Ionic Liquids at BASF SE · Ionic Liquids at BASF SE Dr. Klemens Massonne BASF SE, Ludwigshafen...

Ionic Liquids at BASF SE

Dr. Klemens Massonne

BASF SE, Ludwigshafen

Leuven Ionic liquid Summer School

23. – 27. August 2010

2

R

N

R

RR+

R

N

R

RR++

N

R R

+N

R R

++

N

N

R

R+

N

N

R

R++

Cl -

RSO4-

R2PO4-

CH3CO2-

CH3SO3-

AlCl4-

SCN -

BF4-

literally no vapour pressure

non flammable

high therm. & mechan. stability

broad liquid range

electric conductivity

high electrochem. stability

exceptional diss. properties

liquid salts

m.p. < 100°C

(often: < r.t.)


What are Ionic Liquids ?

3

P

Cl

Cl

P

OEt

OEt

2 EtOH+ + 2 + 2 R3N * HClR3N

DCPP tert. Amine DEPP solid salt


Solution of a Problem with IL: BASIL TM

4

Acid Scavenging with Ionic Liquids: BASIL TM

P

Cl

Cl

P

OEt

OEt

2 EtOH+ + 2 + 2 R3N * HClR3N

P

Cl

Cl

P

OEt

OEt

2 EtOH+ + + N NMeH

+

Cl-

N NMe



5

EtOH

PPhCl

Cl

N N

PPhOEt

OEt

N NHCl

+

NaOH



6

old process (with solids):yield per volume and time unit

8 kg m-3 h-1

yield per volumeand time unit

690.000 kg m-3 h-1

8 x 104



8 kg m-3 h-1

50 % yield

waste



105 kg m-3 h-1

98 % yield

recycling

8


How to get to the IL you really need ?

each IL represents an unique set of properties

chemical compositione.g. cation / anion

pH (in water)

impurities(water, organic volatiles,halides, coloured impurities)

physical properties

e.g. melting point / liquid range

thermal stability

corrosivity & compatability

viscosity

product safety

e.g. LD 50 (oral / dermal)

biodegradability

ecotoxicology

inflammation point

performance parameters

e.g. dissolution properties

miscibility / unmiscibility

electric conductivity

heat capacity

9

Eng.& Functional Fluids

e.g.

• Lubricants

• Hydraulic Liquids

• Absorption Cooling

Separation Processes

e.g.

• extractive distillation

• extraction of aromatics

• lignin / cellulose

Polymer Processing

e.g.

• regenerated cellulose

• cellulose derivatives

• polymer blends

Chemical Processing

e.g. reaction media in

• catalytic reactions

• nucleoph. substitution

• acid scavenging


Broad Range of Application Segments

Metal Processing

e.g.

• electroplating Al

• electroplating Cr

• elctropolishing

Electronic Devices

e.g.

• Lithium Ion Batterie

• Super Capacitors

• Dye Sensitized Cells

10

Electrolytes

e.g.





e.g.

• Lubricants




e.g.




Metal Processing

e.g.



• elctropolishing

Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging



11


An alternative tool for organic chemists

DE 10341308 (BASF)

rawmaterials

IL +catalyst

product

IL +catalyst

12


Nucleophilic HCl: Dichloroalkanes

DE 10341308 (BASF)

HDO

HCl

HMIM Cl

DCH

HMIM Cl

OHOH

ClCl

NN+ H Cl-

OHOH Cl

OHO

ClO

ClClClHCl

+ + +

DCB CBO THF DCBE

OHOH Cl

ClCOCl2



Nucleophilic HCl asalternative to phosgene

DCBCBO

THFDCBE

R1

R20

20

40

60

80

100

DE 10341308 (BASF)

HCl(g)

with IL

Product isolationby phase separation

Neat Product

Ionic Liquid



15

Electrolytes

e.g.





e.g.

• Lubricants




e.g.




Metal Processing

e.g.



• elctropolishing

Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging



16


Ionic Compressor for Gases (H2, CH4)

Gas Inlet Gas Outlet

gas insolubility in IL‘s

liquid piston

heat removal

isothermal compression

1 to 1.000 bars in 1 step

PLC

17

Electrolytes

e.g.





e.g.

• Lubricants




e.g.




Metal Processing

e.g.



• elctropolishing

Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging



18


Cellulose Reshaping

Film

5-20% celluose in IL‘s

specific IL‘s needed (anion!)

no degradation / no ripening

stable solution

re-precipitation with water

easy to degas

short dissolution time

DP‘s up to 2000

WO 2003/029.329 (03.10.2001) (Robin Rogers et.al., UoA BASF)

19

Pulp Activation Derivatisation Dissolution Spinningsince1892

NaOH CS2 NaOH H2O, H2SO4

CS2

Pro

du

cts

Viscose Process

Ionic Liquid H2O

Ionic Liquid

Pulp Direct Dissolution Spinning

Pro

du

cts

Ionic Liquid Process


Cellulose Reshaping

20

pilot plantwet spinning

regeneratedcellulose fibre


Cellulose Reshaping: Trials @ ITCF Denkendorf

cellulosedissolved in IL

EMIM Acetate

21

Pulp

Solid waste(incineration)

Fibers

Water

Ionicliquid

Waste waterWater

Filtration

Pre-paration

Dis-solution

FiltrationDegassing

Coa-gulation

Washing/conditioning

ILpurification

Evaporation


Cellulose Reshaping

22

IL Structure Tdist. /CYield /%

BMIMOAc-O CH3

ONN + 170 > 90

BMIMOProp-O

ONN + 170 > 90

EMIMDEP PO

O-O

ONN + 250 54

EMIMN(CN)2 NN + N-NC

NC250 4

Feed

Vacuum

ResidueDistillate


IL Purification by short path distillation*

•WO 2009027250A2; Prof.Dr. W. Mormann, Siegen;BASF SE

23* Cooperation with Prof. Mormann, Siegen


Cellulose Derivatives

24* Cooperation with Prof. Mormann, Siegen, WO 2008000666 A1, BASF SE

O

O

OO

OR

RR n

R = H,CH3

O

O

O

R´

R´

+

CH3

O O

R´

OR´,

O

O

O

O

OR

RR

R´= -H = C0-AKD-C2H5 = C2-AKD-C4H9 = C4-AKD-C14H29/-C16H33 = C14/16-AKD

C8H16 C6H13

R = H,

=Oleyl-AKD

n

C4-AKD

(4 Mol%)

C2-AKD

(10 Mol%)

C0-AKD

(Mischbar)

AKD

(Löslichkeit in IL)

2,62,57916 (100)1/3.9

1,51,4901 (100)1/4.4

2,02,28816 (100)1/3.4

0,10,2841 (100)1/3.8

2,62,48416 (100)1/3.7

1,01,1843 (100)1/4.9

DSNMR DSEA

Reakt.-zeit / Std.

(T / °C)

AcAcAusb.

/ [%]

nAGU /

nAKD


Cellulose Derivatives

25


e.g.

• Lubricants




e.g.




Metal Processing

e.g.



• elctropolishing

Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging

Electronic Devices

e.g.






26


Dye Sensitized Solar Cell (DSSC)

eee

e

e e e

e

e

eI3

-

3 I-

Ionic Liquid

TCO

counter

electrode

TiO2TiO2

e

TCO

transparent

electrode

dye

high purity components

crucial part of the cell

27

G24i site in Cardiff, UK

www.g24i.com


Dye Sensitized Solar Cell (DSSC)

28


e.g.

• Lubricants




e.g.




Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging

Metal Processing

e.g.



• elctropolishing

Electronic Devices

e.g.






29

- 4 - 3 - 2 - 1 0 1 2 3

water

Cu, Ag, Au,

Cr, Ni ...

IonicLiquids

Al, Ti, Si, Ge ...

IL-AlCl3+Al3+

key properties IL:

• dissolution of Aluminium species

preferred for electrodeposition

• electrochemical stability

( no need for other auxilaries)

• electric conductivity

in order to achieve a deposition with high

densities, additives have to be used together

with the EMIM AlCl4 electrolyte


Elektrodeposition of Aluminum

30


e.g.

• Lubricants




e.g.




Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging

Metal Processing

e.g.



• elctropolishing

Electronic Devices

e.g.






Biorefinery & IL

Proof of Conceptsolution in IL

1. precipitation

2. precipitation

IL

EtOH

water water

filtrationdestillation


amorphouscellulose fraction

enzymatichydrolysis

ligninfraction

69% 7%

93%


current laboratory results

EMIM OAcEEIM OAc

with Hemi-cellulose

up to 30%dissolvedin 1 h

32


e.g.

• Lubricants




e.g.




Polymer Processing

e.g.



• polymer blends

Chemical Processing




• acid scavenging

Metal Processing

e.g.



• elctropolishing

Electronic Devices

e.g.






THF / water

THFin vapor

0

0,2

0,4

0,6

0,8

1

0 0,2 0,4 0,6 0,8 1

THFin liquid WO 02/074718 (BASF)


Breaking of Azeotropes

K1

Entrainer IL

Recycle IL Falling FilmEvaporator

MeOH

TMB

FeedTMB/MeOH

MeOH



• 3 months continously operated• constant performance• no IL purge



Comparison of Manufacturing Costs*

=> Use of IL leads to clear savings in invest and energy costs

=> 3 month miniplant without IL-purge

Entrainer DMF Ionic Liquid

Purification of

entrainerDistillation Evaporator,

condensator,

refrigerator

Educt losses 0% 0%Energy 100% 63%Environment 0% 0%Sum variable cost 100% 63%

Depreciation from

investment costs 100% 78%

Sum total costs 100% 74%

* Assumptions: capacity 10 000 t/a



37

these products are regularily produced @ BASF

in high quality and 100 kg‘s to tons quantities

EMIM Chloride

BMIM Chloride

EMIM Ethylsulfate

EMIM Methanesulfonate

EMIM Acetate

EMIM Methylcarbonate

EMIM TFSI *)

TFSI = bis(trifluormethanesulfonyl)imide

versatile precursor for IL synthesis

low melting point, low viscosity, high thermal stability

low viscosity, high thermal & chemical stability

very low melting point, low viscosity

low viscosity, high electrochemical stability, hydrophobic



*) not availabale in the US


BASIONICS TM BASF`s Standard IL Portfolio

38

OO

R³

R'-NH2

R²

O

H

NH3

N N

R²

R³

R'

N N

R²

R³

R' R4+

X-N N

R²

R³

R' R4+

Y-

Anion Exchange

several concepts

adapted to customer

requirements

Imidazole Synthesis

BASF: flexible multiproduct plant

Alkylation

broad range of alkylation

agents in existing multi

product plants

1-Methyl-

1-Ethyl-

1,2-Dimethyl-


BASIONICS TM General Synthesis Concept

39

advantages: easy access to a broad range of IL‘s with different anions

very broad flexibility by utilizing:

HY = Broensted-Acids or Ammonium Salts

purity profile: in principle halide free synthesis route (corrosion !)

resulting in high purity IL‘s

industrial scale synthesis developed together with pro ionic

WO (proionic / BASF) 2005 / 021.484

NNR

N+

NR Me

N+

NR Me

YHYDMC MC

-

+ CO2 + MeOH


BASIONICS TM flexible Synthesis Platform

40

experience: no single IL meets all criteria

requested for Engineering Fluids

range of products specifically adopted to

customer needs

optimization of performance properties

(esp. viscosity / viscosity index, lubrication properties)

material compatibility (e.g. corrosion behaviour)

environmental aspects (e.g. toxicity, biodegradability)


BASIONICS TM Customized Solutions

41

cation: toxicity & ecotoxicity increases with the length of the alkyl chains

this is more or less independent from the cation chemistry

preferred: Ethyl Methyl IMidazolium (EMIM) cation

anion: first indication can be taken from toxicity of e.g. alkali metal salts

e.g. chloride, methylsulfate, acetate non toxic

fluorinated anions e.g. bis(trifluormethanesulfonyl)imide toxic

• so far no effects on mutagenicity observed

• most IL‘s are not readily biodegradable;unless they contain functional groups (e.g. cholinium)

• dermal toxicity of all IL‘s tested so far is considerably low


First toxicological assessments

42

SupplyBASIONICSTM

supply of standard or customized

Ionic Liquids

SupplyContract

License on BASF‘s

IL know how

access to BASF‘s IP and know howon Ionic Liquids

(incl. BASILTM processes)

LicenseAgreement

JointDevelopment

jointly develop new products orprocesses by utilizing IL‘s

JointDevelopmentAgreement


BASF`s Offers

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