Ionic Liquids at BASF SE

Transcription

1 Leuven Ionic liquid Summer School August 2010 Dr. Klemens Massonne BASF SE, Ludwigshafen

2 What are Ionic Liquids? liquid salts m.p. < 100 C R R + N R R + N R (often: < r.t.) N R R + N Cl - - RS 4 R 2 P - 4 CH 3 C - 2 R SCN - CH 3 S - 3 BF - 4 AlCl - 4 literally no vapour pressure non flammable high therm. & mechan. stability broad liquid range electric conductivity high electrochem. stability exceptional diss. properties 2

3 Solution of a Problem with IL: BASIL TM Cl P Cl Et + 2 EtH + 2 R 3 N P + 2 R 3 N * HCl Et DCPP tert. Amine DEPP solid salt 3

4 Solution of a Problem with IL: BASIL TM Acid Scavenging with Ionic Liquids: BASIL TM Cl P Cl Cl P Cl Et + 2 EtH + 2 R 3 N P + 2 R 3 N * HCl Et Et 2 EtH Me N P Me N Et N N Cl - + H 4

5 Solution of a Problem with IL: BASIL TM EtH Ph P Cl Cl Ph N P Et Et Cl + NH N N NaH 5

6 Solution of a Problem with IL: BASIL TM old process (with solids): yield per volume and time unit 8 kg m -3 h -1 8 x 10 4 yield per volume and time unit kg m -3 h -1 6

7 Solution of a Problem with IL: BASIL TM 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 performance parameters dissolution properties miscibility / unmiscibility electric conductivity heat capacity physical properties melting point / liquid range thermal stability corrosivity & compatability viscosity product safety chemical composition cation / anion ph (in water) impurities LD 50 (oral / dermal) biodegradability ecotoxicology inflammation point (water, organic volatiles, halides, coloured impurities) 8

9 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electronic Devices Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 9

10 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electrolytes Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 10

11 An alternative tool for organic chemists raw materials product IL + catalyst IL + catalyst DE (BASF) 11

12 Nucleophilic HCl: Dichloroalkanes H H Cl Cl HD DCH HCl HMIM Cl N HMIM Cl + ClN H DE (BASF) 12

13 Nucleophilic HCl: Dichloroalkanes H H HCl H Cl H + Cl Cl DCB CCl2 CB H + Cl + Cl THF Cl DCBE Nucleophilic HCl as alternative to phosgene DE (BASF) 20 R2 0 DCB CB R1 THF DCBE HCl(g) with IL Cl

14 Nucleophilic HCl: Dichloroalkanes Neat Product Product isolation by phase separation Ionic Liquid

15 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electrolytes Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 15

16 Ionic Compressor for Gases (H2, CH4) Gas Inlet Gas utlet PLC gas insolubility in IL s liquid piston heat removal isothermal compression 1 to bars in 1 step 16

17 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electrolytes Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 17

18 Cellulose Reshaping W 2003/ ( ) (Robin Rogers et.al., UoA BASF) 5-20% celluose in IL s specific IL s needed (anion!) short dissolution time Film DP s up to 2000 easy to degas stable solution no degradation / no ripening re-precipitation with water 18

19 Cellulose Reshaping Viscose Process since 1892 Pulp Activation CS2 NaH Derivatisation H2, H2S4 Dissolution Spinning Products NaH CS2 Ionic Liquid Process Pulp H2 Direct Dissolution Spinning Products Ionic Liquid Ionic Liquid 19

20 Cellulose Reshaping: ITCF Denkendorf EMIM Acetate cellulose dissolved in IL pilot plant wet spinning regenerated cellulose fibre 20

21 Cellulose Reshaping Water Pulp Ionic liquid Preparation Dissolution Filtration Degassing Coagulation Washing/ conditioning Fibers Waste water Water Evaporation Solid waste (incineration) Filtration IL purification 21

22 IL Purification by short path distillation* Feed Vacuum Residue Distillate IL Structure BMIMAc N +N BMIMProp N +N EMIMDEP N +N EMIMN(CN)2 N +N - CH3 - P NC NNC - Tdist. / CYield /% 170 > > W A2; Prof.Dr. W. Mormann, Siegen; BASF SE 22

23 Cellulose Derivatives * Cooperation with Prof. Mormann, Siegen 23

24 Cellulose Derivatives R R R R = H, R n + R R R = -H -C2H5 -C4H9 -C14H29/-C16H33 R R n C8H16 CH 3 R = H, CH 3 AKD nagu / (Löslichkei t in IL) nakd C0-AKD 1/4.4 1 (100) 1/3.9 (Mischbar) C2-AKD (10 Mol%) C4-AKD (4 Mol%) Reakt.zeit / Std. = C0-AKD = C2-AKD = C4-AKD = C14/16-AKD C6H13 =leyl-akd, R R Ausb. / [%] AcAc DSNMR DSEA 90 1,4 1,5 16 (100) 79 2,5 2,6 1/4.9 3 (100) 84 1,1 1,0 1/ (100) 84 2,4 2,6 1/3.8 1 (100) 84 0,2 0,1 1/ (100) 88 2,2 2,0 (T / C) * Cooperation with Prof. Mormann, Siegen, W A1, BASF SE 24

25 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electronic Devices Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 25

26 Dye Sensitized Solar Cell (DSSC) high purity components TC dye transparent electrode TC crucial part of the cell 3I e - e e e I3 e Ti2 Ti 2 counter electrode - e Ionic Liquid e e e e e 26

27 Dye Sensitized Solar Cell (DSSC) G24i site in Cardiff, UK 27

28 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electronic Devices Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 28

29 Elektrodeposition of Aluminum Ionic Liquids water -1 IL-AlCl3 Al3+ 0 Cu, Ag, Au, Cr, Ni Al, Ti, Si, Ge... key properties IL: dissolution of Aluminium species preferred for electrodeposition in order to achieve a deposition with high densities, additives have to be used together with the EMIM AlCl4 electrolyte electrochemical stability ( no need for other auxilaries) electric conductivity 29

30 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electronic Devices Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 30

31 Biorefinery & IL EMIM Ac EEIM Ac up to 30% dissolved in 1 h IL solution in IL Proof of Concept 93% EtH 1. precipitation filtration destillation water water 2. precipitation filtration destillation 69% with Hemicellulose amorphous cellulose fraction enzymatic hydrolysis filtration destillation 7% lignin fraction current laboratory results

32 Broad Range of Application Segments Metal Processing Chemical Processing Separation Processes reaction media in electroplating Al catalytic reactions electroplating Cr extractive distillation nucleoph. substitution elctropolishing extraction of aromatics acid scavenging lignin / cellulose Eng.& Functional Fluids Polymer Processing Lubricants Hydraulic Liquids Absorption Cooling Electronic Devices Lithium Ion Batterie Super Capacitors regenerated cellulose cellulose derivatives polymer blends Dye Sensitized Cells 32

33 Breaking of Azeotropes THF / water THF in vapor 1 0,8 0,6 0,4 0, ,2 0,4 0,6 0,8 1 THF in liquid W 02/ (BASF)

34 Breaking of Azeotropes Entrainer IL TMB K1 MeH Feed TMB/MeH MeH Recycle IL Falling Film Evaporator

35 Breaking of Azeotropes 3 months continously operated constant performance no IL purge

36 Breaking of Azeotropes Comparison of Manufacturing Costs* Entrainer Purification of entrainer DMF Distillation Educt losses Energy Environment Sum variable cost Depreciation from investment costs Sum total costs Ionic Liquid Evaporator, condensator, refrigerator 0% 100% 0% 100% 0% 63% 0% 63% 100% 100% 78% 74% => Use of IL leads to clear savings in invest and energy costs => 3 month miniplant without IL-purge * Assumptions: capacity t/a

37 BASINICS TM BASF`s Standard IL Portfolio these products are regularily BASF in high quality and 100 kg s to tons quantities EMIM Chloride versatile precursor for IL synthesis BMIM Chloride versatile precursor for IL synthesis EMIM Ethylsulfate low melting point, low viscosity, high thermal stability EMIM Methanesulfonate low viscosity, high thermal & chemical stability EMIM Acetate very low melting point, low viscosity EMIM Methylcarbonate versatile precursor for IL synthesis EMIM TFSI *) low viscosity, high electrochemical stability, hydrophobic TFSI = bis(trifluormethanesulfonyl)imide *) not availabale in the US 37

38 BASINICS TM General Synthesis Concept R³ R³ 1-Methyl1-Ethyl- R' R'-NH 2 N NH 3 H R² N R² Alkylation Imidazole Synthesis broad range of alkylation agents in existing multi product plants BASF: flexible multi product plant R³ R' N +N R² 1,2-Dimethyl- R³ YR 4 R' Anion Exchange several concepts adapted to customer requirements N +N XR 4 R² 38

39 BASINICS TM flexible Synthesis Platform - DMC R N N R N N + MC Y HY Me R N N + Me + C 2 + MeH W (proionic / BASF) 2005 / industrial scale synthesis developed together with pro ionic 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 39

40 BASINICS TM Customized Solutions 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 ( corrosion behaviour) environmental aspects ( toxicity, biodegradability) 40

41 First toxicological assessments 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 alkali metal salts chloride, methylsulfate, acetate non toxic fluorinated anions bis(trifluormethanesulfonyl)imide toxic dermal toxicity of all IL s tested so far is considerably low so far no effects on mutagenicity observed most IL s are not readily biodegradable; unless they contain functional groups ( cholinium) 41

42 BASF`s ffers Supply BASINICSTM supply of standard or customized Ionic Liquids Supply Contract License on BASF s IL know how access to BASF s IP and know how on Ionic Liquids License Agreement Joint Development jointly develop new products or processes by utilizing IL s (incl. BASILTM processes) Joint Development Agreement 42