NAPHTHENIC ACID REMOVAL FROM PETROLEUMCRUDE OIL UTILIZING SODIUM THIOCYANATE WITH THE

AID OF NilCe AND NilCa CATALYSTS

NURSHAHIRAH BINTI MOHD HALIM

Final Year Project Report Submitted inPartial Fulfilment of the Requirements for the

Bachelor of Science (Hons.) ChemistryUniversiti Teknologi MARA

JULY 2017

ABSTRACT

NAPHTHENIC ACID REMOVAL FROM PETROLEUM CRUDE OILUTILIZING SODIUM THIOCYANATE WITH THE AID OF NilCe AND

Ni/Ca CATALYSTS

The Naphthenic Acids (NAs) found in crude oil can leads to corrosion problems inoil refinery equipment, storage, facilities and even reduces the performances of theoil. In this study, catalytic deacidification reaction was done in order to loweringTotal Acid Number (TAN) in crude oil to below than one mg KOHIg utilizingsodium thiocyanate with the aid of Ni/Ca and NilCe catalysts. The catalyst weresupported on the alumina through Incipient Wetness Impregnation (lWI) methodsand calcined at calcination temperature of 800, 900 and 1000Q C. Ni/Ca and Ni/Cecatalyst were characterized by using X-ray Diffraction Spectroscopy (XRD),Brunauer-Emmett-Teller (BET), Fourier Transform Infrared Spectroscopy (FTIR)and Thermogravimetry Analysis-Differential Thermal Analysis (TGA-DTA) tostudy physical properties of the catalyst. The results shows that Ni/Ca(l 0:90)/Ah03and NilCe(lO:90)/Ah03 catalyst successfully reduced number of acids in crude oilto below that 1.00 mg KOH/g. Ni/Ca(10:90)/Ah03 catalyst reduced TAN of crudeoil from original TAN, 2.80 mg KOHIg to 0.28 mg KOH/g whileNi/Ce(10:90)/Ah03 catalyst reduced to 0.65 from 2.80 mg KOHIg at 1000QCcalcination temperature and catalyst loading of 4 bead (0.50%). This proven byBET results that shows both catalysts have the highest surface area, average porediameter and pore volume at calcination temperature of 1000QC that allows moremolecular NAs to enter pores of the catalyst. XRD analysis proposed Ah03 facecentered cubic (fcc) was active site for Ni/Ca(lO:90)/Ah03 catalyst while Ce02 fccwas the active site for Ni/Ce(l 0:90)/Al20 3 catalyst. Stretching of S-C=Nthiocyanate and pure metal oxides stretching modes were detected onNi/Ca(lO:90)/AI20 3 catalyst at wavelength of 2075.90 and 567.51 to 468.94 cm- t

respectively by FTIR analysis after catalytic deacidification process whichindicates that there were impurities have adsorbed on the catalyst. The catalyticreaction was fixed at reaction time of 15 minutes and temperature at 27Q C. As aconclusion, both catalysts can reduce TAN to less than 1.00 mg KOH/g. However,Ni/Ca(lO:90)/Ah03 catalyst shows more potential catalyst compared toNi/Ce(lO:90)/Ah03 catalyst since it can lowered down acid number in crude oil tomost lowest value than Ni/Ce(l0:90)/Ah03catalyst.

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TABLE OF CONTENTS

ACKNOWLEDGEMENTSTABLE OF CONTENTSLIST OF TABLES

LIST OF FIGURESLIST OF ABBREVIATIONSABSTRACTABSTRAK

CHAPTER 1 INTRODUCTION1.1 Background of study1.2 Problem statement1.3 Significance of study1.4 Objectives of study

CHAPTER 2 LITERATURE REVIEW2.1 Naphthenic Acids Removal

2.1.1 Catalytic Decarboxylation2.1.2 Liquid-Liquid Extraction2.1.3 Catalytic Neutralization

2.2 Catalytic Characterization

CHAPTER 3 METHODOLOGY3.1 Materials and Feedstock3.2 Preparation of Catalyst3.3 Catalyst Characterization

3.3.1 X-ray Diffraction Spectroscopy (XRD)3.3.2 Brunauer-Emmett-Teller (BET)3.3.3 Fourier Transfonn Infrared Spectroscopy (FTIR)3.3.4 Thennogravimetry Analysis-DifferentialThennal Analysis (TGA-DTA)

3.4 Deacidification Process3.5 Total Acid Number (TAN) Detennination

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CHAPTER 4 RESULTS AND DISCUSSION4.1 Catalyst Characterization

4.1.1 Thermogravimetry Analysis-DifferentialThermal Analysis (TGA-DTA)4.1.2 X-ray Diffraction Spectroscopy (XRD)4.1.3 Brunauer-Emmett-Teller (BET)4.1.4 Fourier Transform Infrared Spectroscopy (FTIR)

4.2 Total Acid Number (TAN) for Untreated Crude Oil4.3 Effect of Calcination temperature4.4 Effect of Catalyst Dosage4.5 Reusability Testing

CHAPTER 5 CONCLUSION AND RECOMMENDAnONS5.1 Conclusion5.2 Recommendations

CITED REFERENCESAPPENDICESCURRICULUM VITAE

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LIST OF TABLES

394.6

Table Caption Page

4.1 TGA analysis on weight loss and description of Ca based catalyst 28

4.2 TGA analysis on weight loss and description ofCe based catalyst 31

4.3 Peak assignment in the XRD pattern of Ni/Ca(l0:90)/AIz03 34

calcined at 800,900 and 1000°C

4.4 Peak assignment in the XRD pattern of Ni/Ce(10:90)/AIz03 36

calcined at 800, 900 and 1000°C

4.5 BET surface area and average pore diameter at different 37

calcination temperature ofNi/Ca(l 0:90)/Alz03 catalyst

BET surface area and average pore diameter of

4.7

Ni/Ce( 10:90)/Al203 catalyst at different calcination temperature.

FTIR assignment ofNi/Ca(l 0:90)/Ah03 catalyst 43

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