Environ Monit Assess (2007) 128:323328 DOI 10.

1007/s10661-006-9315-5

ORIGINAL ARTICLE

Seasonal Variation of Toxic Benzene Emissions in Petroleum Refinery

P. S. Rao & M. F. Ansari & A. G. Gavane & V. I. Pandit & P. Nema & S. Devotta

Received: 6 March 2006 / Accepted: 8 May 2006 / Published online: 21 October 2006 # Springer Science + Business Media B.V. 2006

Abstract Petroleum refineries are largest chemical industries that are responsible for the emission of several pollutants into the atmosphere. Benzene is among the most important air pollutants that are emitted by petroleum refineries, since they are involved in almost every refinery process. Volatile organic compounds (VOCs) are a major group of air pollutants, which play a critical role in atmospheric chemistry. These contribute to toxic oxidants, which are harmful to ecosystem, human health and atmosphere. The variability of pollutants is an important factor in determining human exposure to these chemicals. The ambient air concentrations of benzene were measured in several sites around the Digboi petroleum refinery, near the city of Gowahati in northeast India, during winter and summer 2004. The seasonal and spatial variations of the ambient air concentrations of this benzene were investigated and analyzed. An estimation of the contribution of the refinery to the measured atmospheric levels of benzene was also performed. The ambient air mixing ratios of benzene in a large area outside the refinery was generally low, in ppbv range, much lower than the ambient air quality stanP. S. Rao (*) : M. F. Ansari : A. G. Gavane : V. I. Pandit : P. Nema Scientist, Air Pollution Control Division, National Environmental Engineering Research Institute (NEERI), Nehru Marg, Nagpur 440 020, India email: ps_rao@neeri.res.in

dards. This article presents the temporal and spatial variation of air pollution in and around petroleum refinery and showed that no health risk due to benzene is present in the areas adjacent to the refinery. Keywords Benzene . Digboi . Petroleum refinery

1 Introduction Volatile organic compounds, in atmosphere, play an important role in the physicochemical process of the troposphere (Finlayson-Pitts & Pitts, 1986; Warneck, 1988) as they largely contribute to the formation of ozone and other photochemical oxidants. Some of them are highly toxic or carcinogenic, such as benzene, toluene and xylene. Benzene present in the urban and industrial atmosphere is essentially as a result of human activities, arising mainly from motor vehicle exhausts and other combustion processes utilizing fossil fuels, petrol storage and distribution, solvent usage and other industrial processes (Finlayson-Pitts & Pitts, 1986; Warneck, 1988). The refining operation, which is in general big industrial installations, is associated with the emission of various substances into the atmosphere mainly originating from the production processes, the storage tanks, the transport pipelines and the waste area. Among the most toxic atmosphere pollutants, which are emitted by petroleum refinery are volatile organic

324 Figure 1 Benzene monitoring sites insides the digboi refinery.

Environ Monit Assess (2007) 128:323328

compounds (mainly hydrocarbons), sulfur compounds, nitrogen oxides as well as particulate matter (Westaway & Brockis, 1978; Blake et al., 1993; Brocco et al., 1997). These atmospheric pollutants once emitted into the atmosphere cause a pollution problem on local scale, but are also involved on other phenomena of air pollution on regional scale, like acid rain or photochemical ozone production in the troposphere initiated by the reaction of hydrocarbons VOCs with OH radicals in the presence of nitrogen oxides and sunlight (Finlayson-Pitts & Pitts, 1986).

In order to control atmospheric pollution around a refinery the usual practice is to monitor the atmospheric concentrations of benzene, sulfur compounds (mainly hydrogen sulfide and mercaptans) and oxides of nitrogen. The usual practices to control benzene emission from different sources are provision of cover in the floating roof tanks, mechanical seal and pressure seal to control the emissions from centrifugal pump and compressor gland, replacement of leaking gasket on existing pipe and valve flanges and steam stripping as an effective control for removing fugitive

Environ Monit Assess (2007) 128:323328 Table I Site no. Benzene levels inside plant battery area limit (Winter 2004) Location Bearing Concentration g m3 4 21 22 23 24 25 NDCU CDU/VDU CDU/VDU CRU NDCU Pump house E NW NE N NE S 136 282 242 42 263 207 SD 68.7 72.3 72.4 190 108 133 Metrological parameters Wind velocity 5 3 3.5 3 5 5 Direction NE N E N NE NE Humidity (%) 75 79 80 78 84 83

325

Temp (C) 20 22 24 23 25 22

emission from process streams etc. The aim of the present work is monitoring of atmospheric pollution levels of benzene in petroleum refinery in Digboi near Gowahati in India. This refinery is a small refinery in northeast India and produces a wide spectrum of petroleum derivatives like gasoline's, LPG, jet fuels, gas oils, fuel oil, naphtha and asphalt. It processes indigenous crude from Assam Oil field India. Many process units are installed in the refinery like an atmospheric distillation unit, a thermal cracking unit, vacuum distillation units, a naphtha hydrodesulfurizer unit, a naphtha reformer unit and a catalytic cracking unit. The existing benzene measurements in Indian urban or industrial areas, usually undertaken by montoring agencies, are mostly in the form of total nonmethane hydrocarbons (NMHC) and only few measurements of speciated hydrocarbons in urban sites have been reported so far (Moschonas & Glavas, 1996; Hatzianestis, Kalabokas, Bartzis, & Mimikos, 1996; Rappenglueck, Fabian, Kalabokas, Viras, & Ziomas, 1998; Vasilikiotis, Bartzis, Hatzianestis, Vosniakos, & Pidilis, 1998;

Rappenglueck, Kourtidis, Melas, & Fabian, 1999; Kourtidis, Ziomas, Zerefos, Gousopoulos, Balis, & Tzoumaka, 2000). In India, the monitoring of such emissions are limited and also the standard are not set, Hence there is an urgent need for generating a data base of such emissions (Padma, Rao et al, 2004; 2005a,b). In the present work, speciated measurements of benzene inside an Indian Petroleum refinery are reported. The field measurements of atmospheric benzene were performed at several sites inside the refinery at different seasons in the year 2004. In most European cities, emission from road traffic has become the most important source of local air pollution. [Aromatic, e.g., benzene, ethyl benzene and xylene (BTX)] are of special concern due to their adverse health impacts (HMSO reports, 1994; WHO 2000). The field measurements of atmospheric benzene were performed at several sites in the refinery in campaigns at different seasons in 2004. A total number of 20 benzene samples have been collected and analyzed. The first objective of this study is to measure the atmospheric levels of benzene and then

Table II Benzene levels outside the plant battery area limit (Winter 2004) Site no. Location Bearing Concentration g m 1 2 3 5 6 7 8 9 10 11 12 CDU-VDU CDU-VDU CRU CDU/VDU CRU NDCU NDCU WHFU NDCU WHFU Product Pump S N S E W NW W NW NE NE W 214 122 27 309 372 7 12 147 45 307 18
3

Metrological parameters Wind velocity 3 3.5 5 3 2 3 5 3 5 5 3 Dir N N NE E SW N NE N NE NE E Humidity (%) 80 84 85 79 81 78 82 85 89 87 80 Temp (C) 25 26 22 24 25.5 22.2 24 21.5 23.1 25 26

SD 70.1 72.3 19 71.5 195 15.5 11.5 113 40.1 113 133

326 Table III Benzene levels inside the plant battery area limit (Summer 2004) Site no. Location Bearing Concentration g m3 1 5 9 10 11 13 14 16 17 18 24 27 28 47 48 49 50 53 55 56 NDCU CDU-VDU CDU-VDU CRU CRU CDU-VDU CDU/VDU HGU HDT HDT HDT SRU CPP SDU SDU SDU SDU SDU Inside pump house Tanker filling E NE NW NE SE SW W N SE NE N NE S NW NE SE SW S S W 133 13 168 4 35 54 159 7 10 198 10 272 199 20 67 23 20 448 57 627 SD 130 11.5 73.5 21.9 25 51 150 5.5 11.5 108 10.5 253 150 19 23 21 19 200 45 500

Environ Monit Assess (2007) 128:323328

Metrological parameters Wind velocity 5 5 5 4 3 3 5 4.5 5 5 5 5 5 4.5 5.0 4.5 3.0 2.5 5 5 Dir N NE N NE W S N NE N W W W W NW N NE E S N NW Humidity (%) 71 72 72 64 75 72 71.5 74.5 69 68 68 67 68.5 70.1 70 72 70.5 75 74 78 Temp (C) 25 26 28 24 21 28 27 22 23 24 28 21.5 27 23 24 28 25 26 24 25

NDCU New delayed cocking unit, CDU/VDU crude distillation unit /vacuum distribution units, CRU catalytic reformer unit, HGU hydrogen generation unit, HDT hydro treater, SRU sulphur recovery unit, CPP captive power plant, SDU solvent dewaxing unit, WHFU was hydro finishing unit

to compare their value with Central Pollution Control Board (CPCB) standard. The second objective is to determine the spatial & seasonal distribution of benzene over the study area.

2 Materials and Methods 2.1 Study area The Digboi refinery is located at latitude and longitude of 27.33N and 95.40E. The refinery is approachable from the National Highway, No. 37 from the state capital Guwahati in India. Figure 1 shows the refinery map which at present stands at a throughput capacity of 0.65 Million Metric Tons Per Annum (MMTPA). 2.2 Benzene emission The sample collection for benzene was done based on ASTM Method D3686. Air was aspirated at a known flow rate through the sampling tubes, containing

activated coconut shell charcoal, to collect air samples in the workplace and ambient air. Battery operated low volume samplers were used for collecting samples at flow rate of 100 ml/min. Pumps having stable low flow rates (10 to 200 ml/min) are preferable for long period sampling (up to 8 h) or when the concentration of organic vapors is expected to be high. Low volumes of air sample will prevent exceeding the adsorptive capacity of the charcoal tubes. As mentioned in the method humidity greater than 60% can reduce the adsorptive capacity of activated charcoal to 50% for some hydrocarbon. Presence of condensed water droplets in the sample tube will indicate a suspect sample. To overcome this situation, a moisture trap containing silica gel was attached with the sampling tube. At sampling locations the pumps were turned on and the flow rate was adjusted as recommended. Flow rates were also rechecked by another rotameter. Generally a long sampling time at a low flow rate is preferable to short-time high-flow air sampling ratio. This is consistent with the fact that most health

Environ Monit Assess (2007) 128:323328 Table IV Benzene level outside the plant battery area limit (Summer 2004) Site no. Sampling location Bearing Concentration g m3 SD 2 3 4 6 7 8 12 15 21 22 23 25 30 35 36 37 39 41 42 43 44 54 CDU-VDU CDU-VDU CDU-VDU NDCU NDCU CRU NDCU KST HGU HGU HDT Between HGU-SRU Opposite Chemical house foam tank platform Between Chemical house & cooling tower CPP DM water Tank Near pump house opposite bitumen filling plant WHFU WHFU WHFU WHFU Finished product storage tank SDU S N E S NE NW NW E SW NW NW SE E SE NW W NW SE SW NW NE SW 10 1 7 BDL 55 8 352 50 BDL 64 57 7 BDL 111 145 70 172 34 BDL 1 BDL 7 9.5 5.5 50 7.5 15.3 45 40.5 45 5.5 6.5 120.5 44.5 155 23.5 1.5 5.5 Metrological parameters Wind velocity Dir 5 4 5 5 5 5 4 5 5 4.5 2 3 5 3 3 2.5 5 4 5 3 2 4 N NE N NE NW NW NE NW N NE E W N S SE W NW NE N W E NE

327

Humidity (%) Temp (C) 71 72 64 73 71 72 78 79 75 76 77 75 76 71 70.5 71.2 72.5 73.2 74.72 71 73 75 20 22 22.5 23.5 24 20 20 22.7 22.5 20 21.5 24 25 23.5 26 24.5 25.6 23 24 25 25.6 25

standards are based on 8 hrs/day time-weighted averages of exposure concentrations. Hence, the sampling time of 4 hrs and 8 hrs was chosen to suit the purpose. At the end of the sampling period the flow rate is rechecked, the pumps are turned off and all pertinent information like time register reading, temperature, site location and any other specific details regarding unit/operation is recorded. The charcoal tube is sealed with the inert rubber caps and stored at 4.0C. The labeling is done as per the code to have appropriate information for identifying the samples. Four charcoal tubes, were preserved for analysis as a field blank for a set of 54 samples collected during the monitoring. 2.3 Analysis of the sample The analysis for benzene was carried out based on ASTM Method 6916. The activated coconut shell charcoal was subjected to thermal desorption by heating up to a temperature of 180C and head space is then injected for analysis by Gas Chromatograph and detected by Mass Spectrophotometer (GC-MS). The analysis of each sample required Helium as

carrier gas at 8 ml/min and the complete chromatogram was obtained in about 40 min. The column used was 25 m 0.53 mm 3.0 m (BP.624) that is specific for benzene as well as other volatile compounds. HPLC grade benzene was used for the preparation of standards of benzene. 3 Results and Discussion Benzene emissions from different unit of the refinery were measured in different season inside and outside the plant/unit battery area. The benzene emission as shown in Tables I and II are higher in inside as compared to outside plant/unit battery area. Benzene concentrations were inside in the range of 42282 g m3 in the month of winter 2004. From Tables III and IV it is observed that the levels of benzene emissions ranged between inside and outside the plant battery area as 7133 to 1352 g m3 in summer 2004, respectively, which is less than the NOISH limit of 1.0 PPM (3,198 g m3 = 1 PPM). Benzene concentration in winter and summer are higher in inside as compared to outside plant/unit battery area.

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Environ Monit Assess (2007) 128:323328 Kourtidis, K., Ziomas, I., Zerefos, C., Gousopoulos, A., Balis, D., Tzoumaka, P. (2000). Benzene and Toluene levels measured with a commercial DOAS system in Thessaloniki, Greece. Atmospheric Environment, 34, 14711480. Moschonas, N., & Glavas, S. (1996). C3 C10 hydrocarbons in the atmosphere of Athens, Greece. Atmospheric Environment, 30, 2769 2772. Padma, B., Rao, S., Gavane, A. G., Ankam, S. S., Ansari, M. F., Pandit V. I. et al. (2004) Performance evaluation of green belt in a petroleum refinery: A case study. Ecological Engineering. Padma, B., Rao, S., Ansari, F., Ankam, S., Gavane, A. G., Pandit, V. I. et al. (2005a). Estimating Fugitive Emission Budget of Volatile Organic Carbon (VOC) in a Petroleum Refinery. Bulletin of Environmental Contamination and Toxicology, 75, July. Padma, B., Rao, S., Ankam, S. S., Ansari, M. F., Gavane, A. G., Kumar, A. et al. (2005b). Monitoring of hydrocarbon emissions in a petroleum refinery. Environmental Monitoring and assessment, 108, 123132. Rappenglueck, B., Fabian, P., Kalabokas, P., Viras, L., & Ziomas, I. (1998). Quasi-continuous measurements of non-methane hydrocarbons (NMHC) in the Greater Athens area during MEDCAPHOT-TRACE. Atmospheric Environment, 32(12), 21032121. Rappenglueck, B., Kourtidis, K., Melas, D., & Fabian, P. (1999). Observations of biogenic and anthropogenic NMHC in the greater Athens area during the PAUR campaign. Physics and Chemistry of the Earth (B), 24, 717724. Vasilikiotis, G., Bartzis, J., Hatzianestis, J., Vosniakos, F., & Pilidis, G. (1998). Determination of volatile organic compounds in the atmosphere of the city of Thessaloniki. Fresenius Environmental Bulletin, 7a, 1 6. Warneck, P. (1988). Chemistry of the natural atmosphere: International geophysical series, Vol. 41. New York: Academic. Westaway, M. T., & Brockis, G. J. (1978). Petroleum refineries. In: Parker, A. (Ed.), Industrial air pollution handbook. London: McGraw-Hill. World Health Organization Reports (2000). NEWSLETTER, WHO Collaborating Centre for Air Quality Management and Air Pollution Control Federal Environmental Agency. Corrensplatz 1-14195 Berlin, Germany.

4 Conclusions In general, the average ambient air concentrations of benzene were relatively low, in the order of few ppb. The concentrations of benzene are different in winter and summer. The benzene concentrations of ambient air were higher in winter season as compared to the summer season. The benzene concentrations were higher in inside as compared to the outside plant/unit battery area. In conclusion the levels of benzene pollution inside the petroleum refinery were lower.
Acknowledgements We thank the Director NEERI, Nagpur for kind permission to publish this work. The cooperation and support provided by the refinery staff during the course of the study is also gratefully acknowledged.

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