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Development and Application of Wüstite-based Ammonia Synthesis

Catalysts

Huazhang Liu, Wenfeng Han, Chao Huo, Yaqing Cen

PII: S0920-5861(19)30596-6
DOI: https://doi.org/10.1016/j.cattod.2019.10.031
Reference: CATTOD 12536

To appear in: Catalysis Today

Received Date: 11 April 2019

Revised Date: 19 September 2019
Accepted Date: 24 October 2019

Please cite this article as: Liu H, Han W, Huo C, Cen Y, Development and Application of
Wüstite-based Ammonia Synthesis Catalysts, Catalysis Today (2019),
doi: https://doi.org/10.1016/j.cattod.2019.10.031

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PERSPECTIVE

Development and Application of Wüstite-based Ammonia Synthesis Catalysts

Huazhang Liu, Wenfeng Han, Chao Huo*, Yaqing Cen
Institute of Industrial Catalysis of Zhejiang University of Technology, Hangzhou 310014, China
* Corresponding author. Tel.: +86-571-8832-0815; E-mail: chaohc@zjut.edu.cn

Graphic Abstract

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The theory, method, technology and practice of the wüstite-based catalyst in
industrial production and application are reviewed.
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Wüstite does not exist in nature and it is a meta-stable phase, and it will
decompose at 570℃ or below. How can Fe1-xO be synthesized? How can maintain
the stability of Fe1-xO? It is the key technical problems that must be solved during
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preparation.
The activity of wüstite catalysts is 70 % higher and the reduction rate is 3~4 times
faster than traditional catalyst (magnetite-based catalyst with Fe3O4 as precursor).
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Reducing the reduction rate and taking out the excess reaction heat are two key
technology problems that must be solved during its industrial application.

Highlights
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 Development of wüstite-based catalyst and ammonia synthesis industrial technology are

reviewed.
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 Wüstite-based catalyst has been used in industry.

 Advantages of wüstite-based catalyst are cheap, high catalytic activity, low energy costs,
long catalyst life-time.
 The reaction mechanism and effects factors in the preparation process are examined.
 Catalysts of ammonia synthesis are still concerns in future.

Abstract: In the 1980s, Zhejiang University of Technology (ZJUT) started developing a new
catalyst for ammonia synthesis which in final form comprises multi-promoters wüstite-based
catalysts with Fe1-xO as precursor. This became the first new iron catalyst for ammonia synthesis
commercialized since Fritz Haber’s promoted iron catalyst. The catalyst is commercialized in the
existing or new low pressure process. In this paper, the basic theory, method, technology and
practice of the wüstite-based catalyst in industrial production and application are reviewed.
The wüstite-based catalysts are still iron-based, however, they are completely different from the
magnetite-based catalyst in the preparation principle, chemical composition, crystal structure, and
chemical-physical properties. Wüstite does not exist in nature, and is a thermodynamically
meta-stable phase. Therefore, the Fe1-xO must be firstly synthesized by a chemical method and
avoid occurrence reactions of oxidation and disproportionation to obtain a commercial
wüstite-based catalyst with single phase and stability during the preparation of catalyst. We
described the development of the catalyst, starting from the 1980s with studies to elucidate the
inhibition mechanism of disproportionation reaction and the effects of temperature and promoters,
and to ensure that a single wüstite phase is obtained during preparation. This is a prerequisite for
ensuring high activity of the catalyst. Scale up of catalyst production and testing were described
briefly, as are some process considerations. Secondly, we described the industrial application of

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the catalyst with studies to elucidate including the industrial bypass testing, the foundation
research on the industrial application technology such as industrial reduction technology due to

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too fast reduction rate, development of industrial technology taking out the excess reaction heat,
optimization of reaction conditions using wüstite-based catalyst, low-pressure ammonia process,
and optimization of synthesis loop process and convertor for existing synthesis ammonia plant,
etc. . -p
The wüstite-based catalysts exhibit about 70 % higher catalytic activity, and 65.9 % higher the
TOF. It is the most advanced commercial iron catalyst with the highest activity and low
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production cost in the world, and it is competitive with ruthenium-based ammonia synthesis
catalysts. In industrial application, compared to the classic magnetite-based catalyst for ammonia
synthesis, the higher activity allows lower operating temperatures and loop pressures. Existing
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loops can utilize it by running at minimum possible loop pressure for extended period of time.
This allows to increase ammonia plant performance, efficiency and economy without the need of
any revamping. New plants could be designed for lower pressure operation and with a smaller
synthesis converter. This all together leads to lower capital expend tureen lower energy costs. The
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activation of this catalyst is fast and easy, which saves time and cost. Wüstite-based catalyst is
clearly a perfect low cost alternative to Ru/C catalyst.
Keywords: Ammonia synthesis; Wüstite-based catalyst; Production; Application; Industrial
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technology; Optimization
1. Introduction
The traditional ammonia synthesis catalyst prepared by the high-temperature melting method,
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developed in the early 20th century by BASF researchers in Germany [1-4], is prepared from
magnetite, and promoter such as oxides of Al, K and Ca. Magnetite is then reduced to metallic
iron by synthesis gas in the reactor itself. The industrial catalyst presently used is not basically
different from that developed about 100 years ago. On the whole, this catalyst was considered well
consolidated and no special improvement was still expected, so that it is necessary to seek new
technology breakthrough [5-7].
In the 1980s, Ozaki et al. [8] reported, in a review, the catalytic efficiency of the elements for
the synthesis and decomposition of ammonia was correlated with the chemisorption energy of
nitrogen. An inverted parabolic function (volcano curve) was obtained, in which iron, ruthenium,
and osmium mark the top of the volcano which are the best catalyst in pure metal.
Os was eliminated by Haber in the early 20th century. Ruthenium-based catalysts have a much
longer history of development [9]. In 1969, Tamaru [10] put forward a transition metals electron
donor-acceptor (EDA) catalyst system for ammonia synthesis. The ruthenium based ammonia
synthesis catalyst with potassium as the promoter and activated carbon as support was invented by
Ozaki in 1972 [11-12]. The ruthenium-based catalyst with ruthenium carbonyl as the precursor
and carbon containing graphite as support was developed by British Petroleum Company (BP) in
1992. The Kellogg Advanced Ammonia Process (KAAP) using the ruthenium catalyst was
developed by Kellogg, and realized the industrial application of ruthenium catalyst [13-15].
The activity of Ru-based catalyst with carbon materials as support is very high, but there is
strong inhibition of H2, and the carbon in support and hydrogen can occur methanation reaction on
ruthenium catalyst under the conditions of synthesis ammonia, which leads to the loss of carbon to
affect the service life of catalyst [16-19]. Nørskov et al. [20] think that we get closest to the
optimum by using Ru or Os as catalysts at relevant conditions in industrial processes. However,

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these metals are very expensive and thus less commercially attractive compared to the third-best
catalyst, Fe. Therefore, it is still necessary to find a more efficient and the cheaper catalyst in

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industry.
In order to find new technological breakthroughs in molten iron catalysts (the iron catalyst
prepared by the high-temperature melting method), it should first get rid of the Fe3O4 system and
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find a new technical route. In 1986, Liu et al. [21] found a novel high-activity ammonia synthesis
catalyst based on wüstite as precursor in place of magnetite. This is an impressive example, the
first significant innovation in the industrial iron-based ammonia synthesis catalyst after the
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development of catalysts for the Haber-Bosch process in 1910 [22-29].
This discovery broke through the traditional conclusion that Fe3O4 was the most active
precursor among all iron oxides. This important breakthrough indicates the first fundamental and
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essential progress since the research of this catalyst over 80 years. This discovery brought the iron
catalyst for ammonia synthesis into a new stage with sharp jump in catalytic activity. Meanwhile,
it has profound effect in the field of ammonia synthesis catalyst community and is of significance
in catalysis science and industry. It has attracted intensive research focus since then [30-41].
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2. The preparation chemistry foundation of wüstite-based catalysts

Iron oxides have three kinds of Fe2O3, Fe3O4 and FeO in chemistry, which are called as
hematite, magnetite and iozite or wüstite in crystallography, respectively. These iron oxides are
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closely related in structure, with the different being only the relative ratios of Fe2+ and Fe3+ ion in
the O2- ion cubic closely accumulation. FeO and Fe2O3 represent the both ends and have a
continuous composition between the two ends, only when Fe2+: Fe3+ is 1: 2 to form a very stable
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phase, i.e., Fe3O4. Therefore, the continuous relationship of various iron oxides in Fe-O system can
be expressed in Fe2+/Fe3+ ratio (denoted as R).
The Fe-O phase diagram (Fig. 1) is the
thermodynamic basis for preparing molten iron
catalysts. According to the ratio of Fe2+ and Fe3+, the
phase diagram of Fe-O can be divided into 6 phase
zones from right to left, and the iron oxide parameters
of each phase zone are shown in Table 1.
It is traditionally believed that the high activity is

Fig.1 Equilibrium phase diagram for Fe-O system

obtained when Fe3O4 with Fe2+/Fe3+ is about 0.5 as the precursor. However, the origin of the
superior activity of Fe3O4 among the three iron oxide phases and their mixtures Fe2O3-Fe3O4,
Fe3O4, Fe3O4-FeO and FeO remains elusive.
Table 1 Iron oxide parameters of different phase regions in Fe-O phase diagram
Phase field I II III IV V VI IV-VI
Temperature/oC <1100 0-1600 0-1600 >570 >570 >570 <570
Phase Fe2O3 Fe2O3+Fe3O4 Fe3O4 Fe3O4+FeO FeO α-Fe+FeO α-Fe+Fe3O4
Fe2+/Fe3+ 0 0＜0.50 0.5 0.50＜3.15 3.15＜10 >10 0.50＜10

We summarized the preparation protocols of iron catalyst, starting from the 1980s, based on the
studies that elucidate the relationship between crystal phase of iron oxides and their activity after
reduction, and obtained a hump-like activity curve when exactly the same promoters are used in
the experiments [5, 29, 32]. Liu et al. [32-36] proposed the concept of molecular ratio (f) of iron

of
oxides (or phase composition fraction) instead of the traditional ionic ratio (R) of Fe2+/Fe3+ to
elucidate the hump-like activity curve, and the relationship between the R and the f was obtained
in 6 phase zones above, and based on this, a single phase principle can be proposed [5, 37-41], i.e.,

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the best iron precursor should be composed of a single phase iron oxide (f=1), and the order of
activity for ammonia synthesis is as follows: Wüstite > Fe3O4 > Fe2O3 > mixture of any two iron
oxides. Clearly, among all iron-melting catalysts with iron oxides as precursor, the catalyst
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prepared from non-stoichiometric ferrous oxide with wüstite structure (denoted as Fe1-xO) has the
highest activity. This is a significant breakthrough for the development of iron catalysts for
ammonia synthesis over the past 80 years.
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The reason of low activity in two phase regions with two kinds of iron oxides coexist is that the
difference of the surface property and structure of active α-Fe, and the surface distribution of
promoters, e.g. the surface is covered excessively by promoters and the competitive reduction in
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two phase area [34, 42].

It must be pointed out emphatically that the wüstite-based catalyst has specific meanings, i.e. it
is composed of only single wüstite phase as precursor (as called a single-phase theory). Although it
has Fe2+/Fe3+ ratio in the range of 4 ~ 12, the catalyst with high Fe2+/Fe3+ ratio cannot be confused
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with the wüstite-based catalyst, nor can the mixture of wüstite and magnetite be called as
wüstite-based catalyst. The mixture of any two iron oxides or two types of crystal structures in
precursor will result in a decrease in activity, when the two iron oxides are mixed in an equimolar
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ratio the catalytic activity will reach the lowest value.

Therefore, a catalyst with high activity can be obtained only when the wüstite phase is present
alone in the catalyst, while, when wüstite and magnetite are present together, the catalysts always
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show a low activity. It is a mistake that the catalyst with the high ratio of Fe2+/Fe3+ from a mix of
wüstite and magnetite is said as wüstite-based catalyst [43]. And it is also wrong to say that the
catalyst is only prepared from the different raw material. In fact, the main raw material for the
preparation of wüstite-based catalyst is still magnetite. Therefore, it cannot be garbled that the
wüstite-based catalyst is the catalyst with high ratio of Fe2+/Fe3+. The presence of wüstite as the
only crystal phase in the catalyst precursor is indispensable precondition of the wüstite-based
catalyst with high activity.
Therefore, wüstite-based catalyst is a novel catalyst for ammonia synthesis which is completely
different from the conventional magnetite-based catalyst in chemical composition and crystal
structure of the precursor.
The basic principle of preparation chemistry for molten iron catalyst is composed of the hump
shape activity curve, iron oxide molecule ratio, single-phase theory, uniformity principle and
active model, etc. . In the previous catalyst research and practice for Fe3O4 as precursor, the
catalysts were prepared in “one pot” which simple physical melting method using natural
magnetite as raw material. Therefore, the preparation chemistry has not been involved and has not
been studied. The above series of new theories and concepts put forward for the first time that the
chemical basic principle of molten iron catalyst preparation, and has a certain generality, which is
undoubtedly the melting iron catalyst invented since the early last century, a major achievement in
the theory of preparation.
3. Production process and technology of wüstite-based catalysts
The wüstite-based catalyst with Fe1-xO as precursor is a new catalyst system which is
completely different from the conventional magnetite-based catalyst with Fe3O4 as precursor in

of
the chemical composition, crystal structure, chemical and physical properties and preparation
process [29]. It brings new challenges to the industrial development of fused iron catalyst, and the
following key technical problems must be solved.

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First of all, how can wüstite be synthesized？Wüstite does not exist in nature, and is a
thermodynamic meta-stable phase. It can be synthesized by chemical method, but will occur the
disproportionation reaction, i.e., 4FeO = Fe3O4 + Fe when the temperature is below 570 ℃,
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therefore, even if chemical synthesis can only get mixture of FeO, Fe3O4 and Fe. However,
according to the single-phase principle, high activity catalyst can be obtained only when the
wüstite phase is present alone in the catalyst, while, when wüstite and magnetite are present
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together, the catalysts always show a low activity. Therefore, how to ensure that a single wüstite
phase is obtained during preparation? This is a prerequisite for ensuring high activity of the
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catalyst.
Secondly, wüstite has the characteristics of oxidation, non-stoichiometric and lattice vacancy,
and it will be ambiguous during the preparation and use, which involves the stability and service
life of the catalyst.
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Therefore, how to solve the meta-stability or disproportionation of wüstite, how to find the
promoters that match the physicochemical properties and structural characteristics of wüstite and
avoid the disproportionation reaction during the preparation to obtain stable wüstite-based catalyst
in physicochemical properties? These are the precondition to ensure the stability and service life
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of the catalyst.
These two key technical problems are related to the disproportionation reaction, which is related
to the preparation process and the promoters of the catalyst, respectively. Therefore, the
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preparation of a single wüstite phase and to find matching promoters to inhibit the
disproportionation reaction become the key technology in the wüstite-based catalyst industrial
development.
3.1 Disproportion reaction and role of 90
o
350 C
80 o
400 C
promoters
Disproportionation radio(%)

70 o
450 C
o
500 C
It is possible that disproportionation 60

reaction will occur both during cooling 50

40
process (from 570 ℃ to 100 ℃) of preparation
30
20
10
0
YCa YMg YMn YBa YZr Y0
and rise temperature (from 100 ℃ to 500 ℃ or above) during reduction in industry [28, 44-46].
Therefore, the disproportionation reaction is a key technological problem that must be solved for
preparation and application of catalysts. Although it was discussed in literature [28], here, it is
necessary again to understand the mechanism of disproportionation reaction and the ways and
methods to inhibit it.
The results of TG-DSC [47] show that disproportionation reaction will be produced when the
temperature is 280 ~ 425 ℃ for Fe1-xO. The variety oxides as promoters in wüstite-based
catalysts can influence its disproportionation behavior. The behaviors of a series of wüstite that is
doped with such oxides as Al2O3, K2O, CaO, MgO, V2O5 etc. were investigated. In which the
inhibited role of CaO and MgO on disproportionation reaction are the biggest as shown in Fig. 2
[24, 28, 50, 52]. It can effectively inhibit the disproportionation reaction of wüstite with
multi-promoters. The modulation effect of more than 20 oxide promoters were studied such as
Al2O3, K2O, CaO, CoO, BaO, CeO2,LaO3, MoO3, MgO, MnO2, Cr2O3, V2O5, ZrO2, TiO2, WO3,
Na2O, B2O3, BeO, etc. . The optimized promoters that are compatible with the properties and

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structure of the wüstite were obtained, and developed successfully wüstite-based catalyst with
multi-promoters (such as A301, ZA-5 etc.),
Fig. 2 Effect of Oxides and temperature on

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which does not occur disproportionation
disproportion rate of Fe1-xO
reaction during preparation and application of
catalysts [28].
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3.2 Process and technology for the preparation of wüstite-based catalysts
Magnetite-based catalyst is prepared with natural magnetite as the raw material by using the
physical “one-pot” melting method at the high-temperature.
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All of the added solid materials will remain in the final product except for the gas generated.
Therefore, as long as ensure the quantity and quality of the raw materials added in, especially the
purity of raw materials, and adjust the Fe2+/Fe3+ to meet the requirements, the active
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magnetite-based catalyst can be obtained. However, the seemingly very simple preparation
process involves numerous chemical and physical processes such as chemical reactions, melting
and solidification, crystallization and phase change, grain growth, solute redistribution and
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segregation etc. .
However, the wüstite-based catalyst can only be synthesized through chemical reaction because
wüstite does not exist in natural, and there is no literature report on the synthesis of wüstite phase
iron oxide. The industrialization of the catalyst must solve the following two key technical
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problems of the methods and processes of chemical synthesis, and how to avoid the occurrence of
disproportionation reaction.
Generally, the FeO can be prepared by decomposing ferrous oxalate in laboratory, however, it
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cannot get pure FeO, and only get the mixture of FeO, Fe3O4 and Fe.
In industrial production, the wüstite-based catalyst can also be prepared by using natural
magnetite as raw material and iron as reducing agent, and can be melted directly in the resistance
furnace or electric arc furnace. However, during its preparation process, the chemical reaction
between magnetite and iron or other reducing agent is shown in eq. (1) in addition to the process
of physical melting.
Magnetite (Fe3O4) + Fe = 4FeO (1)
ɵ ɵ
The Gibbs free energy of the chemical reaction is ΔrGm = 48.4 - 0.058T. When ΔrGm ＜ 0, the
reaction will go to the right direction, i.e. T > 834.5 K. In other words, wüstite can be formed if
temperatures is higher than 834.5 K using magnetite and iron as raw material. That is, the
preparation of wüstite-based catalyst must be adopted by combining processes by the physical
melting and chemical reaction.
However, the chemical reaction will go to the left direction when the temperature is lower than
834.5 K. And the disproportionation reaction will occur and FeO transforms to Fe and Fe3O4 as:
4FeO = Fe3O4+Fe (2)
Therefore, during the preparation of wüstite-based catalyst, the disproportionation reaction will
occur when the molten material is cooled down from 1500 ℃ to 570 ℃ or below, leading a
mixture of Fe3O4, Fe and FeO as shown in Fig. 3.

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Fig. 3 Possible disproportionation reaction during preparation of wüstite-based catalyst
The picture above is the photo of the molten material flowing into the cooler; the picture below is DSC
spectra of disproportionation for wüstite-based (up) and magnetitet-based (down)catalysts.
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During the melting process, the molten material is liquid state, and iron oxides, Al2O3, K2O and
CaO etc. as ionic state exist in the liquid melt. They should be homogeneously distributed in the
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liquid state melt theoretically. In the earlier discussion about the melting temperature, melting time
and other factors only influence the distribution of the promoters in liquid state melt [55]. The
liquid state melt is solidified once depart from the furnace, and the distribution state of the
promoter in the catalyst has been fixated (it may be changed slightly during the reduction process).
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Just during the solidification process, the solutes will redistribute and segregate resulting in
non-uniform distribution of the promoters in final products.
It is generally unavoidable that the solute would redistribute during the solidification process,
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while the accumulation and segregation of solute at the grain boundary are the results of solute
redistribution. Here, iron oxides (Fe3O4 or wüstite) are considered as “solvent”, while promoter
oxide such as Al2O3, K2O and CaO etc. as “solute”. The melting points and the structure are
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different for iron oxides (Fe3O4 or Fe1-xO) and promoters (Al2O3, K2O and CaO etc.), as well as
possibly formed vary solid-solutions (such as FeAl2O4, CaFe2O4, MgFe2O4, KFeO2 etc.), such that
the multi-promoters fused iron catalyst is a complex system composed of multi-phase and
polycrystalline. Its internal structure is not uniform and continuous dense material. Here, the shape
and size of crystal grains are different and there are some impurities and gas holes both inside and
at the boundaries of grains.
Therefore, the following phenomenon will occur when the mixture of several oxides exist
together. Firstly, due to the different phase with different physicochemical properties (such as
solidifying point) and the crystal structure, the piecewise crystallization or peritectic phenomenon
occur, leading to an uneven distribution of iron oxide as precursor during the process of
solidification cooling. For example, melting point of Fe3O4 is 1597 ℃ and wüstite is 1377 ℃.
Secondly, due to the different precursor with different crystal structure and properties, the
requirement of valence state and solubility is different for promoter. For example, the Al3+ ions
can replace Fe3+ ions in Fe3O4 and achieve a uniform distribution, but it cannot replace Fe2+ in
wüstite and achieve an uneven distribution. Uneven distribution of main phase aggravates the
uneven distribution of promoter, which is the main cause of the agglomeration and segregation of
promoter in grain boundary.
Fig. 4 shows the scanning electron microscope photographs and its elements distribution of the
wüstite-based catalyst before reduction. The shape, size and boundaries of grains in the iron
catalyst can be clearly observed. It is clearly seen that the distribution of the promoter such as
Al2O3, K2O and CaO is uneven and especially their accumulation and segregation at grains inside
or at the grain boundaries in the iron oxide are much obvious. Table 2 lists the EDS results of the
element distribution on the surface, inside and boundaries of the grain. It is seen that there is

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serious aggregation of Al, K, Ca and Ti (impurities) on the grain boundaries and their aggregation
degree (the ratio of elements located at grain boundaries to those in the grain) is 12.5, 43.1, 14.5,

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and 6.4, respectively. However, Mg and V do not significantly aggregate and segregate at grain
boundaries. Therefore, how to ensure that uniform distribution of the promoters is a key
technological problem that must be solved during preparation.

Element Al K
-p
Table 2 Element distribution of promoters on the surface, grain and grain boundary / wt% (EDS)
Ca Mg Ti V
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Surface 3.56 0.76 1.81 1.80 0.39 0.49
Grain body 1.40 0.14 0.92 1.32 0.30 0.54
Grain boundary 17.50 6.03 13.30 0.50 1.91 0.74
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The solidification and cooling are natural cooling processes achieved in a cooler with a water
jacket or pedrail-type. It is significant to accelerate the solidification and cooling speed during the
preparation in order to obtain high activity of catalyst with satisfactory crystal structure, grain size,
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and uniform distribution of the promoter.

We found [59] that the cooling rate is determined primarily by the thickness of the layer of
molten material. Fig. 5 and Fig. 6 give the solidification and cooling curves and the cooling speed
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curves of samples with different thickness, respectively.

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 Fe Fe

K K

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Al Al

-p
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Ca Ca
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Fig.4Fig.4
SEM photographs
SEM photographs of fusediron
of fused iron catalyst
catalyst before
before reduction
reduction

(The left
(Thecolumn is the
left column cross
is the crosssection ofthe
section of themelt;
melt;thethe right
right column
column the melt)
is theofplane
is the plane of the melt)
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1400 1 250 1
Cooling rate/( C/min)

2 2
1200
Temperature/oC

200
1000
o
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150
800

600 100
400
50
200

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time/min Time/min
Fig. 5 Solidification and cooling curves Fig. 6 Cooling rate
It is(Thickness
observedoffrom Fig. 5 1and
the sample: ~41Fig.
mm;62~that the solidification process could not be detected for the
8 mm) (Thickness of the sample: 1~41 mm;2~8 mm)
thin sample of 8 mm thickness, while cooling rate is much faster than the one with thickness of 41
mm. However, there is a solidification process for the samples with thickness of 41 mm with the
duration from several to ten minutes. The results of XRD show that the phase of both the thick and
the thin samples are FeO as given in Table 3. Even if the sample with thickness of 41 mm, the

Fe Fe

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Al Al
-p
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K K
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Ca Ca
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Fig. 7 SEM-EDS of surface element distribution (left column: 8 mm; right column: 41 mm)

disproportionation reaction of FeO can be inhibited and wüstite phase with lattice defect of irons
is obtained when the average cooling rate reaches 20 °C·min-1 or above.
 Table 3 Influences of thickness on the distribution of surface element
Distribution of surface element / wt %（EDS）
Thickness / mm Phase by XRD
Fe Al2O3 K2O
41 FeO 81.47 14.95 1.78
8 FeO 92.43 4.20 0.811

However, there appears serious macro-segregation of the promoters in the sample with
thickness of 41 mm, influencing the grain size and distribution of promoter in the catalyst. While
the promoters are uniformly distributed in the sample with thickness of 8 mm. Table 3 lists the
results of analysis of elements on the surface of the catalyst. It is seen that in the samples with
thickness of 41 mm, the surface content of Al2O3 is 6.2 times higher than the bulk, while that of
Al2O3 is only 1.7 times higher in the samples with thickness of 8 mm.

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In the fast-cooling (thin samples) case, all components are suddenly “frozen” due to the rapid
solidification, thus effectively inhibited the disproportionation reaction of wüstite phase, so, single
wüstite is obtained, and there will be no time to distribute again to make promoters already

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uniformly distribute in liquid state so that the distribution of promoters in catalyst is uniform as
shown in Fig. 7 (left column).
In the case of slow cooling rates (thick samples), the solidification in batches, crystal
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transformation or phase transformation is occurred because the components or solid solutions with
different melting points have different freezing points. As a result, the obtained crystal structure is
not homogeneous and the promoters gather or segregate in the grain boundaries, leading to the
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uneven distribution of promoters as shown in Fig. 7 (right column). The SEM back scattered
electron images show that the grain size in the samples with low cooling rate is larger than other
samples with fast cooling rate. In the case of slow cooling rates (thick samples), the
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disproportionation reaction could occur and result in the formation of multiple phases including
the main wüstite phase.
Based on the above experimental results, we propose the physical melting and chemical
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reaction coupled with one-step process and controllable rapid cooling and solidification
technology and equipment for preparation of the wüstite-based catalysts.
We started to scale up the catalyst trial production with capacity of 1300 kg in each in
Shangyu Catalyst Co. Ltd in 1986. The results show that using above one-step process and
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combining with the study of promoters, effectively restrain disproportionation reaction of wüstite,
solved the catalyst amplification effect, and large-scale industrial production of the catalyst was
achieved completely in 1992 [60-64].
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4. The technology characteristic of wüstite-based catalysts

4.1 The activity of wüstite-based catalysts
The wüstite-based catalysts for ammonia synthesis has very high activity, high reducibility, low
active temperature, high mechanical strength, poison resistance and heat-stability and can be used
in wide H2/N2 ratio. Besides, it does not contain any noble metal and has the lower cost for
production [24, 31-41].
 22
ZA-5
20
ICI74-1
18
A110-2
NH3/%vol
16
14
12
10
8
6
4
2
0
300 325 350 375 400 425 450 475 500
o
Temperature/ C
Fig. 8 Conversion curve of wüstite (ZA-5)-, Fig. 9 Conversion curves of wüstite-, magnetite- and
magnetite-based catalysts (ICI74-1and A110-2) Ru/C-based catalysts (100 bar, 430 ℃, H2/N2 is 3
(15 MPa, 3*104 h-1, H2/N2 is 3) [5, 51, 62] for the two Fe catalysts, but 1.5 for Ru/C) [24]

of
The activity of wüstite-based catalysts was compared with magnetite-based (A110-2) and
containing cobalt (ICI74-1) catalysts and ruthenium-based catalysts. Wherein, the activity of ZA-5

ro
wüstite-based catalysts was evaluated completely at five different labs, including Zhejiang
University of Technology (ZJUT) (as shown in Fig. 8), Nanjing Catalyst Company in China,
BASF (Nanjing) Catalyst Company in China (Table 4), Johnson Matthey Company in London and
Pernicone’s lab at Milan University in Italy (as shown in Fig. 9). -p
Table 4 Activity of industrial catalyst for wüstite-based (ZA-5) and magnetite-based (A110-2)
re
Activity after heat-resistant (15MPa, 30000h-1), NH3%
Type of catalysts
425 ℃ 400 ℃
Wüstite-based catalyst(ZA-5) 18.24 16.53
lP

Magnetite-based catalyst( A110-2) 15.20 11.61

*：According to industry standards, each batch represents 20 tons.

It can be seen from Fig. 8 and Table 4 that the activity (ammonia concentration) of ZA-5
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wüstite-based catalysts is higher 4.92 percentage point, increasing 42.36 %, and active temperature
decreasing about 50 ℃ than that of A110-2 magnetite-based catalysts at conditions of 15 MPa, 400 ℃,
30000 h-1 and H2/N2 of 3. While in Fig. 9, the activity of wüstite-based catalysts is higher about 4
ur

percentage point than that of magnetite-based catalysts at conditions of 100 bar, 430 ℃, 30000 h-1
and H2/N2 of 3.
Some paper reported [14] that the best ruthenium-based catalyst is about 20 times more active
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than a commercial Haber catalyst (i.e. magnetite-based), but they did not provide specific activity
data. In Fig. 9, Pernicone et al. [24] compared the activity of A301 wüstite-based catalyst with the
best Ru/C catalyst [65, 66]. It can be seen that they are practically equal, except for very high
conversion, where the lower sensitivity of Ru to ammonia plays a decisive role. So, catalyst A301
appears to be competitive with Ru/C.
The comparison of reaction rate and TOF on our ruthenium catalyst and wüstite-based catalyst
under the same conditions are shown in Table 5.
It can be seen from Table 5 that under the same conditions, the mass reaction rate (rm) of
ruthenium catalyst is higher by 3.9 times and the TOF is higher by about 3.4 times than that wüstite-
 Table 5 Comparison Ru/C and wüstite-based catalyst in activity, rate and TOF（φ0NH3= 0，H2/N2= 3）
-3
Catalysts ρ/g·cm p/MPa t/℃ Sv/h-1 φNH3% rV/mmol·ml-1·h-1 rm/mmol·g-1·h-1 TOF①/s-1
Ru-K-Ba/AC 0.75 10 400 5000 24.43 43.81 58.41 0.137
10 400 30000 15.06 174.81 233.08 0.545
Wüstite（ZA-5） 2.45 10 400 5000 19.23 36.53 14.91 0.042
10 400 30000 11.74 140.65 57.41 0.162
①In Ru-K-Ba/AC catalyst: content of Ru, fm = 4%，dispersion Dm = 30% [66]；in wüstite-based catalyst: content
of Fe, fm = 91.5%, dispersion Dm = 0.06% [28, 68].

based catalyst, which the main reason is that the density of wüstite-based catalyst is 3.3 times
higher than that of ruthenium catalyst, so even at the same ammonia concentration (φNH3), the rm
and TOF of ruthenium catalyst are also higher by about 3.3 times than wüstite-based catalyst.
However, the design of industrial converter is commonly calculated by volume of catalysts, and the

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volume reaction rate (rV) of ruthenium catalyst is only higher by about 20 % ~ 26 % than
wüstite-based catalyst. So, just as Pernicone mentioned [24] that wüstite-based catalyst is
competitive with Ru/AC on activity. At the same time, Jacobsen et al. [20] considered that Ru and

ro
Os are the best catalysts among pure metals for ammonia synthesis, however, ruthenium is very
expensive and thus less commercially attractive compared to the third-best catalyst, iron catalyst,
and has no obvious advantage in saving energy.
-p
Currently, there are three types of ammonia synthesis catalysts used in the industry, i.e.
magnetite-based and wüstite-based and ruthenium-based catalysts, wherein, magnetite-based
catalysts such as KM series of Topsoe in Denmark, ICI74-1 of Johnson Matthey Company in
re
London, and A110 series in China, while wüstite-based catalysts such as A301, ZA-5 in China,
and ruthenium-based catalysts such as KAAP in UK. The results mentioned above of the
comparison show that the wüstite-based catalysts for ammonia synthesis is the most advanced
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commercial iron catalyst with the highest activity and low production cost in the world, and it can
compete in activity and cost with expensive ruthenium-based catalysts for ammonia synthesis,
possessing a strong market competitive advantage. Especially, it is suitable for ammonia synthesis
at low pressure.
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4.2. Reaction kinetics

The fundamental insights into the reaction kinetics are required in order to design the industrial
reactors. The reaction mechanism and kinetic for ammonia synthesis using iron catalyst are
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already understood clearly [68-73].

Ertl and Somorjai et al. [68,69] considered that the nature of the active site at the surface of Fe
is the most active face (111) with C7 sites; the least active face (110) without C7 sites, and the
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activity of Fe crystal faces is in order of (111) > (211) >(100) > (210)>(110).
The wüstite-based catalyst has the following distinguishing features in the adsorption
performance, and the structure of active site at the surface on reduced catalyst.
We studied reduction processes and growth of iron crystal face of magnetite- and
wüstite-based catalysts by situ XRD, and the XRD data acquisition and analysis using Win XRD
software. The results indicated that wüstite-based catalyst shows more (111) face with the highest
activity exposed, while magnetite-based catalyst shows more (110) face with the lowest activity
exposed [28, 76, 77]. The TOF of wüstite-based catalyst was about 65.9 % higher than
magnetite-based catalyst [68].
 It is seen from the results of H2-TPD [28, 78] that wüstite-based catalyst does not have strong
chemisorption species (β3) of H2 on surface, while with β3 for magnetite-based catalysts.
It is seen from the results of N2-TPD [28, 79] that desorption activation energies (Ed) of N2 on
wüstite-based catalysts are obtained, and the Ed and the activation energies (Er) of ammonia
synthesis reaction was practically equal, which indicates the dissociation adsorption of N2 is the
rate-determining step for ammonia synthesis reaction, which means that we could use next kinetic
equation.
It is commonly considered that the dissociation adsorption of N2 is the rate-determining step
for ammonia synthesis reaction, and the kinetic equation on iron catalyst is obtained as shown in
equation (3) and equation (4) [74, 75]:
 1
 fH 3   f NH 3 2 
 k1 f N 2  2 2   k 2 
 f H 3 
rNH 3 （3）
 f NH 
 3   2 
And extended Temkin equation

of
f NH3 2
k * f N2 1 (1  )
K 2f f N2 f H32
rNH3  （4）
 1

ro
 l f 2
  l 
  2 3    1
NH 3
 
 f H 2 K f f N2 f H 2   f H2 

Kinetics
Range of
Catalysts
Activation energy
-p
Table 6 Kinetics parameter for equation (3) and (4)
Pre-exponent Constant
R2
re
temperature/℃ /kJ·mol-1 factor /MPa0.5s-1 k (425 ℃)
Equation(4) Wüstite 159.033 0.817×1013 6.229 0.99955
375 ~ 475
(α=0.5) Magnetite 171.581 2.7837×1013 4.0118 0.99979
lP

Equation(5) Wüstite 151.559 0.4898×1013 22.245 0.99993

325 ~ 475
(α=0.35) Magnetite 171.028 2.5742×1013 4.0811 0.99991

At the pressure of 15 MPa, the temperatures range of 325 ~ 475 ℃, the space velocity range
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of (30 ~ 120) *103 h-1 and H2/N2 ratio of 3, the activities of wüstite-based (ZA-5) and
magnetite-based (A110-2) catalysts were measured. Based on the data, the kinetics parameter is
obtained by equation (3) and equation (4) given in Table 6, respectively.
It can be seen from Table 6 that both the apparent activation energy and pre-exponent factor of
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wüstite-based catalyst are lower than that of magnetite-based catalyst. The activation energy of
wüstite-based catalyst is lower about 12.5 kJ·mol-1 in equation (3) and 19.5 kJ·mol-1 in equation (4)
than magnetite-based catalyst, and the reaction rate constant of wüstite-based catalyst at 425 ℃ is
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82 % higher than that of magnetite-based catalyst due to the high activity of wüstite-based catalyst
at low temperatures, e.g., the relative activity of wüstite-based catalyst is 2 times higher than that
of magnetite catalyst at 325 ℃. It takes note that the kinetics parameters for magnetite-based
catalyst are the same basically in equation (3) and (4).
4.3 Industrial bypass test for wüstite-based catalyst
There are a large number small-sized ammonia plants with capacity of about 300 tons/day in
China. They can be used as a process demonstration unit (PDU). In fact, wüstite-based catalyst is
firstly used in many small ammonia plants, and then gradually extended to large scale ammonia
plants.
In order to investigate the performance of the wüstite-based catalyst under practical working
conditions of the existing large ammonia plant, the industrial test was carried out by setting up an
industrial bypass device at side line in inlet of S-200 convertor in Zhenhai ammonia plant with
capacity of 1000 tons/day using Topsøe process in order to investigate the performance of
wüstite-based catalyst with original particle size. The wealth and invaluable data were obtained
under actual industrial conditions for different process to verify the research results of laboratory.
It was clear, however, that commercial credibility would require going to a larger scale, and the
results are shown in Table 7 [80, 81].

Table 7 Bypass test results of wüstite-based catalyst at ZhenHai Ammonia Plant in China
② ①
Catalyst Reaction conditions Ammonia concentration/%
Process
Pressure/MPa Temperature/℃ Sv/h-1 φNH3,out φNH3,in ΔφNH3

of
Isobric Wüstite(ZA-5) 7 405 6045 14.35 3.61 10.74
Wüstite(ZA-5) 7.5 406 6032 14.80 3.60 11.20
ICI-AMV Wüstite(A301) 10 409 4000 19.69 3.65 16.04

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Kellogg Wüstite(A301) 15 440 10118 21.19 3.64 17.55
Wüstite(A301) 15 454 6000 23.34 3.64 19.70
Topsøe Wüstite(A301) 18.5 464 18000 20.72 3.64 17.08
Magnetite (KM)
③
18.5 500 -p 17770 16.96 3.66
① Syngas composition of 69.71 % H2, 26.52 % N2 and 1.67 % He; ② Catalyst particle size: 1.5 ~ 3.3 mm; ③
13.30

The data are the actual operating data at 18.5 MPa and 17770 h-1 from Topsøe S-200 convertor using Topsøe
re
KM magnetite-based catalyst in ZhenHai Ammonia Plant.

It can be seen from Table 7 that the ammonia net value above 3.78 percentage points and the
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yield of ammonia about 24 % is increased using A301 wüstite-based catalyst than existing
magnetite-based catalyst (KM-type) under the same conditions in this plant. Meanwhile, it can
decrease the pressure and temperature, reduce circulating gas flow and vent gas flow to save
power consumption and reduce gas consumption. For example, if the pressure reduces from 18.5
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MPa to 15 MPa and the space velocity from 18000 h-1 to 6000 h-1, the ammonia net value can be
increased by 6 percentages point above. Therefore, the ZA-5 wüstite-based catalyst is an ideal
catalyst for replacing other catalyst and technical renovation of large-scale ammonia plants.
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A series of engineering design basic parameters including reaction kinetics equation and
complete physical and chemical data of wüstite-based catalyst were obtained by the industrial
bypass and the original particle size catalyst.
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5. Basic research on industrial application technology for wüstite-based catalyst

As mentioned above, the activity of wüstite-based catalyst is 70 % higher [24] and the
reduction rate is 3 ~ 4 times faster than that of magnetite-based catalysts. How to reduce the
reduction rate and to take out the increased reaction heat are two key technology problems that
must be solved during its industrial application.
In order to solve these problems, we put forward a technical route to combine catalyst, catalytic
reactor and catalytic process technology so that the application of catalyst is not isolated, and
combined with the reactor and process to produce cluster effect and improve the overall technical
level of ammonia plant. We have developed a new type of convertor [82, 83] and completed a
series of catalytic reaction engineering studies, and obtained engineering design parameters
including catalytic reaction kinetics, the whole physical and chemical parameters, and designed a
software package that is suitable for the simulation design and optimization of the equipment and
process of synloop, and also solved series of problem of wüstite-based catalyst during being
applied in large scale ammonia plants, making ZA-5 wüstite-based catalyst become a most
well-studied catalyst from theory to practice among iron catalyst.
5.1 Industrial reduction technique for too fast of reduction rate
The reduction of the catalyst in the convertor is the final step in the preparation of iron catalyst,
which is also the most critical step. The reduction process of the iron catalyst in mixture of H2 and
N2 is a complex physical-chemical process, including chemical reaction, non-catalytic gas-solid
reaction, the formation and crystal growth of α-Fe crystallite, and the accompanied with the
formation of ammonia during reduction [5].
The reduction reaction of wüstite-based catalysts is as follows:

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Fe1-xO +H2 = (1-x) Fe+H2O -37.3 kJ·mol-1 (5)
The reduction reaction of magnetite-based catalysts is as follows:

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Fe3O4+4H2 = 3Fe+4H2O -181.7 kJ·mol-1 (6)
As a chemical reaction, the effect of temperature, pressure and gas component on reaction must
be considered from the point view of the kinetics and thermodynamics of the chemical reaction.

fused iron catalysts can be described by shrinking core model (SCM). The intrinsic kinetics of
reduction is expressed as equation (7).
-p
As a non-catalytic gas-solid reaction, if the shape of catalyst is taken as spheroid, reduction of
re
dxB  E  n
 k0 exp   PH 2 1  xB 
2/3
(7)
dt  RT 
lP

Where, xB is the degree of reduction; t is time, k0 is pre-exponential factor, and E is the activation
energy. The intrinsic kinetic equation on the wüstite-based catalyst is expressed as equation (8).
dxB  71680  1.5
 4248exp   PH 2 1  xB 
2/3
(8)
dt  RT 
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The reduction degree is defined as the mass ratio before and after the reaction, and can be
obtained from thermogravimetric analysis (TGA) curves. For example, the H2-TG and H2-DTG
curve of magnetite- and wüstite-based catalyst at hydrogen are shown in Fig. 10 [5, 84, 88].
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100
0.00 100 0.0
95
DTG(%/min)

95 -0.2
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-0.05
DTG(%/min)
Mass (%)

90
Mass (%)

90 -0.4
85
-0.10
85 -0.6
80

75 TG -0.15 80 TG -0.8
DTG DTG
70 75 -1.0
200 300 400 500 600 700 800 250 300 350 400 450 500 550
o o
Temperature( C) Temperature( C)
(a) Magnetite (b) Wüstite

Fig. 10 TG-DTG curves for magnetite-based and wüstite-based catalyst

 Table 8 Reduction parameters of wüstite-based and magnetite-based catalysts (1)
Initial Final Temp. with Reduction Time with Reduction Loss Weight
Catalysts temp. temp. the fastest degree R 85% reduction rate/%.mi mass/ of H2O/
/ ℃ / ℃ rate / ℃ /% degree / min n-1 % kg·t-1
Wüstite 330.0 490 434 98.89 32 3.09 20.55 231.2
Magnetite 366.0 650 585 95.48 153 0.62 26.03 292.8
(1) Instrument of Shimazhi TGA-40; size of 0.054 ~ 0.074 mm; mass of 10 mg; pressure of 101.3 kPa; H2 flow
rate of 175 ml·min-1; heating rate of 3 ℃·min-1.

The reduction parameters are listed in Table 8. It is seen from Table 8 that the reduction
temperature of wüstite-based catalyst is 100 ℃ lower than that of magnetite-based catalyst, that is,
wüstite-based catalyst has been fully reduced at 480 ℃, while only about 24 % magnetite-based
catalyst is reduced, and is not yet fully reduced until 650 ℃. The temperature with the fastest rate

of
of wüstite-based catalyst is lower more 150 ℃ than that of magnetite-based catalyst.
It can be seen from Table 8 that the reduction rate of wüstite-based catalyst is about 4.98 times
faster and the reduction temperature is about 150 ℃ lower than that of magnetite-based catalyst.

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This is not only a great advantage of wüstite-based catalyst which can greatly shorten the
non-productive time. However, the equipments and conditions of the existing ammonia plant
cannot meet the requirements of the reduction. Therefore, it is also a primary problem to be solved
in the industrial application of wüstite-based catalyst. -p
In ammonia plants, the purpose and requirement of catalyst reduction are that all the catalysts
have to be completely reduced and the activity of the reduced catalysts are not lost, the former is
re
"quantity", the latter is "quality", and a single one cannot be omitted. They must be considered at
the same time and no one can be ignored. The good or bad of reduction is directly related to the
economic benefits of the enterprise in the next few years or even more than a decade years.
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The activity of catalysts after reduction is a function of many factors such as surface area of
reduced iron, exposed crystal face structure of α-Fe and surface coverage of the promoters etc. .
These factors are related with the reduction condition and the formation and growth of α-Fe
crystallite during reduction. The mainly factors of influence on "quality" of reduction are
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reduction rate, temperature and concentration of water vapor. The relation between reduction rate
(rH2O) and the concentration of water vapor (θ) are as follows：
dw H 2O
rH 2O   Vin  SVVcatal (9)
ur

d
Average concentration of water vapor:

wH 2O wH 2O
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 ＝ (10)
Vin  SvVcatal
Where, WH2O is the weight of water formed; τ is the effective reduction time; Vin is the syngas flow
at inlet of convertor; SV is space velocity and Vcatal is catalyst volume.
Therefore, in industrial installations, the reduction rate and quality of catalysts are ensured by
the strictly controlling of the concentration of water vapor. Generally, the vapor concentrations are
limited in 0.7 < θ < 3.0 g/m3 (STP).
The wH2O in equation (10) can be obtained according to calculation of the loss mass (i.e. oxygen
content) obtained by TG and the weight of catalyst. For example, for the converter with volume of
60 m3 or 177 tons of un-reduced magnetite-based catalyst with the oxygen content of 26.03 %
(Table 9), then, WH2O=51.832 tons. While wüstite-based catalyst needs catalyst of 186 tons with
the oxygen content of 20.55 % (Table 9), an item, WH2O = 43.0 tons. The results indicate that WH2O
of wüstite-based catalyst is less 8.832 tons than that of the magnetite catalyst.
If average water vapor concentration is limited ≤ 2 g·m-3, the syngas flow is 300×103 m3· h-1 in
inlet of reactor, the required effective reduction time at least is 86.4 h for magnetite-based
catalysts, while wüstite-based catalysts is 71.7 h. The result shows that the effective reduction
time (τ) of the wüstite-based catalysts is saved about 15 h than that of the magnetite-based
catalysts.
Since the reduction rate of wüstite-based catalyst is 4.98 times as high as the magnetite-based
catalyst, the water vapor concentration is also 4.98 times higher than the magnetite-based catalyst
at the same temperature, space velocity (SV) and catalyst volume (Vcatal). For example, even at
400 ℃, the water vapor concentration can reach 10 g/m3 above , which would seriously impair
the activity of the catalyst after reduction. Therefore, the key is to control the reduction speed

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which cannot be too fast during reduction. In other words, controlling the reduction rate and water
vapor concentration are the keys of wüstite-based catalysts to successful application in industry.

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Therefore, we proposed that the low temperature, high space velocity, high concentration of H2,
low concentration of water vapor and fractional steps rise temperature-constant temperature
techniques should be used to suppress the reduction rate and control the water vapor concentration
-p
[84]. However, the specific strategy should be modified according to the equipment and process
conditions of the existing ammonia plant, and the training and guidance of the enterprise technical
personnel is also necessary.
re
5.2 Development of industrial technology for taking out the excess reaction heat
Due to the high activity of wüstite-based catalysts and the low active temperature, the reaction
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heat released under the same conditions is more than magnetite-based catalysts. In the existing
ammonia synthesis process, how to remove the excess reaction heat and maintain the heat balance
of the convertor are key technology problems that must be solved during its industrial application.
Therefore, we systematically researched industrial application technology for wüstite-based
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catalyst.
According to the energy balance of convertor or beds of catalyst (deemed adiabatic), the
relationship between the adiabatic temperature rise
and the net ammonia value and the reaction heat of
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ammonia synthesis is as shown in Fig. 11 [88], in

which, Δt = T2 -T1 is the adiabatic temperature
rise, ℃; T1 and T2 is the temperature in inlet and
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outlet of reactor, respectively, ℃; ΔHT2 is the

reaction heat, kJ/mol; ΔφNH3 is the net ammonia
value, %；φNH3 is ammonia concentration in outlet
of reactor; cp is the average molar heat capacity of
gas between T1 and T2, kJ / (mol·K); the 14 ~ 16 is
Fig. 11The energy balance, Δt and net
the adiabatic temperature rise when the ΔφNH3 for ammonia value of convertor or beds of
each additional 1 % NH3, right upper picture the catalyst
comparison of the activity for wüstite-based and
magnetite-based catalysts.
 It can be seen from above Table 7 that the ammonia net value above 3.78 percentages and the
yield of ammonia about 24 % was increased using ZA-5 wüstite-based catalyst than existing
magnetite-based catalyst (KM-type) under the conditions at 18.5 MPa, 18000 h-1 and 450 ℃ in
Topsøe process [80]. Producing 1 k mol of ammonia at 450 ℃ will give out 54.5 MJ of reaction
heat, if the ammonia net increases 3.78 %, will release 206 MJ reaction heat. For the original
designed convertor using the magnetite-based catalyst, this heat is an extra addition. If it does not
remove the heat from the convertor in time, the adiabatic temperature will rise too high because
the Δt is proportional to the net value (ΔφNH3) of ammonia, while the ΔφNH3 for each additional 1 %
NH3, Δt increase 14 ~ 15 ℃. As above mentioned, the Δt of the wüstite-based catalyst is 56 ℃
higher than that of magnetite-based catalyst (KM-type) under same conditions. In the case of the
same inlet temperature of bed, not only will the bed temperature affect the reaction efficiency due
to deviate optimum temperature, but also the outlet temperature t2 of bed will exceed the
heat-resistant temperature of the catalyst and affect the service life. So, these extra added heats
must be removed from the convertor.

of
Therefore, the reaction condition of industry must be firstly optimized, following, optimize
existing process of synthesis loop for using the wüstite-based catalysts in industry.

ro
5.2.1 Optimization of reaction conditions using wüstite-based catalyst
There are many factors that affect the catalytic reaction of ammonia synthesis, which are based
on the thermodynamics, kinetics of the ammonia synthesis reaction, and the performance of
-p
ammonia synthesis catalyst. The ammonia synthesis reaction is a reversible exothermic reaction,
and the optimal reaction temperature and the optimum gas composition (e.g., H2/N2) are present in
the thermodynamics and kinetics; the optimum reaction pressure, space velocity, the content of the
re
inert gas, the inlet concentration of ammonia in the convertor that is determined to be the
temperature of the ammonia condensation separation, and the like is present from the technical
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and economic considerations. Therefore, when the optimum process conditions are selected, both
the thermodynamics and the kinetics should be taken into account; both the output of the ammonia
and the energy consumption of the synthesis ammonia should be taken into account; both the
process and the equipment should be considered, and none of this cannot leave the possibilities
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offered by the catalyst because the reaction conditions of ammonia synthesis mainly depend on the
performance of the catalyst. The most prominent feature of performance for wüstite-based catalyst
is extremely easy reduction and high catalytic activity. Therefore, the reaction conditions should
also be changed to adapt its performance characteristics, while is not opposite [90-93].
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1. Reaction temperature. The temperature is the key factor to determine the effect of the
catalyst application. The first bed catalyst is responsible for the production task of about 70 % of
the convertor, and the ammonia net value is the highest, the adiabatic temperature rise is the
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maximum, the outlet temperature is the highest and the over temperature is easy to cause, and to
protect the activity of the first bed catalyst is very important. Therefore, the most important of the
temperature control of the convertor is the control of the outlet temperature of the first bed. This is
because the first bed catalyst outlet temperature is too high, which will greatly reduce the
ammonia net value of the first bed and even the whole convertor, and at the same time, because
the outlet temperature is too high, the service life of the catalyst can be affected.
As can be seen from above Fig. 8, the present various iron catalysts, the outlet ammonia
concentration have been near equilibrium, and the difference is already little in activity at 500 ℃
or above. However, as the reaction temperature decreases, the relative activity increases more and
more. Therefore, wüstite-based catalyst is suitable for the low temperature and low pressure,
although it can also be used under high temperature and pressure, but it will lose its advantages.
For example, according to simulation by reaction kinetics equation for wüstite-based catalyst,
the inlet temperature, outlet temperature and net ammonia value at the first bed catalyst in Topsøe
S-200 convertor, as shown in Fig. 12 and Fig. 13, respectively [92].

Ammonia concentration of first bed/ % NH3

525 13
500 12
Temperature of first bed/ C

11
475
o

10
450
9
425 8
400 7
375 6

350 5
4
325
3
300 2

of
275 1
0 6.01 11.06 15.15 18.28 0 6.01 11.06 15.15 18.28
3 3
Volume of catalyst/m (Gas flow from left to right) Volume of catalyst/m (Gas flow from left to right)

Fig. 12
Fig.12
The the
relation
relation
between
between
temperature
temperature of inlet Fig.13
of inlet Fig.13
The
therelation
relationbetween
betweenammonia
ammoniaconcentration
concentration

ro
and and
outlet
outlet
for first
for first
bed bed
of catalyst
of catalyst and
and
temperature
temperature
ofof
outlet
outlet
forfor
first
first
bed
bed
ofof
catalyst
catalyst

It can be seen clearly from Fig. 12 and Fig. 13 that:

(1) Case 8 (big blue line): When the inlet temperature of the first bed is 375 ℃, the outlet
temperature is 501 ℃ and the net ammonia concentration is only 7.92 %. This is because when
the inlet temperature is 375 ℃, the reaction has been completed at about 20 cm (6 m3 catalyst) of
-p
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the inlet and the remaining about 12 m3 (about 60 % of the whole column) catalyst has not act, but
also to with stand high temperature baking, it is not worth gaining the loss, and totally undesirable.
(2) Case 3 (big red line): When the inlet temperature is 310 ℃, the outlet temperature is 467 ℃
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for first bed, the whole catalyst plays a full role, net ammonia reached the highest of 10.12 %,
higher 2.2 % than the Case 8, i.e., increased of 27.8 %, which means that ammonia production can
be increased by more than 20 %. It not only improves the net ammonia, but also protects the
catalyst. Therefore, the first bed outlet temperature of 467 ℃ is the most suitable temperature for
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the wüstite-based catalyst.

(3) Comparing Case 2 with Case 5, the outlet temperature is 451 ℃ and 481 ℃, respectively,
but the net ammonia values is both 9.62 %. The ammonia net value that can reached at 451 ℃,
why make the temperature rise to 481 ℃? Even outlet temperature is 425 ℃, the net ammonia
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value (8.52 %) is also higher 7.92 % than 501 ℃. Therefore, controlling principle of outlet
temperature is rather low than high for first bed.
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Conversely, for magnetite-based catalyst, at the same reaction conditions as wüstite-based

catalysts, the ammonia net value is the highest when the outlet temperature range of 496 ~ 504 ℃
for the first bed catalyst, while the ammonia net value will decrease rapidly if temperature is
below one. That is, for the magnetite-based catalyst, it is suitable outlet temperature to reach about
500 ℃ for the first bed. This is just the normal operating temperature for the magnetite-based
catalyst in industry.
The simulated results mentioned above were validated by the next example. Some ammonia
plant using wüstite-based catalyst with capacity of 2200 t/d and the convertor with diameter
Φ3000 and three adiabatic beds, the actual operation of the axial temperature distribution is shown
in Fig. 14. The T1 to T3 are temperature distributions of the first bed, T4 to T6 are the second bed,
and T7 to T10 are the third bed; and T3 to T4 and T6 to T7 are cooling process in heat exchanger,
respectively.
It can be seen from Fig. 14 that the
525
reaction already carry out complete
500
substantially when from 353 ℃ (T1) to

Temperature of bed / C
475

o
505 ℃ (T2) in the first bed. Similarly, the 450

second bed achieve to 470 ℃ (T5) and the 425

third bed to 454 ℃ (T8) are all over. 400

Therefore, most of catalysts in the convertor 375

did not work, which is in good agreement 350

with the simulation results of the 325

T1 T2 T3 T4 T5 T6 T7 T8 T9 T10
above-mentioned Case 8 in Fig. 12 above. Position of temperature (T1,T4,T7 is inlet
temperation of bed each)
The reason caused the results is that the

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design of the convertor was based on Fig. 14 Operating temperature distribution at the axial for
kinetics equation of magnetite-based convertor with Ф3000 and three adiabatic bed of catalyst

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catalysts rather than that of wüstite-based
catalyst.
As a result, three principles for controlling the outlet temperature of the first bed in the design
and industrial operation of the synthesis convertor can be derived: -p
(1) The outlet temperature of the first bed of about 470 ℃ is the most suitable outlet
temperature for wüstite-based catalyst;
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(2) The principle for design and operation of outlet temperature of the first bed is that it is
better to choose lower temperature than to choose higher temperature, and strictly controlled at
480 ℃ below.
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(3) The temperature of bed of catalyst is ultimately determined by the active temperature of the
catalyst and the optimal reaction temperature in the thermodynamics and kinetics.
2. Optimum H2/N2 ratio in syngas. It is considered [5] that H2/N2 ratio in syngas is related
with both the thermodynamics and kinetics of reaction. According to the chemical equilibrium of
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the synthesis ammonia reaction, optimum H2/N2 is 3 when the maximum equilibrium ammonia
concentration is reached. According to the kinetics equation of the Temkin-Pyzheve, the H2/N2
ratio at the initial stage of the reaction reaches a maximum value of 1.5. As the reaction proceeds,
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if it is desired to keep the reaction rate at a maximum, the H2/N2 ratio should gradually increase
from the initial 1.5 to 3.0 when the reaction reaches equilibrium. The above-described operation
method is impractical due to the fact that the ammonia-synthesized H2 and N2 are consumed in a
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ratio of 3:1. However, for a certain structure of convertor, under certain working conditions, there
is an optimum H2/N2 which the reaction rate is the fastest, the ammonia concentration of the
reactor outlet is the highest, and the yield is the largest. It is clear that this optimum H2/N2 is
associated with the rate of progress of the reaction which is related to degree of outlet ammonia
concentration approach the equilibrium. The concept of catalyst efficiency K is used to
characterize the degree of the outlet ammonia concentration (φNH3) approach equilibrium (φ*NH3),
that is, K = φNH3 / φ*NH3 under the same reaction conditions.
The author [90] studied the relationship between H2/N2 ratio and catalyst efficiency under 7. 0
and 15.0 MPa, 350 ℃, 400 ℃ and 450 ℃, the range of H2/N2 is 1. 6 ~ 3.0, and obtained the
relationship between the optimum (H2/N2)m ratio and the catalyst efficiency (K) as shown in Fig.
15 and obtained following equation by Fig. 15:
(H2/N2)m = 1.5047 + 1.487K ≈ 1.5 (1 + K) (11)

3.0

H / N2 Ratio
2.5

2
2.0

1.5
0.00 0.25 0.50 0.75 1.00
Catalyst efficiency(K)

Fig. 15 The relationship between the optimum H2/N2 ratio and the catalyst efficiency (K)

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Any factors that reduce the catalyst efficiency (catalyst activity) will reduce the optimum
H2/N2 ratio. The catalyst efficiency and the optimum H2/N2 ratio decrease with decreasing the

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temperature and reaction rate, and increasing equilibrium ammonia concentration. According to
the outlet ammonia concentration of wüstite-based catalyst at 15 MPa and 10000 h-1, the optimum
H2/N2 ratio was 2.55 ~ 3.0 at 450 ℃, 2.23 ~ 2.55 at 400 ℃ and 1.76 ~ 2.22 at 350 ℃, respectively.
Therefore, the suitable H2/N2 ratio is 1.8 ~ 2.6 for wüstite-based catalyst with the performance
under low temperature. This is the theoretical basis for UD-ICI-AMV low pressure process (12
MPa) of with H2/N2 of about 2.25 [94].
-p
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5.2.2 Low-pressure process for ammonia synthesis
One of the major research directions for ammonia synthesis is low-pressure technology. In
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general, after a new and highly efficient catalyst was developed successfully, it requires the
development of the new corresponding process technology and suitable convertor and its synthesis
loop processes. For example, the UD-ICI-AMV low-pressure process was corresponding to ICI
74-1 containing cobalt magnetite-based catalyst [94], and the newly KAAP technology was
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compatible with Ru catalyst [95].

The high-activity wüstite-based catalyst is more suitable for low-pressure ammonia synthesis,
and provides a technical basis for the development of low energy consumption and low-pressure
ammonia synthesis technology. When wüstite-based catalyst was industrialized, we have
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committed to promoting the development

of low-pressure process matching to a new 22
generation of highly efficient catalyst, and 20
Ammonia concentration/%
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18
industrial bypassed test was made in a 300
16
kt/year of large-scale ammonia plant [5, 80, 14
81]. 12
10
Wüstite-based catalyst is a low -1
8 1000 h
temperature and low pressure catalyst with 6 1500 h
-1

-1
4 3000 h
most active and the low of active -1
2 6000 h
temperature, especially suitable for low 0
200 250 300 350 400 450
pressure process. As can be seen from Fig. o
Temperature/ C
16 [5], wüstite-based catalyst has initial
Fig. 16 Activity of wüstite catalyst at 7.0 MPa and H2/N2 = 3.0
activity at 200 ℃, and the outlet ammonia concentration reaches more than 18 % ~ 20 % at 7.0
MPa, 375 ~ 400 ℃ and 1000 ~ 1500 h-1.
It can be seen from above Table 7 that the results by bypass test show that the outlet ammonia
concentration reaches 14.4 ~ 14.8 % and the net ammonia value of with industrial significance
reaches 10.7 ~ 11.2 % at 7.0 ~ 7.5 MPa and 6025 h-1 under the actual working conditions of
Topsøe large-scale plant.
Therefore, it is feasible that isobaric process in 7.0 MPa or 7.5 MPa using wüstite-based
catalyst, especially, for the gasification process with residual oil or coal water slurry (CWS) as raw
material at 8.53 MPa.
It is generally believed that with the reduction of pressure, in order to ensure the net value of
ammonia in industrial significance, inert gas concentration and ammonia condensation
temperature should be lowered, which leads to increase the power of circulating compressor and
ammonia compressor and the power consumption of three compressors were substantially
constant. Therefore, some experts believe that low pressure does not save energy [96].

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As we all know, pressurized synthesis ammonia is to overcome the energy barrier for the
reaction of ammonia synthesis, and the height of energy barrier is determined by the activation

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energy of the catalyst. The activation energy of newly efficient wüstite-based catalyst is much
lower than the magnetite-based catalyst, and the required pressure should also be reduced because
of the lower pressure can reach the net ammonia value of conventional catalyst under high
pressure. -p
For this, the author [97-103] studied detailed the relationship between the power of the three
compressors and the catalyst activity and process parameters in the synthesis loop. The results
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show that the power consumption of the three compressors depends on the ammonia content (net
ammonia) of inlet and outlet in convertor, the content of inert gas in fresh syngas and vent gas and
condensation temperature of ammonia, and they are mainly determined by the activity of the
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catalyst.
The author proposed [99] a concept of
30000
using high activity of the new catalyst to
Compression work/kW

25000
offset the net ammonia lost due to
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pressure reduce. Based on this idea, a 20000

new low-pressure and low-energy 15000 Syngas compressor

consumption ammonia synthesis Recycle compressor
10000 Refrigeration compressor
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technology was proposed over ZA-5 Total compression work

5000
wüstite-based catalyst. Without changing
the existing process flow, with 0
7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0
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minimizing the total power consumption Pressure/MPa

of the three compressors as the objective
Fig. 17 Relation between compression work and pressure
function optimization design for the
for new process using ZA-5 catalyst
process parameters of the synthesis loop
is carried out using the high active
wüstite-based catalyst. The result is shown in Fig. 17.
As can be seen from Fig. 17, in the new process technology, the power of the recycle
compressor and the refrigerator are basically unchanged as pressure is reduced. As a result, the
total power is decreased with the syngas compressor power decreases, and the change of the total
power and energy saving with pressure are shown in Table 9.
Especially noteworthy is that when using residue, coal water slurry or pulverized coal to
produce syngas at 4 ~ 9 MPa, and using wüstite-based catalyst can achieve isotonic process of 7.5
MPa. In the process without a syngas compressor, the total power can be reduced by half, reducing
the energy consumption per ton of ammonia in 6.17 GJ.t-1 or saving standard coal by 210.6 kgce.
t-1 and reducing the energy efficiency of 50.62 %. The results are basically the identical of 2.3 ~
6.9 GJ.t-1 that Kellogg proposed isotonic pressure processes at 4 MPa [88].

Table 9 Three compressors total power and its energy-saving effect for ammonia plant with 200 kt/year
Loop pressure/P/MPa 30 25 20 15 10 7.5*
Total power/kW 28604 27552 26907 25074 23367 14125
Saving power/kW - 1051.9 1697.1 3529.9 5236.4 14478
Energy efficiency/η/% - 3.68 5.93 12.34 18.31 50.62
Save energy/GJ.t-1

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- 0.448 0.723 1.505 2.232 6.17
Save standardcoal/kgce.t-1 - 15.3 24.7 51.3 76.2 210.6
* In the 8.53 ~ 7.5 MPa isobaric process, without the syngas compressor, the table shows the power consumption

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calculated by the oxygen or air compressor compressed to 8.53 MPa.

Our results are gradually accepted by the design and industry sectors. At present, the pressure

14 ~ 15 MPa in China.
-p
of the ammonia plant with capacity of 660 ~ 1000 t/d is been gradually reduced from 30 MPa to

In summary, in order to reduce the adiabatic temperature rise, the appropriate reaction
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conditions are low temperature, low pressure and low H2/N2 ratio, the actual process parameters
depend on the specific conditions of plant using wüstite-based catalyst.
5.2.3 Optimization of synthesis loop process for existing ammonia plant
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As mentioned above, in order to make the low temperature and high activity of wüstite-based
catalyst be effectively used in the existing convertor and process for ammonia synthesis, and give
full play to its excellent performance, the existing ammonia synthesis convertor and its synthesis
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loop process parameters necessary adjustments and transformation.

For this reason, the design and optimization software package for the convertor and loop
process and equipment are designed. According to the structure and conditions of the process and
convertor, the design and optimization are carried out to adapt the case of application plant and
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choose the best operating conditions to provide the basis and guidance for wüstite-based catalyst
with low temperature and low pressure [100-103].
For example, for Topsøe S-200 ammonia plant with capacity of 1000 t/d and with Ф3000
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two-bed indirect heat exchange radial convertor, through the simulation design and optimization,
proposed transformation and use of programs for process parameters and equipment:
(1) The inlet gas temperature of the convertor needs to be reduced from 145 ℃ originally
designed to about 125 ℃ required by wüstite-based catalyst.
(2) The inlet temperature of first bed requires from the existing 360℃ ~ 370 ℃ to 310 ℃ ~
335 ℃. Within the margin of pipeline designed can meet the requirement by adjusting the
proportion of the flow of three stream cold gas and reducing the inlet gas temperature.
The actualized results showed that (Table 10) after optimization, the inlet temperature of
convertor dropped from 141 ℃ to 130 ℃,while outlet temperature increased from 319 ℃ to
359 ℃,respectively; the inlet temperature of first bed decreased from 361 ℃ to 325 ℃; the
inlet temperature of second bed decreased from 401 ℃ to 365 ℃. At the time, outlet ammonia
concentration of convertor was increased from 14.18 % to 17.76 %, an increase of 3.58 %;
ammonia production was increased from 931 t/d to 1158 t/d, i.e., increase of 24.4 %, and compare
with before of optimization, save energy of 177 MJ/t.

Table 10 Wüstite-based catalyst- synthesis loop simulations for Topsøe S-200 converter by ZJUT
Catalyst A110-1(Base case) ZA-5(Base case) ZA-5(Optimum)
Pressure/MPa 13.5 13.5 13.5
Gas flux at inlet of reactor/(Kmol/h) 21216 21216 21216
Temperature ofinlet and outlet of reactor/℃ 141/305 141/319 130/359
Ammonia at inlet and outletof reactor/% 1.89/12.86 1.89/14.18 2.0/17.76
Temperature of inlet and outlet of first bed/℃ 361/493 361/501 325/470

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Temperature of inlet and outlet of first bed/℃ 401/434 401/446 365/423
Output of liquid ammonia/ t/d 893 931 1158
Total Energy Saving/( kJ/t) - 48,000 225,000

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The activity of AmoMax-10–wüstite-based catalysts is about 43 % higher than
magnetite-based catalysts. Commercial experience with AmoMax-10 shows very significant
-p
advantages over magnetite-based catalyst in terms of activity and start-up time. Combining the
best AmoMax-10–wüstite-based catalyst technology from Süd-Chemie and the best converter
technology from Ammonia Casale provides significant value to ammonia producers as listed
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Table 11. It is seen from Table 11 that the calculated savings of 20,000 kcal/MT correspond to
approx 0.3 % of total energy consumption（30 GJ/MT）and 140,000 ~ 450,000 USD/year (9.2
USD/mm BTU-360 Days of Production) (depending on region). It can be realized as increased
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production and/or improved energy efficiency - increasing your competitiveness [104].

Table 11 AmoMax-10 – synthesis loop simulations by Ammonia Casale

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1-A(Base 1-B (IAC & 1-C (IAC

Unit
Case) Magnetite) &AmoMax)
Converter capacity MTD 1600 1600 1600
Ammonia content at converter inlet % mol. 1.3 1.3 1.3
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Ammonia content at converter outlet % mol. 15.5 17.4 18.3

Converter outlet pressure Barg 140 138 138
Total Energy Saving kcal/MT - 50,000 70,000
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5.3 The scale and examples of industrial application

Up to now, the wüstite-based catalysts has become the widely used catalyst in the ammonia
synthesis industry all over the world.
The commercial wüstite-based catalysts has A301, ZA-5 and AmoMax-10 type catalyst, which
are all developed by Zhejiang university of technology (ZJUT), and the technology of
wüstite-based catalysts was licensed to Süd-Chemie in Germany and named AmoMax-10, and
started to produce AmoMax-10 wüstite (Fe1-xO) -based ammonia catalyst in 2003 [105-107].
 The A301 and ZA-5 are produced by Shangyu catalyst Co. Ltd. (A301), Zhejiang University of
Technology catalyst Co. Ltd. (ZA-5), BASF (Nanjing) catalyst factory (ZA-5) and so on,
respectively.
Before 2018, about 45,000 tons of wüstite-based catalysts were widely applied in industry in
all over the world, in which the largest plant is with capacity of 2220 t/d. The distribution of
factories using wüstite-based catalyst is as shown in Fig. 18 and Fig. 19.

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Fig. 19 Distribution of factories used

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Fig. 18 Distribution of factories used wüstite-based AmoMax-10 catalyst in the World from

catalysts in China [5] Süd-Chemie [104]

-p
For example, Haoyuan chemical group Co. Ltd. in China has with capacity of 1300 t/d and
93 tons of ZA-5 wüstite-based catalysts. Compared with the original use of A110 magnetite-based
catalyst, the reduction time shorten 2 days, the temperature lower 20 ℃, the pressure reduce 1.5
re
MPa, the outlet ammonia concentration reach to 14.5 %, the net value of ammonia increase by
1.5 %, and the ammonia production increase by 5 %. The comprehensive energy consumption was
decreased from 1458 kgce/tNH3 to 1342 kg/t NH3 in standard coal, and reduced 116 kg/t NH3, namely
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energy saving 8 %. The cumulative production of ammonia is 80 kt (it increases 860 tNH3/tcatal) and
the production of urea is 130 kt. The new increased output value is 234 million in RMB, the new
increased tax paid is 70 million in RMB, new increased profit is 20 million in RMB, and the
energy saving is 162.4 kt in standard coal. It achieves important economic benefits and energy
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saving effects.
In summary, product benefits in industrial application is as follows: (1) Low temperature and
start-up time for reduction; (2) Low operating temperature and pressure and its drop; (3) High
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activity; (4) High physical strength; (5) Low shrinkage; (6) Good poison tolerance; (7) Longevity;
(8) Low energy consumption.
6. Conclusion and Perspective
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At present, the annual production of ammonia is about 250 million tons in the world, the
average annual value of sales are more than $100 billion, and it is the second largest chemicals. In
which, about 70 % of ammonia is used to manufacture fertilizers, the per capita expends the 31.1
kg, and about 60 % of nitrogen in the human body come from ammonia. The energy consumption
is 350 million tons during ammonia production process, covering 2 % of total global energy
supply. And the emission CO2 is more than 400 million tons, covering 1.6 % of global CO2
emissions [92]. Therefore, the never-ending story of catalytic synthesis of ammonia has not ended
yet [105]. It yet requires to increases energy efficiency in order to saving energy consumption
using high-performance of catalysts [109-110].
 Wüstite-based catalysts for ammonia synthesis are the most advanced commercial iron catalyst
with the highest activity and low cost of production in the world. This novel ammonia synthesis
catalyst allows a more efficient ammonia production and new ammonia plant with smaller
synthesis converter catalyst volume or lower temperatures and pressures. This high performance
catalyst provides the user with significant economical benefits resulting from faster start-up time,
more efficient ammonia production at lower operating pressure and/or recycle rates and longer
catalyst life-time. This leads to significant lower energy consumption. It is a very significant
contribution to improve ammonia plant efficiency and economy. Therefore, it is also an important
contribution in the reduction of Green House Gases (GHG).
Based on the current shortage of global energy supply and more and more severe CO2 emission
problem, the application of new and high efficient wüstite-based catalyst is vigorously promoted,
which is of great practical significance to achieve energy-saving and emission reduction of
synthesis ammonia industry. In this paper, it has guidance and reference function for industrial
production and industrial application of new and high efficiency wüstite-based catalysts.

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Declaration of Interest Statement

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There are no conflicts of interest to declare. -p
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Acknowledgements Many others have contributed to this story. We can count nearly twenty
research and academia who were involved in the surface science, catalyst development, and
analytical backup over a thirty years period up to 1986. We would like to acknowledge the
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financial support from the National Natural Science Foundation (Grant No. 20473074, 20376075,
20203016, 29706011) and Zhejiang Provincial Natural Science Foundation (Grant No.
LY18B060015, Y406294, 289033, 293015, 295056, 296022), and other project from
governmental agencies and enterprise.
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