Chapter 8Carbonylation process
Carbonylation process Chapter 8
8.1IntroductionThe reactions introducing carbonyl to the organic moleculesby using the transition metal complexes (carbonyl complexes)catalyst are called carbonylation reactions (or oxo synthesisreaction)HRCH2=CH2+ CO) +H2 RCH2CH2C=O (main)+ RCHCH311923年德国鲁尔化学公司的罗兰（Roelen）C=0发现，称为罗兰反应(Roelenreaction)。H
8.1 Introduction The reactions introducing carbonyl to the organic molecules by using the transition metal complexes (carbonyl complexes) catalyst are called carbonylation reactions （or oxo synthesis reaction） RCH2 CH2+ CO 1923年德国鲁尔化学公司的罗兰（Röelen） 发现，称为罗兰反应(Röelen reaction)。 RCH2CH2C=O (main) + RCHCH3 C=O H H + H2
-, Carbonylation reaction of unsaturated compounds(1) Hydroformylation of olefinsCHCH,CHOCH2 = CH2 + CO +H2CH3CHz = CH2 + CO + H2CH2CH2CH2CH0(2) HydroformylationofolefinderivativesHOCHCH （CHO) CH3HOCH2CH2= CH2 + CO + H2HOCH,CH,CH,CHO (main)
一、Carbonylation reaction of unsaturated compounds (1) Hydroformylation of olefins CH2 CH2 + CO + H2 CH2CH2CHO CH3CH2 CH2 + CO + H2 CH2CH2CH2CHO (2) Hydroformylation of olefin derivatives HOCH2CH2 CH2 + CO + H2 HOCH2CH2CH2CHO（main） HOCH2CH（CHO）CH3
(3) Hydrocarboxylation of unsaturated compoundsCH,CHCOOHCH2 = CH2 + CO +H2OCH2=CHCOOHCH = CH + CO+H2O(4) Hydrogenation esterification reaction of unsaturated compoundsRCH = CH2 + CO +R1 OHRCH2CH2COORCH= CH + CO +ROHCH2=CHCOOR
(3) Hydrocarboxylation of unsaturated compounds CH2 CH2 + CO + H2O CH2CH2COOH CH CH + CO + H2O CH2=CHCOOH (4) Hydrogenation esterification reaction of unsaturated compounds RCH CH2 + CO + R１OH RCH2CH2COOR1 CH CH + CO +ROH CH2=CHCOOR
二、 Carbonylation of methanol(1)Carbonylationofmethanolto synthesizeaceticacidI + COCHCOOHCH3OH→RCOOHCOROH +(2) Carbonylationof methyl acetate to synthesize acetic anhydrideCH3COOCH3 + CO ---→ (CH,CO)2OMethyl acetate can be synthesized by methanol carbonylationand thenesterificationCH:OHCH,OH +CO → CH,COOHCH,COOCH3
二、Carbonylation of methanol (1) Carbonylation of methanol to synthesize acetic acid CH3OH + CO CH3COOH (2) Carbonylation of methyl acetate to synthesize acetic anhydride ROH + CO RCOOH Methyl acetate can be synthesized by methanol carbonylation, and then esterification
(3) Carbonylation of methanol to synthesize formic acidCH,OH +CO → HCOOCH3HCOOCH, +HO → HCOOH +CH3OH(4) Carbonylation and oxidation of methanol to synthesizedimethyl carbonate, dimethyl oxalate or glycol2CH3OH + CO+→CO(OCH3)2+H2O22CH3OH + 2CO +→(COOCH3)2+H2OO(COOCH3)2 + 2H2O --→ (COOH)2 + 2CH3OH(COOCH3)2+4H2→(CH2OH)2+2CH3OH
(3) Carbonylation of methanol to synthesize formic acid (4) Carbonylation and oxidation of methanol to synthesize dimethyl carbonate, dimethyl oxalate or glycol
三、 Catalyst of carbonylation reactionCarbonylation reaction is typical coordination catalyticreaction。Catalyst of carbonylation reaction is complexes formed bytransition metal as central atom (M) with ligard (L)H M, (CO)z Ln X, y, z, n:CoordinationnumberTransitioncentralatomsLigandsRh, Co, Pd etc.Organic phosphorus,iodide ion etc
三、Catalyst of carbonylation reaction Carbonylation reaction is typical coordination catalytic reaction。 Catalyst of carbonylation reaction is complexes formed by transition metal as central atom (M) with ligard (L) Hx My (CO)z Ln Transition central atoms Rh, Co, Pd etc. x, y, z, n: Coordination number Ligands Organic phosphorus、iodide ion etc
8.2 Acetic acid synthesizing from methanol carbonylation,Basicprincipleofaceticacid synthesisfrommethanolcarbonylationMain reactionCat.CH3OH+ COCH,COOHAH=-138.6kJ/molT, PSide reactions2CH,0H CH,0CH, +H,0CH,COOH + CH,OH二 CH,COOCH +H,0CO +H,O CO2 + H2
8.2 Acetic acid synthesizing from methanol carbonylation 一、Basic principle of acetic acid synthesis from methanol carbonylation CH3OH + CO CH3COOH ∆HӨ = -137.9kg/mol Cat. T, P ∆H = -138.6kJ/mol Main reaction Side reactions 2CH3OH CH3OCH3 + H2O CH3COOH + CH3OH CH3COOCH3 + H2O CO + H2O CO2 + H2
Two production methods:CarbonylcobaltismaincatalystHighpressure method:250°C,70MPa (BASFcompany);Methyliodide(iodomethane)ispromoterDiiodo dicarbonyl rhodium is main catalystLow pressure method:180C,3MPa (Monsantocompany)Methyliodide is promoter
High pressure method: 250 ºＣ，70MPa （BASF company); Carbonyl cobalt is main catalyst Methyl iodide (iodomethane) is promoter Diiodo dicarbonyl rhodium is main catalyst Methyl iodide is promoter Low pressure method: 180 ºＣ，3MPa（Monsanto company) Two production methods：
Catalyticmechanismof acetic acid synthesisfrommethanol carbonylation by high pressure method:Catalyst: Co2(CO): / CH,Co2(CO) + H,O +CO-2HCo(CO)4 + CO,CH.OH +HI CHI + H2OHCo(CO)4 H+ + [Co(CO)4][Co(Co)4]: + CH3I :CH3Co(CO)4 + ICH,Co(CO)4 → CH,CO-Co(CO)3CH,CO一Co(CO)3 + CO =CH,CO-Co(CO)4CH,CO-Co(CO)4 + HI --CH,COI + H+ + [Co(Co)4]CH,COI + H,OCH,COOH + HI
▲ Catalytic mechanism of acetic acid synthesis from methanol carbonylation by high pressure method: Catalyst: Co2 (CO)8 / CH3 I Co2 (CO)8 + H2O +CO 2HCo(CO)4 + CO2 CH3OH +HI CH3 I + H2O HCo(CO)4 H+ + [Co(CO)4 ] - [Co(Co)4 ] - + CH3 I CH3Co(CO)4 + ICH3Co(CO)4 CH3CO－Co(CO)3 CH3CO－Co(CO)3 + CO CH3CO－Co(CO)4 CH3CO－Co(CO)4 + HI CH3COI + H+ + [Co(Co)4 ] - CH3COI + H2O CH3COOH + HI