Hydroformylierung - TU Dortmund - TC [PDF]

Prof. Dr. Dieter Vogt Fakultät Bio- und Chemieingenieurwesen Lehrstuhl für Technische Chemie

Homogene Katalyse

Dieter Vogt Freitag, 05-05-2017 D. Vogt

Homogeneous Catalysis last change: 170503

Catalytic Cycle and Elementary Steps H oxidative addition

Ln-1M n = 18, 16

+ HY

Y

-L dissociation

dissociation

MLn

-L

Ln-2M

MLn-1

n = 18, 16

n = 16, 14

n = 16, 14

H Y association

reductive elimination

H

+L Y association

R

D. Vogt

H n = 18, 16

Homogeneous Catalysis last change: 170503

insertion

Ln-2M n = 16, 14

n = 18, 16

R

R

Y

Catgen_sw1

Factors Controlling Activity and Selectivity in a Metal Complex Transition metal  e--configuration (d0-d10)  orbital symmetry  number of coordination sites  ion or atom radius  ionic or neutral  nature of counter ions

Ligands  donor / acceptor properties  dissociation constant  space filling (cone angle)  chelate effect  bite angle  symmetry L L

D. Vogt

Homogeneous Catalysis last change: 170504

R M Substrate & Solvent  in principle like ligands Catgen_sw2

Hydroformylation CHO

CO/H2 R

R



+

R

CHO

[catalyst]

The Co-catalyzed hydroformylation reaction was found by O. Roelen in 1938 during his work on Fischer-Tropsch synthesis

 Very important reaction (about 10 Mt/a of aldehydes) for the production of - softeners for plastics O. Roelen, 1897-1993 - detergent alcohols - solvents - lubricants, and - pharmaceuticals.

 Bulky substituents on the alkene increase the linearity of the product.  Acceptor ligands increase the rate of the reaction by accelerating ligand and CO dissociation and olefin coordination.

 Acceptor ligands increase the ratio of linear product. D. Vogt

Homogeneous Catalysis last change: 170504

Catalysis_15

Hydroformylierung - Geschichte

Die weltweit erste Oxoanlage in Oberhausen/Holten im Bau (~1944)

D. Vogt

Homogeneous Catalysis last change: 170504

Hydroformylierung Neben- und Folgereaktionen 1) Hydrierung des Alkens zum Alkan

2) Doppelbindungs-Isomerisierung des Alkens 3) Hydrierung der Aldehyde zu Alkoholen 4) Kondensation der Aldehyde (Aldolkondensation) 2

D. Vogt

Homogeneous Catalysis last change: 170504

CHO - H2O

OHC

Industrial Hydroformylation Overview Catalyst

Co(CO)4H

Co(PBu3)(CO)3H Rh(CO)4H

Rh(TPP)3(CO)H Rh(TPPTS)3(CO)H

T

110-180°C

160-200°C

100-140°C

85-115°C

50-130°C

p

200-350 bar

30-100 bar

200-300 bar

15-20 bar

10-100 bar

Products

aldehydes

alcohols

aldehydes

aldehydes

aldehydes

l/b (propene)

80:20

88:12

50:50

92:8

95:5

Byproducts

medium

high

low

low

low

Poisoning

low

medium

high

Feed stocks

C2-C20

Higher alkenes

spec. alkenes, ethene

Processes

BASF 1950

Shell 1960

Separation cat./product

several

Catalyst recycling

several

D. Vogt

-

high

lower alkenes

lower alkenes

-

UCC, 1974 Low Pressure Oxo (LPO)

Ruhrchemie/ Rhône Poulenc 1984

distillation under increased pressure

-

distillation

phase separation

in residue

-

cat. remains in reactor

in aqueous phase

Homogeneous Catalysis last change: 170504

Catalysis_16

Mechanismus der Co-katalysierten Hydroformyl. Reaktion:

R-CH2-CH2-CHO

R-CH=CH2 + CO + H2

HCoI(CO)4 (18) CO-Dissoziation CO RCH2CH2CHO

HCoI(CO)3 (16)

CH2=CHR

reduktive Eliminierung

Assoziation

RCH2CH2COCoIII(H2)(CO)3 (18)

HCoI(CO)3(CH2=CHR) (18)

oxidative H Addition 2

Insertion in Co-H

RCH2CH2COCoI(CO)3 (16)

RCH2CH2CoI(CO)3 (16)

Assoziation CO Insertion in Co-Alkyl D. Vogt

Homogeneous Catalysis last change: 170504

RCH2CH2CoI(CO)4 (18)

CO

Hydroformylierung  1. Katalysatorgeneration Katalysator :

Cobalt (ohne Phosphorliganden) aktive Spezies : HCo(CO)4

Zeitraum

:

seit ~ 1950 bis heute

Prozesse

:

- BASF-Prozeß - Exxon-Prozeß

Reaktionsbedingungen : Produkte

:

T = 120-180 °C p = 270-300 bar Aldehyde

n/iso-Verhältnis : 80 : 20 D. Vogt

Homogeneous Catalysis last change: 170504

Hydroformylierung

BASF-Prozeß Abgas

Kreislaufgas

Zyklon H+/O2

Reaktor

Cobalt-Ausfällung

Phasenabscheider

Rohaldehyde org. Phase

wässr. Phase

Olefin

Aufkonzentration CO/H2

Katalysatoraufbereitung

SynthesegasReinigung CO/H2

Cobalt

D. Vogt

Homogeneous Catalysis last change: 170504

Abwasser

Hydroformylierung  2. Katalysatorgeneration Katalysator :

Cobalt + Phosphanliganden PR3 aktive Spezies : HCo(CO)3(PR3)

Zeitraum: Prozesse:

seit ~ 1960 bis heute Shell-Prozeß

Reaktionsbedingungen :

T = 150-190 °C p = 40-80 bar Aldehyde, Alkohole („Dobanole“)

Produkte:

n/iso-Verhältnis : 88 : 12

D. Vogt

Homogeneous Catalysis last change: 170504

Hydroformylation (Cobalt-Catalyzed)  Sterically demanding phosphines increase linearity of the product aldehyde C20H41

 Tolman cone angle P

Shell hydroformylation process

 Co catalyst can hydroformylate internal alkenes to linear aldehydes • Fast alkene double bond isomerization due to acidic H-Co • Conversion to aldehyde (CO insertion) predominantly via linear Co-alkyl species • Hydrogenation of aldehydes to alcohols & aldol condensation D. Vogt

Homogeneous Catalysis last change: 170503

Hydroformylierung 3. Katalysatorgeneration Katalysator :

Rhodium + Phosphanliganden PR3 aktive Spezies : HRh(CO)(PPh3)3

Zeitraum

:

1974 bis heute

Prozesse

:

- UCC-Prozeß (Union Carbide Corporation) - Celanese - Mitsubishi et al.

Reaktionsbedingungen :

Produkte

T = 85-90 °C p = 15-18 bar Low-Pressure-Oxo-Verfahren (LPO)

:

Aldehyde

n/iso-Verhältnis : D. Vogt

92 : 8

Homogeneous Catalysis last change: 170504

Hydroformylierung  Formation of the catalyst complex H2

 Cobalt systems:  Rhodium systems:

Co2(CO)8

2 HCo(CO)4 CO/H2 ; L

(acac)Rh(CO)2 - Hacac

H L Rh CO L CO

 At high Rh concentration and low pressure there is an equilibrium between catalytically inactive dimeric species and the active hydride. O O C C L Rh Rh L C C L O O L

D. Vogt

Homogeneous Catalysis last change: 170503

H + H2 2 L

Rh

CO L

CO

Catalysis_17

Hydroformylierung 

H L Rh In most cases, esp. for -donor ligands, L CO CO or ligand dissociation is the rate limiting step, together with olefin ligand coordination. dissociation O

R

CO n = 18 CO

H L Rh

reductive elimination H H L Rh L CO O n = 18

R alkene coordination

L CO n = 16

H

R

L L

R

Rh CO

oxidative addition H2

migratory insertion O L

Type I rate law: r=

Rh

D. Vogt

migratory insertion

[CO] Homogeneous Catalysis last change: 170503

Rh

n = 16

L CO

k [H2][Rh]

LR

R

L CO n = 16 R L L

Rh CO CO n = 18

CO ligand association Catalysis_18

Hydroformylierung 3. UCC-Prozeß (LPO) Katalysator: Temperatur: Drücke: n/i-Verhältnis:

HRh(CO)(PPh3)3 85 - 95 °C 15 - 18 bar 92:8

 Katalysatorabtrennung abhängig vom Siedepunkt der Produkte: Gas-Recycle-Prozess

Flüssig-Recycle-Prozess

Kreislaufgas Propan ( + Edukte)

Kompressor

P, E

Butanale

Reaktor

E Wärmetauscher K K L L L LK K L Propen

D1

g l

P P P

P

Butanal

Propen Höhersieder

Reaktor

L = hochsiedendes Lösungsm.

D. Vogt

D3

E E E

+ CO/H2

+ CO/H2

D2

Abscheider

Homogeneous Catalysis last change: 170504

Katalysatorrecycle

Hydroformylierung  LPO-Anlage (dreisträngig)

• • • •

D. Vogt

Homogeneous Catalysis last change: 170504

T = 80°C p = 20 bar Aldehydausbeute: 96% E-Faktor: 0,06

Hydroformylierung 4. Katalysatorgeneration Katalysator :

Rhodium + wasserlösliche Phosphanliganden z.B. Triphenylphosphantrisulfonat-Natriumsalz TPPTS-Na aktive Spezies : HRh(CO)(TPPTS)3

Zeitraum

:

1986 bis heute

Prozesse

:

Ruhrchemie / Rhône-Poulenc (RCH / RP)-Prozeß

Reaktionsbedingungen :

Produkte

:

n/iso-Verhältnis :

D. Vogt

T = 110-130 °C p = 40-60 bar Aldehyde > 95 : 5

Homogeneous Catalysis last change: 170504

Hydroformylierung Sulfoniertes Triphenylphosphin  Synthese Oxid.

NaOH

SO3 P HO3S

3

- H2O

3P

NaO3S

3

P

NaO3S

 Sulfonierte Triphenylphosphine SO3Na

SO3Na

D. Vogt

P

P

TPPMS

TPPDS

Homogeneous Catalysis last change: 170505

SO3Na

SO3Na

NaO3S

P

TPPTS

SO3Na

3

P O

Prinzip der Zweiphasenkatalyse Ruhrchemie/Rhône Poulenc, Rhodium + Phosphine two Phase Process

C HO

+ CO / H2

reactor

product

CO / H2

decanter substrate P

HRh(CO)(L)3 in aqueous layer make up

Rhône-Poulenc Recherche (E.G. Kuntz), FR 2.314.910 (1975) E.G. Kuntz, CHEMTECH 1987, 17, 570. D. Vogt

Homogeneous Catalysis last change: 170505

L=

purge (tars)



SO3Na

3

limited by alkene solubility in water ! Hydroform_06

Hydroformylierung Dr. Boy Cornils Entwicklung des RCH/RP-Verfahrens • Jahrgang 1938 • Promotion 1964 in Technischer Chemie an der TH Hannover • Leiter der Abteilung Forschung & Entwicklung der Ruhrchemie AG/Oberhausen • 1989-1998 Honorarprofessor in TC an der RUB

D. Vogt

Homogeneous Catalysis last change: 170505

Hydroformylierung Entwicklung des Ruhrchemie/Rhône-Poulenc-Verfahrens Labor

Pilotanlage

T (°C)

125

125

122

p (bar)

30

50

50

Reaktorinhalt

5L

50 L

120 m³

1

1:10

1:24.000

3,1 Mio.

3,6 Mio.

>5 Mio.

94:6

95:5

96:4

Scale-Up-Faktor TON n/iso-Verhältnis

D. Vogt

Homogeneous Catalysis last change: 170505

Produktionsanlage

Hydroformylierung TPPTS replentishment

D. Vogt

Homogeneous Catalysis last change: 170505

Propen Hydroformylierung zu Butanalen Ruhrchemie/Rhône Poulenc 1

6

2

5 4

3

1 2

D. Vogt

Reaktor mit eingebautem Fallfilmverdampfer 6 Phasentrenner

Homogeneous Catalysis last change: 170505

3 4 5

Wärmetauscher Desorptionskolonne Destillationskolonne

BASF Verfahren zur Propen Hydroformylierung

D. Vogt

Homogeneous Catalysis last change: 170505

Hydroformylierung Entwicklung der C4-Produktionskapazitäten 2002:

7,5 Mio. t/a

2012: 10 Mio. t/a 6

Total

5

Mt/a

4

Rhodium-basiert 3 2

Cobalt-basiert

1

0 1978

1980

1982

1984

1986

1988

Jahr D. Vogt

Homogeneous Catalysis last change: 170505

1990

1992

1994

1996

1998

Hydroformylierung Synthese von Dioctylphthalat 2

CHO

Hydrierung + 2 H2

Base - H2O

OH

OHC 2-Ethylhexenal

n-Butanal

2-Ethylhexanol

Phthalsäureanhydrid (PSA) Veresterung O O O O

 Weichmacher für PVC

D. Vogt

Homogeneous Catalysis last change: 170505

Di-octylphthalat (DOP)

Catalyst-Recycling I Ruhrchemie, Cobalt

C HO

+ CO / H2

reactor

HCo(CO)4

catalyst decomposition substrate steam

CO / H2

Co-powder

filtration

catalyst regeneration product

D. Vogt

Homogeneous Catalysis last change: 170505

Hydroform_01

Catalyst-Recycling II BASF, Cobalt

C HO

+ CO / H2

HCo(CO)4

reactor

catalyst oxidation aqueous acetic acid

product

decanter

catalyst extraction

aqueous Co-acetate

substrate CO / H2 D. Vogt

Homogeneous Catalysis last change: 170505

catalyst reduction Hydroform_02

Catalyst-Recycling III Ugine / Kuhlman, Cobalt

C HO

+ CO / H2 NaOH

HCo(CO)4

reactor

catalyst neutralization

CO / H2

HCo(CO)4 (aq)

product

decanter catalyst extraction

substrate

Na2SO4 , waste D. Vogt

Homogeneous Catalysis last change: 170505

NaCo(CO)4 (aq)

H2SO4

catalyst acidification Hydroform_03

Catalyst-Recycling IV Shell, Cobalt + Phosphine

C HO

+ CO / H2

reactor

product

CO / H2

flash distillation substrate HCo(CO)3PR3 stable in high boilers make up

D. Vogt

Homogeneous Catalysis last change: 170505

purge (tars)

   

HCo(CO)3(PBu3) stable CO pressure temperature hydridic character Hydroform_04

Catalyst-Recycling V Union Carbide, Rhodium + Phosphine

C HO

+ CO / H2

reactor

product

CO / H2

flash distillation substrate HRh(CO)(PPh3)3 stable in molten PPh3 make up

D. Vogt

Homogeneous Catalysis last change: 170505

purge (tars)

   

low CO pressure low temperature very hydridic character limited to light alkenes ! (volatile aldehydes) Hydroform_05

Catalyst-Recycling VI Ruhrchemie/Rhône Poulenc, Rhodium + Phosphine two Phase Process

C HO

+ CO / H2

reactor

product

CO / H2

decanter substrate P

HRh(CO)(L)3 in aqueous layer make up

Rhône-Poulenc Recherche (E.G. Kuntz), FR 2.314.910 (1975) E.G. Kuntz, CHEMTECH 1987, 17, 570. D. Vogt

Homogeneous Catalysis last change: 170503

L=

purge (tars)



SO3Na

3

limited by alkene solubility in water ! Hydroform_06

Catalyst-Recycling VII Ruhrchemie/Rhône Poulenc, Rhodium + Phosphine two Phase Process

CHO

+ CO / H2

gas recycle & off gas

organic layer hydrophilic ligand: TPPTS

NaO3S

3

product

P

solubility: > 1 kg / l H2O

Rhône-Poulenc Recherche (E.G. Kuntz), FR 2.314.910 (1975) E.G. Kuntz, CHEMTECH 1987, 17, 570. CO / H 2

propene D. Vogt

Homogeneous Catalysis last change: 170505



process intensification

=> reactor & decanter in one unit Hydroform_07