Nitrosamine Formation in Amine Scrubbing Nathan A. Fine Texas - - PowerPoint PPT Presentation

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Nitrosamine Formation in Amine Scrubbing Nathan A. Fine Texas - - PowerPoint PPT Presentation

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Nitrosamine Formation in Amine Scrubbing Nathan A. Fine Texas Carbon Management Program University of Texas at Austin Department of Chemical Engineering September 18, 2013 1 Outline Motivation Carcinogenicity Nitrosamine Cycle

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SLIDE 1

Nathan A. Fine

Texas Carbon Management Program University of Texas at Austin Department of Chemical Engineering September 18, 2013

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Nitrosamine Formation in Amine Scrubbing

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Outline

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Motivation

Carcinogenicity Nitrosamine Cycle

Current Work

NO2 absorption Nitrosation from nitrite

Nitrosamine accumulation

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SLIDE 3

Maximize environmental benefit of amine scrubbing

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Motivation

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Nitrosamine Carcinogenicity

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 React in target organs to form diazonium-carbocation

intermediates

 Leads to DNA alkylation and tumor growth  Over 80% are carcinogenic

Inami et. al 2009

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SLIDE 5

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Stri ripper Absorb

  • rber

Nitrosamine Cycle

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NO2 absorption Nitrosation from nitrite

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Nitrosamine Formation

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NO2 Absorption Chemistry

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The Wetted Wall Column

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Solvent reservoir

N2 CO2 Vent

NO2 flux

Kg and kg’

FTIR [NO2]WWC [NO2]bypass 5000ppm NO2/N2

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SLIDE 9

NO2 Absorption into Water

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WWC Shen 1997

0.001 0.01 0.1 1 10 0.1 1 10 100

NO2 Flux*105 (mol/s m2) PNO2 LM (Pa) 6% NO2 absorption For 5ppm NO2

0.01 M NaOH, T=20 °C

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SLIDE 10

NO2 Absorption into MEA

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MEA

Water

0.001 0.01 0.1 1

1 10

NO2 Flux*105 (mol/s m2)

PNO2 LM (Pa)

9m MEA, α=0.38 T=40 °C

Absorption dominated by k’g MEA at 5 ppm NO2

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NO2 Absorption Into Amines

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Loaded 9m MEA Loaded 8m PZ Unloaded MDEA

1 10 100 0.01 0.1 1 10

k'g Am *105 (mol/s m2 Pa) Free Alkalinity (m) β=65% NO2 absorption β=98% NO2 absorption β=100% NO2 absorption

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Stri ripper Absorb

  • rber

Nitrosation from Nitrite

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Nitrosation of 1°/2° Amines with Nitrite

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ME MEA MAE AE DE DEA PZ PZ

1 10 100 1000 1 10 100 1000

kMo

Mode del *10

106

6 (s

(s-1) kObs

bs *10

106

6 (s

(s-1)

k3 100C (M-2s-1) Ea (kJ/mol) 84 62 42 680 73

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Nitrosamine yield: 1° Amines

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0% 1% 2% 3% 4% 5% 0.000 0.005 0.010 0.015 0.020

NDELA Yield

[DEA]/[MEA]

Dilute DEA in MEA

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DEA diluted in 9m MEA, α=0.38 T=150 °C for 3 hours

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Reactivity in 9m MEA

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HEEDA HEGly

1 10 0.1 0.2 0.3 0.4

Relative Reactivity (R) MEA Loading (Mol CO2/mol MEA)

DEA Experimental

*Carbamate and protonate stability for DEA/MEA extrapolated from 40 °C

2° Amine diluted in 9m MEA, α=0.38 Heated at 120 °C for 24 hours

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Nitrosamine yield: 2°/3° Amine Blends

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 Tertiary amines do not form carbamates

 Nitrosate very slowly  Yield from 2° amine nitrosation is close to unity at promoter

concentrations

Blend MNPZ Yield (%) 0.1-8m PZ 95±11 PZ/Methyldiethanolamine (MDEA) 85 PZ/Triethanolamine (TEA) 102 PZ/Dimethylaminopropanol (DMAP) 93 PZ/Diethylaminoethanol (DEAE) 96 2m PZ / 7m 3° amine; α=0.25; Heated for 3 hours at T = 150 °C

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Balancing NO2 absorption and nitrosation with nitrosamine decomposition

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Nitrosamine Accumulation

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Nitrosamine Accumulation

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0.1 1 10 100 9m MEA, 10 mM HeGly, T=120 °C 9m MEA, 50 mM HeGly, T=120 °C 8m PZ, T=150 °C 7m MDEA/2m PZ T=135 °C

Nitrosamine (mM)

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Nitrosamine Accumulation

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0.1 1 10 100 9m MEA, 10 mM HeGly, T=120 °C 9m MEA, 50 mM HeGly, T=120 °C 8m PZ, T=150 °C 7m MDEA/2m PZ T=135 °C

Nitrosamine (mM)

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SLIDE 21

Nitrosamine Accumulation

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0.1 1 10 100 9m MEA, 10 mM HeGly, T=120 °C 9m MEA, 50 mM HeGly, T=120 °C 8m PZ, T=150 °C 7m MDEA/2m PZ T=135 °C

Nitrosamine (mM)

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SLIDE 22

Nitrosamine Accumulation

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0.1 1 10 100 9m MEA, 10 mM HeGly, T=120 °C 9m MEA, 50 mM HeGly, T=120 °C 8m PZ, T=150 °C 7m MDEA/2m PZ T=135 °C

Nitrosamine (mM)

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SLIDE 23

Nitrosamine Accumulation

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0.1 1 10 100 9m MEA, 10 mM HeGly, T=120 °C 9m MEA, 50 mM HeGly, T=120 °C 8m PZ, T=150 °C 7m MDEA/2m PZ T=135 °C

Nitrosamine (mM)

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October 5 - 9, 2014 | AUSTIN, TX - USA

www.GHGT.info

UTCCS-1 January 28-30, 2014 Austin, TX

Open to sponsors of the Texas Carbon Management Program And to non-profit institutions with presentations Titles and abstracts due October 15, 2013 to gtr@che.utexas.edu

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Thermal Cylinder Experiments

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 Solution Preparation

 0.1-8m amine, α=0.1-0.4  50 mmol/kg NaNO2

 Batch Experiment

 Loaded in \ inch Swagelok thermal cylinders  Convection oven at 80-150°C  Quenched in water bath at 21 °C  Stored in amber vials and analyzed within a week

 Pseudo-first order observed rate determined from nitrite

disappearance

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