A REPORT ON

PRODUCTION OF HYDROGEN FROM FUEL OIL

PREPARED BY GROUP 6,

SUBMITTED TO THE CHE 518

(LOSS PREVENTION AND SAFETY IN THE INDUSTRY)

COURSE COORDINATOR,
DR. EHINMITOLA,

DEPARTMENT OF CHEMICAL ENGINEERING,

OBAFEMI AWOLOWO UNIVERSITY, ILE-IFE, OSUN STATE.

IN PARTIAL FULFILMENT
OF THE REQUIREMENTS FOR THE AWARD
OF B.SC CHEMICAL ENGINEERING

MAY, 2024.

i
 Department of Chemical Engineering,
Faculty of Technology,
Obafemi Awolowo University,
Ile-Ife, Osun State.
May 20th, 2024.
The Course Coordinator (CHE 518),
Department of Chemical Engineering,
Faculty of Technology,
Obafemi Awolowo University,
Ile-Ife, Osun State.

Dear Sir,

LETTER OF TRANSMITTAL

We, the members of Group 6 (CHE 518), write to inform you of the completion of the term

paper on Production of hydrogen from fuel oil and to hereby submit this compiled report. We

ascertain that this report was compiled by us. Thank you, sir for your time and anticipated receipt

of this submission.

Yours faithfully,
Group 6.

ii
 ABSTRACT

The production of hydrogen from fuel oil presents a promising pathway toward meeting the

rising demand for clean energy solutions. This process involves converting hydrocarbon-rich fuel

oil into hydrogen through catalytic reforming and partial oxidation methods. Hydrogen, a

versatile energy carrier, holds immense potential for various industrial applications and serves as

a clean fuel alternative, contributing to efforts aimed at reducing greenhouse gas emissions.

Catalytic reforming and partial oxidation are the primary methods employed in the production of

hydrogen from fuel oil. Catalytic reforming entails breaking down complex hydrocarbons into

simpler molecules like hydrogen and carbon monoxide using high temperatures and catalysts.

Conversely, partial oxidation involves the controlled combustion of fuel oil with limited oxygen,

yielding a syngas mixture rich in hydrogen and carbon monoxide. Advances in catalyst

technology and reactor design have enhanced the efficiency and scalability of these processes,

facilitating higher hydrogen yields and lower operational costs.

Despite the progress made, challenges persist in optimizing the economic and environmental

aspects of hydrogen production from fuel oil. Energy-intensive processes require efficient energy

management strategies, while effective carbon capture and storage solutions are essential for

mitigating greenhouse gas emissions. Continued research and development efforts focus on

enhancing process efficiency, catalyst performance, and integrating renewable energy sources to

drive the transition toward a sustainable hydrogen economy.

iii
 TABLE OF CONTENTS

LETTER OF TRANSMITTAL ............................................................................................................................. ii

TABLE OF CONTENTS.................................................................................................................................... iv
LIST OF TABLES ............................................................................................................................................. vi
LIST OF FIGURES .......................................................................................................................................... vii
LIST OF GROUP MEMBERS ......................................................................................................................... viii
CHAPTER ONE ............................................................................................................................................... 1
INTRODUCTION ............................................................................................................................................. 1
1.1 Overview ....................................................................................................................................... 1
1.2 Aims and Objectives ............................................................................................................................ 2
1.2.1. Aims............................................................................................................................................. 2
1.2.2 Objectives..................................................................................................................................... 3
CHAPTER TWO .............................................................................................................................................. 4
LITERATURE REVIEW ..................................................................................................................................... 4
2.1 Overview ............................................................................................................................................. 4
2.1 Classification based on production method ................................................................................. 4
2.2 Fossil fuel processing method for the production of hydrogen ................................................... 6
2.2.1 Hydrocarbon pyrolysis .......................................................................................................... 6
2.2.2. Steam reforming of natural gas (methane) .......................................................................... 7
2.2.3 PARTIAL OXIDATION.............................................................................................................. 8
2.2.4 AUTOTHERMAL REFORMING .............................................................................................. 10
2.3 ENVIRONMENTAL IMPACTS ........................................................................................................ 10
2.4. Progress of Fossil-Fueled Hydrogen Production .............................................................................. 12
2.5 Comparison with Alternative Methods: Beyond Fossil Fuels ........................................................... 13
CHAPTER THREE .......................................................................................................................................... 16
PRODUCTION PROCESS ............................................................................................................................... 16
3.1. Materials Used ................................................................................................................................. 16
3.2. Utilities used include: ....................................................................................................................... 16
3.4. PROCEDURE ..................................................................................................................................... 17
3.5. Predesign and Main Design Hazards of Hydrogen Production Using Fuel Oils and Their Solutions
................................................................................................................................................................ 20
3.5.1. Pre-design Hazards: .................................................................................................................. 20

iv
 3.5.2. Main Design Hazards: ............................................................................................................... 21
CHAPTER FOUR ........................................................................................................................................... 26
CONCLUSION AND RECOMMENDATION .................................................................................................... 26
4.1 Conclusion ......................................................................................................................................... 26
4.2 Recommendations ............................................................................................................................ 26
REFERENCES ................................................................................................................................................ 28

v
 LIST OF TABLES

Table 2.1 Colors that refer to method of hydrogen production 8

Table 2.2 Comparing SMR with Partial Oxidation 15

Table 2.3 20
How different methods stack up against fossil fuel-
based hydrogen production.

vi
 LIST OF FIGURES

Figure The SMR Process: A Step-by-Step 10

1 Breakdown
Figure Process Flow Diagram for the production of 24
2 hydrogen from fuel oil.

vii
 LIST OF GROUP MEMBERS

Afolabi Elizabeth CHE/2017/018

Asama Iyanuoluwa CHE/2018/065
Adedokun Benjamin CHE/2017/005
Oladipo Ifeoluwa CHE/2017/065
Sulaiman Lateef CHE/2017/085
Ogungbesan Tobiloba CHE/2017/058
Martins Olamide CHE/2017/048
Odeyemi Bolaji CHE/2017/026
Akinniyi Toyyib CHE/2017/025
Omisore Misbaudeen CHE/2017/075
Alabi Emmanuel CHE/2017/028
Lebile Ajoke CHE/2017/045
Salam Idris PHY/2017/058
Olanrewaju Emmanuel CHE/2017/068
Adebajo Emmanuel CHE/2017/095

viii
 CHAPTER ONE

INTRODUCTION

1.1 Overview
Hydrogen was first identified by the English scientist Cavendish in 1776 when dissolving metals

in dilute acids. Since the discovery, a number of chemical transformations were used to produce

hydrogen in the laboratory and for small-scale usage. These included, among others, the

electrolysis of water, the reaction of zinc with hydrochloric acid, the reaction of sodium with

water, and the dissolution of aluminum or silicon in caustic alkali sodium hydroxide solutions.

[M. Steinberg]

All hydrogen required in the H-Oil reactor for hydro conversion and desulfurization is ultimately

produced from the residual oil feed material, by using the heavy product residue material to

produce a fuel gas and converting the light hydrocarbons to hydrogen. [R. H. Wolk et al.,].

One of the primary methods for producing hydrogen industrially is through the processing of

fossil fuels, such as natural gas, coal, and oil. This process is known as steam reforming or steam

methane reforming (SMR).

1. Feedstock Preparation: Natural gas, coal, or other fossil fuels are the primary feedstocks for

this process. The feedstock may undergo preprocessing, such as desulfurization, to remove

impurities.

2. Steam Reforming: The preprocessed fossil fuel is mixed with superheated steam and

undergoes a catalytic reaction at high temperatures (700-1100°C). The main reaction is the steam

reforming of methane: CH4 + H2O => CO + 3H2

1
3. Water-Gas Shift Reaction: The carbon monoxide (CO) produced in the previous step is

further reacted with steam to produce additional hydrogen: CO + H2O => CO2 + H2

4. Hydrogen Purification: The resulting gas mixture, which contains hydrogen, carbon dioxide,

and other impurities, undergoes purification steps to separate the hydrogen. Common

purification techniques include pressure swing adsorption (PSA), membrane separation, or

cryogenic distillation.

5. Hydrogen Storage and Distribution: The purified hydrogen is then compressed, liquefied, or

stored in a suitable form for transportation and use.

The key advantages of hydrogen production from fossil fuels include the relatively low cost, the

availability of the feedstock, and the established infrastructure for processing and distributing the

hydrogen. However, this process also has environmental drawbacks, as it typically produces

carbon dioxide as a byproduct, contributing to greenhouse gas emissions.

To address these environmental concerns, researchers are exploring ways to capture and

sequester the carbon dioxide or to combine the steam reforming process with carbon capture and

storage (CCS) technologies.

1.2 Aims and Objectives

1.2.1. Aims
• Provide a reliable and cost-effective source of hydrogen to meet the growing demand for

the gas.

• Leverage the existing infrastructure and expertise in the fossil fuel industry to scale up

hydrogen production.

2
 • Contribute to the diversification of the energy mix and the transition towards more

sustainable energy solutions.

1.2.2 Objectives
• Optimize the efficiency and yield of the steam reforming process to maximize hydrogen

production from fossil fuel feedstocks.

• Develop advanced purification and separation techniques to obtain high-purity hydrogen.

• Improve the environmental sustainability of the process by reducing carbon dioxide

emissions and exploring carbon capture and storage (CCS) technologies.

• Enhance the safety and reliability of hydrogen production, storage, and distribution to

ensure safe handling and deployment.

• Reduce the overall cost of hydrogen production from fossil fuels to make it more

competitive with other hydrogen production methods, such as water electrolysis.

• Foster the development of a robust and sustainable hydrogen economy by ensuring a

reliable and affordable supply of the gas.

• Contribute to the overall transition towards a more sustainable and diversified energy

landscape by positioning hydrogen as a key component of the future energy mix.

3
 CHAPTER TWO

LITERATURE REVIEW

2.1 Overview
Hydrogen was first identified by the English scientist Cavendish in 1776 when dissolving metals

in dilute acids. Since the discovery, a number of chemical transformations were used to produce

hydrogen in the laboratory and for small-scale usage. These included, among others, the

electrolysis of water, the reaction of zinc with hydrochloric acid, the reaction of sodium with

water, and the dissolution of aluminum or silicon in caustic alkali sodium hydroxide solutions.

However, by far the greatest amount of hydrogen produced for industrial purposes is produced

by the steam reforming of natural gas (methane).

2.1 Classification based on production method

Manufacturing elemental hydrogen requires the consumption of a hydrogen carrier such as fossil

fuel or water. The former carrier consumes the fossil resource and in the steam methane

reforming (SMR) process produces greenhouse gas carbon dioxide. However, in the newer

methane pyrolysis process no greenhouse gas carbon dioxide is produced. Hydrogen produced

by electrolysis of water using renewable energy sources such as wind and solar power, referred

to as green hydrogen. When derived from natural gas by zero greenhouse emission methane

pyrolysis, it is referred to as turquoise hydrogen. (Schneider et al, 2020) When fossil fuel

derived with greenhouse gas emissions, is generally referred to as grey hydrogen. If most of the

carbon dioxide emission is captured, it is referred to as blue hydrogen. (Sampson, 2019)

Hydrogen produced from coal may be referred to as brown or black hydrogen.

4
Table 2.1: Colors that refer to method of hydrogen production

Colour Production source Notes

Green In most definitions, renewable electricity

via electrolysis of water. Less frequently,

definitions of green hydrogen include

hydrogen produced from other low-

emission sources such as biomass

Turquoise Thermal splitting of methane Via methane pyrolysis

Blue Hydrocarbons with carbon capture and CCS networks required

storage

Gray Fossil hydrocarbons, mainly steam

reforming of natural gas

Brown or black Fossil hydrocarbons: brown (lignite) or Via coal gasification or in a

black coal suitable reactor

Red, pink or purple Nuclear power Via thermochemical water

splitting, electrolysis of water, or

contributing steam to natural gas

reforming

Yellow Sometimes understood to mean solar Via photovoltaic

photovoltaics

Gold or white Hydrogen that occurs naturally deep within Obtained by mining; also referred

the Earth’s crust to as white

5
2.2 Fossil fuel processing method for the production of hydrogen

Hydrogen can be extracted through the breakdown of hydrocarbons as a primary reaction

product and as by-products using methods which rely on the contents of fossil fuels such as high-

temperature thermal decomposition of hydrocarbons, or modification of the molecule structure.

There are multiple ways to initiate the thermal reformation of hydrocarbons, including partial

oxidation, autothermal reformation, and steam reformation. (Megia, 2021)

2.2.1 Hydrocarbon pyrolysis

Hydrocarbon pyrolysis refers to the process of producing hydrogen through the thermal

decomposition of hydrocarbons. A thermo-catalytic decomposition is used to produce hydrogen

and carbon from hydrocarbons (e.g., methane, ethane, propane, etc.) by an endothermic reaction

known as pyrolysis. In general, the reaction is as follows:

𝐶𝑛 𝐻𝑚 → 𝑛𝐶 + 0.5𝑚𝐻2

Natural gas (methane) can be converted into COX-free hydrogen through thermo-catalytic

decomposition for use in PEM fuel cells, oil refineries, ammonia, and methanol production. The

reaction temperature is high, typically at or above 700 °C, and it can be lowered by using suitable

catalysts. (Schneider,2020) Methane reacts as follows:

𝑘𝐽
𝐶𝐻4 → 𝐶 + 2𝐻2 ; ∆𝐻𝑅0 = 74.9 𝑚𝑜𝑙

where ∆𝐻𝑅0 is the enthalpy of reaction under the standard condition of 25°C and 1 atm producing

solid carbon and gaseous hydrogen.

6
2.2.2. Steam reforming of natural gas (methane)

Steam methane reforming (SMR) stands as the undisputed champion in industrial-scale hydrogen

production, leveraging the readily available resource of natural gas (CH₄).

Figure 1 - The SMR Process: A Step-by-Step Breakdown

1. Feedstock Preparation: The journey begins with natural gas. While readily available, it

may undergo a pre-treatment stage to remove impurities like sulfur compounds.

2. Reaction Conditions: After any necessary pre-treatment, the natural gas is meticulously

mixed with steam (H₂O) in a specific ratio. This mixture is then preheated before entering

the heart of the operation – the reformer reactor.

3. Syngas Production: The reaction within the reformer reactor doesn't directly produce

pure hydrogen. Instead, it yields a mixture of gases called "syngas" (synthesis gas). The

key components of syngas in this context are hydrogen (H₂), carbon monoxide (CO), and

some carbon dioxide (CO₂) along with water vapor (H₂O) and other minor components.

7
The Reactions Chemistry

The seemingly simple process of SMR actually involves a series of chemical reactions. Here is a

breakdown of the key reactions at play with their associated heat changes.

● Synthesis Gas Generation: This reaction represents the initial conversion of methane

and steam into a mixture of carbon monoxide and hydrogen:

CH4 + H2O => CO + 3H2 + ∆HR⁰ (endothermic; ∆HR⁰ = 205kJ/mol CH4)

● Water-Gas Shift Reaction: The syngas produced still contains a significant amount of

CO. To maximize hydrogen yield, an additional step called the water-gas shift reaction

comes into play:

CO + H₂O → CO₂ + H₂ + ∆HR⁰ (exothermic; ∆HR⁰ = -41.16 kJ/mol)

● Direct Steam Reforming (DSR): While not always explicitly mentioned, the overall

SMR process can also be represented by a single reaction combining the effects of both

the initial methane conversion and the water-gas shift reaction:

CH₄ + 2H₂O → CO₂ + 4H₂ + ∆HR⁰ (endothermic; ∆HR⁰ = 165.12 kJ/mol)

2.2.3 PARTIAL OXIDATION

While steam methane reforming (SMR) reigns supreme, partial oxidation presents an alternative

method for extracting hydrogen from fossil fuels. This approach offers some key advantages

over SMR, but it also comes with its own set of considerations.

Feedstock Flexibility: Unlike SMR, which primarily relies on natural gas, partial oxidation

boasts greater feedstock flexibility. Natural gas remains the most common choice, but the

process can also handle heavier hydrocarbons like fuel oil.

The Reaction Theory: High Temperatures and Controlled Oxygen

8
The core of the partial oxidation process revolves around a controlled environment with high

temperatures. The chosen fossil fuel is mixed with either air or pure oxygen, depending on the

desired level of control and product yield.

The Key Difference: Incomplete Combustion for Syngas Production

The defining characteristic of partial oxidation lies in the amount of oxygen used. In contrast to

SMR, there's not enough oxygen present for complete combustion of the fuel. This "partial"

oxidation leads to the formation of a key intermediate product – syngas.

Water-Gas Shift Reaction and Hydrogen Separation: Borrowing from SMR

Following syngas production, the subsequent steps in partial oxidation mirror those employed in

SMR.

CO + H₂O → CO₂ + H₂

This reaction utilizes the remaining CO in the syngas and reacts it with water vapor to produce

additional hydrogen and CO₂.

Finally, the hydrogen product needs to be isolated from the syngas mixture. Separation

techniques like pressure-swing adsorption (PSA) or membrane separation come into play, similar

to the downstream processing required in SMR.

The Reactions Chemistry

Partial oxidation involves a series of chemical reactions. The key reactions involved include:

Reforming Process: The reforming process can be either catalytic or non-catalytic.

Catalytic reaction: CnHm + 0.5nO2 => nCO + 0.5mH2;

Non-catalytic reaction: CnHm + nH2O => nCO + 0.5mH2;

9
 ● Water-Gas Shift Reaction: CO + H₂O → CO₂ + H₂; ∆HR⁰ = -41 kJ/mol (exothermic)

Table 2.2 Comparing SMR with Partial Oxidation

Feature Steam Methane Reforming Partial Oxidation

(SMR)

Feedstock Primarily natural gas Natural gas, fuel oil

Reaction Conditions Lower temperature (700°C- Higher temperature (around

1,000°C) 1,500°C)

Oxygen Requirement Requires steam Requires air or pure oxygen

Product Yield Generally higher hydrogen Lower hydrogen yield

yield compared to SMR

2.2.4 AUTOTHERMAL REFORMING

A steam reforming process and an exothermic partial oxidation process combine to produce

hydrogen through autothermal reforming. The reactor is filled with oxygen and steam

simultaneously in contrast with partial oxidation reaction where only oxygen is present, and the

reforming and oxidation reactions occur simultaneously. Combining the two processes results

in the following reaction (Nikolaidis et al, 2017):

𝑘𝐽
𝐶𝑛 𝐻𝑚 + 𝑛𝐻2 𝑂 + 0.25 𝑛𝑂2 → 𝑛𝐶𝑂 + (0.5𝑛 + 0.5𝑚) 𝐻2; ∆𝐻𝑅0 = 84 𝑚𝑜𝑙

2.3 ENVIRONMENTAL IMPACTS

Most hydrogen is produced from fossil fuels, resulting in carbon dioxide emissions. Hydrogen

produced by this technology has been described as grey hydrogen when emissions are released to

the atmosphere, and blue hydrogen when emissions are captured through carbon capture and

10
storage (CCS). Blue hydrogen has been estimated to have a carbon footprint 20% greater than

burning gas or coal for heat and 60% greater when compared to burning diesel for heat,

assuming US up- and mid-stream methane leakage rates and production via Steam Methane

Reformers (SMR) retrofitted with carbon dioxide capture. (Robert et al, 2021)

The use of autothermal reformers (ATR) with integrated capture of carbon dioxide allows higher

capture rates at satisfactory energy efficiencies and life cycle assessments have shown lower

greenhouse gas emissions for such plants compared to SMRs with carbon dioxide capture.

(Antonini, et al, 2020) Application of ATR technology with integrated capture of carbon dioxide

in Europe has been assessed to have a lower greenhouse gas footprint than burning natural gas,

e.g., for the H21 project with a reported reduction of 68% due to a reduced carbon dioxide

intensity of natural gas combined with a more suitable reactor type for capture of carbon dioxide.

Hydrogen produced from renewable energy sources is often referred to as green hydrogen. Two

ways of producing hydrogen from renewable energy sources are claimed to be practical. One is

to use power to gas, in which electric power is used to produce hydrogen from electrolysis of

water, and the other is to use landfill gas to produce hydrogen in a steam reformer. Hydrogen

fuel, when produced by renewable sources of energy like wind or solar power, is a renewable

fuel. (Dvorak, 2023) Hydrogen produced from nuclear energy via electrolysis is sometimes

viewed as a subset of green hydrogen, but can also be referred to as pink hydrogen. The

Oskarshamn Nuclear Power Plant made an agreement in January 2022 to supply commercial

pink hydrogen in the order of kilograms per day. As of 2020, estimated costs of production are

$1–1.80/kg for grey hydrogen and blue hydrogen, and $2.50–6.80 for green hydrogen. (Collins,

2022) 94 million tonnes of grey hydrogen are produced globally using fossil fuels as of 2022,

11
primarily natural gas, and are therefore a significant source of greenhouse gas emissions.

(Castlevecchi, 2022)

2.4. Progress of Fossil-Fueled Hydrogen Production

The relentless pursuit of cleaner and more efficient hydrogen production from fossil fuels

necessitates a deep dive into the latest research. This section delves into recent publications,

analyzing advancements in process configurations, catalysts, separation techniques, and techno-

economic assessments.

Process Optimization

A recent study by Jin 2023., explores the effectiveness of integrating a pre-reforming step with

SMR. This configuration preheats the natural gas feedstock using the reactor outlet stream,

reducing the external heat requirement and potentially improving the overall process efficiency.

However, the authors acknowledge the need for further research to optimize the pre-reforming

stage and ensure catalyst stability under the modified conditions.

Another research group [Sunaro 2022], investigates the utilization of oxygen-selective

membranes in partial oxidation for hydrogen production. Their findings suggest that this

approach offers the potential for a single-step process, eliminating the need for the water-gas

shift reaction and potentially simplifying the overall production scheme. However, the long-term

durability and performance of these membranes under real-world operating conditions remain a

point of exploration.

Catalysts Effects

The role of catalysts in hydrogen production from fossil fuels cannot be overstated. A study

published by [Rezaei 2023] examines the development of novel nickel-based catalysts with

12
improved resistance to sulfur poisoning, a common challenge in SMR. These new catalysts

demonstrate extended operational lifetimes and potentially translate to lower production costs.

Further research on catalyst design that optimizes activity, selectivity, and durability for specific

process conditions is crucial.

Separation Techniques: Refining the Final Product

High-purity hydrogen is essential for many applications. A recent report by [Liu 2022] explores

the potential of advanced adsorption materials for hydrogen separation from syngas. These

materials exhibit promising separation performance, but challenges remain regarding their large-

scale implementation and regeneration strategies. Research on cost-effective and scalable

adsorption processes for high-purity hydrogen production is warranted.

2.5 Comparison with Alternative Methods: Beyond Fossil Fuels

While hydrogen production from fossil fuels has dominated the scene, a shift towards cleaner

and more sustainable methods is underway. Here, we explore three promising alternatives:

Electrolysis

Electrolysis offers a compelling approach – splitting water into hydrogen and oxygen using

electricity. The key factor determining its environmental footprint lies in the source of the

electricity. When powered by renewable sources like solar, wind, or hydro, electrolysis produces

truly green hydrogen with minimal greenhouse gas emissions. However, the efficiency of the

process can vary depending on the technology used, and the cost of electricity significantly

impacts the overall economic viability.

Biomass Gasification

Biomass gasification utilizes organic materials like wood chips, agricultural waste, or algae to

produce syngas, which can be further processed to extract hydrogen. Compared to fossil fuels,

13
biomass is a renewable resource, offering a potential path towards sustainable hydrogen

production. However, feedstock logistics and sustainability considerations regarding biomass

source are crucial. Additionally, the gasification process itself can generate air pollutants if not

carefully managed.

Photoelectrochemical Water Splitting

This emerging technology harnesses the power of sunlight to directly split water into hydrogen

and oxygen. Photoelectrochemical (PEC) cells hold immense promise for clean and efficient

hydrogen production. However, current PEC technologies face challenges regarding efficiency,

material stability, and scalability. Significant research and development efforts are needed before

PEC can become a mainstream hydrogen production method.

Highlighting the Key Differences

Here's a breakdown of how these methods stack up against fossil fuel-based hydrogen

production:

14
Table 2.3 – How different methods stack up against fossil fuel-based hydrogen production.

Feature Fossil Fuels Electrolysis Biomass Photoelectrochemical

(Renewables) Gasification Water Splitting

Feedstock Limited Renewable Renewable Renewable

Sustainability

Energy High Variable High Moderate (after initial

Consumption (depends on investment)
source)

Environmental High CO2 Low (with Moderate Very Low

Impact emissions renewables) (depends on
feedstock)

Cost and Established, Higher, Moderate to High (developing

Feasibility but dependent on high technology)
fluctuating electricity cost (developing
costs technology)

15
 CHAPTER THREE

PRODUCTION PROCESS

The process employed for the production of hydrogen from fuel oil is the partial oxidation of oil

feedstock.

3.1. Materials Used

1. Heavy fuel oil feedstock of viscosity 900 seconds Redwood One (2.57ð104 m2/s) at 100ŽF

with the following analysis:

Carbon 85 percent wt
Hydrogen 11 percent wt
Sulphur 4 percent wt
Calorific value 18,410 Btu/lb (42.9 MJ/kg)
Specific gravity 0.9435
The oil available is pumped from tankage at a pressure of 30 psig (206.9 kN/m2 gauge) and at

500C

2. Oxygen at 95 percent purity (the other component assumed to be wholly nitrogen) and at 200C

and 600 psig.

3.2. Utilities used include:

(1) Steam at 600 psig saturated.

(2) Cooling water at a maximum summer temperature of 250C

(3) Demineralized boiler feedwater at 20 psig and 150C suitable for direct feed to the boilers.

16
(4) Electricity at 440 V, three-phase 50 Hz, with adequate incoming cable capacity for all

proposed uses.

(5) Waste low-pressure steam from an adjacent process. With an on-stream time of 8050

hours/year.

3.4. PROCEDURE
Heavy fuel oil feedstock is delivered into the suction of metering-type ram pumps which feed it

via a steam preheater into the combustor of a refractory-lined flame reactor. The feedstock must

be heated to 2000C in the preheater to ensure efficient atomisation in the combustor. A mixture

of oxygen and steam is also fed to the combustor, the oxygen being preheated in a separate steam

preheater to 2100C before being mixed with the reactant steam.

The crude gas, which will contain some carbon particles, leaves the reactor at approximately

1300 0C and passes immediately into a special waste-heat boiler where steam at 600 psig (4140

kN/m2 gauge) is generated. The crude gas leaves the waste heat boiler at 2500C and is further

cooled to 500C by direct quenching with water, which also serves to remove the carbon as a

suspension.

The carbon produced in the flame reaction, and which is subsequently removed as carbon

suspension in water, amounts to 1.5 per cent by weight of the fuel oil feedstock charge. Some H2S

present in the crude gas is removed by contact with the quench water. The quenched gas passes to

an H2S removal stage where it may be assumed that H2S is selectively scrubbed down to 15 parts

per million with substantially nil removal of CO2. Solution regeneration in this process is

undertaken using the waste low-pressure steam from another process. The scrubbed gas, at 35ŽC

and saturated, has then to undergo CO conversion, final H2S removal, and CO2 removal to allow

17
it to meet the product specification. CO conversion is carried out over chromium-promoted iron

oxide catalyst employing two stages of catalytic conversion; the plant also incorporates a saturator

and desaturator operating with a hot water circuit.

Incoming gas is introduced into the saturator (a packed column) where it is contacted with hot

water pumped from the base of the desaturator; this process serves to preheat the gas and to

introduce into it some of the water vapour required as reactant. The gas then passes to two heat

exchangers in series. In the first, the unconverted gas is heated against the converted gas from the

second stage of catalytic conversion; in the second heat exchanger the unconverted gas is further

heated against the converted gas from the first stage of catalytic conversion. The remaining water

required as reactant is then introduced into the unconverted gas as steam at 600 psig (4140 kN/m2

gauge) saturated and the gas/steam mixture passes to the catalyst vessel at a temperature of 370ŽC.

The catalyst vessel is a single shell with a dividing plate separating the two catalyst beds which

constitute the two stages of conversion.

The converted gas from each stage passes to the heat exchangers previously described and thence

to the desaturator, which is a further packed column. In this column the converted gas is contacted

countercurrent with hot water pumped from the saturator base; the temperature of the gas is

reduced and the deposited water is absorbed in the hot-water circuit. An air-cooled heat exchanger

then reduces the temperature of the converted gas to 400C for final H2S removal. Final H2S removal

takes place in four vertical vessels each approximately 60 feet (18.3 m) in height and 8 feet (2.4m)

in diameter and equipped with five trays of ironoxide absorbent. Each vessel is provided with a

locking lid of the autoclave type. The total pressure drop across these vessels is 5 psi (35 kN/m2).

Gas leaving this section of the plant contains less than 1 ppm of H2S and passes to the CO2 removal

18
stage at a temperature of 350C. CO2 removal is accomplished employing high-pressure potassium

carbonate wash with solution regeneration. [H.E. Benson et al., 1956].

Figure 2: Process Flow Diagram for the production of hydrogen from fuel oil.

19
3.5. Predesign and Main Design Hazards of Hydrogen Production Using Fuel
Oils and Their Solutions

3.5.1. Pre-design Hazards:

1. Inadequate process understanding (PHA - Process Hazard Analysis, HAZID - Hazard

Identification)

Definition: Insufficient knowledge of the process flow design (PFD) for hydrogen production

from fuel oils, which can lead to overlooked hazards and inadequate safety measures.

Solution: Conduct a thorough PHA and HAZID study to ensure a comprehensive understanding

of the process. This involves:

- PHA: A systematic approach to identify and evaluate potential hazards, operability issues, and

potential failure modes.

- HAZID: A structured process to identify and assess potential hazards, focusing on

identification, not evaluation.

2. Insufficient training and expertise (OSHA - Occupational Safety and Health

Administration)

Definition: Designers and operators lacking the necessary knowledge, skills, and experience in

hydrogen production and processing, leading to potential mistakes and accidents.

Solution: Ensure that designers and operators receive:

- Training: Provide regular, up-to-date training on hydrogen production, processing, and safety

procedures.

20
- Expertise: Ensure that personnel have the necessary experience and qualifications for their

roles.

3. Inadequate safety standards and regulations (NFPA - National Fire Protection

Association, OSHA - Occupational Safety and Health Administration)

Definition: Failure to comply with relevant safety standards and regulations, leading to

inadequate safety measures and potential accidents.

Solution: Familiarize yourself with relevant safety standards and regulations, such as:

- NFPA 2, Hydrogen Technologies

- OSHA 29 CFR 1910, General Industry Standards

3.5.2. Main Design Hazards:

1. Fire and Explosion Risks

- Hazard: Handling flammable materials (fuel oil, hydrogen, and oxygen).

- Solution: Implement proper storage, handling, and ventilation procedures.

- Safety Analysis: Conduct HAZOP (Hazard and Operability) studies to identify potential failure

scenarios and implement recommendations.

2. Toxic Gas Exposure

- Hazard: Exposure to toxic gases (H2S, CO, CO2) during operations.

21
- Solution: Design and install adequate ventilation systems and provide personal protective

equipment (PPE) to all relevant personnel.

- Safety Analysis: Perform a HAZID (Hazard Identification) analysis to identify potential

sources of toxic gas exposure and implement controls.

3. High-Pressure Equipment Failure

- Hazard: Failure of high-pressure equipment.

- Solution: Ensure proper design, installation, and maintenance of high-pressure systems.

- Safety Analysis: Conduct a FMEA (Failure Mode and Effects Analysis) to identify potential

failure modes and implement mitigation measures.

4. Electrical Hazards

- Hazard: Risks from high-voltage electrical systems.

- Solution: Implement stringent electrical design, installation, and maintenance procedures.

- Safety Analysis: Perform a risk assessment using a method such as LOPA (Layer of Protection

Analysis) to identify potential electrical hazards and implement controls.

5. Heat Exchanger Design Issues

- Hazard: Overheating or cooling issues due to inadequate heat exchanger design.

- Solution: Conduct thorough heat exchanger design calculations and consider appropriate

material selection.

22
- Safety Analysis: Use a method such as HAZOP or FMEA to identify potential design flaws

and implement recommendations.

6. Gas Flow Control and Pressure Regulation

- Hazard: Insufficient control of gas flow and pressure.

- Solution: Design and install appropriate control systems, pressure regulators, and relief valves.

- Safety Analysis: Conduct a HAZOP study to identify potential failure scenarios and implement

recommendations.

7. Catalyst Handling and Storage

- Hazard: Inadequate procedures for handling and storing catalysts.

- Solution: Design safe catalyst handling and storage systems and provide detailed training for

personnel.

- Safety Analysis: Perform a HAZID analysis to identify potential hazards and implement

controls.

8. Instrumentation and Control Systems

- Hazard: Inadequate instrumentation and control systems.

- Solution: Design and install reliable instrumentation and control systems and ensure proper

calibration and regular maintenance.

- Safety Analysis: Use a method such as FMEA to identify potential failure modes and

implement mitigation measures.

23
9. Emergency Shutdown and Depressurization Systems

- Hazard: Inadequate emergency shutdown and depressurization systems.

- Solution: Design and install reliable emergency shutdown systems and ensure regular testing

and maintenance.

- Safety Analysis: Conduct a HAZOP study to identify potential failure scenarios and implement

recommendations.

10. Fire Protection and Suppression Systems

- Hazard: Inadequate fire protection and suppression systems.

- Solution: Design and install appropriate fire protection and suppression systems and conduct

regular testing and maintenance.

- Safety Analysis: Perform a risk assessment using a method such as LOPA to identify potential

fire hazards and implement controls.

11. Ventilation and Gas Removal Systems

- Hazard: Inadequate ventilation and gas removal systems.

- Solution: Design and install adequate ventilation and gas removal systems and ensure regular

testing and maintenance.

- Safety Analysis: Conduct a HAZID analysis to identify potential hazards and implement

controls.

12. Electrical Area Classification and Explosion-Proof Equipment

24
- Hazard: Inadequate classification of electrical areas and use of non-explosion-proof

equipment.

- Solution: Ensure proper electrical area classification and design and install explosion-proof

equipment where necessary.

- Safety Analysis: Use a method such as HAZOP or FMEA to identify potential electrical

hazards and implement controls.

13. Personnel Protection and Access Restrictions

- Hazard: Inadequate protection measures and access restrictions for personnel.

- Solution: Design and implement comprehensive personnel protection measures and establish

strict access restrictions to hazardous areas.

- Safety Analysis: Perform a risk assessment using a method such as LOPA to identify potential

hazards and implement controls.

14. Waste Management and Disposal Procedures

- Hazard: Inadequate waste management and disposal procedures.

- Solution: Design and implement robust waste management and disposal procedures and ensure

compliance with environmental regulations.

- Safety Analysis: Conduct a HAZID analysis to identify potential hazards and implement

controls

25
 CHAPTER FOUR

CONCLUSION AND RECOMMENDATION

4.1 Conclusion
Fuel oil can be used to produce hydrogen if the proper technology and process optimization are

used. It is possible to produce hydrogen in an effective and sustainable manner by tackling the

three main issues of desulfurization, carbon control, and energy integration. Maintaining optimal

performance and adjusting to changing needs will be made easier with regular maintenance and

keeping up with technological changes. To achieve maximum efficiency and environmental

compliance, it necessitates the appropriate treatment of impurities and by-products as well as

complex chemical processes.

4.2 Recommendations
Producing hydrogen from fuel oil can be an efficient and sustainable option, but it requires

careful planning and optimization. Here are some recommendations to get effective product:

1. Select the Appropriate Process

- Partial Oxidation (POX):

- Advantages: Handles heavy hydrocarbons well, exothermic process (doesn’t require external

heat).

- Considerations: Manage CO production effectively with a subsequent water-gas shift

reaction to maximize hydrogen yield.

- Steam Reforming:

26
 - Advantages: Higher hydrogen yield, suitable for a variety of hydrocarbons when combined

with proper desulfurization.

- Considerations: Requires external heat, thorough desulfurization, and advanced catalyst

management.

2. Invest in Advanced Desulfurization

-Techniques: Consider using hydrodesulfurization (HDS) or advanced adsorbent-based

methods to remove sulfur compounds efficiently.

- Importance: Protects catalysts from poisoning, ensuring long-term efficiency and

effectiveness.

3.Optimize the Water-Gas Shift Reaction

- Two-Stage Shift: Implement both high-temperature and low-temperature shift stages to

maximize conversion of CO to CO₂ and hydrogen.

- Catalysts: Use high-activity catalysts tailored for each stage to enhance reaction efficiency.

4. Ensure Feedstock Flexibility

- Design Considerations: Build flexibility into the system to handle variations in fuel oil

composition, maintaining stable operations and efficiency.

- Testing and Adjustment: test fuel oil quality and adjust process parameters accordingly.

27
 REFERENCES

Castelvecchi, D; (2022-11-16). "How the hydrogen revolution can help save the planet — and

how it can't". Nature. 611 (7936): 440–443. Bibcode:2022 doi:10.1038/d41586-022-

03699-0. PMID 36385542. S2CID 253525130.

Collins, L; (25 January 2022). "World first for nuclear-powered pink hydrogen as commercial

deal signed in Sweden ". Latest renewable energy news.

Collins, Leigh (19 March 2020). "A wake-up call on green hydrogen: the amount of wind and

solar needed is immense ". Latest renewable energy news. Archived from the original on 4

June 2021.

Dvorak, P; (December,2022) "WSJ News Exclusive: Green Hydrogen Gets a Boost in the U.S.

With $4 Billion Plant: The planned factory, a joint venture by Air Products and AES ".

Wall Street Journal, December 8, 2022. Retrieved 2023-11-14.

Jin, Y., Wang, Z., Liu, H., & Li, Y. (2023). Integration of pre-reforming with steam methane

reforming for hydrogen production: Process simulation and techno-economic assessment.

International Journal of Hydrogen Energy, 48(12), 12822-12834.

Li, J., Sunarso, J., & Jiang, S. (2022). Recent advances in oxygen-selective membranes for

hydrogen production via partial oxidation of methane. Journal of Membrane Science, 642,

120172.

Liu, C., Xiang, S., Hu, Y., Xing, W., & Li, J. (2022). Recent advances in materials for hydrogen

separation from syngas. Chemical Society Reviews, 51(14), 5467-5514.

M. Steinberg. ENERGY CARRIERS AND CONVERSION SYSTEMS – Vol. I - Hydrogen

Production from Fossil Fuels

Malaika A, Krzyzyńska B, Kozłowski M. (2010) “Catalytic decomposition of methane in the

28
 presence of in situ obtained ethylene as a method of hydrogen production”. International

Journal of Hydrogen Energy, 2010, 35(14): 7470-7475

Megia P. J, Vizcaino A. J, Calles J. A, et al. (2021) “Hydrogen Production Technologies: From

Fossil Fuels toward Renewable Sources”. A Mini Review. Energy and Fuels, 2021,

35(20): 16403–16415

Nikolaidis P, Poullikkas A. (2017) “A comparative overview of hydrogen production processes.

Renewable and Sustainable Energy Reviews”, 2017, 67, 597-611

R. H. Wolk, A.R Johnson, G. Nongbri. “Production of low sulfur fuel oil and hydrogen from
petroleum residuum.”

Rezaei, M., & Haghighi, M. (2023). Bimetallic Ni–Mo catalysts supported on Al2O3 for steam

methane reforming: A review of recent progress. International Journal of Hydrogen Energy,

48(13), 13222-13242.

Sampson, J;(11 February 2019). Gas world. Archived from the original on 2019-05-09. Retrieved

2019-06-03. 2019-02-11T10:48:00+00:00

Schneider S, Bajohr S, Graf F, et al. (2020) “State of the Art of Hydrogen Production via

Pyrolysis of Natural Gas”. ChemBioEng Reviews. 2020, 7(5): 150-158

Schneider, S; Bajohr, S; Graf, F; Kolb, T (October 2020). "State of the Art of Hydrogen

Production via Pyrolysis of Natural Gas". ChemBioEng Reviews. 7 (5): 150–158.

doi:10.1002/cben.202000014.

Skovgaard, E., Østergård, L., & Jensen, J. R. (2022). Techno-economic assessment of SMR for

large-scale hydrogen production with and without CCS. International Journal of Hydrogen

Energy, 47(2), 1231-1243.

ZEP (Oct, 2021). “Facts on low-carbon hydrogen – A European perspective", Confirmed 2023-

29
12-12

30