Evaluation of Ambient VOCs Levels at a Power

Station Using Remote Canister Sampling

Ashraf Ramadan
Environmental Pollution and Climate Program
Kuwait Institute for Scientific Research

15-17 March 2016

 SETTING THE SCENE

FOLLOW-UP WORK APPROACH

VOC Level
Assessment at
Power Station
Using Canisters

CONCLUDING
METHODOLOGY
REMARKS

RESULTS
 Setting the Scene
• Emission sources in Kuwait:
– six electrical power generation/desalination plants (fossil fuels)
– three refineries/petrochemical plants
– miscellaneous industries (WSIA)
– flaring (gas/crude oil production)
– transport sector (fossil fuels)
• The Middle East has 60% of the world desalination capacity
• GCC countries: 58% of energy goes to AC/water desalination
• In 2006: energy consumption per capita ≈ 6 x world average
 Setting the Scene
• High rates of electricity consumption .... high emission rates
• Sharp rise in energy consumption: peak power demand
increase 6−8% annually
• Annual CO2 emissions per capita ≈ 8 x world average
• Vehicular emissions (fossil fuels + vehicles per 1000 ≈ 2.4 x
world average (ranks 32) National Annual Electrical Energy Consumption [source: NCC - Load Demand Analysis Sheet]
Predicted National Annual Electrical Energy Consumption [4th order ploynomial fits for 1968-2003 data

• 90,000t NMHCs per year (2008) 140000

120000

Annual Electrical Energy Consumption [MkWh]

National annual 100000

electrical energy
consumption 80000

values
(Source Ramadan 60000

et al. 2005)
40000

20000

0
1960 1970 1980 1990 2000 2010 2020 2030
Year
 Setting the Scene
• MEW-Kuwait decided to extend the power-generation
capacity by installing OCGTUs at four power plants
• This upgrade has an impact on the air quality, hence needs
careful assessment before permit is given by KEPA
 Approach
• Prior to MEW’s plan to install/operate OCGTUs at four
power stations....EIA
• Measure ambient air pollution levels using continuous
analyzers, time-weighted average samplers, and
numerical modelling
• Concentrations of 72 VOCs using canister sampling
(10 per plant)
Approach

SPS

DWPS

• DWPS: largest desalination/power plant in SHDP

Kuwait
• Water production capacity 110.4 MIGD
• Electricity production capacity 10855
million kWh per year
• Eight 300 MW steam turbines + five 28.2
MW gas turbines

ZSPS
Methodology
• GC/FID-ECD system:
– 6l SILONITETM coated polished SS canisters
(Entech Inst)
– combined cryogenic pre-concentrator
(ENTECH 7100A) with a an Agilent-7890A-
G3440a GC/FID+ECD
– passive canister sampler (24 h flow regulator)
Entech 39-CS1200E4
Methodology
Cryogenic Trap

Pressure Gauges

PC

1
2
Liquid H 6
N2 e 3 5
4

FID

Pump Canister 6-Port

Valve GC Column
Methodology
• Method: TO-14A / US-EPA (modified)
• 72 VOCs detected:
• Aromatics (8 incl. BTEX) • Halogenated (29)
• Oxygenated (26) • Aliphatic (9)

• Triplicate sampling 24-h TWA (<20%)

• Passivated canisters cleaned (<0.2 ppbv)
• N2 purging → evacuation + 100oC (removal of the
internal surface-bound contaminants)
• Min five cycles (purge/evacuation + heating)
Methodology
• Canisters evacuated (min 29˝ Hg) + leak tested
• -ve pressure → natural flow - flowrate precisely
controlled (NIST-traceable flow calibration)
• Once full, canisters retrieved/transported to lab
• GC/FID-ECD system 3-stage pre-concentrator with
micro-scale purge and trap water management
 Methodology
• MPC 5-50 ppbv external standard calibration
mixture (Apel-Riemer Environmental Inc.)…
calibration factor for each target compound
• Good (R2 >0.99) linear fit for all compounds
• Further analysis/variations in calibration factors
(response factor + retention time)
• Calibration factors within the limits
• Midway calibration to quantify VOC samples (QA)
Methodology
• Selection of locations took into account:
– representative of area selected
– not be near pollution sources
– convenience of access + security/safety
• ASTM: meteorological measurement:
– Portable weather station (Visala): WS, WD, T, BP, SR,
RN – short-term.
– KNMN fixed meteorological stations (MetOne) – long-
term
Methodology
• Care was taken to ensure no high buildings
existed nearby the sampling sites in any direction
to avoid the effects of downwash and the
accumulation of pollutants
• Also minimum human activities (e.g., traffic) to
capture the real impact of the power stations on
the background concentrations
Results

Aliphatics Aromatic Halogenated Oxygenated

Loc Ma M Ma
TC AC x TC AC ax TC AC x TC AC Ma
ppbv ppbv ppbv ppbv x%
% % %
AP01 6.50 Propene 63 1.66 Toluene 38 60.36 1,2,4-Trichlorobenzene 52 11.54 Nonanal 30
AP02 6.32 Propene 66 0.95 Toluene 57 42.67 1,2,4-Trichlorobenzene 40 31.39 Nonanal 71
AP03 6.49 Propene 70 2.99 Toluene 46 40.76 Vinyl Chloride 26 18.83 Methanol 53
AP04 8.29 Propene 69 3.66 Toluene 32 69.14 1,1,2,2-Tetrachloroethane 32 58.85 Nonanal 72
AP05 8.59 Propene 69 2.89 Toluene 37 95.31 1,2,4-Trichlorobenzene 28 19.71 Nonanal 32
1,3,5-
114.0
AP06 25.12 Propene 52 2.72 Trimethyl 25 6 Vinyl Chloride 33 24.37 Nonanal 57
benzene
AP07 8.64 Propene 72 0.39 Benzene 52 27.96 Vinyl Chloride 40 8.03 Nonanal 35
AP08 5.03 Propene 65 1.25 Benzene 45 34.83 Vinyl Chloride 25 12.26 Methanol 44
AP09 4.71 Propene 67 1.68 Toluene 39 48.07 1,2,4-Trichlorobenzene 48 25.70 Nonanal 36
AP10 21.75 Propene 73 3.59 Toluene 26 80.24 Vinyl Chloride 31 18.38 Methanol 45
Results
 Results – ALPH (9)
• Concentrations ranged: 4.71 - 25.12 ppbv
• MAC: propene (52-73%) T-ALPH
• Propene:
– petrol combustion derived hydrocarbon
– characteristic product of IC engines
– reported as a good indicator of vehicle exhaust
Results – AR (8)
• Concentrations ranged: 0.39 - 3.66 ppbv
• MAC: toluene at 7/10
• Toluene formed (26-57%) T-AR
• MAC: benzene at 2/10
• Benzene formed (45-52%) T-AR
• AR: veh. exh., gasoline evap., solvent emissions
• Benzene + toluene: toxic gases (Clean Air Act)
• Toluene:
– emitted from vehicles, painting, industrial processes
– related to leakage from LPG/NG
Results – HG (29)
• Concentrations ranged: 27.96 - 114.06 ppbv
• MAC: vinyl chloride at 5/10
• Vinyl chloride formed (25-40%) T-HG
• MAC: 1,2,4-trichlorobenzene at 4/10
• 1,2,4-trichlorobenzene formed (28-52%) T-HG
• Vinyl chloride:
– production of polyvinylchloride in PC industries
– largely associated with PC industries
– ranks high only at the industrial sites
Results – HG (29)
• 1,2,4-trichlorobenzene:
– solvent
– dielectric fluid
– dye carrier
– chemical intermediate
– synthetic transformer oil
– Lubricant
– heat transfer medium
– forms: comb. of chlorine-containing polymers
Results – OX (26)
• Concentrations ranged: 8.03 - 58.85 ppbv
• MAC: nonanal at 7/10
• Nonanal formed (30-72%) T-OX
• MAC: methanol at 3/10
• Methanol formed (44-53%) T-OX
• OX organic compounds: major portion of solvents
emissions
• Incomplete combustion of gasoline: significant
source of methanol
Results – Spatial Variation
• AP01 + AP02 on western side of DWPS + DEPS
• AP01 close to station’s main gate
• AP02 not far from the western perimeter road
• WD: NW → negligible effect of DWPS + DEPS
– low AR cons
– slight increase in HG + OX cons at AP01 due to
proximity to the main gate suspecting vehicular
emissions to be a contributing factor
Results – Spatial Variation
• AP03: SW corner
• AP10 midway DWPS + DEPS stacks + N fuel tanks
• 58% wind signal range: 0.5-2.1 m/s
• 12% wind signal: calm winds (< 0.5 m/s)
• Concs much affected by local settings (i.e., fuel
storage tanks) - DWPS + DEPS very little effect
• Correlate high AR and ALPH concs at AP10 with
fuel storage tanks (evaporative fuels)
• Propene (ALPH major const.
of fuels stored in the tank)
highest concentration
Results – Spatial Variation
• AP04: main DWPS road – 1km downwind stacks
• AP07: 0.5km upwind DWPS
• WD: N-NW
• High AR conc at AP04 (fuel comb + evap)
• Highest OX at AP04 (DWPS emissions)
• Lowest AR + OX + HG conc at AP07
Results – Spatial Variation
• AP05: < 1km S DEPS/SE DWPS – by main road
• AP08: < 1km N DEPS/NE DWPS
• Calm wind conditions - WD hard to define
• AP05: 2nd highest HG + high OX due to high
volatility
• AP08: lower conc than AP05 for AR, OX, HG, HC
• AP05: combined effect of DWPS + PEPS + road
emissions
Results – Spatial Variation
• AP06: 0.27km S fuel tanks + 0.85km/0.64km from
DWPS and DEPA stacks
• WD two main components: NE brings the effect
of DEPA + stronger NW brings the effect of DWPS
• Highest HG + ALPH conc
• AP09: N DWPS + DEPS
• WD: N – NE (wind coming across Arabian Gulf)
• Very low AR + ALPH (fingerprint of sources) conc
 Concluding Remarks
• Results reflected the meteorological conditions
(WS & WD) and emissions:
– low concentrations for points upwind major emission
sources and vice versa
– high AR + ALPH conc due to a leak in fuel tank
• Propene, toluene, benzene, vinyl chloride, and
nonanal that characterize industrial sites were
abundant in this sampling campaign
 Concluding Remarks
• MEW took recommendations of KISR to introduce
a more efficient co-generation (power + water)
plant utilizing CCGTUs + multi-stage firing/reverse
osmosis (MSF/RO) type distillation units instead
of conventional thermal power plant
• The OCGTUs which were the subject of this study
have been converted to CCGTUs in order to
increase their thermal efficiency and reduce fuel
consumption, hence emissions per MW
 Concluding Remarks
• Where possible, sampling at different sites should
happen simultaneously to avoid the effect of
difference in emissions and meteorological
conditions on ground-level concentrations
 Follow-up Work
• Convert daily conc to hourly + annual conc using
US-EPA scaling factors
• Compare to relevant standards
• Assess health risk due to exposure to measured
concentrations
Acknowledgement

The author would like to acknowledge the

generous sponsorship of this study by
Ministry of Electricity and Water – Kuwait