GLDA: The new Green

Chelating agent

J. Seetz, Sweden Sepawa, May 8, 2007

Dissolvine® GL

What is wrong with the current used chelating agents NTA and EDTA in detergents?

Question?

Dissolvine® GL

• Use of NTA is restricted and poses a PR risk for the detergent producers due to

the re-classification & re-labeling

• Use of EDTA is prohibited in some countries and is restricted in others in the EU due to its

slow biodegradabilityin 30% of German surface water > 10 ppb EDTA

Restrictions on NTA & EDTA in detergents

New GHS system for NTA: carcinogenic textexploding chest label

Phrase (R40): Limited evidence of carcinogenic effects

Restrictions on NTA & EDTA in detergents

• Sweden: near elimination from household detergents (early1990s)

• Also restrictions in: UK, France, Germany, Austria, Italy, Swiss• EU: detergents regulation (2004) enforces labeling when >0.2%

NTA and EDTA (will also control I&I detergents)

• Green labels: no NTA and no EDTA

– Euroflower (ecolabel EU)

– Nordic Swan

– Blaue Engel

– Umweltzeichen (Austria)

Discussions leading to more changes in detergents

1. On eutrophication • In some countries Phosphates are banned from laundry detergents• Now discussion in EU on encouraging the detergents industry to

develop Phosphate free ADW detergents • Ban of phosphates in all detergents in Washington state, US as of Q1

20082. On safety: advice to scientific committee of EU (RPA, June 2006)

• Ban Phosphates in ADW in EU too and while doing so, ban all other ingredients that poses a risk to people and/or the environment

• 11 Risks identified in detergents (4 chelating agents)• Phosphonates (not readily biodegradable, aqua tox of HEDP)• EDTA (not readily biodegradable)• NTA (carcinogen)• Polycarboxylates PAA (not readily biodegradable)

Why use Dissolvine GL?

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power • In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Solubility of GLDA at high & at low pH

0

0.5

1

1.5

2

2.5

3

0 2 4 6 8 10 12 14

pH

Sol

ubili

ty (m

ol/k

g w

ater

)

GLDANTAEDTA

Conclusion: GLDA has excellent solubility !

Solubility of GLDA in caustic

0

10

20

30

40

50

60

70

0 20 40 60

wt% NaOH

wt%

sod

ium

che

late

GLDANTAEDTAMGDA

GLDA has excellent

Solubility in caustic !

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power • In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Some interesting properties of Dissolvine® GL

Chelating power of GLDA

0

2

4

6

8

10

12

14

16

EDTA NTA GLDA

mean value stability constant for 7 metals(Ba, Ca, Cu, Fe, Mg, Ni, Zn)

mea

n K

GLDA has strong chelating power Stability constant close to NTA !

0102030405060708090

100

HNB CaCV Relative %

DTPAEDTAHEDTAPDTAGLDAMGDANTAIDSEDDSEDG

Very HighHigh

Intermediate

Low

GLDA

Conclusion: Ca binding efficiency even

better than expected

Calcium Chelating power in functional test at pH=10 With competitive chelating agent HNB = Hydroxy Naphtyl Blue

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power • In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

New eco-friendly chelating agent: GLDA

• Based on sugar (bio)chemistry

MSGL-Sodium Glutamate

L-GLDA-Na4

Strecker chemistry

2 NaCN2 H2CO

3NaOHN

COONa

COONa

COONa

NaOOCNH2

COONa

HOOC

New eco-friendly chelating agent: GLDA

• Largely made from sustainable raw materials (molasses)• According to the Bra Miljöval protocol of the Swedish

society for Nature Conservation GLDA is 86% based on natural, replaceable and sustainable raw materials

86%

14% GLDAdesigned for

eco-effectiveness

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power • In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Biodegradation of Dissolvine® GL

• Readily biodegradablein Closed bottle test (OECD 301D = imposed

by EU detergents regulation)

• 100% degradation in Ultimate biodegradability test(which means total mineralization)

0 10 20 30

Time (days)

0

20

40

60

80

100

Bio

degra

dation (

%)

OK

Toxicity Dissolvine® GL

• Low aquatic toxicity LC50 > 100 mg/l

• Low acute oral toxicity LD50 Oral (Rat): > 2000mg/kg

• Not irritating to skin or eyes

• Not a skin sensitizer (Guinea Pig)

• Not Mutagenic for bacteria

• Not Mutagenic for cells

• Not genotoxic to micronucleus (mice)

Conclusion: GLDA has no apparent safety issues

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power• In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Readily biodegradable biocide formulationInfluence of type of sequestering agent on the biocidal activity

1

2

3

4

5

6

7

8

350 400 450 500

Arquad MCB-50 (ppm active substance)

log

redu

ctio

n

15.0% Dissolvine E-39

15.4% Dissolvine GL-38

max. log reduction

log reduction to pass the test

Pseudomonas aeruginosa ( DSM 939 )Test method: EN 1276

0,03% protein load, 17°dH water hardness

Formulation.

Arquad MCB-50 15 %Dissolvine GL-38 15.4%Berol 175 3 %Water 100 %

GLDA more effective than EDTA

(and far more than NTA)

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power• In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Dissolvine® GL products characteristics

• GL-38 = standard product– 38% active ingredient– < 0.5% NTA as of q1 2008

• GL-45-S = NTA free product– 45% active ingredient– < 0.1% NTA

• GL-PD = powder of standard product– White colored solid d50 =140 µm– Free flowing granular product (slightly hygroscopic)

Some interesting properties of Dissolvine® GL

• High solubility over wide pH range• Very good calcium sequestration at high pH &• Good sequestering power over wide pH range• Largely made from sustainable raw materials• Suitable for Eco-labeling

– Biodegradability– Good ecotox properties

• High alkaline and acid stability• Good biocide boosting power • In liquid (GL-38, GL-45-S) and solid (GL-PD) form• Excellent (tea) stain removal

Stain removal in machine dishwashing test performed by Rhone Poulenc

0

10

20

30

40

50

60

70

80

90

100

% stain removed

GLDA K - TPP Na -Citrate K4 -PP

Builder

Effect of chelate on tea stain removal

• Lab test with recipe containing 8 % NAOH and 40% builder

GLDA superior to Phosphates and citrates

For I&I: GLDA superior to EDTA and close to NTA

AkzoNobel is proud to AkzoNobel is proud to introduce introduce

DissolvineDissolvine®® GLGL--We wish you a We wish you a GGreener reener LLifeife--

Thank you for your attention.