New Emulsifiers for MWF: balancing performance, regulation and economics F+L week 2016, Singapore, March v2 Claude-Emmanuel Hédoire

Transcription

1 New Emulsifiers for MWF: balancing performance, regulation and economics F+L week 2016, Singapore, March 2016 v2 Claude-Emmanuel Hédoire

2 Agenda Overview of emulsifiers landscape Market information Common emulsifier types in MWF Pros / Cons of common emulsifier types Trends in MWF and challenges for emulsifiers Development of new non-ionic emulsifiers Molecular design of alkoxylated fatty alcohols to answer to performance, regulation and commercial criteria Regulation: Short alcohol ethoxylates more favorable classification and labelling than long chain ethoxylates Performance: Long alcohol ethoxylates currently give better performance Commercial: feedstock availability Development of new non-ionic emulsifiers: optimising performance, labelling and economics 2

3 Emulsifiers for MWF Emulsifiers are backbone additives for water soluble MWF: soluble oils and semi-synthetic fluids They stabilize the oil in water emulsions The oil droplet size distribution is a result of the choice of emulsifiers Some of them bring valuable side benefits With corrosion inhibitors, emulsifiers are the type of additives the most used in MWF They represent 140 kt/y out of a global additive consumption of 600 kt/y Additives for MWF (WW), 600 kt WW MWF market (million MT) CAGR = 2,3 %/y Antiwear 3% Others 12% Buffer 6% Corrosion inhibitors 24% 2,5 Extreme pressure 13% Emulsifiers 23% 2, % additives 60-90% base oil Friction modifiers 19% (Kline) 3

4 Common Emulsifier types in MWF Anionics and non-ionics are used in MWF formulations Besides emulsion stability, emulsifiers can provide MWF with other sidebenefits Emulsifier systems are elaborated blends of components to finely balance their benefits and their limitations Low foam Corrosion / staining protection Lubricity Anti-wear Stability in HW Anionics Amine soaps of fatty acids Synthetic and natural sulfonates Amine soaps of phosphate-esters Amine soaps of ether-carboxylates Non-ionics Ethoxylated fatty alcohols Ethoxylated fatty acids Ethoxylated amines and amides

5 Common emulsifiers are based on cetyl-oleyl Cetyl oleyl: C16-C18:1 Non-ionics: cetyl oleyl + 5 EO Anionics: phosphate-ester of (cetyl oleyl + 5 EO) Good emulsion stability Low foam both in DI and hard water Poor defoaming in DI water, acceptable defoaming in hard water Good emulsion stability Low foam in DI water, ultra lowfoam in HW due to soap formation No defoaming in DI water, excellent defoaming in hard water due to soap formation No corrosion / staining inhibition No AW performance Good corrosion / staining inhibition Good AW performance blank 1% PE 5

6 Spiders; An overall Evaluation of Performance Higher Emulsion stability Lower foam Improved defoaming 6

7 Common emulsifiers are based on cetyl-oleyl Cetyl oleyl: C16-C18:1 Non-ionics: cetyl oleyl + 5 EO Anionics: phosphate-ester of (cetyl oleyl + 5 EO) Good emulsion stability Low foam both in DI and hard water Poor defoaming in DI water, acceptable defoaming in hard water Good emulsion stability Low foam in DI water, ultra lowfoam in HW due to soap formation No defoaming in DI water, excellent defoaming in hard water due to soap formation No corrosion / staining inhibition No AW performance Good corrosion / staining inhibition Good AW performance blank 1% PE 7

8 Trends in MWF and challenges for emulsifiers Trends in MWF Challenges for emulsifiers Performance New generation of high speed machine tools require much improved foam control Development of a new generation of emulsifiers with ultra low foam and enhanced defoaming, without defoamer addition and without soap formation Regulation GHS in place for substances and formulations More and more stringent regulations for biocides (boric acid, formaldehyde releasers ) Change in classification and labelling for some emulsifiers Development of a new generation of emulsifiers with millder labelling Development of biostable emulsifiers Commercial Cost-effectiveness of RM and MWF WW availability of RM New generations of emulsifiers should be based on commonly and globally available raw materials A lot of challenges faced by MWF formulators and emulsifiers suppliers! 8

9 Agenda Overview of emulsifiers landscape Market information Common emulsifier types in MWF Pros / Cons of common emulsifier types Trends in MWF and challenges for emulsifiers Development of new non-ionic emulsifiers Molecular design of alkoxylated fatty alcohols to answer to performance, regulation and commercial criteria Regulation: Short alcohol ethoxylates more favorable classification and labelling than long chain ethoxylates Performance: Long alcohol ethoxylates give better performance Commercial: feedstock availability Development of new non-ionic emulsifiers: optimising performance, labelling and economics 9

10 Molecular design of alkoxylated fatty alcohols R (CH 2 - CH 2 - O) n (CH 2 - CH 2 - O) m - CH 3 O H Regulation More favorable classification and labelling for short alcohol ethoxylates vs long alcohol ethoxylates (CESIO guidelines) Cetyl oleyl 5 EO is now labelled with a dead fish More favorable classification and labelling for higher EO and PO degrees (CESIO guidelines) Commercial Availability depends on feedstock type and manufacturing Performance Within the currently commercial emulsifiers, cetyl oleyl alcohol ethoxylates give the best performance PO insertion can be used to control foam the challenge is to maintaing good emulsification performance 10

11 Regulation: classification and labels Chapter 2.1: classification Chapter 2.2: labels (appearing on the packaging) 11

12 Short alcohol ethoxylates have a more favorable labelling than long alcohol ethoxylates CESIO guidelines for environmental classification. CESIO is European Committee of Organic Surfactants and Intermediates. Most of the surfactant manufacturers belong to CESIO Environmental classification of surfactant according to 2 nd ATP, public revision 2015 Chemical name Alcohols, C8, ethoxylated Acohols, C10, ethoxylated Alcohols, C12-C16, ethoxylated Alcohols, C14, ethoxylated Alcohols, C16-C18, ethoxylated Saturated and unsaturated 12 Carbon chain length EO degrees Hazard statement (classification) Hazard phrase (classification) 8 All NC None _ 10 All NC None _ < 5 H400 H412 Very toxic to aquatic life Harmful to aquatic life with long lasting effect 5 15 H412 Harmful to aquatic life with long lasting effects _ > 15 NC None _ < 6 H400 H412 Very toxic to aquatic life Harmful to aquatic life with long lasting effects 6-15 H412 Harmful to aquatic life with long lasting effects _ > 15 NC None _ < 5 H411 Toxic to aquatic life with long lasting effects 5 10 H400 H412 Very toxic to aquatic life Harmful to aquatic life with long lasting effects H412 Harmful to aquatic life with long lasting effects > 20 EO NC None _ Label

13 Commercial: availability depends on the feedstock type and manufacturing Lauryl alcohol Manufactured from palm kernel oil and synthetically from crude oil Commonly and widely available: > 10 suppliers in Asia > 5 suppliers in Europe Approx. 5 suppliers in North America Base feedstock for numerous types of surfactants (home and personal care) Branched alcohols Synthetically manufactured from crude oil Base feedstock for numerous types of surfactants (coatings) Cetyl oleyl alcohol Manufactured from palm kernel oil, with a patented technology Only 3 suppliers in the world, with production sites in Asia and Europe 13

14 Performance: long chain alcohol ethoxylates give better performance Cetyl oleyl 5 EO Lauryl 4 EO Emulsion stability Foam Defoaming Cetyl oleyl 5 EO gives more stable emulsions, with better defoaming 14

15 Development of new non-ionic emulsifiers; optimising performance, labelling and economics R (CH 2 - CH 2 - O) n (CH 2 - CH 2 - O) m - CH 3 O H PO insertion in short chain alcohol ethoxylates Technical Performance Level 1: similar performance to cetyl oleyl alcohol ethoxylates (emulsion stability, foam and defoaming) Level 2: new generation of emulsifiers, with ultra low foam and enhanced defoaming Optimisation of performance through degree of PO Short chain alcohol Low EO/PO degree Short chain alcohol Medium EO/PO degree Short chain alcohol High EO/PO degree 16 Regulation Fine-tune EO and PO distribution to avoid the dead fish label EO degree < 6 Hazard statement H400 H412 Hazard phrase Very toxic to aquatic life Harmful to aquatic life with long lasting effects 6-15 H412 Harmful to aquatic life with long lasting effects _ > 15 NC None _ Label

16 Results for the best candidates Cetyl oleyl 5 EO Lauryl 4 EO Short chain alcohol Low EO/PO degree Short chain alcohol Medium EO/PO degree Short chain alcohol High EO/PO degree Emulsion stability Low foam Defoaming 17 Labels

17 Conclusion Trends in MWF Challenges for emulsifiers Performance New generation of high speed machine tools requires a even better foam control Solvay delivering a new generation of emulsifiers with ultra low foam and enhanced defoaming, without defoamer addition Regulation GHS in place for substances and formulations More and more stringent regulations for biocides (boric acid, formaldehyde releasers ) Change in classification and labelling for some emulsifiers Solvay delivering of a new generation of emulsifiers with millder labelling Development of biostable emulsifiers Commercial Cost-effectiveness of RM and MWF WW availability of RM Solvay Delivering a new generation of emulsifiers based on commonly and globally available raw materials 18 Short chain alcohol Low EO/PO degree Short chain alcohol Medium EO/PO degree Short chain alcohol High EO/PO degree Emulsion stability Foam Defoaming Labels

18 The additives described in the presentation are available under the following tradenames: Rhodasurf LF5, Rhodasurf LF21, Rhodasurf LF22 and Rhodasurf LF3000 For more information, please contact: Joseph See: Claude-Emmanuel Hédoire: Matthias Braem: