i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8

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Natural gas based hydrogen production with zero carbon

dioxide emissions

Jorge A. Pena Lopez, Vasilios I. Manousiouthakis*

Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, 5531 Boelter Hall, Los Angeles,
CA 90095-1592, USA

article info abstract

Article history: A novel process flowsheet is presented that co-produces hydrogen and formic acid from
Received 27 April 2011 natural gas, without emitting any carbon dioxide. The principal technologies employed in
Received in revised form the process network include combustion, steam methane reforming (SMR), pressure swing
14 July 2011 adsorption, and formic acid production from CO2 and H2. Thermodynamic analysis
Accepted 15 July 2011 provides operating limits for the proposed process, and the use of reaction clusters leads to
the synthesis of a feasible process flowsheet. Heat and power integration studies show this
flowsheet to be energetically self-sufficient through the use of heat engine and heat pump
Keywords: subnetworks. Operating cost/revenue studies, using current market prices for natural gas,
Hydrogen hydrogen and formic acid, identify the proposed design’s operating revenue to cost ratio to
Natural gas be 9.29.
Formic acid Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Energetically self-sufficient reserved.

1. Introduction High temperature methane and steam are fed to the SMR
reactor, where three reversible reactions occur:
Of all energy resources, natural gas is the resource most
ðgÞ ðgÞ
commonly used for hydrogen production. Typically, natural CH4 þ H2 OðgÞ 4COðgÞ þ 3H2 ðR1 Þ (1)
gas (which consists mainly of methane) is converted to
ðgÞ ðgÞ
hydrogen through steam methane reforming (SMR). In 1999, COðgÞ þ H2 OðgÞ 4CO2 þ H2 ðR2 Þ (2)
99% of hydrogen’s world production was reported to be carried
out using SMR [1,2]. This figure changed to 90% by 2001 [3], and ðgÞ ðgÞ ðgÞ
CH4 þ 2H2 OðgÞ 4CO2 þ 4H2 ðR3 Þ (3)
to 50% by 2005 [4], with the remaining hydrogen production
coming from oil (30%), primarily for hydroprocessing appli- The kinetics of these reactions on a Ni/MgAl2O4 catalyst
cations in oil refineries, from coal (19%) primarily for have been studied by Xu and Froment [7]. The overall reaction
ammonia production, and the remaining (w1%) coming from is endothermic, thus combustion of a fuel (methane) is needed
electricity via water electrolysis. Aside from their potential to provide the required heat. Hydrogen is first produced
operating cost advantages, SMR plants also require lower through the SMR reactor and then additional hydrogen is
capital costs. An SMR plant with a capacity higher than one produced in a water-gas shift reactor which depletes the
million Nm3 H2/day has the lowest investment cost in content of carbon monoxide in the stream exiting the SMR
comparison with other hydrogen production processes [5,6]. reactor by carrying out only reaction (R2) at a lower

* Corresponding author. Tel.: þ1 310 206 0300; fax: þ1 310 206 4107.
E-mail addresses: jpenalopez@ucla.edu (J.A. Pena Lopez), vasilios@ucla.edu (V.I. Manousiouthakis).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.07.061
12854 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8

temperature. Next, water is condensed and removed to be studies are thus carried out to identify the exact values of X
recycled back to the process. The hydrogen rich stream is then corresponding to an energetically self-sufficient flowsheet.
sent to a pressure swing adsorption (PSA) unit, to obtain Finally, conclusions are drawn. A detailed description of
hydrogen at 99.999þ% purity [8e10], through a multi-step the notation used in this paper is included in a separate
cyclic process, in which the unit is first pressurized, then section.
species other than hydrogen are selectively adsorbed (along
with a fraction of hydrogen) on a solid bed (e.g. activated
carbon, 5A zeolite) by contacting the gas with the solid, thus 2. Thermodynamic feasibility of proposed
producing a highly purified hydrogen gas stream [9]. When the hydrogen production method
bed approaches saturation, it is depressurized, leading to
desorption of species from the solid and thus to the bed’s First, the concept of energetic self-sufficiency is introduced.
regeneration, and to the generation of PSA waste gas. Let U be a steady-state open system with inlets in SI; outlets in
Continuous flow of product is maintained by using multiple, SO; heat transfer rates Q_ j j˛SQ entering ðQ_ j > 0Þ or exiting
properly synchronized adsorption beds. ðQ_ j < 0Þ the system at temperatures Ts;j j˛SQ ; and shaft work
rates W _ s;j j˛SW entering (consumed by) W _ s;j > 0 or exiting
The present work puts forward the position that
_
(produced by) Ws;j < 0 the system. This system has to satisfy
“hydrogen can be produced from fossil fuels without gener-
ation of carbon dioxide emissions”. In 2006, Posada & Man- the overall mass, element, energy, and entropy conservation
ousiouthakis [11] set a precedent with an integrated steam laws. These latter two laws are often referred to as the 1st and
methane reforming process which generated hydrogen and 2nd laws of thermodynamics, which at steady-state require
carbon dioxide in dry ice form so it can be sequestered at the that the energy entering the system must equal the energy
bottom of the ocean [12]. The next level proposes that carbon exiting the system, and that the system’s rate of entropy
contained in the fossil fuel will not be emitted as carbon generation is non-negative. Under the assumption of steady-
dioxide, but rather in the form of a valuable carbon state and neglecting the effects of kinetic- and potential-
econtaining chemical. This approach will not only eliminate energy, the above conservation laws are represented by
carbon dioxide emissions from hydrogen production plants, Eqs. (4) through (7) [15]:
but will also enhance the economics of these plants since X X
they will no longer be generating a byproduct that needs to 0¼ m
_i m
_i (4)
i˛SI i˛SO
be dealt with at some cost, but rather will be producing
a valuable co-product that can be sold, thus contributing to
XX xi;j XX xi;j
a reduced (or possibly even negative) cost for hydrogen. This 0¼ nj;k m
_i nj;k m
_i ck˛SE (5)
Mj Mj
co-production of hydrogen with valuable carbonecontaining i˛SI j˛SC i˛SO j˛SC

chemicals from a fossil fuel energy source holds therefore

X X X X
the promise of producing “clean” hydrogen at reduced cost, 0¼ Hi m
_i Hi m
_iþ Q_ j þ _ s;j
W (6)
thus accelerating the onset of a hydrogen carrier trans- i˛SI i˛SO j˛SQ j˛SW

portation era. The particular fossil fuel and co-product

considered in this work are methane (natural gas) and for- X X X Q_ j
0¼ Si m
_i Si m
_iþ þ S_ G ; S_ G  0 (7)
mic acid respectively. The industrial uses of formic acid and Ts;j
i˛SI i˛SO j˛SQ
its global and regional production capacity can be found in
Refs. [13,14]. where, SC and SE are the sets of all chemical species and
The remainder of this work is structured as follows: chemical elements respectively comprising the system, yj,k is
First, a novel hydrogen producing reaction scheme is the stoichiometric coefficient of the constituent element k in
proposed, that utilizes natural gas as both a raw material the formation reaction of the j-th chemical species, xi,j is the
and an energy source and does not emit any carbon dioxide. mass fraction of the j-th chemical species in the ith stream,
Then the concept of energetic self-sufficiency, for an open Hi and Si are the specific mass enthalpy and entropy
thermodynamic system is introduced. Then, using the 1st respectively of the ith stream at its temperature and pressure
and 2nd laws of thermodynamics, an exact thermodynamic conditions Ti and Pi; and S_ G is the total rate of entropy
analysis is carried out that identifies a range of values of the generation due to irreversibilities both within the system’s
water/methane molar ratio (X ) over which the proposed control volume and in the heat transfer across finite
hydrogen production scheme can be energetically self- temperature differences between the control volume and its
sufficient. Subsequently, pinch analysis is carried out to surroundings.
estimate the energetic self-sufficiency of a process realiza- Definition. Let U be a steady-state open system with inlets in
tion for the proposed reaction scheme, which utilizes steam SI, outlets in SO, no heat transferred from the surroundings to
methane reforming, natural gas combustion, reverse water- the system, heat possibly transferred from the system to the
gas shift, and hydrogen/carbon dioxide to formic acid surroundings Q_ j  0 j˛SQ at the uniform surroundings
technologies. Having established thermodynamic feasi- temperature ðTs;j ¼ T0 Þ, and the system’s net shaft work to be
bility, a flowsheet is proposed, which co-produces hydrogen non-positive
P _
Ws;j  0 (Fig. 1). Such a system is called
and formic acid, does not emit carbon dioxide, and consists j˛SW

only of available technologies. The flowsheet’s operating energetically self-sufficient.

conditions have a significant dependence on the afore- The definition of energetic self-sufficiency can be mathe-
mentioned ratio X. Detailed heat and power integration matically stated as:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8 12855

temperature condition of the surroundings (T0 ¼ 298.15 K),

X
Q_ 0  0; _ s;j  0
W (8)
j˛SW then the above necessary conditions can be written as:
X X
m
_i _i¼0
m (15)
X X
0¼ m
_i m
_i (9)
i˛SI i˛SO i˛SI i˛SO

XX xi;j XX xi;j
XX xi;j XX xi;j nj;k m
_i nj;k _ i ¼ 0 ck˛SE
m (16)
0¼ nj;k m _i nj;k m _i ck˛SE (10) i˛SI j˛SC
Mj i˛SO j˛SC
Mj
i˛SI j˛SC
Mj i˛SO j˛SC
Mj
X X
X X X DH_ s ðT0 Þa Hi m
_i _i0
Hi m (17)
Q_ 0 ¼ Hi m
_iþ Hi m
_i _ s;j
W (11) i˛SI i˛SO
i˛SI i˛SO j˛SW X X X
! DG_ s ðT0 Þa Gi m
_i Gi m
_ i¼ ðHi T0 $Si Þm
_i
X X
T0 $S_ G ¼ T0 $ Si m
_i Si m
_i Q_ 0  0 (12) i˛SI
X i˛SO i˛SI

i˛SO i˛SI ðHi _ i 0

T0 $Si Þm (18)
i˛SO
This can be equivalently stated as:
where DH_ s ðT0 Þ and DG_ s ðT0 Þ are respectively the system’s
enthalpy and Gibbs free energy change rates at T0 ¼ 298.15 K.
S_ G  0 In this work, carrying out a thermodynamic analysis of
X X
m
_i _i¼0
m energetic self-sufficiency requires evaluation of DH_ s ðT0 Þ and
i˛SI i˛SO
DG_ s ðT0 Þ, which in turn requires evaluation of the inlet and
XX xi;j XX xi;j
nj;k m
_i _ i ¼ 0 ck˛SE
m nj;k outlet streams’ specific mass enthalpies and Gibbs free ener-
Mj M j
i˛SI j˛SC i˛SO j˛SC gies. To this end, all streams are considered to consist of pure
substances, except for the inlet air stream which is considered
!
X X
Q_ 0 ¼ T0 $ Si m
_i Si m
_i T0 $S_ G  0 to be an ideal gas mixture. In addition, all streams are
i˛SO i˛SI
! considered to be ideal gases, and to enter and exit the system
at T0 ¼ 298.15 K and P0 ¼ 1 bar, except for hydrogen which is
X X X
_ s;j ¼ T0 $S_ G
W ðHi T0 $Si Þm
_i ðHi T0 $Si Þm
_i 0
j˛SW i˛SI i˛SO considered to be a real gas and is considered to exit the system
(13) at T0 ¼ 298.15 K and P0 ¼ 354.6 bar. Under these assumptions,
the specific mass enthalpies and Gibbs free energies via ideal
The above imply that necessary conditions, independent of
gas state, residual, and heat of formation properties are
S_ G , for a system to be energetically self-sufficient are:
calculated as follows p. 140, p. 170 and p. 393, [15]:
Case 1, i ¼ mixture; ideal gas; i ¼ CH4 ; H2 O; air; j ¼ CH4 ;
X X
m
_i m_i¼0
i˛SI i˛SO
H2 O; N2 ; O2 ; Ar :
XX xi;j X X xi;j
m
_i
nj;k nj;k m _ i ¼ 0 ck˛SE
i˛SI j˛SC
M j i˛SO j˛SC
Mj For mixtures with n components the following mass-molar
X X X (14) fraction relations hold:
Q_ 0 W _ s;j ¼ Hi m
_i _i0
Hi m
j˛SW i˛SI i˛SO
yi;j Mj xi;j =Mj
xi;j ¼ n
; yi;j ¼ n j ¼ 1; n; i˛SI WSO
X X X X
ðHi T0 $Si Þm
_i ðHi _i0
T0 $Si Þm yi;k Mk xi;k =Mk
i˛SI i˛SO k¼1 k¼1

Let Gi aHi Ti $Si be the specific mass Gibbs free energy of Additionally, the following relations for the calculation of
the ith stream at its temperature and pressure conditions Ti mixture properties hold:
and Pi. When all the system inlets and outlets are at the Then, from p. 393, [15]

n n n n n
X X ig xi;j =Mj X X ig
X ig
Hi aHi ðTÞ ¼ hi ðTÞ$ xi;k =Mk ¼ hj ðTÞ n $ xi;k =Mk ¼ hj ðTÞxi;j =Mj ¼ Hj ðTÞxi;j
X
k¼1 j¼1 k¼1 j¼1 j¼1
xi;k =Mk
k¼1
X
Dhof;j ðT0 Þ þ nj;k $hok ðT0 Þ
2 3
T ig
n
X6 R Z Cp;j k˛SE
¼ dT þ 5xi;j
7
M R M
4
j¼1 j j
T0

n n n n
X X ig xi;j =Mj
X xi;j =Mj X
Si aSi ðT; PÞ ¼ si $ xi;k =Mk ¼ sj ðTÞxi;j =Mj PnR lnPn $ xi;k =Mk
k¼1 j¼1 j¼1
x
k¼1 i;k =M k x
k¼1 i;k =M k k¼1
0 1 !
n n n n
ig
X X     X X
¼ Sj ðTÞxi;j R xi;j =Mj ln xi;j =Mj þ R @ xi;j =Mj ln
A xi;k =Mk
j¼1 j¼1 j¼1 k¼1

Dsof;j ðT0 Þ þ nj;k $sok ðT0 Þ

2 P 3
ZT Cig
0 1 !
n n n n
6R R P
 
p;j k˛SE
X X     X X
¼ dT ln þ R xi;j =Mj ln xi;j =Mj þ R@ xi;j =Mj Aln xi;k =Mk
7
5xi;j
M RT Mj P0 Mj
4
j¼1 j j¼1 j¼1 k¼1
T0
12856 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8

n n n n
X X ig
X xi;j =Mj xi;j =Mj X
Gi aGi ðT; PÞ ¼ gi $ xi;k =Mk ¼ gj ðTÞxi;j =Mj þ RT n
ln n $ xi;k =Mk
X X
k¼1 j¼1 j¼1
xi;k =Mk xi;k =Mk k¼1
k¼1 k¼1
0 1 !
n n n n
ig
X X     X X
¼ Gj ðTÞxi;j þ RT xi;j =Mj ln xi;j =Mj RT@ xi;j =Mj Aln xi;k =Mk
j¼1 j¼1 j¼1 k¼1
X
Dhof;j ðT0 Þ þ nj;k $hok ðT0 Þ
2 3
ZT Cig
6 R p;j k˛SE
dT þ
7
M R Mj
6 7 0 1
n 66 j T0 n n
X 7 X X
7    
¼ 6
o
X
o
7xi;j þ RT xi;j =Mj ln xi;j =Mj RT@ xi;j =Mj A
Ds ðT Þ þ n ðT Þ
2 3
0 0
6 $s
j;k k
7
j¼1 6 ZT Cig f ;j 7 j¼1 j¼1
R R P
 
6 p;j k˛SE 77
4 T$6 dT ln þ 55
Mj RT Mj P0 Mj
4
T0
!
Xn
ln xi;k =Mk
k¼1

Case 2, i ¼ pure; real gas; i ¼ H2 : Gi aGi ðT; PÞ ¼ Hi ðT; PÞ T$Si ðT; PÞ


ig
hi ðT; PÞ hi ðTÞ ZT Cig
  R p;i
ig ig ig ig
Hi aHi ðT; PÞ ¼ Hi ðT; PÞ Hi ðTÞ þ Hi ðTÞ Hi ðT0 Þ þ Hi ðT0 Þ ¼ þ dT
Mi Mi R
 T0
ig
hi ðT; PÞ hi ðTÞ ZT Cig
R
X
¼ þ
p;i
dT Dhof;i ðT0 Þ þ ni;k $hok ðT0 Þ
Mi Mi R k˛SE
T0 þ
X Mi
Dhof;i ðT0 Þ þ ni;k $hok ðT0 Þ 2
ig

ZT Cig
þ
k˛SE 6 si ðT; PÞ si ðT; PÞ R p;i
T$4 þ dT
Mi Mi Mi RT
T0
X
Dsof ;i ðT0 Þ þ ni;k $sok ðT0 Þ
  3
ig ig ig
Si aSi ðT; PÞ ¼ Si ðT; PÞ Si ðT; PÞ þ Si ðT; PÞ Si ðT0 ; P0 Þ
 
R P k˛SE
ln þ
7
Mi P0 Mi
5
ig
þ Si ðT0 ; P0 Þ

ig
si ðT; PÞ si ðT; PÞ ZT Cig   where n is the number of species, SE is the set of constituent
R p;i R P
¼ þ dT ln elements comprising the system, ni;k  0 k˛SE i ¼ 1; n is the
Mi Mi RT Mi P0
T0 stoichiometric coefficient of the constituent element k in the
X
Dsof;i ðT0 Þ þ ni;k $sok ðT0 Þ formation reaction of the j-th chemical species, and the
þ
k˛SE hydrogen’s residual properties are calculated from the generic
Mi cubic equation of state as shown in Appendix A. The standard-
state specific mass enthalpy and specific mass entropy of the
ig ig
ith species at T0 are denoted as Hi ðT0 Þ and Si ðT0 ; P0 Þ respec-
ig ig
tively. Hi ðT0 Þ ðSi ðT0 ; P0 ÞÞ is equal to the molar standard
enthalpy (entropy) of formation of the ith species at T0,
Dhof ;i ðT0 Þ Dgof ;i ðT0 Þ
!
o
Dhf ;i ðT0 Þ , over its molecular weight, Mi,
T0
plus the weighted sum of the standard-state specific mass
enthalpies (entropies) of its constituent elements,
hok ðT0 Þ ðsok ðT0 ÞÞ, with weights the ratios of the stoichiometric
coefficients of the constituent elements ni;k  0 k˛SE i ¼ 1; n
over the molecular weight, Mi [15]. Typically, hok ðT0 Þ, are chosen
to be zero for all elements, while sok ðT0 Þ are evaluated based on
the 3rd law of thermodynamics, p. 188, [15].
To simplify the preliminary thermodynamic calculations,
Fig. 1 e Energetically Self-Sufficient Open Steady-State the case in which oxygen is being fed to the system in lieu of air
System. U is a well delimited open system with streams is considered. This simplification is not employed in the
from the set SI entering the system and streams leaving the detailed pinch assessment calculations which consider that air
system into the set SO, at temperature T0; heat (Q0, red containing nitrogen, oxygen and argon enters the flowsheet,
arrow) and shaft work (Ws, blue arrow) are negative and while nitrogen and argon are among the flowsheet outlets.
therefore generated by the system. (For interpretation of The standard-state molar enthalpy and Gibbs free energy of
the references to color in this figure legend, the reader is formation values at T0 were taken from the literature (Table 1)
referred to the web version of this article.) [15e18].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8 12857

Table 1 e Standard Enthalpies and Gibbs Energies of a

Formation (J/mol).
Speciesa Dhof,i(298) Dgof,i(298) Reference

CH4(g) 74,520 50,460 [14]

CO2(g) 393,509 394,359 [14]
H2O(g) 241,818 228,572 [14]
H2O(l) 285,830 237,129 [14]
H2(g)b 459.888 15,085 [15]
CO(g) 110,525 137,169 [14]
HCOOH(l) 424,760 361,414 [16]
HCOOH(g) 378,610 351,000 [17]
O2(g) 0 0 [14]

a (g) ¼ gas state, (l) ¼ liquid.

b Standard-state value plus contribution calculated from depar-
ture function of RK equation of state at 354.6 bar.

b
As discussed earlier, the most common industrial process
for the production of hydrogen is steam reforming (SMR) of
natural gas, which involves the incomplete endothermic
transformation of methane and water to hydrogen, carbon
dioxide and carbon monoxide [19e21]. Since the overall
process does not release any carbon monoxide, it can be
captured by the following overall chemical reaction:
 
Z
CH4 þ 1 O2 þ Z H2 O/CO2 þ ð2 þ ZÞH2 (19)
2

An industrially implemented realization of this was dis-

cussed earlier in some detail [8,9]. An inputeoutput repre-
sentation of the above overall chemical reaction is shown in
Fig. 2. It considers that all process inlets and outlets are at
T0 ¼ 298.15 K and P ¼ 1 bar, except for the purified hydrogen
product which is delivered at T0 ¼ 298.15 K and P ¼ 354.6 bar,
so as to meet the first-generation hydrogen-fueled automobile
storage requirements.
The single energy resource for this process is the incoming
natural gas (which is used both as an energy source and as raw
material for the hydrogen production) and it is thus desired to
identify the water to methane molar ratio Z so that the overall
process is an energetically self-sufficient system.
Fig. 3a shows the enthalpy change rate ðDH_ s Þ and Gibbs free
energy change rate ðDG_ S Þ for Eq. (19) per 1 mol/s of CH4. Based
on the graph in Fig. 3a we can reach the conclusion that the
Fig. 2 e Energetically Self-Sufficient Hydrogen Production
System. A well delimited hydrogen production system
with methane, water and oxygen streams entering the
system; hydrogen and carbon dioxide exiting the system.
No heat/work entering the system and heat/work
generated leaving the system.
Fig. 3 e (a) Enthalpy and Gibbs Free Energy Change in Mass
Balance of Eq. (19) at 298 K and 1 bar (H2 at 354.6 bar); (b)
Enthalpy and Gibbs Free Energy Changes in Hydrogen/
Formic Acid Co-production Process, Eq. (20). The horizontal
line marks the level at which both of the values are zero
and the vertical line indicates the energetically self-
sufficient parameter value at this intersection.
self-sufficiency conditions of the system carrying out reaction
(19) are met, for maximum hydrogen production, at
Z þ 2 ¼ 3.325 moles of hydrogen per mol of methane which
occurs at a water to methane molar ratio of Z ¼ 1.325. Various
inefficiencies in bringing about a realization of reaction (19)
may lead to a hydrogen/methane molar ratio smaller than
Z þ 2 ¼ 3.325. As discussed in Ref. [22] the realization of
reaction (19) has a methane/hydrogen molar ratio of
Z þ 2 ¼ 2.797.
To eliminate carbon dioxide emissions we explore in this
work the feasibility of coproducing hydrogen with formic acid,
while maintaining energetic self-sufficiency. The overall
chemical reaction for this proposed hydrogen production
process is shown below:
X
 
CH4 þ 1 O2 þ XH2 O/HCOOH þ ð1 þ XÞH2 (20)
2
The requirement that this alternative hydrogen production
process is energetically self-sufficient is first analyzed based on
12858 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
the 1st law of thermodynamics. All process inlet and outlet
streams are considered to be at 298 K and 1 bar, except for the
hydrogen product which is to be delivered at 298 K and 354.6 bar
(meeting the first-generation hydrogen-fueled automobile
storage requirements). The process enthalpy and Gibbs free
energy changes, normalized on a per mole per second of
methane basis, are then evaluated as a function of the water to
methane molar ratio (X ). As Fig. 3b indicates the proposed
system is energetically self-sufficient for values of X  1.195 thus
placing a thermodynamic upper bound of X þ 1  2.195 on the
number of moles of H2 that can be produced per mole of CH4 with
simultaneous co-production of a mole of formic acid (HCOOH).
This kind of 1st law of thermodynamics based analysis of
energetic self-sufficiency can be carried out for a variety of
other carbon containing chemicals that can be co-produced
with hydrogen from natural gas. In Table 2, several such
possible carbon containing chemicals are considered. For each
of these chemicals, a similar 1st law based energetic self-
sufficiency analysis is carried out, and the maximum
hydrogen to methane ratio is quantified. As can be seen from
Table 2 [23e26], co-production of hydrogeneformic acid,
hydrogeneacetic acid, and hydrogenemethanol, all lead to
maximum hydrogen to methane ratios that are smaller than
the corresponding ratio of 3.325 achieved when CO2 is
hydrogen’s co-product. Since the hydrogeneformic acid
maximum hydrogen/methane ratio of X þ 1  2.195 is the
closest to 3.325, it is this production process that is the focus of
our investigation.
The next step in formulating a viable hydrogeneformic
acid co-production process is to identify technologies that
have been industrially implemented for the production of
these chemicals individually, and then to integrate these
technologies. Since no process exists that can carry out the
desired transformation in a single step, its implementation
can be pursued through the use of a reaction cluster, that is,
through a set of reactions whose sum is the overall reaction.
Each step within the reaction cluster must be thermody-
namically feasible [27e29]. A set of reactions satisfying these
conditions consists of steam methane reforming, water-gas
shift, combustion, and formic acid production from
hydrogen and carbon dioxide (Fig. 4), as shown below.
The reaction cluster shown in Fig. 4 consists of five reac-
tions and possesses two degrees of freedom X  1; Y  0,
due to the bifurcation of the methane input into hydrogen
production (SMR) and energy production (combustion). To
assess whether this system requires no external heat input,
a 2nd law based thermodynamic analysis based on pinch
Table 2 e Carbon Containing Chemical Candidates for Hydrogen Co-production.
Carbon Containing Max H2/CH4
Chemical molar ratio
Carbon Dioxidea 3.325
Formic Acid 2.190
Acetic Acid 1.700
Methanol 1.140
a Reference point.
inequalities can be carried out [30e32]. Such an analysis can,
and will, be rigorously carried out following the construction
of an integrated co-production flowsheet. However an
approximate pinch analysis can be carried out before the
construction of any particular flowsheet based only on
knowledge of the cluster reactions listed in Fig. 4, and of the
temperatures at which these reactions are carried out indus-
trially. This approximate analysis ignores the sensible heat
effects in transporting reactants and products from one
reaction temperature to another (considering that appropriate
heat integration will approximately cancel out any such
effects), considers that all reactions proceed to completion,
and also ignores any heat/work input required to carry out any
needed separations. The enthalpy and Gibbs free energy
change of each reaction is calculated using Eqs. (17) and (18) at
the corresponding temperature of the reaction.
In this context, this approximate pinch analysis is carried
out for the cluster using a minimum approach temperature
DTmin ¼ 10 K, and considering that the first reaction
(combustion) is carried out at 1150 K, the two endothermic
reforming reactions take place in the SMR at 1090 K (consid-
ered as 1100 K in the cold stream temperature scale shifted
upward by the minimum approach temperature DTmin ¼ 10 K),
the WGS reaction (exothermic) takes place at 623 K, and finally
the formic acid reaction (exothermic) takes place at 353 K. The
resulting pinch inequalities represent the requirement that
the cluster’s net available enthalpy at each of the above (hot
stream scale) temperatures should be negative, since the
heats of reaction are negative (positive) for exothermic
(endothermic) reactions:
ð0:5 0:25XÞDH1  0 .T1 ¼ 1150 K (21)
ð0:5 0:25XÞDH1 þ ðYÞDH2 þ ð0:5 þ 0:25X YÞDH3  0 .T2
¼ 1090 K
(22)
ð0:5 0:25XÞDH1 þ ðYÞDH2 þ ð0:5 þ 0:25X YÞDH3
þ ð0:5 þ 0:25X YÞDH4
 0 .T3 ¼ 623 K (23)
ð0:5 0:25XÞDH1 þ ðYÞDH2 þ ð0:5 þ 0:25X YÞDH3
þ ð0:5 þ 0:25X YÞDH4 þ DH5
 0 .T4 ¼ 353 K (24)
ð0:5 0:25XÞDH1 þ ðYÞDH2 þ ð0:5 þ 0:25X YÞDH3
þð0:5 þ 0:25X YÞDH4 þ DH5
þQc ¼ 0 .T5 ¼ 298 K (25)
Main Application World Production Capacity
[1000 tons/year]
e e
Leather treatment, Food 610
Preservative
Vinyl acetate monomer synthesis 4815
Methyl tertiary-butyl ether synthesis 9230
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
Fig. 4 e Reaction Cluster for Hydrogen and Formic Acid Production. Shown are 5 chemical reactions as a function of two
parameters (X, Y ), whose addition results in an overall reaction with only one parameter (X ).
0:5 þ 0:25X Y0
Qc  0
DH1 ¼ 801943; DH2 ¼ 192607; DH3 ¼ 226256; DH4
¼ 38505; DH5 ¼ 29406; all in kJ=mole
The constraints in Eq. (26) ensure that the direction of the
reactions in the cluster is to the right. The constraint in Eq. (27)
ensures that the cold utility load Qc, that must be removed
from the system at the bottom of the temperature cascade to
keep both the 1st and 2nd laws of thermodynamics satisfied,
be non-negative, i.e. Qc  0. The above set of inequality
constraints, combined with X  1; Y  0, describes a two
dimensional feasible region in XeY space (Fig. 5). The point of
maximum production of hydrogen lies at X ¼ 1.225, Y ¼ 0.8,
where constraints (22), (23) and (26) intersect. This suggests
there is a possibility of increasing the production of hydrogen
by carrying out the reforming reactions separately, but the
technology employed in this case study requires reforming
reactions occurring in a single reactor.
Fig. 5 e Feasible Region Describing Cluster Constraints.
( ) Constraint (21), ( ) Constraint (22), ( ) Constraint
(23), ( ) Constraint (24), ( ) Constraint (26). Shown is the
region constructed through the set of constraints given by
Eqs. (21e26); any point in the region satisfies constraint 21
since it has a degree of freedom in Qc.
12859
(26)
3. A realization of the proposed hydrogen
production method
(27)
The overall hydrogeneformic acid co-production process can
be divided in four parts:
1. Steam Methane Reforming Plant. This consists of a pressuri-
zation system, the SMR reactor and a flash distillation process.
2. Hydrogen PSA Plant. The hydrogen PSA receives the stream
coming from the top of the flash distillation process located
downstream of the SMR reactor. Hydrogen is purified and
pressurized for its final delivery.
3. Air separation and Combustion Plants. Air separation PSA
system, a burner, an atmospheric pressure water
condenser and a high pressure water condenser.
4. Formic Acid Plant. Feedstock pressurization system, the
formic acid reactor and the dual pressure distillation column
system.
3.1. Steam methane reforming and Hydrogen PSA
subsystems
The plant is fed with water and natural gas (methane) at
atmospheric conditions, which are then brought to typical
SMR conditions (10.1e30.4 bar, 800 Ke1200 K)
[8,9,21,22,33e36]. The overall reaction occurring in the SMR
ðgÞ ðgÞ ðgÞ
CH4 þ 2H2 OðgÞ /CO2 þ 4H2 ðR3 Þ (28)
is an endothermic reaction and, by the Le-Chatelier principle,
hydrogen production increases with temperature. Thus for
high conversion and heat integration purposes an operating
temperature of 1090 K is chosen, which is 60 K below the
combustion reactor’s temperature of 1150 K. To avoid exces-
sive pressurization, the SMR pressure of 21.3 bar is chosen,
which is the same as the high pressure of the hydrogen PSA
subsystem. The SMR is followed by a series of Water-Gas Shift
(WGS) reactors where additional hydrogen is produced and
carbon monoxide is significantly reduced. These reactors are
considered part of the SMR subsystem in Fig. 6. The stream
exiting the WGS reactor is then cooled to the operation
temperature of the H2 e PSA and subsequently sent to a flash
column where most of the water is removed. The water is
recycled back into the SMR reactor, with a portion of it being
sent to the combustor feed to be used as steam dilution to lower
the speed of combustion and act as a heat sink that keeps the
combustor from overheating. The light ends of the separator
12860 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
Fig. 6 e Steam Methane Reformer and Hydrogen Pressure Swing Adsorber Diagram. A simple methane reforming diagram is
shown; water and methane are compressed, heated and fed into the SMR reactor, along with other indicated streams; the
exit is cooled and separated through a separation column and a PSA block, from which hydrogen is purified and delivered.
are sent to the H2 e PSA. The conditions at which the PSA is
operated (21.3 bar maximum pressure and 311 K) are taken
from Ref. [22]. Two streams come out of the PSA system, one
containing H2, CO and CO2 at 1 bar, which is sent to the
combustion plant and the other one consisting of pure H2 at
21.3 bar (99.999þ%). The latter is separated into two streams,
one of which is sent into the formic acid plant and the other of
which is pressurized to 354.6 bar to be delivered as a final
product.
3.2. Two-stage PSA air separation and combustion
subsystems
Two fresh feeds come into this section of the plant; one con-
sisting of methane and the other one of air. The air stream is fed
into an air separation subsystem, which consists of a two-stage
PSA. In the first stage, nitrogen is removed from the air by
a zeolite packed PSA unit [33,34] and in the second stage argon
contained in the first stage’s oxygen-rich product is removed
through a PSA packed with carbon molecular sieve (CMS)
adsorbent. Conventional air separation PSA systems use only
a zeolite packed PSA, however this adsorbent does not remove
the argon, leaving the oxygen product with a purity less than 95%
[37,38]. The addition of the CMS PSA allows a purity up to 99.5%
[33,39]. The energy needs of the two-stage PSA process are esti-
mated from the literature [9] under the following assumptions:
1) Oxygen is produced at 100% recovery and purity. Incom-
plete recovery only affects the amount of air fed into the
plant. In regard to energy consumption, the incomplete
recovery of oxygen can be readily taken into account [40].
Ar is the leading impurity present in oxygen produced from
air using zeolite PSA. If the Ar was not completely removed,
it would exit the system in small quantities together with
the formic acid stream, not affecting the functionality and
energetic performance of the flowsheet.
2) The air enters the air separation PSA system at 298 K and
1 bar, and the oxygen product leaves the system at the
same conditions.
The oxygen produced from the PSA is then mixed with the
fresh methane, the waste from the hydrogen PSA, water
stream from the SMR, and a recycle stream coming from the
formic acid plant. The mixture is heated to 1130 K and fed into
the combustion reactor which operates at 1150 K and 1 bar.
The feed to the burner contains 20% steam to prevent the
combustor from overheating. The rest of the feed is stoichio-
metric (to the methane, hydrogen, carbon monoxide, and
formic acid entering the reactor) and the combustion is
considered to be a complete conversion reaction, generating
only water and carbon dioxide as its products. The combustor
exit stream is cooled down to room temperature so most of its
water content is condensed and subsequently separated from
the carbon dioxide using two condensers, the first condenser
operating at 1 bar and the second one at 21.3 bar (matching the
pressure of the hydrogen stream with which it will be mixed).
Pure CO2 is collected at the light end of the second separator,
while water collected at the bottom of both separators is
mixed and sent to the SMR plant. The water is sent to the SMR
reactor and the carbon dioxide to the formic acid plant (Fig. 7).
3.3. Formic acid plant subsystem
In this subsystem formic acid is produced from hydrogen and
carbon dioxide. Two streams come into this part of the plant:
the hydrogen stream which is derived from the hydrogen
exiting the H2-PSA; and the carbon dioxide dehydrated exiting
the distillation system following the combustion reactor.
These streams (21.3 bar, 308 K) are mixed and then
compressed and heated to 40.5 bar and 354 K, the pressure and
temperature at which the reactor operates [41e43]. Water is
used as reaction solvent and is recycled within the reaction
and purification systems [41,44e46]. Most of the water is
recovered from the bottom of the first distillation column and
recycled to the entrance of the formic acid reactor. The rest of
the water comes from the second distillation column along
with formic acid, due to the azeotrope these two species form.
The exit of the formic acid reactor is depressurized to 11 bar,
heated close to the water’s boiling point at this pressure
(470 K) and then fed into a distillation column operating at
11 bar (high pressure distillation column). The light end
stream at the top of this high pressure distillation column
contains mostly water with traces of carbon dioxide, while the
heavy end stream at the column’s bottom consists of the high
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8 12861

Fig. 7 e Dual Pressure Swing Adsorber (PSA) Air Separation and Combustion Plant Diagram. A simplified diagram of a dual
PSA, burner and separation columns is shown. Oxygen is obtained from the dual PSA separation of air, then fed into the
burner along with methane and recycled material; the exit is separated into carbon dioxide and water through two
separators.

pressure azeotropic mixture of water and formic acid. This
mixture is expanded to atmospheric pressure and fed into
a second distillation column (low pressure distillation
column) operating at 1 bar. The heavy ends of the low pressure
distillation column consist of the atmospheric azeotropic
mixture of water and formic acid, while the light ends consist
of 99.9% pure formic acid, which is the final product (Fig. 8).
4. Simulation and heat/power integration of
proposed process realization
The proposed process flowsheet is first simulated and then heat
and power integrated. The flowsheet simulation is carried out
using the software UniSim Design R360 and R380. Heat and
power integration is carried out using the UCLA in-house soft-
ware which implements the theory developed in Ref. [30]. A
process flow diagram is presented in Fig. 9. The system is
initially simulated at the operational point for X ¼ 1.195,
previously explained. The converged flowsheet’s temper-
atureeenthalpy data are then entered into the heat and power
integration software, to identify the flowsheet’s hot/cold/elec-
tric utility needs. This process is repeated for various values of
X. A value of X ¼ 0.654 is identified as the one leading to the
highest production of H2 for this process realization, while
maintaining the flowsheet to be energetically self-sufficient.
The PengeRobinsoneStryjekeVera equation of state is used
to simulate most of the plant except for the Formic Acid plant in
which the van Laar liquid activity coefficient model coupled
with an ideal gas model for the vapor phase [47] was found to be
the thermodynamic model that most accurately captured the
watereformic acid azeotropic vaporeliquid equilibria.
The material inputs to the flowsheet are the raw materials:
natural gas (methane), water, and air at ambient temperature
(298 K) and atmospheric pressure. The material outputs
consist of pure nitrogen and pure argon at 1 bar and 298 K,
hydrogen at 354.6 bar and 298 K and high purity formic acid
(99.9%) at 1 bar and 298 K. The natural gas input is split into
a SMR input and a Combustion plant input, with the split ratio
being a direct function of the previously defined water to
methane molar ratio (X ). A higher value of X yields a higher
production of hydrogen and a larger flow of natural gas into
the SMR, while a lower value of X yields higher energy
production and a larger flow of methane to the combustion
plant. The SMR and combustor are represented by Gibbs free
energy reactors (without specified reactions) and the formic
acid reactor is represented as a conversion reactor with
a conversion fixed at 20%. The heat exchangers (heaters and

Fig. 8 e Formic Acid Production Plant Diagram. A simplified diagram of the formation and purification of formic acid is
shown. Carbon dioxide and oxygen are fed into a reactor at the indicated conditions; the gaseous exit of the reactor is
partially recycled, while the liquid phase is sent to a system of distillation columns to extract and purify formic acid.
12862 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
Fig. 9 e UniSim Flowsheet of Hydrogen- Formic Acid co-production process. Shown is the simulation created in the
process modeling software UniSim Design.
coolers) were assumed to have negligible pressure losses, and
the compressors to work at a 75% adiabatic efficiency. The
pressurization operations are represented by a single
compressor and a cooler that may in reality correspond to
a multi compressor intercooler train system.
A mixture of recycled water, fresh water and natural gas is
fed into the reformer at 1090 K and 21.3 bar, resulting in
a molar ratio of steam/methane of 3.52 at the reactor
entrance. This steam excess over the stoichiometric steam/
methane molar ratio of 2 leads to reduced byproduct carbon
formation [21,48,49]. At the given conditions, the equilibrium
conversion of natural gas in the reformer is 81.17%, generating
a stream containing primarily water and hydrogen with
significant amounts of carbon dioxide, monoxide and
methane. The water in this stream is condensed and sepa-
rated, through a flash separator at 21 bar and 311.15 K, to
a liquid stream consisting mostly of water and to a vapor
stream that is rich in hydrogen and is sent to the pressure
swing adsorber (PSA) unit. The PSA process is considered to be
adiabatic and almost isothermal, thus only requiring its power
consumption to be incorporated in the heat and power inte-
gration analysis. A cyclic operation of a series of PSAs allows
the overall system to operate in a steady-state mode. For
purposes of heat and power integration, the PSA system is
represented in the process diagram by a component splitter.
The exits of the PSA are set to comply with the literature
reported compositions [50,51]. The high pressure adsoption
step generates hydrogen while the low pressure (1.3 bar)
desorption step outputs a waste stream. The waste stream
generated is sent to the combustion plant to be oxidized to
carbon dioxide and water along with other waste recycles and
fresh natural gas. The hydrogen exiting the H2-PSA is split into
the final product (1.654 mol of hydrogen per mole of methane)
and the hydrogen feed to the formic acid plant. The final
hydrogen product stream is compressed and cooled to be
delivered at commercial conditions (354.6 bar and 298 K).
The burner is operated at 1150 K and 1 bar. This high
temperature allows the unit to generate a high quality hot
stream that is used to satisfy the energy requirements of
energy demanding units such as the SMR. An air stream
undergoes oxygen purification through the air-PSA units
previously described; these units are also represented in the
process diagram as component splitters. The air-PSA process
requires work of 48,000 kJ per kmol of oxygen produced [9]. This
work load requirement is accounted for during heat and power
integration analysis. The amount of oxygen required is already
given by the overall balance equation which is the stoichio-
metric amount to oxidize all carbon containing products and
unreacted hydrogen entering the burner into carbon dioxide
and water. The remaining streams going into the burner come
from waste streams from the hydrogen PSA, formic acid
reactor, water from the SMR plant and fresh natural gas. The
combustion is carried out at 1 bar and 1150 K and is modeled on
a Gibbs free energy minimization basis, yielding a vapor stream
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8 12863

exit composed essentially of water and carbon dioxide. Water streams involved are characterized as “hot streams” if their
is separated by condensation in two stages, at 308.15 K and required enthalpy change is negative, and as “cold streams” if
1 bar in the first stage, and subsequently at 308.15 K and 21.3 bar this change is positive. Since we wish the flowsheet to be
in a second stage. The condensed water is then sent to the SMR, energetically self-sufficient, hot utility use must be zero.
and the CO2-rich stream is then mixed with an equimolar Additionally, cold utilities are allowed, as well as the use of
amount of hydrogen and sent to the formic acid reactor. The heat engines and heat pumps. Cold utility is available at 293 K,
hydrogen/CO2 mixture is pressurized from 21.3 bar to 40.5 bar the work/cold utility cost ratio is 25 to 2, and the minimum
and heated up to 354.15 K, conditions at which the reaction approach temperature is 10 K. The objective function for the
takes place [41e43]. According to the literature, this reaction heat and power integration problem minimizes the total
can be carried out at various conditions with a great variety of power and cold utilities cost. The resulting optimization
solvents and catalysts [42,43]. For this work, a water-soluble problem is linear and it is solved using an optimization solver.
Rhodium-based catalyst (RhCl(TPPTS)3) was chosen that The details of the formulation are discussed in Refs. [22,30].
allowed the use of mild temperature and pressure conditions
in the formic acid reactor. The input to the formic acid reactor
consists of an equimolar mixture of hydrogen and carbon
5. Results and discussion
dioxide with water and traces of formic acid, the water being
used to dissolve the Rhodium-based catalyst (RhCl(TPPTS)3)
A number of iterations were carried out to find the maximum
and largely originating as recycle from the formic acid purifi-
hydrogen/methane molar ratio X þ 1 that would still allow the
cation system. The formic acid reactor is considered to have
converged flowsheet to be energetically self-sufficient. The
a low conversion (20% conversion), thus generating an exit
starting point is the thermodynamic limit of X þ 1 ¼ 2.195
stream with significant amounts of unreacted hydrogen and
identified earlier in Fig. 3b. For this value of X a converged
carbon dioxide. The liquid output of the reactor has a 1.08
flowsheet is first obtained, and subsequently analyzed from
formic acid to water molar ratio, along with 0.8% and 2.3% mole
a heat and power integration viewpoint using the cold/power
of dissolved hydrogen and carbon dioxide respectively. This
utility minimization procedure outlined earlier. It turns out
mixture is depressurized to 11 bar where it is separated via
that the obtained flowsheet is not energetically self-sufficient,
distillation.
i.e. it requires the use of hot utility to satisfy the 1st and 2nd
Water and formic acid form an azeotropic mixture whose
laws of thermodynamics. Repeating this utility cost minimi-
purification through distillation is carried out in a two-step
zation procedure for various values of X yields a total work
process. The first step is at 470 K and 11 bar, conditions at
(work generated from heat and power plus work demand of the
which the water is the lighter component. This first step is also
flowsheet) that varies in a nearly linear manner with X (Fig. 10).
necessary since hydrogen and carbon dioxide must be recov-
Close examination of Fig. 10 identifies the optimal water/
ered to be recycled to the formic acid reactor, while the dis-
methane molar ratio to be X ¼ 0.654. At this ratio, close
solved catalyst remains in the liquid phase stream. A second
examination of the temperatureeentropy change diagram,
distillation step at 1 bar and 381.2 K is carried out, and the phase
Fig. 11a, associated with the minimum cold/power utility cost
equilibrium simulations show water as the heavier compo-
solution, reveals that optimal heat-power integration leads to
nent, meaning water along with catalyst will be recovered at
three heat engine and two heat pump regions. Indeed, the
the liquid exit of the column, thus producing a highly pure
solid line corresponding to the hot composite curve and the
formic acid (99.5%) stream at the top of the column that will be
dotted line corresponding to the cold composite curve at the
delivered as final product at 1 bar and 298 K.
Having completed the detailed simulation of the proposed
hydrogeneformic acid co-production flowsheet, a rigorous
heat and power integration analysis is now carried out on the
converged flowsheet. To this end, the technique outlined in
Ref. [30], for the calculation of the minimum hot/cold/electric
utility cost problem for a heat exchange network, is employed.
In this approach, individual heat exchange/heat engine/heat
pump units are not considered, but rather a global thermo-
dynamic approach is considered which holds for all possible
networks of such units. The problem is stated as follows
“given a set of streams with specific flowrates, inlet temper-
atures, and fixed outlet target temperatures; hot and cold
utility streams with known inlet and outlet temperatures and
unit cost; an electrical (work) utility with known unit cost;
identify among all possible heat exchange/pump/engine
networks, the minimum total (hot/cold/electricity) utility cost
necessary to accomplish the desired changes”.
To carry out this integration analysis, we first examine all Fig. 10 e Total Work vs. Parameter X in Process Flowsheet
enthalpy changing processes in the converged flowsheet that Simulation. Indicated are the regions corresponding to the
require external heating and cooling. These processes are work generated and consumed, and the equation
further classified into isothermal and non-isothermal, and the correlating the total work to parameter X.
12864 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8

Fig. 11 e (a) TemperatureeEntropy Diagram: Heat Engine/Pump Network Featuring Minimum Cold Utility for the Overall
Process; (b) TemperatureeEnthalpy change Diagram: Heat/Power Integration Featuring Minimum Cold/Power Utility Cost
Shown in Fig. 11a is the temperatureeentropy diagram obtained from the heat and power integration of the identified
optimal flowsheet; indicated are the heat engines (red) and heat pumps (blue) regions required for the integration of the
flowsheet. Shown in Fig. 11b is the temperatureeenthalpy diagram from the heat and power integration of the optimal
flowsheet; the width of the pictured column corresponds to the amount of power generated from the network of heat
engines and heat pumps. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

cold/power utility cost minimum, intersect each other at four
locations. The two heat pump regions are the first between the
first intersection point at 370 K and the second intersection
point at 382 K, and the second between the third intersection
point at 453 K and the fourth intersection point at 485 K. These
points correspond to the condenser and the reboiler of the two
distillation columns separating the azeotropic mixture of
formic acid and water. Within these temperature regions the
hot composite curve is below the cold composite curve and
heat pumping action is required.
The overall enthalpy balance of the heat and power inte-
gration network is represented in the temperatureeenthalpy
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
diagram (Fig. 11b). The imbalanced energy corresponds to the
work generated by the heat exchange/engine/pump network,
and assuming 100% of the work is converted to electricity,
this energy is the input to all the electricity-powered (pump,
compressors, PSA) units of the plant. In creating this
diagram, the hot (cold) composite curve is lowered (raised) by
5 K so that the minimum approach temperature of
DTmin ¼ 10 K, holds throughout the heat exchange/engine/
pump network.
Having established the optimal hydrogen/methane molar
ratio for maximum hydrogen production, an operating cost
analysis of the converged flowsheet can be carried out. The
system’s operating cost consists only of the cost of natural
gas. The cost of water is negligible with respect to the cost of
natural gas and all of the plant’s electricity needs are met by
the plant itself, since it is energetically self-sufficient.
According to the U.S. DOE, the national average industrial
price of natural gas during April 2011 [52] was 5.23 $/(1000 ft)3.
This figure can be translated into 4.52 $/kmol of CH4. With
this information, a hydrogeneformic acid price diagram can
be constructed which illustrates the price region in which
these two chemicals could be sold at a profit. Marked in
Fig. 12 are the commercial price for formic acid (0.70 $/kg)
[23,26] and the energy-price equivalent (3.64 $/kg) [53]of
hydrogen to gasoline (1 kg of hydrogen is energetically
equivalent to 1 gallon of gasoline). An operating cost analysis
of the plant suggests a return of 6.76 times the money
invested in natural gas, when selling the formic acid at
current commercial prices and dispensing hydrogen for free,
or 9.29 times when selling formic acid at current commercial
Fig. 12 e HydrogeneFormic Acid Profitable Region. The
diagonal line intersecting both axes is the lower bound
operating cost corresponding to the optimal flowsheet. The
region labeled as “profitable region” comprises of all the
points at which one can price the hydrogen and formic acid
and generate revenue, from an operating cost perspective.
Marked are also the commercial price of formic acid and the
gasoline-equivalent price of hydrogen. Since these two
points are away from the lower bound line, there is
a competitive opportunity to implement this technology.
12865
prices and hydrogen at a price equivalent to gasoline. This
suggests that the proposed process possesses a large profit
margin (e.g. selling formic acid at 20% of its current
commercial price and hydrogen at 0 $/kg is still profitable).
Future research plans include the replacement of steam
reforming with adsorption enhanced reforming, as discussed
in Refs. [54e56]and references therein.
6. Conclusions
An energetically self-sufficient process for the production of
hydrogen and formic acid from natural gas was developed. Its
maximum hydrogen production was 1.654 mol of H2 and 1 mol
of formic acid per mole of CH4.The heat and power integration
featuring minimum cold/power utility of the process deter-
mined that the heating and cooling requirements of the plant
can be met through 3 heat engine and 2 heat pump subnet-
works. This heat engine/pump network generates enough
power to supply all the electricity needs of the flowsheet,
including pumps, compressors and PSA systems. An oper-
ating cost analysis of the plant suggests a return of 676% when
selling the formic acid at current commercial prices and
dispensing hydrogen free of charge, or 929% when selling
formic acid at current commercial prices and hydrogen at
a price equivalent to gasoline.
Role of the funding source
Funding for this project came from NSF through grant CBET
0829211 and CONACYT Mexico. NSF provided financial
support to both authors and CONACYT Mexico provided
financial support to the first author (Jorge A. Pena Lopez). The
funding sources were not directly involved in the contents
presented in this work.
Acknowledgments
The authors gratefully acknowledge financial support from
the National Science Foundation through grant CBET 0829211
and CONACYT Mexico.
Appendix A.
Hydrogen thermodynamic properties using residual
properties
Constant pressure heat capacity of hydrogen in ideal gas state,
p. 684 [15]
ig
CP
¼ 3:249 þ 0:422$10 3 T þ 0:083$105 T 2 ; TðKÞ˛½298; 3000Š
R
Generic Cubic Equation Thermodynamic Model for Real
Gases, p. 93e98 [16].
12866 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8

1 T P a½Tr ŠR2 T2c Nomenclature

ra ; Tr ðTÞa ; Pr ðPÞa ; aðTÞaJ ;
v Tc Pc Pc
RTc bP Pr a½Tr Š Pv
baU ; ba ¼ U ; qðTr ÞaJ ; za
Pc RT Tr UTr RT Cop;i , J/mol K standard state constant pressure heat capacity Cp
RT aðTÞ RT aðTÞ=bðs εÞ of the ith species
P¼ ¼
v b ðv þ εbÞðv þ sbÞ v b ðv þ εbÞ ig
Cp;i , J/mol K ideal gas constant pressure heat capacity Cp of the
aðTÞ=bðs εÞ 1 rb ith species
þ 5z ¼ q
ðv þ sbÞ 1 rb ð1 þ εrbÞð1 þ srbÞ gi, J/mol molarGibbs free energy of material stream i
Gi, J/kg specific mass Gibbs free energy of material stream i
The generic cubic equation has as special cases the Van-der
hi, J/mol molar enthalpy of material stream i
Waals, Redlich/Kwong, Soave/Redlich/Kwong, and Peng/Rob-
Hi, J/kg specific mass enthalpy of material stream i
inson models. Table A.2 summarizes the parameter values ig
hj , J/mol molar enthalpy of j-th species at ideal gas state
corresponding to each of these models. ig
Hj , J/kg specific mass enthalpy of j-th species at ideal gas
The thermodynamic properties of hydrogen are evaluated
state
by combining ideal gas and residual properties. Let
m_ i , kg/s mass flowrate of material stream i
T0 ¼ 298.15 K, P0 ¼ 1 bar. Then, from p. 212e219, [15].
Mj, kg j/mol molecular weight of j-th species
Specific mass enthalpy H

h i h i h i
HðT;PÞ HðT0 ;P0 Þ ¼ HðT;PÞ Hig ðT;PÞ þ Hig ðT;PÞ Hig ðT0 ;P0 Þ þ Hig ðT0 ;P0 Þ HðT0 ;P0 Þ
2 3
ZT
16 d½lna½Tr ŠŠ d½lna½T

  
  
 ig r ŠŠ 
¼ 4RT z 1 þ 1 qðTr ÞI  þ CP dT RT0 z 1 þ 1 qðTr ÞI 
7
M dðlnTr Þ dðlnTr Þ
5
T;P T0 ;P0
T0

Specific mass entropy S

h i h i h i
SðT; PÞ SðT0 ; P0 Þ ¼ SðT; PÞ Sig ðT; PÞ þ Sig ðT; PÞ Sig ðT0 ; P0 Þ þ Sig ðT0 ; P0 Þ SðT0 ; P0 Þ
2 3
ZT
16 d½lna½Tr ŠŠ ig dT P d½lna½Tr ŠŠ




 
¼ 4R lnðz bÞ þ qðTr ÞI  þ CP Rln R lnðz bÞ þ qðTr ÞI 
7
M dðlnTr Þ T P0 dðlnTr Þ
5
T;P T0 ;P0
T0

8 1 Q_ j , W rate of heat entering the system at temperature Ts;j

z þ sb
  9
> ln if εss > SC index set of components (species) present in at least
z þ
< =
where I ¼ s ε εb : one material stream
: b
>
if εss
>
si, J/mol K molar entropy of material stream i
;
z þ εb
Si, J/kg K specific mass entropy of material stream i
ig
Sj , J/kg K specific mass entropy of j-th species at ideal gas
state
Table A.1 e Hydrogen Thermodynamic Properties. SE index set of constituent elements
Species Molar mass Critical Critical Acentric S_ G , J/K s rate of entropy generation
M (kg mol 1) Temperature Pressure factor u SI index set of inlet material streams
Tc (K) Pc (bar) SO index set of outlet material streams
Hydrogen 2.016e-3 33.19 13.13 0.216 SQ index set of heat rates entering and exiting the
(h2) system

Table A.2 e Parameter Values Corresponding to Van-der Waals, Redlich/Kwong, Soave/Redlich/Kwong, and Peng/Robinson
models.
da
Equation of State a½Tr ðTފ s ε U J ½Tr ðTފ
dTr
vdW (1873) 1 0 0 1/8 27/64 0
1=2 1 3=2
RK (1949) Tr 1 0 0.08664 0.42748 Tr
2
1=2
SRK (1972) aSRK ðTr ; uÞa 1 0 0.08664 0.42748 uSRK2 uSRKð1 þ uSRKÞTr
pffiffiffi pffiffiffi 2 1=2
PR (1976) aPR ðTr ; uÞb 1þ 2 1 2 0.07780 0.45724 uPR uPRð1 þ uPRÞTr
1=2
a aSRK ðTr ; uÞ ¼ ½1 þ ð0:480 þ 1:574u 0:176u2 Þ$ð1 Tr ފ2 ; uSRK ¼ 0:480 þ 1:574u 0:176u2 :
1=2
b aPR ðTr ; uÞ ¼ ½1 þ ð0:37464 þ 1:54226u 0:26992u2 Þ$ð1 Tr ފ2 ; uPR ¼ 0:37464 þ 1:54226u 0:26992u2 :
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 2 8 5 3 e1 2 8 6 8
Sw index set of work rates entering (consumed by) and
exiting (produced by) the system
T0, K reference temperature
Ts;j , K temperature at s; j surroundings region
W_ s;j , W rate of shaft work consumed by j-th source in the
system
W_ s , W rate of shaft work entering (consumed by) the
system
xi;j , kg j/kg mass fraction of j-th species in stream i
X water to methane molar ratio with formic acid
production
yi;j , mol j/mol molar fraction of j-th species in stream i
Z water to methane molar ratio without CO2 capture
Greek letters
Dhof;i , J/mol standard state enthalpy of formation of the ith
species
DH_ s , J/s rate of enthalpy change of system
Dgof;i , J/mol standard state Gibbs free energy of formation of
the ith species
DG_ s , J/s rate of Gibbs free energy change of system
Dsof;i , J/mol K standard state entropy of formation of the ith
species
nj;k stoichiometric coefficient of element k in j-th species
U open, well delimited system or control volume
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