The Dangers Of Heavy Oil

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Atmospheric Environment 41 (2007) 1053–1063 www.elsevier.com/locate/atmosenv

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments Ha-Na Janga, Yong-Chil Seoa, Ju-Hyung Leea, Kyu-Won Hwanga, Jong-Ik Yoob, Chong-Hui Sokc, Seong-Heon Kima,d, 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 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. r 2006 Elsevier Ltd. All rights reserved. Keywords: Combustion; Heavy oil; Vanadium; Nickel; Ultra-fine particles

Corresponding author. Air and Waste Engineering Labora-

tory, Department of Environmental Engineering, #305 Back-Un Building, Yonsei University, Heung-up, Won-Ju, Gang-Won 220-710, Republic of Korea. Tel.: +82 33 760 2380; fax: +82 33 763 5224. E-mail address: [email protected] (S.-H. Kim). 1352-2310/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2006.09.011

1. Introduction Airborne particulate matter has been the primary focus of several epidemiological studies, which reported a correlation between adverse health effects and the particle concentration levels

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(Dockery et al., 1993; Ozkaynak et al., 1993). US Environmental Protection Agency (EPA) established National Ambient Air Quality Standards (NAAQS) for the six major criteria air pollutants, among which particulate matters less than 10 mm (PM10) and particulate matters less than 2.5 mm (PM2.5) in aerodynamic diameter are associated with adverse health effects such as asthma, respiratory disease, and mortality (US EPA, 1997). World Health Organization (WHO regional office for Europe) reported various exposure studies designed for the evaluation of toxic effects associated with physico-chemical properties of fine particulates (WHO Europe, 2000). Recent epidemiological studies have also indicated a strong correlation between lung cancer-induced mortality and the concentration level of fine particulates (Burnett et al., 2001; Pope et al., 2002; Krewski et al., 2005). Both the size and the chemical composition of the particulates are attributed to the adverse health effects. Adverse health effects of particulates becomes severer as particulates are enriched by hazardous metal elements such as vanadium and nickel, which are usually originated from the fuel combustion of heavy oils (Campen et al., 2001; Kodavanti et al., 2001). Heavy oil combustion facilities produce fine particles in the size range of submicron, which could be enriched by heavy metals such as vanadium, nickel and zinc contained in liquid fuel. The very small size of these ultra-fine particulates makes it difficult to remove them by existing air pollution control devices from the flue gas. Industrial boilers and electricity generation boilers consuming heavy oil are regarded as one of the main sources of such fine particulate pollutants, and cause adverse health effect by emitting particulates enriched with heavy metals into the atmosphere. Some advanced countries have proved hazardousness of nickel and vanadium in heavy oil and the concentration of these elements have been limited by emission standard. Particulates from combustion process are formed when inorganic compounds and metals in fuel evaporate at high temperature and then condensate or coagulate. Linak et al. (2000, 2003, 2004) have reported a series of studies on the size distribution and chemical properties of fine particles formed in the combustion process of heavy oil. According to Linak et al., the combustion of heavy oils resulted in relatively pronounced fraction of ultra-fine particles smaller than 0.1 mm, in the size range of which transition metals such as nickel and vanadium were mostly enriched. Anthro-

pogenic sources such as heavy oil combustion facilities or electricity generation plants release fine particles containing mainly vanadium and nickel, due to the limited removal efficiency of the existing air pollutants control devices (APCD) for these small particles (Lighty et al., 2000). Fine particles are thought to be originated from the metal vapor at high combustion temperature and formed via nucleation, condensation, coagulation processes (Linak and Wendt, 1993). The temperature of the furnace and the residence time were the controlling factors and the particle size distribution depended on the interaction between chemical reactions, nucleation, condensation, and coagulation (Biswas and Wu, 1997). There is a strong relationship between the size distribution and the chemical properties of atmospheric particulates mainly originated from such an anthropogenic source. Shaheen et al. (2005) carried out a measurement of the atmospheric concentration of 10 heavy metals (Na, K, Fe, Zn, Pb, Mn, Cr, Co, Ni, and Cd) in the four size ranges (o2.5 mm, 2.5–10 mm, 10–100 mm, 4100 mm), and reported that transition metals such as nickel existed mainly in fine particle mode (o2.5 mm) and coarse mode (2.5–10 mm) of airborne particulates. Espinosa et al. (2001), who measured the size distribution of total suspended particles (TSP) and heavy metals in Spain, reported that PM10, PM2.5, PM0.61 constituted 85%, 61%, 50% of TSP, respectively. More than 60% of Ni, V, Pb, Cd, Pb, and Cd among the 11 metals analyzed were contained in ultra-fine particles less than 0.61 mm in aerodynamic diameter. According to Singh et al. (2002), particulate matter in the size range of 1–2.5 mm were constituted mainly by organic carbons, heavy metals, nitrate, and sulfate. And the smaller particle size was more associated with heavy metals such as Pb, Sn, Ni, Cr, V, 70–85% of such metals were distributed in the submicron diameter and 40% of which in particle size less than 0.35 mm. The strong correlation between the size distribution of airborne particles and heavy metal contents was attributed to the anthropogenic source emission (Espinosa et al., 2001; Singh et al., 2002). According to source apportionment study by Vallius et al. (2003), heavy oil combustion contributed 13% of PM2.5 and vanadium, nickel, and SO2 were recognized as index materials for heavy oil combustion. Li et al. (2004) reported that PM2.5 in New York City was apportioned to six major factors of heavy oil combustion, automobile, suspended particulates, sea salts, and two secondary sources as sulfate and nitrate.

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Fuel combustion has been known to make a significant contribution to PM2.5, particularly to ultra-fine particles which explains most of number concentration of atmospheric aerosols (Lighty et al., 2000) with potential adverse health effects. Therefore, it has become important to have a better understanding of the emission characteristics and the formation mechanism of ultra-fine particles. The objective of this study was to investigate the physico-chemical properties of mainly ultra-fine particles emitted from heavy oil combustion with special focus on vanadium and nickel. The size distribution of particulate matter and the contained hazardous metal elements were determined for the anthropogenic sources including industrial boilers and power plant. A laboratory combustion experiment in drop-tube furnace was performed using three major domestic heavy oils to confirm such metal enrichment in ultra-fine particulates which have been observed in case of industrial boilers and power plant. Model simulation was carried out to predict the chemical equilibrium and particle growth by means of CEA and MAEROS codes. The results thus obtained were compared and used to support the experimental results from laboratory and commercial combustion processes. 2. Facilities and experimental methods 2.1. Lab-scale drop-tube furnace A drop-tube furnace was designed for the laboratory experiment under the similar condition in temperature and residence time as those of industrial boiler and power plant. The drop-tube furnace consists of alumina tube as heating body, in the center of which fuel injector and air jet gun were located. The burden capacity was up to 25 kW with the temperature control range from 25 to 1550 1C. A schematic diagram of the drop-tube furnace utilized in the present study is depicted in Fig. 1. Fuel oil was injected by a cartridge pump (Model No 7521–50, Col-Parmer Inc.) with the rate of 3–5 g h 1. The combustion experiment was performed at 1400 1C followed by two cooling steps through water circulation and air dilution.

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boilers utilized bunker-C oil (S content: 40.3%) with steam generation capacity of 4.5 and 10 ton h 1, respectively. The tested power plant utilized bunker-C oil (0.3% of sulfur content) with steam generation capacity of 1135 ton h 1 (350 MW in electricity). Sampling probe was located at the stack point after the cyclone, the air pollution control device of industrial boilers. Another sampling probe was located before the electrostatic precipitator (ESP) in addition to the stack point after ESP in case of power plant. Detailed information of facilities is listed in Table 1. 2.3. Sampling and analysis A cascade impactor (Anderson Instrument Co. Ltd.) was utilized for the sampling and the determination of size fractionized mass concentration of particulate matter emitted from anthropogenic oil combustion. Iso-kinetic coefficient was maintained in the range of 95–110%. Table 2 shows the ultimate compositions of three domestic heavy oils tested in the drop-tube furnace. The tested three types of bunker-C oils were characterized by relatively high fraction of vanadium and nickel as well as high sulfur content. Micro-Orifice Uniform Deposit Impactor (MOUDI, MSP Co. Ltd., Minneapolis, MN) was utilized for the sampling and the determination of size segregated mass concentration of particulates emitted from the laboratory combustion experiment. MOUDI impactor consists of ten stages with the 50% collection efficiency cut-points in the range of 0.05–18 mm under the operating flow rate of 30 L min 1. For both field and lab scale tests, sampling process was followed to EPA method 201A—Determination of PM10 emission and size distribution (US EPA Method, 1997) and was repeated three times. Metal elements in particulates were analyzed by ICP/MS (Varian Co. Ltd., Ultra mass 700) after pretreatment of samples as documented in EPA Method 3050B (US EPA Method, 1986). 3. Result and discussion

2.2. Facilities tested for the anthropogenic sources

3.1. Emission characteristics of PM10 emitted from the laboratory drop-tube furnace

The facilities, tested for the anthropogenic source combustion in this study, were two boilers (Oil_ind 1, Oil_ind 2) and 1 power plant (Oil_pwr). Two

Particle size distribution (PSD) of PM10 emitted from laboratory drop-tube furnace is shown in Fig. 2. The highest mass fraction was observed

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Oil Inlet

A

B

Water inlet

Water outlet

Pump B-Coil Water bath

C D

Main controller A : Oil inlet probe B : Thermo couple C : Alumina Furnace Tube D : Heating area E : Sampling probe F : Pressure gauge G : Pump H : Water controller

air E

F

H G MOUDI (Filter)

Water inlet Air

Water outlet Air Sample port

Fig. 1. Schematic diagram of lab-scale drop-tube furnace.

around 0.1 mm within the ultra-fine particle size range. More than 90% of PM10 existed in the size range less than 3.1 mm (PM2.5), 80% of which existed within PM0.5. Especially, the averaged mass fraction of PM0.1 consisted of more than 50% of PM10, 60% of PM2.5, and 67% of PM0.5,

respectively. The above results indicated that particulate matter emitted from the heavy oil combustion mainly consisted of fine particulates less than 2.5 mm in aerodynamic diameter, with dominating mass fraction in the size range of ultrafine particles.

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Table 1 Identification and capacity for tested boilers ID

Capacity (steam generation)

Fuel

Boiler type

APCDa

Oil_ind 1 Oil_ind 2 Oil_pwr

4.5 ton h 1 10 ton h 1 1135 ton h

B/B oil B/C oil B/C oil

Fire tube Fire tube Electric generation

Cyclone Cyclone ESP

a

1

(350 MW)

APCD denotes Air Pollutants Control Device.

Table 2 Ultimate analysis of heavy oil used in lab-scale oil combustion

Water (%) Carbon (%) Hydrogen (%) Nitrogen (%) Sulfur (%) Ash (%) Oxygen (%) Vanadium (mg g 1) Nickel (mg g 1) Iron (mg g 1) Zinc (mg g 1)

Oil-1

Oil-2

Oil-3

0.03 83.15 9.79 0.76 1.65 5.67 0.96 38.70 18.50 — 56.80

0.01 82.72 10.52 1.18 3.02 3.92 0.91 58.80 22.40 — —

0.05 85.63 11.09 0.81 1.23 5.78 0.86 40.87 17.57 — —

3.2. Emission characteristics of PM10 emitted from oil combustion facilities Particle size distributions (PSD) of PM10 emitted from the heavy oil combustion facilities are shown in Fig. 3. On average, 23% of PM10 mass concentration at the stack point was contained within ultra-fine particle size range (o0.1 mm), and 80% within 2.5 mm. As shown in Fig. 3, bi-modal size distribution was dominant except for Oil_pwr stack. The formation of fine mode around 1 mm was explained by either incomplete burnout of oil or residuals of inherent cenospheres contained in oil (Miller et al., 1998; Linak et al., 2000). Single mode in the size range of ultra-fine particles observed in case of Oil_pwr stack can be interpreted to come from vaporization and following condensation processes of trace metals, while particles larger than 0.3 mm are efficiently removed by Electrostatic Precipitator (ESP). The average mass concentration of PM10 was decreased from 6.4 mg m 3 before the ESP to 0.4 mg m 3 after the ESP. The submicron mode (o1 mm) observed before APCD in power plant is related to further aging process of ultra-fine particles formed from metal vapors. Metal vapor can undergo condensational nucleation and then grow via condensation and

Fig. 2. Particle size distribution of PM10 emitted from lab-scale combustion.

Fig. 3. Particle size distribution of PM10 emitted from the oil combustion facilities.

coagulation processes for the residence time between the boiler and the stack. As confirmed in laboratory experiment by means of drop-tube furnace combustion, ultra-fine mode within 0.1 mm is formed via vaporization/condensation processes of trace metals such as V and Ni, and then grow to

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fine mode up to 1 mm by coagulation process. In order to validate the assumption that the ultra-fine particle are formed by nucleation, condensation, coagulation processes from the evaporated metal vapors, laboratory experiments using drop-tube furnace were performed and the results were compared with the computational calculation by MAEROS code as described in following section. 3.3. Model prediction for particle growth In order to illustrate particle growth by nucleation, condensation, and coagulation, MAEROS was used to simulate particle growth (Gelbard and Seinfeld, 1980). Initial concentration was given as 14 mg m 3, the measured value in drop-tube furnace according to EPA method 5. The result from labscale combustion of Oil-1 was taken as input data used in model prediction. Primary particle diameter of 2 nm was allocated to the Section 2 (0.0021–0.0046 mm) in the simulation process for nucleation. Pressure was maintained to 1.01  105 Pa, while temperature was ramped in 0.1 s from the tube temperature of 1650 K down to 373 K which is the sampling probe temperature adjusted by EPA method 5. The initial number concentration was 1.1  1017 m 3. Fig. 4 shows the predicted particle size distribution after 0.1, 0.5, 1, 2, 5, and 10 s of residence time. As time increased from 0.1 to 10 s, number concentration decreased to 8.3  1016, 4.9  1015, 9.2  1014, 1.9  1014, 2.5  1014, and 6.0  1012 m 3, respectively. As shown in Fig. 4, the accumulation mode around 0.05 mm appeared

after 5 s of residence time, which was consistent with the experimental result of Oil-1 combustion. Fig. 4 also showed that the accumulation mode started to diminish distinctly after 10 s of residence time indicating the difficulty for particles to grow larger than 1 mm only by the coagulation mechanism. The above model calculation implied that the accumulation mode around 0.3 mm observed before APCD in Oil_pwr was the result of further growth of ultrafine particles after longer residence time.

3.4. Evaporation prediction by chemical equilibrium The chemical equilibrium analysis (CEA) code (McBride et al., 1993) was used to predict the element speciation and, more importantly, the fractions of vapor-phase species as a function of temperature for principle metals. References for the thermo-chemical properties and species data sets used are found in Linak et al. (2003). The predicted compound speciation of nickel and vanadium at various temperature ranges are shown in Fig. 5. Data from the US EPA study (Linak et al., 2004) were depicted also for the comparison. Both vanadium and nickel exist in the vapor phase at the temperature range higher than 1400 1C. As shown in Fig. 5, the combustion temperature of 1600 K inside drop-tube furnace was high enough to vaporize V and Ni. V and Ni are predicted to form sulfates at lower temperature (400–900 K) and oxides at higher temperature (higher than 1000 K). Sulfate formation affects the solubility and perhaps

Mass Concentration (mg/m3)

20 0.1sec 0.5sec 1sec 2sec 5sec 10sec

15

10

5

0 0.001

0.01

0.1 Aerodynamic Diameter (µm)

Fig. 4. Model prediction by MAEROS.

1

10

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0.6

NiO2H2

0.4

NiSO4(S) NiO(3)

0.2

NiS

0.0 800

2400

*Ni

0.6

NiO NiO2H2

0.4

NiSO4(S) NiO(3)

0.2

NiS

800

1200 1600 Temperature (K)

2000

2400

*V *VO

0.6

VO2 V2O4(I)

0.4

V2O5(L) VOSO4(S)

0.2

800

(e)

1200 1600 Temperature (K)

2000

2400

NiSO4(S) NiO(3)

0.2 0.0 400

NiS

800

1200 1600 Temperature (K)

2000

2400

0.8 *V *VO

0.6

VO2

0.4

V2O4(I) V2O5(L)

0.2 0.0 400

VOSO4(S)

800

1200 1600 Temperature (K)

2000

2400

0.8

*V *VO

0.6

VO2 V2O4(I)

0.4

V2O5(L) VOSO4(S)

0.2 0.0 400

800

1200

1600

2000

2400

Temperature (K)

(f)

1.0

1.0

0.8 Ni NiO Ni(OH)2 NiSO4(s) NiFe2O4(2) NiO(3) Condensed phase

0.6 0.4 0.2

800

1200 1600 Temperature (K)

2000

Fraction of Each Compound

Fraction of Each Compound

NiO2H2

0.4

1.0

0.8

0.0 400

NiO

(d)

1.0

0.0 400

*Ni

0.6

1.0

0.8

0.0 400

0.8

(b)

1.0

(c) Fraction of Each Compound

2000

Fraction of Each Compound

Fraction of Each Compound

(a)

1200 1600 Temperature (K)

Fraction of Each Compound

0.8

400

(g)

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1.0

Fraction of Each Compound

Fraction of Each Compound

H.-N. Jang et al. / Atmospheric Environment 41 (2007) 1053–1063

0.8

(h)

V2O4(II) V2O5(s)

0.4

V2O5(L) Condensed phase

0.2 0.0 400

2400

VO2

0.6

800

1200 1600 Temperature (K)

2000

2400

Fig. 5. Speciation of vanadium and nickel compounds from Oil-1, Oil-2 and Oil-3 depending on temperature variation. (a) Ni from Oil-1, (b) Ni from Oil-2, (c) Ni from Oil-3, (d) V from Oil-1, (e) V from Oil-2, (f) V from Oil-3, (g) Ni from EPA, (h) V from EPA.

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the bioavailability and toxicity associated with V, Ni (Linak et al., 2000). 3.5. Metal element analysis Fig. 6 shows the size segregated mass fraction of nickel in particulates emitted from the anthropogenic source. The averaged mass fraction of nickel in PM0.5 was considerably high around 63% as shown in Fig. 6. The mass fraction of nickel in PM0.5 (90%) was much higher at the stack point of Oil_pwr than the value (50%) measured before the APCD. On the contrary, the mass fraction of nickel in coarse particles (2.5–10 mm) did not show a significant change between sampling points before APCD and at the stack point. This result of higher enrichment of nickel in fine mode indicated that fine particles were grown as a result of metal evaporation followed by nucleation, condensation, and coagulation. A similar enrichment pattern of metal elements was observed in the laboratory combustion experiment. The mass fraction distribution for both vanadium and nickel showed the peak value in ultra-fine particle size range as depicted in Figs. 7 and 8. The mass fractions of nickel and vanadium in fine particles were 66% and 74%, respectively. And the ratio of nickel content in PM0.1 to that in PM2.5 was 48% and the ratio of vanadium content in PM0.1 to that in PM2.5 was 53%. It could clearly confirm that metals were vaporized at high combustion temperatures as predicted by chemical equilibrium code, then formed ultra-fine particulates by a

suggested particle growth model up to the size under 1 mm. The enrichment portion of metals and particle size distribution were compared between lab-scale furnace and industrial oil boilers as summarized in Table 3. Both data from lab-scale furnace and real industrial boilers for oil combustion showed similar pattern with high enrichment of metals in ultra-fine particulates. The portion of metal enriched in fines from field experiment was less than that from laboratory experiment. 4. Conclusions The emission characteristics of fine particles was investigated 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. PM10 emitted from the facilities mainly consisted of fine particles (80%), which was dominated by ultrafine particles (23%), on average. Particularly in power plant, the mass fraction of ultra-fine particles (PM0.1/PM10) was greatly enhanced during the transfer from 1% measured before APCD to 40% at the stack point. The averaged mass fraction of nickel in PM0.5 also showed considerably high value of 63%. The ratio of nickel fraction in ultra-fine particles to that in PM10 was increased almost twice during transfer from before APCD to the stack of the oil power plant. The implication of the field results is that conventional control device might be

100 Oil_Ind1 stack Oil_Ind2 stack Oil-Pwr(before APCD) Oil_Pwr stack Average(stack)

Mass Fraction (%)

80

60

40

20

0 < 0.5

2.5-0.5

10-2.5

Aerodynamic Diameter (µm) Fig. 6. Size segregated mass fraction of nickel in PM10 from anthropogenic oil combustion sources.

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60 Oil 1 Oil 2 Oil 3

Mass Fraction (%)

50

Avg.

40

30

20

10

0 <0.1

0.1-0.18 0.18-0.31 0.31-0.51 0.51-1.0 1.0-1.8

1.8-3.1

3.1-6.2

6.2-10

Aerodynamic Diameter (µm) Fig. 7. Size segregated mass fraction of nickel in PM10 from lab-scale oil combustion.

70 Oil 1 Oil 2 Oil 3 Avg.

60

Mass Fraction (%)

50 40 30 20 10 0 <0.1

0.1-0.18 0.18-0.31 0.31-0.51 0.51-1.0 1.0-1.8

1.8-3.1

3.1-6.2

6.2-10

Aerodynamic Diameter (µm) Fig. 8. Size segregated mass fraction of vanadium in PM10 from lab-scale oil combustion.

ineffective for the removal of ultra-fine particles being grown during the transfer by nucleation, condensation, and coagulation of metal vapor. The above results were verified by laboratory combustion experiments in drop-tube furnace and model simulation using MAEROS code. The primary nano-size particles were predicted by MAEROS computation to grow in 2 s to ultra-fine particle size of 0.1 mm, which was in a good agreement with experimental results from lab-scale drop-tube furnace. Ultra-fine

particles consisted more than 50% of PM10 from the lab-scale oil combustion. Furthermore, the enrichment of nickel and vanadium elements was more pronounced in the smaller particle size, with the peak value at 0.1 mm. It was difficult for the conventional air pollution devices to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel, which would raise a request for new establishment or the revise of emission regulatory standards.

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Table 3 Comparison of PSD in PM10 and mass fraction of metals in different size ranges between lab-scale experiment and industrial boilers Lab-scale data

Field data

PM10 PSD (%) o2.5 mm o0.5 mm o0.1 mm

90.49 81.60 54.35

79.53 54.10 22.70

Nickel MF (%) o2.5 mm o0.5 mm o0.1 mm

90.04 66.35 43.21

85.24 63.20 41.16a

Vanadium MF (%) o2.5 mm o0.5 mm o0.1 mm

91.25 74.05 48.33

— — —

a The prediction value of Ni mass fraction in PM0.1 by the combustion of drop-tube furnace (%).

Acknowledgements This work was supported by R&D fund from Korea Energy Management Corporation and Korea Institute of Environmental Science and Technology. Model calculations and analysis were assisted by W.P. Linak in US EPA.

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