Bài giảng Tổng hợp hữu cơ hóa dầu - ĐH Bách Khoa TPHCM

TOÅNG HÔÏP HÖÕU CÔ & HOÙA DAÀU GV: ÑAØO THÒ KIM THOA Boä moân CNCB Daàu khí, Khoa CNHH, ÑH Baùch Khoa Tp. HCM Hoaù chaát vaø polymers töø propylene: polypropylene propylene oligomers Acrylic acid Acrylo nitrile Propylene oxide Cumene Phenol Bisphenol A Epoxy resins Polycarbonate resins Phenolic resins Acetone Methyl methacrylate Isopropyl alcohol Acetone n-butyraldehyde 2-ethylhexanol n-butyl alcohol iso-butyraldehyde isobutyl alcohol Epichlorohydrin Epoxy resins Glycerol 30% propylene 15% propylene 15% propylene 10% propylene 10% propylene 12% propylene Caùc phaûn öùng Polymer hoùa vaø oligomer hoaù a. CH3-CH=CH2 poly-propylene b. CH3-CH=CH2 propylene dimer, C6H12 propylene trimer, C9H18 propylene tetramer, C12H24 Oxi hoaù c. CH3-CH=CH2 CH2=CH-CHO CH2=CH-COOH acrolein acrylic acid CH2=CH-COOR Acrylic ester d. CH3-CH=CH2 CH2=CHCN + sp phuï (HCN + CH3CN) xt acrylonitrile acetonitrile xt xt O2, xt O2, xt ROH, xt CH2=CH H - C- H H H: allylic hydrogen e. CH 3 - CH=CH 2 CH 3 - CHCH 2 Cl CH 3 CH - CH 2 + NaCl propylene oxide Cl2, H2O 3 C - C - OOH hoaëc C 6 H 5 - C - CH 3 t - butyl et hylbenzene hydroperoxide hydroperoxide f. CH 3 - CH=CH 2 CH 3 CH - CH 2 + propylene oxide H 3 C - C - OH hoaëc C 6 H 5 C H OH t - butyl alcoho l phenyl methyl carbinol - H 2 O C 6 H 5 CH=CH 2 Styrene OH NaOH O H CH3 CH3 H OOH CH3 CH3 CH3 O g. CH 3 - CH=CH 2 C 6 H 6 C 6 H 5 CH O 2 C 6 H 5 C - OOH H 2 SO 4 loaõng xt xt Cumene Cumene Hydroperoxide C 6 H 5 OH + CH 3 C OCH 3 Phenol Acetone h. CH 3 CH=CH 2 CH 3 CHCH 3 CH 3 COCH 3 Isopropyl acetone Alcohol CH 3 CH 2 CH 2 CHO H 2 CH 3 CH 2 CH 2 CH 2 OH Butyraldehyde n - butanol i. CH 3 CH=CH 2 CO + H 2 xt (CH 3 ) 2 CHCHO (CH 3 ) 2 CHCH 2 OH iso butyraldehyde iso butanol H2O H2SO4 -H2 xt xt H xt 2 j. CH 3 CH=CH 2 ClCH 2 CH=CH 2 ClCH 2 CHCH 2 Cl + ClCH 2 CHCH 2 OH allyl chloride 1,3 - dichloro - 1,2 - dichloro - 2 - hydroxy - 3 - hydroxy - propane propane ClCH 2 CH - CH 2 - HCl Ca(OH) 2 E pichlorohydrin Cl2 500oC + HCl Cl2 H2O OH Cl O POLY PROPYLENE iso-tactic syndio-tactic a-tactic n n POLY PROPYLENE Poly propylene vôùi chæ soá isotactic 99% hieän ñang ñöôïc saûn xuaát. PP: Ñoä beàn hoùa hoïc cao Khaû naêng haáp thuï nöôùc ít Tyû troïng thaáp Beàn vôùi löïc Khoâng ñoäc haïi Coù theå caùn thaønh baûn moûng laøm container Nheï vaø cöùng: laøm caùc chi tieát trong xe hôi Coù theå keùo sôïi, giaù reû. ACRYLIC ACID ( CH 2 =CHCOOH ) Coù nhieàu caùch ñeå toång hôïp acryli c acid Ñi töø acrolein: CH 3 CH=CH 2 + O 2 xt CH 2 =CHCHO + H 2 O Xt: CuO (QT Shell) Bi 2 O 3 /MoO 3 (QT Sohio) T : 300 - 360 P: 1 - 2 atm CH 2 =CHCHO + 1/2 O 2 CH 2 CHCOOH Xt: MoO 3 , V 2 O 5 T o : 250 Acrylic acid vaø acryl ic ester: sx acrylic resins: keo daùn, sôn, CN nhöïa. propylene acrolein o C = Acrylonitrile Acrylic acid Acrylate Rượu + acid hữu cơ ester ACRYLONITRILE ( CH 2 =CHCN ) · Ammoxidation: laø phaûn öùng chuyeån hoùa nhoùm methyl thaønh nhoùm nitrile söû duïng NH 3 vaø O 2 vôùi söï coù maët xuùc taùc oxide hoãn hôïp. CH 2 =CHCH 3 + NH 3 + 3/2 O 2 CH 2 =CHCN + 3 H 2 O · Phaûn öùng toûa nhieät cao, caàn giaûi nhieät cho heä phaûn öùng · Saûn phaåm phuï: acetonitrile: CH 3 CN Hydrogen cyanide: HCN Coù theå thu hoài ñeå baùn ÖÙng duïng : saûn xuaát sôïi acrylic, acrylic resins, chaát deûo Copolymer cuûa acrylonnitrile vôùi butadiene vaø styrene: ABS resins Copolymer cuûa acrylonnitrile vôùi styrene: styrene - acrylonitrile resins: SAN, moät plastic quan troïng. PROPYLENE OXIDE Chlo hydro hoùa: CH 3 CH=CH 2 + HOCl CH 3 CH(OH)CH 2 Cl Hypochlorous acid propylene chlorohydrin Khoâng xt T o : 35 P: 1 atm Hieäu suaát: 87 - 90% Saûn phaåm phuï: propylene dichloride (6 - 9%) Dehydro chlo hoùa vôùi dung dòch 5% Ca(OH) 2 : 2CH 3 CH(OH)CH 2 (Cl) + Ca(OH) 2 2CH 3 CH - CH 2 + CaCl 2 + 2H 2 O Saûn phaåm phuï: propylene dichloride: CH 3 CH(Cl)CH 2 (Cl): laøm dung moâi B aát lôïi: boû CaCl 2 Propylene glycol: CH 3 CH(OH)CH 2 (OH) CH 3 CH - CH 2 + H 2 O CH 3 CH(OH)CH 2 (OH) Phuï thuoäc vaøo tyû leä PO/H 2 O maø di, tri vaø polypropylene glycol ñöôïc taïo thaønh nCH 3 CH - CH 2 + H 2 O HO[CH(CH 3 )CH 2 O] n H n=2: HO - CH - CH 2 - O - CH - CH 2 - O - H : dipropylene glycol CH3 CH3 O O Chlorohydrin route to propylene oxide Cumene plant PHENOL VAØ ACETON TÖØ CUMENE Cumene cumene hydroperoxide Xt: muoái kim loaïi T o : 100 - 130 o C P: 2 - 3 atm Cumene hydroperoxide phenol acetone T o : 80 o C P: <1 atm CH3CHCH3 + O2 (CH3)2COOH (CH3)2COOH H+ OH + CH3 C CH3 Phenol: tinh theå traéng vôùi muøi ñaëc tröng, thaønh maøu h ôi ñoû khi tieáp xuùc vôùi aùnh saùng, hoøa tan nhieàu trong nöôùc, dung dòch laø acid yeáu. 50% duøng ñeå saûn xuaát phenolic resins. Phenol vaø acetone taïo bis - phenol A, monomer quan troïng cho nhöïa epoxy vaø poly - c arbonate. Phenol acetone bis- phenol A Phenol coøn laø chaát trung gian cho nhieàu saûn phaåm. Aceton: - Dung dòch deã bay hôi vôùi muøi ngoït ñaëc tröng. - Hoøa tan trong nöôùc, alcohol vaø nhieàu hydrocarbon:duøng laøm dung moâi l yù töôûng cho sôn. - Laø moät ketone ñoái xöùng, acetone laø moät hoùa chaát hoaït ñoäng vôùi nhieàu öùng duïng. OH + CH3 C CH3 H+ Saûn xuaát methyl methacrylate: CH 2 =C - COOCH 3 - Phaûn öùng hydro cyanua hoùa acetone baèng HCN. Ñaàu tieân laø phaûn öùng CH 3 CCH 3 + HCN CH 3 C - CN - Sau ñoù phaûn öùng vôùi H SO vaø methanol cho ra MMA CH 3 C - CN + H 2 SO 4 CH 2 =C - C - NH 3 HSO 4 CH 2 =C - C - NH 3 HSO 4 + CH 3 OH CH 2 =C - COOCH 3 + NH 4 HSO 4 Nhöôïc ñieåm: Phaûi boû doøng NH 4 HSO 4 MMA duøng ñeå saûn xuaát nhöïa poly methacrylate. CH3 CH3 CH3 CH3 + _ CH3 + _ CH3 phenol plant Isopropyl alcohol plant · Dehydro hoùa: CH 3 CHOHCH 3 CuO 2 CH 3 CCH 3 + H 2 (ZnO) 450 – 550 o C HS: 95% · Ox y hoùa: CH 3 CHOHCH 3 + O 2 CH 3 CCH 3 + H 2 O 2 Xt: khoâng T o C: 90 – 140 P: 15 – 20 atm Sp phuï: H 2 O 2 Ngaøy nay, acetone chuû yeáu ñöôïc saûn xuaát töø cumene (cuøng vôùi phenol). 2 EPICHLOHYDRIN Cholor h oùa propylene: allyl chloride: CH 2 =CHCH 2 Cl Allyl chloride: dd khoâng maøu, khoâng tan trong nöôùc, tan trong dung moâi höõu cô, muøi haêng maïnh vaø aên da. Sx: allyl alcohol, glycerol, epicholohydrin Sx allyl chloride: Chlo r hoùa tröïc tieáp propylene T o cao: 500 P: 1 atm CH 2 =CHCH 3 + Cl 2 CH 2 =CHCH 2 Cl + HCl Phaûn öùng thay theá nguyeân töû H (allylic) baèng Chlorin. Sp phuï: HCl ÖÙng duïng qu an troïng nhaát cuûa allyl chloride: sx glycerol thoâng qua hôïp chaát trung gian laø epichlorohydrin. Epichlorohydrin sau ñoù ñöôïc thuûy phaân ñeå taïo glycerol. BUTYRALDEHYDES CH 3 CH 2 CH 2 CHO Phaûn öùng hydroformylation propylene, ph aûn öùng oxo. CH 3 CH=CH 2 + CO + H 2 CH 3 CH 2 CH 2 CHO + CH 3 CH - CHO n - butyraldehyde iso - butyraldehyde sp chính sp phuï Xt: Rh (rhodium) Butyraldehyde thöôøng ñöôïc hydro hoùa ñeå taïo thaønh alcohol töông öùng CH3 N - BUTANOL CH 3 CH 2 CH 2 CH 2 OH CH 3 CH 2 CH 2 CHO + H 2 CH 3 CH 2 CH 2 CH 2 OH Phaûn öùng hydrogen hoùa xuùc taùc. P: cao Hieäu suaát: ca o n - butanol: chuû yeáu duøng laøm dung moâi hay taùc nhaân ester hoùa. Ví duï: ester cuûa n - butanol vôùi acrylic acid duøng laøm sôn, chaát keát dính vaø nhöïa. 2 - ETHYLHEXANOL CH 3 (CH 2 ) 3 CH(C 2 H 5 )CH 2 OH 2 - ethylhexanol laø moät chaát loûng khoâng maøu hoøa ta n trong nhieàu dung moâi höõu cô. Laø moät trong caùc hoùa chaát duøng trong saûn xuaát chaát laøm deûo cho PVC (phaûn öùng vôùi phthalic acid taïo di - 2 - ethylhexyl phthalate). 2 - ethylhexanol ñöôïc taïo ra bôûi söï ngöng tuï aldol cuûa butyraldehyde vôùi sö ï coù maët dung dòch soda vaø taïo ra 2 - ethylhexanal. Sau ñoù, aldehyde ñöôïc dehydrate hoùa vaø hydro hoùa taïo 2 - ethylhexanol. 2 CH 3 CH 2 CH 2 CHO CH 3 (CH 2 ) 2 CHOHCHCHO CH 3 (CH 2 ) 2 CHOHCHCHO CH 3 (CH 2 ) 2 CH=CCHO + H 2 O CH 3 (CH 2 ) 2 CH=CCHO + H 2 CH 3 (CH 2 ) 3 CHCH 2 OH