Effective Utilization of By-Product Oxygen From Electrolysis Hydrogen Production
Effective Utilization of By-Product Oxygen From Electrolysis Hydrogen Production
Effective Utilization of By-Product Oxygen From Electrolysis Hydrogen Production
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Abstract
Hydrogen should be produced by renewable energy resources to avoid fossil fuel consumptions and
greenhouse gas emissions. A water electrolysis using PEM is considered a promising hydrogen
production method although the hydrogen cost by PEM would be very high as compared with the other
mature technologies such as steam methane reforming (SMR). We focus on the effective utilization of
by-product oxygen of electrolysis hydrogen production. In this study, we discuss the potential demand of
by-product oxygen and evaluate the contribution of by-product oxygen for improving process efficiency.
In terms of economy, taking into account the utilization of by-product oxygen for a medical use, we
compare the hydrogen production cost between PEM electrolysis and SMR.
1. Introduction
Hydrogen is one of the most promising energy carriers for future energy system and it can be used
(in gas or liquid form) to store and transmit energy, and can be supplied to fuel-cell vehicles (FCVs) as
well as fuel cell power generation system. Hydrogen used as main energy carrier could offer an answer to
the threat of global climate change and avoid undesirable factors associated with the use of fossil fuels.
Although it is estimated that hydrogen is more expensive than fossil fuels, hydrogen made from
renewable energy resources is a virtually inexhaustible, environmentally benign energy resources that
could meet most of our future energy needs and avoid the cost for environment and health problems
associated with fossil fuels.
Hydrogen is a long term option. The production, storage and distribution facilities must be improved
and developed. In the short run, hydrogen will be produced from fossil fuels such as natural gas by steam
methane reforming (SMR), existing very mature technology. In the long run, however, hydrogen must be
produced by renewable energy resources to avoid fossil fuel consumptions and greenhouse gas emissions.
In other words, hydrogen has a considerable potential to overcome the limitation of intermittent
renewable energy resources and can therefore benefit the development of them. For example, a water
electrolysis by proton exchange membrane (PEM) is considered a promising method to produce
hydrogen by renewable energy resources, such as wind, photovoltaic, etc., due to the high efficiency.
Currently, even in case of well-established alkaline water electrolysis, the hydrogen production cost by
electrolysis is high in comparison to fossil fueled hydrogen production technologies such as SMR
because of the high investment cost and the high electricity cost. However, technological improvements
in both electrolysis technologies and electricity production technologies from renewable energy
resources could make the production of hydrogen by electrolysis very attractive for the future.
When hydrogen is produced by water electrolysis process, half the number of moles of oxygen is
produced simultaneously as a by-product of hydrogen. If large quantities of hydrogen are required to be
produced from renewable resources by electrolysis process, by-product oxygen also will be produced in
large scale. In such the situation, by-product oxygen should be fully utilized, because oxygen is an
important industrial gas utilized in many processes such as combustion, semiconductor production,
wastewater treatment, etc. The effective utilization of oxygen would improve energy efficiency of some
industrial processes [1]. While by-product oxygen in electrolysis hydrogen production can be harmlessly
vented, it seems more prudent to explore its possible large-scale utilization.
Fig. 1 shows the conceptual diagram of simultaneous utilization of hydrogen and by-product oxygen.
For example, the use of oxygen-enriched combustion air in a number of energy-intensive industrial
applications has the potential to reduce the amount of heat lost to the atmosphere by about two-thirds. As
concern for the global environment rises, demand for oxygen is expanding in such areas as electric
furnace and glass melting as well as for treatment of municipal solid waste (MSW) and wastewater. In
addition, the utilization of by-product oxygen could contribute to reduce the large amount of electricity
consumed in the oxygen production by air separation technologies, such as cryogenic air separation and
pressure swing absorption (PSA). In order to fully utilize by-product oxygen, the balance between
by-product oxygen and oxygen demand is very important. If the oxygen demand is not so large relative
to the potential supply of by-product oxygen by water electrolysis hydrogen production, large quantities
of by-product oxygen must be wasted.
In this study, we discuss the potential demand of by-product oxygen and its contribution to energy
saving. First we show the brief introduction of oxygen production technologies and hydrogen production
technologies. Second, we show the current and future oxygen demand and the potential of energy
efficiency improvement by utilizing by-product oxygen in industry. Then we compare the oxygen
demand with potential supply of by-product oxygen of hydrogen production by electrolysis. Finally, we
evaluate the economy for utilizing by-product oxygen for medical use.
An air separation unit using a conventional, multi-column cryogenic distillation process produces
oxygen from compressed air at high recovery and purity. Cryogenic air separation is currently the most
efficient and cost-effective technology for producing large quantities of oxygen, nitrogen, and argon as
gaseous or liquid products. The energy requirement of the latest technology is about 0.5 kWh/Nm3-O2.
Oxygen purity of cryogenic process can be higher than 99 vol. %. Because of high purity requirement,
the oxygen for medical use is normally produced by cryogenic process. Neither technology excepting
electrolysis is expected to challenge cryogenic air separation for large quantities production of oxygen
especially at high purity. In Japan, oxygen demand was 9,615×106 Nm3 in 2001 [2, 3], and is produced
mainly by cryogenic process. Because cryogenic air separation consists of five major processes, i.e. air
compression, air pre-treatment, heat exchange, cryogenic separation and oxygen compression, it is
utilized for large scale production larger than 8,000 Nm3/h, and is not suitable for a small scale on-site
oxygen production.
Adsorption process is based on the ability of some natural and synthetic materials such as zeolites to
preferentially adsorb nitrogen. The regeneration of adsorbent is necessary and can be accomplished by
heating the bed of zeolitic material (temperature swing adsorption, TSA) or reducing pressure in the bed
(pressure swing adsorption, PSA). Because of the faster cycle time and simplified operation, PSA is
usually used. Oxygen purity of adsorption process is typically 93 – 95 vol.%. The required energy in
adsorption process is also about 0.5 kWh/Nm3-O2. Adsorption process is used for smaller application as
compared to cryogenic process.
Some non-cryogenic processes, i.e. chemical air separation process, membrane process and ion
transport membrane, are also available.
Hydrogen can be produced from a variety of fossil and non-fossil resources through energy use such
as heat or electricity. The major processes for hydrogen production include SMR, catalytic
decomposition of natural gas, partial oxidation of heavy oil, coal gasification, water electrolysis,
thermo-chemical water decomposition, and photo-chemical, -electrochemical and - biological processes.
SMR, coal gasification and water electrolysis are the most important industrial processes for hydrogen
production today.
SMR is a well-established, commercialized process, and the most common method to produce large
quantities of hydrogen. Currently, about 99% of world hydrogen is produced from fossil fuels, primarily
natural gas [4]. Hydrogen production efficiencies of SMR with the capacity of over one million
Nm3-H2/day are in the range of 63 to 85 % (based on higher heating value (HHV) of hydrogen) and the
investment costs range from 270 to 500 US$/kW [5-8]. In the capacity of over one million Nm3-H2/day,
SMR technology has the least-expensive investment cost in comparison to other fossil fueled hydrogen
production methods. This process also produces carbon dioxide, one of the main greenhouse gases,
which is unwanted. In order to obtain pure hydrogen, purification steps in the downstream of the SMR
plant are necessary to remove undesired compounds (carbon dioxide, etc.).
Water electrolysis is also well-established technology and the most widely used method for
producing high purity hydrogen. Several processes are available for water electrolysis ranging from
established alkaline systems to developing advanced methods, such as PEM. The conventional
electrolytic methods are known as alkaline water electrolysis, which has been a mature technology for
decades and its efficiencies are around 70 to 80 % (HHV). Alkaline water electrolysis is striving to
pursue higher efficiency by increasing operating temperature or electrolyzing under pressurized
circumstances. The current investment cost of an alkaline electrolysis is approximately 500 US$/kW [5,
7, 9, 10]. The investment cost of alkaline electrolysis hydrogen production is higher than that of SMR,
though the efficiency is comparable with SMR. PEM is used as electrolyte instead of alkaline aqueous
solutions, and is considered a promising method due to the extreme volume reduction. Currently, the
investment cost for PEM electrolysis is over 1,000 US$/kW [10, 11], and high cost of the components is
the main drawback of this technology. In addition to the high investment cost, the major cost factor of
electrolysis is the electricity, making water electrolysis the most expensive method among the current
commercial processes. Because of cost reasons, electrolysis is used mainly in small plant.
Renewable energy resources, e.g. wind, photovoltaic (PV), solar thermal and hydropower, are all
efficient resources of the electricity required for water electrolysis. Although the hydrogen produced by
renewable resources based electricity is very expensive in most cases, it is attractive because of very pure
and clean energy carrier. In the long run, however, hydrogen should be produced by renewable energy
resources to avoid fossil fuel consumptions and greenhouse gas emissions.
Water electrolysis powered by renewable energy resources would produce only hydrogen and oxygen,
avoiding the emission of CO2. When large quantities of hydrogen are produced from renewable resources
by water electrolysis process in a future, by-product oxygen also will be produced in large scale. When
DC electricity is passed between 2 electrodes (anodes and cathode) immersed in water, hydrogen collects
at the negatively charged cathode and oxygen collects at the positively charged anode. The main
chemical reactions occurring at the two electrodes are:
For example, when the electrolysis efficiency is 71 %, the electricity of 5,000 kWh would produce
hydrogen of 1,000 Nm3 of and oxygen of 500 Nm3. Because the electricity of 250 kWh is required to
oxygen production of 500 Nm3 by cryogenic air separation, the full utilization of by-product oxygen
corresponds to the reduction of electricity consumption to 4,750 kWh on electrolysis, raising the
electrolysis efficiency to 76 %.
While by-product oxygen can be harmlessly vented, it seems more prudent to explore its possible
large-scale utilization. In this case, the balance between by-product oxygen and oxygen demand is very
important. If the oxygen demand is not so large relative to the possible supply of by-product oxygen in
hydrogen production by water electrolysis, large quantities of by-product oxygen must be wasted. In this
study, therefore, we discuss the potential demand of oxygen on the basis of the survey of both current
oxygen demand and new technologies utilizing oxygen for improving energy efficiency.
4. Oxygen Demand
Fig. 2 shows the oxygen demand in Japan. The total oxygen demand was about 9,615×106 Nm3 in
2001. There are some new applications utilizing oxygen for improving energy efficiency of industrial
processes. Followings are details of oxygen demand in some industrial processes.
4.1 Blast Furnace
A blast furnace process involved in steelmaking process is the largest oxygen consumer in industry.
In the latest blast furnace process, oxygen is highly utilized to improve the productivity. In Japan, blast
furnace consumed oxygen of 8,037×106 Nm3 in 2001, corresponding to 84 % of the total oxygen demand.
Oxygen for blast furnace is normally produced on site, because of the large oxygen demand. Normally
cryogenic air separation process is utilized. In Japan, almost 70 % of cryogenic air separation is used for
supplying oxygen to blast furnace, but 75 % of these systems were built before 1980. Therefore, the
existing system will be replaced with new oxygen production system in the near future. At that time, if
hydrogen demand for FCVs is large enough and some portion of hydrogen is produced by renewable
electricity, electrolysis hydrogen production system can be a good alternative, which supplies hydrogen
and by-product oxygen to FCVs and blast furnace, respectively.
Electric arc furnace is the largest consumer of oxygen on market place, because large quantities of
oxygen used in blast furnace are produced and consumed on site. In 2001, the oxygen demand for
electric arc furnace was about 888×106 Nm3, corresponding to 9.2 % of the total oxygen demand in Japan.
Adsorption process for producing oxygen is mainly utilized. In electric arc furnace process, production
efficiency has been improved by increasing the amount of oxygen. In the conventional electric arc
furnace process, the electricity consumption rate was about 380 kWh/t-billet, where 33 Nm3/t-billet of
oxygen was consumed. Recently, the innovative electric furnace developed by NKK, Japan, improves
heat efficiency remarkably [12]. The newly developed electric arc furnace process is a fully closed
melting shaft furnace, into which scrap is continuously charged from the top of the shaft portion. As
scrap falls to the furnace portion, it mixes with molten steel and is melted rapidly. Due to this furnace
structure, which enables scrap to be fed into molten steel without interval, heat loss on water-cooled
panels and fingers is effectively prevented, thereby maintaining scrap-preheating temperature at around
1,000°C, which results in lower consumption of electricity. In the new electric arc furnace, the
consumption of electricity is only 150 kWh/ton-billet with oxygen consumption of 45 Nm3/ton-billlet.
The reduction of electricity consumption per unit oxygen use is 19 kWh/Nm3-O2, which corresponds to
the reduction of primary energy of 182 MJ/Nm3-O2 in the case that the efficiency of electric power
generation (ηe) is 38 %.
In Japan, annually 29×106 ton of steel is produced by electric arc furnace in 2002. If all existing
electric arc furnace is replaced with newly developed electric arc furnace, electricity of 6,634 GWh/yr (or
62,849 TJ/yr with ηe=38%) would be reduced, while additional oxygen of 346×106 Nm3/yr is required,
increasing total oxygen demand for electric arc furnace to some 1,300×106 Nm3/yr.
Glass manufacture is a high temperature, energy intensive process. The majority of large glass tank
furnaces incorporate regenerative heat recovery systems. As structural heat losses from such furnaces
typically account for some 40% of the total heat input, improving efficiency can lead to significant
reductions in energy consumption. In a conventional air-blown combustion melting process, energy
requirement is approximately 11 MJ/kg-glass [13]. Overall efficiency can be improved by rebuilding the
furnace to incorporate a number of energy saving features, i.e. electric boost and supplementary
oxygen-blown combustion. Fig. 3 shows the comparison of energy consumption, NOx emission and CO2
emission between conventional air-blown combustion furnace and new oxygen-blown combustion
furnace. By utilizing oxygen, the energy efficiency can be improved by 40 %. NOx and CO2 emissions
also can be reduced remarkably. In the oxygen combustion furnace, the ideal oxygen requirement is
about 0.3 Nm3/kg-glass. Taking into account the energy consumption per unit production shown in Fig. 3,
the reduction of primary consumption per unit oxygen use is 16 MJ/Nm3-O2.
Because of cost reasons, oxygen-blown combustion furnace is not used so much except electric glass
production where the price of glass product is relatively high compared to the other glass products.
Therefore, if fossil fuel price increases, the shift to the oxygen combustion furnace would be accelerated.
In Japan, the annual production of glass product including sheet glass, glass fiber wool products, glass
fiber continuous textiles, glass foundation products and glass containers was approximately 4.4×106
ton-glass in the last 3 years. If these glass products are produced by oxygen-blown combustion furnace,
the estimated oxygen requirement is approximately 1,313×106 Nm3/yr. This would reduce the annual
energy consumption of glass melting process by 20,951 TJ/yr.
An electric power plant has a potential to be one of the largest consumer of by-product oxygen. We
have proposed a new concept of power generation system with pure oxygen-blown natural gas combined
cycle (NGCC). Fig. 4 shows the schematic flow diagram of our proposed system. In our proposed system,
85 % of exhaust is recycled as a working medium of gas turbine. One of the most important features of
our proposed system is the component of exhaust, consisting of only CO2, H2O and O2. After the
condensation of H2O, CO2 can be easily captured without the CO2 separation unit. This feature could be
advantage over a conventional NGCC with air-blown combustion, the cheapest option for electricity
production. At present, electric power plants with CO2 capture unit draw widespread attention as an
environmental benign electric power plant. Although the capital cost of conventional NGCC is lower
than that of power plants using other fossil fuel, the capital cost including CO2 capture unit is estimated
to be about 1,000 $/kW, 2 to 3 times higher than that without CO2 capture [14-17]. The total thermal
efficiency is around 45 % instead of 53 % of conventional NGCC without CO2 capture, because CO2
separation from flue gas requires large power. Because our proposed system does not need to have CO2
separation unit, our proposed system could be a cost effective option as a CO2 capture power plant fueled
with natural gas. The economic assessment on our proposed system is not performed in this paper, but
will be done as a future study.
As shown in Fig. 4, the oxygen requirement of our proposed system is 72 kg/s (50 Nm3/s) for
producing the electricity of 400 MW at sending-end. If this system is operated with the load factor (LF)
of 80 %, the annual oxygen requirement is 1,273×106 Nm3/yr, corresponding to 13 % of the current total
oxygen demand in Japan.
4.5 Gasification
A gasification process converts any carbon-containing material into a synthesis gas or syngas
composed primarily of carbon monoxide and hydrogen, which can be used as a fuel to generate
electricity or steam, or used as a basic chemical building block for a large number of uses in the
petrochemical and refining industries. Typical raw materials used in gasification are coal, petroleum
based materials (crude oil, high sulfur fuel oil, petroleum coke, and other refinery residuals), gases, or
materials that would otherwise be disposed of as waste, i.e. municipal solid waste (MSW). If the syngas
is to be used to produce electricity, it is typically used as a fuel in an integrated gasification combined
cycle (IGCC) power generation configuration. The syngas can also be processed using commercially
available technologies to produce a wide range of products, fuels, chemicals, fertilizer or industrial gases.
Gasification is endothermic chemical reaction, so heat has to be supplied externally or by partial
combustion. In the case of partial combustion, the oxidant for the gasification process can be either
atmospheric air or pure oxygen. In the simplest gasification system with partial combustion process, air
is used. Although air gasification itself is relatively cheap, downstream gas cleaning is expensive due to
the large volumes to be handled. On the other hand, Oxygen-blown gasifiers offer a higher heating value
gas and faster reaction rates than air-blown systems, but have the disadvantage of additional capital costs
associated with the oxygen plant. The use of by-product oxygen for gasification might solve the
economic problem for using oxygen.
Based on the survey of gasification plant, there are 163 commercial gasification projects consisting
of a total of 468 gasifiers [18]. Fig. 5 shows the cumulative capacity of gasification projects. The
capacity is large in coal and petroleum gasification and increases rapidly. Currently, gasification is not
commonly used for household waste. Nevertheless, the most significant growth in the market for waste
management systems in the near future is likely to be for the treatment of municipal solid waste (MSW)
[19]. The requirement of oxygen depends on the feedstock to be gasified. For example, api Energia
integrated gasification combined cycle (IGCC) plant being built at Falconara Marittima, on Italy`s
Adriatic coast, requires 62 t/h of oxygen to gasify 59.2 t/h of high sulphur heavy oil produced by the
Falconara refinery, and convert it to syngas and use the gas to generate 280 MW of electricity, plus steam
and other gases for use in the refinery [20]. When this plant is operated with the annual load factor of
80 %, the annual requirement of oxygen is 304×106 Nm3/yr.
Because oxygen gas used for medical care is categorized to a sort of medicinal supplies, it is
produced and delivered within a highly controlled environment. Therefore pure and clean oxygen
produced by electrolysis is suitable for medical use. The oxygen demand for medical use was about
105×106 Nm3 in 2001, which is only 1.1 % of total oxygen demand including the oxygen produced on
site. With the exception of on site produced oxygen in blast furnace, however, the oxygen for medical use
is the third largest demand in Japan. Utilizing oxygen for medical use is not related to the improvement
of energy system. However, because of very high price of medical oxygen, effective utilization of
by-product might decrease the high cost of electrolysis hydrogen production, especially electrolysis using
PEM. We surveyed the retail price of oxygen for medical use at 877 hospitals in Japan as shown in Fig.6.
Depending on total oxygen demand, the oxygen price is basically very high ranging from 60 yen/Nm3
(82 UScent/Nm3) to 10,000 yen/Nm3 (35 US$/Nm3). These prices almost correspond to fuel price on Nm3
basis.
In the latter section, we discuss the economy for using by-product of electrolysis hydrogen
production for medical use based on the survey of oxygen demand and price in hospitals.
For example, when the total floor space is 10,000 m2, suitable electrical capacity of CGS would be
194kWe. Because actual demand data is not available for each 160 hospital, we used the typical demand
data set on electricity and heat as shown in Table 2. The maximum electricity demand in hospital is
assumed to be 0.05 kW/m2. Considering the capacity of PEFC-CGS assumed in eq.(1), almost 40% of
maximum electricity demand can be met by PEFC-CGS.
7. Conclusion
In this study, we discussed the potential demand of by-product oxygen and its contribution to energy
saving. Because there are the large quantities of potential oxygen demand, the by-product oxygen of
electrolysis hydrogen production could be fully utilized, which would contribute to the improvement of
various energy efficiency of industrial processes and electric power production, the reduction of CO2
emission. Even if the large quantities of by-product oxygen are wasted, the use of by-product oxygen in
hospital would be economic merit.
References
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Renewable
electricity Nuclear
electricity
electrolysis
H2 O2
- +
Hydrogen Oxygen
utilization utilization
Blast furnace
Electric arc furnace
FCV Glass melting
Biomass gasification
electricity
12000
10000
pulp bleaching
oxygen demand (10 Nm )
3
glass melting
8000
6
stainless steel
non-ferrous metals
6000
medical care
shipbuilding
4000
electric furnace
blast furnace
2000
0
1996 1997 1998 1999 2000 2001
year
10 0.005 0.25
6 0.003 0.15
3
4 0.002 0.10
2 0.001 0.05
0 0.000 0.00
air oxygen air oxygen air oxygen
200
3
Coal
Petroleum
6
150
Gas
100 Biomass/MSW
Petcoke
50
0
1950 1960 1970 1980 1990 2000 2010
year
10
0.1
1 10 100 1000 10000 100000 1000000
3
annual oxygen demand (Nm )
1,600
Oxygen
1,400
6
1,200 Hydrogen
1,000
800
600
400
200
0
1996 1997 1998 1999 2000 2001 2002
year
180
3
Fig. 8 Comparison between potential supply of by-product oxygen and oxygen demand
energy demand
grid electricity
electricity
15 yen/kWh
70%
absorption
cooling
chiller
PEM PEFC
electrolysis ηe=36%
η= 90% H2 ηh=40% heat exchanger heating
energy demand
grid electricity
electricity
15 yen/kWh
70%
absorption
cooling
chiller
PEFC
SMR
ηe=36%
η= 70%
H2 ηh=40% heat exchanger heating
100%
gas-fired double-
effect absorption 80%
city gas chiller-heaters
50 yen/Nm3
80%
boiler
Table 1
Assumption of electricity price and city gas retail price
14.47 yen/kWh (0.13 US$/kWh) Jul. - Sep.
variable
13.15 yen/kWh (0.12 US$/kWh) others
electricity
1,625yen/kW/month
fixed
(15.08 US$/kW/month)
city gas variable 50 yen/Nm3 (0.46 US$/Nm3)
PEM 206 yen/Nm3 (1.91 US$/Nm3) include investment cost
hydrogen
SMR 110 yen/Nm3 (1.02 US$/Nm3) include investment cost
Table 2
Assumption of electricity and heat demand in hospital
annual demand maximum demand
2
electricity 170 kWh/m /yr 50 W/m2
hot-water 80 Mcal/m2/yr 40 kcal/m2/h
heating 74 Mcal/m2/yr 82 kcal/m2/h
cooking 80 Mcal/m2/yr 90 kcal/m2/h
10000000
(100000
10000
1000
100
10
1000 10000 100000
2
total floor space (m )
Fig.10 Comparison between annual oxygen demand and available by-product oxygen
300
in system-A with PEM electrolysis
250
(% of system-B with SMR)
200
hydrogen cost
150
100
50
0
1000 10000 100000
2
total floor space of hospital (m )
Fig.11 Comparison of hydrogen cost between system-A and system-B including oxygen cost