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The dangers of heavy oil

The dangers of heavy oil

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Published by Bereliku Ailaran
Abstract
The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are
typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted
by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM10 emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.
Abstract
The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are
typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted
by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM10 emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.

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Published by: Bereliku Ailaran on Feb 02, 2009
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06/17/2009

 
Atmospheric Environment 41 (2007) 1053–1063
Formation of fine particles enriched by V and Ni fromheavy oil combustion: Anthropogenic sources anddrop-tube furnace experiments
Ha-Na Jang
a
, Yong-Chil Seo
a
, Ju-Hyung Lee
a
, Kyu-Won Hwang
a
, Jong-Ik Yoo
b
,Chong-Hui Sok
c
, Seong-Heon Kim
a,d,
Ã
a
Department of Environmental Engineering, YIEST, Yonsei University, Republic of Korea
b
Air Pollution Prevention and Control Division, RTP, NC, US EPA
c
LG Chem/Research Park, Republic of Korea
d
Air and Waste Engineering Laboratory, Department of Environmental Engineering, #305 Back-Un Building, Yonsei University,Heung-up, Won-Ju, Gang-Won 220-710, Republic of Korea
Received 5 May 2006; received in revised form 11 July 2006; accepted 8 September 2006
Abstract
The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickeland vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which aretypical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emissioncharacteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavyoils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioningenrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particlesize distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpretedby chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles werethe major portion of PM
10
emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. Theformation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmedby field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fineparticles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched withhazardous transition metal elements such as vanadium and nickel.
r
2006 Elsevier Ltd. All rights reserved.
Keywords:
Combustion; Heavy oil; Vanadium; Nickel; Ultra-fine particles
1. Introduction
Airborne particulate matter has been theprimary focus of several epidemiological studies,which reported a correlation between adversehealth effects and the particle concentration levels
ARTICLE IN PRESS
www.elsevier.com/locate/atmosenv1352-2310/$-see front matter
r
2006 Elsevier Ltd. All rights reserved.doi:10.1016/j.atmosenv.2006.09.011
Ã
Corresponding author. Air and Waste Engineering Labora-tory, Department of Environmental Engineering, #305 Back-UnBuilding, Yonsei University, Heung-up, Won-Ju, Gang-Won220-710, Republic of Korea. Tel.: +82337602380;fax: +82337635224.
E-mail address:
 
(Dockery et al., 1993;Ozkaynak et al., 1993). US Environmental Protection Agency (EPA) estab-lished National Ambient Air Quality Standards(NAAQS) for the six major criteria air pollutants,among which particulate matters less than 10
m
m(PM
10
) and particulate matters less than 2.5
m
m(PM
2.5
) in aerodynamic diameter are associatedwith adverse health effects such as asthma, respira-tory disease, and mortality (US EPA, 1997). WorldHealth Organization (WHO regional office forEurope) reported various exposure studies designedfor the evaluation of toxic effects associated withphysico-chemical properties of fine particulates(WHO Europe, 2000). Recent epidemiologicalstudies have also indicated a strong correlationbetween lung cancer-induced mortality and theconcentration level of fine particulates (Burnettet al., 2001;Pope et al., 2002;Krewski et al., 2005). Both the size and the chemical compositionof the particulates are attributed to the adversehealth effects. Adverse health effects of particulatesbecomes severer as particulates are enriched byhazardous metal elements such as vanadium andnickel, which are usually originated from the fuelcombustion of heavy oils (Campen et al., 2001;Kodavanti et al., 2001).Heavy oil combustion facilities produce fineparticles in the size range of submicron, which couldbe enriched by heavy metals such as vanadium, nickeland zinc contained in liquid fuel. The very small sizeof these ultra-fine particulates makes it difficult toremove them by existing air pollution control devicesfrom the flue gas. Industrial boilers and electricitygeneration boilers consuming heavy oil are regardedas one of the main sources of such fine particulatepollutants, and cause adverse health effect by emittingparticulates enriched with heavy metals into theatmosphere. Some advanced countries have provedhazardousness of nickel and vanadium in heavy oiland the concentration of these elements have beenlimited by emission standard. Particulates fromcombustion process are formed when inorganiccompounds and metals in fuel evaporate at hightemperature and then condensate or coagulate.Linaket al. (2000, 2003, 2004)have reported a series of studies on the size distribution and chemical proper-ties of fine particles formed in the combustion processof heavy oil. According to Linak et al., the combus-tion of heavy oils resulted in relatively pronouncedfraction of ultra-fine particles smaller than 0.1
m
m, inthe size range of which transition metals such asnickel and vanadium were mostly enriched. Anthro-pogenic sources such as heavy oil combustionfacilities or electricity generation plants release fineparticles containing mainly vanadium and nickel, dueto the limited removal efficiency of the existing airpollutants control devices (APCD) for these smallparticles (Lighty et al., 2000). Fine particles arethought to be originated from the metal vapor at highcombustion temperature and formed via nucleation,condensation, coagulation processes (Linak andWendt, 1993). The temperature of the furnace andthe residence time were the controlling factors and theparticle size distribution depended on the interactionbetween chemical reactions, nucleation, condensation,and coagulation (Biswas and Wu, 1997).There is a strong relationship between the sizedistribution and the chemical properties of atmo-spheric particulates mainly originated from such ananthropogenic source.Shaheen et al. (2005)carriedout a measurement of the atmospheric concentra-tion of 10 heavy metals (Na, K, Fe, Zn, Pb, Mn, Cr,Co, Ni, and Cd) in the four size ranges (
o
2.5
m
m,2.5–10
m
m, 10–100
m
m,
4
100
m
m), and reportedthat transition metals such as nickel existed mainlyin fine particle mode (
o
2.5
m
m) and coarse mode(2.5–10
m
m) of airborne particulates.Espinosa et al.(2001), who measured the size distribution of totalsuspended particles (TSP) and heavy metals inSpain, reported that PM
10
, PM
2.5
, PM
0.61
consti-tuted 85%, 61%, 50% of TSP, respectively. Morethan 60% of Ni, V, Pb, Cd, Pb, and Cd among the11 metals analyzed were contained in ultra-fineparticles less than 0.61
m
m in aerodynamic diameter.According toSingh et al. (2002), particulate matterin the size range of 1–2.5
m
m were constitutedmainly by organic carbons, heavy metals, nitrate,and sulfate. And the smaller particle size was moreassociated with heavy metals such as Pb, Sn, Ni, Cr,V, 70–85% of such metals were distributed in thesubmicron diameter and 40% of which in particlesize less than 0.35
m
m. The strong correlationbetween the size distribution of airborne particlesand heavy metal contents was attributed to theanthropogenic source emission (Espinosa et al.,2001;Singh et al., 2002). According to source apportionment study byVallius et al. (2003), heavyoil combustion contributed 13% of PM
2.5
andvanadium, nickel, and SO
2
were recognized as indexmaterials for heavy oil combustion.Li et al. (2004)reported that PM
2.5
in New York City was appor-tioned to six major factors of heavy oil combustion,automobile, suspended particulates, sea salts, andtwo secondary sources as sulfate and nitrate.
ARTICLE IN PRESS
H.-N. Jang et al. / Atmospheric Environment 41 (2007) 1053–1063
1054
 
Fuel combustion has been known to make asignificant contribution to PM
2.5
, particularly toultra-fine particles which explains most of numberconcentration of atmospheric aerosols (Lighty et al.,2000) with potential adverse health effects. There-fore, it has become important to have a betterunderstanding of the emission characteristics andthe formation mechanism of ultra-fine particles.The objective of this study was to investigate thephysico-chemical properties of mainly ultra-fineparticles emitted from heavy oil combustion withspecial focus on vanadium and nickel. The sizedistribution of particulate matter and the containedhazardous metal elements were determined for theanthropogenic sources including industrial boilersand power plant. A laboratory combustion experi-ment in drop-tube furnace was performed usingthree major domestic heavy oils to confirm suchmetal enrichment in ultra-fine particulates whichhave been observed in case of industrial boilers andpower plant. Model simulation was carried out topredict the chemical equilibrium and particlegrowth by means of CEA and MAEROS codes.The results thus obtained were compared and usedto support the experimental results from laboratoryand commercial combustion processes.
2. Facilities and experimental methods
 2.1. Lab-scale drop-tube furnace
A drop-tube furnace was designed for thelaboratory experiment under the similar conditionin temperature and residence time as those of industrial boiler and power plant. The drop-tubefurnace consists of alumina tube as heating body, inthe center of which fuel injector and air jet gun werelocated. The burden capacity was up to 25kW withthe temperature control range from 25 to 1550
1
C. Aschematic diagram of the drop-tube furnace utilizedin the present study is depicted inFig. 1. Fuel oilwas injected by a cartridge pump (Model No752150, Col-Parmer Inc.) with the rate of 3–5gh
À
1
. The combustion experiment was per-formed at 1400
1
C followed by two cooling stepsthrough water circulation and air dilution.
 2.2. Facilities tested for the anthropogenic sources
The facilities, tested for the anthropogenic sourcecombustion in this study, were two boilers (Oil_ind1, Oil_ind 2) and 1 power plant (Oil_pwr). Twoboilers utilized bunker-C oil (S content:
4
0.3%)with steam generation capacity of 4.5 and 10tonh
À
1
, respectively. The tested power plant utilizedbunker-C oil (0.3% of sulfur content) with steamgeneration capacity of 1135 tonh
À
1
(350MW inelectricity). Sampling probe was located at the stackpoint after the cyclone, the air pollution controldevice of industrial boilers. Another sampling probewas located before the electrostatic precipitator(ESP) in addition to the stack point after ESP incase of power plant. Detailed information of facilities is listed inTable 1.
 2.3. Sampling and analysis
A cascade impactor (Anderson Instrument Co.Ltd.) was utilized for the sampling and thedetermination of size fractionized mass concentra-tion of particulate matter emitted from anthropo-genic oil combustion. Iso-kinetic coefficient wasmaintained in the range of 95–110%.Table 2showsthe ultimate compositions of three domestic heavyoils tested in the drop-tube furnace. The tested threetypes of bunker-C oils were characterized byrelatively high fraction of vanadium and nickel aswell as high sulfur content.Micro-Orifice Uniform Deposit Impactor(MOUDI, MSP Co. Ltd., Minneapolis, MN) wasutilized for the sampling and the determination of size segregated mass concentration of particulatesemitted from the laboratory combustion experi-ment. MOUDI impactor consists of ten stages withthe 50% collection efficiency cut-points in the rangeof 0.05–18
m
m under the operating flow rate of 30Lmin
À
1
. For both field and lab scale tests,sampling process was followed to EPA method201A—Determination of PM
10
emission and sizedistribution (US EPA Method, 1997) and wasrepeated three times. Metal elements in particulateswere analyzed by ICP/MS (Varian Co. Ltd., Ultramass 700) after pretreatment of samples asdocumented in EPA Method 3050B (US EPAMethod, 1986).
3. Result and discussion
3.1. Emission characteristics of PM 
10
emitted fromthe laboratory drop-tube furnace
Particle size distribution (PSD) of PM
10
emittedfrom laboratory drop-tube furnace is shown inFig. 2. The highest mass fraction was observed
ARTICLE IN PRESS
H.-N. Jang et al. / Atmospheric Environment 41 (2007) 1053–1063
1055

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