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Chapter 17

Exergy Analysis of Hydrogen Production


Systems
Chapter Outline
17.1 Introduction 347 17.5.2 Process Descriptions 353
17.2 Hydrogen Production Processes 348 17.5.2.1 Coal Gasification 354
17.3 Hydrogen Production from Fossil Fuels 348 17.5.2.2 SMR 354
17.3.1 Hydrogen Production by Steam Reforming of 17.5.2.3 Water Electrolysis 355
Hydrocarbons 348 17.5.2.4 Thermochemical Water
17.3.2 Hydrogen Production by Partial Oxidation of Decomposition 355
Hydrocarbons 349 17.5.3 Results and Discussion 357
17.4 Hydrogen Production from Renewable Energy 349 17.5.3.1 Hydrogen Production from
17.4.1 Hydrogen Production by Water Electrolysis 349 Hydrocarbons 358
17.4.2 Hydrogen Production by Thermochemical 17.5.3.2 Hydrogen Production from
Water Decomposition 350 Nonhydrocarbons 361
17.4.3 Hydrogen Production from Biomass 350 17.5.3.3 Generalizations 361
17.5 Case Studies 350 17.6 Closing Remarks 361
17.5.1 Approach and Methodology 351 Problems 361

ABSTRACT 17.1 INTRODUCTION


Energy and exergy analyses are used in this chapter to perform
Hydrogen is used as a fuel and as a feed for producing other
thermodynamic performance analyses and comparisons of four
types of hydrogen production processes. Energy and exergy fuels and commodities. In the future, the role of hydrogen may
efficiencies and losses are evaluated for each of the overall become more important, with some researchers suggesting
production processes and for the subprocesses within each that the worlds energy systems may undergo a transition to an
process. Hydrogen is used as a fuel (or energy carrier), and as era in which the main energy carriers are hydrogen and
a feed for producing other fuels and commodities. In the future, electricity (Penner, 2006; Bose and Malbrunot, 2007; Scott,
the role of hydrogen may become more important, with some 2007). Hydrogen production is a key challenge to a hydrogen
researchers suggesting that the worlds energy systems may energy system (Holladay et al., 2009). To support the devel-
undergo a transition to an era in which the main energy carriers opment, enhancement, and optimization of hydrogen
are hydrogen and electricity. The development, enhancement, production processes, energy and exergy analyses have been
and optimization of hydrogen production processes is a key
applied to many such processes (Rosen and Scott, 1998) to
challenge to a hydrogen energy system, and exergy analysis
improve understanding of their thermodynamic performances
can assist such work and provide information that assists in
decision making regarding alternative hydrogen-production and to provide information that assists in decision making
processes. regarding alternative hydrogen-production processes.
Energy and exergy analyses are used here to perform
KEYWORDS thermodynamic performance analyses and comparisons of
Exergy; Hydrogen; Hydrogen production; Energy carrier; Fuel;
four types of hydrogen production processes. Energy and
Steam reforming of hydrocarbons; Steam-methane reforming;
exergy efficiencies and losses are evaluated for each of the
Partial oxidation of hydrocarbons; Water electrolysis; Thermo-
chemical water decomposition; Renewable energy; Biomass. overall production processes and for the subprocesses
within each process. In general, energy and exergy

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

Production process category Production process Status


Hydrocarbon-based processes Steam reforming of natural gas Mature
Catalytic decomposition of natural gas Mature
Partial oxidation of heavy oil Mature
Coal gasification Research-mature
Steam-iron coal gasification Research
Electrolysis of water Mature

Nonhydrocarbon-based processes Thermochemical cycles (pure) Research


Thermochemical cycles (hybrid) Research
Photochemical processes Early research
Photoelectrochemical processes Early research
Photobiological processes Early research
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 349

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

FIGURE 17.2 Simplified process


diagrams for hydrogen production from
water, potentially using renewable energy:
water electrolysis (left) and thermochem-
ical water decomposition (right).

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.

17.4.2 Hydrogen Production by 17.5 CASE STUDIES


Thermochemical Water Decomposition
Case studies involving energy and exergy analyses of
In thermochemical water decomposition (Figure 17.2, a range of hydrogen production processes are presented in
right), a series of chemical reactions occur for which the net this section. The hydrogen production processes considered
reaction is water decomposition (Eq. 17.8). Intermediate are listed in Table 17.2 by category (hydrocarbon-based and
reactants are continuously recycled. Thermochemical nonhydrocarbon-based). Only processes that are significant
water decomposition generally involves at least three and for which substantial and reliable design and operating
distinct steps: data are available are considered. Two categories of water
electrolysis are considered: (1) conventional, which repre-
l Hydrogen production
sents approximate present water electrolysis technology,
l Oxygen production
and (2) advanced, which is based on a predicted future
l Materials regeneration
version of water electrolysis comprised of advanced
High-temperature heat (often exceeding 550 C) drives the components and technologies. The case studies draw
endothermic chemical reactions. Multistep cycles for water extensively on previous investigations of hydrogen
decomposition are used because very high temperatures are production by SMR, coal gasification, water electrolysis,
required before an appreciable amount of water decom- and thermochemical water decomposition, and comparisons
poses in single-step cycles. of these (Casper, 1978; Rosen and Scott, 1998).

TABLE 17.2 Hydrogen Production Processes Considered in the Case Studies

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

FIGURE 17.3 Simplified process flow diagram


for hydrogen production by coal gasification.
352 Exergy

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.

FIGURE 17.4 Simplified process flow diagram


for hydrogen production by SMR.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 353

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.

FIGURE 17.6 Simplified process flow diagram


for hydrogen production by advanced water
electrolysis.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 355

17.5.2.3 Water Electrolysis hydrogen and oxygen purification. The thermochemi-


calewateredecomposition step involves the following five
Water electrolysis processes based on both conventional principal reactions:
and advanced technology are considered in this case study.
The main steps in both cases are electrical generation, 2H2 O 5O2 I2 4NH3 /2NH4 I NH4 2 SO4
transforming and rectification, electrolysis, hydrogen and (17.9)
oxygen cooling, water removal, and hydrogen compres-
2NH4 I/2NH3 H2 I2 (17.10)
sion. The conventional and advanced processes are illus-
trated in Figures 17.5 and 17.6, respectively, and details and NH4 2 SO4 Na2 SO4 /Na2 S2 O7 H2 O 2NH3
data are presented in Table 17.5. (17.11)
Na2 S2 O7 /SO3 Na2 SO4 (17.12)
17.5.2.4 Thermochemical Water Decomposition
1
Thermochemical water decomposition based on the Ispra SO3 /SO2 O2 (17.13)
2
Mark-10 cycle is considered in this case study. The
main steps for this process are heat and electricity gener- These reactions occur over a range of temperatures:
ation, thermochemical water decomposition, and 325, 900, 675, 825, and 1140 K, respectively. The net

FIGURE 17.7 Simplified process flow diagram


for hydrogen production by thermochemical water
decomposition.
356 Exergy

TABLE 17.3 Description of Process for Hydrogen Production by Coal Gasification

Process step Description


Coal preparation l Raw coal (22% moisture) is input as feed and fuel.
l Feed coal is dried to 2% moisture and pulverized.
Steam generation l Steam is generated by combusting boiler-fuel coal.
Compression and air separation l Raw gas is compressed from 20 to 700 psig.
l Product gas is compressed from 700 to 1000 psig.
l Air separation plant produces O2.
l Superheated steam drives the turbines.

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 17.4 Description of Process for Hydrogen Production by SMR

Process step Description


Reforming and steam generation l CH4 feed is desulfurized and mixed with superheated steam.
l Reforming occurs and raw gas exits at 370 C and 3.5 MPa.
l Steam is generated in the boiler for compression and CO2 stripping.
l Required process heat is supplied by combusting CH4 fuel.
High-temperature shift l 94% of the CO in the raw gas is shifted over a high-temperature catalyst.
l Gas exits at 220 C and preheats incoming boiler and methanator feeds.
Low-temperature shift l 83% of the remaining CO in the raw gas is shifted over a low-temperature catalyst.
l Gas exits at 150 C and preheats incoming feedwater.
Compression and CO2 removal l Raw gas is compressed to 3.5 MPa in steam turbine-driven centrifugal compressors.
l CO2 content of raw gas is reduced to 0.1 wt% using the monoethanolamine process.
l Steam supplies energy (821 Btu/lb CO2 recovered) to the CO2 stripper.
Methanation l Steam preheats the methanator feed to 350 C and 2.4 MPa.
l Methanation occurs over a catalyst.
Cooling l Gas preheats feedwater and is cooled to 25 C with cooling water.
l Water is separated.
l Product H2 with a 97% purity on a weight basis exits at 25 C and 2.4 MPa.
Chapter | 17 Exergy Analysis of Hydrogen Production Systems 357

TABLE 17.5 Description of Conventional and Advanced Processes for Hydrogen Production by Water Electrolysis

Process step Description


Electricity generation l Electricity is generated from heat at an efficiency of 39% (conventional) or 50% (advanced).
l Some electricity is delivered to the compressor, and most to the transformer.
Transformation and l Electricity is converted from AC to DC at 97% efficiency.
rectification
Electrolysis l Water is decomposed in the electrolysis unit.
l Raw gases exit at 359 K and 0.101 MPa.
l Feedwater is purified.
l Feedwater is mixed with recycled water from the coolers and compressors in the electrolyte circulation
loop (only conventional).
Hydrogen and oxygen l H2 and O2 streams are cooled to 308 K with cooling water separately (conventional) or together (advanced).
cooling l Moisture condenses and is recycled.
l Feedwater is preheated to 800 K and 0.101 MPa (only advanced).
l Feedwater preheating uses hot gases from electrolysis (at 80% heat recovery) and direct heat input.
Hydrogen compression l H2 is compressed in a four-stage compressor with intercooling to 308 K.
l Moisture condenses and is recycled.
l Product gas (99.5 wt% H2) exits at 10.3 MPa and 308 K.

TABLE 17.6 Description of Process for Hydrogen Production by Thermochemical Water Decomposition

Process step Description


Thermal and electrical generation l Helium delivers thermal energy from a high-temperature gas-cooled reactor at 1255 K
and returns at 773 K.
l Remaining heat is delivered over a range of temperatures to the other units.
l Electricity is generated at 80% of the thermodynamic ideal efficiency.
l Electricity is used in the primary reactors.
Primary thermochemical-water-decomposition l Five main reactions in Equations 17.9e17.13, netting water decomposition, occur at
reactions various temperatures.
l 17% of the water in the cycle decomposes.
l Waste gas exits at 325 K and 0.101 MPa.
Oxygen purification l O2 exits at 300 K and 5.00 MPa.
l Feedwater enters at 290 K and 0.101 MPa.
Hydrogen purification l Helium (entering at 815 K and exiting at 798 K) delivers heat for purification.
l Product gas (99.9 wt% H2) exits at 300 K and 0.210 MPa.

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 (%)

Process Main energy input(s) Energy Exergy Internal External


Coal gasification Coal 59 49 94 6
SMR Natural gas 86 78 91 9

Water electrolysis (conventional) Electricity and process heat 77 67 96 4


Heat 30 46 89 11
Hypothetical heat source 30 26 95 5
Water electrolysis (advanced) Electricity and process heat 92 83 83 17
Heat 49 73 75 25
Hypothetical heat source 49 41 93 7

Thermochemical water decomposition Electricity and process heat 21 26 93 7


Heat 21 25 93 7
Hypothetical heat source 21 19 95 5

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

Input Output Consumption

Process Flow Energy Exergy Flow Energy Exergy Process Exergy


Coal gasification Coal feed 76 76 H2 product 59 49 Gasification 11
Coal dryer fuel 3 3 Stack gas 3.5 1 Combustion 14
Coal boiler fuel 21 21 Cooling 35 2 Others 19
water
CO2 waste 0 4
N2 waste 0 0

H2O waste 2.5 0


Total 100 100 Total 100 56 Total 44
SMR Natural gas feed 67 67 H2 product 86 78 Furnace 11
Natural gas fuel 33 33 Stack gas 6 1.5 CO2 removal 4
Cooling 8 0.5 Others 3
water
CO2 waste 0 2
Total 100 100 Total 100 82 Total 18
Water electrolysis (conventional) High-temp. heat 100 100 H2 product 30 26 Electrolysis 10
source
O2 waste 0 0 Electricity generation 15
Cooling 70 3 High-temp. heat 43
water production
Others 3

Total 100 100 Total 100 29 Total 71


Water electrolysis (advanced) High-temp. heat 100 100 H2 product 49 41 Electrolysis and others 3
source

O2 waste 0 0.5 Electricity generation 4


Cooling 51 2.5 High-temp. heat 44
water production

Preheating and cooling 5


Total 100 100 Total 100 44 Total 56
Thermochem. water High-temp. heat 100 100 H2 product 21 19 Primary reactions 47
decomposition source
O2 waste 0 0.5 High-temp. heat 23.5
production
Cooling 77 4 Others 6
water

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.

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