SUSTAINABLE SOLVENTS PRODUCTS AND PROCESS · PDF filePropoxur 20% Chlorpyrifos 40%...

Thierry Vidal : June 14th, 2012

SUSTAINABLE SOLVENTS PRODUCTS AND PROCESS INNOVATIONS

Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

The reasons to develop new solvent based solutions MGN Chain or how reduce NOx release by creating innovative solutions

Rhodiasolv® Iris

Rhodiasolv® PolarClean

Outlook

Contents


Aspiring to a Greener World

The world is requiring a new chemistry to provide a better environmental-cost-efficiency balance.

Green alternatives not competitive so far as costs are driven mostly by oil price

Solvent innovation lagging behind evolving legislation to protect environment and humans

The right performance for the

application

Competitiveness of the new solution

Renewable Source, Reduction of HSE

impact


Hazardous solvents substitution by responsible solutions

MGN Chain : Rhodiasolv® IRIS based solutions

New biodegradable and Eco-friendly solvents and formulations


“Green Solvent” Platform, Roots in the valorisation of Polyamide 6-6 by-products

Mar

kets

Pro

duct

and

inte

rmed

iary

Adipic Acid + Diacides

Polyurethane

ADN KA Oil

Cyclohexane Ammonia Butadiene Natural gas

Nylon 66 Textiles, automotive polymers Diesters & Esteramides families

RPDE IRIS

HMDA

Salt Nylon

Raw

m

ater

ials

MGN

Methanol

Polarclean

C4, C5 ,C6 linear by-products already valorised

by-product burned until now (energy valorisation)

NOx release


From a classical synthesis to the Graal (no effluent process)

MGN Diacide IRIS

NH4HSO4 Effluents Sulfuric Acid

MeOH

• Traditional process • Use of Acid/Base reactants • Generation of high quantities of salts and effluents (more salts than the product itself) • Non environmentally sustainable

MGN

Liquid phase catalysis Gas phase calatysis Imide IRIS

NH3 MeOH NH3

• New catalytical process • Process without salt generation • R&D to develop an extensive chemistry with the use of efficient catalytical systems. • Raw material and energy efficient (high catalytical yield, no reactant, ammonia recycling on the Nylon chain)

Recycled in Nylon chain


New process highlights.

Step 1 Step 2

Process Heterogeneous gas phase Homogeneous liquid phase

T < 250°C 150 - 250 °C

P Atm Under pressure

Catalyst Ti based catalyst La based catalyst

Performances

Selectivity Very High Very High

Step1: MGN Catalytic hydrolysis for the Imide formation Step 2: MGI catalytic esterification to get Iris

NC CN

MGN

+ 2 H2O + NH3

NH

O O

MGN- Imide

+ 2 MeOH + NH3

MeOOC COOMe

Rhodiasolv IRIS

NH

O O

MGN- Imide


One of the lowest carbon footprint of its generation

• New process strength • No salts generation • NH3 valorisation in Nylon chain • No release – all by/co-products may be valorised • Raw material and energy significant savings • Process using intensified technologies

Initial process New Process

Process Cost Comparison

Others

Utilities

Raw Materials

Rhodiasolv ® Iris Acetone Dichloromethane N-Methylpyrrolidone

Climate Change (Kg CO2 Eq.) 1.8 2.2 3.4 4

Natural Resources (MJ) 47 69 41 89

Risk R11, R36, R66, R67 R20, R22, R40 R36, R37, R38, R61

Classification F+, Xi Xn, CMR3 T, Xi, CMR 2

Main Label


Rhodiasolv® IRIS may replace toxic, carcinogenic or volatile solvents (NMP, DCM, Acetone)

• IRIS has excellent Health, Safety and Environmental profile:

• biodegradable • non toxic • non mutagenic • non flammable • low VOC emission (1999/13/EC)

• With good solvency properties allowing replacement of existing formulations containing high concern solvents:

• Chlorinated (DCM) • Pyrrolidone (NMP), Butyrolactone • Ketone (Acetone, MEK) • Aromatics (Toluene) • Glycols ethers (MEG), DMSO

S2 2009: Reprotoxic Low 86°C NMP

Toxic Pot. Carc. Very high Non flammable DCM

Flammable Very high Flammable Acetone

Non toxic Non irritant Very low Non flammable Rhodiasolv

IRIS Diester

Health and safety

Evaporation lose

Flammability (Flash point) Solvent


Composition : - dimethyl 2-methylglutarate : 87 - 89 % - dimethyl ethylsuccinate… : 9 -11 % - dimethyl adipate………… : 1 - 2 % Molar masse……………….. : 174.2 g/mol Refractive index nD at 20°C : 1.4259 ± 0.0003 Density at 20 °C…………… : 1.055 ± 0.001 g/cm3 Dynamic viscosity at 20 °C… : 2.85 ± 0.01 mPa.s Surface tension at 23°C……. : 33.0 ± 0.2 mN/m Boiling pt (1013 hPa)……….. : 218 ± 2 °C Vapor pressure (20°C)……… : 6.3 Pa Freezing point………………. : < - 60 °C Kb value ……………………. : 84.5

δD = 16.6 (J/cm3)½

δP = 8.7 (J/cm3)½ δH = 5.0 (J/cm3)½

Hansen solubility parameters :

Hildebrand solubility parameter : δ = 19.4 (J/cm3)½

Evaporation rate (at 50°C)…. : 0.040 ± 0.003 (n-butyl acetate = 1) Flash point……………….…. : 98 ± 1 °C (Closed cup) Solubility at 23°C – g in 100 g - - of the solvent in water…… : 2.5 ± 0.2 % - of water in the solvent…… : 2.2 ± 0.1 %

Rhodiasolv® Iris : Physical Properties O O

CH3-O-C- -C-O-CH3 Branched

C4

Rhodiasolv IRIS CAS number [14035-94-0]


Efficient alternative for Resin Clean-up

• Resin clean up

• Powerful solution for dissolving resins : Epoxy, Polyester, Alkyd, Polyurethane, Vinyl, etc • Alternative for: NMP (reprotoxic, irritant); DCM (dangerous); Acetone (Flammable, irritant) as

dissolution times are in the same range as existing solutions • The low evaporation rate makes it a cost effective solution: limits atmospheric emission, reduces

fire risk in industrial installations, and allows recyclability

Unsaturated Polyester Resins Dissolution Time Epoxy Resins Dissolution Time


Efficient alternative for Paint Stripping formulations

• Paint stripping • Replacement of: DCM (Dangerous and limited use by European directive 76/769/EEC) • Our offer is a full formulation based on Rhodiasolv ® IRIS that boost performance; customers

use this product to formulate paint-strippers with the correct balance of performance and labeling for the intended application and user group

• Rhodiasolv® IRIS formulations give similar performance to other DCM free product on this market, but

• Biodegradable, No “Harmful” and flammable labeling • Non flammable, efficient on a wide range of paint and coatings

• On classical paint, (alkyds), same efficiency than best stripper on market after few minutes application.


Rhodiasolv® INFINITY, an efficient subsitution solution for cleaning and degreasing

• Aqueous formulations and micro-emulsions based on Rhodiasolv® IRIS for safer cleaning and degreasing solutions:

• No Hazardous classification allowing a cleaning at neutral pH, • Solutions not VOC and flammable classified , • Very low odour solutions,

• Can substitute aromatic BXTs and flamable solvents, used for example in caustic cleaning. In

relation with directives 1999/13/EC & EC/1907/2006.

• Rhodiasolv® INFINITY presents a wide

application range • Cleaning applications (paints, graffiti, resins,

textiles, taches murales) • Wide range (ink, pen, food, greases) • Comparable efficiency as aromatics & caustic

solutions.

Rhodia Agrochemical Formulations

Rhodia’s Novel Safe Polar Solvent For Crop Protection Formulations Rhodiasolv® PolarClean


Solvent key role in crop protection

Direct impact of the solvent choice on the ai’s performance. First selection after all other inerts (emulsifier package, adjuvants…) for liquid formulation

development Solvent play many roles in crop protection

Synthesis Chemical reaction and by-products

Diluents Ai’s concentration

Ai’s stability

Carriers enhance Coverage

Wetting, sticking, rain fastness Penetration, translocation


Solvent Benchmark: new solvent recently launched or currently used as green or safer solvents in plant protection formulations.

Chemistry Raw materials Tox Ecotox Labelling

Biodegrad. Boilling point °C

N, N dimethyl octa/decamide

Fatty acid short chain from oil

Xi, R36/R38

Readily

274

N, N dimethyl lactamide Lactic acid Xi, R36/R38

Readily

223

2 ethyl hexyl lactate

Lactic acid Xi R36/38 Skin, eyes

Readily

246

Gamma butyro lactone

GHB, THF Xn Harmful R22/R36

Readily

205

Tetrahydrofurfuryl alcohol Furfural Xi, R36 Readily

178

Glyceryl carbonate Glycerol None Readily

110 - 115

Methyl caprylate caprate

Fatty acid short chain from oil

None

Readily

200


Rhodiasolv® PolarClean has a good environmental profile

Toxicological and ecotoxicological data

Acute Daphnia immobilisation OECD202 CE50 (48H) > 100 mg/l Algal Growth Test OECD201 CE50 (72H) > 100 mg/l Acute toxicity on Fish OECD203 LC50 (96H) > 100 mg/l Biodegradation (dosed bottle) OECD301F/302B Inherently biodegradable Acute Skin irritation in vivo OECD404 Not irritant Acute eye irritation in vitro (BCOP test) OECD437 Not R41 Acute eye irritation in vivo OECD405 Classified as R36 Skin sensitization (local lynde node assay) OECD429 Not sensitizing Acute oral toxicity in the rat OECD423 > 2000 mg/kg Gene Mutation in bacteria (Ames test) OECD471 Not mutagenic

STUDY GUIDELINE RESULT


Rhodiasolv® PolarClean Chemistry Purity: > 98 % Mixture of esteramide and diamide, ratio = 20 : 1


Physical Properties of Rhodiasolv® PolarClean

Rhodiasolv® PolarClean is easy-to-use and to-handle

Molar Mass 187.8 Refractive Index, nD at 20°C 1.4610 ± 0.0005 Density at 20°C 1.043 ± 0.001 g/cm3

Surface tension 36.3 ± 0.3 mN/m Boiling Point (1013 hPa) 280 ± 2 °C

Vapore pressure (20°C) <0.001 Pa Dynamic viscosity (23 °C) 9.82 ± 0.02 mPa.s

Freezing Point <-60 °C Evaporation rate (50 °C) 0.0017 ± 0.0003 (n-butyl acetate=1)

Flash Point 145 ± 1°C (Closed cup) Solubility at 23°C – 50/50 v/v in water Miscible


Solubility of various agricultural actives in Rhodiasolv® PolarClean compared to raw material and other amides commonly used in agrochemicals.

Application Tests on market products 0 = not soluble 1 = stable 7d @ RT 2 = stable 7d @ O°C 3 = stable 7d @ 0°C with seeding

.

Rhodiasolv® Polarclean is a powerful solution compared to conventional solvents 1/2

0

3Alachlor 48%

Rhodiasolv®Polarclean

Tebuconazole 25%

Difenoconazole 25% Phenmedipham 16%

Propanil 36%Trifluralin 40%

Oxyfluorfen 22%

Propoxur 20% Chlorpyrifos 40%

alpha-Cypermethrin 10%

Pendimethalin 33%Triadimenol 23%

2

1

NN Dimethyl octa/decanamide The market reference

in terms of crystal growth inhibitor

RhodiaSolv IRIS

0

1

2

3Alachlor 48%

Chlorpyrifos 40%


Phenmedipham 16%

Propanil 36%

Pendimethalin 33%

Tebuconazole 25%

Triadimenol 23%

Trifluralin 40%

Difenoconazole 25%

Oxyfluorfen 22%

Propoxur 20%

0

3Alachlor 48%

ADMA 8-10

Tebuconazole 25%



Oxyfluorfen 22%




2

1


Solubility of various agricultural actives in Rhodiasolv® PolarClean compared to other harmful but performant agrochemical solvents.

Application Tests on market products 0 = not soluble 1 = stable 7d @ RT 2 = stable 7d @ O°C 3 = stable 7d @ 0°C with seeding

. Rhodiasolv® Polarclean is a powerful solution compared to conventional solvents 2/2

0

3Alachlor 48%

Rhodiasolv®Polarclean

Tebuconazole 25%



Oxyfluorfen 22%




2

1

The market reference For high performance but

harmful solvents

0

3Alachlor 48%

Isophorone

Tebuconazole 25%



Oxyfluorfen 22%




2

1

0

3Alachlor 48%

NMP

Tebuconazole 25%



Oxyfluorfen 22%




2

1

δD δP δH

PolarClean 15.8 10.7 9.2

NMP 18 12.3 7.2

Isophorone 16.6 8.2 7.4

ADMA 16.5 6.4 7.3


Suitable solutions for various EC Formulations

Rhodiasolv

Eco-friendly solution blends

Composition General uses Solutions for

MATCH G Polarclean, ADMA* Polar solvents for azole and others

Cypermethrin 200 Ethofumesate – PMP – DMP (110 – 90 - 70) Oxyfluorfen 240 Tebuconazole 300 Fluoxypyr 250

MATCH M Polarclean, ADMA* Polar solvent composition

Prochloraz 450

MATCH 111 Polarclean, ADMA*, DBE**

Cyclohexane, isophorone, NMP, NEP substitution

Amicarbazone 250 Uniconazole 50 Lufenuron 50

MATCH VB Polarclean, ADMA*, esters

Cyclohexane, isophorone substitution

Propanil 360 & 400

MATCH UBF Polarclean, DBE** Urease and nitrification inhibitors

NBPT 250

* ADMA = AlkylDiMethylAmide ** DBE = DiBasicEster (dimethylester)


Highlights of Rhodiasolv® members

Wide range of Polarity

From water soluble to almost insoluble.

Excellent toxicological & ecotoxicological

profiles

Non-flammable and with very low vapour

pressure

Based on Rhodia raw material Reduced

carbon foot print

Chemical structure flexibility to develop the

whole range of solvents

Proprietary solutions for a wide range of

applications

O N

O O

H3C CH3

CH3

4

O O

O O

H3C CH3

4

THANK YOU FOR YOUR KIND ATTENTION

SUSTAINABLE SOLVENTS PRODUCTS AND PROCESS · PDF filePropoxur 20% Chlorpyrifos 40%...

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