Catalytic Neutralization of Naphthenic Acid from Petroleum Crude Oil by Using Cerium Oxide Catalyst and 2- Methylimidazole in Polyethylene Glycol

Author(s):  
Norshahidatul Akmar Mohd Shohaimi ◽  
Norfakhriah Jelani ◽  
Ahmad Zamani Ab Halim ◽  
Nor Hakimin Abdullah ◽  
Nurasmat Mohd Shukri

: The presence of relatively high naphthenic acid in crude oil may contribute to the major corrosion in oil pipelines and distillation units in crude oil refineries. Thus, high concentration Naphthenic Acids crude oil is considered tobe of low quality and is marketed at lower prices. In order to overcome this problem, neutralization method had been developed to reduce the TAN value in crude oil. In this study, crude oil from Petronas Penapisan Melaka was investigated. The parameters studied were reagent concentration, catalyst loading, calcination temperature and reusability of the potential catalyst. Basic chemical used were 2- methylimidazole in polyethylene glycol (PEG 600) with concentration 100, 500 and 1000 ppm. Cerium oxide-based catalysts supported onto alumina prepared with different calcination temperatures. The catalyst was characterized by using Brunauer-Emmett-Teller (BET), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetry Analysis-Differential Thermal Gravity (TGA-DTG) to study physical properties of the catalyst. The Ce/Al2O3 catalyst calcined at 1000°C was the best catalyst due to larger surface area formation which lead to increment of active sites thus will boost the catalytic activity. The result showed that the Ce/Al2O3 catalyst meet Petronas requirement as the TAN value reduced to 0.6 mgKOH/g from original TAN value of 4.22 mgKOH/g. The best reduction of TAN was achieved by using catalyst loading of 0.39% and reagent of 1000 ppm.

2019 ◽  
Vol 7 (SI-TeMIC18) ◽  
Author(s):  
Norshahidatul Akmar Shohaimi ◽  
Wan Azelee Wan Abu Bakar ◽  
Nurasmat Mohd Shukri ◽  
Khairan Shaidi

Naphthenic acids (NAs) is one of the major sources of corrosion in oil pipelines and distillation units in crude oil refineries. Removing NA compounds from crude oils is regarded as one of the most crucial processes in heavy oil upgrading. Catalytic deacidification method had been developed in order to reduce the total acid number values in crude oil. Crude oil from Petronas Penapisan Melaka had been chosen to be studied with original total acid number (TAN) of 2.43 mg KOH/g. The parameters used were different catalyst calcination temperatures, catalyst loading, reagent concentration, reaction times and reaction temperature. Acid removal agent of 2-methylimidazole in ethanol and monometallic calcium and cerium doped with alumina were used as a catalyst. The results showed that with the aid of catalyst, the TAN can be reduced to lower than 1 mg KOH/g. Catalyst of Ca/Al2O3 calcined at 900oC gave a better reduction than Ce/Al2O3 with 83.54% of TAN reduction (2.43 to 0.4) for Ca/Al2O3 catalyst and 71.19% (2.43 to 0.7) for Ce/Al2O3 catalyst. The best catalyst underwent several characterization methods such as X-Ray Diffraction Spectroscopy (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetry Analysis (TGA-DTA) for its physicochemical properties. It can be concluded that catalytic deacidification method was effective in extracting NAs from the crude oil thus lowered the TAN value to less than 1 mg KOH/g. Keywords: Naphthenic acids; Crude oil; Catalysts


2021 ◽  
Vol 1025 ◽  
pp. 337-342
Author(s):  
Noraini Safar Che Harun ◽  
Norshahidatul Akmar Mohd Shohaimi ◽  
Shaari Daud

The Naphthenic Acid (NA) found in the acidic crude oil is one of the main challenges that can lead to corrosion problem in oil refinery equipment and reduces the quality of the oil. In this study, catalytic neutralization reaction was investigated in order to lowering Total Acid Number (TAN) in crude oil to less than one mg KOH/g utilizing 2-Methylimidazole in Polyethylene Glycol (PEG) with aid of Ca/Al2O3 catalyst. The catalyst were supported on the alumina beads through Incipient Wetness Impregnation (IWI) methods and heated in an oven for 24 hours at 80-90°C then calcined at calcination temperatures of 800, 900 and 1000°C. The result showed that Ca/Al2O3 catalyst successfully reduced to 0.52 mg KOH/g from original TAN value 4.22 mg KOH/g by using a catalyst at calcination temperature 1000°C, 0.39 wt % (7 beads) of catalyst loading and 1000 ppm of 2-Methylimidazole in PEG. It can be concluded that catalytic deacidification method was effective method in reducing NAs from the crude oil and can lowered the TAN value to less than 1 mg KOH/g.


2018 ◽  
Vol 32 (9) ◽  
pp. 9142-9158 ◽  
Author(s):  
Are Bertheussen ◽  
Sébastien Simon ◽  
Johan Sjöblom

2021 ◽  
Vol 1195 (1) ◽  
pp. 012013
Author(s):  
A Hussain ◽  
J Basar

Abstract Desalting process concept was tested using methyltrimethylammonium methylcarbonate [N4441][MeCO3] treated Pyrenees crude oil (initial Total Acid Number (TAN) of 1.6 mg KOH/g oil) with the aim to gain empirical evidences on the effectiveness of in-line water washing and electrostatic aided phase separation as mean to recover the naphthenic acid derivatives for recycling. The treated crude oil (final TAN value of less than 0.3 mg KOH/g oil) was subjected to typical operating scheme such as single stage desalting and effects of water wash volumes. The novelty of the work comes from the utilisation of ionic liquids to neutralise acid components of the crude oil. Furthermore, the work is also able to test the hypothesis of whether naphthenate salts behave as is its inorganic counterpart and quantify the solubility behaviour in water as extraction medium. The effectiveness of such scheme will be measured against naphthenic acids derivative percent recovery in the wash water. The results indicate the electrostatic conditions can facilitate the recovery of the naphthenate salts post neutralization with high recovery rate of average of 70.6 % with 30 % water wash volume in a single-stage contact, observed over 12 hours steady-state operation. The water wash weight was observed to increase post separation which indicate hydrocarbon carry-over in the heavy phase due to formation of tight water – oil emulsion. The technique is viable should the amount of water required is available and the process water can be recycled safely into the desalter again without causing tripping to the desalter. Ionic liquid can be used in conjunction with desalter and the presence of electrostatic field did hasten the separation of the phases, however the amount of water used may hinder the viability of the solution.


2021 ◽  
Vol 1025 ◽  
pp. 284-289
Author(s):  
Nurul Hidayah Aziz ◽  
Norshahidatul Akmar Mohd Shohaimi ◽  
Noraini Safar Che Harun

Processing of petroleum crude oil with high total acid number (TAN) lead to corrosion problems in oil refinery equipment, storage, facilities and even reduces the performances of the oil. The purpose of this study is to overcome the corrosion problem in oil refinery by reducing the TAN in the oil to less than 1 mgKOH/g. A 2-methylimidazole in ethanol with the aid of Ni/Ce (10:90)/Al2O3 catalyst through the catalytic deacidification technique. The catalyst was prepared by using Incipient Wetness Impregnation (IWI) methods on alumina beads as catalyst support and calcined at 800°C, 900°C and 1000°C. Ni/Ce (10:90)/Al2O3 catalyst was characterized by using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction Spectroscopy (XRD) and Brunauer-Emmett-Teller (BET) to study physicochemical properties of the catalyst. The results shows that Ni/Ce (10:90)/Al2O3 catalyst successfully reduced TAN in crude oil to 0.50 from 4.22 mg KOH/g at 1000°C calcination temperature and catalyst loading of 0.39% (7 beads). XRD analysis proposed Al2O3 and CeO2 fcc was the active site for Ni/Ce (10:90)/Al2O3 catalyst. C-H alkanes stretching, -CH2- alkanes stretching and pure metal oxides stretching modes were detected on the catalyst at wavelength of 2952.49 to 2852.82, 1599.38, and 862.81 to 537.27 cm-1 respectively by FTIR analysis after catalytic deacidification process which indicates that there were impurities that have adsorbed on the catalyst surface. As a conclusion, the catalysts successfully reduced the TAN value of acidic crude oil to less than 1.00 mg KOH/g.


2020 ◽  
Vol 606 ◽  
pp. 117835
Author(s):  
Kanghee Cho ◽  
Bharat Singh Rana ◽  
Dong-Woo Cho ◽  
Hee Tae Beum ◽  
Cheol-Hyun Kim ◽  
...  

Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 482
Author(s):  
Hilmar Guzmán ◽  
Federica Zammillo ◽  
Daniela Roldán ◽  
Camilla Galletti ◽  
Nunzio Russo ◽  
...  

Electrochemical CO2 reduction is a promising carbon capture and utilisation technology. Herein, a continuous flow gas diffusion electrode (GDE)-cell configuration has been studied to convert CO2 via electrochemical reduction under atmospheric conditions. To this purpose, Cu-based electrocatalysts immobilised on a porous and conductive GDE have been tested. Many system variables have been evaluated to find the most promising conditions able to lead to increased production of CO2 reduction liquid products, specifically: applied potentials, catalyst loading, Nafion content, KHCO3 electrolyte concentration, and the presence of metal oxides, like ZnO or/and Al2O3. In particular, the CO productivity increased at the lowest Nafion content of 15%, leading to syngas with an H2/CO ratio of ~1. Meanwhile, at the highest Nafion content (45%), C2+ products formation has been increased, and the CO selectivity has been decreased by 80%. The reported results revealed that the liquid crossover through the GDE highly impacts CO2 diffusion to the catalyst active sites, thus reducing the CO2 conversion efficiency. Through mathematical modelling, it has been confirmed that the increase of the local pH, coupled to the electrode-wetting, promotes the formation of bicarbonate species that deactivate the catalysts surface, hindering the mechanisms for the C2+ liquid products generation. These results want to shine the spotlight on kinetics and transport limitations, shifting the focus from catalytic activity of materials to other involved factors.


CORROSION ◽  
2009 ◽  
Vol 65 (12) ◽  
pp. 831-844 ◽  
Author(s):  
J. Hau

Abstract This paper reviews the factors that are hindering the development of models to predict corrosion due to sulfur compounds, naphthenic acids, or both, acting simultaneously on steels within the temperature range typically from 230°C to 400°C. These factors are identified as data scattering that do not distribute normally, variables or factors that do not exert their influence in a gradual manner but as a threshold behavior, and the interactions between the factors of sulfidic and naphthenic acid corrosion; exposure time, temperature, and velocity (shear stress); and the chromium and molybdenum content of the steels (Si content is not discussed). Not dealing with the interactions is probably the largest obstacle, followed by data scattering.


2016 ◽  
Vol 9 (12) ◽  
pp. 3736-3745 ◽  
Author(s):  
Haihua Wu ◽  
Haobo Li ◽  
Xinfei Zhao ◽  
Qingfei Liu ◽  
Jing Wang ◽  
...  

High-density coordination unsaturated copper(i)–nitrogen embedded in graphene demonstrates a high performance and stability in primary zinc–air batteries with ultralow catalyst loading.


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