1st Faculty of Engineering and Technology Conference (FETiCON 2023), Jun.

5 -7, 2023,
University of Ilorin, Nigeria
1 OPTIMISATION OF THE OIL YIELD FROM FLUIDISED CATALYTIC
2 CRACKING OF OIL SHALE.
3 B. O. UMEH1, P.E. DIM2, M.B. BABA3 A.G. Olugbenga4, S.O. ENESSI5
4
5 Department of Chemical Engineering, Federal University of Technology Minna, Niger State, Nigeria.
1,2

6 3
Department of Water Aquaculture and Fishery Technology Minna WAFT, Federal University of Technology
7 Minna, Niger State, Nigeria
8 4,5
Department of Chemical Engineering, University of Abuja, Abuja, Nigeria.
9 1
bobbyfrank.umeh.@st.futminna.edu.ng
10 2
paul.dim@futminna.edu.ng
11 3
choiceangel@futminna.edu.ng
12 4
grace.olugbenga@uniabuja.edu.ng
13 5
samodxdy@gmail.com
14
15 ABSTRACT
16 An unconventional fuel oil is obtained by fluidised catalytic cracking of oil shale using abundant deposit of
17 gypsum mineral resources as catalyst. Shale oil is an Unconventional source of energy which is abundantly
18 present in Nigeria as reported by Olawuyi in 2014. The material is significant to Nigeria’s economic
19 sustainability but yet remain untapped efficiently. The aim of this work is to improve the yield of fuel oil from
20 shale oil via fluidised catalytic cracking using ZSM-5 as catalyst. The ultimate and proximate analysis proves
21 the good viability of Ikwo Oil Shale obtained at the anticlinorium of Abakiliki in Ebonyi State. The
22 Optimisation of the produced oil was achieved by 80% through the correlation exhibited by the Kinetic and
23 Design of Experiment Study. At a corresponding temperature of 328oC in the virtual and physical lab at twenty
24 (20) runs under a residence time ranging from 10 to 40mins, the 1.5 ratio addition of ZSM-5 Catalyst in the
25 thermal cracking of oil shale produced 97.57% of oil in the Virtual lab (D.O.E) and 95% of oil in the fluidised
26 catalytic bed reactor_FCBR (Physical Lab). The inclusion of ZSM-5 catalyst increase the production of oil yield
27 as recorded often in industrial modular and conventional refineries.
28
29 KEYWORDS: Ikwo Oil Shale, ZSM-5 Catalyst, Optimisation, Design of Experiment ,Kinetic

30 1. INTRODUCTION

31 Currently, Nigeria and the world face a significant challenge to meet future demand for liquid fuels. These
32 challenges are caused by rising demand for oil and other petroleum products. The world demand for petroleum
33 is expected to continue to increase over the next twenty-five years from approximately 80 million barrels to
34 nearly 120 million barrels-per-day by 2025 (Biglarbigi et al., 2007). Therefore, the question now is, where will
35 the additional supply comes from to cushion the increased demand? So far, the Organization of Petroleum
36 Exporting Countries (OPEC) productive capacity has not increased as fast as production demand (Cameron et
37 al., 2006). In Nigeria pres, the oil and gas sector is being bombarded with numerous problems which include:
38 the rising demand for oil, gas and other petroleum products, a turn-around decrease in conventional oil and gas
39 reserves, worldwide volatility of oil prices, among others (Obasi, 2013). This situation has exposed the
40 dependency of the Nation in conventional crude oil to recession; as about 75 percent of Nigeria's revenue is
41 from crude oil (Agbaeze et al., 2015).
42
43 2. THEORETICAL ANALYSIS
44 2.1 SYNTHESIS OF ZSM-5

45 According to an article published by Lerner, H et al 1985 titled: “Synthesis and structure refinement of ZSM-5
46 single crystals” reports shows that there are many ways to synthesize ZSM-5; a common technique includes: An
47 Aqueous Solution of silica, sodium aluminate, sodium hydroxide and tetrapropylammonium bromide are
48 combined in appropriate ratios

49 SiO2+NaAlO2+NaOH+N(CH2CH2CH3)4Br + H2O ZSM-5 + analcime+alpha –quartz.

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 1st Faculty of Engineering and Technology Conference (FETiCON 2023), Jun. 5 -7, 2023,
University of Ilorin, Nigeria
50 The preparation of ZSM-5 requires high temperature and high pressure in a Teflon coated autoclave and can be
51 prepared using ranging ratios of SiO2 and Al comprising compounds.

52 2.2 RESPONSE SURFACE METHODOLOGY

53 Response Surface Methodology (RSM) is a statistical tool use for the modeling and analysis of statistically
54 generated data to determine the true optimal condition of a process (Nuran, 2007). In recent time, response
55 surface methodology has shown to be a valuable tool for finding solutions to problems in which a definite
56 response of interest is affected by various processing parameters (Mohammad et al., 2012). The primary goal of
57 using response surface methodology is to model a response of a process, however, response surface
58 methodology was later used to develop models for the optimization of numerical experiments (Kathleen et al.,
59 2004). When understudy treatments are based on continuous array of values, then response surface methodology
60 can be applied to the development, improvement and optimization of response parameters which is
61 mathematically expressed as:

62 y = f(x1, x2) + e (2.1)

63 In most RSM problems, the true response function f is unknown. In order to develop a proper approximation
64 for f, the experimenter usually starts with a low-order polynomial in some small region. If the response can be
65 defined by a linear function of independent variables, then the approximating function is a first-order model. A
66 first-order model with 2 independent variables can be expressed as
67 y=β 0 + β 1 X 1+ β 2 X 2 + ε (2.2)
68 If there is a curvature in the response surface, then a higher degree polynomial should be used. The
69 approximating function with 2 variables is called a second-order model:
70 y=β 0 + β 1 X 1+ β 2 X 2 + β 11 x 211 + β 22 x 222+ β 12 x 1 x2 + ε (2.3)

71 2.3 DESIGN OF EXPERIMENT

72 An imperative part of response surface methodology is the design of experiments (DoE). These strategies were
73 primarily developed for the model fitting of physical experiments, but can also be used for numerical
74 experiments. The goal of design of experiment is to determine points where the response of a process should be
75 assessed (Montgomery, 2005).
76 The conditions for optimal design of experiments are linked with the mathematical model of the process.
77 Basically, these models are polynomials with an unknown structure, so the corresponding experiments are
78 designed only for every particular problem. The choice of the design of experiments can have a large effect on
79 the correctness of the approximation and the cost of developing the response surface (Montgomery, 2005).

80 2.3.1 CENTRAL COMPOSITE DESIGN

81 In recent years, central composite design (CCD) has gained much consideration as the most suitable second
82 order design for the comprehensive estimation of response surfaces based upon second order models
83 (Mohammad et al., 2012). In 1951, central composite design was introduced by Box and Wilson to response
84 surface optimization. Central composite design accounts for either a full factorial design with two levels (2 k) or
85 fractional factorial designs (2k–f) fabricated with numerous design points (Mohammad et al., 2012). Central
86 composite design involved three types of design points which are factorial points (n f), central points (nc) and
87 axial points (na). Equation 2.4 gives an expression for cumulative design points:
88 n = 2k(nf) + 2k (na) + k (nc) (2.4)

89 A second-order model can be developed effectively with CCD. Central composite design is a first-order (2N)
90 design improved by additional centre and axial points to permit estimation of the tuning variables of a second-
91 order model. Figure 2.4 shows a CCD for 3 design variables.

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 1st Faculty of Engineering and Technology Conference (FETiCON 2023), Jun. 5 -7, 2023,
University of Ilorin, Nigeria

92
93 Figure1: Central composite design for 3 design variables at 2 levels
94
95 In Figure 2.4, the design includes 2N axial points, 2N factorial points, and 1central point. Central composite
96 design can be used for 3N designs in the construction of second-order models because when compared to a full
97 factorial design, the number of experiments is reduced, for example, 27 number of experiment in the case of
98 full-factorial design compared to 15 number of experiment in the case of central composite design. In recent
99 time, central composite design has been used for multi objective design of a flywheel, but as the number of
100 designs variables increases, the experiments becomes tedious even with the use of central composite design
101 (Montgomery, 2005).

102 3. MATERIALS AND METHODS/METHODOLOGY/EXPERIMENTAL PROCEDURE

103 3.1 MATERIAL
104 Table1: Sample Materials
Material(s) Souce(s)

Ikwo Oil Shale Ikwo, Ebonyi State.

ZSM-5 Prof. A.S. Kovo

105

106
107 Figure 2: Process Flow Diagram of Experimental Methodology

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 1st Faculty of Engineering and Technology Conference (FETiCON 2023), Jun. 5 -7, 2023,
University of Ilorin, Nigeria
108 4. RESULTS AND DISCUSSION

109 4.1 DESIGN OF EXPERIMENT STUDY

110 The Predicted R² of 0.8006 is in reasonable agreement with the Adjusted R² of 0.9345; i.e. the difference is less
111 than 0.2. Adeq Precision measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of
112 16.377 indicates an adequate signal. This model can be used to navigate the design space.
113 Table 2: ANOVA Statistics
Fit Statistics

Std.
8.24 R² 0.9655
Dev.
Mea 47.2 Adjuste
0.9345
n 4 d R²
C.V. 17.4 Predicte
0.8006
% 4 d R²
Adeq
16.377
Precisio
5
n
114
115 4.2 KINETIC STUDY
116 The activation energies calculated at different conversion degree using Flynn-Wall-Ozawa method are shown in
117 Table 3 and the relationship between E0 and conversion degree α are showed in Figure 3. The results show that
118 the correlation coefficients (R2) of FWO method is better, the values of activation energy is between 81.508 and
119 122.206 kJ/mol and increase with the increasing of conversion degree. From Table 3 and Figure 6, the average
120 value of activation energy Eo is 104.203kJ/mol and the pre-exponential factor lgAo is 9.968.

121
122 Table 3. Flynn Wall Ozawa Kinetic Data
α Eo(kJ/mol) lgAo(min-1) R2

0.15 81.508 8.134 0.9852

0.20 95.988 9.286 0.9896
0.25 106.374 10.132 0.9886
0.30 114.937 10.840 0.9903
0.35 122.206 11.448 0.9913
Mean* 104.203 9.968 0.989

123

124 Formula Model: lg ꞵ=lg

( Rg(AEα) )−2.315−0.4567( RTE )

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 1st Faculty of Engineering and Technology Conference (FETiCON 2023), Jun. 5 -7, 2023,
University of Ilorin, Nigeria
FLYNN WALL OZAWA (F.W.O)METHOD
1.8
1.6
1.4 f(x)
f(x) === 0.842092795360313
f(x) 0.410680337085467 xxx +++ 0.219465241152861
0.596974745169566 0.560923885402472
0.814753298504373
1.2
logB Values

1
0.8
0.6
0.4
0.2
0
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
1/T Values
125
126 Figure 3: Flynn Wall Ozawa (F.W.O) Method
127
128 5. CONCLUSION
129 The Design of Experiment and Kinetic Study are both correlated in term of R 2 Value. The use of Central
130 Composite Design (CCD) in the Design Expert Version 13, proves a great correlation in the obtained R 2 value.
131 The value of the adjusted R2=0.9345, the predicted R2=0.8006 with a less significant difference of 0.2. The final
132 adequate (adeq.) value of the R2 value from the CCD Anova Contour Plot shows that R 2 =0.9655; these obtained
133 values tallies with the values of R2 obtained for the various kinetic model considered in this experimental study
134 i.e. where values of R2 obtained as 0.812, 0.9712, 0.987, 0.989 for Arrhenius, Coats Redfern, Kissinger and
135 Flynn Wall Ozawa (F.W.O). The Optimisation of the produced oil was achieved by 80% through the correlation
136 exhibited by the Kinetic and Design of Experiment Study.

137 ACKNOWLEDGEMENT
138 Author and Co-Authors wishes to acknowledge Step B Nanotech Lab, Department of Chemical Engineering
139 and Department of WAFT Lab in the Federal University of Technology Minna.
140
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