Activating Metal Catalyst Of Refinery Process

Published Date: 02 Nov 2017

Student: Mohammed Abdulrahim

Student I.D: 200747617

Supervisor: DR. Valerie Dupont

2 May 2013

ABSTRACT

The Crude distillation process does not yield in a high amount of gasoline with a satisfactory cetane and octane number. Therefore some processes such as Hydrotreating, Hydrocracking, Catalytic cracking, Catalytic reforming, Steam reforming, isomerisation and Fischer-Tropsch process should be carried out in order to produce a large amount of gasoline with required standard.

However, this process cannot be feasible and suitable without a catalyst. But most of the metallic catalysts are delivered to the refinery in oxide form, and it is the refinery does the reduction processes in order to activate the catalyst to perform the action that they were design for. Nevertheless they used high costly hydrogen, Ammonia or high diluted methane steam feed for the reduction step and all these processes are very expensive and they carried a lot of carbon print.

Moreover bio-fuels are expected to play a vital role in providing world’s transport fuel and forerunners of plastic material in the nearest future. For these process to become independent from fossil a lot of effort is needed to take care of all aspect of refinery process.

This research is aimed to determine the possibilities of using a model compound of bio-fuel (glucose) for the reduction of nickel oxide (NiO) catalyst, and to determine the suitable condition of the experimental process such as temperature, steam to carbon ratio and using glucose as reduction agent of NiO catalysts and by describing the reduced catalyst Ni base on surface morphology, crystalline structure and coke amount

ACKNOWLWEDGEMENT

I wish to express my sincere gratitude to Almighty Allah who gave me the ability and strength to be here for my studies.

Firstly I would like to acknowledge my research supervisor Dr.Valerie Dupont for her precious time to put me through this great project, her availability, patience and guidance make this research project feasible.

Exceptional thanks goes to my mentor Feng Cheng Alice for her time and guidance during this work.

Special thanks go to my parent, my wife, my children and friends for patience they endure during my absence.

Contents

List of Tables

NOMENCLATURE

TGA –Thermogravimetric Analysis

XRD- X-Ray Diffraction

SEM- Scanning Electron Microscope

EDX- Energy Dispersive X-ray analysing system

IEA- Internal Energy Agency

HHV- High Heating Value

1.0 INTRODUCTION

Today refining process play a very important role in upgrading the products of oil companies which is the biggest business on earth, it attracts nearly $ two trillion ($2,000,000,000) every year. Globally, there’s demand of one hundred and eighty million boe/d and the refining process provides seventy six million boe/d(silvy, 2002)

Therefore in order to obtained high production yield and qualitative products that will meet the standard demand of customers, catalyst must be used to speed up of the reaction and gives out desired product. In 2001 about $ 2.3 billion has been spent in catalytic process in the refinery which is equivalent to 82% of whole crude volume. The demand of these refining catalysts is always increasing by 5% every year which cost $2.8 billion in 2005 and it has been projected to increase in future. (Silvy, 2002). Most of these catalyst are metallic in nature which need chemical reduction before they become active for the purpose where designed for, usually manufactures supplies these catalysts in oxidized form and it’s the refinery that do the activation process in the initial stage and these is been done by using of high cost hydrogen, Ammonia or a highly diluted methane steam feed and all of these process are energy intensive and they carry a significant carbon foot print.

The major sources of fuel and some derived-hydrogen products such as fibers, chemicals, pharmaceuticals and lubricants all over the world are from crude oil. Predominantly consist of hydrocarbon with the ratio of 0.5 hydrogen and 2 carbons and some compound of nitrogen, sulfur, oxygen and organometallic particles such as Iron (Fe), Nickel (Ni), Titanium (Ti) and Vanadium (V). Its boiling point differs significantly starting from less than room temperature to about 650oC with molecular weight of about 2000. Due to their different range in terms of molecular weight and their structure that extensively varies their usage as a fuel oil, chemical feed stock and lubrication product , (Meyers, 2004, Hoffman, 1993)

Catalytic process has developed an important role of upgrading the refined products of crude oil from fuel oil, diesel, gasoline, lubrication and jet fuel. Nearly 60% of product from petrochemical plants and 90% of processes in petrochemical are catalytic in nature (Nationalresarchcouncil, 1992).

The processes that required the reduced metallic catalyst are:

Hydrotreating, which eradicate the major contain particles, Nitrogen and sulphur.

Hydrocracking which breaks down the heavy hydrocarbons in to smaller once and it do away with composite that contain impurities such as nitrogen, oxygen, sulphur and its escalate hydrogen content (Garry, 2001).

Catalytic cracking which is the heart of refining process it cracks large hydrocarbon of C30 - 40+ into lower molecules of gasoline, diesel oil, automotive turbine kerosene and feed stock for petro-chemical plants.

Catalytic reforming which upgrade the RON and combustion behaviors of engine.

Isomerisation which increase the rate of octane number C5 and C6 alkane to Isoalkanes , Isobutene from n-butane (C4) and P-xylene from xylenes.(Meyers, 2004, Speight, 2002)

The homogenous and heterogeneous catalysts used in industries are physically and chemically complex. Best heterogeneous catalysts are made from well designated combined active substance, promoter and support carrier; but some of them have no supportive and promoted metals. Heterogeneous catalyst is mainly consisting of 3 components and these are:

Active catalytic phase

Promoter (increases stability and activity)

Support (high surface carrier)

Table 1.1: Catalyst material types and their components (Clark, 2003)

Component

Material types

Example

Active

Promoters

Textural

Chemical

Carrier (supporter)

Metals

Metal oxide

Metal sulphide

Metal oxide

Metal oxide

Stable, high surface area

Stable, high surface area

Metal oxides, carbon

Noble metals Pt, Pd; metals Ni, Fe

Transition metal oxide MoO2, CuO

Transition metals sulfide: MoS2, Ni3S2

Transition metal group 3A,: Al2O3, SiO2, MgO, BaO, TiO2 ZrO2

Alkali, alkaline earth: K2O, PbO

Group3A, alkaline earth and transition metals oxide, e.g. Al2O3 SiO2

MgO, Zeolites and activated carbon

Active phases: These are substances that have ability to speed–up chemical reaction e.g. sulphide, transition metals and their oxides, nitrides and carbides due to their low range of energy space electronic situation, that can simply donate or accept electron when breaking or making bonds (Clark, 2003)

Table 1.2: The active phases and reaction (Sarup, 1989)

Active

Phase

Elements/compound

Reaction catalyzed

Metals

Oxides

Sulphide

Carbides

Fe ,Co, Ni, Ru, Rh, Pd, Ir, Pt, Au

Oxide of V, Mn, Fe, Cu, Mo, W, Al, Si, Sn, Pb, Bi

Sulphide of Co, Mo, W, Ni

Carbides of Fe, Mo, W

Hydrogenation , steam reforming , hydro-carbon reforming, dehydrogenation, synthesis , oxidation

Complete and partial oxidation of hydrocarbon and CO, acid-catalysed reactions (e.g. cracking, Isomerisation, alkylation) methanol synthesis

Hydrotreating, hydrodeoxygenation, hydrogenation

Hydrogenation, FTS

Aims and Objectives

Research Aims

The aim of this project is to characterize the reducing properties of modern bio-fuels (glucose) in activating metal catalysts (Nickel Oxide) that is use in refining process.

Research Objectives

The main objectives of this research project are as follows;

To determine the possibilities of using a model compound of bio-fuel (glucose) for the reduction reforming of nickel oxide (NiO) catalyst

To determine the suitable condition of the experiment process i.e. pressure, temperature and steam to carbon ratio.

To determine the difference between using hydrogen and using glucose as reduction agent of NiO catalysts and by describing the reduced catalyst Ni base on surface morphology, crystalline structure and coke amount.

2.0 Literature Review

2.1 Hydrotreating Process.

In this process, impurities such as sulphur, oxygen, metals and nitrogen are removed in a high percentage (90%) from the fractional distillation. The removal of these pollutants is necessary to avoid destruction of equipment, catalyst performance and end products. Moreover hydrogenation is used for improving standard the of lube oil, saturation of olefins, and upgrading of colour, odour etc. under a preheating temperature 350oC a compressed hydrogen of 100atm is been blended with a compressed feed into Hydrotreating unit at the initial stage and these goes into different series of reactors with Big pores, small surface area and those with greater surface area and reduced pores. Heat exchanger may cool down the inlet of second and third reactor due to the fact that the reaction is exothermic. Less molecular mass hydrocarbons, hydrogen and hydrogen sulphide are been removed when the product passes over a separator of a high pressure (Bartholomew, 2006).

The most frequent problem faced in Hydrotreating process is the stumbling block of pores cause by coke, and metals plugging as well as poisoning, which leads to the de-activation of catalyst. The changes area of from a high performance of molybdenum or cobalt molybdenum sulfide to vanadium or nickel sulfide of less activity permanently poison the area (Bartholomew, 2006)

The deactivated catalyst from coke can be renewed in situ for couple of time if the coke is been burn off in a steam. Nevertheless when metal of large volume deactivated the catalyst, only the small fraction will be recovered for activity (Inoguchi, 1972).

2.1.2The types of reaction involve in Hydrotreating

Desulfurisation

Denitrification containing start up oil through the Often spiked

Hydrocarbon Saturation

Oxygen Removal

These are the primary reaction in Hydrotreating process (Surinder, 2003).

2.1.3 Hydrotreating Catalyst

The catalyst used in this process is Nickel oxide, Cobalt, and molybdenum with the support of highly clean alumina. These catalysts are basically classified in to classes 1. Active element and 2. Support catalyst. The catalyst support is design to withstand the operational condition that’s pressure and temperature with environment concern in hydrodesulphurisation reactor in the form of extrudes or ball alumina. While the metallic deposit in the form of oxide on the support are the active element. But the catalyst used in the Desulfurisation service (HDS) has small pore and volume than the catalyst used in Demetallisation service (HDM).

http://www.tricatgroup.com/guardian.jpg

Fig.2.1: Ni/Mo and Co/Mo in various trilobe and hollow cylinder size (Tricat, 2012)

Table 2.1: Properties of catalyst used in Hydrotreating unit. (Surinder, 2003)

Properties

Demetallisation

Desulfurisation

Surface area m2/g

115

200

Base

Al2O3

Al2O3

Bulk density

0.51

0.67

Pore volume m3/g

0.9

0.50

Composition

MoO3 wt%, on γ – alumina

CoO wt%, on γ – alumina

NiO3 wt%, on γ – alumina

Feed

HHK, naphtha, VGO,CGO, Residual

12

-

2.5

14

3.0

0.2

Catalysts with bigger pore are arranged on the top part of the reactor to take care metals and other impurities, and catalyst with smaller pores is arranging on the lower part of the reactor. Mostly these catalyst are produced as MoO3 1/8, CoO 1/4, and NiO3 1/20 in (Surinder, 2003).

2.2 Hydrocracking Process

These are usually done in two step fixed bed reactor under a condition of 100-170 atm and a temperature of 375-425oC. Hydrotreating is endothermic reaction so its recommended to design a large conversion cracking unit due to the heat emits by hydrogenation reaction. Thus, if cold hydrogen is been injected the stream products will be chilled within the fixed bed.

The reuse and temperature hydrogen are blended together and the product obtained from feed are fed in to the (next) reactor, the first reactor is operated under high pressure in which it separate hydrogen from the rest of gases , so the temperament and reused hydrogen they will be subjected to compression and recycled again in to a top performance reactor.(Garry, 2001).

2.2.1 Hydrocracking Catalyst

The catalyst used in these process are basically metal oxide of NiMo, W or Co which is reinforced with AL2O3 (which is treated with acid), zeolite or AL2O3-SiO2 (Ayhan, 2008).the catalyst are been regenerated through ex situ process.

The addition of hydrogen over powers the formation of coke in hydrogenation reaction. Moreover formation of coke usually deactivates the operational performance of catalyst, so in this situation catalyst will be in used for 2-6 year until they become exhausted. The table below shows the catalyst that is used in hydrocracking process and their composition in different stages.

Table 2.2: Hydrocracking catalyst, composition and operating parameters (Bartholomew, 2006)

Feeds heavy gas oil vacuum gas oil

Coker gas oil residual oil

Catalyst NiMo on γ- alumina HDN aromatic saturation and HDN

NiMo or NiW on zeolite (hydro- cracker)

NiMo or NiW on amorphous silica-alumina (hydro- cracker)

Pb on zeolite (hydro- cracker)

Typical process condition

Reactor temperature:315 -425oC, pressure 8375-17338 Kpa

2.2.2 Activation of catalyst

The catalyst have to be activated before they are used for instance Nickel are been presulfided after or before fed in to reactor, similarly palladium are activated at 350oC with hydrogen. And zeolite is activated by using classic ammonia level (Bartholomew, 2006)

http://www.freewtc.com/images/products/como_catalyst_5_15369.jpg

Fig 2.2: CoMo Catalysts (FreeWTC, 2012).

2.3 Basic Reaction of Hydrocracking Processes

Desulfurisation reaction

Denitrification

R-CH2CH2NH2 → RCHCH2CH3 + NH3

Amine Paraffin Ammonia

Olefin Hydrogenation

RCH2CH = CH2 + H2 = RCH2CH2CH3

Olefin Paraffin

Saturation Aromatic

(Surinder, 2003)

2.3 Catalytic cracking process

The main role of catalytic cracking process is reaction in which feed will have direct reaction with catalyst and then breakdown. Regeneration of catalyst is done when coke is been burn off and fractionation by separating the cracked product into various component (Zhou, 1999). The basic properties disturbing product dispersion are pressure contact period, catalyst bustle, temperature and the ratio of oil/catalyst (Speight, 2002). Usually catalyst are more functional at temperature of 510-550oC with pressure of 2-3 atm, mass ratio of catalyst is/oil (5-30) but 10 is usual, and period of 2-6sec.

During the regeneration of the catalyst a lot of coke are been taken out and these helps in enhancing the conversion rate and. In the of cracking catalyst become highly de-activated indirectly after the contact period of seconds and these is cause by coke which is 2 to 5% and these coke will be burn away at temperature of 650oC to 750oC with pressure of 3atms in which is channel to the regenerator and return to the catalytic cracking unit by using of compressed air (farranto, 2006).

2.3.1 Basic reaction in catalytic cracking

C12H26 → 2CH5H10 + C2H6

C12H25 → C2H4 + 2C3H6 + C4H10

C12H25 → 6C2H4 + H2 (Borhnia and Zhou, 1999)

Nickel Catalyst For Ammonia CrackingNickel Catalyst For Endogas Generatio... Nickel For Endogas Generation

Fig.2.3: Different types of Nickel catalyst used in catalytic cracking (sichuan, 20012)

2.4 Catalytic Reforming

Catalytic of is key process in the production of gasoline. The major component of petroleum naphtha is paraffin’s, naphthenes and aromatic hydrocarbon. The relative amount of these hydrocarbons depends on origin of crude oil. The aromatic content of the reforming feed is usually below 20% of the total hydro-carbons where the paraffin’s and naphthenes vary between 10 and 70% depending on the origin of the crude(Ayhan, 2008)

The different reactor system have involve since the process was first introduce in 1952 and then use first reactor dehydro- isomerization, dehydrogenation with catalyst volume of 8-10% and the life cycle of 4-5years.

Second reactor dehydroisomerisation, dehydrogenation, Dehydrocyclization and some hydrocracking with catalyst volume of 30-35% and life cycle of 5-15 years

Third reactor Dehydrocyclization, hydrocracking with catalyst volume 50% and life cycle of 8-20years (Vento, 1979)

Picture of catalyst pellets

Fig.2.4: catalytic cracking catalyst (miton, 2011).

2.4.1 Catalytic Reforming Reaction

The naphthenic hydrocarbons are dehydrogenating to from aromatic the extremely fast and yield obtained.

Dehydrogenation of naphthenic to aromatic with energy absorption.

Isomerization of normal paraffin to isoparaffin

Dehydrocyclization of paraffin’s

Hydrocracking reaction

2.5 The isomerization process

The feed to butane (C4) isomerization unit should contain maximum amounts of n-butane and only small amounts of isobutene, pentanes, and heavier material. The feed is dried, combined with dry makeup hydrogen, and charged to the reactor section at 230 to 340oF (110 to 170oC) and 200 to 300 psig (1480 to 2170Kpa.Pentane/hexane (C5C6) isomerization processes increase the octane of light gasoline. In a typical unit, dried, hydrotreated feed is mixed with a small amount of organic chloride and recycled hydrogen, and then heated to reaction temperature. Process objective determine whether one or two reactors are used. In two-reactor units. The feed flows first to saturation reactor which removes olefins and benzene (Smart, 1999).

Table2.3: composition and properties of Isomerisation process (Smart, 1999)

Purpose

Convert n-butane to isobutene

Conversion and properties(C5C6)

Conversion (with recycle) RON

Up to 97%

85 to 9

Feed (C4)

Feed (C5)

Dry n-butane

Light straight run, end point

Process condition (Pt on alumina , HCl promoter)

Reactor temperature

Reactor pressure

Pt on zeolite

121 – 149oC

1411 – 3135 Kpa

Process conditions (Pt on zeolite)

Reactor temperature

Reactor Pressure

221-309 oC

2859 – 3135 Kpa

Catalyst C4

Catalyst C5 C6

Pt on γ-alumina, HCl promoter

Pt on γ-alumina, HCl promoter

2.6 Steam Reforming

Refining process required a lot of hydrogen for processing petroleum and heavy oils. Moreover chemical industries and petrochemical need hydrogen for their activities and steaming reforming is viable way of producing syntheses gases and hydrogen. The properties of different naphtha is comparatively complex when compare to that of methane because it consist of aromatic, cyclane and straight chain of alkanes. When reforming naphtha with steam, the presence of catalyst is highly needed for the homogenous thermal cracking reaction and catalytic cracking reaction.

The temperature of catalyst inside the steam reformer bed reactor in most of the refining unit is around 500-800oC. Therefore high product of cracked hydrocarbon will be produce with some carbon deposition when further polymerised. However, a good catalyst should be used in naphtha steam–reforming process; that can withstand the carbon deposition. This is very essential because it’s the main difference between natural gas and steam reforming and catalytic naphtha steam-reforming. The basic principal process between liquid and gas hydrocarbon steam reforming is similar.(Hao, 1999)

Moreover any hydrocarbon that contain 20% aromatic i.e. from natural gases to heavier naphtha with FBP of 210oC are suitable as a feed into steaming forming and hydrogen can be produce by using methanol as a feed. With a tube-type reactor when passes over a double charged catalyst in the shell side, and as result of that there will be CO shift is exothermic and these saves energy. In this reaction, shift and methanol decomposition occur in a single and same reactor. Below is the mechanism of these reactions.

CO + H20 → CO2 + H2 + Q -------------------------------1

CH3OH → CO+ 2H2 –Q------------------------------------2

Therefore the reformed gas will be passing in to the washing tower and then goes to the PSA, in which pure hydrogen of 99.99% purity will be stored.

Similar most of the off gases from refining process can be used as feed stock for hydrogen production. They contain paraffin’s, olefins and hydrogen sulphide. There’s need for the separation of hydro-saturation of olefins (sichuan, 20012)

Table2.4: Operational condition of ATR/Tubular reforming (Rostrup-Nelson, 2002)

Condition

H2forNH3

H2

Aldehydesa

Methanolb

Fisher tropschc

Feedstock

Temperature exit reforming

Pressure exit reforming

Space vel. (Vol.CH4/volcat-h

H2O/C (Mol/atm)

CO2 (Mol/atm)

H2/CO (product)

Naphtha

1170

34

1170

3.5

0.0

4.5

Naphtha

700

40

700

6.5

0.0

4.4

NG

950

16.5

-

0.6

1.7

2.9

NG

950

27

1425

2.5a

0.3

2.1

NG

1050

15

-

0.6

0.1

2.0

a for Aldehydes: sulfur-passivated nickel catalyst CO2 reforming(Rostrup-nelson, 1984)

b for methanol plant in Iran (Holms-Larsen, 2001)

c for auto-thermal reforming, Cobalt catalyst in fisher tropsch (Dybkjaer, 2001)

2.6.1 Steam Reforming Catalyst

The main steam reforming of hydrocarbon is quite simple but it’s very complex when choosing suitable and good catalysts not only due to the different composition of the feed stock, but because of some vital factors like furnace design and operational condition. When considering heavy hydrocarbon as a feed, there’s need of very high resistance catalyst that can withstand carbon deposition. But the carbon deposition can be decrease if the ratio of steam to carbon is increased and this is not economical wise.

. It can specifically reform methane to naphtha with less than 210oC FBP and this catalyst can be used inside-fired and top-fired furnace with good resistivity for carbon deposition, low temperature reductively, high activity, stability and strength.

Below is the picture of Z207Y catalyst. The main active is nickel (Ni) with calcium aluminate as a suporter and this catalyst can be used in I- methanol unit, synthetic ammonia unit and hydrogen unit with feedstock as natural gas.(X.song, 2006)

II- methanol unit and synthetic ammonia unit with feedstock as coke oven. III- hydrogen unit and methanol unit with feedstock as coke-oven. IV-hydrogen unit with fedstock as light oil.

http://www.tkgf.chemchina.com/sctyen/rootimages/2012/05/29/1338190491685542-1338190491712951.jpgHydrocarbon steam catalysts for secondary reformer

Fig.5: steam reforming catalyst NiO with aluminum oxide as supporter(sichuan, 20012)

Table 2.5: The chemical and physical properties of the catalyst (Z207Y) (sichuan, 20012)

Size

Appearance

Bulk density(Kg)

NiO%

SiO2%

Inner diameter 19mm

Outside diameter 18m

5 hole and 4 fluted dentate drum

1.0±0.05

≥ 14.5

≤ 0.1

Deactivation of steam refining catalyst are caused by amalgamation of coke and carbon deposition sintering and poisoning and these can cause a de-activation of catalyst cataclysmically because of fouling and poisoning that is cause by carboneous materials straining of catalysts hole and damaging the pellets (Figueiredo, 1982, Albright, 1982)

Regeneration: steam gasification is an ease way of regenerating catalyst from a cooked or carbon fueled catalyst at temperature of 400-500oC. To help burn off the coke deposition, a little amount of oxygen is added. Partially the steam gasification removes some amount of sulphur absorbed.

NiS + H2O → NiO + H2S --------------------------------------------- 1

H2S + 2H2O → SO2 3H2 ------------------------------------------------2

while the sulfur-passivated nickel catalyst has less cost but it has to be subjected under a very high temperature and the required oxygen plant is very expensive (Rostrup-Nelson, 2002). The table below describes the process step reactions and catalyst used in steam reforming of hydrocarbon.

Table 2.6: process step, reaction and catalyst used in steam reforming (Bartholomew, 2006)

Process step

Reaction

Catalyst

Methanation

Water-gas-shift (low temperature)

Water-gas-shift (high temperature)

Secondary steam reforming

Primary steam reforming and prereforming

Desulfurization

CO + 3H2 →CH4 + H2O

CO + H2O →H2 + CO2

CO + H2O →H2 + CO2

2CH4 + 3H2O→ 7H2+ CO +

HC +H2O→H2 + CO + CO2 +CH4

R-S + H2 →H2S + R-H

Ni/Al2O3

Cu/ZnO/Al2O3

Fe3O4/Cr2O3

Ni/CaAl2O4;Ni/αAl2O3

Ni/MgO (naphtha)

CoMo/Al2O3

There are six steps involves in the production of hydrogen by steam reforming of hydrocarbons and these are:

1 – Methanation, 2- low temperature water-gas-shift reaction

3- High temperature water-gas shift reaction, 3- secondary steam reforming, 4- desulfurization

Moreover these six processes are the back bone hydrogen production (99%).

http://3.bp.blogspot.com/_dpZfkyjb7QI/TACwWokGUOI/AAAAAAAAAkk/t-U_xKpB9Qk/s400/New+Picture+%2822%29.png

Fig.2.6: process flow diagram of steam-methane reforming for hydrogen production (rayelshoutenergy, 2010).

2.6. 2 Water-Gas-shift (High temperature)

In order to increase hydrogen concentration and lower carbon monoxide conc., the obtainable gas in the secondary reformer with composition of 10-13% CO2 will be process to upsurge the concentration of hydrogen to nearly 2-3% inside adiabatic fixed bed reactor functioning at GHVS of 400- 1200h-1 and pressure of 20-30atms, with temperature of 350-500oC . H2 to is been converted sharply from H2O and CO2 under less temperature(Lioyd L., 1989).

. From there it will go through a catalyst at higher-temperature and these catalysts are made up of Cr2O3 and Fe3O4, then the temperature will be rise by 50oC adiabatically in the reactor. The operation should be around 200oC thermodynamically but the temperature is not sufficient to activate Fe3O4 (catalyst). Subsequently Cr2O3 is economical good in preventing sintering and the gives guard for low temperature shift catalysts and also adsorb compound that passes the purification step such containing substance and residual sulfur. Finally the catalyst should be wash to avoid any presence of alkali or sulfur substances (Kocholoefl, 1997)

The table 2.7 below described constant application with equilibrium expression of o water-gas-shift

Table 2.7: Reaction of ammonia and methanol synthesis at equilibrium constant (Lioyd L., 1989)

KP

Reactions

T(oC)

P (bar)

KP1

KP2

KP3(k)

KP4(k2/bar)

PH2O/PH2S

PCOP3H2/ PHCH

PH2PCO2/PH2OPCO

-

-

PCH4PH2O/PCOP3H2O

PCH4P2H2O/PCO2PH2

PNH3/PN2PH2

PCH3CH/PH2PCO

Desulfurisation over zinc oxide

Reforming

WG Shift

HT WG shift

LT WG shift

CO Methanation

CO2 Methanation

Ammonia synthesis

300-400

750-1050

750-1050

≈440

≈250

≈350

≈ 350

350-550

240-300

0-50

0-50

0-50

0-50

0-50

0-50

0-50

0.50

100

-.18339

30.345

-3.670

-4.2939

-4.3701

-29.254

-24.845

-27.366

11900

9149

278

3971

4546

4604

26,627

21627

12500

-0.015

-

1.42

-

2100

So to maximize the rate of the reaction since high temperature water gas at the temperature of > 350oC and 3atm face high pores diffusional resistance, the catalysts of 6 x 6mm ring or tablets with H x D x OD = 8 x 4 X10mm and 60-80m2 internal diameter are used to capitalize the rate of reaction. The catalyst are good to pressure drop, with an active side of magnetic Fe3O4, and this is been generated by H2 + CO from in the gas steam process if the catalyst is been prepared in 10% H2O at 400oC so the Cr will react directly with magnetite to produce chromium spinel (Iron) Fe11F111Cr4O4 (thermal stability unusual)

Fe2O3 + H2 + CO → Fe3O4 + CO2

Poisoning cause by chlorine and sulphur in high temperature WG shift they are not significant because of its resistance.

Deactivation is usually caused by the cooking due to poisoning by metals and alkynes. And these can be regenerated at temperature of 450oC with steam of 1-2% O2, moreover it has life span of 1-3 years (Bartholomew, 2006)

2.6.3 Water-Gas-Shift (Low-temperature)

To make the process suitable at equilibrium, the concentration of carbon monoxide from preserved gas in high temperature was gas shift reactions almost 2-3%, therefore is composition should be reduced to 0.2% and the temperature of the gas feed should be reduced to 200oC before passing it to low temperature, adiabatic fixed bed reactor with (CuO/ZnO/Al2O3) of high selectivity and less activity of Methanation. The table below described the operational condition of low temperature was gas shift reaction.(Zhao, 2004)

Table 2.8: Operational condition water-gas-shift (low temperature) (Tabakova, 2003)

Operating parameter

Unit

Temperature

Pressure

GHVS

Ratio of steam/dry gas

Dry gas feed composition of carbon monoxide

Carbon dioxide

H2

Pd/Caria; Au/ceria and Pt/ceria catalyst

15oC

10-30 atm

3600h-1

0.4

2-3%

20%

77-78%

(for fuel cell)

Catalyst Activation: Cu/ZnO/Al2O3 catalyst is been activated commercially by coprecipating by base (PH7). This provided highest surface area of 60-90m2/g and then made them into tablets or sphere of about 3-6mm (diameter). The prepared catalyst is made up of 15-35% Al2O, 30% CuO and 35-55% ZnO (Goodman, 1989). Poisoning occurs due sulphur and chlorine compounds are the deactivation happens by less sintering. Moreover if the feed purity and temperature of the process are handle with care the catalyst will last four 2-3 years (Kocholoefl, 1997)

2.6.4 Methanation

The left over in most of the ammonia plants are 0.1-0.2% CO2 and 0.2-0.5% and these are removed when methane is been reduced to hydrogen, and these process is knows as methanation which occur in a fixed in the presence of Ni/Al2O3 catalyst. However this catalyst is be prepared by impregnation of large portion of γ-alumina by soluble salt or otherwise Ni salt soluble. MgO can be used as promoter and thus preventing sintering of nickel. The catalysts are made into tablets, pellets or sphere (i.e. 3-5mm diameter) after been dried and calcinated and all these happens in the reactor (Chang, 2006)

Methanation process usually occur inside fixed bed reactor at operational condition of 300oC inlet temperature, 365oC outlet temperature, pressure of 30 atm and GSHSV (STP) of 6000 to 10,000h-1. But in order to prevent carbon deposition and sintering, the bed temperature is maintained less than 400oC. Good concern must be shown to tackle poisonous formation Ni (CO) 6 which happens between 200-250oC with pressure of 0.2atm (CO2 and CO partial pressure). (Pearce, 1989).

2.7 Fischer Tropsch

The manufacturing of hydrocarbon in liquid form from syngas i.e. hydrogen and carbon mono oxide is extremely favourable for environment pollution which basically deals with production of oil fuels and chemical from coal, natural gas and biomass. This process is expected a vital role in coming years due to high demand of liquid fuel form declining petroleum wells, coal and natural gas reserves. It’s the main method designated worldwide for processing gas to liquid products.

FTS has a very wide application for different gas feedstock, generally there are different four steps used in processing GTL, BTL or CTL and these are:

Syngas production ,2- Purification of syngas

Fischer and tropsch synthesis, Product separation and upgrading

Firstly oxygen and steam are used to gasify coal to generate synthesis gas, compounds that will deactivate the catalyst such as sulphur and nitrogen are been removed. Fluidised bed, slurry reactor or fixed beds are used in conversion of syngas in the presence of Iron catalyst. If the syngas is on purified Co catalyst can be used instead (Tricat, 2012). Then the separation of hydrocarbon into different classes will follow.

In the second phase methane is been directly convert into syngas with H2/Co ratio 2, and then passes in to slurry bubble reactor that have Fe or Co as catalyst to higher waxes and liquids. Furthermore the waxes are process to (Hydro isomerization and hydrocracking) produces qualitative distillate.

2.7.1 Fisher-Tropsch Catalyst

The catalyst used in Fischer tropsch process is mainly Co and Fe which is relatively cheap with high activity and selectivity with supporters of SiO2 and TiO2. The composition of catalyst is 0.01-0.3% Pt., 35Wt% Co, Ru or Re, 1-3% La2O3 or BaO with alleviated Al2O3 (stabilized α-Al2O3 ) with 3% La2O3, Vpore = 0.5cm3/g. Pretreatment and preparation: the calcination of Al2O3 can be achieve at 650- 750oC, with Co nitrate at 3- step impregnation, then subjected to dried for about 12-24h at 120oC, calcine for 12hr at about 250-300oC, with drying heat rate of 360oC. Emphasis should be given using TiO or SiO instead of Al2O3, ± 10% can be verified during metal loading, among dozens of oxides one of them can stabilized the support and La2O3 or BaO can be used as additives.

2.7.2 Catalyst deactivation and generation

The main causes of catalyst deactivation are

Fouling due carbon and hard waxes

Poisoning of catalyst due to nitrogen or/and sulphur compounds

Generation of oxide which is active phase, metallic support and in active carbides.

Catalyst abrasion

Sintering due hydrothermal (LeViness, 1998).

Basically deactivation in Fischer tropsch synthesis is been classified into two classes

Short deactivation that’s half life for 20-40 days cause by deposition of hard waxes, reversible oxidation , reversible poisoning and accumulation of organic acids

Long term deactivation: with a half-life of 101-200 days because of the generation of carbide and metal support compounds (irreversible) (Clark, 2003)

Table 2.9: Kinetics expression, conditions and activation energies of FTS on Co and Fe catalyst (VanderLaan., 1999b) .

Catalyst

Reactor

T oC

P (bar)

H2/CO

Kinetic expression

EApp (KJ/Mol)

Co catalyst

Co/kieselguhr

Co/MgO/SiO2

Supported Co

Co/TiO2

Co/TiO2

Co/MnO

Co/SiO2

Co/Zr/SiO2

Fe catalysts

Fe used Fe/K

Ppt Fe/K/Cu

Ppt. Fe

Ppt. Fe/K/Cu

Fe and Fe/K

Ppt. Fe/K/Cu

SGRR

Slurry

verified

FBR-diff

FBR

FBR

SGRR

SGRR

SGRR,FBR

SGRR,slurry

Slurry

Slurry

SGRR

SGRR

190

220-240

Verified

200

200-210

210-250

200

190-230

250-315

220-280

220-260

235-265

200-240

250

2-15

5-15

Verified

20

1-30

6-26

20

3-15

20

5-26

15-30

10

8-50

5-80

1.5-3.5

Varied

1.0-3.0

1-10

1.4-3.4

1.4-3.4

1-3

2.0

0.5-3.5

0.5-2.0

0.6-1.0

1.0-2.0

0.25-4.0

C4

C2

C1

C1,C2

C3

C4

C4

C3

F2

F2

F2

F2

F1

F2,F3

93-95

102

83

80

129

85

56,89

80-105

86

101,92

2.8 Previous work at Leeds on reduction of NiO by bio feedstock

The following section summarise previous work carried out in 2013 by PhD student Feng Cheng on the reducibility of NiO / Al2O3 catalyst using model bio compounds. This MSc project will contribute to this subject via extension and continuation of these results.

2.8.1 Sample Preparation

The catalyst used in this research is 18wt NiO/α- Al2O3 catalyst manufactured by Johnson matthey. The catalyst were received in pellet form, it will be crushed and sieved to size particle ranging from 0.85-2mm before use. For instance if nickel was obtained in reduced form, it will be oxidized by using an air flow at 700oC in a quartz bench-scale reactor. Then in the night time the sample will be impregnated by using aqueous solution of glucose, furthermore the sample will be subjected to an oven of 110oC to dry (the sample is known as NiO). The overall weight ratio of glucose to catalyst is will below 1:10

Similarly α- Al2O3 pellets will be crushed and sieved in to size particle ranging from 0.85-2mm before use. The crushed α- Al2O3 was treated using an aqueous solution of glucose same as in above and then dried. The sample is know as Al2O3

TGA-FITR experiment was carried out through a heading rate of 5oC/min ranging from normal room temperature to 900oC under to pure air flow or N2. About 200mg of sample was used in every test. Background data collected in consistent gas flow of approximately 25 min is used to correct the FTIR test background. However, integral absorbance of a specified spectral region is shown on chemigram profile as a function. The main reason of using chemigram profile was to identify region that contains peaks of one component. The table below shows the parameters of this experiment.

Table 2.10: parameter for collecting chemigram profile

Component

Base line (cm-1)

Region (cm-1)

CO

CO2

Formic acid

Water

2000-2250

2250-2400

900-1200

1300-2000

2000-2250

2250-2400

900-1200

1300-2000

2.8.2 Investigation of reactivity of NiO using Thermogravimetric analysis

The behavior of mass loss of NiO is almost the same to that of Al2O3 under N2 at the beginning of 430oC as shown in fig.2.7 and fig.2.8. However after 430oC there’s slight mass drop in Al2O3, whereas NiO sample experience two important mass losses. This is shown the variation occurred at the temperature below 430oC include glucose. Subsequently NiO play a significant role in reaction above the temperature of 430oC

Fig.2.7: The TGA curves

Fig.2.8: The DTG curves

Generally the composites that exit in bio-oil (bio-oil compounds) belongs to one of these chemical groups; alcohols, hydroxyaldehydes, ketones, carboxylic acid, phenolic, furan and phenolic(Garcia-Parez, 2007). But the phenolic compounds mostly exit in oligomers with molecular weight of 900-2500. While sugar, ketones, alcohol, hydroxyaldehydes and carboxylic acid are derivatives of carbohydrates and they are very soluble in water. Furans are from lignin and are hypophobic.

2.8.3 Result of XRD

Figure 4.4 below shows the presence of about 1.8% NiO (pattern No. 04-013-0889), 85.2% Al2O3 (pattern No.04-007-1400) and 13.0% Ni (pattern 04-010-6148)

Thus the goodness of fitting refinements and the weighted profile are 5.27 and 3.88 respectively. This signifies the refinement result is reliable. The absolute conversion of NiO is 90.2% for using catalysts that is impregnated with glucose (glucose-impregnated catalyst).

Fig. 2.9: Rietveld refinement of XRD profile of glucose-impregnated catalyst under N2 after 900°C

2.8.4 Result obtain from FTIR analysis

From fig. 2.16 below, chemigram of Al2O3 and NiO sample are shown in which the following remark are made.

Both sample (Ni and Al2O3) released no CO below the temperature of 800oC; there are lesser quantities of CO exhaust.

But at the temperature above 430oC there are two strong signal peak I the separation of NiO, which correspond to the two import mass loss in fig. 2.in the case of reducing NiO by charcoal other intermediates of glucose pyrolysis, there is a huge released of CO2 quantity.

Fig.2.10: Chemigrams of NiO and Al2O3 sample

Conclusion: The preliminary experiment show glucose can reduce NiO catalyst. The reducing properties of glucose as one bio-oil model compound on metallic catalyst (NiO) will be investigated systematically in a fixed bed reactor in this project.

2.9 Biomass

Biomass is a biological substance obtain from plant, it’s a carbon built with some mixture of molecule that contain hydrogen, oxygen, nitrogen and some atoms in smaller quantities such as alkali earth, alkali and heavy metals. Most of the metals are available in prophyrins and chlorophyll that contain mostly magnesium. There different types of biomass use for production of energy are been basically categories into five different classes; Energy crops - Virgin wood - food waste - Agricultural residue – and industrial waste.

The potentiality of biomass is very clear because it will replace the usage of fossil fuel in the nearest future due to its sustainability and carbon-neutral nature. Even though it’s tender as fuel is still at an improvement level, it has been projected by the year 2050 the use of bio-fuel will arise up to 50% of primary energy consumption. Moreover biomass is been converted into energy via thermochemical, direct combustion, agrochemical process and biochemical process. For instance, thermochemical process can be divided into pyrolysis, gasification, direct liquefaction and supercritical fluid extraction (Demir bas, 2001).

2.9.1 First Pyrolysis of Biomass

This refers to the thermal decomposition of biomass in absence of air producing charcoal, liquid oil and gases. In which feedstock is quickly subjected to heat, it then vaporized and condensate into viscous dark brown oil (Bridgwater, 2000). (Named a bio-crude, bio-oil or pyrolysis oil) and a little amount of char and gas of by-product of fast has some crucial feature and these are;

The temperature is to be regulated carefully (500oC)

The heat transfer rate and high heating need a pulverized biomass feed

Short residence time (the pyrolysis vapor cooled down rapidly) (Bridgwater, 1995)

2.9.2 Physical Properties of Bio-oil

Bio-oil is a free-flowing liquid, dark brown in colour with smoky odor. It consists of various compounds with distinct molecular weight resulting through depolymerisation, hydrogenation and fragmentation reaction (Czeernik, 2004)

The composition of bio-fuel is almost similar to that of biomass unlike that of petroleum. The table below shows the basic data of heavy fuels oil and that of bio-oil(Bridgwater, 2000)

Table 2.11: Comparison between physical properties of heavy and bio-oil (Bridgewater, 2000)

Physical properties

Heavy fuel oil

Bio-oil

Specific gravity

Moisture content

PH

Elemental composition wt%

N

O

H

C

Ash

HHV,MJ/Kg

Viscosity at 500oC

Solid, wt%

Distillation residue, wt%

0.94

0.1

-

0.3

1.0

11

85

0.1

40

180

1

1

1.2

15-30

2.5

0-0.02

35-40

5.5-70

54-58

0-0.02

16-19

40-100

0.2-1

Up to 50

2.9.3 Composition of Bio-oil

They are many component of bio-oil, but it composition is influence by type of biomass used s feed and the operational condition in pyrolysis process. Variety of composition of bio-oil is describe in table below(Wang, 1997)

Table 2.12: Composition of pyrolysis oils from different feedstock by two processes (Wang, 1997)

Fluidized bed

(University of Waterloo)

Vortex

(NREL)

Product

Poplar(504 °C)

Maple(508 °C)

Spruce(500 °C)

Oak(~500 °C)

acetic acid

5.4

5.8

3.9

5.0

formic acid

3.1

6.4

7.2

3.3

Hydroxyacetaldehyde

10.0

7.6

7.7

4.3

Glyoxalin

2.2

1.8

2.5

3.0

Methylglyoxal

Not found

0.65

Not found

Not found

Formaldehyde

Not found

1.2

Not found

2.2

Acetol

1.4

1.2

1.2

1.8

ethylene glycol

1.1

0.6

0.9

Not found

Levoglucosan

3.0

2.8

4.0

3.8

1,6-anhydroglucofuranose

2.4

Not found

Not found

Not found

Fructose

1.3

1.5

2.3

Not found

Xylose

Not found

Not found

Not found

0.9

Glucose

0.4

0.6

1.0

Not found

Cellobiosan

1.3

1.6

2.5

Not found

Oligosaccharides

0.7

Not found

Not found

Not found

pyrolytic lignin

16.2

20.9

20.6

24.9

Unidentified

11.9

17.1

12.9

5.8

Oil

65.8

67.9

66.5

55.3

Water

12.2

9.8

11.6

10.4

Char

7.7

13.7

12.2

12.4

Gas

10.8

9.8

7.8

12.2

Generally the composites that exit in bio-oil (bio-oil compounds) belongs to one of these chemical groups; alcohols, hydroxyaldehydes, ketones, carboxylic acid, phenolic, furan and phenolic(Garcia-Parez, 2007). But the phenolic compounds mostly exit in oligomers with molecular weight of 900-2500. While sugar, ketones, alcohol, hydroxyaldehydes and carboxylic acid are derivatives of carbohydrates and they are very soluble in water. Furans are from lignin and are hypophobic.

Bio-oil separated easily into 2 immiscible phases if water is been added to it. An oligomer-rich hydrophobic that contain lignin by-product and a monomer-rich aqueous phases that consist of carbohydrate by-product compounds(Garcia-Parez, 2010).

3.0 Methodology and Experiment

3.1Sample Preparation

The catalyst used in this research is 18wt NiO/α- Al2O3 catalyst manufactured by Johnson Matthey. The catalyst were received in pellet form, it will be crushed and sieved to size particle ranging from 0.85-2mm before use. Pure glucose will be dissolve in a distillate water to make glucose solution

3.2 Reactor set-up for carrying out Reduction Reaction

Firstly the reduction experiments are to be carried out inside a down flow bed reactor as describe in fig. 3.1 below. An aqueous solution of glucose with specific steam/carbon ratio will be introduce at a given flow rate by using a springe of pump into a reactor and flow rate of the gases i.e. hydrogen or nitrogen is regulated by using MKS mass flow rate controller, where the gases is cooled down through double condenser at temperature of -7oC

A silica gel is to be used in order to remove moisture from condensable constituents that is trapped inside condensate collector. Further more in every 5second, a composition of dry outlet gas will be reduced by using Advanced Optima Analyzer (ABB), which is capable of identifying CO, H2, CO2 and CH4. The concentration of CH4, CO, and CO2 are measured by using infrared absorption (Uras-14). While the hydrogen concentration will by thermal conductivity detector (aldos 15).

Fig.3.1: The reactor set –up

3.3 The TGA-FTIR: This is use to examine the combustion performance of coke on the surface of reacted catalyst base on temperature –programmed.

TGA-FTIR is a method which comprises TGA and FTIR through an interface. The mass change of the sample under particular given time is measured with TGA device by air at heating rate of 10OC/min. The FTIR device used to observe the evolution of gases while the TGA is running. Consequently FTIR device release a three different dimensional spectrum i.e. IR absorbance, time and wave number. Details of changes of gas emission with temperature are shown by chemigram profile. Therefore it is very essential to use OMNIG software to obtain chemigram profile that describes the relative amount of H2O, CO and CO2 from FTIR.

3.4 X-Ray Diffraction (XRD): This is used to measure the degree of reduction and crystalline proportion of product.

Basically particles catalyst are been crushed into a fine powder in order carried out XRD test. In which X’pert High score Plus Software by PAN analytical are used for rietveld refinement phase analysis

Rietveld Refinement is used to analyze the composition of sample which is full –pattern fit method. Beaucause the calculated profile and measured profile are compared by different parameters such as thermal factor, lattice parameter, stain effect and size effect. Consequently, the result obtained will show level of phases exist in every sample (in wt %). Moreover in this project rietveld refinement will be used to find the portion of conversion of NiO to Ni.

Size measurement of crystalline by rietveld refinements

Automatically calculation is performed where as rietveld refinement is carried out.

3.5 FTIR of solid sample to check the adsorption of glucose on the reacted catalyst.

FTIR spectra of catalyst at various reaction states will be noted, to find out whether there’s any adsorption of bio-compound on the surface of catalyst during the reaction. Based on infrared absorption frequency, FTIR method will identifies compounds in to different groups. Furthermore absorption happens if energy of infrared light is transmitted into molecules initiates some rotational stations or vibration

3.6 Detection of Carbon Content in reduced catalyst by using CHN Analysis

CHN analysis assist in determine the content of carbon in catalyst in which the sample reacted is put in to capsule and then subjected to heat on furnace in the presence of oxygen. The carrier gas in this process is Helium which conveys the product of combustion such as NO2, CO2 and H2O into chromatography column where the gases are separated. Then the thermal conductivity detector will be used to detect the relative amount of each gas. The analysis will show the weight fraction of nitrogen, carbon and hydrogen in the sample.

3.7 SEM-EDX: This gives detail on surface morphology of reduced catalyst

SEM is used to analyses the morphology changes of catalyst even before changes or after reduction process and the formation of carbon on surface of catalyst. The SEM is an electron microscopic device that describes a sample through scanning with an electron beam of high energy so that the electron will interrelate with atom consisting of the sample surface and gives out secondary electrons. The sample topography can be determined by detecting the excited secondary electron.

EDX device is used to carried out semi-quantity analysis on the surface of the sample, which detects the X-ray releases from sample when it is been bombard by an electron beam. Moreover it’s more likely to characterize elemental composition of different sample region by EDX due to the content of X-ray energy poses in various elements

PROJECT PLAN

The work plan for summer term is given in the grand chart below. The experiment session involving TGA-FTIR, X-Ray Diffraction, and Detection of carbon catalyst by using CHN analysis and SEM-EDX will be done during the summer. The result obtained at the last of this work will be compared to the research work that is done previously for result validation. Last the completion and submission of final report.

 

Semester Two

Semester Three

Feb.

Mar.

April.

May.

June.

July.

Aug.

Sept.

Work

week 1

week 3

week 4

week 6

week 7

week 9

week 10

week 13

week 14

week 17

week 18

week 21

week 22

week 25

week 26

week 29

Literature research, reading & taking notes

 

 

 

 

 

 

 

 

 

 

Examinations

 

Drafting of literature review

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Developing of Methodology

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Completion & submission of interim report

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Familiarisation with apparatus, equipment, experimental procedures, SEM/EDX training

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Performing Laboratory experiments

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Determine impact of temperature on reduction process

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Determine the impact of steam/carbon ratio on the reduction process

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Write up on processed data, results, discussion of results, conclusion & recommendation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Writing Abstract & introduction

 

 

 

 

 

 

 

 

 

 

 

 

Final Editing of thesis (Including references and appendices compilations)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Preparation of Project slides

 

 

 

 

 

 

 

 

 

 

 

 

 

Project Defence

 

 

 

 

 

 

 

 

 

 

 

 

 

Submission of project

 

 

 

 

 

 

 

 

 

 

 

 

 

Completed Task

Yet to be completed.

5.0 CONCLUSION

Now day’s catalyst technology is grouped in to different main areas that have essential activities in global economy and these are chemical manufacturing, petroleum refining and environmental clean-up. The refinery units that required metallic catalyst in petroleum refining can be broadly classified into in Hydrotreating unit, Hydrocracking unit, Catalytic reforming unit, Catalytic cracking unit, Steam reforming unit, Isomerization unit and Fisher tropsch.

Nickel oxide supported alumina catalyst (NiO/α- Al2O3) is one of the most common used catalysts in all the refining process that required metallic catalyst; which under goes in to reduction phase from nickel oxide (NiO) to active nickel metal (Ni) catalyst before it can performed the reaction that is been design for and this reduction is been done by using high costly hydrogen, Ammonia or high diluted methane steam feed and all these processes are capital intensive and they carried a lot of carbon print.

This research project will focus on the reduction ability of model compound of bio-fuel (Glucose) in the reduction of metallic oxide (NiO) by using a down flow bed reactor at certain operational condition. Moreover when the experiment is being conducted, more information will be given after the reduction reaction by using TGA-FTIR which tells about combustion performance of coke on the surface of the reacted catalyst, X-Ray Diffraction (XRD) which tells about the degree of reduction and crystalline proportion of product, CHN analysis which tells about the carbon content in the reduced catalyst and SEM-DEX which tells about surface morphology of the reduced catalyst.

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