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Exergy. http://dx.doi.org/10.1016/B978-0-08-097089-9.00017-6
2013 Ibrahim Dincer and Marc A. Rosen. Published by Elsevier Ltd. All rights reserved 347
348 Exergy
efficiencies are determined as the ratio of the energy 17.3 HYDROGEN PRODUCTION FROM
(or exergy) of the product(s) to the energy (or exergy) of the FOSSIL FUELS
input(s). For the overall processes, for instance, the energy
efficiency h is evaluated as follows: Hydrogen production from fossil fuels refers to processes
in which the hydrogen is derived in whole or in part from
h Net energy output with product hydrogen= a hydrocarbon feedstock, usually in the form of a fossil
(17.1)
Energy input fuel. The remaining hydrogen is derived from the hydrogen
in water. Such hydrogen production processes, since they
and the exergy efficiency j is evaluated analogously as already utilize fossil fuels, normally use fossil fuels to
follows: provide the energy needed to drive the process, which is
j Net exergy output with product= typically in the form of process heat, or a heated media-like
(17.2) steam, and electricity.
Exergy input There are two main types of processes for hydrogen
production from hydrocarbons: (1) steam reforming of light
hydrocarbons and (2) partial oxidation of hydrocarbons.
17.2 HYDROGEN PRODUCTION Simplified process diagrams for these processes are pre-
PROCESSES sented in Figure 17.1. The main processing of the hydro-
The main processes for hydrogen production include steam- carbon differs for the two processes, but both include shift
methane reforming (SMR); catalytic decomposition of natural conversion and purification.
gas; partial oxidation of heavy oil; coal gasification; water
electrolysis; thermochemical water decomposition; and 17.3.1 Hydrogen Production by Steam
photochemical; photoelectrochemical, and photobiological
processes (Casper, 1978; Rosen and Scott, 1998; Holladay
Reforming of Hydrocarbons
et al., 2009). The first four processes are based on fossil fuels. There are three basic steps in conventional steam
Many of the main processes for hydrogen production, reforming (Figure 17.1, left). The first is synthesis gas
broken down into hydrocarbon-based and nonhydrocarbon- generation, in which a desulfurized hydrocarbon is mixed
based processes, and their states of development are with process steam over a nickel-based catalyst in the
summarized in Table 17.1. SMR, coal gasification, and reformer. There, the endothermic reforming reaction
water electrolysis are the most important industrial occurs at 900 C:
processes for hydrogen production today. Thermochemical
water decomposition is undergoing extensive research
(Funk, 2001; Naterer et al., 2010; Rosen, 2010). Cn Hm nH2 O/nCO n m=2H2 (17.3)
TABLE 17.1 Summary and State of Technology of the Selected Hydrogen Production Processes
FIGURE 17.1 Simplified process diagrams for hydrogen production from hydrocarbons: steam reforming of light hydrocarbons (left) and partial
oxidation of hydrocarbons (right).
Here, n 1 and m 4 if the hydrocarbon is methane, and the reforming reaction is normally provided by combustion
n 1 and m 2.2 if it is naphtha. A gaseous mixture of of hydrocarbon fuel.
CO, CO2, H2, and H2O is produced. Only light hydrocar- Three principal types of partial oxidation processes
bons are used because they can be vaporized completely exist:
without carbon formation. Process heat is normally
l Partial oxidation of light hydrocarbons such as methane
provided by the combusting hydrocarbon fuel:
and naphtha over a catalyst at about 600 C
Cn Hm n m=4O2 /nCO2 m=2H2 O (17.4) l Partial oxidation of heavy hydrocarbons such as heavy
oils without a catalyst at about 1400 C, a temperature at
The second main step is supplemental hydrogen generation which catalysts are not required to promote the
in which the synthesis gas enters the shift converter and the reforming reaction
exothermic wateregas shift reaction occurs at l Partial oxidation of solid hydrocarbons such as coal
200 Ce400 C: without a catalyst (i.e., coal gasification)
CO H2 O/CO2 H2 (17.5)
The third main step is gas purification, where the primary 17.4 HYDROGEN PRODUCTION FROM
diluent, CO2, is removed in a scrubbing unit. Residual CO RENEWABLE ENERGY
is converted in the methanator, where the exothermic Hydrogen production from renewable energy refers to
methanation reaction occurs: processes in which the hydrogen is derived wholly by
CO 3H2 /CH4 H2 O (17.6) separating the hydrogen in water or from a renewable
hydrogen-containing feedstock like biomass. The remain-
The product hydrogen typically has a purity of 97%e98%. ing hydrogen derived in biomass-based processes comes
Half of the hydrogen is derived from H2O when the from the biomass. Hydrogen production processes in the
hydrocarbon feedstock is methane and 64.5% when it is first group can utilize fossil fuels to drive the processes
naphtha. directly or indirectly by generating process heat and elec-
tricity, but often do not. Biomass-based processes for
hydrogen production may often use biomass to drive the
process, although they can also use fossil fuels or other
17.3.2 Hydrogen Production by Partial renewable energy forms to provide process heat, electricity,
Oxidation of Hydrocarbons and other required energy commodities.
Simplified process diagrams are presented in Figure 17.2
Hydrogen production by partial oxidation of hydrocarbons for the two of the main types of processes for hydrogen
(Figure 17.1, right) and by catalytic steam reforming are production from water (rather than hydrocarbons), poten-
similar. The synthesis gas generation step is slightly tially using heat from renewable energy: (1) water electrol-
modified. A hydrocarbon feedstock is mixed with process ysis and (2) thermochemical water decomposition.
steam and oxygen in the partial oxidation unit, where the
reforming reaction (Eq. 17.3) and the following exothermic
partial oxidation reaction occur: 17.4.1 Hydrogen Production by Water
Electrolysis
Cn Hm n=2O2 /nCO m=2H2 (17.7)
Water electrolysis (Figure 17.2, left) involves the catalytic
For heavy oils n 1 and m 2, while for coal n 1 and decomposition of water into hydrogen and oxygen using
m 0.8. Half of the hydrogen is derived from H2O for electricity:
a methane feedstock, 64.5% for naphtha, 69% for heavy oil,
and 83% for coal. The product hydrogen typically has
a purity of 93%e98%. Excess energy required to promote 2H2 O/2H2 O2 (17.8)
350 Exergy
The total energy required to decompose water is given by 17.4.3 Hydrogen Production from Biomass
the negative of the heat of combustion of hydrogen, and the
minimum electrical energy by the change in the Gibbs free Hydrogen can be produced from many types of biomass via
energy. For ideal electrolyzers, heat is added to make up for chemical processes in which hydrogen is separated from
the difference between the minimum electrical and total the biomass feedstock (if it contains hydrogen) and from
energy requirements; for practical electrolyzers, enough water. The chemical processes involved are similar to those
heat is evolved due to cell inefficiencies to more than make used in producing hydrogen from hydrocarbons, but are not
up for the difference. discussed extensively in this chapter.
Hydrocarbon-based Nonhydrocarbon-based
SMR Water electrolysis*
Coal gasification Thermochemical water decomposition
*Two categories of water electrolysis are considered: (1) conventional and (2) advanced.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 351
17.5.1 Approach and Methodology to produce these secondary energy forms, and the corre-
sponding processes required to convert these resources found
The approach and methodology used in the energy and in nature to the secondary energy forms. Consequently, for
exergy analyses of the hydrogen production processes water electrolysis and thermochemical water decomposition,
considered in these case studies are described. where high-temperature heat is a key input, we consider three
Resources found in nature are the main external inputs to cases of possible main inputs in the analyses:
some of the hydrogen production processes considered (i.e.,
l Electricity and process heat
hydrogen production from hydrocarbons), while for others
l Heat
(i.e., water electrolysis and thermochemical water decom-
l A hypothetical heat source
position), secondary energy forms like process heat and
electricity are utilized. To permit fair comparisons, it is useful The process includes heat and electricity generation steps
to consider, at least hypothetically, resources found in nature in the third case and an electricity generation step in the
second. The hypothetical heat source is intended to be an and Po). The base enthalpy of a fuel is equal to the enthalpy
environmental resource. The existence of a heat source is change in forming the fuel from the components of the
hypothesized so that processes in which some inputs (e.g., environment (the same environment used in exergy calcu-
high-temperature heat) are not resources found in nature lations). A compound that exists as a stable component of
can be compared with processes in which all inputs are the reference environment is defined to have an enthalpy of
resources found in nature. For simplicity, the exergy of zero at To and Po.
a hypothetical heat source is considered equal to its energy, The following assumptions are made to simplify the
which is approximately valid for many fossil fuels. energy and exergy assessments of the considered hydrogen
To facilitate comparisons between the results of energy production processes:
and exergy analyses, base enthalpy values are used. The
base enthalpy is the enthalpy of a component (at To and Po) l Combustion occurs in 40% excess air.
relative to the stable components of the environment (at To l Hydrocarbons are sulfur free.
l Natural gas is pure methane. The energy and exergy analyses are performed using
l Coal is pure carbon. data (e.g., chemical exergy) reported in the literature and
l Air is composed of 79% nitrogen and 21% oxygen on obtained via process simulation, based on Aspen Plus.
a volume basis. Properties from the process simulation database are used,
which include steam properties based on the American
A reference-environment model based on the natural
Society of Mechanical Engineers steam tables.
environment (and discussed in Section 2.8 of this book) is
used in the evaluation of energy and exergy quantities, but
with a reference-environment temperature (To) of 15 C (the
approximate mean temperature of the lake cooling water).
17.5.2 Process Descriptions
The reference-environment pressure (Po) is 1 atm, and the Detailed process diagrams for the considered production
chemical composition consists of air saturated with water processes are presented in Figures 17.3e17.7, and corre-
vapor, and the following condensed phases at To and Po: water sponding process data and descriptions in Tables
(H2O), gypsum (CaSO4$2H2O), and limestone (CaCO3). 17.3e17.6.
FIGURE 17.5 Simplified process flow diagram
for hydrogen production by conventional water
electrolysis.
354 Exergy
17.5.2.1 Coal Gasification illustrated in Figure 17.3, and details and data are presented
in Table 17.3.
In this case study, coal gasification is considered, which is
a process for hydrogen production by partial oxidation of
hydrocarbons, where the hydrocarbon is coal. The coal- 17.5.2.2 SMR
gasification process considered is based on the Koppers- In this case study, we consider SMR, which is a type of
Totzek process, for which the main steps are coal steam reforming of hydrocarbons where the hydrocarbon is
preparation (drying and pulverizing), steam generation, gas methane from natural gas. The main steps for the SMR
compression, oxygen production by air separation, gasifi- process considered in this study are reforming, steam
cation of coal with O2 and steam, gas cleaning, primary generation, high- and low-temperature shifts, gas
upgrading of raw gas (H2S removal, shifting, CO2 compression, carbon-dioxide removal, methanation, gas
removal), and secondary upgrading of raw gas (methana- cooling, and water separation. This process is illustrated in
tion, cooling, water removal, compression). This process is Figure 17.4, and details and data are presented in Table 17.4.
Coal gasification l Feed coal is gasified in the presence of O2 and low-pressure steam.
l 50% of the molten slag is removed from the raw gas (at 2730 F and 20 psi).
l Water is added to quench the gas to 100 F.
l Superheated steam at 1200 psig and 900 F is generated from the raw gas.
l Raw gas (180 F) is cleaned with a Venturi scrubber and electrostatic precipitator.
Primary upgrading of raw gas l H2S is removed with the Rectisol system.
l Steam and quench water are added.
l CO concentration is reduced from 59% to 3% by shifting the raw gas.
l Raw gas (at 370 F and 700 psig) preheats feedwater.
l Raw gas is cooled to 115 F with cooling water.
l CO2 is removed with the monoethanolamine process.
Secondary upgrading of raw gas l Raw gas is preheated to 550 F and the CO content reduced to 0.1% by methanation.
l Raw gas is cooled from 900 F to 125 F by heat recovery and water cooling.
l Raw gas is dried to 7 lb-water/106-scf-gas.
l Product gas (93% H2) is compressed to 1000 psig.
TABLE 17.5 Description of Conventional and Advanced Processes for Hydrogen Production by Water Electrolysis
TABLE 17.6 Description of Process for Hydrogen Production by Thermochemical Water Decomposition
reaction of Equations 17.9e17.13 is water decomposition external (emissions) parts. Byproduct credits are not
(Eq. 17.8). This process is illustrated in Figure 17.7, and considered, although no significant change is observed in
details and data are presented in Table 17.6. the efficiencies if byproduct credits are allowed. The
overall efficiencies range widely, from 21% to 86% for
energy efficiencies, and from 19% to 83% for exergy effi-
17.5.3 Results and Discussion ciencies. The great majority of exergy losses are associated
Energy and exergy efficiencies, determined as the ratio of with exergy consumptions (75% to 96% of the total exergy
the energy (or exergy) of product(s) to the energy losses) rather than external waste exergy emissions.
(or exergy) of input(s), are presented for the overall Overall energy and exergy balances are shown in
processes in Table 17.7, along with a breakdown of the Table 17.8 for the hydrogen production processes consid-
exergy consumption rates into internal (consumptions) and ered in the case studies. Those sections in Table 17.8
358 Exergy
TABLE 17.7 Energy and Exergy Efficiencies and Breakdown of Exergy Losses for the Hydrogen Production Processes
Considered
Exergy loss
Efficiency (%) breakdown (%)
involving water electrolysis and thermochemical water exergydapproximately from 50% for coal gasification to
decomposition consider hypothetical heat sources as the 80% for SMR. Furthermore, since the hydrogen-to-carbon
main inputs. atomic ratios for coal (0.8) and methane (4) bracket the
As a sample illustration, a simplified energy diagram range covered by most of the hydrocarbons used in
showing normalized energy flow rates is presented for coal hydrogen production, the efficiencies for hydrogen
gasification in Figure 17.8, and a corresponding simplified production from hydrocarbons having intermediate ratios
exergy diagram containing normalized exergy flow rates often lie between those determined here for coal gasifica-
and normalized exergy consumption rates is presented in tion and SMR.
Figure 17.9. For each hydrocarbon-based process, the overall energy
and exergy efficiencies are similar (see Table 17.7).
17.5.3.1 Hydrogen Production from However, these efficiencies differ for many plant devices.
That is, the main energy and exergy losses are associated
Hydrocarbons
with different devices. In general, all energy loss is asso-
All the input energy and exergy to coal gasification and ciated with waste emissions, while most (over 90% for
SMR are associated with the hydrocarbons (coal or natural most processes) of the exergy loss is associated with
gas). Most of the output energy is associated with waste internal consumptions (see Table 17.7).
cooling water, stack gas and hydrogen, and most of the Cooling water and stack gas account for almost all of
output exergy with the hydrogen. For the hydrocarbon- the energy losses and less than 10% of the exergy losses.
based processes (and all other hydrogen production Internal consumptions are responsible for most of the
processes considered in the case studies), little exergy is exergy losses. The main exergy consumptions for coal
associated with the output cooling water because it is near gasification occur in the gasifier (40% of the total exergy
the temperature of the environment, and the exergy asso- consumption) and combustor (32%), and for SMR in the
ciated with the stack gas, where it is present, is mainly combustor (50%). Another significant exergy consumption
chemical exergy. These observations are visible in the for both processes occurs in the CO2-removal systems due
energy and exergy diagrams for coal gasification presented to the use of steam to regenerate the CO2 absorbent by
in Figures 17.8 and 17.9, respectively. heating. Remaining exergy consumptions are primarily
The efficiencies (see Table 17.7) for these processes attributable to compression, air separation, and other
are relatively high, rangingdbased on energy or chemical reactions and heat transfers.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 359
TABLE 17.8 Overall Energy and Exergy Balances for Considered Hydrogen Production Processes
Waste gas 2 0
Total 100 100 Total 100 23.5 Total 76.5
Note: Energy values are expressed as a percentage of the total energy input, and exergy values as a percentage of the total exergy input.
360 Exergy
FIGURE 17.8 Simplified energy diagram for coal gasification. Energy flow rates are shown for each flow, normalized to 100 units of external energy
supply to the process. The small boxes within the boiler and coal preparation processes represent combustion. External inputs and outputs are written in
upper case.
FIGURE 17.9 Simplified exergy diagram for coal gasification. Exergy flow rates are shown for each flow and exergy consumption rates (negative
values) are shown for each process. Exergy values are normalized to 100 units of external energy supply to the process. The small boxes within the boiler
and coal preparation processes represent combustion, and the negative values in the small boxes represent exergy consumptions due to combustion.
External inputs and outputs are written in upper case.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 361
The losses associated with air separation could be combustion and heat transfer across large temperature
reduced using an integrated process where the oxygen differences).
requirement of the gasifier is met using byproduct O2 from l Different devices are usually responsible for significant
water electrolysis or thermochemical water decomposition. energy and exergy losses (e.g., typical efficiencies for
boilers are 30% based on exergy and 85% based on
17.5.3.2 Hydrogen Production from energy).
Nonhydrocarbons l Products of fuel production processes often have high
energy and exergy contents and waste high energy and
All of the input energy and exergy to conventional and low exergy contents. Thus, energy analyses often indi-
advanced water electrolysis and to thermochemical water cate that wastes are valuable, and, to increase efficiency,
decomposition is associated with high-temperature heat or quantities of waste effluents must be reduced, while
the hypothetical heat source. Most of the output energy is exergy analyses indicate that wastes are not valuable and
associated with waste cooling water and hydrogen, and internal consumptions must be reduced to significantly
most of the output exergy with the product hydrogen. increase efficiency.
The efficiencies (based on energy or exergy) range from
low (about 20%) for thermochemical water decomposition
to high (over 90%) for water electrolysis. The efficiencies 17.6 CLOSING REMARKS
for the advanced water electrolysis case exceed those for Energy and exergy analyses are presented and compared
the conventional case. The exact values of the efficiencies for a range of hydrogen production processes, including
for the processes depend on what sources of electricity and/ processes based and not based on hydrocarbons. The
or high-temperature heat are used. former normally utilize fossil fuels as a feedstock, while the
Efficiencies for thermochemical water decomposition latter usually derive hydrogen from water and can utilize
have been reported in the literature that are higher than the renewable sources of thermal energy. Overall efficiencies
ones determined here for the Ispra Mark-10 process. These range widely (21%e92% based on energy and 19%e83%
proposed efficiencies are often based on conceptual based on exergy), but thermodynamic losses exhibit many
designs. The Ispra Mark-10 process was chosen because commonalities. The great majority of the overall exergy
detailed data for a proposed commercial process existed. losses for the processes are associated with internal
When heat is considered as the primary input, cooling consumptions and little with emissions, even though all of
water accounts for nearly all of the energy losses, but only the energy losses are associated with waste emissions. This
3%e7% of the exergy losses. The remaining exergy losses information can assist efforts to design, improve, and
are associated with internal consumptions, mainly in the optimize hydrogen production processes.
following locations:
l Electrolysis unit and electrical generation plant for PROBLEMS
conventional water electrolysis
l Feedwater preheater and electrical generation plant for 17.1 Perform energy and exergy analyses of hydrogen
advanced water electrolysis production processes other than those considered in
l Primary reactors (where high-temperature heat is the case studies in this chapter.
degraded to low-temperature heat) for thermochemical 17.2 For the case studies in which the main driving input is
water decomposition a hypothetical heat source, identify three possible
resources that can be the hypothetical heat source.
17.5.3.3 Generalizations Modify the energy and exergy analyses for those
cases, accounting for each hypothetical heat source.
Several general trends are demonstrated:
Hint: Do not make the assumptions invoked in the
l Overall efficiencies range widely (~20%e90%) for the case studies regarding the hypothetical heat source,
processes considered but, for any given process, the but instead consider the actual resource you identify.
energy and exergy efficiency values are usually similar. 17.3 To simplify exergy analyses, it is sometimes assumed
This similarity occurs because input energy and exergy for hydrocarbons that the ratio of chemical exergy to
magnitudes are similar, and product energy and exergy energy is one. For each hydrocarbon involved in the
magnitudes are similar. For other processes, where these hydrogen production processes considered in the case
conditions do not hold, values of energy and exergy studies, determine the actual ratio of chemical exergy
efficiencies are different. to energy. Also, determine the percentage error in the
l All energy losses in a process are associated with waste overall efficiencies for the hydrogen production
emissions (mainly with output cooling water), and most processes if the simplifying assumption (chemical
exergy losses with internal consumptions (mainly due to exergy-to-energy ratio 1) is invoked.
362 Exergy
17.4 Identify options to reduce the exergy consumptions purpose within the process or in an external process.
for each of the hydrogen production processes. Determine the change in the energy and exergy effi-
Determine the change in the energy and exergy effi- ciencies and losses if the wastes are deployed in this
ciencies and losses if the exergy consumptions are manner.
reduced in this manner. 17.7 Identify options to integrate two or more hydrogen
17.5 Identify options to reduce or eliminate the waste productions to achieve some benefits. Explain quan-
emissions for each of the hydrogen production titatively and qualitatively the anticipated benefits.
processes. Determine the change in the energy and Perform energy and exergy analyses of the integrated
exergy efficiencies and losses if the wastes are systems.
reduced or eliminated in this manner. 17.8 Identify a biomass-based process for hydrogen
17.6 Identify options to utilize the waste emissions from production, and perform energy and exergy analyses
the hydrogen production processes for some useful of the process.