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UNIVERSITAS INDONESIA

PRELIMENARY DESIGN OF POWER-TO-GAS SYSTEM TO


ABSORB PHOTOVOLTAIC POWER

Report Midterm

GROUP 23
GROUP PERSONNEL:
AHMAD HAMIDI (1306446370)
ASTRINI PRADYASTI (1306370404)
CHAIRANI SHAFIRA U. (1306370732)
IMAM TAUFIQ R. (1306370612)
MARIA ULFA (1306370625)
RADEN RIDZKI ADITYA (1306370530)

CHEMICAL ENGINEERING DEPARTMENT


ENGINEERING FACULTY
DEPOK
OCTOBER, 2016
EXECUTIVE SUMMARY

About 88% of Indonesias power generation is from fossil fuels, which has
led to heavy import dependence and excessive reliance on government subsidies.
Because of the need to increase the electrification ratio, demand of electricity is
also increase. To this end, the Government of Indonesia plans to build 35,000
MW of power plants in the next 5 years. By having photovoltaic power plants in
Indonesia, government plan to increase the electrification ratio can be happened.
Moreover, Indonesia can decrease its dependency of fossil fuel. Besides, the
excess of PV power plant can be used as an energy in power-to-gas.
Power-to-gas is the process of converting surplus renewable energy into
hydrogen gas by rapid response electrolysis. Power-to-Gas (P2G) involves
transferring excess energy from the power system to the gas grid in the form of
electrolytic hydrogen. The P2G process not only helps avoid waste of renewable
energy in electrical system due to system constraints, but also realizes the two-
way coupling for the integrated gas and electrical systems.
In the first step, gaseous hydrogen is formed by the process of electrolysis
using an electrolyzer convert electricity to hydrogen, which can be stored and
transformed back into electricity via fuel cells later, with certain efficiency. The
technology of Proton Exchange Membrane (PEM) is considered to be favorable
for the P2G process due to its faster ramping rates, which can better accommodate
wind power fluctuations. H2 generated in the first step can be stored for usage
later, injected into the gas network blended with natural gas, or use as a raw
material for other industries.
Electrolysis of aqua demineralization will have products of pure hydrogen
and oxygen. But, there is sometimes a leak at electrolyzer, so there is still remain
of raw material. Because the raw material is only being feed to the anode, there is
no water in the cathode output. So, the output is just hydrogen. Hydrogen from the
cathode then being compressed from 15 bar to 200 bar. Oxygen from separator is
then compressed from 2 bar to 137 bar. Both of these gases go into the cooler to
make their temperature to go down to the ambient temperature. With this process,

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we will produce hydrogen as main product with capacity of 31 kg/h and oxygen as
a side product with capacity of 246 kg/h from water with mass flow of 277 kg/h.
Heat exchanger network (HEN) is needed to determine and optimize the
utility system that would be used in this plant. HEN is used to decrease the usage
of unnecessary utilities since heat of fluid can be used in place of the utilities. The
first step to determine the amount of heat can be recovered by pinch method is by
generating a composite curve. From the composite curves, we see that we would
need to supply 5,839 kW and that we would have to reject 59.9 kW.
Although composite curves can be used to set energy targets, they are
inconvenient since they are based on a graphical construction. A method of
calculating energy targets directly without the necessity of graphical construction
can be developed. This pinch design method is used for determine the use for hot
or cold fluid for heating or cooling the stream itself.
Utilities are the main supporting unit in the running of a production
process. Because of a production process does not work if the utility does not
exist. Therefore, all the facilities and infrastructure should be designed in such a
way as to ensure continuity of operation of the plant. Based on the needs, utilities
on manufacturing plant are water utility and electricity utility.
Chilled water is needed for cooler to cool down hydrogen, oxygen, and
demineralized water (as process water) in this plant. Total requirement of chilled
water for before HEN is 4,512 kg/h, where after HEN chilled water requirement is
4,112 kg/h. Liquid nitrogen also can be used to decrease the temperature of hot
streams. Total requirement of liquid nitrogen for before HEN is 623 kg/h, where
after HEN, liquid nitrogen requirement is 578.55 kg/h.
Electric utility for our Power-to-Gas system is required from our
photovoltaic power. Our PV Power can supply up to 45,000 kWh per day, so there
is enough supply for our electricity requirement. From calculation, we calculated
that the electricity requirement for one year which is 13,660,780 kWh.

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TABLE OF CONTENTS

EXECUTIVE SUMMARY .................................................................................... ii


TABLE OF CONTENTS ....................................................................................... iv
LIST OF FIGURE ................................................................................................. vi
LIST OF TABLE ..................................................................................................vii
CHAPTER 1 INTRODUCTION ............................................................................ 1
1.1 Background ...................................................................................................... 1
1.2 Basic Theory .................................................................................................... 2
1.2.1 Power-to-Gas System ................................................................................ 2
1.2.2 Excess PV Power ...................................................................................... 4
1.2.3 Application of H2 and O2........................................................................... 6
1.3 Analysis ........................................................................................................... 8
1.3.1 Raw Material Analysis .............................................................................. 8
1.3.2 Plant Location Analysis ............................................................................ 9
1.3.3 Capacity and Market Analysis ................................................................. 11
CHAPTER 2 PROCESS SELECTION ............................................................... 15
2.1 Alternative Process & Selection ..................................................................... 15
2.1.1 Alternative Process ................................................................................. 15
2.1.2 Selection Process .................................................................................... 18
2.2 Process Description ........................................................................................ 18
2.2.1 Feed Preparation ..................................................................................... 18
2.2.2 Electrolysis of Water ............................................................................... 18
2.2.3 Power...................................................................................................... 32
2.2.4 Gas-Water Separation ............................................................................. 33
2.3 Diagram ......................................................................................................... 34
2.3.1 Block Flow Diagram (BFD) .................................................................... 34
2.3.2 Process Flow Diagram (PFD) .................................................................. 35
2.4 Equipment and Technology Selection............................................................. 36
2.4.1 Storage Tank ........................................................................................... 36
2.4.2 Pump ...................................................................................................... 37
2.4.3 Electrolyzer ............................................................................................. 37
2.4.4 Heat Exchanger ....................................................................................... 39
2.4.5 Gas and Water Separator ......................................................................... 40
2.4.6 Compressor ............................................................................................. 40
2.4.7 Hydrogen Pipeline .................................................................................. 40
CHAPTER 3 MASS AND ENERGY BALANCE ............................................... 41
3.1 Process Simulation ......................................................................................... 41
3.2 Mass Balance ................................................................................................. 42
3.2.1 Overall Mass Balance ............................................................................. 42
3.2.2 Mass Balance of Each Process ................................................................ 43
3.3 Energy Balance .............................................................................................. 44
3.3.1 Overall Energy Balance .......................................................................... 44
3.3.2 Energy Balance of Each Process ............................................................. 45
CHAPTER 4 HEAT EXCHANGER NETWORK .............................................. 50
4.1 Stream Classification...................................................................................... 50
4.2 Heat Recovery Pinch Method ......................................................................... 51

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4.2.1 Composite Curves ................................................................................... 51
4.2.2 Problem Table Cascade ........................................................................... 53
4.3 Pinch Design Method ..................................................................................... 55
CHAPTER 5 UTILITY ........................................................................................ 58
5.1 Utility Equipment Selection and Description .................................................. 58
5.1.1 Water Utility ........................................................................................... 58
5.1.2 Electric Utility ........................................................................................ 59
5.1.3 Liquid Nitrogen Utility ........................................................................... 60
CHAPTER 5 CONCLUSION............................................................................... 61
REFERENCE........................................................................................................ 62
APPENDIX ........................................................................................................... 65

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LIST OF FIGURE

Figure 1.1 Pontianak, West Kalimantan ............................................................... 9


Figure 1.2 Location of Photovoltaic Power Plant and P2G ................................. 11
Figure 2.1 Sketch of an Electrochemical Cell ..................................................... 20
Figure 2.2 Water electrolyzer thermodynamics and cell voltage ......................... 23
Figure 2.3 Electrical Circuit Analogy of Water Electrolysis ............................... 24
Figure 2.4 Potential Losses Contributions from Water Electrolysis .................... 25
Figure 2.5 Effect of Temperature on Overpotential of Cathode and Anode ......... 28
Figure 2.6 Unipolar Electrolyzer Layout ............................................................ 29
Figure 2.7 Bipolar Electrolyzer Layout .............................................................. 30
Figure 2.8 Schematic of Three Phase Boundary ................................................. 31
Figure 2.9 Block Flow Diagram (BFD) .............................................................. 34
Figure 2.10 Process Flow Diagram (PFD) .......................................................... 35
Figure 2.11 Simplified Basic Design of a Single Cell in a PEMWE Stack .......... 38
Figure 3.1 Power-to-gas System Simulation with SuperPro Designer ................. 42
Figure 4.1 Combined Hot and Cold Fluid Composite Curves before HEN.......... 52
Figure 4.2 Combined Hot and Cold Fluid Composite Curves after HEN ............ 52
Figure 4.3 Hot and Cold Fluid Program Table Cascade ...................................... 55
Figure 4.4 Grand Composite Curve .................................................................... 55
Figure 4.5 Pinch Design Method ........................................................................ 57

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LIST OF TABLE

Table 1.1 Average of Solar Intensity .................................................................. 10


Table 1.2 Pontianak Human Resource Availability ............................................ 10
Table 1.3 Hydrogen Demand in Indonesia and GDP .......................................... 12
Table 1.4 Economic Elasticity and Growth ........................................................ 13
Table 1.5 Calculation of Hydrogen Demand in Indonesia ................................... 13
Table 2.1 Comparison of Electrolysis Type ........................................................ 15
Table 2.2 Nafion 117 Advantages ...................................................................... 17
Table 3.1 Overall Mass Balance ......................................................................... 42
Table 3.2 Tee Mass Balance............................................................................... 43
Table 3.3 Separator Mass Balance ...................................................................... 43
Table 3.4 Electrolyzer Mass Balance.................................................................. 44
Table 3.5 Overall Energy Balance ...................................................................... 44
Table 3.6 Tee Energy Balance............................................................................ 45
Table 3.7 Separator Energy Balance ................................................................... 46
Table 3.8 Electrolyzer Energy Balance............................................................... 46
Table 3.9 Pump Energy Balance ........................................................................ 47
Table 3.10 Oxygen Compressor Energy Balance ................................................ 47
Table 3.11 Hydrogen Compressor Energy Balance ............................................ 47
Table 3.12 Raw Material HE Energy Balance .................................................... 48
Table 3.13 Leak Water HE Energy Balance ....................................................... 48
Table 3.14 Hydrogen HE Energy Balance .......................................................... 49
Table 3.15 Oxygen HE Energy Balance ............................................................. 49
Table 4.1 Classification of Hot and Cold Fluid in Power-to-Gas System ............ 51
Table 4.2 Shifted Temperature for the Data from Table 4.1 ................................ 53
Table 4.3 Temperature Interval Heat Balance ..................................................... 54
Table 5.1 Mass Flow of Chilled Water ............................................................... 58
Table 5.2 Electricity Calculation after HEN ....................................................... 59
Table 5.3 Electricity Calculation before HEN .................................................... 60
Table 5.4 Flow of Liquid Nitrogen ..................................................................... 60

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CHAPTER 1
INTRODUCTION

1.1 Background
About 88% of Indonesias power generation is from fossil fuels, which has
led to heavy import dependence and excessive reliance on government subsidies.
In its INDCs submitted to the United Nations Framework Convention on Climate
Change (UNFCCC), Indonesia sets an unconditional target of achieving a 29%
reduction in emissions by 2030 compared to the business as usual scenario. It
targets an additional emissions reduction of 12% conditional on international
support. In order to meet the twin challenges of climate change and energy
security, Indonesia also established the development of clean energy sources as a
national policy directive, aiming to achieve at least 23% energy generation from
renewable sources by 2025 (nearly six times the 2014 baseline of 4%).
In accordance with the government plan which wants to raise
electrification ratio every year, it takes the availability of electricity in sufficient
quantities. Because of the need to increase the electrification ratio, demand of
electricity is also increase. To this end, the Government of Indonesia plans to
build 35,000 MW of renewable power plants in the next 5 years. As the
renewables sector strives to promote a federal energy policy that would encourage
further development of renewable power and attract investment, industry
participants should consider production-based cash grants and feed-in tariffs as
solar and wind approach grid parity in more regions of the country. Currently,
Global Green Growth Institute (GGGI) is in dialogue with various stakeholders in
energy sector proposing renewable energy in some parts of Indonesia. GGGI
seeks to prove commercial viability for incorporating solar PV in Indonesia, and
prove that Feed in Tariff would not be required if diesel sources are replaced by
solar PV in some parts of Indonesia.
In theory and policy, the market for renewable energy should be strong in
Indonesia. There are abundant resources and the governments goal is to develop
the resources to 25% of generation mix. Thereby, solar and wind energy play an
important role. In 2013, solar and wind power had already comprised a high share

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of the electricity supply. In Denmark (34%) and Spain (21%), solar and wind
energy has become the largest source of electricity; also Portugal (>20%), Ireland
(>16%), and Germany (9%) have reached high shares. The total world installed
solar and wind capacity increased from 17,400 MW in 2000 to 318,105 MW in
2013. However, solar and wind energy are fluctuating and intermittent and have to
be balanced for electric grid stability purposes. Consequently, long term and large
capacity electricity storage is required, as well as reserve production capacity. In
Germany, e.g., the residual power capacity is estimated to be 30-60 GW.
Power-to-Gas is the process of converting surplus renewable energy into
hydrogen gas by rapid response electrolysis and its subsequent injection into the
gas distribution network. Most developed countries already own a vast energy
storage infrastructure through the pressurization of existing transmission and
distribution infrastructure. This allows it to be recharged without the need of it
being discharged first, so when the wind blows, this can be taken and used to top
up storage, this is critical for storing renewable energy which is intermittent in its
generation.
Among the increase of energy demand in Indonesia, one of which in need
is hydrogen. Hydrogen gas is one that has many functions in the industrial world.
But in fact, the production of hydrogen in Indonesia still have not been able to
cover the needs of the industrial market, thus resulting the government must
import hydrogen from abroad to meet domestic demand. Until now, the
manufacture of hydrogen in Indonesia is still using natural gas. When viewed by
reserves, natural gas will be exhausted over time and thereafter we must look for
other sources to produce hydrogen. By using power-to-gas system, electricity used
to split water into hydrogen and oxygen by means of electrolysis. Hydrogen
produced from this process can be used to supply the needs of hydrogen in the
industrial sector.

1.2 Basic Theory


1.2.1 Power-to-Gas System
Power-to-gas (P2G) involves transferring excess energy from the power
system to the gas grid (or a gas-consuming industrial process) in the form of

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electrolytic hydrogen. This is distinct from power-to-power (P2P) storage, where


the excess energy is stored and subsequently discharged back into the power
system. The amount of hydrogen generated by a P2G plant that can be injected
into the gas grid at any given time is limited by the need to ensure the mixture
concentration always complies with the safety limits associated with gas
distribution, storage and combustion.
In this context, there has been widespread discussion of the power-to-gas
(P2G) process whereby electrical energy can be converted to hydrogen (H2),
stored, and recovered at a later time through combustion to generate low-carbon
electricity and/or heat. The P2G process not only helps avoid waste of renewable
energy in electrical system due to system constraints, but also realizes the two-
way coupling for the integrated gas and electrical systems. Surplus renewable
energy due to system constraints in electricity systems can be utilized to produce
hydrogen by the P2G process. From the perspective of long-term operation, the
benefits of P2G are investigated in terms of wind curtailment and carbon
emissions displacement, economic cost-saving, and congestion relief in both the
gas and electrical networks. The chemical process of P2G can be described as:
2H2O 2H2 + O2
In the first step, gaseous hydrogen is formed by the process of electrolysis
with certain efficiency. The technology of proton exchange membrane (PEM) is
considered to be favorable for the P2G process due to its faster ramping rates,
which can better accommodate solar power fluctuations. H2 generated in the first
step can be stored for usage later. P2G facilities can be considered as gas supplier
using solar power with a certain efficiency.
The concept of P2G was first established in 2009 by Dr. Michael Sterner
who investigated a new concept for storing and balancing surplus renewable
power for his dissertation at Kassel University in Germany. He recognized that
the full potential of renewable generation goes beyond the electrical power grid to
impact the heat and transport energy systems as well and that hydrogen gas
derived from electrolysis was the ideal energy carrier.
Simply stated, P2G provides a service enabling the power grid operator to
integrate large amounts of surplus renewable generation when it is not needed and

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provides options to store and transport this energy as renewable hydrogen. Power-
to-Gas provides unparalleled scale of energy storage and enhances system
flexibility. In its comprehensive review of Power-to-Gas, the SBC Energy
Institute examined the technical and economic basis for hydrogen-based energy
conversion and storage. (Decourt et al., 2014).
Electrolyzers (ELY) convert electricity to hydrogen, which can be stored
and transformed back into electricity via fuel cells (FC) later. These processes are
often called P2G and re-electrification, respectively. Hydrogen originating from
renewable energy sources (via electrolysis) can play a major role in decarbonizing
the transport sector, since it can be used as a fuel. However, operating electrolysis
profitably with renewable energy is challenging. Fuel cells (FC) and electrolyzers
are among the technology options which are able to reduce the forecast error
power by supplying electric energy (FC) or transforming surplus energy (ELY)
into hydrogen, thereby reducing both negative forecast deviations (FC) and
positive deviations (ELY).

1.2.2 Excess PV Power


Photovoltaics (PV) covers the conversion of light into electricity using
semiconducting materials that exhibit the photovoltaic effect, a phenomenon
studied in physics, photochemistry, and electrochemistry. A typical photovoltaic
system employs solar panels, each comprising a number of solar cells, which
generate electrical power. The first step is the photoelectric effect followed by an
electrochemical process where crystallized atoms, ionized in a series, and generate
an electric current. PV Installations may be ground-mounted, rooftop mounted or
wall mounted.
Solar PV generates no pollution. The direct conversion of sunlight to
electricity occurs without any moving parts. Photovoltaic systems have been used
for fifty years in specialized applications, standalone and grid-connected PV
systems have been in use for more than twenty years. They were first mass-
produced in 2000, when German environmentalists and the Eurosolar organization
got government funding for a ten thousand roof program.

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Photovoltaics are best known as a method for generating electric power by


using solar cells to convert energy from the sun into a flow of electrons. The
photovoltaic effect refers to photons of light exciting electrons into a higher state
of energy, allowing them to act as charge carriers for an electric current. The
photovoltaic effect was first observed by Alexandre-Edmond Becquerel in 1839.
The term photovoltaic denotes the unbiased operating mode of a photodiode in
which current through the device is entirely due to the transduced light energy.
Virtually all photovoltaic devices are some type of photodiode.
Photovoltaic power generation employs solar panels composed of a
number of solar cells containing a photovoltaic material. Materials presently used
for photovoltaics include monocrystalline silicon, polycrystalline silicon,
amorphous silicon, cadmium telluride, and copper indium gallium
selenide/sulfide. Copper solar cables connect modules (module cable), arrays
(array cable), and sub-fields. Because of the growing demand for renewable
energy sources, the manufacturing of solar cells and photovoltaic arrays has
advanced considerably in recent years.
Solar photovoltaics power generation has long been seen as a clean energy
technology which draws upon the planets most plentiful and widely distributed
renewable energy source, the sun. The technology is inherently elegant in that
the direct conversion of sunlight to electricity occurs without any moving parts or
environmental emissions during operation. It is well proven, as photovoltaic
systems have now been used for fifty years in specialized applications, and grid-
connected systems have been in use for over twenty years.
When the sun shines at its brightest, many of homes with rooftop
photovoltaic (PV) solar panels generate more electricity than they use. When this
happens, excess electricity is exported to the grid. Since hydrogen gas is not found
on Earth, it must be manufactured. There are several ways to do this. Industry
produces the hydrogen it needs by a process called steam reforming. High-
temperature steam separates hydrogen from the carbon atoms in methane (CH 4).
The hydrogen produced by this method isnt used as a fuel, but for industrial
processes. This is the most cost-effective way to produce hydrogen today, but it
uses fossil fuels both in the manufacturing process and as the heat source.

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Another way to make hydrogen is by electrolysissplitting water into its


basic elementshydrogen and oxygen. Electrolysis involves passing an electric
current through water to separate the atoms. Hydrogen collects at the cathode and
oxygen at the anode.
Hydrogen produced by electrolysis is extremely pure, and electricity from
renewable sources can power the process, but it is very expensive at this time.
Today, hydrogen from electrolysis is 12 times more costly than natural gas and
1.5 times more costly than gasoline per Btu. On the other hand, water is abundant
and renewable, and advances in renewable electricity could make electrolysis a
more attractive way to produce hydrogen in the future.

1.2.3 Application of H2 and O2


1.2.3.1 Hydrogen
Hydrogen is the simplest element known to exist. An atom of hydrogen
has one proton and one electron. Hydrogen has the highest energy content of any
common fuel by weight, but the lowest energy content by volume. It is the lightest
element and a gas at normal temperature and pressure. Hydrogen is also the most
abundant gas in the universe, and the source of all the energy we receive from the
sun. Hydrogen as a gas (H2), however, doesnt exist naturally on Earth. It is found
only in compound form. Hydrogen is also one of the most abundant elements in
the Earths crust. Hydrogen is one of the most promising energy carriers for the
future. It is a high efficiency, low polluting fuel that can be used for
transportation, heating, and power generation in places where it is difficult to use
electricity.
The U.S. Hydrogen Industry currently produces twenty million metric tons
of hydrogen a year. Most of this hydrogen is used for industrial applications such
as refining, treating metals, and food processing. It currently produces around 4
million cubic feet of hydrogen every day. Most of this hydrogen is used for
industrial applications such as refining, treating metals, and food processing.
Liquid hydrogen is the fuel that once propelled the space shuttle and other rockets.
Hydrogen fuel cells powered the shuttles electrical systems, producing pure
water, which was used by the crew as drinking water. In the future, however,

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hydrogen will join electricity as an important energy carrier, since it can be made
safely from renewable energy sources and is virtually non-polluting. It can also be
used as a fuel for zero-emissions vehicles, to heat homes and offices, to produce
electricity, and to fuel aircraft. Cost is the major obstacle.
The first widespread use of hydrogen will probably be as an additive to
transportation fuels. Hydrogen can be combined with compressed natural gas
(CNG) to increase performance and reduce pollution. Adding 20 percent
hydrogen to CNG can reduce nitrogen oxide (NOX) emissions by 50 percent in
todays engines. An engine converted to burn pure hydrogen produces only water
and minor amounts of NOX as exhaust. A few hydrogen-powered vehicles are on
the road today, but it will be some time before you can walk into your local car
dealer and drive away in one. Today 23 hydrogen fuel stations are operating in 4
states, but not all are open to the public. With 20 stations, California has 87
percent of the nations hydrogen fuel stations.
In addition to these uses, hydrogen is also widely used in the industrial
manufacture of fertilizer. Here, the use of hydrogen is by the reaction between the
hydrogen and nitrogen. The results of the chemical reaction of hydrogen with
nitrogen to produce ammonia which is useful as a basic ingredient of fertilizer.
Ammonia is made by the Haber-Bosch process, at a temperature of 370-540 C
and a pressure of 10-1000 atm, using a catalyst Fe3O4. The catalyst serves to
expand the grid and increase the active surface, while the high temperature carried
out to obtain the desired reaction rate.

1.2.3.2 Oxygen
Oxygen is an abundantly found element in the Earths atmosphere. It is an
odorless, colorless and tasteless gas which is absolutely vital for sustaining life on
earth. It is the third most commonly occurring element in the universe after
hydrogen and oxygen. It comprises 21 percent of air in the atmosphere and is part
of the air that people breathe. We breathe oxygen which travels to lungs from
where it is transported to all parts of the body and is used in every cell. Should
there be no oxygen in the air, it would have been impossible for us to survive.
Oxygen is found in the atmosphere, the human body, the sun and oceans.

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Oxygen has numerous important applications in industries ranging from


welding to the chemical and petroleum. The most important use of oxygen is
sustaining life. All living organisms require oxygen to survive. Through aerobic
respiration, energy is generated from food, allowing organisms to carry on with
their daily activities. Oxygen is usually used in health care institutions to aid
breathing in people with respiratory problems.
The main commercial application of oxygen is steel production where
oxygen reacts with steel to remove carbon impurities. Oxygen is also used in
ethylene and methanol production, in oxyacetylene welding, and to oxidize rocket
fuel. Oxygen is essential for all combustion processes, such as burning of fuels
(oil, petrol, natural gas, coal), which heat homes and power vehicles. Fires need
oxygen to burn, and one way to put out fires is to remove oxygen by smothering it
or using carbon dioxide. Oxygen used in various industrial chemical applications.
It is used to make acids, sulfuric acid, nitric acid and other compounds. Its most
reactive variant is ozone. It is applied in assorted chemical reactions. The goal is
to boost reaction rate and oxidation of unwanted compounds. Hot oxygen air is
required to make steel and iron in blast furnaces. Some mining companies use it to
destroy rocks. As well as these uses, oxygen is used by scuba divers,
mountaineers and astronauts. It is also used in glass making, water treatment,
petroleum processing, destroying bacteria, ceramic production, and pulp and
paper production.

1.3 Analysis
1.3.1 Raw Material Analysis
Our Power-to-gas system needs demineralized water as a raw material for
Proton Exchange Membrane (PEM) electrolysis. If there is a mineral in the raw
material, the mineral can damage the membrane and decrease the lifespan of the
membrane. Membrane used in PEM electrolysis is really expensive and by using
water with high concentration of mineral means more operational expend to buy
new membrane once the membrane is damaged.
Our system can get demineralized water by buy it from water treatment
industry or by treating salt water with reverse osmosis system or ion exchange

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system. But, we choose to buy it from the water treatment industry because the
cost of demineralized water is not high compared with the installation and
maintenance of salt water treatment system.

1.3.2 Plant Location Analysis


To select the location, some important factors need to be considered. The
best location of a plant is the location where the unit cost of production and
distribution process will be low and sales of products will be able to generate
maximum profits for the company. Plant location selection is one of the main
factors that determine the success of the plant. We decide to make a scenario that
PV Power Plant will be built in Pontianak so we can make our Power-to-Gas
system also in Pontianak, West Kalimantan.

Figure 1.1 Pontianak, West Kalimantan


There are several analysis why we choose Pontianak as the location of the
PV Power Plant and Power-to-Gas system:
Solar Intensity
Solar energy is potential to be used as an alternative to generate electricity
energy in Pontianak. Pontianak is a city that is located in the Equator so it has the
highest solar intensity. Average of solar intensity in Pontianak is about 5 kWh/m 3
per day. Table 1. 1 shows the comparison of solar intensity in other regions.

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Table 1.1 Average of Solar Intensity


Region Average of Solar Intensity (kWh/m2 per day)
Medan 2.20
Padang 3.28
Palembang 2.40
Bengkulu 3.80
Bogor 2.87
Bandung 3.33
Semarang 3.67
Malang 3.56
Pontianak 5.00
Manado 3.43
Makassar 3.11
Mataram 2.54
Kupang 3.43
(Source: BMKG, 2014)
Transportation and Availability of Raw Material
Demineralized water is available in Pontianak, West Kalimantan. There is
an industry which is selling demineralized water. PT. Kimia Sakti Kalista in
Pontianak is dealing with water and waste water treatment, including water
demineralization. It is an advantage because we will be easy to buy and transport
demineralized water to our Power-to-Gas system.
Topography
Topography in Pontianak is flat so it is easy to build PV Power Plant and
Power-to-gas system. It also makes the raw material easier to be transported.
Pontianak is suitable for our plant so there is no need in land area modification.
Labor

Table 1.2 Pontianak Human Resource Availability


Year Total Labor Working Job Less
2012 356,087 337,791 18,296
2013 350,084 329,119 20,685

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Table 1.2 Pontianak Human Resource Availability (contd)


Year Total Labor Working Job Less
2014 376,824 351,953 24,781
(Source: Badan Pusat Statistik, 2015)

1.3.3 Capacity and Market Analysis


In this section, we will predict the capacity and market analysis, especially
about the hydrogen demand in Indonesia. Our capacity of photovoltaic power
plant is determined by benchmarking with other Concentrated Solar Power (CSP)
plant in another country. The largest CSP plant in the world is in China with
capacity of 578 MW. This plant is built in land which area is 13 km2 with solar
intensity of 2.33 kWh/m2. We found that there is a suitable land in Pontianak
which area is 9 ha that can be used for our photovoltaic power plant. This area is
located in Central Siantan, North Pontianak. With this area, we can build
photovoltaic power plant with capacity of 9 MW.
kWh
9 ha 5 578 MW
PV Power Plant Capacity = m2 = 9 MW
2 kWh
13 km 2.33 2
m

Figure 1.2 Location of Photovoltaic Power Plant and P2G


With our photovoltaic power plant, we can make electrical energy about
45 MWh every day by heating the photovoltaics cell. By using 54 kWh of

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electricity, 1 kg of hydrogen can be produce by electrolysis of 9.1 kg water every


day and there is also a by-product which is 8.1 kg oxygen. With our photovoltaic
power plant capacity, our P2G can produce 744 kg of hydrogen by electrolysis of
6,648 kg water every day and there is also a by-product which 5,904 kg of
oxygen. Both of the product and by-product which are get from electrolysis of
water are pure components so it can be sold easily at high cost. From the
calculation before, we can conclude that our P2G capacity is 245.52 ton of
hydrogen every year.
744 kg H2 330 day 245.52 ton H2
Capacity = =
day year year
Although the hydrogen from electrolysis is mostly used for source of clean
energy, we choose to sell our hydrogen for industries that needed hydrogen as a
raw material. Demand of hydrogen in Indonesia as a raw material industry is still
high. With our P2G capacity, we can know how much of hydrogen demand that
can be filled with our P2G.
First of all, our photovoltaic power plant and P2G system are scheduled to
be built in 2017 with an estimated construction time is one year, so it will be able
to operate in 2018. From this information, we can estimate the hydrogen demand
in few years after our photovoltaic power plant and P2G are built. To find out how
much hydrogen demand in Indonesia, we have to know a few things, such as the
amount of hydrogen demand in Indonesia, Gross Domestic Product (GDP),
economic elasticity, and economic growth.

Table 1.3 Hydrogen Demand in Indonesia and GDP


Year Demand (ton) Demand GDP (IDR Billion) GDP
2007 23,681.00 18,409.40
2008 26,405.00 2,724.00 21,494.10 3,084.70
2009 28,522.00 2,117.00 25,989.00 4,494.90
Table 1.3 shows the hydrogen demand and GDP. All of these factors
always increase every year. We can use this data to calculate the economic
elasticity and economic growth. Table 1.4 shows the calculation.
Demand GDP
Elasticity = (1-1)
Demand GDP

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GDP
Growth = 100% (1-2)
GDP

Table 1.4 Economic Elasticity and Growth


Year Elasticity Growth
2007 - -
2008 0.72 14.35
2009 0.43 17.30
We can assume the elasticity and growth for several years ahead will be
stable on the value of 0.57 for economic electricity and 15.82% for economic
growth. The economic elasticity and growth will give impact directly to electricity
demand in Pontianak. By make them stable, we can calculate the electricity
demand in Pontianak.

Table 1.5 Calculation of Hydrogen Demand in Indonesia


Year Demand (ton) Demand Elasticity GDP (IDR Billion) GDP Growth
2007 23,681.00 - 18,409.40 -
2008 26,405.00 2,724.00 0.72 21,494.10 3,084.70 14.35
2009 28,522.00 2,117.00 0.43 25,989.00 4,494.90 17.30
2010 30,651.15 2,129.15 0.57 30,101.34 4,112.34 15.82
2011 32,792.52 2,141.37 0.57 34,864.39 4,763.05 15.82
2012 34,946.19 2,153.66 0.57 40,381.12 5,516.73 15.82
2013 37,112.21 2,166.03 0.57 46,770.78 6,389.66 15.82
2014 39,290.67 2,178.46 0.57 54,171.50 7,400.72 15.82
2015 41,481.63 2,190.96 0.57 62,743.27 8,571.77 15.82
2016 43,685.17 2,203.54 0.57 72,671.38 9,928.11 15.82
2017 45,901.36 2,216.19 0.57 84,170.45 11,499.07 15.82
2018 48,130.27 2,228.91 0.57 97,489.07 13,318.62 15.82
2019 50,371.97 2,241.70 0.57 112,915.14 15,426.07 15.82
2020 52,626.54 2,254.57 0.57 130,782.14 17,867.00 15.82
2021 54,894.05 2,267.51 0.57 151,476.31 20,694.16 15.82
2022 57,174.57 2,280.52 0.57 175,444.99 23,968.68 15.82

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Table 1.5 Calculation of Hydrogen Demand in Indonesia (contd)


Year Demand (ton) Demand Elasticity GDP (IDR Billion) GDP Growth
2023 59,468.19 2,293.61 0.57 203,206.33 27,761.34 15.82
2024 61,774.97 2,306.78 0.57 235,360.45 32,154.12 15.82
2025 64,094.99 2,320.02 0.57 272,602.45 37,242.00 15.82
2026 66,428.32 2,333.34 0.57 315,737.39 43,134.94 15.82
2027 68,775.05 2,346.73 0.57 365,697.74 49,960.35 15.82
2028 71,135.25 2,360.20 0.57 423,563.51 57,865.77 15.82
2029 73,509.00 2,373.75 0.57 490,585.60 67,022.09 15.82
Table 1.5 shows the hydrogen demand in Indonesia. It shows that our
hydrogen capacity is still small compared to the demand in Indonesia. From this
table, we can calculate the market share of our hydrogen which is just 0.48% in
2019 and 0.33% in 2029.
H2 capacity 245.52 ton
Market share = 100% = 100% = 0.33%
H2 demand 73,509 ton

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CHAPTER 2
PROCESS SELECTION

2.1 Alternative Process & Selection


2.1.1 Alternative Process
Process of power to hydrogen gas system consist of electrolysis and gas-
water separation. These is comparison of advantages and disadvantages for
electrolysis types:

Table 2.1 Comparison of Electrolysis Type


Electrolysis Advantages Disadvantages
Type
Proton Solid electrolyte membrane is The membrane (solid
Exchange very thin, allowing for a shorter electrolyte) is more expensive
Membrane proton transport pathway and than the liquid electrolyte.
(PEM) thus lower ohmic loss.
Electrocatalysts made from the The membrane is a thin and
elements of the platinum group sensitive foil that can be
metal (PGM) enable high mechanically damaged by
efficiency and fast kinetics. inappropriate cell design and
operation.
Since the electrode is coated as Chemical degradation may
thin layer directly on the occur depending on the used
membrane, the proton transport materials
from the reaction sites to the
solid electrolyte is facilitated,
which minimizes the mass
transport limitation.
The electrolyte is immobilized The corrosive nature of the
in the membrane and cannot be membrane requires more
leached out of the membrane or expensive metal components for
contaminate the produced BPP, CC and PGM
gases. electrocatalysts.

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16

Table 2.1 Comparison of Electrolysis Type (contd-1)


Electrolysis Advantages Disadvantages
Type
Proton The membrane provides high The electrodes are mostly
Exchange gas tightness (active cell area catalyst systems with structures
Membrane wider than AEM is 10 - 750 at the nanoscale that requires a
(PEM) cm). comprehensive understanding
for a high electrochemical
durability.
The cell design is very compact Only filter press design that
resulting in low thermal masses cant use for high voltaic.
and fast heat-up and cooling-off
times and in combination with
the fast kinetics of the
electrocatalysts, in a very fast
response time even at ambient
conditions.
Simpler system design. Higher pressure tightness than
AEM (up to 207 bar).
Demineralized water only can
be fed of this system.
Just can be used for density up
to 2.5 A/cm @ 2.2 V.
Anion The membrane (liquid Active cell area is less than 4.0
Exchange electrolyte) is cheaper than the m which is low high tightness.
Membrane solid electrolyte.
(AEM) The membrane tougher than Liquid electrolyte membrane is
PEM for mechanically damaged not allowing for a shorter proton
of operation condition. transport pathway and thus
lower ohmic loss.
Bipolar filter press design Unit operation needed to
(several 100 cells) that can use separate the alkaline from water.
for high voltaic.

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Table 2.1 Comparison of Electrolysis Type (contd-2)


Electrolysis Advantages Disadvantages
Type
Anion Lower pressure than PEM Just can be used for density 0.2-
Exchange (atmospheric - 30 bar). 0.45 A/cm @ < 2.4 V.
Membrane Water (not demineralized
(AEM) water) can be fed to this system.
Compression and fine
purification.
High Bipolar construction. No commercial product.
Temperature No pressurized stacks. Cell area: ~ 100 cm.
Electrolysis Only concept.
(HTEL) Coupling with HT source
(nuclear reactor) which is
dangerous.
Electricity generation with
steam turbine can cause
environmental harm.
(Source: www.wtert.eu, 2012)
In PEM electrolysis, a perfluorosulfonic acid membrane (PFSA) is used as
a solid electrolyte. This the following membrane product that can be used for
PEM electrolysis:

Table 2.2 Nafion 117 Advantages


Membrane Type Advantages
Polymer Membrane, Excellent chemical stability.
example: PFSA (Nafion High proton conductivity (0.15 S/cm at 80 C).
NR-117), heterocycles, Area specific resistance of about 0.15 cm2.
sulfonated aromatics Higher area-specific resistance.
Low crossover.
High mechanical strength.
The ability to work at high temperature (>100C).

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Table 2.2 Nafion 117 Advantages (contd)


Membrane Type Advantages
Composite membrane Excellent chemical stability.
(polymer and inorganic High proton conductivity (10 -5-10-3 S/cm at 0-200 C
membrane combination), and 10-3-10-2 S/cm at >200 C).
example: Nafion/HPA, High specific resistance.
Nafion/PBI-H3PO4, Low crossover.
sulfonated aromatics/ High mechanical strength.
hygroscopic oxides The ability to work at high temperature (>100 C).
(Source: www.wtert.eu, 2012)

2.1.2 Selection Process


Based on the advantages and disadvantages which describe before, process
selected is PEM electrolysis. PEM needed demineralized water that cheap enough
compared to constructing additional unit operation for separate alkaline for AEM.
While HTEL has more disadvantages than advantages and only concept (lab
scale), this process can be eliminated. Selected membrane is polymer membrane
because it has higher proton conductivity in low temperature.

2.2 Process Description


2.2.1 Feed Preparation
Feed of P2G system is only demineralized water. After careful
consideration, we decided that were going to buy our demineralized water from a
partner corporation given that our production rate is not that high thus buying
demineralized water from a third party would definitely cost less than buying the
contraption necessary (Reverse Osmosis Demineralizer) to demineralize it
ourselves.

2.2.2 Electrolysis of Water


Electrolysis is an electrochemical process in which electrical energy is the
driving force of chemical reactions. Substances are decomposed, by passing a
current through them. The first observation of this phenomenon was recorded in

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1789. Nicholson and Carlisle were the first who developed this technique back in
1800 and by the beginning of the 20th century, there were already 400 industrial
water electrolysis units in use.
As mentioned before, water is decomposed to hydrogen and oxygen, by
passing a current through it in the presence of suitable substances, called
electrolytes. Electric current causes positively charged hydrogen ions to migrate
to the negatively charged cathode, where a reduction takes place in order to form
hydrogen atoms. The atoms formed then combine to form gaseous hydrogen
molecules (H2). On the other hand, oxygen is formed at the other electrode (the
positively charged anode). The stoichiometry of the reaction is two volumes of
hydrogen to one volume of oxygen. The most important part of the construction of
electrolysis units is to use adequate electrodes to avoid unwanted reactions, which
produce impurities in the hydrogen gas. Another necessary component of such a
unit is a separating membrane that allows the passage of ions, or electrons and not
oxygen, or hydrogen atoms. This membrane allows the gases to be kept separate
in order to avoid the risk of an explosive mixture being formed in the electrolysis
unit.
Electrolysis is considered as the cleanest way to produce hydrogen, when
the required electricity is derived from renewable energy sources. In countries
with a lot of waterfalls, hydroelectricity can be used as the energy source for water
electrolysis. Other renewable sources that could be used for supplying electrolysis
units are solar energy. Photo electrolysis, in which the photovoltaic cells are also
electrodes that decompose water to hydrogen and oxygen gas could be used for
the production of hydrogen. These technologies could be used in order to store
energy as hydrogen, which can be transformed to electricity in fuel cells, when the
natural source of energy is not available. The production of hydrogen through
electrolysis using renewable energy sources has the smallest impact on the
environment.

2.2.2.1 Thermodynamic of Water Electrolysis


The electrolysis of water is considered a well-known principle to produce
oxygen and hydrogen gas. In the figure below, a schematic of an electrochemical

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cell is presented. The core of an electrolysis unit is an electrochemical cell, which


is filled with pure water and has two electrodes connected with an external power
supply. At a certain voltage, which is called critical voltage, between both
electrodes, the electrodes start to produce hydrogen gas at the negatively biased
electrode and oxygen gas at the positively biased electrode. The amount of gases
produced per unit time is directly related to the current that passes through the
electrochemical cell. In water, there is always a certain percentage found as ionic
species; H+ and OH- represented by the equilibrium equation.

Figure 2.1 Sketch of an Electrochemical Cell


(Source: Symes, D.R., 2015)
The overall equation of the basic water splitting reaction is noted as below:
2H2O 2H2 + O2

The model below determines the Gibbs free energy of reaction ( )


from the specific heat capacity and gases in the ideal state:
0 0 0 1

= [ + + ] (2-1)
0 0 0

Where G and H are the Gibbs energy and standard enthalpy of formation
respectively, of liquid water at reference temperature T 0.
Enthalpy (H) is an intrinsic property of a material that is a function of
temperature and pressure, thus H(T) is the total amount of energy that has to be
supplied to an electrolysis cell in order to split water molecules according to the
reaction above. Gibbs free energy (G) is defined as the net internal energy
available to work, therefore less work is done by changes in temperature and
pressure, therefore the change of Gibbs free energy G(T) represents the amount
of electrical energy. Meanwhile, TS(T) represents the amount of heat, which
have to be supplied to an electrolysis cell to drive the water splitting reaction.

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In electrolysis, the energy is supplied to the cell by heat (Q) and electrical
energy (Welec). The relationship between enthalpy, energy input and Gibbs free
energy is shown in the equation below:
() = + = () + () (2-2)
where T is temperature and S is change in entropy. By considering the change in
the functions above, the overall change in Gibbs free energy and the operating
potential can be calculated.
At standard temperature and pressure (S.T.P., 298 K, 1 atm), Gibbs free
energy of formation represents the thermo-neutral voltage and is where hydrogen
and oxygen are produced with 100% thermal efficiency. To enable electrolysis
mode, the voltage must be greater than the voltage corresponding to zero current
(open circuit voltage (OCV)). It is determined by the variation in Gibbs free
energy of formation between reactants and products. As previously mentioned,
Gibbs free energy varies with temperature and state (gas or liquid). The equation
below shows this relationship:

= (2-3)

and

= (2-4)

where E is the theoretical minimum reversible potential of an electrolysis cell,
Vrev is the minimum applied cell potential for starting a water splitting reaction is
represented by the reversible voltage, z is the number of electrons transferred in
the reaction, and F is the Faraday constant (96,485 Coulomb mol-1).
At S.T.P., the Gibbs free energy of formation of water is +237.2 kJ mol-1 ;
therefore, E is 1.23 V. It is the minimum voltage required to split water. Ignoring
heat transfer in the system, the total enthalpy required must be provided by the
inputted electrical energy. In reality however, heat transfer does exist and the
thermo-neutral potential (1.48 V) is required to enable the electrochemical
reaction, as explained in the equation below:

= = + (2-5)

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With Vth being the thermo-neutral voltage, H of 285.84 kJ/mol, and a


temperature T of 298 K.
If the voltage Ecell, which is applied to the electrolysis cell, is higher than
Vrev but lower than Vth water, splitting just takes place by absorbing heat from the
environment as the cell dissipates the heat associated with the change in entropy
irreversibly. If Ecell = Vth, the Joule heat generated within the electrolysis cell
equals the heat consumption of the endothermic electrolysis reaction and
therefore, no heat exchange with the environment would be required. If E cell > Vth,
the electrolysis cell produces surplus heat due to joule heating and has to be
properly cooled in order to reduce degradation of the system.
The operating temperature and pressure are important parameters for
electrolyzer systems and have to be carefully chosen. Figure 2.3 shows the
temperature dependence of the particular energy demands and the corresponding
cell voltages for water electrolysis from a pure thermodynamic point of view. Due
to vaporization of water at 373 K the total energy demand (H resp. V th) curve is
discontinuous and remains almost unchanged within a particular state of matter.
The figure clearly shows that if steam is available as feedstock, steam electrolysis
requires less energy compared to liquid water electrolysis. The electrical energy
demand (G resp. Vrev) continuously decreases with increasing temperature
resulting in a ~30 % reduction by switching from 273 to 1,273 K.

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Figure 2.2 Water electrolyzer thermodynamics and cell voltage


(Source: Dorf, 2004)
The real potential (Ecell) needed to split water at a reasonable rate will
require Ecell to be greater than Eo. The difference between the two is known as
overpotential, losses or polarization. The Nernst potential (V n) accounts for the
changes in the activity of the reaction and is shown in the equation below:
1
2 22
= + ln ( ) (2-6)
2 2

where 2 , 2 and 2 , are the partial pressures of hydrogen, oxygen and water
respectively.
In practice however, as previously mentioned, hydrogen evolution does
not occur at the reversible potential (1.23 V). This is the result of resistances
(overpotential) in the electrolysis system. These resistances in the process mean a
higher potential is required to split water in order to overcome these barriers. An
electrical circuit analogy can be used to illustrate the various resistances
encountered during the electrolysis process, as shown in the figure 2.3.

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Figure 2.3 Electrical Circuit Analogy of Water Electrolysis


(Source: Symes, D.R., 2015)
where
= 1 + 1 + ,2 + ,2 + +
(2-7)
+ +
The three main types of resistance in the electrolysis cell are electrical,
transport and electrochemical reaction resistances:
Electrical resistances
Electrical resistances (R1 & R1) directly result in heat generation which
points to waste electrical energy in the form of heat according to Ohms law. In
water electrolysis, the resistances in electrical circuits. The resistances of the
electrodes and connecting circuits are determined by the material types and
dimensions, preparation methods, and the conductivities of each component. It
can be expressed as follows:
1
= (2-8)

where is the electrical conductivity ( -1 m-1 ), subscript g represents each
component of the circuit, which includes wires, connectors and electrodes. These
items can be improved by decreasing the length of wire, using a higher surface
area of electrode and using a material with higher electrical conductivity.
Transport resistances
Transport resistances (,2 , ,2 , & ) are
physical resistances such as gas bubbles covering the electrode surface,
resistances to ionic transfer of species in the electrolyte, and due to resistance of
ion flow in the membrane. These losses are known as ohmic loss. Mass transfer,
temperature distribution and bubble sizes, are determined by the viscosity and the
flow field of the electrolyte. Other parameters affected include: bubble
detachment and rising velocity, of which all functions are transport related

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resistances. It is important to note, that during electrolysis the concentration of


electrolyte increases (since water is being consumed), and therefore the solution
will become increasingly viscous; therefore, resulting in a rise in transport related
resistances.

Figure 2.4 Potential Losses Contributions from Water Electrolysis


(Source: Symes, D.R., 2015)
Electrochemical resistances
Electrochemical reaction resistances (Ranode and Rcathode), also known as
activation losses, are overpotentials required to overcome the activation energies
on the cathode and anode surface for the formation of hydrogen and oxygen
respectively. These are inherent energy barriers of the reactions and determine the
reaction kinetics of the electrochemical reaction.

2.2.2.2 Electrolysis Efficiencies


In electrolysis, there are many forms of efficiency measurements. The
efficiency of an electrolysis cell is inversely proportional to the cell voltage,
which is dictated by the current density. The current density is also directly
correlates to the hydrogen productivity per unit electrode surface area.
It is commonly seen that higher potentials result in higher rates of
hydrogen production, however, this results in low efficiencies. As a result of this,
commercial electrolyzers usually operate around 2 V, which maximizes the
electrolyzer efficiency, where hydrogen output is not as important as the overall
electrolysis efficiency.

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The system efficiency can be calculated from the electrolysis cell energy
and the ancillary losses. The system efficiency uses the higher heating value
(HHV) of hydrogen (39 kWh/kg), the energy used by the cell (kWh), the DC
power supply efficiency, and the ancillary loads e.g. pumps, values etc. (kWh), as
shown in the equation below:

=

+ (2-9)

( )

where HHV is measured in kWh/kg, cell input energy and ancillary losses are in
kWh, and hydrogen produced is measured in kg. To calculate the cell efficiency,
the Nernst equation can be used to calculate the theoretical cell potential and then
the cell efficiency can be calculated from the equation below:

= (2-10)

Voltage efficiency allows the measurement of effective voltage to split
water in the total voltage applied to the whole electrolysis cell. This is shown in
the equation below:
( )
= (2-11)

where Ea and Ec are the potential of the anode and cathode respectively.
Two other types of efficiency measurement of electrolysis reactions,
which are based on energy changes in the system, are the Faraday Efficiency and
the Thermal Efficiency. They used Gibbs free energy and enthalpy of the water
splitting reaction respectively. Both use the theoretical open-circuit energy
requirement plus ancillary losses as the energy input, as shown in the equations
below:

= = (2-12)
+
and

= = (2-13)
+
The Faraday efficiency is the percentage of theoretical energy needed for
water to decompose in the actual cell potential. In contrast, the thermal efficiency

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defines that additional cell potential is required, above the open-circuit voltage, to
maintain the thermal balance throughout the reaction. Theoretically, this means
that if the reaction is occurring endothermic, then the thermal efficiency may
exceed 100% (heat being consumed from the environment).
The Faraday efficiency will always be less than 1, because there are
always resistances (losses) in an electrochemical system. Thermal efficiency can
be higher than 1, if the cell potential is between the open-circuit voltage and the
thermo-neutral voltage.
Another type of efficiency calculation is the measurement of hydrogen gas
output from the electrolysis cell in terms of the total electrical energy applied to
the system. These are with respect to the HHV of hydrogen and the hydrogen
production rate, as shown in the equation below:
2
(2-14)
= =

where E is the cell energy input (kJ), V is the hydrogen productivity per unit
volume (m3/m3h), U is the cell potential (V), i is the current (A), and t is the time
(s). Alternatively, the yield of hydrogen produced can be measured in terms of
electrical energy input, as shown in the equation below:
283.8
= = (2-15)

where 283.8 kJ is the HHV of one mole of hydrogen and time t, corresponds to
the time required to produce one gram of hydrogen.
Lastly, energy efficiency can also be calculated by subtracting the energy
losses (sum of resistances) from the energy input. This is shown in the equation
below

= 1 (2-16)

Applying the equation above allows the identification of high resistance
locations in the electrolysis cell, which need to be improved. A method for
increasing efficiency is to lower these resistances which contribute a significant
amount to the overall resistance of the electrolysis cell. This can include electrode

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materials with a lower activation overpotential, and the movement of electrodes


together to reduce ohmic resistance.

Figure 2.5 Effect of Temperature on Overpotential of Cathode and Anode


(Source: Symes, D.R., 2015)
Another way is to thermodynamically reduce the energy needed for water
splitting, whilst maintaining a high hydrogen yield. This can be achieved by
increasing the temperature and/or pressure. The temperature of reaction,
electrolyte type and properties, as well as electrode materials, has huge
implications on the performance of the electrolysis reaction, as shown in figure
2.5.

2.2.2.3 Electrolyzer Layout


Traditionally, electrolysis cells do not produce a sufficient output of
hydrogen for most applications. Therefore, a number of electrolysis cells are
electrically connected in series to produce a higher yield of hydrogen. This is
called stacking. Most electrolyzers produced consist of more than one cell, and are
called the electrolysis, or electrolyzer stack.
There are two basic designs of these electrolyzer stacks, unipolar and
bipolar. In the unipolar design, shown in the figure below, the electrodes (cathode

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and anode) are held apart by microporous separators which are alternatively
suspended in a tank filled with the water-based solution. The positive electrodes
are all coupled together in parallel, as are the negatives.

Figure 2.6 Unipolar Electrolyzer Layout


(Source: Symes, D.R., 2015)
It is the oldest design of electrolysis stacks, due to its simplicity and it
requires relatively few parts. Any damage to individual electrolysis cells can be
easily located, removed and repaired, before being inserted back into the stack.
The remaining cells can continue operation while the maintenance is occurring,
since the electrical energy supply and gas remove is separate for each individual
cell.
The unipolar stack, due to its design, does limit the electrochemical
performance of the stack. This design suffers from low current densities however
it can operate at lower temperatures.
The bipolar (filter-press) design, shown in the figure 2.7, consists of
alternative layers of electrodes (cathode and anode), and separation membranes
that are clamped together. This configuration uses metal sheets (bipoles) to join
adjacent cells. These bipoles make one face of the metal sheet act as the negative
electrode, and the other face, the positive electrode. The electrolysis cells are

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connected in series to produce higher stack potentials. Therefore, only the end
plates of the stack are connected to the positive and negative DC power supply.
These cells are relatively thin, so have a smaller footprint that the unipolar
design. The bipolar design also operates at higher current densities, and has the
capability to produce higher pressure gas. When a problem with the stack arises
however, the whole stack is under shutdown i.e. the individual cell(s) cannot be
repaired without servicing the whole stack.

Figure 2.7 Bipolar Electrolyzer Layout


(Source: Symes, D.R., 2015)
The main differences between the two designs are that, in the unipolar
design, each half reaction takes place on both sides of the electrode. Whilst with
the bipolar design, the Hydrogen Evolution Reaction (HER) takes place on one
side of the electrode, and the Oxygen Evolution Reaction (OER) takes on the
other side simultaneously. This happens on all electrodes which are not connected
to the DC power supply.

2.2.2.4 Bubble Dynamic


The key purpose of water electrolysis is to produce hydrogen and oxygen
gases. These gases evolve in the form of bubbles on the surfaces of the cathode
and anode respectively. The bubbles maintain contact on the electrode surface

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until the bubble grows large enough to produce a buoyancy force, greater than the
interfacial tension holding the bubble to the electrode. When this occurs, the
bubble discharges from the surface of the electrode, rises to the surface the water-
based solution, and the bubble collapses to release the hydrogen or oxygen gas.
The attachment of bubbles to the electrode surface adds resistance to the
electrolysis process (the bubble overpotential). The bubble formation reduces the
contact area between the electrodes and electrolyte. This is turn limits the number
of active sites on the surface of the electrodes available for electron transfer, and
hence can be characterized as a transportation issue and thus is an ohmic loss.
Attempts to reduce these resistances include the addition of surfactants to
the water-based solution that decrease the surface tension between the bubbles and
the electrode surface. Other methods include, the mechanical removal of bubbles
from the electrode surface through continuous circulation of the water-based
solution through the electrolysis cell, and modifications to the surface of the
electrode which make it less favorable for bubble formation to occur. This could
however, reduce the productivity of hydrogen and oxygen gas evolution reactions.
The cell operation potential for the designs differs also. For the unipolar
design the stack usually operates at 2.0 V, whereas for the bipolar design the stack
operates, for the same input potential as the unipolar design, 2.0 x (n-1) Volts,
where n is the number of electrodes.

.
Figure 2.8 Schematic of Three Phase Boundary
(Source: Symes, D.R., 2015)

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2.2.3 Power
Photovoltaic (PV) devices generate electricity directly from sunlight via an
electronic process that occurs naturally in certain types of material, called
semiconductors. Electrons in these materials are freed by solar energy and can be
induced to travel through an electrical circuit, powering electrical devices or
sending electricity to the grid.
Photons strike and ionize semiconductor material on the solar panel,
causing outer electrons to break free of their atomic bonds. Due to the
semiconductor structure, the electrons are forced in one direction creating a flow
of electrical current. Solar cells are not 100% efficient in part because some of the
light spectrum is reflected, some is too weak to create electricity (infrared) and
some (ultraviolet) creates heat energy instead of electricity.
The cost of PV has dropped dramatically as the industry has scaled up
manufacturing and incrementally improved the technology with new materials.
Installation costs have come down too with more experienced and trained
installers.
Most modern solar cells are made from either crystalline silicon or thin-
film semiconductor material. Silicon cells are more efficient at converting
sunlight to electricity, but generally have higher manufacturing costs. Thin-film
materials typically have lower efficiencies, but can be simpler and less costly to
manufacture. A specialized category of solar cells - called multi-junction or
tandem cells - are used in applications requiring very low weight and very high
efficiencies, such as satellites and military applications. All types of PV systems
are widely used today in a variety of application
The amount of power needed from the solar cells is depend on the
production capacity of the plant and the electrolyzer itself. If the production
capacity is high, which mean if we want to produce many hydrogen, so it also
needs high amount of energy to do the electrolysis process to convert water into
hydrogen and oxygen. Because of the electrolysis is the main process of our plant,
so if it needs high amount of energy, this means that the overall process in our
plant need high amount energy from the solar cell.

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2.2.4 Gas-Water Separation


Separator is a device used to separate two phases, gas and liquid. In this
case separator used to separate water that is contained in output of anode. The
gas/water separator is positioned above the stack of electrolyzer, above the anode
stack of the electrolyzer. After the water is separated with oxygen, the water in
liquid form can be use again as a feed for the electrolysis process, whereas the
oxygen gas can be transported to the storage and ready for sale.

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2.3 Diagram
2.3.1 Block Flow Diagram (BFD)

Figure 2.9 Block Flow Diagram (BFD)

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2.3.2 Process Flow Diagram (PFD)

Figure 2.10 Process Flow Diagram (PFD)

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2.4 Equipment and Technology Selection


2.4.1 Storage Tank
Storage tanks are containers that hold raw material and compressed gas
(gas tank) used for the short- or long-term storage.

2.4.1.1 Demineralized Water Storage


Our main raw material is demineralized water. This demineralized water is
store in demineralized water tank storage. Generally stainless steel 304 piping is
used for demineralized water. Demineralized water is often called "Hungry
Water" as it rarely contains mineral and demineralized water is a very good
solvent and will corrode the carbon steel. However, by this process demineralized
water quality will degrade. Normal carbon steel easily looses its elements in
demineralized water because of poor corrosion stability and hence stainless steel
used. Even in stainless steel, we have to maintain a minimum flow rate and if
there is any stagnancy, stainless steel can also get pitted and punctured due to
local concentration cell.

2.4.1.2 Oxygen Storage


Once the oxygen is compressed to 137 bar pressure and cooled to ambient
temperature, it is transported to oxygen storage tank. Several probable methods
exist for the oxygen storage: compressed gas tanks, cryogenic compressed liquid
oxygen tanks, metal hydride storage, physical storage, and underground storage
(e.g. salt caverns). Storage of oxygen as a cryogenic liquid is a technical challenge
as well as energetically inefficient. The unstable pressure, continuous leakage of
gas, and expensive insulation, make cryogenic liquid oxygen storage a poor
choice for P2G applications.
Another option for oxygen storage is the physical storage of oxygen in
underground caverns. Although this option is the cheapest option of all storage
methods mentioned here, this storage is better suited for high capacity, long term
oxygen storage. Thus, it is not a viable option for P2G systems, which require
small scale, onsite, and temporary hydrogen storage.
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The two best options for the temporary oxygen storage are high pressure
gas tanks or metallic hydride tanks. According to Gahleitner (2012), oxygen
storage in high pressure gas cylinders is the current and future method of choice.
As an alternative, metal hydride tanks were installed in 12% of the P2G. The
oxygen then will be sold to the consumer that need this pure oxygen.

2.4.2 Pump
Pump is a device that moves fluids by mechanical action. Pump in our
manufacture is used to moves demineralized water from storage tank to
electrolyzer. The condition of demineralized water is at room temperature, so we
use centrifugal selfless magnetic drive chemical pump made up of plastic with
encapsulated impeller. This kind of pump is ideal for applications such as
chemical recirculation and chemical transfer. The standard wet end (the materials
that come into contact with the solution) is composed of Propylene, Viton, and
Ceramic. This pump is capable of handling mildly or highly corrosive chemicals,
acids, and solvents. So, this pump is suitable for our process.

2.4.3 Electrolyzer
An electrolyzer is an electrochemical device to convert electricity and
water into hydrogen and oxygen. The standard membrane material used in PEM
electrolysis is Nafion 117 which is produced by DuPont. Nafion is a co-
polymer of tetrafluorethylene and perfluorinated vinyl-ethersulfonyfluoride.
Perfluorinated sulfonic acid membranes, such as Nafion have proved to be
extremely resistive to the oxidative power of oxygen.

2.4.3.1 Main Cell Components


In PEM electrolysis cells, an acidic membrane is used as a solid electrolyte
instead of a liquid electrolyte. The basic design of such a cell with its main
components is depicted in Figure 2.11. The two half-cells are separated by the
solid acidic membrane, which is commonly called proton exchange membrane or
polymer electrolyte membrane (PEM). Sometimes, the expression solid
electrolyte membrane (SPE) is used as well. In most cell designs, the electrodes
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are deposited directly onto the membrane, creating the key component of a PEM
electrolysis cell, the membrane electrode assembly (MEA). The MEA is
sandwiched between porous current distributors/collectors (current collectors,
CC). In some cell designs, the electro catalysts are coated onto the current
collectors. Following the nomenclature known from fuel cells, this combination is
called gas diffusion electrode (GDE). The current collectors enable an electric
current to flow from the bipolar plates to the electrodes and, simultaneously, the
supply of reactant water to and the removal of the generated gas bubbles from the
electrodes. The bipolar plates encase the two half-cells and provide the electrical
contact to the external power supply. Usually, they include flow field structures to
enhance the transport of liquid water to the electrodes and oxygen and hydrogen
out of the cell. Frames with sealing elements or gaskets tighten the half-cells to
prevent gas and water leakage from the inside to the environment.

Figure 2.11 Simplified Basic Design of a Single Cell in a PEMWE Stack


(Source: Bessarabov et al., 2016)
To yield higher hydrogen flow rates, several single cells are connected
electrically in series and hydraulically in parallel as a stack. In Figure 2.11, a
39

bipolar plate (BPP) separates two adjacent cells, so that it simultaneously acts as
the anode of one cell and the cathode of the adjacent cell. The most common stack
type is the filter press bipolar pressurized cell stack for PEM water electrolysis.
Pressure plates fix the components of the cells and provide the clamping force by
thread bolts and nuts.

2.4.3.2 General System Layout


The PEM stack is the core component of an electrolysis (EL) system to
produce hydrogen and oxygen from water. However, operation of the stack is only
possible with the help of several additional components of the EL module and
further subsystems. The basic layout of a PEM electrolysis system is presented in
Figure 2.11. There is no general standard for a layout of PEM electrolysis
systems, but the figure comprises all relevant components and subsystems of such
a system. It is similar to that of alkaline electrolysis system (Smolinka et al.,
2014). But due to the absence of lye as the liquid electrolyte, components such as
gas scrubbers are not needed and the PEM system is less complex.
An EL system is made up of two layers. The PEM stack itself is the
chemical reactor in which water is decomposed with the help of a DC current into
hydrogen and oxygen. The PEM module comprises all peripheral components to
operate the stack properly at the desired operating conditions (temperature and
pressure) and to provide the stack with the reactants and to remove the products.
The rectifier converts the incoming AC power into a regulated DC current.

2.4.4 Heat Exchanger


We have four heat exchanger in this P2G system. First heat exchanger (E-
101) is used to preheat the demineralized water. Demineralized water should be
preheated before enter the electrolyzer to reduce the energy demand of
electrolysis. Heat from this heat exchanger is from hydrogen output of the
compressor because hydrogen from compressor have high temperature. Other
three heat exchangers are used to decrease the temperature of process streams to
ambient temperature. Second heat exchanger (E-102) is installed after separator to
decrease the temperature of water. Installation of this HE is to maintain the
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temperature of electrolyzer input still lower than the condition operation of PEM
electrolyzer. Other heat exchangers are required to decrease the temperature of
oxygen gas and hydrogen gas.

2.4.5 Gas and Water Separator


This separator is to separate both oxygen and demineralized water from
output of the electrolyzer. The top of the output separator is pure oxygen gas. This
oxygen stored in an oxygen storage tank. The bottom of the output separator is
demineralized water that will be the input for electrolyzer.

2.4.6 Compressor
Compressors is required to increase the pressure of H2 up to 200 bar
pressure and O2 up to 137 bar. Compressed hydrogen will be transmitted using
hydrogen pipeline and compressed oxygen will be stored in the oxygen storage
tank. The pressure relief valve is set at 10% higher than operating pressure.

2.4.7 Hydrogen Pipeline


Hydrogen pipeline is installed to transmit our hydrogen gas to the buyer,
which is fertilizer industry in Bontang. Material that is used in hydrogen pipeline
is stainless steel 316L because this material can handle hydrogen gas with high
pressure.
CHAPTER 3
MASS AND ENERGY BALANCE

3.1 Process Simulation


Simulation is done with SuperPro Designer. Raw material for P2G system
with PEM electrolysis is demineralized water. Electrolysis of demineralized water
will have products of pure hydrogen and oxygen. But, there is sometimes a leak at
electrolyzer, so there is still remain of our raw material. We called it leak water.
Leak of raw material doesnt have a specific amount. It is depended on the
performance of the electrolyzer at that moment of process, so we assumed the leak
for our process is 1% weight of the raw material. Because the raw material is only
being feed to the anode, there is no water in the cathode output. So, the output is
just hydrogen. Meanwhile, the output from anode is oxygen and leak water. There
is also no leak of water from the anode to cathode because PEM electrolysis is
using a membrane that can only let H+ to the cathode.
Output of electrolyzer is then being separated. Our separator will separate
the vapor phase and the liquid phase. Oxygen will come out from the top of the
separator whereas water will remove from the bottom. Water from the separator
then mixed with water from storage tank and then will be heated before go to the
electrolyzer. The higher the temperature of the raw material, the energy we used
for electrolysis will decrease. But, we must aware of the change of temperature in
the electrolyzer because we used an external energy from photovoltaic power.
PEM electrolysis cannot operate in temperature higher than 80 C. So, the
temperature we set in heater output is just 45 C. With this temperature, there will
be an increase in temperature in the electrolyzer to 75 C.
Hydrogen from the cathode then being compressed from 15 atm to 200
bar. This is because hydrogen from P2G system will be transmitted and then be
used as a raw material for fertilization. Pressure of hydrogen in fertilization input
is 200 bar. After being compressed, hydrogen then go to heat exchanger to make
its temperature to ambient temperature. Oxygen from separator then being
compressed from 2 atm to 137 atm. This is because oxygen will be used as a raw
material for welding or cutting. Minimum pressure of oxygen for welding or

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cutting is 137 bar. After being compressed, oxygen then go to heat exchanger to
make its temperature to ambient temperature.

Figure 3.1 Power-to-gas System Simulation with SuperPro Designer

3.2 Mass Balance


3.2.1 Overall Mass Balance
From capacity analysis, we will produce hydrogen as main product with
capacity 31 kg/hr. Table 3.1 shows the overall mass balance of our P2G. Overall
input is water with mass flow of 277 kg/h. Overall output are hydrogen with mass
flow of 31 kg/h and oxygen with mass flow of 246 kg/h.

Table 3.1 Overall Mass Balance


Input (kg/h) Output (kg/h)
Stream 1 11 15
H2O 277 0 0
H2 0 0 31
O2 0 246 0
246 31
Total 277
277

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3.2.2 Mass Balance of Each Process


3.2.2.1 Tee
Table 3.2 shows the mass balance of Tee-101. Tee input are water from
Stream-2 and leak water from Stream-8. Tee output are water with mass flow of
279.77 kg/h.

Table 3.2 Tee Mass Balance


Input (kg/h) Output (kg/h)
Stream 2 8 3
H2O 277 2.77 279.77
H2 0 0 0
O2 0 0 0
277 2.77
Total 279.77
279.77

3.2.2.2 Separator
Table 3.3 shows the mass balance of separator. Separator input are water
and oxygen from Stream-5. Separator output are water in Stream-6 and oxygen in
Stream-9.

Table 3.3 Separator Mass Balance


Input (kg/h) Output (kg/h)
Stream 5 9 6
H2O 2.77 0 2.77
H2 0 0 0
O2 246 246 0
246 246 2.77
Total
248.77 248.77

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3.2.2.2 Electrolyzer
Table 3.4 shows the mass balance of electrolyzer. Electrolyzer input are
water Stream-4. Electrolyzer output are hydrogen in Stream-12 and oxygen in
Stream-5.

Table 3.4 Electrolyzer Mass Balance


Input (kg/h) Output (kg/h)
Stream 4 12 5
H2O 279.77 0 2.77
H2 0 31 0
O2 0 0 246
31 248.77
Total 279.77
279.77

3.3 Energy Balance


3.3.1 Overall Energy Balance
Table 3.5 shows the overall energy balance of P2G. Overall energy input
is feed water enthalpy in Stream-1, PV Power, heater, pump, and compressor. On
the other hand, overall energy output obtained from oxygen product enthalpy in
Stream-15, hydrogen product enthalpy in Stream-11, cooler, and heating value of
hydrogen. Electrolyzer output are hydrogen in Stream-112 and oxygen in Stream-
105.

Table 3.5 Overall Energy Balance


Input (kJ/h) Output (kJ/h)
Stream-1 31,236.19 Stream-15 6,080.65
Electrical 6,026,400 Stream-11 11,974.40
Heater 21,022.37 Cooler 215,876.98
Pump 12.10 Loss 3,890,008.65
Compressor 183,029.71
Total 6,261,700.37 4,123,940.68

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Energy output 4,123,940.68


Efficiency = 100% = 100% = 65.86%
Energy input 6,261,700.37
The efficiency of this plant is 65.86%, this value is still included in
interval of P2G plant efficiency of hydrogen production which is 54-72%. The
biggest contributor to the energy produced is the heating value or HV amounting
to 3,890,008.65 kJ/h and a large supply of energy derived from photovoltaic
power is 6,026,400 kJ/h. The second largest energy after photovoltaic power is the
energy requirements of the compressor. There are two compressors used in the
system, the first compressor (C-101) is used to increase the oxygen pressure of 15
atm to 137 atm before entering the cooler with the energy needs of 54,936.35 kJ/h
and second compressor (C-102) increasing the hydrogen pressure of 15 atm up to
200 atm with the energy needs of 128,093.36 kJ/h. So the total energy required by
the compressor is 183,029.71 kJ/h. Meanwhile, for the second largest energy
output is a cooler that is 215,876.98 kJ/h.

3.3.2 Energy Balance of Each Process


3.3.2.1 Tee
Table 3.6 shows the energy balance of Tee-101. Tee input are Stream-102
and Stream-108. Tee output is Stream-103.

Table 3.6 Tee Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 2 8 3
Enthalpy 31,248.291 315.517 31,563.808
Total 31,563.808 31,563.808

3.3.2.2 Separator
Table 3.7 shows the energy balance of separator. Separator input is
Stream-5. Separator output are Stream-6 and Stream-9.

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Table 3.7 Separator Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 5 9 6
Enthalpy 17,873.693 16,997.257 876.436
Total 17,873.693 17,873.693

3.3.2.3 Electrolyzer
Table 3.8 shows the energy balance of electrolyzer. Electrolyzer input is
water in Stream-4. Electrolyzer output are hydrogen in Stream-12 and oxygen
Stream-5.

Table 3.8 Electrolyzer Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 4 12 5
Enthalpy 52,586.178 33,344,146 17,873.693
Electrical 6,026,400 - -
HV and Heat - 5,328,684,93
Total 6,078,986.178 5,379,902.769
Energy output 5,379,902.769
Efficiency = 100% = 100% = 88.5%
Energy input 6,078,986.178
The efficiency of electrolyzer is 88.5%. The same value with the
efficiency electrolyzer generally, such as ITM Power. The high demand for
photovoltaic power mentioned above compared with heating value is
5,328,684.93 heat kJ/h with the calculation of input energy generated from
photovoltaic power and enthalpy of demineralized water at the Stream-4, while
the calculation of the energy output resulting from the enthalpy stream of oxygen
(Stream-5) and stream of hydrogen (Stream-12) were added its heating value and
heat generated due to electrolysis process.

3.3.2.4 Pump
Table 3.9 shows the energy balance of pump P-101. P-101 input is Stream-
1. P-101 output is Stream-2. Work of pump P-101 is difference of enthalpy both
in Stream-1 and Stream-2.

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Table 3.9 Pump Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 1 2
Enthalpy 31,236.19 31,248.291
Work 12.101 -
Total 31,248.291 31,248.291

3.3.2.5 Oxygen Compressor


Table 3.10 shows the energy balance of C-101. C-101 input is Stream-9.
C-101 output is Stream-10. Work of compressor C-101 is difference of enthalpy
both in Stream-9 and Stream-10.

Table 3.10 Oxygen Compressor Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 9 10
Enthalpy 16,997.257 71,933.605
Work 54,936.348 -
Total 71,933.605 71,933.605

3.3.2.6 Hydrogen Compressor


Table 3.11 shows the energy balance of C-102. C-102 input is Stream-12.
C-102 output is Stream-13. Work of compressor C-102 is difference of enthalpy
both in Stream-12 and Stream-13.

Table 3.11 Hydrogen Compressor Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 12 13
Enthalpy 33,344.146 161,437.505
Work 128,093.359 -
Total 161,437.505 161,437.505

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3.3.2.7 Raw Material Heat Exchanger


Table 3.12 shows the energy balance of heat exchanger E-101. E-101 cold
input is Stream-3 and the output is Stream-4. E-101 hot input is Stream-13 and the
output is Stream-14.

Table 3.12 Raw Material HE Energy Balance


Cold Stream Hot Stream
Input (kJ/h) Output (kJ/h) Input (kJ/h) Output (kJ/h)
Stream 3 4 13 14
Enthalpy 31,563.809 52,586.178 161,437.505 140,415.135
Heat 21,022.369 - - 21,022.369
Total 52,586.178 52,586.178 161,437.505 161,437.505

3.3.2.8 Leak Water Heat Exchanger


Table 3.13 shows the energy balance of heat exchanger E-102. E-102
input is Stream-7. E-102 output is Stream-8.

Table 3.13 Leak Water HE Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 7 8
Enthalpy 876.436 315.517
Heat - 560.919
Total 876.436 876.436

3.3.2.9 Hydrogen Heat Exchanger


Table 3.14 shows the energy balance of heat exchanger E-103. E-103
input is Stream-14. E-104 output is Stream-15.

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Table 3.14 Hydrogen HE Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 14 15
Enthalpy 140,415.135 11,974.403
Heat - 128,440.732
Total 140,415.135 140,415.135

3.3.2.10 Oxygen Heat Exchanger


Table 3.15 shows the energy balance of heat exchanger E-104. E-104
input is Stream-10. E-104 output is Stream-11.

Table 3.15 Oxygen HE Energy Balance


Input (kJ/h) Output (kJ/h)
Stream 10 11
Enthalpy 71,933.605 6,080.648
Heat - 65,852.957
Total 71,933.605 71,933.605

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CHAPTER 4
HEAT EXCHANGER NETWORK

Heat exchanger network is needed to optimize and to determine of utilities


system that would be used in this plant. HEN is used to decrease the using of
unnecessary utilities since heat of fluid can be used in purpose to replace utilities.
An overall goal of using the available energy sources in the most efficient way
can be satisfied by optimal heat recovery from different parts of a given process
Good heat recovery from a given process can be achieved through
effective use of heat exchangers. Often, heat exchangers are combined in a heat
exchanger network to distribute the available hot streams effectively. Now that we
have the system requirements, we turn our attention to heat-exchanger network
design and explain how to construct a network that will accomplish the necessary
heat transfer and satisfy the stream data using the least amount of heating and
cooling utilities and the fewest number of heat exchanger units.
To analyze HEN there are two ways. They are Heat Recovery Pinch
Method (Composite Curves and Program Table Cascade), and Pinch Design
Method. In order to use heat recovery pinch method. We have to classify the
stream first.

4.1 Stream Classification


There are several streams in our plants, but only a few streams are
necessary to evaluate the heat transfer. Flow to be evaluated is divided into two
types, namely cold fluid and heat fluid. Cold fluid is the flow of heat that requires
hot utility to increase the temperature. Meanwhile, hot fluid is a flow that requires
a cold utility to decrease the temperature. The initial temperature (termed supply
temperature), final temperature (termed target temperature), and enthalpy change
of both streams are given in table 4.1.

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Table 4.1 Classification of Hot and Cold Fluid in Power-to-Gas System


Stream F Cp (kW/ Tin
Condition Tout (C) Q (kW)
No. C) (C)
3 Cold 0,324388889 27 45 -5,839
7 Hot 0,003229167 75 27 0,155
10 Hot 0,065360154 306,88 27 18,293
13 Hot 0,124753606 359,8 27 41,518

4.2 Heat Recovery Pinch Method


The term pinch was introduced by Linnhoff and Vredeveld to represent a
new set of thermodynamically based methods that guarantee minimum energy
levels in design of heat exchanger networks. There are two kinds of methods that
can be used to determine the pinch from all heat exchanger in one plant; they are
composite curve and problem table cascade.

4.2.1 Composite Curves


The first step to determine the amount of heat can be recovered by pinch
method, composite curve is generated. Composite curve is generated for hot fluid,
cold fluid and combination of both fluids. This section describes the use of a heat
exchanger network (HEN). Composite curves consist if temperature (T)-enthalpy
(H) profiles of heat availability in the process (the hot composite curve) and heat
demands in the process (the cold composite curve) together in a graphical
representation. Hence, we can plot composite curve directly based on the stream
data that we deliberated before in table 4.1.
From figure 4.1, we can see that we would need to supply 5,839 kW and
we would have to reject 59,9 kW. The figure would correspond to very poor
engineering because we are transferring heat from the highest possible
temperature interval directly to a cold utility, rather than using this available heat
to supply some of the energy requirements at lower temperature intervals.

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400
350
300

T (C) 250
200
HOT
150
COLD
100
50
0
0 10 20 30 40 50 60 70
H(kW)

Figure 4.1 Combined Hot and Cold Fluid Composite Curves before HEN
For heat exchange to occur from the hot stream to the cold stream, the hot
stream cooling curve must lie above the cold stream-heating curve. The premium
approach temperature (Tmin) can be measured directly from the T-H profiles as
being the minimum vertical difference between the hot and cold curves. We are
using temperature difference about 10 C. The graph after Heat exchanger
networks can be seen in the figure 4.2. Minimum cold utility requirement based
on cumulative curve after pinch is 54.13 kW.

400
350
300
250
T (C)

200
HOT
150
COLD
100
50
0
0 10 20 30 40 50 60 70
H(kW)

Figure 4.2 Combined Hot and Cold Fluid Composite Curves after HEN

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4.2.2 Problem Table Cascade


Although composite curves can be used to set energy targets, they are
inconvenient since they are based on a graphical construction. A method of
calculating energy targets directly without the necessity of graphical construction
can be developed.

Table 4.2 Shifted Temperature for the Data from Table 4.1

Stream No. Condition Tin (C) Tout (C) Tin* (C) Tout* (C)
103 Cold 27 45 32 50
107 Hot 75 27 70 22
110 Hot 306.88 27 301.88 22
113 Hot 359.8 27 354.8 22
The basic approach can be developed into a formal algorithm known as the
problem table algorithm. The algorithm will be explained using the data from
table 4.1 for Tmin. The first step is determined the shifted temperature intervals
(T*) from actual supply and target temperatures. Hot streams are shifted down in
temperature by Tmin/2 and cold streams up by T min/2 as detailed in Table 4.2.

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Table 4.3 Temperature Interval Heat Balance


Surplus/
Ti Stream Population T DH
Deficit

354.88

-0.12475 52.92 -0.12475 -6.60196 SURPLUS

301.88

-0.12475 -0.06536 231.88 -0.19011 -44.0836 SURPLUS

70

-0.00323 -0.12475 -0.06536 20 -0.19334 -3.86686 SURPLUS

50
0.324389 -0.00323 -0.12475 -0.06536 18 0.131046 2.358827 DEFICIT
32
-0.00323 -0.12475 -0.06536 10 -0.19334 -1.93343 SURPLUS
22
No 1 2 3 4
FCp 0.324389 0.003229 0.06536 0.124754
After we have the problem table, we can cascade any surplus heat down
the temperature scale from interval to interval. This is possible any excess heat
available from the hot streams in an interval is hot enough to supply a deficit in
the cold streams in the next interval down. From the figure above we can
determine the minimum utility requirement:

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Figure 4.3 Hot and Cold Fluid Program Table Cascade


Another way to see the minimum utility requirement is based on the grand
composite curve. The grand composite curve is a more appropriate tool for
understanding the interface between the process and the utility system. The grand
composite curve is obtained by plotting the problem table cascade.

400
350
300
250
T (C)

200
150
54.13 Cold Utility Minimum
100
50
0
0.00 10.00 20.00 30.00 40.00 50.00 60.00
Q(kW)

Figure 4.4 Grand Composite Curve

4.3 Pinch Design Method


This pinch design method is used to determine the use for hot or cold fluid
for heating or cooling the stream itself. The determination of the heat transfer is
based on the area above and below the pinch and also the loading of heat

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exchanger. Before that, we can calculate the amount of heat exchanger needed
using equation below,
Number of Exchanger = Number of Stream + Number of Utility 1
Number of Exchanger = 4 + 1 1
Number of Exchanger = 4
The design is shown in the figure 4.5.

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Figure 4.5 Pinch Design Method

Universitas Indonesia
CHAPTER 5
UTILITY

5.1 Utility Equipment Selection and Description


Utilities are the main supporting unit in the running of a production
process. In a factory, utilities are important utility role. Because of a production
process does not work if the utility does not exist. Therefore, all the facilities and
infrastructure should be designed in such a way as to ensure continuity of
operation of the plant. Based on the needs, utilities on manufacturing plant are
water utility, electricity utility, and liquid nitrogen utility.

5.1.1 Water Utility


In our power-to-gas plant, we need chilled water as a feed to cooling
water. Chilled water is needed for cooler to decrease the temperature of hydrogen,
oxygen and demineralized water. Water will be supplied either by PT. Kimia
Sakti Kalista or PDAM. Water then will be chilled by chiller machine to have
temperature of 5 C. From sheet condition operation we know the rate flow of
cooling water per cooler. Data before and after HEN for chilled water will
explained in the table 5.1.

Table 5.1 Mass Flow of Chilled Water


Before HEN After HEN
Equipment m (kg/h) Equipment m (kg/h)
E-102 12 E-102 12
E-103 3,000 E-103 2,600
E-104 1,500 E-104 1,500
Total requirement 4,512 Total requirement 4,112
Mass Reduced 400
From the table above, we know that chilled water needed in before HEN
higher than after HEN. This condition occur causing heat exchanger added to
optimize chilled water output cooler that has high temperature to transferring heat

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to hydrogen gas want to heating. Total requirement for before HEN is 4,512 kg/h,
whereas after HEN chilled water requirement is 4,112 kg/h.

5.1.2 Electric Utility


Electric utility for our Power-to-Gas system is required from our
photovoltaic power. Our PV Power can supplied up to 45,000 kWh per day, so
there is enough supply for our electricity requirement. Electricity requirement for
process utility is calculated based on the total requirement per day. Power
requirement is calculated from equipment quantity, time usage, and power.
Electricity process unit calculation can be seen in table 5.2.

Table 5.2 Electricity Calculation after HEN


Energy
Usage Power
No. Equipment Quantity Required
Time (h) (kW)
(kWh)
Raw Material Pump
1 1 24 0.003 0.07
(P-101)
Oxygen Compressor
2 1 24 15.261 366.26
(C-101)
Hydrogen
3 1 24 35.582 853.97
Compressor (C-102)
4 Electrolysis 1 24 1,674 40,176
Total 41,396.30
From calculation in table 5.2, we can calculate the electricity requirement
for one year which is 13,660,780 kWh.
kWh 330 days kWh
Electricity = 41,396.30 = 13,660,780
day 1 year year

For our startup process, there is no stream that can supply hot utility, so we
decided to use our excess PV power to heat the cold stream. Cold stream in
Stream-3 needs -5.839 kWh. Our electricity requirement in startup process is
different with process after HEN. It is shown in table 5.3.

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Table 5.3 Electricity Calculation before HEN


Energy
Usage Power
No. Equipment Quantity Required
Time (h) (kW)
(kWh)
Raw Material Pump
1 1 24 0.003 0.07
(P-101)
Oxygen Compressor
2 1 24 15.261 366.26
(C-101)
Hydrogen
3 1 24 35.582 853.97
Compressor (C-102)
4 Electrolysis 1 24 1,674 40,176
5 Heater (E-101) 1 24 5.839 140.14
Total 41,536.44

5.1.3 Liquid Nitrogen Utility


Another choice that can be used to cold the hot stream in our process is by
using liquid nitrogen. Liquid nitrogen is a refrigerant that can change its phase to
gas after cooling the hot stream. Liquid nitrogen can be supplied by PT. Air
Liquide Indonesia. Data before and after HEN for liquid nitrogen will explained
in the table 5.4.

Table 5.4 Flow of Liquid Nitrogen


Before HEN After HEN
Equipment V (L/h) Equipment V (L/h)
E-102 1.85 E-102 1.85
E-103 412.45 E-103 368
E-104 208.70 E-104 208.70
Total requirement 623 Total requirement 578.55
Volume Reduced 44.45

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CHAPTER 5
CONCLUSION

Our plant design regarding the conversion of excess PV power into gas
(P2G) was chosen due to the high demand of electricity in Indonesia
coupled with a pressure to change lane into renewable energy.
Most of Indonesia lies on the Equator line making it have the highest solar
intensity on the planet and thus making it have the potential to develop a
thriving Power-to-Gas system.
Our plant location selection is based on Pontianak because of its strategic
location to set up PV cells and its high solar intensity.
Currently, our plant will produce about 31 kg of hydrogen per hour and
246 kg of oxygen per hour.
We pursued the endeavor to optimize systems energy balance in terms of
utilizing its excess energy for different parts of the plant.
This goal is aided by creating a heat exchanger network of our plant which
comprises of 4 heat exchangers.
From the composite curve, we calculated that the minimum utility
requirement based on Cumulative Curve After Pinch is 54.13 kW.
In terms of utility, our plant uses 4,112 kg/h of chilled water or 578.55 L/h
of liquid nitrogen.
Our PV Power can supply up to 45,000 kWh per day, so there is enough
supply for our electricity requirement. Thus, the electricity requirement for
one year is 13,660,780 kWh.

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REFERENCE

Bessarabov, Dmitri dkk. 2016. PEM Electrolysis for Hydrogen Production


Principles and Applications. New York: CRC Press.
Bockris, J.O.M., Recent Developments in the study of hydrogen overpotential.
1948: p. 525-577.
Bowen, C.T., et al., Developments in advanced alkaline water electrolysis.
International Journal of Hydrogen Energy, 1984. 9(1-2): p. 59-66.
Branan, Carl. 2002. Rules of Thumb for Chemical Engineers. Houston: El-Sevier.
Brownell, Lloyd E and Edwin H. Young. 1959. Process Equipment Design. John
Wiley & Sons, inc.
Cheremisinoff, Nicholas P. 2000. Handbook of Chemical Processing Equipment.
Butterworth-Heinemann.
Choi, P., A simple model for solid polymer electrolyte (SPE) water electrolysis.
Solid State Ionics, 2004. 175(1-4): p. 535-539.
Coulson & Richardson. 1983. Chemical Engineering Design. Oxford: El-Sevier.
Chemical and Process Design Handbook. New York: McGraw-Hill.
De Levie R. 1999. The electrolysis of water. Journal of Electroanalytical
Chemistry 476:9293.
Dorf RC. 2004. CRChandbook of engineering tables, 2nd edition. CRC Press
LLC, Boca Raton.
DuPontTM Nafion PFSA Membranes NR-211 and NR-212. FuelCell Store.
2016. [online] http://fuelcellstore.com/spec-sheets/nafion-211-212-spec-
sheet.pdf , diakses 10 September 2016
Harrison, K., Levene, J. I., Electrolysis of Water. 2004, National Renewable
Energy Laboratories.
Jones, S.F., G.M. Evans, and K.P. Galvin, Bubble nucleation from gas cavities
a review. Advances in Colloid and Interface Science, 1999. 80(1): p. 27-
50.
Kementerian Energi dan Sumber Daya Mineral. (2012) Kajian Supply Demand
Energi. http://prokum.esdm.go.id (Accessed on 16th September 2016)
Kerres, J., et al., Advanced alkaline electrolysis with porous polymeric
diaphragms. Desalination, 1996. 104(1-2): p. 47-57.
Kreuter W, Hofmann H (1998) Electrolysis: the important energy transformer in
a world of sustainable energy. International Journal of Hydrogen Energy
23:661666.
Lee, T.S., Hydrogen Over potential on Pure Metals in Alkaline Solution. Journal
of the Electrochemical Society, 1971. 118(8): p. 1278-1282.
LeRoy, R.L. and A.F. Hufnagl, Progress in industrial demonstration of advanced
unipolar electrolysis. International Journal of Hydrogen Energy, 1983.
8(8): p. 581-588.
LeRoy, R.L., C.T. Bowen, and D.J. LeRoy. The Thermodynamics of Aqueous
Water Electrolysis. Journal of the Electrochemical Society, 1980. 127(9):
p. 1954-1962.
Ludwig, E. E. 1997. Applied Process Design for Chemical and Petrochemical
Plants, Gulf Professional Publishing.

62 Universitas Indonesia
63

Manage, M.N., et al., A techno-economic appraisal of hydrogen generation and


the case for solid oxide electrolyser cells. International Journal of
Hydrogen Energy, 2011. 36(10): p. 5782-5796.
Millet, P., et al., PEM water electrolyzers: From electrocatalysis to stack
development. International Journal of Hydrogen Energy, 2010. 35(10): p.
5043-5052.
O'Brien, J.E., et al., Parametric study of large-scale production of syngas via
high-temperature co-electrolysis. International Journal of Hydrogen
Energy, 2009. 34(9): p. 4216-4226.
Overview on Water Electrolysis for Hydrogen Production and Storage. 2016. Tom
Smolinka. [online].
http://www.hydrogennet.dk/fileadmin/user_upload/PDF-
filer/Aktiviteter/Kommende_aktiviteter/Elektrolysesymposium/Tom_Smol
inka.pdf, diakses 10 September 2016
PEM Electrolysis for Hydrogen Production Principles and Application. 2016.
Taylor and Farncis Group: London, New York
Perry, Robert H. 1999. Perrys Chemical Engineers Handbook. McGraw-Hill
Companies, Inc.
Pettersson, J., B. Ramsey, and D. Harrison, A review of the latest developments in
electrodes for unitised regenerative polymer electrolyte fuel cells. Journal
of Power Sources, 2006. 157(1): p. 28-34.
Pollet, B., Basics of Electrochemistry. 2009.
R.L, L., Industrial water electrolysis: Present and future. International Journal of
Hydrogen Energy, 1983. 8(6): p. 401-417.
Rand, D.A.J., Dell, R. M., Hydrogen Energy - Challenges and Prospects. 2008:
The Royal Society of Chemistry.
Seider, W. D., Seader, J. D. & Lewin, D. R. 2003. Product and Process Design
Principles, John Wiley and Sons, Inc.
Sinnott, R. K. 2005. Chemical Engineering Design 4th edition. Elsevier.
Siracusano, S., et al., Optimization of components and assembling in a PEM
electrolyzer stack. International Journal of Hydrogen Energy, 2011. 36(5):
p. 3333-3339.
Smith, J.M., H.C.V. Ness, and M.M. Abbott, Introduction to chemical
engineering thermodynamics. 2005: McGraw-Hill.
Trasatti S (1999) Water electrolysis: who first? Journal of Electroanalytical
Chemistry 476:9091.
Vogt, H. and R.J. Balzer, The bubble coverage of gas-evolving electrodes in
stagnant electrolytes. Electrochimica Acta, 2005. 50(10): p. 2073-2079.
Vogt, H., . Aras, and R.J. Balzer, The limits of the analogy between boiling and
gas evolution at electrodes. International Journal of Heat and Mass
Transfer, 2004. 47(4): p. 787-795.
Wallas, Stanley M. 1988. Chemical Process Equipment Selection and Design.
Butterworth-Heinemann.
Wang, M., Z. Wang, and Z. Guo, Water electrolysis enhanced by super gravity
field for hydrogen production. International Journal of Hydrogen Energy,
2010. 35(8): p. 3198-3205.

Universitas Indonesia
64

Zeng, K. and D. Zhang, Recent progress in alkaline water electrolysis for


hydrogen production and applications. Progress in Energy and
Combustion Science, 2010. 36(3): p. 307-326.
Zoulias, E., Varkaraki, E., Lymberopoulos, N., Christodoulou, C. N., Karagioris,
G. N., A Review of Water Electrolysis. TCJST, 2004. 4(2): p. 41-71.

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APPENDIX

Appendix 1. Process Flow Diagram before HEN

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