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Harcros Narrow Range Ethoxylation Technology

Harcros Narrow Range Ethoxylation Technology. Patent Approved August 2006, “Method of Preparing Alkoxylation Catalysts and their use in Alkoxylation Reactions” (US 7,119,236). Presented by Dr. Peter Radford President, Organics Division Harcros Chemicals Inc. Narrow Range Ethoxylation.

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Harcros Narrow Range Ethoxylation Technology

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  1. Harcros Narrow Range Ethoxylation Technology Patent Approved August 2006, “Method of Preparing Alkoxylation Catalysts and their use in Alkoxylation Reactions” (US 7,119,236) Presented by Dr. Peter Radford President, Organics Division Harcros Chemicals Inc

  2. Narrow Range Ethoxylation Typical ethoxylation processes rely upon KOH, NaOH, or Methylate Catalysts. For Alcohol Substrates, this results in • a broad ethoxymer distribution • higher free, un-reacted alcohol • increased PEG’s • lower overall concentration of surfactant range ethoxymers

  3. Narrow Range Ethoxylation Narrow range processes utilize unique catalyst systems to produce a tighter ethoxymer distribution. Narrow Range Alcohol Ethoxylates (NRE’s) have • a compressed ethoxymer curve similar to the distribution of alkylphenol ethoxylates • lower free alcohol = lower VOC’s • increased concentration of surfactant range adducts • lower PEG levels • In some cases, an improved aquatic toxicity profile

  4. NP-8 NRE 6 mole BRE 6 mole Mole % 0 2 4 6 8 10 12 14 16 Moles EO Ethoxymer Distribution Comparison Unreacted Alcohol Surfactant Range Ethoxylates

  5. Linear Alc. Ethoxylate Branched Alc. Ethoxylate 35 BRE 30 25 NRE 20 % Free Alcohol 15 None Detected for NRE 10 5 0 TDA-6 C1216-6 TDA-2.5 TDA-9.5 C1216-2.5 C1216-9.5 Free Alcohol Comparisons Branched substrates contain higher levels of un-reacted alcohol due to the steric bulk of the hydrophobe.

  6. BRE NRE

  7. Wetting Time Comparison (Skein Test) 25 C 45 40 87ºC 86ºC 35 8.6 mole NRE 30 NRE BRE 25 5.8 mole NRE Wetting Time (sec) 20 5.8 mole NRE 15 72ºC NP-9.5, 8 sec. 10 5 42ºC 37ºC 37ºC 0 43ºC 36ºC 36ºC C1216-6 C1216-9.5 Isodecyl-6 Wetting Time Comparison NRE’s display a higher cloud point versus the BRE of the same EO level. When comparing certain properties, it is necessary to match cloud points, not moles of EO. NRE’s show better wetting times if cloud point is matched.

  8. Less stable foam for NRE’s NRE BRE 14 1min 1min 12 10 5 min Foam Height (cm) 8 5 min 6 4 2 0 C1216-6 C1216-6 C1216-9.5 C1216-8.6 C1216-9.5 Foam Height Comparison Less high mole adducts and lower free alcohol lead to decreased foam stability for NRE’s.

  9. Interfacial Surface Tension 3 8.6 Mole NRE 2.5 2 NP-9.5 (dynes/cm) 1.5 1 0.5 0 C1012-6 C1216-6 TDA-9.5 C1216-9.5 C1012-9.5 NRE BRE Interfacial Surface Tension NRE’s display higher surface tensions than BRE’s due to increased hydrophilicity. If the EO level is adjusted to match surface tension of the BRE (8.6 mole NRE), a much lower IFT is achieved. Even with higher surface tensions, NRE’s show better wetting times than BRE’s.

  10. Narrow Range Technology Acid Catalyst Systems • Limited to low-mole adducts • Produce high levels of 1,4 dioxane which must be scrubbed Metal Cyanide • Used predominately for polyol production Calcium Based Systems • Milder catalyst yields neutral pH ethoxylate, no neutralization step required • Higher catalytic activity, lower levels required (100 ppm Ca+ vs 350 ppm K+) • Catalyst residue is water soluble • Ethoxylation of alternative substrates possible – Soybean Oil, Methyl Esters, etc. • Commercial products – Harcros NR series,

  11. General Summary of NRE Benefits Narrow Range Ethoxylation technology utilizes a milder, higher active catalyst to produce robust ethoxylates of alcohol, ester, and other hydrophobes yielding • Tailored wetting performance • Lower CMC’s and IFT’s • Less un-reacted alcohol = lower VOC’s and Ether Sulfates with lower irritation indices (less alcohol sulfate) • Greater concentration of surfactant range ethoxymers • Decreased foam stability • Reduced PEG’s Formulators seeking to replace Alkyl Phenol Ethoxylates can turn to Narrow Range Ethoxylates as performance alternatives.

  12. Products used in Energy Recovery- NRE Benefits • Fatty alcohol ethoxylates • Lower interfacial surface tensions for lower mole adducts • Mutual Solvents (short chain ethoxylates) • Perform considerably more efficiently at higher temperature, in the presence of electrolytes.

  13. Products Used in Energy Recovery- NRE Benefits (Continued) • Foamer Products (short chain ether sulfates) • Retain form density better than their NRE counterparts • Perform very well in higher brine systems. • Soap Sticks (highly ethoxylated NPE’s): • High mole NPE’s are considerably more crystalline, and have higher melt points when prepared with the NRE catalyst.

  14. Mutual Solvents – Improved efficiency under real world conditions Graphs show milliliters of ethoxylate required to reach one single phase at the indicated temperature –note the improvement with the NRE version

  15. Foamers - Foam Heights for Linear Ether Sulfates (NRE vs. BRE) • NRE Based Foamers have Improved Brine Foam Height Height, mm

  16. Foamers- Foam Stability and Branched Ether Sulfates (NRE vs. BRE ) HalfLife (minutes)

  17. Foamers – Foam Density on Standing (NRE vs. BRE)

  18. High mole adducts- higher melt points, greater crystallinity.

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