Stephanie freeman january 10 th 2007
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Degradation of ROC16, a Novel Amine Solvent. Stephanie Freeman January 10 th , 2007. Rochelle Group University of Texas at Austin – Dept. of Chemical Engineering. Presentation Outline. Introduction to ROC16 CO 2 Solubility Solid-Liquid Equilibrium of ROC16 Volatility of ROC16

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Stephanie Freeman January 10 th , 2007

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Stephanie freeman january 10 th 2007

Degradation of ROC16, a Novel Amine Solvent

Stephanie Freeman

January 10th, 2007

Rochelle Group

University of Texas at Austin – Dept. of Chemical Engineering


Presentation outline

Presentation Outline

  • Introduction to ROC16

    • CO2 Solubility

    • Solid-Liquid Equilibrium of ROC16

    • Volatility of ROC16

    • Capacity and Viscosity

    • Comparison of Kinetics

  • Oxidative Degradation with Metals

  • Thermal Degradation

  • Conclusions and Current Issues

  • Future Work on ROC16


Introduction to roc16

Introduction to ROC16

  • ROC16 is a novel amine solvent recently patented by the Rochelle Group

  • The Rochelle group is currently investigating ROC16 as an viable alternative to 7 m MEA


Co 2 solubility in roc10 at 40 c

Hilliard (2007)

CO2 Solubility in ROC10 at 40°C

PCO2 = 7.5 kPa

PCO2 = 0.75 kPa


Solubility of roc20

Hilliard (2007)

Solubility of ROC20

At a loading of ~0.22, ROC20 is soluble at ambient temperature


Solubility of roc16 cont

Hilliard (2007)

Solubility of ROC16 (cont.)

Current optimized absorber loadings


Expected volatility at 40 c

Hilliard (2007)

Expected Volatility at 40°C


Kinetics roc16 vs 7 m mea

Kinetics: ROC16 vs. 7 m MEA

  • Comparison at 60°C, PCO2* = 1 kPa

  • kg’ = 1.5x10-9 kmol/m2-Pa-s, 7.0 m MEA(a)

  • kg’ = 2.7x10-9 kmol/m2-Pa-s, ROC04 (b)

  • kg’ for ROC16 was estimated

  • Aboudheir (2003)

  • Cullinane (2005)

Rate of ROC16 is roughly 2X faster than 7 m MEA


Oxidative degradation methods

Oxidative Degradation - Methods

  • Low gas flow experiments

    • 100 mL/min 98% O2 / 2% CO2

  • Analysis using Anion and Cation IC to detect:

    • Organic acids (formate, acetate, etc.)

    • Inorganic ions (nitrite and nitrate)

    • Amides (through formate production)

    • Amines

  • Not yet testing for:

    • Amino Acids

    • Aldehydes


Oxidative degradation results

Oxidative Degradation - Results


Thermal degradation methods

Thermal Degradation - Methods

  • Degradation of ROC20 studied at 135°C and 150°C

    • Loadings of α=0.3 and α=0.4

  • Stainless steel bombs used

  • Amine concentration analyzed by:

    • Cation IC

    • Acid pH titration


Thermal degradation over 5 weeks

Thermal Degradation over 5 weeks


Conclusions

Conclusions

Advantages of ROC16 over MEA

  • Faster rates of absorption (Cullinane 2005)

  • Higher capacity for CO2:

    • CapROC16 = 1.44 mol CO2 / kg solution

    • CapMEA = 0.84 mol CO2 / kg solution

  • Negligible oxidative degradation (w/o Cu2+)

  • Negligible thermal degradation (potentially greater stripper P and T)

  • Comparable heat of absorption

  • Comparable volatilities


Conclusions cont

Conclusions (cont.)

Issues that Need to be Addressed

  • Increased viscosity decreases diffusion

  • Precipitation with loss of CO2 loading or over-loading

  • Feasibility of onsite loading of ROC16

  • Narrow solubility range

  • Volatility management


Conclusions cont1

Conclusions (cont.)

Potentially Intractable Obstacles

  • Pseudo-polymerization of ROC16

    • Rapid increase in viscosity

    • Trigger unknown

  • Anomalous gas/liquid behavior

    • Oxidation experiments with either Fe/Cr/Ni or Cu produced some kind of “foam”


Future work on roc16

Future Work on ROC16

  • Additional degradation experiments with higher concentrations of Cr, Ni, and Fe

  • Obtain rate data for ROC16

  • Further study phase equilibrium behavior of ROC16

  • Investigate pseudo-polymerization

  • Develop plausible onsite loading procedures

  • Determine true extent of foaming


Questions

Questions?


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