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FEASIBILITY STUDY OF BIOREMEDIATION OF OIL WASTE CONTAMINATED SOIL USING AEROBIC BACTERIA AT WONOCOLO TRADITIONAL OIL FIELD

ABSTRACT Environmental pollution caused by petroleum exploitation activities can easily occur. Pollution that occurs includes; destruction of nutrient content in the soil, polluted ground water and air. The most harmful effect is ground water becoming toxic and unfit for consumption because it contains benzene, toluene and xylene (BTX) compounds. The Decree of the Minister of Environment no. 128 of 2003 stipulates rules regarding the procedures and technical requirements for waste and soil treatment contaminated by petroleum using biological methods. Previous research (Maria Assumpta, 2017) discusses the bioremediation of BTX compounds by the addition of 17.5% concentration of Bacillus cereus, Pseudomonas putida and Rhodococcus erythropolis on contaminated soil in Pertamina Petrochina East Java (PPEJ) Bojonegoro field producing from the Ngrayong Formation. The initial concentration of BTX compounds on that field were: benzene 26.44 ppm, toluene 121 ppm, and xylene 109 ppm. After bioremediation these levels fell to: benzene 0.489 ppm, toluene 0.726 ppm and xylene 3.45 ppm. These values are below the maximum limits that have been decreed. Based on analysis of the percentage of hydrocarbon component, oil phase diagram, o API, oil density, initial formation volume factor (Boi) and gas gravity obtained there is a similarity between oil from PT. PPEJ Bojonegoro Field (Ngrayong Formation) with oil at Wonocolo Field (Wonocolo Formation). Both oils are light oils with API gravity of 31.4 – 32.27 oAPI and also similar values of oil density (53.93 – 54.2 lb/ft3). The hypothesis is the biodegradation of BTX compounds carried UPN Veteran Yogyakarta

out on contaminated soil on PT. PPEJ Bojonegoro Field by adding 17.5% concentration of Bacillus cereus aerobic bacteria, Pseudomonas putida, and Rhodococcus erythropolis can also give similar results when applied to Traditional Wonocolo Oil Field. This is expected to have a positive impact on the environment around Wonocolo Field. Keywords : Bioremediation, Benzene, toluene, xylene (BTX)

INTRODUCTION Benzene, Toluene dan Xylene (BTX) The hydrocarbon monoaromatics consist of benzene, toluene, ethyl benzene and three xylene isomers, called BTX. BTX can directly contact with the environment through petroleum-related processes, leakage from oil storage tanks, oil spills from wells and industrial waste. BTX is soluble and it is a volatile toxic substance. BTX is highly susceptible to microbial attack, so it can be degraded under aerobic conditions. Toluene is the most easily degraded compound compared to the other compounds. The degradation process requires dissolved oxygen (DO) to activate the ring overhaul the aromatic ring and become an electron acceptor for complete degradation reaction by bacteria, fungi, or algae. An aromatic compound can only be considered perfectly degraded when its aromatic ring has broken. (Assumpta, Maria., 2017) Influential Bacteria Degradation Process

In

The

BTX

Of the bacterias that contribute to the degradation process of BTX compounds, there are: Bacillus cereus Bacillus cereus (Figure 1) is an aerob grampositive bacteria with rod-shaped cells. It is facultative aerobic, and it can make spores. This bacteria can grow optimally in the temperature range 28- 35oC and pH between 4.9 – 9.3. (Assumpta, Maria., 2017) Pseudomonas putida Pseudomonas putida (Figure 2) is an aerob gram-negative bacteria, it has rod –shaped (2-4 μm) and a flagellum. This bacteria lives at a normal pH of ±7 and temperatures between 2530oC. (Assumpta, Maria., 2017) Rhodococcus erythropolis Rhodococcus erythropolis (Figure 3) is an aerobic bacteria and has no spores. It is included in the actinomycetes group. Based on taxonomy, these bacteria are closely related to Nocardia and Mycobacterium. This bacteria can lives in temperature range of 26-37oC and pH of ±7. (Assumpta, Maria., 2017) Quality Standard of Oil Waste Processing Minister of Environment Decree No. 128 of 2003 year regulates the technical procedures and requirements for the biological treatment of waste and soil contaminated by oil waste. The final value requirements of petroleum sludge processing results are shown in Table 1. (Assumpta, Maria., 2017) PVT ANALYSIS Oil Density Oil density is defined as the mass of a unit volume of the oil at a specified pressure and temperature. It is usually expressed in pounds per cubic foot. The specific gravity of an oil is defined as the ratio of the density of the oil to the water. (Rukmana, Dadang., 2012) Both densities are measured at 60oF and atmospheric pressure:

Where : Ɣo = specific gravity of the oil ρo = density of the crude oil, lb/ft3 ρw = density of the water, lb/ft3 Although the density and specific gravity are used extensively in the petroleum industry, the API gravity is the preferred gravity scale. This gravity scale is precisely related to the specific gravity by the following expression :

Gas Solubility (Rs) The gas solubility (Rs) is defined as the number of standard cubic feet (SCF) of gas that will dissolve in one stock-tank barrel (STB) of crude oil at certain pressure and temperature. (Ahmed, Tarek., 2001) Standing (1981) expressed his correlation in the following mathematical form:

Where : T = temperature, oR P = pressure, psia Ɣg = specific gravity of dissolved gas Oil Formation Volume Factor (Bo) The oil formation volume factor, Bo, is defined as the ratio of the volume of oil (plus the gas in solution) at the prevailing reservoir temperature and pressure to the volume of oil at standard condition. (Ahmed, Tarek., 2001). Standing’s (1981) showed that the oil formation volume factor can be expressed more conveniently in a mathematical form by the following equation:

Where :

T Ɣo Ɣg

= temperature, oR = specific gravity of the stock-tank oil = specific gravity of the solution gas

Oil Viscosity (μo) Oil viscosity is defined as the internal resistance of the fluid to flow. (Ahmed, Tarek., 2001) Vasquez dan Beggs (1980) proposed the following expression for estimating the viscosity of undersaturated oil:

where

These multicomponent pressure-temperature diagrams are essentially used to:  Classify reservoirs  Classify the naturally occuring hydrocarbon systems  Describe the phase behavior of the reservoir fluid PREVIOUS RESEARCH Characteristics of PT. PertaminaPetrochina East Java Bojonegoro Field Previous research was conducted to analyze the soil taken from PT. Pertamina-Petrochina East Java Bojonegoro field with the characteristics shown in Table 2.

with

Oil Compressibility (Co) Vasquez and Beggs (1980) correlated the isothermal oil compressibility coefficients with Rs, T, oAPI, Ɣg, and p (Ahmed, Tarek., 2006). They proposed the following expression:

Soil characteristics indicate that land in the oil field exceeds the minimum requirements of the Quality Standard set by the government in accordance with KepmenLH No.128 of 2003 as in Table 1. While result of Aerobic Bacteria Research at PT. PPEJ Bojonegoro Field. (Shown in Table 3).

Where : T = temperature, oR p = pressure above the bubble-point pressure, psia Rsb = gas solubility at the bubble-point pressure Ɣgs = corrected gas gravity Pressure-Temperature Diagram The conditions under which these phases exist are a matter of considerable practical importance. The experimental or the mathematical determinations of these conditions are conveniently expressed in different types of diagrams commonly called phase diagrams. One such diagram is called the pressure-temperature diagram (Figure 4). (Ariadji, Tutuka., 2016)

METHODS The research methods applied in this paper are mathematical analysis and literature study. 1. Literature Study Various literatures related to existing problems were studied to support the paper writing. 2. Mathematical Analysis Mathematical analysis is performed to establish the relationship and correlation between oil characteristic in PT. PPEJ Bojonegoro Field and Wonocolo Traditional Oil Field. Oil properties comparison can be used to determine the similarity of oils properties. Oils with the same characteristics have similar hydrocarbon component. The hydrocarbon component will be degraded by aerobic

bacterias. Thus, oils with the same properties will show the same degradation results.

ANALYSIS Wonocolo Traditional Oil Field is a traditional oil field located in Wonocolo Village, Bojonegoro District. The method of oil production in this field uses very simple equipment to produce the oil making oil spills unavoidable. The oil spills are increasingly degrading the surrounding environment (Figure 5). The previous research conducted by Maria Assumpta (January, 2017) at PT. PertaminaPetrochina East Java (PPEJ) Bojonegoro Field (Ngrayong Formation) observes the degradation of oil waste using aerobic bacteria. That research explains that there are 3 optimum bacterias used to degrade benzene, toluene, and xylene (BTX) compounds, namely Bacillus cereus, Pseudomonas putida, and Rhodococcus erythropolis. The BTX concentration of PT. PPEJ Bojonegoro Field before bioremediation were benzene 26.44 ppm, toluene 121 ppm, and xylene 109 ppm. These values exceed the maximum limit stated by Decree of the Minister of Environment No. 128 of 2003. Addition of bacteria with concentrations of 17.5% in soil samples from PT. PPEJ Bojonegoro Field resulted in benzene degradation by Bacillus cereus bacteria reached 98.148% (0.489 ppm). Degradation of toluene reached 99.4% (0.726 ppm) by Pseudomonas putida, while the best xylene degradation by Rhodococcus erythropolis reached 96.83% (3.45 ppm). In this paper, the author compare the oil characteristics between oils from PT. PPEJ Bojonegoro and Wonocolo Field. This comparison aims to determine what the bioremediation at PT. PPEJ Bojonegoro can be applied in Wonocolo Traditional Oil Field. Based on the geological structure of the North East Java Basin, Wonocolo Formation is above Ngrayong Formation. Wonocolo Formation is

the target zone of Wonocolo Traditional Oil Field, while Ngrayong Formation is the target zone of PT. PPEJ Bojonegoro. The characteristics data of formation and reservoir fluids of both formation are obtained from SKK Migas’s data in POD (Plan of Development) Competition. The analyzed data are PVT and hydrocarbon component in wellstream condition. The results of PVT data analysis are: oil phase diagrams, oil density, API gravity, initial formation volume factor (Boi), oil viscosity (μo) and oil compressibility (Co). Oil phase diagram is obtained by using PVT-P software, while other physical properties are obtained from the mathematical correlations listed in the previous chapter. Based on the results of wellstream-PVT analysis, the oil density of Wonocolo Formation is 54.2 lb/ft3 and 53.93 lb/ft3 for Ngrayong Formation. API gravity of Wonocolo’s oil is 31.4oAPI and Ngrayong’s oil is 32.27oAPI. Based on the value of oil density and API gravity, both oils are light oils. Then, the initial solubility of gas (Rsi) for Wonocolo’s oil and Ngrayong’s oil are 314 scf/stb and 498.61 scf/stb. The value of initial formation volume factor (Boi) of Wonocolo’s oil is 1.13 Rb/stb and 1.505 Rb/stb for Ngrayong’s oil. Both oils have oil viscosity value, 0.736 cp for Wonocolo’oil and 0.789 cp for Ngrayong’s oil. Then, oil compressibility (Co) value of Wonocolo’s oil is 1.6089E-05 psi-1 and 1.7735E-05 psi-1 for Ngrayong’s oil. The last oil characteristic is oil phase diagram. The result of PVT-P Software shows that both oils have similar shape of phase diagram dan that is the phase diagram of light oil. Based on analysis of some oil characteristics, it can be concluded that both oils in Wonocolo formation and Ngrayong formation are light oil. These are indicated by the similarity of API gravity and oil phase diagram values. Therefore, both oils exhibit similar properties and characteristics and also they have hydrocarbon component which not much different.

The hypothesis is the biodegradation of BTX compounds conducted at PT. PPEJ Bojonegoro Field by adding 17.5% concentration of Bacillus cereus, Pseudomonas putida, and Rhodococcus erythropolis could give similar results at Wonocolo Traditional Oil Field. CONCLUSIONS 1. Biodegradation of Benzene, Toluene and Xylene (BTX) compounds at PT. PPEJ Bojonegoro Field can be optimized by adding 17.5% solution of aerob bacterias, these being; Bacillus cereus, Pseudomonas putida, and Rhodococcus erythropolis. This degradation of 98.148% (0.489 ppm) for benzene, 99.4% (0.726 ppm) for toluene and 96.83% (3.45 ppm) for xylene. 2. The biodegradation results after application of 17.5% aerobic bacterias gave a positive result that meets the requirements of the quality standard set by the Decree of the Minister of Environment No. 128 of 2003. 3. The oil characteristic of Wonocolo Formation (Wonocolo Traditional Oil Field) and Ngrayong Formation (PT. PPEJ Bojonegoro) are similar, i.e. light oil with API gravity between 31.4 – 32.27 OAPI and oil density between 53.93 – 54.2 lb/ft3. 4. Analysis of physical properties of oil are based on percentage of hydrocarbon component, oil phase diagram, API gravity (oAPI), oil density, initial formation volume factor (Boi), oil viscosity (μo), oil compressibility (Co) and gas gravity. 5. The hypothesis is that the biodegradation of BTX compunds conducted at PT. PPEJ Bojonegoro Field by using 17.5% concentration of aerobic bacteria (Bacillus cereus, Pseudomonas putida, and Rhodococcus erythropolis) could give

similar results at the Wonocolo Traditional Oil Field. RECOMMENDATIONS Communities that exploit oil in Wonocolo Traditional Field should use closed oil storage tanks, so that oil does not spill to the soil which will ultimately contaminate and degrade soil and groundwater. ACKNOWLEDGEMENT The authors wish to thank to Mrs. Indah Widiyaningsih ST., MT as the mentor for her assistance and help to complete and edit this paper. REFERENCES Ahmed, Tarek, “Reservoir Engineering Handbook 2nd Edition”. Gulf Publishing Company : Houston, Texas. ISBN 088415-770-9, 2001. Ahmed, Tarek., “Reservoir Engineering Handbook 3rd Edition”. Gulf Publishing Company : Jordan Hill, UK. ISBN 13: 987-0-7506-7972-5, 2006 Ariadji, Tutuka., “Esensi & Fondasi Perencanaan Pengembangan Lapangan/POD Migas”. Penerbit ITB : Bandung. ISBN 978-602-7861-64-0, 2016. Assumpta, Maria., “Bioremediasi Benzene, Toluene dan Xylene (BTX) dari Lahan Terkontaminasi Minyak Bumi Oleh Bakteri Aerobik Pada Fase Slurry dalam Bioreaktor”. Institut Teknologi Sepuluh Nopember (ITS), 2017. Rukmana, Dadang. Kristanto, Dedy. Aji, Dedi Cahyoko., “Teknik Reservoir, Teori dan Aplikasi”. Pohon Cahaya : Yogyakarta. ISBN 978-602-9485-05-9, 2012. SKK Migas., “Case Study of Plan Of Development (POD) Competition of Oil and Gas Intellectual Parade (OGIP) 2018”.

Petroleum Engineering UPN Veteran Yogyakarta, 2018.

ATTACHMENTS

TABLE 1 QUALITY STANDARD OF OIL WASTE PROCESSING Parameters Unit Result Analysis of sludge *) pH 6-9 TPH (μg/g) 10,000 Benzene (μg/g) 1 Toluene (μg/g) 10 Ethylbenzene (μg/g) 10 Xylene (μg/g) 10 Total PAH (μg/g) 10 *) Chemical analysis results for the concentration value of oil waste specified in dry weight (Source : KEPMENLH 128, 2003) TABLE 2 THE SOIL CHARACTERISTIC OF PPEJ BOJONEGORO FIELD Parameters Characteristic Color Glossy brown pH 9.1 Temperature 28°C BTX Value Benzene 26.44 ppm Xylene 121 ppm Toluene 109 ppm PAH Value Napphthalene 115.64 ppm Fluorene 30.27 ppm Anthrancene 101.18 ppm Fluoranthene 9.69 ppm Pyrene 18.26 ppm Chrysene 24.47 ppm (Assumpta, Maria, January 2017)

TABLE 3 BTX DEGRADATION OF EACH BIOREACTOR

BTX Concentration (μg/g) Days

BTX Concentration (μg/g) Days

BTX Concentration (μg/g) Days

(Assumpta, Maria, January 2017)

TABLE 4a HYDROCARBON COMPONENT COMPARISON BETWEEN WONOCOLO’S OIL & NGRAYONG’S OIL Formation Wonocolo

Component

Ngrayong

Wellstream Calculation Mol %

Mol %

N2

Nitrogen

0.231

0.165

CO2

Carbon Dioxide Hydrogen Sulfide

0.835

0.906

-

-

C1

Methane

8.411

7.2

C2

Ethane

1.747

5.101

C3

Propane

5.294

4.067

iC4

iso-Butane

4.321

6.17

nC4

n-Butane

4.285

5.833

iC5

iso-Pentane

4.155

4.354

nC5

n-Pentane

2.896

4.717

C6

Hexanes

5.331

3.769

C7

Heptanes

4.984

5.305

C8

Octanes

5.18

6.247

C9

Nonanes

6.546

4.821

C10

Decanes

5.598

4.122

C11

Undecanes

7.289

7.384

H2S

C12+ Dodecanes plus 32.987 30.839 (Study Case of POD Competition – OGIP 2018 by Petroleum Engineering of UPN Veteran Yogyakarta)

TABLE 4b CHARACTERISTICS OF WONOCOLO’S OIL AND NGRAYONG’S OIL Oil Density

T

Pres

lb/ft³

°F

Psia

Gas Gravity

Wonocolo

54.2

205.6

2,113

0.73

Ngrayong

53.93

219.6

2,600

0.71

Formation

Source : SKK Migas – Case Study of POD Competition of OGIP 2018 UPN Veteran Yogyakarta

TABLE 4c CHARACTERISTICS RESULTS OF WONOCOLO’S OIL AND NGRAYONG’S OIL Oil Density lb/ft³

T

Pres

°F

Psia

Wonocolo

54.2

205.6

Ngrayong

53.93

219.6

Formation

Rsi

Boi

μoi

Coi

SCF/STB

Rb/STB

cp

psi-1

31.4

314

1.13

0.736

1.6089E-05

32.27

498.61

1.505

0.789

1.7735E-05

Gas Gravity

°API

2,113

0.73

2,600

0.71

TABLE 5 CHARACTERISTICS RESULTS OF WONOCOLO’S OIL P psia 2113.0 1913.0 1713.0 1513.0 1313.0 1113.0 1097.99 913.0 713.0 513.0 313.0 113.0 14.7

Rs scf/stb 314.00 314.00 314.00 314.00 314.00 314.00 314.00 252.784 189.385 129.445 73.987 25.207 3.279

Bo rb/stb 1.13 1.150 1.168 1.185 1.200 1.213 1.206 1.178 1.150 1.123 1.100 1.080 1.071

po Co psi¯¹ lb/ft³ 50.691 1.60887E-05 49.809 1.77708E-05 49.042 1.98456E-05 48.338 2.24689E-05 47.734 2.58914E-05 47.222 3.0544E-05 47.201 3.09615E-05 47.872 3.72349E-05 48.572 4.76795E-05 49.236 6.6268E-05 49.846 0.000108612 50.376 0.000300845 50.610 0.002312616

μo cp 0.736 0.715 0.696 0.679 0.664 0.651 0.650 0.641 0.634 0.630 0.631 0.640 0.648

TABLE 6 CHARACTERISTICS RESULTS OF NGRAYONG’S OIL P psia 2600 2400 2200 2000 1800 1600 1400 1373 1200 1000 800 600 400 200 14.7

Rs scf/stb 498.61 498.61 498.61 498.61 498.61 498.61 498.61 498.61 405.62 327.26 251.99 180.39 113.40 52.77 6.6

Bo rb/stb 1.175 1.195 1.215 1.235 1.255 1.275 1.295 1.305 1.259 1.222 1.187 1.154 1.125 1.099 1.077

po Co psi¯¹ lb/ft³ 42.417 1.77358E-05 41.871 1.92138E-05 41.340 2.09605E-05 40.821 2.30566E-05 40.315 2.56184E-05 39.822 2.88207E-05 39.340 3.2938E-05 39.104 3.35857E-05 40.451 3.84276E-05 42.073 4.61131E-05 43.755 5.76414E-05 45.465 7.68552E-05 47.146 0.000115283 48.707 0.000230566 50.052 0.003136948

μo cp 0.789 0.767 0.747 0.728 0.710 0.695 0.682 0.680 0.670 0.662 0.656 0.653 0.655 0.662 0.678

Time (days)

Time (days)

Time (days)

Chart 1 - Degradation of (a) benzene, (b) toluene dan (c) xylene for Adding 17.5% Concentration of Bacillus cereus, Pseudomonas putida And Rhodococcus erythropolis (Assumpta, Maria, January 2017)

Phase Diagram of Wonocolo's Oil

Pressure, psia

800 600 400 200 0 -400

-200

0

200

400

600

800

Temperature, °F

Chart 2 – Oil Phase Diagram of Wonocolo Formation (Wonocolo Traditional Oil Field) using IPMPVTP Software

Pressure, psia

Phase Diagram of Ngrayong's Oil 800 700 600 500 400 300 200 100 0 -400

-200

0

200

400

600

800

Temperature, °F

Chart 3 – Oil Phase Diagram of Ngrayong Formation (PT. PPEJ Bojonegoro) using IPM-PVTP Software

Oil Characteristics of Wonocolo Formation Bo vs Pressure of Wonocolo's Oil

400 350 300 250 200 150 100 50 0

1.25 1.2

Bo, rb/stb

Rs (scf/stb)

Rs vs Pressure of Wonocolo's Oil

1.15 1.1 1.05 1

0

500

1000

1500

2000

2500

0

500

1000

1500

2000

2500

Pressure, psia

Chart 4 - Rs vs Pressure

Chart 5 - Bo vs Pressure

Oil Viscosity vs Pressure of Wonocolo's Oil

Oil Density vs Pressure of Wonocolo's Oil Oil Density, lb/ft³

0.76 0.74 0.72 0.7 0.68 0.66 0.64 0.62

0,051 0,049 0,047 0,045 0,043

0

500

1000

1500

2000

0

2500

500

1000

Chart 6 - Oil Viscosity vs Pressure

2000

Chart 7 - Oil Density vs Pressure

Oil Compressibility vs Pressure of Wonocolo's Oil 0.0025 0.002 0.0015 0.001 0.0005 0 00

1500

Pressure, psia

Pressure, psia

Co, psi¯¹

μo, cp

Pressure (psia)

500

1,000

1,500

2,000

Pressure, psia

Chart 8 - Oil Compressibility vs Pressure

2,500

2500

Oil Characteristics of Ngrayong Formation Bo vs Pressure of Ngrayong's Oil

600 500 400 300 200 100 0

1.4

Bo, rb/stb

Rs (scf/stb)

Rs vs Pressure of Ngrayong's Oil

1.3 1.2 1.1 1

0

1000

2000

0

3000

1000

3000

Chart 9 - Rs vs Pressure

Chart 10 - Bo vs Pressure

Oil Viscosity vs Pressure of Ngrayong's Oil

Oil Density vs Pressure of Ngrayong's Oil Oil Density, lb/ft³

0.8 0.75 0.7 0.65 0.6 0

1000

2000

0,050 0,045 0,040 0,035 0

3000

1000

2000

Pressure, psia

Pressure, psia

Chart 11 - Oil Viscosity vs Pressure

Chart 12 - Oil Density vs Pressure

Co vs Pressure of Ngrayong's Oil 0.00025 0.0002

Co, psi¯¹

μo, cp

2000

Pressure, psia

Pressure (psia)

0.00015 0.0001 0.00005 0 0

1000

2000

3000

Pressure, psia

Chart 13 - Oil Compressibility vs Pressure

3000

Figure 1 - Bacillus cereus

Figure 2 - Pseudomonas Putida

Figure 3 - Rhodococcus erythropolis

Figure 4 - Typical p-T Diagram for a Multicomponent System

Figure 5 – The Condition in Wonocolo Traditional Oil Field (Alfiza Danistya Suseno’s Document)

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