6. greener detergents (lanxess)
TRANSCRIPT
SEPAWA-Congress Sweden 2006 Page 1
Greener Detergents – Improvements Possible?
Dr. Hermann SiciusDr. Thomas KleinDr. Ralf-Johann Moritz LANXESS Deutschland GmbH
SEPAWA-Congress Sweden 2006 Page 2
Introduction:
Detergent ingredients - Changes over time
Biodegradable ingredients :• Polycarboxylates – e.g. polyaspartate • Complexing agents – e.g. iminodisuccinate
Summary and Outlook
SEPAWA-Congress Sweden 2006 Page 3
Detergent ingredients and their functions:
Surfactants removal of soil from fabrics approx. 21
Builders reduction of water hardness; support of the cleaning effects approx. 57
Bleaching oxidation of dyes and pigments max. 18agents Enzymes degradation of protein, starch and fat- approx. 1
containing soil particlesOthers optical brighteners, fragrances,
stabilisers (complexing agents)corrosion inhibitors etc.
see : G. Wagner: Waschmittel, Wiley, VCH, 2005* typical heavy-duty detergent
Product Function % by weight * type
SEPAWA-Congress Sweden 2006 Page 4
Powder detergents - Changes over the course of time:Focus on surfactants
Ingredients / % by weight 1907 1953 1959 1964 1983 2004SurfactantsSoap 32 44 3,5 3 1Tetrapropylene benzene sulfonate (TPS) 13Fatty alkohol sulfates (FAS) 2Linear alkyl benzene sulfonate (LAS) 14 8 12Nonionic surfactants 2,5 3 3Builders (softeners) / complexing agentsSoda ash 24 12 20Sodium diphosphate 10 23Sodium-tripolyphosphate (STPP)Pentasodium triphosphate
43 24
Zeolite A 18 22Polycarboxylate 1 3Phosphonate 0,2 0,5Bleaching agentsSodium perborate or sodium percarbonate 9 6 7 16 22 141
TAED (bleach activator) 1,5 2,5Enzymes + +Others / water to 100 to 100 to 100 to 100 to 100 to 100
1 Sodium percarbonate+ = contained
see : G. Wagner: Waschmittel, Wiley-VCH, 2005
SEPAWA-Congress Sweden 2006 Page 5
Powder detergents - Changes over the course of time: Focus on builders and complexing agents
1
Ingredients / % by weight 1907 1953 1959 1964 1983 2004SurfactantsSoap 32 44 3,5 3 1Tetrapropylene benzene sulfonate (TPS) 13Fatty alkohol sulfates (FAS) 2Linear alkyl benzene sulfonate (LAS) 14 8 12Nonionic surfactants 2,5 3 3Builders (softeners) / complexing agentsSoda ash 24 12 20Sodium diphosphate 10 23Sodium-tripolyphosphate (STPP)Pentasodium triphosphate
43 24
Zeolite A 18 22Polycarboxylate 1 3Phosphonate 0,2 0,5Bleaching agentsSodium perborate or sodium percarbonate 9 6 7 16 22 141
TAED (bleach activator) 1,5 2,5Enzymes + +Others / water to 100 to 100 to 100 to 100 to 100 to 100
1 Sodium percarbonate+ = contained
see : G. Wagner: Waschmittel, Wiley-VCH, 20051 sodium percarbonate+ = contained
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Builder*/Cobuilder Systems Replace Triphosphate:
- - - -COO COOCOO COO
- - --COO COO COO COO
-COO
-COO
-COO
-COO
Zeolite A
Acrylic / maleic acid copolymer
Acrylic acid - homopolymer
Builder CobuilderBuilder* Cobuilder
* in the narrower sense (ion exchanger)
SEPAWA-Congress Sweden 2006 Page 7
product type total consumption [t]
Ingredients in detergents and cleaners: Consumption in Germany (2003)
Source: Industrieverband Körperpflege und Waschmittel (IKW), Qquoted from: G. Wagner: Waschmittel, Wiley, VCH, 2005
Anionic surfactants 102,300 77,100
Zeolites 95,300 95,100
Polycarboxylates 12,400 10,900
Sodium citrate 14,100 12,000
Phosphonates 2,900 2,500
Product type Total consumption in detergents [t]
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Polypeptides: An Active Principle of Nature
bio-mineralization
PolypeptidesHigh content ofaspartic acid
Poly-anionic
Controlof
SEPAWA-Congress Sweden 2006 Page 9
Sodium Polyaspartate:A Polypeptide Based on Aspartic Acid Units
Idealized structure
n dependent on the synthesis route - and -link polydisperse
N
O
O
O
OH
NH2
O
N
OO OH
NH
OH
O
NH
OH OHOO
O
HH
NH
OH
OH
O
O
n
Peptide bond
SEPAWA-Congress Sweden 2006 Page 10
Sodium Polyaspartate: Convergent Ways Of Synthesis
O
O
OOHNH2
O
O
NH3 Sodium polyaspartatehydrolysis
n
N
O
ONaOH
-H2O
OHO
O
O
N-4+H
O
OHOH
OH2O -H2O
H2O O
OHOH
O
NH3
OHOH
O
OH2N
+H
O
OHO
O
H2N
N 4+H-
O
OHOH
O
-H2O
SEPAWA-Congress Sweden 2006 Page 11
Sodium Polyaspartate: Biodegradation
Modified OECDtest 301 B
0
10
20
30
40
50
60
70
0 5 10 15 20 25 30Days [d]
CO
2 de
v. [%
]
GlucosePolyaspartatePolyacrylate
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Sodium Polyaspartate: Stability to Hydrolysis
1 2 4 5 6 8 10 12 13 1424121
0
20
40
60
80
100
poly
aspa
rtate
[%]
pH
time
[h]
Stability of a solutioncontaining 1 %polyaspartate in water at 95 °C
SEPAWA-Congress Sweden 2006 Page 13
Sodium Polyaspartate: Stability to Enzymes
Stability of apolyaspartate solution treated with protease for detergents
38.5 38.6 38.4
0
10
20
30
40
% b
y w
eigh
t
at the beginning
6 weeks 26 weeks
Aspartic acid, monomer
Polyaspartate
SEPAWA-Congress Sweden 2006 Page 14
Results of Washing Trials Made By Using Sodium Polyaspartate: Primary Detergency
Remission* [%] Fett/Pigmente Bleichmittel- Kosmetika Enzym-
Standardized test for thecleaning efficiency of heavy-duty detergents
Standard polymer 75.0 85.8 79.5 79.0
Baypure® DS100 73.0 84.4 78.7 78.0
Degree of coloration (gray) of different fibers (25 washing cycles)
WFK OG-FT OM-B averageStandard polymer 1.1 0.7 0.9 0.8Baypure DS100 1.7 0.2 1.4 0.7
* Gemittelte Remissionswerte der gewaschenen Gewebestücke unter Normlicht
Remission* [%] Fat Bleachable Cosmetic Enzymaticpigments stains soil ptl.
* average remission values of the textile under standard light conditions
SEPAWA-Congress Sweden 2006 Page 15
Conditions: 260 mg/l total hardness (as CaCO3), 60 °C, 3 kg of textiles, 15 washing cyclesDosage: 75 g of detergent formulation, powder containing 4.5 % of graying inhibitor
60
65
70
75
80
85
90
cotton polyester/cotton
refle
ctan
ce (%
)
unwashed
polyacrylate
Baypure® DS100
Graying effectbased on testsfor heavy-duty detergents
Results of Washing Trials With Sodium Polyaspartate:Secondary Detergency
SEPAWA-Congress Sweden 2006 Page 16
Trend Towards Liquid Detergent Formulations:
Source: P. Krings, Henkel KGaA, 2005
Market volume 2003 (Western Europe): 7.1 billion euros
Heavy-duty detergent
Liquid detergent
Compactheavy-duty detergents
Tablets
Shar
e of
mar
ket v
olum
e [%
]
SEPAWA-Congress Sweden 2006 Page 17
Conventional Complexing Agents by Comparison :
Calcium binding capacity at pH 11 and 23 °C
Cal
cium
bin
ding
cap
acity
[mg
CaC
O3
/g N
a-Sa
lt ]
050
100150200250300350400
Na-citrate EDTA Na-salt
NTA Na-salt
SEPAWA-Congress Sweden 2006 Page 18
Main Ingredients*: Separate Liquid Water Softener
Builder citrate 10 - 20
Dispersing agent polyacrylate 5 - 10
Potential for optimization of water softeners :Citrate - performance Polyacrylate - ecology
* Other ingredients: suspending and binding agent, thickener
Function Ingredients Weight in %
SEPAWA-Congress Sweden 2006 Page 19
Baypure® Products: Builder and Complexing Agent
O
O
ONaOH,
NH3
, NH3
NaOH
Baypure® DSPPolysuccinimide
Baypure® CX100Tetrasodium
iminodisuccinate
Baypure® DS100Polyaspartic acid
sodium salt
SEPAWA-Congress Sweden 2006 Page 20
Iminodisuccinate: A biodegradable complexing agent
O
O
O
H2O
OH
OH
O
O
NaOH
ONa
ONaNaO
NaON
O
O O
O
H
NH 3
C8H7NO8Na4 337.1g/mol
C-termpolyaspartate ONa
ONa
N
O
O
H
O
SEPAWA-Congress Sweden 2006 Page 21
Conditions : pH 11 and 23 °C
Cal
cium
bin
ding
cap
acity
[mg
CaC
O3
/g N
a-Sa
lt ]
050
100150200250300350400
Na-citrate IDS Na-salt
EDTA Na-salt
NTA Na-salt
Iminodisuccinate: Various Calcium Binding Capacities
SEPAWA-Congress Sweden 2006 Page 22
Softening Effect Under Practical Conditions:
Liquid softener under NACE test conditions: comparison of apolyacrylate/citrate formulation (red, brand product) with a polyaspartate/iminodi-succinate formulation (yellow)
0
10
20
30
40
50
0 1 2 3 4 5 6 7 8 9 10
Inhibitor [ppm]
Inhi
bitio
n [%
]
13.8 g Baypure® DS 100/40% 25.0 g Baypure® CX 100/34% 2.4 g citric acid monohydrate1.6 g CMC
Brand product
SEPAWA-Congress Sweden 2006 Page 23
Example: peroxide-containingliquid detergent
Stabilization of H2O2 at 40 °C and pH 4.5 2 % complexing agent (as is)
5,9
6,0
6,1
6,2
6,3
6,4
6,5
6,6
0 2 4 6 8 10Period of storage [d]
without complexing agent
with Baypure CX 100
with phosphonate
Iminodisuccinate As A Bleach Stabilizer:
H2O
2[%
]
SEPAWA-Congress Sweden 2006 Page 24
Summary
The following proposals for substitution are made:
• Polyacrylate to be replaced by Polyaspartate
• Citrate to be replaced by Iminodisuccinate
• Phosphonate to be replaced by Iminodisuccinate
Washing processes have potential for ecological and functional optimization by using biodegradable builders and complexing agents.
Baypure is a registered trademark of Bayer AG, Leverkusen, Germany