phosphonates in oxidizing environments: from the
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Expanding Chemistry Seminar - Dr. Ulrich Stoeck
Phosphonates in oxidizing environments:
From the enablement of “gentle bleaching“
to the stabilization of bulk chemicals
ZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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CORPORATE HISTORY (I)
Transformation from wholesale to large-scale production of chemical products. Production
sites at Greiz-Dölau, Heinrichshall (Thuringia) and Grünberg (Bohemia) were acquired
1894Zschimmer & Schwarz was established in 1894 as a wholesale business for
chemicals, dyestuffs and pharmaceuticals in Chemnitz (Saxony) by
Otto Zschimmer & Max Schwarz
1909
1939Acquisition of a production plant for tanning products at Lahnstein/Rhine. After the complete destruction of the Z&S Headquarter in
Chemnitz in 1945 and the expropriation of several production sites, Zschimmer & Schwarz was rebuild in Lahnstein, which is now the
headquarter of today's international group.
1993“BACK TO THE ROOTS” - The ZSCHIMMER & SCHWARZ group acquired a research and
production site in Mohsdorf near Chemnitz (Saxony).
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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CORPORATE HISTORY (II)
ZSCHIMMER & SCHWARZ MOHSDORF where TRADITION meets FUTURE
▪ originally owned by Th. Böhme Fettchemie, a subsidiary of Henkel
▪ In the 1930‘s: Development of the first fully synthetic detergent
based on FAS (fatty alcohol sulfates)
▪ nearly 90 years history of manufacturing chemical products
▪ State-of-the-art production plant –
High degree of process automatization
▪ ZSM is the exclusive phosphonate production site within the Z & S group
▪ ISO certified and continuously recertified since 1995
▪ Production capacity 50000 – 70000 to/annum (liquid and solid)
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
ZSM - Site 2016
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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CUBLEN®
Phosphonates
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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CUBLEN®
Phosphonates
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
Basic Features of CUBLEN® - Phosphonates
Threshold Effect/Hardness Stabilization Chelation/Sequestration
Dispersion/Deflocculation Corrosion Inhibition
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Stabilization of Alkaline Bleaching Baths
Blank Test
Conditions:
deionized water
adjusted to pH ~ 10,5
temperature 65°C
500 ppm sequestrant
(EDTMP or DTPMP)
2 ppm of transition metal
Copper Stabilization
Manganese Stabilization
Iron Stabilization
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Complexing Performance in Hard Water
12°dH equals 213 mg CaCO3 / liter
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Stabilization in hard water at 20 °dH
Copper Stabilization
Manganese StabilizationIron Stabilization
Conditions:
hard water (20 °dH)
(1.19 mmol/l Mg, 2.38 mmol/l Ca)
adjusted to pH ~ 10,5
temperature 65°C
500 ppm sequestrant
2 ppm of transition metal
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
Conditions:
w ater 18°dH (equals 320 mg CaCO3 / liter)
Adjusted to pH ~ 10,5
temperature 65°C
100 ppm sequestrant (DTPMP or DTPA)
Manganese (from 0.1 to 5 ppm)
▪ CUBLEN® phosphonates are highly effective stabilizers of alkaline bleaching baths
▪ CUBLEN® D – Series (DTPMP) is the most versatile stabilizer under “real“ conditions
DTPA – high affinity to earth alkalinemetal - ions
DTPMP – highly effective sequestrant forheavy metals in hard water
Stabilization of “real“ Alkaline Bleaching Baths
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Long-Term-Stability of Gentle/Mild Bleach Detergents Formulations
Mild bleach - laundry detergent:
Phosphonate
Fatty alcohol 6,5 EO
Optical brightener
Sodium laureth sulfate 3 EO
Caustic soda
Perfume
Dye
Water
Hydrogen peroxide 50 %
Comparative Study using:
CUBLEN® K 60
CUBLEN® D 5113
CUBLEN® D 3217 N
CUBLEN® DNC 450
CUBLEN® NCD 732
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Residual H2O2 Content after 1 year
▪ DTPMP is significantly more effective than HEDP
▪ CUBLEN® DNC 450 and NCD 732 are most effective
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Stabilization of Acidic Peroxides – Enhancement of PAA Yield
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Enhancement of Peracetic acid (PAA) Yield
▪ chloride content is crucial for the stabilization performance
▪ special CUBLEN® D grades boosts PAA Yield
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Phosphonates DivisionZSCHIMMER & SCHWARZ MOHSDORF GmbH & Co. KG
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Chlorine-Stable Phosphonates
ATMP - N - Oxide vs. PBTC
Complexation Calcium Tolerance
Chlorine Stability
The Full Package -
CUBLEN® ACS 402
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Thank You For Your Attention!