu hugnh cing phii duge Loai bd bing qué trinh hydro héa va hap phy bing oxyt kém. Néu ham luong C1 16n hon 1 ppm thi cén phi téch bing qué tinh hap phy kiém. Sy c6 mat ca COs trong thinh phan nguyén Tigu ela qué trinh san xudt NH, va Hy ¢6 thé lam gidm higu qui cla qua tinh, do vay cing cn phai loai bd. Dé trénh qué tinh metan héa, him lugng CO, phai dim bio nhé hon 5%, Nito la chat pha loang khong anh huding tdi qué trinh va sé thu duge ciing sin phim hydro, tay nhién néu san phém khi téng hop duge ding cho qué trinh sin xudt metanol thi Luong niter trong nguyén li¢u dau cing céin duge loai bo. = Naphta Phan doan naphta ¢6 nhiét do s6i cui nhd hon 220°C thich hgp lam nguyen ligu ligu cho qué trinh reforming hoi nuée. Him Mong naphten trong nguyén ligu diu_phdi nhd hon 40% dé trénh to thin hydrocacbon thom trong giai doan hydrodesunfua héa true khi dua vio thiét bj reforming hoi nuée. Cie hop chit olefin cing phai nhd hon 1%. DE tranh ngd doe xtc téc, Khi dua vio thiét bi reforming hei au 98cae hop chat chifa liu huynh phai nhd hon 0.5 ppm, hgp chat chita clo duéi 1 ppm. Ngodi ra ham luong Pd (xuat hign trong qué trinh tén chifa va van chuyén naphta) phai nhd hon | ppm. 4.2.1.2, Hoa If ctia qué trinh reforming hoi nude Mue dich cita qué trinh reforming hoi nude [a tach ra mot lugng hydro lén nht tir nude va hydrocacbon. Qua trinh reforming hoi mde so edip khi ty nhién bao gém 2 phin img thuan nghich d6 1 phan tng reforming (1) va phn tg chuyén héa CO bing hoi nude (water-gas shift) (2). CH,+H;0 == CO+3H, AH = +206 ki/mol a) CO+H,O S* CO)+ HH, AH=~4I kJ/mol @ Phan ting reforming (1) la phan ting thu nhiét va tang thé tich, do vay vé mat nhiét dong hoc thich hgp & nhiét d6 cao, ap suat thap. Trong khi 6 phan img chuyén, héa CO bang hoi nude (2) Ta phan ting ta nhigt va khong thay doi thé tich nén thich hop & nhiét do thap va khong bj anh huéng bdi sy thay di cita dp swat. Tir phan ung (J) va (2) cho thay he sé ti lnong gitia hoi nudc/eacbon Ia 1,0. Phan ting reforming duge Lang cuding néu sir dung luong hoi née du va trong thye t& 11 s6 nay thuting duge duy tri ¢ 3.0 + 3.5. Tuy nhién, hién nay dé tang cudng higu qua kinh té cia qué trinh, ngudi ta dang co ging gidm ti 1¢ hoi nude/C xudng thap hon. Qué trinh reforming naphta dya trén 3 phan ing: reforming (3), metsn hoa (4) vi chuyén héa CO (5) C\Haya + nO > CO + (2n#1) Hy a CO+3H, == CH, + HO AH =-206 KI/mol @ CO+H,O = CO, + Hy AH = -41 kJ/mol 6) Phan tng reforming (3) thu niet nhiéu hon 2 phin ting tba nhiét (4) va (5) (vi du d6i vi CyH,, AH = + 1108 ki/mol), do vay higu Ging nhigt téng cong cla qué trinh thudng Bi thu nhigt, Cang giéng nhu qué trinh reforming hoi nude khi ty nhién, vé mat nhigt dong hoc phn ting reforming hoi nudc véi nguyén ligu dau 1A naphta ciing thich hop & nhiet d6 cao va dp suat thap, trong khi dé phin «ing chuyén héa hoi nue bi the ché G nhiét dO cao va khong bj anh hudng ciia su thay déi Ap sudt. Neu ti 1g hoi nude/naphta Lén thi sé thtic day phan tmg reforming. Trong thuc té, ti 1¢ hoi nudc/cachon =3,5 + 4,5 thug duge sit dung. Néu ti Ig hoi nuic/C thap thi phan dng metan héa sé chiGm uu thé, vA trong mot sé digu kign nhiét do va dp suat dae biet thi higu dng nhiét téng cong cia qué trinh sé 18 toa nhiét (bang 4.1). 99Bang 4.1. Higu ing nhiét ctia phan tag reforming hoi muée so edp Getic diéu kign phan tang kde whew Digu kign phim img an Apsuat]Nhier do | Tile Phi ny (hPa) |) hot nes . Geievol CHa) 207 | 800 | 30 | CH, +34,0 >020n,+04C0,+ +1025 0,400 + 19H, + 1,8H,0 276 | 750 | 30 | Cli; +3H,O>03SCH, +0.4C0,+ +75 0,250 + 1.45H, + 1,95H,0 310 | 450 | 20 | CH, +240 40,75CH, + 0.2500, + "a8 L.14H, + L,5H,O Phan ting chinh xay ra trong thiét bj reforming thi cap [a phan tmg oxy héa khdng hoan toiin metan véi lugng thigu oxy howe khong khi. CH, + 1/20, == CO +2H, AH = ~32,1 kI/mol (6) Day 1a phan ting toa nhigt nén nhiet d6 & thiét bi reforming thit cap ¢6 thé len 16i tren 900°C. 4.2.1.3. Cong nghé reforming hoi nude Qué trinh reforming hoi nude san xuét hydro bao gém 6 giai doan xtic téc. Cée phn img cg ban va xiic te dién hinh cho ede giai doan nay duge ligt ké trong bing 4.3, Dé thu duge khi téag hgp o6 thé ding & giai doan thir 3 (steam reforming thi fp). Dé thu duge hydro cho qué trinh téng hyp amoniac ein thyc hign cic giai doan tiép theo nhim Lim gidm him lugng CO xuéng mic thép nhat. Bang 4.3. Cée giai doan co bein ctia qué trink reforming hai auie sin suai hydro Giai doan Phan tng Xue tac Desunfua hoa R-S +H, -» H,S+RH Co-Mo/AlL,Oy Steam reforming sé edp | RH + H,O > H,+CO+CO;+CH, | Ni/Mg (naphtha) Ni/CaAl,O, (CH) Steam reforming thitedp | 2CH,+3H,0 == 7H,+CO+CO, | Ni/Caal0,, CH, + 1/20, = CO + 2H Nifo-AlsOs Chuyén hoa CO G mhiét dd | CO +H,0 > Hy + 00; Fe,0,- Cr,0; cao Chuyén hod CO & nhiat do | CO+H,0 > H, + CO, cud thap Metan hoa CO + 3H) > CH, + H,0 Ni/AL:0, 100So dé cong nghé cila qué trinh sin xudt H, 99% bing phuong phap reforming xtéc tc duge trinh bay trong hinh 4.1. DESUNEUA BOA REFORMING REFORMING CHUYEN HOA CO HOINUGCSGCAP HOINUSC THUCAP Hal ate Niet do evo shige thi Hoi awe hi wy mhier Go coe, 9968 My That Thi TACHCO; METAN HOA Hinh 4.1: So dé sdn xudt Hy being phuong phap reforming hoi Digu kign phin tng: Pyro/Pous= 2. Tutv n= 900 + 1100°C Pao? 3 MPa a, Lam sach RH ‘Trong nguyén ligu dau hydrocacbon cé chita c&c hgp chit lu hujnh ¢6 thé gay ng@ doe cho xtic tc cia qua trinh chuyén hod, vi vay cdc hgp chat nay cin duge lim sach khdi nguyén ligu déu. Cac hgp chat lua hujnh duge chuyén sang dang H,S bing qua trinh hydrodesunfua hod (HDS) v6i xtic tée Co-Mo/Al,05. Sau d6 HS duce hap phu bang ZnO (bé mat rigng 25 m?/2) 1011S + ZnO > ZnS + H,0 Ham Iuong luu huynh duge gidm xudng mec nhé hon 0,01 ppm. Cée hop chat clo gay an mn céc thiét bi trao déi mhiét va gay ngo doc xtic téc khf hod mhiet do thap cing duve gidm xudng mic dui 5 ppb sit dung chat hap phy Al,O, da duce xit 1y vai kien b. Reforming hoi nuée so edp (Primary steam reforming) Hydrocacbon sach va nuée mém duge ton v6i ti 1¢ H,0:C=2.5-4 (1uong ing véi néng do CH, tf 20 = 25% & du vio). Hén hop nguyen ligu dau duge gia nhiet dén 400°C, dp sudt 2 + 3 MPa va duce dua vio thiét bi phan tng gém hang tram ong chita xc dc véi duding kinh 25 + 50 mm lam bang hop kim Cr-Ni. Cac dng phin ting duoc dat trong mot budng dot vi duge gia nhiét qua thanh 6ng. Dé dim bao an toan cho thigt bi, nhiet dQ diu ra thuimg chi duy tri G 800°C va ham lugng HO khong vugt qué 80%. Digu kign phan dng déi voi nguyén ligu diu metan vA naphta rat khiie nhaw Doi véi nguyen Ligu diu 1a CH,: nhiet do 800 + 900°C, ti 1g H,O/CH, = 1.8 + 3. Nhigt do phan ting doi véi nguyen ligu naphta théip hon khodng 100 + 200°C (600 = 800°C) va ti le H,O:C cao hon (2,5 + 4). Dé gidm thé tich thiét bi phan ting va gidm su chenh Iéch 4p sust gitta du vio vi diu ra cia thiét bj trong cé hai trudng hgp ap sudt duge duy tri & 2 + 3 MPa va tc 49 thé tich khé tir 2500 + 8700 h” ¢. Reforming hoi nuée thit edp (Secondary steam reforming) Kh di sa tir thiét bj reforming hoi nude so c&p 6 chifa 10 + 13% CH, sé duge tigp tue phin cing trong thiét bi reforming thit hai dé gidm Ivong CH, xudng < 1%, ting ham Iugng hydro trong sin pham. Qué trinh duge tign hinh trong thiét bi phan ting doan nhiet. Nhigt d6 phan ting cao hon qué tinh reforming hoi nue so cp. Nhiét do dau vio 800°C, du ra 900- 1000"C. Nhigt phan ting duge cung cp them béi phin ting oxy héa eta oxy vi CH, Hy va CO bing céch dua thém oxy vao vdi ti I¢ ©,/C khoang 0,22. Trong trudng hop téng hgp amoniac, ¢6 thé ding khong khf thay cho oxy nguyen chit. San phdm 6 ham lugng CH, < 1%, CO = 10 + 13% d. Chuyén hod CO 6 nhiét dé cao (High temperature water-gas-shift) Khi san phim tir Steam Reforming tha ctip c6 chita 10 + 13% CO sé duge tigp tue xii 1y dé lam tang ham lugng Hy va gidm ham lugng CO xuéng khoing 2 + 3% trong thiét bi lép xiie tae e6 dinh, & ché 6 doan nhiét (AT = 50°C). Nhiét d6 phan ing 350+ 500°C, dp suit 2 + 3 MPa va t6e dé thé tich : 400 = 1200 h”! 102Vé mat nhiét dong hoc, phan img thich hgp ¢ 200"C, ty nhién tai nhiét do may xGic tc Fe,O, 66 hoat tinh khong cao, Cr,O déng vai td chit tro xe te, lam cho xc tc Fe,O, khong bi thigu két (Két tu). Xiic tée duge digu ché bing phuong phap déng két tia. Dang hoat tinh eda xtic tac (FeyO,) duge tao ra bang phiin dng khir cia Fe,, bing CO va H, trong dong khi phan ting. Fe,0, + Hy +CO > Fe,0, +H,0 + CO; Hoi nude duge thém vio trong qué trinh hoat héa xiie téc dé diéu khién nhigt 446 va trdnh phn ing khir hodn (oan FeO, thaah Fe kim loai. e.Chuyén hod CO é nhiét dd thdp (Low temperature water-gas-shift) Ham Iuong CO trong khi san pham ca qué trinh khi hod & nhiét d6 cao vao khoing 2-3% can duge tigp tue giim xudng duéi 0,2% trong thidt bj Khi hod & ahiét do thép. Qué trinh duge tién hanh trong thigt bi phan ting véi lp xc te ©6 dink & ché dé doan nhiet (AT = 15"C). Nguyen ligu tir thiét bi chuyén héa CO 6 niet do cao duge ha xudng nhiét do. 200°C trudc khi dua vao thiét bj chuyén héa nhigt 46 théip. Qué inh duge én hank G nhiét do 230°C, dp suat | + 3 MPa, tc do thé tich (GHSV): 3600 h”. Xe tae od hoat tinh cao CuO/ZnO/AL;O, & dang hinh cdu thudng chifa 30% CuO, 55% ZnO vA 15 + 35% AljOg. ZnO c6 vai tro trénh cho CuO khong bi thigu ket. ZnO va 1,0, sé hap phu cde hgp chat chia S va Cl, bao vé cho CuO khong bi ngo doc bai cae hgp chat nay. (f. Metan hod (Methanation) hay qué trinh téch COICO, cui cing Tuy ham lugng CO trong khi sin phim cita qué trinh khi hoa 6 mhigt do hip chi ta 0.2 + 0,5%, nhumg dé sit dung khi téng hop lm nguyen ligu cho qua trinh tng hop NHj vin cn tiep tue gidm Iwang CO xuéng 5 ppm. Luong CO; trong khi sin phim duge giém xung 0,1 + 0,2% trong thiét bj rita ‘bang amin va duoc thu hdi cho céc muc dich sit dung khac. Qué trinh metan hod duge tign hanh trong thiét bi doan nhiét, lop xUc tic co dinh, six dung xc téc Ni/Al,O,, Qué trinh duge tién hanh 6 dp sudt 3 MPa, nhiét do dau vao 300°C, dau ra 365°C, 10 dé thé tich 6000 = 10000 ht 4.2.2, San xuat khi téng hep bing phuong phap oxy hoa khong hoan toan Vé ly thuyét, qua trinh nay ¢6 thé ding cho bait ky dang nguyén ligu nao tir khi, Jong hay rin, tuy nhién qué trinh thudng si dung céc loai nguyén ligu ré tién, sn 6 nhu: khé ty nhign, hydrocacbon ngng (phan doan FO), than da... Doi khi qué trinh ny con duge gol I qué trinh khi hod (gasification), 103Qué tinh dua tren cée phan ting sau: + Phin tng chiy: xy ra 6 nhigt d9 cao > CO Ia sén phim chinh CH, + 3/20) + CO + 2H,0 + Phan tng cia CO v6i hoi nude (hoi nude duge tao ra trong phan ing chay hoac duge dua them vio) CO+H,O = CO; +H, ~ Phan tg phan huy hydrocacbon CH, == C(khi) + 2H, ~ V6i sy.c6 mat cita CO, va hai nude, C tao thanh sé tiép tue tham gia cée phan ting sau: CO, + =™ 2co C+HLO = CO+, Doi Véi qué trinh sir dung nguyen ligu dau 1a khi ty nhien, phin dng tdng quit CH, +120; > CO+2H; Trong trudmg hop nguyén ligu dau la cac hydrocacbon nang hon, phan ting xdy ra nh sau CyHp + Qn+my/40, —» nCO + m/2H;0 Vi ti te H/C trong nguyén ligu gidm, nén phan ing 06 xu huéng two thinh ahigu CO hon, lugng H;O tg0 1a trong phan ting chiy gi, nén cén phii them hoi utc vio Qué uinh tod nhiét, do vay nang Iuvong tigu thy thap hen trong phan img steam reforming, Toc d6 phan ting Ién nén thiét bi phin Gng rat nhd. Chi phi cho thi chi bing 30% so véi cde phuong phap truyén théng. Trong trudng hop sit dung nguyén ligu déu 1a Khi tw nhign, sin phim thu duce 6 ti I Hy/CO = 2 rat thich hop cho qué trinh téng hop FT va téng hop metanol So dé cong nghé sin xuat khi tng hop bing phuong phip oxy hod khong hoin ton ciia hing Texaco va Shell dugc trinh bay trong hinh 4.2 va 4.3. Ci hai so dé ny déu ¢6 cong doan thu héi cacbon tuo thinh bang céch rita véi nuéc, sau 6 trich ly phan bin bing naphta. Tigp theo phin trich duge tron v nguyén ligu dau vi dua true tigp vao thiét bj oxy hod (cong nghé Shell), hode xit ly bang trudc bing cach gia nhiet va tich véi sy e6 mat cia hydrocacbon nang hon (nh FO hoac dau thd) dé téch va tuan hoan naphta (cong nghé Texaco). 104_| veg sens 2 4g z 3 i 2] bien : Thaw ‘ : i ene : a T z é Nine Nate wh sachon l sie 2 )& Pos easton Hinh 4.2. Sa dé sin sudt khi tng hop bang plucong phép oxy hod khéng hedn toan ciia Texaco Ons hose Wis hi 7 Hoi nue dp susie ole hoik Whig hi" Nge cho. git, |<] Sin xa ho nue Oxy bo hong ho Sain, Rte cxcon sung Nude thi Hinh 43. Sordd sd audit khi tng hap baug pluemy php oxy hod khéng hodn roan etia Shell4.3. CAC PHUONG PHAP TACH VA XU LY KHi SAN PHAM ‘Thanh phén cia khi nhién va qué trinh oxy hod khéng hoan toan phan doan FO nang dude so sinh trong bang 44 ing hop thu duge tir qua trinh steam reforming khi uw Bang 4.4. Thanh phan kit tong hop ctia qué trink steam reforming Khi nt nhién va oxy hod khong hodn toan FO nding Qua tinh! Ory hoa khong hoan toan Steam reforming Neuyén ligu Khitwnbién | Naphta | FO [Than da] Khi tw nhien Cau tir Hy 61 31 47 40 55-57 co. 35 45, 47 35 12-15 co; 2-3 2-3 | 4 a 7-12 cH, : : 1 2 : N o-1 0-1 : 2 22-24 Tap chat khée 2-0 2-0 L : 4-2 4.3.1, Sin xuat hydro Hi (1, = -249.4°C, d = 0,0697) 6 thé duge sin xudt tir nhiéu nguén Khe nhau: Ja sén phém phy cia qui trinh san xuat c6c, cracking hoi nude, reforming xtic tic, ti qué Uinh oxy hod khéng hoin toin, reforming hoi mudc, ti qué tinh dign phan nude... ‘Tir bang 4.4 cho thay sin phdm khi téng hgp cia qua trinh oxy hod khong hoan todn va qua trinh steam reforming cé chita nhiéu CO, vi vay dé c6 thé san xuat hydro cho qua tsinh téng hgp amoniac cén cdc cong doan chuyén hod CO, tich CO, va cde tap chat, Khi sin pham thu dugc sau qué trinh chuyén hod CO & mhigt do thap (L-T.W.G.S) cin qua c&e giai doan tach céc tap chat sau: © Tach dm: bang phuong phép lam lanh ngung w hoge hap phy bing zeo! © Tach khi axit, dic biet 18 CO, hodc HS sinh ra trong qua trinh oxy hod khong hodn ton ede nguyén ligu dau khong duge khir teu hugh. «Tach vét CO edn lai, \h 4.4 mo ta cde cOng doan trong qué trinh sin xuat Hy tir khi tng hap cba qué trinh reforming hoi nude va oxy héa khong hoan toan, 106Metan kr Desunfua héa ‘Steam reforming H,0 Oxy hoa khong Sin xuat S|} Hap phy HS H,0 |} 4 chuyén hda co /-— Hap thy CO, ws + co, | Say, Hinh 4.4, San xudit Hy tit khi téng hop i 2 4.3.01. Tach khé axit Phu thugc vio nguén nguyen ligu, phuong phdp san xuat, loai xtic téc sit dung cho qué trinh chuyén hod CO. véi hoi nude, €6 cde qué trinh teh khi axit sau day. (a) Téch bing héip thy hod hoc thuan nghich, giaii hap thy bing céch tang nbigt 46 va giim dp suat. Céc dung méi duge sit dung bao gém: Alkanolamin (monoetanolamin, dictanolamin, trietanolamin, diisopropylamin va Iycolamin), musi kiém: cacbonat natri hoie kali, két hgp véi amin hode khong va dung dich amoniac (b) Tich bing hap thu vat ly: higu qua hap thu phy thudc vio ap suat rigng phan cia khi axit. Céc dung moi duce sit dung bao gém: dimetyl ete, metanol, N-metylpyrolidon, propylen cacbonat, polyetylen glycol/metyl isopropyl ete. (c) Ket hgp gitta hap thu hod hoe va hip thy vat ly: sit dung hén hop dung moi dé két hop kha nang hip phu hod hoc va vat IY nhu: metanol va etanolamin, sunfolan va diisopropylamin. 107(d) Hip phu: str dung oxyt sit, oxyt kém, than hoat tinh va sting phan tit, (e) Mang théim thaw: mang Pd, hoe ede ming vat figu polyme (mang polyamit, polyeste, polysunfon. polyvinyl trimetyl silan, polytetrafloctylen, axetat xenluto...) (8) Lam lanh sa jung metan long hode nite long. 43.1.2. Tach vi Dd co ich CO 6 dang vét, ¢6 thé ap dung cic phuong phdp sau day: (a) Hap thy bing dung dich mudi déng (axetat amon déng, format amoni dong), bang metanol fanh hode tetraclo nhém déng. (b) Metan hoa (da trinh bay trong mue 4.2.1.3). (c) Oxy hod xtic tée CO thank CO,: phuong phap nay khong chon loc nén it duge sit dung. 4.3.2, Sin xuit CO Cae phuong phép dugc sit dung trong cong nghigp dé eh CO tir khé téag hep bao gém: hap thu va téch bing ky thugt im anh stu, Phuong phap hép phy thay déi ip suit cling ¢6 thé duge siz dung néu him Iugng CO trong nguyen ligu di dudi 40% 43.2.1. Sdn xudt CO bang phuong phap hap thu CO duge tich bing dung dich clo amoni déng véi su two thinh phic cia CO V6i mudi déng theo phan tmg thuan nghich sau day: Cr + CUNT) + CO =* Cu(NH,),CO" + Cr Dé gidm an mon va giim Ivong Cu bém ten bé mat thiet bi phan ting, ede ion clo duge loai bé bing cich sit dung cée axit hdu co yéu hon nhu axit formic, axit axctic... Qué trinh hap thy duge tign han trong thép hip thu nguge dong & 2 MPa. nhigt do nguyen liga vao 40°C, nhigt do dong sin phim ra 65°C. Phite thu duge s duge nha hap thy bing cich gia nhiét dén 100 + 105°C va dua sang thap téi sinh Kim vige 6 Sp sutt thap 0,15 MPa 4.3.2.2. Sdn xudt CO bang phurong phap tam tanh sin Trong cong nghiép qué trinh nay tua thye hign bang hai ech: a, Ngumg tr: Nguyen Jigu dau sau khi duge say kho dé giim ham Luong sim xudng duéi 1 ppm duye xit ly qua ede cong doan sau: * Lam lanh xudng —185°C bing eich trao déi nbiet vai dong sin phim lanh. 10s© Ngung tu mot sé edu ti, + Tach khifléng. Sau méi bude, hén hop khf duge gidm 4p suat. Dé gidim sy mat mat nang lugng VA tang do tinh khiét ciia sin pham cn tign high ce cong doan phu tra sau day. © Gin né khi trong turbin dé 1m anh. + Bay hoi mot phin bang céch gin né sin phdm bj hod long. * Tach cic cau ti trong pha long bing phuong phdp chimg cat, Ny va CO thu duge & sin pham dinh, metan thu duge a day. ip thy bing metan Jong, Neuyén ligu sau khi say téch dm, duge am anh xuéng kho’ng -120°C bing cich tra déi nhigt véi ding sin phim lanh va duge dua vao diy thip dia. Metan tong duoc dua vao tir dinh thap. Qua trinh hap thu xy ra 6 4p suat 1,6 MPa, hydro khéng hip thu ¢6 d9 tinh khiet hon 98,5%, Sau khi gidin nd va bay hoi mot phén, phan trich duro dua vio thip chung Jam vige & 4p suat 0,2 MPa, CO thu duge é dinh thap, metan long thu & day thap duge tudn hodn lai thap hip thu 4.4. ONG DUNG 4.4.1. Tong hop amoniac Qué trinh duge tién hanh theo phuong trinh chink sau: 3H; +N, = 2NHy AH (300°C) = -109 kJ/mol Ny Phan tmg giim thé tich va tod nhigt manh, vé mat nhiét dong hoc thuan loi tai dip suat cao va nhiet do thap. Do vay yéu cau xtic tac o6 hoat tinh cao dé cé thé tien hanh & nhigt dO thaip. Xtc te oxyt sit (Fe,O,) c6 bé sung mot sO chat 11g xiic tic nb AlOs dé tang dign tich bé mat, KzO, SiO,, MgO, CaO dé tang do bén, tang hoat tinh va tang kha nang chong chit doc xie téc. Thé he xtc the méi c6 thé chia Ru thay thé cho Fe hoac két hgp véi Fe, duge bd sung cae chal trg xiic tée nh Rb, Ti va Ce. Nhiét d6 phan ung khong 450 = 500°C, 4p swat 20 + 25 MPa. Cac khi nguyen ligu phai khong 6 céc tap chat 18 cde hop chat ciia lu buYnh, asen, phospho va clo dé tinh ngd déc xtic téc, Ham Iugng cic hgp chat chia oxy cing phai han che dén mate thaip nhat (vi du: O3, CO; < 1 ppm; CO, H,0, CO + CO, <2 ppm). Cac so dé khéi cia qué trinh téng hop amoniac tit cde ngudn nguyen lieu khic nau duge trinh bay trong hinh 4.5 (a va b).nip apy n3y) 98) THN [THN doy Bug, you UE ‘oo +—| ‘oo A dey Dent OH & t SHEEN FEIN & *HN dou Bug Op at opquowin diy Suor yuaty pub py2 Wy Op.IS Sb Yet SN Hung 1yy ony «| 00 fur dee yugny wry | web 0 poy updntty, i snnjg doy Bug, |—[ S41 PRL ayn & ar e>—[_ rae, Dont OH P< Buon uniu9jo S9n0 OH [ Het ou eRyINSACL [Sonu 1H qo Suny SoM OFT oe rH ‘UROT UEO Sugyy poy XO wey s uSo dé dua tren nguyén ligu khi téng hop 1a sin phém cia qua trinh oxy hod khong hodn toan bao gm céc cong doan sau: © Chung ct khéng khi ‘+ Oxy hod khong ho&n toan hydrocacbon véi oxy + Tach cacbon va thu héi ni * Téch HyS va chuyén hod luu huynh © Chuyén hod xtic tac CO bing hei nude © Tach CO, * Téch CO bing nita tong So d6 dya tren nguyén ligu khi tng hop la sin phim eta qué tinh steam reforming bao gém cde cong dogn sau: * Reforming sa ep «Reforming tht ep (chuyén hod CH, con du bing khong khi) * Chuyén hod xtic téc CO bang hoi nude * Tach CO, « Tach CO bing phuong phép hap thu vi mudi déng hoac véi metanol hoae bing phuong phép metan hos. 4.4.2. Téng hop metanol Metanol duge sir dung lam nguyén ligu déu cho cc qué trinh sin xudt formaldehit, clorometan, amin, metyl metacrylat, MTBE... va lam dung moi, Qué trinh téng hgp metanot dya trén hai phin ing toa niet saw: CO+2H; 5™ CH,OH AH (298) =-90.6K/mol (1) CO, 43H; == CH,OH+H,O AH (298)=-49,5ki/mol (2) Phan ting thi hai c6 thé duoc xem niu hé qua cia phin ting thet nhat va phan ting nghich cia qué tinh chuyén hog CO bing hoi nude CO, +H, == CO+H,0 AH (298) = 41,3 kI/mol a Metanol cé thé duoc téng hop tir hén hop Hy-CO hoe H)-CO,, tuy nhién hén hgp phin tng chia déng thai H»-CO-CO, cho higu suat metanol cao pap 6,7 Lan. Tuy thuge vio thanh phin CO va CO, dé dat duge do chuyén hod yeu céu hén hop khi phai c6 ti 1é mol H/C bang 2 + 3. Hén hop niiy c6 thé thu duge tir qué trinh oxy hod khong ho’n ton, khi hod hodc steani reforming. So dé khoi cita qua trinh tng hgp metanol tir céc nguén nguyen ligu hdc nhau bing céc phuong phap khie nhau duge tinh bay trong hinh 4.6 va hinh 4.7a, bSteam reforming Ricatien i Hoi nude Tong hop metanol | Chung cat Hinh 4.6. So dé khoi cita qué trink ting hop metanol it sein phim ciia qué trink steam: reforming Qué tinh téng hop metanol tir sin phim cua qua trinh steam reforming don gidn hon nbigu so véi qué trinh sén xudt hydro tink khiet va qui trinh téng hop amoniac. Trong so dé hinh 4.6 giai doan chuyén hod CO, téch CO, va metan hod duge loai bd, tuy nhien tai céin mot may nén phy tra. Qua tinh bao gm hai bo phan chinh. ‘ (a) Xir IY nguyen ligu ddu: nhim téch ede hop chat uu huynh va ede tap chit khac cé hai cho xtie te ahu clo. (b) Steam reforming. So d6 khoi cita qué trinh téng hop metanol tir sin phim khi tng hop cia qué (Finh oxy hod khong hoan toin cing wong ty nhu céc qué trinh sin xuat hydro va amoniac. Do sy ¢6 mat cla cde hop chat chifa tau huynh trong nguyen ligu du, c6 hai loui so d6 cong nghé dutgc ung dung wy thudc vao xtic tic sit dung trong qué trinh chuyén hod CO (hinh 4.7 a va b) * Sod6 a): xc tic trong qua trinh chuyén hod CO khong bén véi ede hop chat cla lau huynh. Do vay nguyén ligu diy phii Khir cae hop chat hw huynh i ham Iuong 0,05 + 0,1 ppm. Sau d6 sin phim khi dug dua qua thiét bi chuyén hod CO va duve trén véi mot phin khi chua chuyén hod CO. 112por upoy Suptyy por @ yo Bunty I HO'HO doy Bug, Sone oH S'H+0D>—| ‘00 841 deH 03 oy uaKnui9 A BUOUy pnb ona woyd ups zy pouvraur diy Bor yee & HOHD |HO*HD dy Supp 700_<—[_‘00 un dey 1b D1 OUY OP OS Lb Meat 02, yugny ary yoy upanny I | I qo Suny, "UROT UeOY Bugyy Poy XO @p ueqiOs ay Fug, }-—[_s‘H i eH MPI Buy, 5 Wy Bun U3* So dé b): xtic tée bén vdi céc hgp chat lew huynh. Mot phan sin phim sau khi fa khoi thigt bi oxy hod khong hoan to’n dugc chuyén hos CO va sau d6 dng thoi duge tach CO, va HS. ‘Trong cé hai trudmg hop truéc Khi dua vao thiét bj tong hop metanol, dé béo ve xiic téc, khi téng hop can dugc dua qua Iép oxyt kém dé loai bé Iuu huynh. > Xtie te: Hai loai xtic te chinh duge sit dung trong cong nghiép (a) Xie téc Zn-Cr: he nite tée nay duge sit dung cho hau hét céc qué tinh sin xuit metanol trong cong nghiép cho dén cui nhiing nam 1960. Day 1a mot hén hoy dong thé cila oxyt kém va oxyt crom, Hé xii téic nay cé hoat tinh tuong déi thap, di hai phai tign hanh & nhiet dg 300 + 400°C, tai nhiét do nay, dé dim bio do chuyén hod yeu céu thi ap suat phdi duy ti 4 30 + 35 MPa nén khong kinh t@. Do vay hé xc tée nay dn dan duge thay thé bing xtic tie trén co sé Cu. (b) Xiic tac tren co sé Cu: hé xc téc may 6 hoat tinh cao hon nhung nhay cdm véi cdc chat doc, dac bigt 1a cde hop chat chia liu huynh va halogen. Xtic tic cho dd chon loc cao hon, ft sin phém phu, thai gian séng dai hon, 1am vige & diéu kien mém hon: nhiét do 240 = 270°C, ap suat 5 = 10 MPa. 4.4.3. Téng hop Fischer- Tropsch (FT) Qué tinh téng hyp FT duge tmg dung san xusi hydrocacbon long tit khi téng hop, Cac phan img chinh xy ra trong qué trinh metan hod va téng hop FT. CO + 3H, > CH, +H,0 wo NCO + 2nH, > C,Hy_ + nH; (ea) 2CO + (2n+1)Hy > C,Haa,2 + 9H,O a Negoai ra trong qué trinh cdn xay ra céc phan ding phu: CO + H,0 > CO, +H; (4) 2CO + +00, 6) Ni c6 hoat tinh cao di véi phan ting (1), Co, Fe, Ru c6 hoat tinh cxo déi véi (2) va (3). Qué trinh duge tien hanh & nhiét db 180 + 250°C, ti le Hy/ CO = 2. 4.4.4, Téng hop Oxo hay ph ing hydroformyl hos Qué trinh téng hop Oxo nhiim san xuat andehit va rugu cao duoc Rohlen phit hign vao nim 1938, Day 1a qué tinh dua hydro vi nhém formyl (-CHO) vao tién ket doi cia olefin. Phan ng chinh xdy ra nhu sau 14Olefin + CO +H, — andehit > rugu CH=CH, + CO + H; -> CH,CH;CHO ~ CH,CH,CH;0H RCH=CH, + CO +H, > RCH;CH,CHO RCH,CH,CH,OH Qua trinh tign hanh véi ti 1g CO/H, = 1/1 + 1/1.2. Nhiét do 110 = 180°C, ap sudt 20 + 35 MPa, thai gian hiru 1 + 5 phat. Trude day ding xile te octocacbonyl coban: Coy(CO), va hydrocacbonyl coban: HCo(CO),. Hign nay xtc tac chit yeu duge sit dung la hydrocacbonyl rodi: HRh(CO),, 4.4.5, Sin xuat axit formic (Qué trinh duge tién hanh dya trén hai phan ting chinh sau CH,OH + CO > HCOOCH, wD HCOOCH, + H,O + CH,OH + HCOOH Q) Phin img téng cong: CO + H,0 > HCOOH Giai doan | sit dung xtc téc natri methoxyde NaOCH,, 4p suat 4,5 MPa, nhigt dg 80°C. Giai doan 2 (thuy phan metyl format) sit dung xtc tac axit manh. 4.4.6. Sin xuat axit axetic Qua ‘inh dua trén phan ting cacbonyl héa metanol: CH,OH + CO > CH,COOH Phin ting thich hgp trong pha long & nhigt do 220 + 250°C, dp suat trén 30 MPa (qua trinh BASF: Nhigt do 250°C, 4p sudt 65 + 70 MPa, xiic tae & dang hop chat co kim hoac mudi coban, vi du Col,). Vai sit c6 mat cia nude (trén 30% thé tich) va xtic te thé he moi, dp suat cé thé gidm xudng 3 = 7 MPa, nhiét do 150 = 200°C (qué tinh Monsanto: nhiét do 180 = 200"C, dp suat 3 + 3,5 MPa). He xtic tdc sit dung thuimg c6 3 thanh phan: ir hoat dong (oxyt, hyp chat co kim, mudi cita kim logi quy, vi du: rodi-clo- cacbonyl-bisphenylphosphyl: Rh(CO)[PC.H;);]sC] hoae rodicacbonyl _todua: [Rh(CO),131) . chat trg xtic te (halogen hoge hop chit halogen héa, vi dy metyl iodua: CHyl) va dung moi (vi du hén hgp axit axetic vA née). Pha hoat tinh va chat tg xtic tac c6 néng dé tuong ting 1a 10 va 1 mol/l. 415