.Gauthier~Lafaye
`
`RH5NE-PUULENC RECHERCHES
`PUBLISHED BY
`
`EDITIONS TECHNIP
`
`000001
`000001
`
`(cid:44)(cid:51)(cid:53)(cid:21)(cid:19)(cid:20)(cid:24)(cid:16)(cid:19)(cid:19)(cid:20)(cid:26)1
`IPR2015-00171
`(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:25)(cid:21)
`Exhibit 1062
`
`
`
`RH5NE-PUULENC RECHERCHES
`PUBLISHED BY
`
`EDITIONS TECHNIP
`
`000001
`000001
`
`(cid:44)(cid:51)(cid:53)(cid:21)(cid:19)(cid:20)(cid:24)(cid:16)(cid:19)(cid:19)(cid:20)(cid:26)1
`IPR2015-00171
`(cid:40)(cid:91)(cid:75)(cid:76)(cid:69)(cid:76)(cid:87)(cid:3)(cid:20)(cid:19)(cid:25)(cid:21)
`Exhibit 1062
`
`
`
`Contents
`
`PREFACE .......................................................
`
`V
`
`INTRODUCTION ..................................................
`
`1
`
`1
`
`INDUSTRIAL IMPORTANCE
`OF CARBON MONOXIDE
`
`
`
`1.1 APPLICATIONS OF CARBON MONOXIDE ..........................
`
`1.1.1 Synthesis of fuels .................................
`
`1.1.1.1 F1sher—Tropsch synthesis....................
`
`1.1.1.2 Mobil process ..............................
`
`1.1.1.3 IFP process ................................
`
`1.1.2 Olefin and aromatic synthesis.......................
`
`1.1.2.1 Aromatics (BTX) ............................
`
`1.1.2.2 Olefins ....................................
`
`1.1.3 Synthesis of basic chemicals........................
`
`1.1.4 Synthesis of fine chemicals ........................
`
`1.1.5 Conclusion .........................................
`
`3
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`\ta\LnJ-\
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`\l
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`7
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`8
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`8
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`11
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`12
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`1.2 SYNTHESIS OF CARBON MONOXIDE .............................
`
`13 '
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`1.2.1 Preparation of synthesis gas .......................
`
`1.2.1.1 Steam reforming processes ..................
`
`1.2.1.2 Gasification processes .....................
`
`1.2.1.3 Other processes ............................
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`13
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`13
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`14
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`15
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`1.2.2 Purification of synthesis gas ......................
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`18
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`20
` O0O00COOOIOIIOIIOIICOIIOOCCOIOIOOIIO00000000000000
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`\/H
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`000002
`000002
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`
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`2.1.2.4 Acetic acid.......................
`2.1.2.5 Acetic anhydride ...........................
`2.1.2.6 Vinyl acetate.......................
`
`
` 3.1.3 Results .................................
`
`000003
`000003
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`CONTENTS
`
`2
`
`SYNTHESIS OF C2 OXYGENATES
`STARTING FROM CO-H2
`
`2.1 OXYGENATED C MOLECULES ........................
`2
`
`2.1.1 Definition ...............................
`
`2.1.2 Industrial importance ..............................
`
`2.1.2.1 Acetaldehyde ...............................
`
`2.1.2.2 Ethanol ..........................
`
`2.1.2.3 Ethyl acetate ....................
`
`24
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`24
`
`26
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`2.1.2.7 Glycol ............................
`
`2.2 METHANOL
`
`2.3 MTHANOL AS FEEDSTOCK FOR C2 OXYGENATES, THE MAIN
`RELATIONSHIPS ....................................
`
`BIBLIOGRAPHY .........................................
`
`
`
`3
`
`CONVENTIONS AND METHODS
`OF CALCULATIONS
`
`3.1 CONVENTIONS ...................................
`
`3.1.1 Physical parameters ......................
`
`3.1.2 Reagents .................................
`
`3.2 CALCULA1
`
`3.2.1 Ca
`
`3.2.2 Ca
`
`30
`
`I
`2 3 Ca
`
`3 INTRODUCT
`
`2; REACTION :
`FOP CALCUL
`
`4‘2'1 F°”
`
`5.2.2 Conv
`
`
`
`
`
`4.3.3 Reactions catalyzed by cobalt.
`iodine and an
`organic ligand .....................................
`4.3.3.1 Quaternization of ligands ..................
`V
`4.3.3.2 Reactions carried out with an excess of
`33
`33
`V
`34
`IICOOIIOOIOIIICIIOICIIOOIIIOIC
`
`
`4.3.3.3 Reactions carried out in the presence of
`
`ligand in excess ...........................
`
`000004
`000004
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`CONTENTS
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`3.2 CALCULATION OF RR, TT, RT, PS and Pi .....................
`
`3.2.1 Calculation of yields RR and RRc ...................
`
`3.2.2 Calculation of conversion TT and TTc ...............
`
`34
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`35
`
`36
`
`3.2.3 Calculation of selectivities RT and RTc ............
`
`36
`
`4
`SYNTHESIS OF ACETALDEHYDE
`AND ETHANOL
`
`401
`
`OOOCOIOOIOOIIIIIOIOOOOIIIIOOOOIJIIOOOUOIIIOII
`
`4.2 REACTION PRODUCTS, CONVENTIONS AND METHODS
`or CALCULATIONS
`
`40
`
`4.2.1 Formation of reaction products .....................
`
`41
`
`4.2.2 Conventions used for calculations ..................
`
`43
`
`4.3 NATURE OF THE CATALYTIC SYSTEM ...........................
`
`44
`
`E
`
`4.3.1 Cobalt-catalyzed synthesis .........................
`
`4.3.2 Cobalt and iodine-containing catalytic systems .....
`
`4.3.2.1 Influence of the nature of iodized promoters
`
`4.3.2.2 Effect of iodized promoters concentration...
`4.3.2.3 Special case of co/C331/A+1’
`
`44
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`46
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`47
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`50
`52
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`_
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`;
`
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`‘
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`j
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`23
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`23
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`24
`24
`25
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`25
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`25
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`26
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`27
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`27
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`28
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`29
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`31
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`33
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`54
`55
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`
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`4.6.2 By
`
`4.
`
`4.6.3 By
`
`4.
`
`4.
`
`BIBLIOGRAPHY
`
`5.1 INTRODUC7
`
`5.2 REACTION
`
`5.2.1 F0]
`
`5.2.2 Co:
`
`5.3 THE DIFFI
`
`5.3.1 Cot
`
`5.3.2 Rut
`
`5.3
`
`5.3
`
`5.3
`
`5.3
`
`CONTENTS
`
`iodine, a metallic
`4.3.4 Reactions catalyzed by cobalt,
`co-catalyst and,
`in certain cases, a ligand ........
`
`4.3.4.1 Cobalt—ruthenium system ....................
`
`4.3.4.2 Other metallic co-catalysts ................
`
`60
`
`61
`
`64
`
`4.3.5 Catalytic systems using other metals than cobalt
`
`.....65
`
`4.3.5.1 Iron-containing catalysts ..................
`
`4.3.5.2 Nickel-containing catalysts ................
`
`4.3.5.3 Ruthenium-containing catalysts .............
`
`4.3.5.4 Rhodium-containing catalysts ...............
`
`4.3.5.5 Rhenium and manganese-containing catalysts .
`
`65
`
`66
`
`66
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`66
`
`66
`
`4.4
`
`PHYSICAL PARAMETERS OF THE REACTION ....................... 67
`
`4.4.1 Influence of temperature ............................ 68
`
`4.4.2 Influence of total pressure and CO/H2 ratio ......... 68
`
`4.4.3 Influence of the duration time ...................... 71
`
`4.4.4 Effect of solvents ... . . . . . .......................... 72
`
`4.5
`
`COBALT-CATALYZED REACTION MECHANISM ....................... 73
`
`4.5.1 Reaction carried out with cobalt alone ..... . . . . ..... 73
`
`4.5.2 Reaction in the presence of cobalt and methyl iodide. 75
`
`ionic iodide and
`4.5.3 Reaction in the presence of cobalt,
`methyl iodide .................... . . . . ... . . . . ........ 77
`
`4.5.4 Reaction in the presence of cobalt and ruthenium .... 78
`
`4.6
`
`BY—PRODUCTS:
`
`IMORTANCE AND FORMATION ..................... 80
`
`4.6.1 By-products common to the synthesis of acetaldehyde
`and ethanol ......................................... 80
`
`4.6.1.1 Methane formation ........................... 80
`
`4.6.1.2 Formation of acetic acid and its esters ..... 81
`
`4.6.1.3 Formation of CO2 ............................ 83
`
`
`
`
`
`
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`000005
`000005
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`
`.
`
`.
`
`60
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`61
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`64
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`...65
`
`.
`
`66
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`66
`
`66
`
`.. 67
`
`. 68
`
`.. 71
`
`. 73
`
`.. 73
`
`Lde. 75
`
`1nd
`.. 77
`
`... 78
`
`CONTENTS
`
`4.6.1.4 Formation of dimethyl ether ................. 84
`
`4.6.2 By-products specific to acetaldehyde systhesis ...... 84
`
`from
`(DMA)
`4.6.2.1 Formation of dimethylacetal
`acetaldehyde ................................ 84
`
`4.6.2.2 Formation of C4 oxygenates .................. 87
`
`4.6.3 By-products specific to ethanol synthesis ........... 87
`
`4.6.3.1 Formation of ethyl ethers ................... 89
`
`4.6.3.2 Formation of ethyl acetate .................. 89
`
`BIBLIOGRAPHY .. ................................................ 90
`
`5
`
`HOMOLOGATION OF METHYL ACETATE
`INTO ETHYL ACETATE
`
`5.1 INTRODUCTION .............................................. 97
`
`5.2 REACTION PRODUCTS - CONVENTIONS — METHODS OF CALCULATION .. 98
`
`5.2.1 Formation of products ............................... 98
`
`5.2.2 Conventions - Methods of calculation ................1OO
`
`5.3 THE DIFFERENT CATALYSTS ...................................101
`
`5.3.1 Cobalt ..............................................102
`
`5.3.2 Ruthenium ...........................................102
`
`5.3.2.1 Type of solvent .............................103
`
`5.3.2.2 Type of iodized promoter ....................103
`
`5.3.2.3 Transformation of the water formed ..........105
`
`5.3.2.4 The mechanism ...............................106
`
`000008
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`000006
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`CONTENTS
`
`5.3.3 Cobalt-ruthenium catalysts ..........................107
`
`6.3 CATALYS
`
`6.3.1 I
`
`6 6 6 6
`
`5.3.3.1 Cobalt-ruthenium synergy and the
`Ru/Co ratio .................................107
`
`5.3.3.2 Iodized promoters ...........................109
`
`5.3.3.3 Co-catalysts ................................110
`
`5.3.3.4 The reactive pattern ........................111
`
`5.3.4 Ruthenium—rhodiu or palladium catalysts ............11l
`
`6.3.2 P
`
`5.3.5 Ruthenium-manganese catalysts .......................112
`
`BIBLIOGRAPHY ..................................................114
`
`6
`
`SYNTHESIS OF ACETIC ACID
`
`6.1 REACTION PRODUTS, CALCULATION CONVENTIONS ................119
`
`6.1.1 Formation of products ...............................119
`
`6.1.2 Calculation conventions .............................119
`
`6.2 CATALYSIS WITH RHODIUM ....................................12O
`
`6.2.1 The catalytic system ................................120
`
`6.2.2 The effects of temperature and pressure .............l22
`
`6.2.3 The reactive mchanis ..............................122
`
`6.2.4 Conclusion ..........................................124
`
`6.4 OTHER C!
`
`6.4.1 Cc
`
`6.4.2 Rx
`
`6.4.3 It
`
`6.4.4 Co
`
`6.5 ISOERIZ
`
`6.5.1 Pr
`
`6.5.2 Me
`
`6.5.3 Co
`
`BIBLIOGRAPHY
`
`)(H
`
`
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`000007
`000007
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`
`
`
`
`CONTENTS
`
`
`
`
`
` 6.3 CATALYSIS WITH NICKEL .....................................124
`
`
`
`
`
`
`
`6.3.1 The catalytic system ....................-.-~~------.125
`
`6.3.1.1 The catalyst ................................126
`
`6.3.1.2 Methyl iodide ...............................127
`
`
`
`6.3.1.3 Promoters ...................................127
`
`
`
`6.3.1.4 Heterogenization of the catalyst ............131
`
`
`6.3.2 Physical parameters .................................132
`
`
`6.3.2.1 Solvents ....................................132
`
`
`6.3.2.2 The effects of partial pressures of
`C0 and hydrogen .............................133
`
`
`
`6.3.3 The reaction mechanism ...........................,..133
`
`
`6.3.3.2 The overall mechanism .......................135
`
`6.- 4 Conclusion ..........................................135
`
` OTHER
` CATALYSTS ...........................................137
`
`6.4.1 Cobalt...............................................137
`6.4.2 Ruthenium - Acetic acid homologation ................137
`
`
`
`6.3.3.1 The active complex ..........................133
`
`6.4.3 Iridium .............................................138
`
`6.4.4 Conclusion ..........................................141
`
`
`
`..141
`ISOMERIZATION OF METHYL FORMATE INTO ACETIC ACID ........
`
`
`
`
`6.5.1 Preparation of methyl formate .......................141 6.5.2 Methyl formate isomerization ........................142
`
`
`
`6.5.3 Conclusion ..........................................l42
`
`BIBLIOGRAPHY ..................................................144
`
`
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`000008
`000008
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`CONTENTS
`
`7
`
`CARBONYLATION OF METHYL ACETATE
`INTO ACETIC ANHYDRIDE
`
` 7.1 THE HALOLYSIS REACTION ....................................150
`
`7.1.1 Definition s.........................................15O
`
`7.1.2 Halolysis in methyl acetate carbonylation ...........151
`
`7.1.3 Determination of halolysis constants ................l51
`
`7.2 REACTION PRODUCTS - CONVENTIONS -
`METHODS OF CALCULATION ....................................153
`
`7.2.1 Formation of reaction products . . . . . .................153
`
`7.2.2 Conventions - Methods of calculation ................154
`
`7.3 CATALYSTS BASED ON A NOBLE GROUP VIII METAL;
`THE CASE OF RHODIUM .......................................154
`
`« 7.3.1 The different constituents of the catalytic system ..156
`
`7.3.1.1 Catalyst ....................................156
`
`7.3.1.2 Iodized activator............................158
`
`7.3.1.3 Metallic promoters ..........................159
`
`7.3.1.4 Organic promoters ...........................164
`
`7.3.1.5 Conclusion ..................................167
`
`7.3.2 The physical parameters of the reaction .............167
`
`7.3.2.1 The effects of solvents .....................168
`
`7.3.2.2 The effects of pressure .....................168
`
`7.3.2.3 The effects of temperature ..................168
`
`7.3.3 Mechanisms of the reaction ..........................169
`
`7.3.4 By—products and processing of reaction liquor .......17O
`
`)(H/
`
`7.4 NICKEL CA
`
`7.4.1 Rea
`
`7.4.2 The
`
`7.4
`
`7.4
`
`7.4
`
`7.4
`
`7.4
`
`7.4.3 Phy
`7.4
`
`7.4
`
`7.4
`
`7.4.4 Rea
`
`7.5 COBALT CA
`
`7.5.1 The
`
`7.5
`
`7.5
`
`7.5.2 Mec
`
`7.5
`
`7.5
`
`7.6 DIMETHYLE
`
`BIBLIOGRAPHY
`
`
`
`000009
`000009
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`
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`CONTENTS
`
`7.4 NICKEL CATALYSTS ..........................................176
`
`7.4.1 Reaction mechanisms .................................177
`
`7.4.2 The catalytic system ................................178
`
`7.4.2.1 Nickel ......................................179
`
`7.4.2.2 Methyl
`
`iodide ...............................179
`
`7.4.2.3 Ionic iodides .............. . . . . .............179
`
`7.4.2.4 Promoters ...................................18O
`
`7.4.2.5 Conclusion ..................................182
`
`7.4.3 Physical parameters of the reaction .................182
`
`7.4.3.1 The effects of solvents .....................182
`
`7.4.3.2 The effects of partial pressures of carbon
`moxonide and hydrogen .......................183
`
`7.4.3.3 The effect of the temperature ...............183
`
`7.4.4 Reaction by—products ...........
`
`7.5 COBALT CATALYST ....................
`
`7.5.1 The catalytic system ..............
`
`7.5.1.1 The function and effects of
`metallic promoters ........
`
`7.5.1.2 The effects of hydrogen - selectivity
`
`7.5.1.3 Iodized promoters .....................
`
`7.5.1.4 The effects of the solvent .................
`
`the carbon monoxide pressure
`7.5.1.5 The effects of
`and the temperature ........................
`
`7.5.1.6 Conclusion ... . . . . .........
`
`............
`
`7.5.2 Mechanisms of the reaction ...
`
`..............
`
`7.5.2.1 Acetoxycarbonylation of methyl
`
`iodide ......
`
`7.5.2.2 The mechanism of methyl acetate
`carbonylation ..............................
`
`7.6 DIMETHYLETHER CARBONYLATION ....
`
`BIBLIOGRAPHY ...
`
`000010
`000010
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`
`
`CONTENTS
`
`8
`
`SYNTHESIS OF 1,1-ETHYLIDENE DIACETATE
`ROUTE TO VINYL ACETATE
`
`8.1 SYNTHESES OF VINYL ACETATE ................................201
`
`8.2 SYNTHESIS OF EDA VIA CONDENSATION OF ACETALDEHYDE
`WITH ACETIC ANHYDRIDE .....................................205
`
`8.2.1 Synthesis of VA (Mitsubishi gas)
`
`8.2.2 Synthesis of VA by the Halcon process
`
`8.2.3 Conclusion..........................................21O
`
`8.3 DIRECT SYNTHESIS OF EDA VIA HYDROCARBONYLATION
`OF METHYL ACETATE .........................................2l3
`
`8.3.1 THE DIFFERENT CATALYTIC SYSTEMS .....................2l3
`
`8.3.1.1 Group VIII noble catalysts: rhodium and
`palladium...............M....................213
`8.3.1.2 Nickel catalysts
`
`8.3.2 Reaction products-mechanistic hypotheses ............216
`
`1
`
`E
`
`5
`
`9
`1
`I
`
`8.3.3 Conclusion
`
`8.4 EDA SYNTHESIS VIA HYDROGENATION or‘ ACETIC ANHYDRIDE .......213
`
`8.4.1 Catalytic systems
`
`8.4.2 Reaction products — Mechanistic hypothesis ..........221
`
`8I4I3
`
`ICUO.UII.CI.U.CUII..UIOIII.UIII..I.ClC.OIQ221
`
`-..o..........9...-ua.-....-..age;-on-..-.........222
`
`
`
`S
`
`9.1 ROUTE T
`
`9.2 DIRECT
`
`9.3 FORMALD
`
`9.3.1 S}
`9
`
`9.
`9.
`9.
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`9.3.2 S5
`
`9.
`9
`9
`
`9.4THE0x-AL
`
`9""1 55'
`
`9'4'2 Hy‘
`
`9‘4'3 Cm
`
`XVI
`
`00001 1
`
`000011
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`
`
`
`
`
`
`CONTENTS
`
`9
`
`SYNTHESIS OF 1,2-GLYCOL AND OXALIC ACID
`
`9.1 ROUTE T0 1,2—GLYCOL AND OXALIC ACID .......................225
`
`9.2 DIRECT SYNTHESIS ex—CO/H2 .................................226
`
`9.3 FORMALDEHYDE ROUTES .......................................229
`
`9.3.1 Synthesis of glycolic acid ..........................229
`
`9.3.1.1 Acid catalysis ..............................229
`
`9.3.1.2 Metal catalysis .............................23O
`
`9.3.1.3 Hydrogenation of glycolic acid ..............23O
`
`9.3.1.4 The industrial interest of the ex—g1ycolic
`acid process ................................231
`
`
`
`9.3.2 Synthesis of glycolaldehyde .........................231
`
`9.3.2.1 Cobalt catalysis ............................231
`
`9.3.2.2 Rhodium catalysis ...........................232
`
`9.3.2.3 The industrial future of the glycolaldehyde
`process .....................................232
`
`
`
`IOOIOOOIICUIIIIIOUIIOJIIIIICIIIIOCOCOIICIZBB
`
`9.4.1 Synthesis of oxalic esters ..........................233
`
`9.4.2 Hydrogenation of oxalates into glycol ...............235
`
`9.4.3 Conclusion on the oxalate process ...................235
`
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`Basic Chemic
`of the Divis
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`res
`Our
`Saint-Fons,
`of the Organ:
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`
`I Q
`
`
`
`CONTENTS
`
`10
`
`CARBON MONOXIDE: HEALTH AND SAFETY
`
`10.1
`
`TOXICOLOGICAL HAZARDS 1,2 ...............................241
`
`10.1.1
`
`Causes of the toxicity of CO ....................241
`
`10.1.2
`
`Sources of CO in the blood ......................242
`
`10.1.3
`
`The kinetics of CO fixation on and elimination
`
`from hemoglobin .................................243
`
`10.1.4
`
`Cumulative effects of small amounts of CO . . . . . ..243
`
`10.1.5
`
`10.1.6
`
`Acute CO poisoning .....
`
`..............244
`
`Treatment of acute poisoning ....................244
`
`10.2
`
`SAFETY
`
`MEASURES IN A RESEARCH LABORATORY ................245
`
`10.2.1
`
`10.2.2
`
`Medical precautions .............................245
`
`Technical precautions............................246
`
`REFERENCES ....................................................248
`
`)(\/HI
`
`
`
`000013
`000013
`
`
`
`
`
`
`
`
`Conventions and methods
`of calculations
`
`3
`
`Throughout this book, it has been necessary to adopt certain
`conventions in order
`to make a comparison of
`the results which
`are scattered in some hundreds of publications and patents. As a
`general
`rule,
`these results have
`been. expressed in specific
`units,
`according to criteria that have been defined by each
`research group and which often have been specifically determined
`to meet
`the objectives of that work.
`
`
`
`
`
`
`
`
`
`
`
`
`
`the information published (experimental parameters and
`Thus,
`to allow the necessary
`results) had to be standardized in order
`
`comparisons. This
`standardization has enabled us
`to define a
`single method of calculation which is applicable to the results
`as a whole.
`
`
`
`
`
`
` 3.1 CONVENTIONS
`
`3.1.1
`
`
`PHYSICAL PARAMETERS
`
`
`
`
`Temperatures are expressed in degrees Celsius (°C).
`
`
`
`Pressure values, expressed in bars
`(bar), are recorded at
`the temperature of the experiment.
` Reaction time, expressed in hours (h):
`is counted when the
`reaction mixture reaches the operational temperature.
`
`
`
`000014
`000014
`
`
`
`0.12 mo
`
`0.10 mo
`
`0.03 mo
`
`0.005 m
`
`3.2.1 CALCU]
`
`The yie]
`
`RR
`
`CONVENTIONS AND METHODS OF CALCULATIONS
`
`3
`
`3.1.2 REAGENTS
`
`and co-catalyst are
`The quantities of metallic catalyst
`expressed in gram-atoms of metal (except in the case of bi—metal-
`lic clusters for which the charges will be given in moles so that
`neither of the two component metals will be privileged.
`
`Iodine derivatives are reduced to the gram—atom of iodine.
`
`All
`
`the other charges are given in moles.
`
`
`
`3.1.3 RESULTS
`
`Yields are recorded as RR.
`
`Conversion are recorded as TT.
`
`Selectivity values are recorded as RT;
`ratio RR/TT.
`
`they are equal to the
`
`where n is tt
`
`Spatial productivities P3 are expressed in gram of product
`per hour of reaction and per litre of initial reaction volume at
`20°C (g/h.1)
`
`Intrinsic productivities Pi are expressed in gram of product
`hour of
`reaction and per gram of charged metal
`(g/h.g
`per
`metal).
`
`
`
`3.2 CALCULATION OF RR, TT, RT. P5 et P,
`
`the following reaction as
`Let us consider
`illustrate the calculation method utilized.
`
`an example
`
`to
`
`is hydrocarbonylated
`40 ml)
`(i.e.
`0ne mole of methanol
`without solvent with a catalyst "X" at 200°C under 200 bar. After
`2 hours of reaction,
`the following determinations are made in the
`reaction mixture:
`
`34
`
`Our exau
`
`RR
`
`RR
`
`RR
`
`RR
`
`Actually
`of methyl et
`acetic acid 2
`methanol. Thu
`RR of the lat
`
`The foll
`
`Eth
`
`Met
`
`
`
`000015
`000015
`
`
`
`
`
`
`3
`
`CONVENTIONS AND METHODS OF CALCULATIONS
`
`0.12 mole of ethanol...CH30H + C0 + 2H2 ——> C2H50H + H20
`
`0.10 mole of acetic acid... CHQOH + C0 ———- CH,C02H
`
`0.03 mole of methyl ether...2CH OH ———-CH OCH + H 0
`3
`3
`3
`2
`
`
`
`0.005 mole of methane...CH30H + H2——> CH4 + H20
`
`3.2.1 CALCULATION OF YIELDS RR and RRc
`
`
`
`
`
`The yield RR of product "P" versus substrate 5 is equal to:
`
`
` RR ‘ n x Number of moles of product P x 100
`
`
`
`where n is the stoichiometric coefficient of the reaction S——>P
`
`Our example gives the following results:
`
`RR ethanol = 1 x 0.12 x 100 - 12 Z
`
`RR acetic acid = 1 x 0.10 x 100 = 102
`
`RR ether = 2 x 0.03 x 100 - 6%
`
`RR methane - 1 x 0.005 x 100 s 0.5%
`
`
`
`
`
`involved in the formation
`Actually, carbon monoxide is not
`of methyl ether and methane. On
`the other hand, ethanol
`and
`acetic acid are directly implied in this hydrocarbonylation of
`methanol. Thus, it has been decided to record as RRc the yields
`RR of the latter products.
`
`
`
`
`The following is an illustration of our example:
`
`Ethanol and acetic acid will be expressed as RRc
`
`Methyl ether and methane will be expressed as RR
`
`000018
`000016
`
`Initial number of moles of substrate S
`
`
`
`CONVENTIONS AND MTHODS OF CALCULATIONS
`
`3
`
`3.2.2 CALCULATIONS OF CONVERSION TT and TTc
`
`The conversion rate TT of
`follows:
`
`the substrate is defined as
`
`(moles initial substrate S — moles final substrate S) x 100
`moles initial substrate S
`
`TT.
`
`the number of moles of the substrate contained in
`Actually,
`the raw material of
`the reaction is seldom specifid in the
`patents. This lack of precision does not allow us to calculate
`TT. Rather
`than to ignore this fundamental parameter, we have
`preferred to adopt the following definition:
`
`TT= ERR +\ZRRc
`
`that TT represents the total
`then means
`This
`yields of the quantified products.
`
`sum of
`
`the
`
`this definition can be used only if the
`In simplified form,
`products formed are identified and quantified, which is seldom
`the case. This
`is why we have
`introduced the notion of
`the
`carbonylation conversion TTc;
`in effect, if the majority of
`the
`sub—products are often ignored,
`the carbonylation products, on
`the contrary, are accurately quantified. The equation becomes
`
`TTc = £RRc
`
`Although this definition is purely inferred on the grounds
`of hypothesis
`(absence of data in the literature),
`it is not
`completely deprived of physical meaning:
`in fact, TTc corresponds
`to the methanol "usefully" transformed into products which have
`incorporated at least one molecule of carbon monoxide.
`
`In our example,
`
`the equation is as follows:
`
`TT
`
`= ZRR+ ZRRc = (6 + 0.5) + (12 + 10- = 28.52
`
`TTc = XRRC = 12 + 1O - 22%
`
`3.2.3 CALCULATION OF SELECTIVITIES RT and RTc
`
`By definition the selectivity is equal to the ratio: yield/—
`conversion, i.e.:
`
`36
`
`RT
`
`Our exax
`
`Ethanol:
`
`Acetic acid:
`
`Ether:
`
`Methane:
`
`a. Calcx
`
`sp
`
`The
`importance.
`ensure produ
`(g/h.1) and i
`
`II
`
`“D
`
`Thus,
`
`it
`
`(h
`
`Althougk
`
`its
`(a)
`reactions of
`
`the
`(b)
`take int
`not
`the "aeratior
`
`
`
`000017
`000017
`
`
`
`
`
`3
`
`CONVENTIONS AND METHODS OF CALCULATIONS
`
`
`
`
`RT
`
`_ RR x 100
`-
`TT
`
`and
`
`RTc
`
`
`RRc x 100
`TTC
`
`Our example shows the following results:
`
`
`
`Ethanol:
`
`RT —
`
`12x100
`28.5
`
`— 422, RTc =
`
`12x100 =
`22
`
`552
`
`
`
`
`
`Acetic acid:
`
`RT -
`
`I
`
`II
`
`10x100
`28.5
`
`35Z, RTc =
`
`10x100
`22
`
`= 45%
`
`
`
`
`Ether:
`
`6x100
`28.5
`
`= 21%
`
`RT =
`
`
`
`Methane:
`
`RT =
`
`O,5x1OO _
`28.5
`— 22
`
`
`
`a. Calculation of spatial productivity values Ps
`
`
`
`
`
`Weight (g) of Product
`
`Reaction time (h) x volume (L) of the reaction mixture
`
`Thus,
`
`in our example:
`
`industrial
`factor of
`a
`is
`spatial productivity Ps
`The
`the reactor necessary to
`importance. It defines the volume of
`ensure production. It
`is expressed in grams per hour and liter
`(g/h.l) and is calculated as follows:
`
`
`
`= 69 g/h'1
`
`= 75 g/h.l
`
`
`
`P
`
`s
`
`of ethanol =
`
`gLLL3Lé§
`2x0.040
`
`
`
`P of acetic acid =
`S
`
`94l9§§9
`2x0.040
`
`Although very useful,
`
`this definition is obviously limited:
`
` (a)
`its independence
`reactions of zero order;
`
`from the conversion is limited to
`
`
`
`
`
`the volume of the initial reaction mixture at 20°C does
`(b)
`take into account
`the expansion of
`the reaction mixture or
`not
`the "aeration" of the liquid phase by gaseous reactants.
`
`000018
`000018
`
`
`
`CONVENTIONS AND METHODS OF CALCULATIONS
`
`3
`
`b. Calculation f
`o
`
`intrinsic roductivities Pi
`
`
`
`P =
`W 1
`i Reaction time ?h)h: fiuibof Aroduct P
`er
`:_
`mass of metal %g§at' 1°aded x atomic
`
`This definiti
`only in reactions :?,z;:z Eizegrivigss one.
`3
`e subst
`
`
`
`Hydrocarbonylatb
`9,10, 11, was first m
`
`CHBOH +
`
`CH30H + C
`
`The reaction was
`H. Dreyfus,
`(at 250-
`cobalt catalysts /9/.
`cobalt,
`iron and nick
`
`reaction we
`The
`Vorbach, G. Wietzel a
`stages with
`a mt
`,hydrocarbonylated at
`e
`:feedstock is hydroget
`
`CH30H
`
`Two years later
`3
`2 first direct homolo
`% methanol at
`180°C l
`
`cobalt catalyst, bi
`ethanol was obtain
`productivity of abou
`
` 000019
`
`000019
`
`
`
`aer of
`
`4
`
`(g/h.g
`armula
`
`of TT
`vever,
`us to
`
`ry to
`
`Synthesis of ocefoldehyde
`and ethanol
`
`4.1 INTRODUCTION
`
`Hydrocarbonylation of methanol into acetaldehyde or ethanol,
`9,10, 11, was first described in 1929.
`
`
`
`CH3OH + C0 + H2
`
`CH30H + C0 + 2H2
`
`-—>
`
`-F
`
`CH3CHO + H20
`
`CZHSOH + H20
`
`The reaction was carried out in the vapor phase by
`H. Dreyfus,
`(at 250-400°C under 150 to 200 bar) using iron and
`cobalt catalysts /9/, copper phosphates /10/, and the borates of
`cobalt,
`iron and nickel /11/.
`
`then studied in the liquid phase by 0.
`reaction was
`Thc
`Vorbach, G. Wietzel and A. Scheurmann of BASF in 1941 /50/ in two
`stages with
`a mixed
`cobalt-nickel
`catalyst: methanol
`is
`hydrocarbonylated at
`215°C under
`600 bar,
`and
`the
`reaction
`feedstock is hydrogenated at 220°C under 600 bar.
`
`CH3OH
`
`CoO—NiO
`
`————-—a>
`CO/H2
`
`CoO—NiO
`
`———————>
`H2
`
`CZHSOH
`
`the same authors /51/ realized the
`in 1943,
`Two years later,
`first direct homologation in liquid phase. Working with pure
`methanol at
`180°C under approximately 1 000 bar CO/H2 with a
`cobalt catalyst, bismuth powder, and silver or copper
`iodide,
`ethanol was obtained with a
`672 selectivity and
`a spatial
`productivity of about 4003/h.l.
`
`000020
`000020
`
`
`
`
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`4
`
`and then the heavy shipments of
`II,
`With the World War
`petroleum products to Western markets in 1945-1947,
`the synthetic
`process lost all of
`its economic importance,
`and research was
`stopped. Thus, only seven patents /12-14, 52, 72, 74, 75/ were
`filed between 1941
`and 1973,
`and only nine academic studies
`/85-91, 115-116/ were published. However
`the petroleum crisis of
`1973 brought renewed industrial interest for this reaction.
`
`As a result, during the last decade a dozen general reviews
`/1-8, 119/ and more than 60 patents on the hydrocarbonylation of
`methanol have been published between 1975 and 1982.
`
`4.2 REACTION PRODUCTS
`CONVENTIONS, AND METHODS OF CALCULATIONS
`
`The hydrocarbonylation of methanol always gives a mixture of
`products. The main reactions
`(1
`and 2),
`are accompanied by
`carbonylation (3), hydrogenation (4) and dehydration (5) of
`the
`substrate:
`
`CH3CH=CHCH(
`
`CH3CHO + 21
`
`(b)
`
`e1
`tr.‘
`(12) ,
`hydrocarbor
`
`CH3CH2OH +
`
`2CH3CH2OH
`
`CH3CH2OH +
`
`CH3CH2OH +
`
`CH3CH2OH +
`
`CH3CH2OH +
`
`(c) ac
`
`(12):
`
`CH3CO2H + G
`
`(d) wa
`shift equil
`
`H.
`
`fl
`
`All
`
`importance 1
`point of vb
`of a detaile
`
`4.2.1 FORMA
`
`CH3OH + C0 + H2 ——> CH3CHO + H20
`
`CH3OH + C0 + 2H2 —->- CH3CH2OH + H20
`
`CH3OH + CO
`
`——- CH3CO2H
`
`CH3OH + H2
`
`——- CH4 + H20
`
`—->- CH3OCH3 + H20
`
`(1)
`
`(2)
`
`(3)
`
`(4)
`
`(5)
`
`products
`
`are
`
`themselves
`
`sources
`
`of
`
`new
`
`2CH3OH
`
`primary
`thus:
`
`The
`reactions;
`
`(a) acetaldehyde can. be crotonised,
`give C4— aldehydes and alcohols
`(6-8), or
`(9):
`
`then. hydrogenated to
`react with methanol
`
`If the
`2CH3CHO
`-—>-
`CH3CH=CHCHO + H20
`(6)
`of ethanol
`reaction is
`
`
`(7)
`
`mixture.
`CH3CH-CHCHO + H2
`->-
`CH3CH2CH2CHO
`
` 000021
`
`000021
`
`
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`CH=CHCHO + 2H9
`
`23
`
`CH CH CH CH OH
`3
`2
`2
`2
`
`CH3CH(OCH
`
`3)2 + H20
`
`(9)
`
`leads to etherification (l0,11), esterification
`(b) ethanol
`transesterification
`(13),
`carbonylation
`(14)
`and
`
`CH3CH2OH + CH3OH
`
`CH3CH2OCH3 + H20
`
`2CH3CH2OH
`
`CH3CH2OCH2CH3 + H20
`
`€H3CH2OH + CH3CO2H
`
`CH3CO2CH2CH3 + H20
`
`CH3CH2OH + CH3CO2CH3
`
`CH3CO2CH2CH3 + CH3OH
`
`CH3CH2OH + CO
`
`——>-
`
`CH3CH2CO2H
`
`CH3CH?OH + CO + 2H
`
`2
`
`CH CH CH OH + H O
`3
`2
`2
`2
`
`(10)
`
`(11)
`
`(12)
`
`(13)
`
`(14)
`
`(15)
`
`(c) acetic acid is esterified into methyl and ethyl acetate
`
`C(12):
`
`CH3CO2H + CH3OH
`
`CH3CO2CH3 + H20
`
`(16)
`
`(d) water may react with CO to give CO2 and H2
`shift equilibrium 17):
`
`(water-gas
`
`H2O + CO
`
`CO2 + H2
`
`(17)
`
`same
`the
`not‘ have
`do
`reactions
`secondary
`these
`All
`the same consequences as seen from an industrial
`importance nor
`point of view. The most significant reactions will be the object
`of a detailed analysis in paragraph 4.6.
`
`4.2.1 FORMATION OF REACTION PRODUCTS
`
`the synthesis
`If the two main reactions are considered, i.e.
`of ethanol
`and acetaldehyde,
`it must
`be
`admitted that
`the
`reaction is not
`selective; both products are obtained as
`a
`mixture.
`
`000022
`000022
`
`
`
`
`
`The
`
`1
`
`hydrocarbou
`
`Fig
`
`4.2.2 CONV
`
`A conq
`literature
`
`and
`data,
`denominator
`
`The po
`obtained af1
`
`Potent:
`
`Potent:
`
`Potentj
`
`
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`4
`
`Mechanistic
`
`studies
`
`show that
`
`ethanol
`
`is derived from
`
`hydrogenation ot
`71 98/:
`
`the intermediate acetaldehyde /14, 64, 66, 69,
`
`CHO!-‘{+C0+H
`3
`
`2
`
`CH3CH0 + H2
`
`[Cat&J
`——-—->
`
`[Cata.]
`-——————>
`
`CHCI-I0+H0
`3
`2
`
`(1)
`
`CZHSOH
`
`(18)
`
`is illustrated in figure 1: acetaldehyde and acetic
`This
`acid are primary products, whereas ethanol
`results from the
`conversion of aldehyde.
`
`0
`
`so
`
`TS
`
`
`; Toluene = 50 ml
`Conditions: CH30H - 350 ml
`Bu4NFeCo3(C0)12 - 1 mmol
`; CH3I = 16 mmcl — 220°C
`270 bar ; C0/H2 = I
`
`
`
`
`
`Fig. 1. Influence of conversion TT of methanol on yield
`RR of alcetaldehyde (0), ethanol (x), acid acetic (+);
`
`/66/.
`
`TTc, RE
`on the basis
`
`42
`
`
`
`000023
`000023
`
`
`
`
`
`d
`
`from
`
`66, 69,
`
`(1)
`
`(18)
`
`acetic
`'om the
`
`4
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`relationship of main and by—products obtained from
`The
`hydrocarbonylation of methanol is summarized in Fig.2.
`
`caacazcnfmhoa
`
`H2
`C33CE2G$fE@ —————.
`
`_
`
`cnaca
`
`_
`
`ca
`
`can
`
`232
`....__..
`
`L Cflaizfi
`
`°33‘3°2C255
`
`Fig.2. Diagram showing the formation of products and
`by-products from hydrocarbonylation of methanol.
`
`4.2.2 CONVENTIONS USED FOR CALCULATIONS
`
`results published in the
`the different
`A comparison of
`rigorous standardization of experimental
`literature demands
`a
`an
`accurate definition of
`the highest
`data,
`and
`requires
`denominator related to all these publications.
`
`The potential product is the product which is theoretically
`obtained after complete hydrolysis of the reaction feedstock.
`
`
`
`Potential acetaldehzde: Free aldehyde + acetal
`
`
`Potential ethanol: free ethanol + ethers + ethyl esters
`
`Potential acetic acid: free acetic acid + acetic esters
`
`C /66/.
`
`TTc, RRc and RTc of these three products will be calculated
`on the basis of potential products.
`
`000024
`000024
`
`
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`4
`
`4.3 NATURE OF THE CATALYTIC SYSTEM
`
`of
`hydrocarbonylation
`that
`4.3.5. mentions
`Paragraph
`/45, 117/,
`iron /72, 80, 98,
`methanol can be induced by nickel
`100/, manganese
`/24/,
`ruthenium /15/,
`and rhodium /96/ based
`catalyst.
`
`the most
`Cobalt—catalyzed reactions, however, are by far
`numerous and yield the best results. The metal element is seldom
`used alone and the reaction generally involves ligand promoters
`and/or co—catalysts
`to increase the activity and selectivity.
`Thus, systems of cobalt—iodine, cobalt—iodine—phosphine or amine
`and, finally, cobalt—ruthenium—iodine—phosphine have successively
`appeared in the literature.
`
`this classification of
`Although schematically represented,
`catalytic systems by successive addition of various promoters,
`clearly shows the effect produced by each of these co—catalysts.
`
`4.3.1. COBALT—CATALYZED SYNTHESIS
`
`The hydrocarbonylation of methanol can be carried out in the
`presence of cobalt only, without
`the use of bridging ligands or
`co—catalysts. However,
`the reaction is slow and the selectivity
`is low.
`
`
`
`
`
`
`
`
`
`the
`/85/,
`Described for the first time by I. Wender in 1951
`reaction is done in the presence of Co (CO)
`in mnethanol, at
`about180—190°C under 250 to 350 bar C0/H . Resu ts are summarized
`2
`in table 4.1.
`
`by W. Slinkard
`results have been improved
`these
`Recently,
`and G. Koermer;
`using more
`sophisticated analytical
`/71/;
`methods,
`these authors have made a complete weight balance of the
`reaction, which leads to results as summarized in table 4.1;
`the
`selectivity of hydrocarbonylation to ethanol is brought back to
`68% when taking into account all the reaction products (a total
`of 13).
`
`000025
`
`000025
`
`
`
`SYNTHESIS OF ACETALDEHYDE AND ETHANOL
`
`tion
`
`of
`
`80, 98,
`6/ based
`
`the most
`Ls seldom
`promoters
`activity.
`or amine
`
`zessively
`
`ation of
`:omoters,
`
`zalysts.
`
`1t in the
`
`gands or
`Lectivity
`
`the
`'85/,
`anol, at
`nmmarized
`
`Slinkard
`
`Lalytical
`:e of
`the
`
`the
`4.1;
`back to
`
`(a total
`
`TABLE4.1
`
`
`
`
`
`Hydrocarbonylationofmethanolcatalyzedbycobaltalone
`
`
`
`
`Discontinuous
` Author
`
`1.Wander
`
`
`
`Continuous
`
`Discontinuous
`
`
`.E.Slinkard [711
`
`
`
`G.Koerner
`
`[Ref]
`
`[351
`
`000028
`000026
`
`
`
`
`
`SYNTHESIS OF ACET
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