1 s2.0 S2772826922000074 Main

Sustainable Chemistry for Climate Action 1 (2022) 100008
Contents lists available at ScienceDirect
Sustainable Chemistry for Climate Action

journal homepage: www.elsevier.com/locate/scca
Green pathways for urea synthesis: A review from Australia’s perspective

Dia Milani a,∗, Ali Kiani a, Nawshad Haque b, Sarabjit Giddey b, Paul Feron c
a
CSIRO Energy Centre, 10 Murray-Dwyer Circuit, Mayfield West, NSW 2304, Australia
b
David Rivett Laboratory, 36 Gardiner Road, Clayton VIC 3168, Australia
c
Private Bag 10, Clayton South VIC 3169; 36 Gardiner Road, Clayton VIC 3168, Australia
a r t i c l e i n f o a b s t r a c t
Keywords: This paper discusses the status of the global fertilizer industry with a primary focus on Australian market. The
Green hydrogen conventional energy- and carbon-intensive ammonia production industry is taking serious steps in transforming
Green ammonia to more environmentally benign pathways via utilizing ‘green’ hydrogen (hydrogen production via water elec-
Haber-Bosch
trolysis powered by renewable energy) feedstock into their production process and utilizing more of the CO2
Direct air capture
by-product into downstream processes such as urea production. However, it is very challenging for ammonia and
Fertilizer
Urea synthesis other fertilizer production routes to use ‘green’ pathway to completely decarbonize agriculture and food industry.
Here, we argue that urea synthesis can only be considered as a ‘green’ technology if ammonia feedstock is pro-
duced via a ‘green’ pathway and the CO2 feedstock comes from non-fossil-fuel and carbon-neutral sources. Three
possible resources for carbon-neutral CO2 are identified and discussed within Australia’s context: from biomass,
renewable methane, and from direct air carbon capture (DAC). Each of these carbon-neutral CO2 routes has many
opportunities and challenges that may affect the cost of production, but the trajectory urea prices and growing
market demand if supported by an adequate government regulatory framework would be able to make the ‘green’
urea production cost affordable. Achieving this goal however would require proper energy management systems
to synchronize and optimize such a multi-player orientation for a common objective of maximizing the pene-
tration of renewable sources at competitive costs. In this review, it is emphasized that this challenge could be
addressed more effectively via a rigours intelligent energy network (IEN) by managing the dynamics of the supply
and demand, integrating reliable storage systems, reclaiming the waste heat, and improving process efficiencies.
Local ‘green’ urea production at competitive costs would help Australia realizing ambitions to become a leading
green fertilizer and renewable energy exporter in the region.
Introduction ficiency of agricultural crops production. Nitrogen (N), Phosphorus (P),

and Potassium (K) are three essential nutrients for plant growth where
According to the United Nations, the world population is expected nitrogen enhances vegetative growth, phosphorus improves roots and
to reach 8.5 billion in 2030, 9.7 billion in 2050 and 11.2 billion in 2100 flowering rate, while potassium strengthens the resistance to environ-
[1]. The projections show that by 2050, feeding a world population mental assaults from extreme weather to pest attacks. The availability of
would require raising overall food production by almost 60% from cur- these nutrients in the form of fertilizers represents a key factor in sustain-
rent levels [2]. The key challenge: will there be enough agriculture land ing global food security in future [3]. Among chemical fertilizers, urea,
and plant nutrients to feed a world of over 9 billion in 2050? By then, comprising 46% nitrogen, is the market’s most important nitrogenous
the world can only feed its population in either of two ways: via inten- fertilizer and one of the primary sources of nitrogen supply for plants
sifying agriculture or by converting more land from natural eco-systems [4]. Commercially available as prills or granules, this white organic sub-
(i.e. rain forests) into agricultural production. Certainly, increasing land stance is synthesized when ammonia reacts with carbon dioxide under
yield and food production efficiency are among the crucial decrees to specific operating conditions [5]. Urea is also used in the production of
stand up for this challenge. Hence, modernized agricultural technologies melamine, urea-formaldehyde resin, and as a ruminant dietary supple-
and advanced chemical fertilizers are instrumental in improving the ef- ment [6]. Moreover, a water solution of urea named AdBlue is used as
Abbreviations: ACOHA, ambient CO2 harvester; AE, alkaline electrolysis; ASU, air separation unit; CCS, carbon capture and sequestration; DAC, direct air capture;
DMC, dimethyl carbonate; DMR, dry methane reforming; EMS, energy management system; FOB, free on-board; HEN, heat exchange network; IEN, intelligent energy
network; LCA, life-cycle analysis; LCOH, levelized cost of hydrogen; LNG, liquefied natural gas; MOF, metallic organic framework; POM, proton exchange membrane;
POX, partial oxidation; SBR, steam biogas reforming; SMR, steam methane reforming; TRL, technology readiness level; USP, urea synthesis plant.
∗
Corresponding author.
E-mail address: Dia.Milani@csiro.au (D. Milani).
https://doi.org/10.1016/j.scca.2022.100008
Received 25 August 2022; Received in revised form 5 November 2022; Accepted 14 November 2022
2772-8269/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)
D. Milani, A. Kiani, N. Haque et al. Sustainable Chemistry for Climate Action 1 (2022) 100008
Fig. 1. A schematic of a simple urea synthesis plant (USP) consists of four stages: (1) the urea reactor, (2) the distillation column, (3) vacuum decomposer, and (4)
the granulator [15].
a critical ingredient for the reduction of hazardous substances at the ex- duction, Haber-Bosch is the most suitable process because the syngas
haust of diesel engines [7]. Urea synthesis is a mature chemical process produced via SMR has the highest H2 /CO ratio [17].
operated at an industrial scale using different techniques as in conven- Syngas production (endothermic):
tional and stripping technologies. Conventional technologies comprise ΔH𝑟
Stamicarbon total recycle, Montedison urea process, Chemico urea pro- 𝐶 𝐻4 + 𝐻2 𝑂 ↔ 𝐶 𝑂 + 3𝐻2 ΔH𝑟 = +206 𝑘𝐽 ∕𝑚𝑜𝑙 (R.1)
cess, and Mitsui-Toatsu total recycle process [8,9], while stripping tech-
Water-Gas shift (exothermic):
nologies include Stamicarbon CO2 stripping process [10], Snamprogetti
ΔH𝑟
NH3 stripping process [11], and the TEC ACES process [12]. Irrespec- 𝐶 𝑂 + 𝐻2 𝑂 ↔ 𝐶 𝑂2 + 𝐻2 ΔH𝑟 = −41 𝑘𝐽 ∕𝑚𝑜𝑙 (R.2)
tive of minor differences between these technologies, the urea synthesis
plant commonly consists of 4 major stages as presented in Fig. 1: (1) In the green ammonia synthesis process, nitrogen is produced by
urea reactor to produce urea solution; (2) distillation column to purify air separation units (ASU) mostly via cryogenic processes [18,19]. The
the urea solution and recycle unreacted CO2 and NH3 ; (3) decomposer hydrogen and nitrogen then react in an exothermic reaction to produce
to evaporate the water under vacuum; and (4) granulator to solidify ammonia (R. 3). Ammonia itself has many industrial applications and is
and granulate the urea product. Granulating urea product can substan- also widely recognised as an important non-carbon energy carrier [20].
tially ease the storage and transport, but most importantly, to reduce its Urea, one of the key applications of ammonia, is often produced in two
excessive volatility and leaching when applied into the soil. In contact stages; first ammonium carbamate is formed at a fast and exothermic
with soil’s moisture content, urea is highly soluble and can easily react reaction rate (R. 4), and then urea is produced at a slow and endothermic
and be degraded into CO2 and ammonia [13]. Therefore, to reduce urea reaction rate (R. 5) [17].
vulnerability and consequently food production cost, advanced coating Ammonia production (exothermic):
materials are often used to control urea release to the soil and crops ΔH𝑟
[14]. 3𝐻2 + 𝑁2 ↔ 2𝑁𝐻3 ΔH𝑟 = −92 𝑘𝐽 ∕𝑚𝑜𝑙 (R.3)
Traditionally, urea production plant is erected downstream to com- Ammonium carbamate formation (fast & exothermic):
plement the ammonia production plant. The magnitude of ammonia vs
ΔH𝑟
urea production is merely driven by economic factors and market pref- 2𝑁 𝐻3 + 𝐶𝑂2 ↔ 𝑁 𝐻2 𝐶𝑂𝑂𝑁𝐻4 ΔH𝑟 = −117 𝑘𝐽 ∕𝑚𝑜𝑙 (R.4)
erences. For urea synthesis, hydrogen is the building block for ammonia
compound, which is used as a feedstock for urea production. In the pro- Urea production (slow & endothermic):
cess of making ammonia and urea, hydrogen is the most sought-after ΔH𝑟 ( )
𝑁𝐻2 𝐶𝑂𝑂𝑁𝐻4 ↔ 𝐶𝑂 𝑁𝐻2 2 + 𝐻2 𝑂 ΔH𝑟 = +16 𝑘𝐽 ∕𝑚𝑜𝑙 (R.5)
commodity because it does not freely exist in the nature. Hydrogen can
be produced from a variety of feedstock, such as fossil fuels, biomass, In the ammonia production plant, CO2 is massively generated from
and water in processes that often consumes substantial amount of en- two sources; first as a by-product of hydrogen production in the ammo-
ergy to obtain pure hydrogen. It is reported that 96% of the world’s nia synthesis process (R. 1&2), and second via fossil fuels combustion
commercially produced hydrogen comes from fossil fuels, where 48% to provide the necessary heat for the SMR reactor. In the urea plant,
of that proportion from natural gas, 30% from heavy oils and naphtha, ammonia is reacted with a portion of the CO2 by-product from the SMR
and 18% from coal. Only 4% of the global hydrogen production is cur- process in the ammonia plant (R. 4). Eventually, each tonne of urea
rently obtained from water electrolysis [4]. The hydrogen production product consumes 0.735–0.75 tonne of CO2 [21]. However, the amount
from natural gas reforming is the most accessible and affordable tech- of overall CO2 emissions from the urea production process is estimated
nology using either steam methane reforming (SMR), partial oxidation at 2.27 tonne of CO2-eq per tonne of CO2 utilized [21]. Thus, the tradi-
(POX), or dry methane reforming (DMR) routes [16]. In the SMR pro- tional method of ammonia and urea production (i.e. via SMR) is counted
cess, methane and steam react in a highly endothermic catalytic process as one of the most carbon-intensive industries that is responsible for
to primarily produce syngas, a mixture of carbon monoxide and hydro- 1.2% of the total global GHG emissions [22]. From a life cycle perspec-
gen (R. 1). Carbon monoxide (CO) is then upgraded with steam in the tive, the concept of CO2 utilization in urea production is not recognized
water-gas shift reaction to produce more H2 (R. 2). For ammonia pro- as an effective carbon abatement measure, because the CO2 will end
2
up in the atmosphere as urea will eventually decompose in soil. Fur- the production and consumption rate of the major nitrogenous fertilizer
thermore, natural gas feedstock among other fossil fuels not only cause (i.e. ammonium phosphates and urea) players in the global market. It
severe climate impact but is also subject to extreme cost volatility due is evident that the supply and demand of the nitrogenous fertilizers in
to the ongoing global geopolitical tensions. As global decarbonization the last five decades have an overall growing trend. China has expe-
momentum accelerates, the time has come for ammonia and urea in- rienced the fastest growth of nitrogenous fertilizer in both production
dustries to promote alternative greener pathways to decarbonize, or at and consumption rates. On the consumption side, China’s consumption
least reduce their carbon footprint, to meet the obligations of the net- increased almost constantly until the year of 2000 then exponentially
zero emissions target by 2050 as an international commitment that has onwards. India, currently the second largest producer/consumer of the
been adopted and reinforced lately at COP26 [23]. nitrogenous fertilizers and surpassing the USA after the year of 2000
The alternative sustainable pathway for ammonia production is via has also demonstrated similar trend of China. USA has almost constant
green hydrogen obtainable from water electrolysis and powered by re- production rate of nitrogenous fertilizers with slight fall in the produc-
newable energy sources [24]. Down the track, green hydrogen is also tion between 1990 and 2010, while the consumption pattern started
regarded as a key commodity to decarbonise fertilizers industry and the to pick up since 2010. The other three major contributors; Pakistan,
overall food production value chain. In the last few years, there has Canada, and Indonesia show almost consistent trajectory over the last
been an increasing interest and investment where many new technology five decades, while the rest of the world has a sinusoidal trend on both
pathways are competing to produce affordable green hydrogen [25]. As production and consumption, but almost imitating the USA pattern on
a result, the concept of green ammonia production has progressively the consumption trend.
accelerated to challenge the traditional fossil-based ammonia synthe-
sis [26,27]. However, the pathway for urea synthesis to track the green Fertilizer market in Australia
pathway of ammonia is not straightforward. To maintain the green path-
way of urea synthesis, the CO2 stream cannot be coming from, yet an- Australia’s gross value of agricultural production is forecasted to
other fossil-fuel based process. Hence, to eliminate (or at least minimize) reach a record high of AU$78 billion in 2021–22 [28]. The value of
the carbon footprint of urea synthesis, a carbon-neutral technology for the fertilizer industry to the Australian economy is much greater than
the CO2 feedstock must be considered. Achieving this goal will maintain its direct value-added to the broad economic aggregates. Its downstream
the carbon balance even when CO2 is emitted back at the urea usage or contribution to the total economy is magnified by its impact on the pro-
end-of-life, because the engaged CO2 in urea synthesis was originated duction pipeline of Australia’s agricultural sector. Due to Covid-19 and
from the natural carbon cycle and not from the extraction and/or flaring other regional/international geopolitical tensions, the cost of many farm
additional fossil fuels. The main source for such a carbon-neutral CO2 is inputs such as fertilizers, fuel, farm chemicals and equipment has signifi-
either via biomass combustion/ gasification, renewable methane, or via cantly increased in 2021–22. Increased shipping costs are also contribut-
direct capture of CO2 from the atmosphere known as Direct Air Capture ing to higher prices for imported goods. Fig. 3 provides an overview of
(DAC). The consistency, reliability, purity, and cost of this CO2 feedstock the price movement of the main agricultural crops and livestock in Aus-
are very important factors influencing the whole value chain of green tralia in the last 10 years with an evident surge in the last 2–3 years for
urea synthesis and are often categorized as location-specific parameters. most commodities.
In this study, we analyze the urea synthesis as a complementary Generally, 5–6 million tonnes of fertilizers are sold each year in Aus-
downstream process of ammonia production and shed light on the prod- tralia, about half of which is manufactured locally. The major domestic
uct sustainability in both conventional and green pathways. Evaluating fertilizer manufacturers are Incitec Pivot holding 38.4% and Wesfarm-
the production and consumption trends in the global market, this study ers holding 16.3% of the local market share, and the rest is distributed
exclusively emphasises the key drivers for local production of green by smaller manufacturers [29]. The industry supplies a range of phos-
urea. It underlines that ammonia and consequently urea production can- phorus, nitrogen, potassium and sulfur fertilizers, in addition to blends
not be green-labelled by only using green hydrogen in the feedstock, but and trace elements. Nitrogenous fertilizer products are used in over the
would require to disconnect from using fossil fuels in their processes, half of all fertilized agricultural land in Australia, which constitutes a
and the CO2 contribution should only come from carbon-neutral ori- key industry product segment. Most of the fertilizer products manufac-
gins. This study then identifies three primary routes for carbon-neutral tured in Australia are consumed locally with less than 10% of the rev-
CO2 contribution in the urea synthesis: biomass, renewable methane, enue is attributed to overseas trades. In 2021 alone, Australia imported
and DAC. Then, it provides a detailed analysis of these primary routes AU$2.3 billion of various fertilizer products and raw materials and ex-
from Australia’s perspectives with a particular emphasis on DAC as a ported AU$321.5 million mostly to Pakistan, India, and New Zealand
key climate change mitigation technology because of its flexibility and [29].
scalability. With optimized process integration and energy management Normally, the fertilizer industry performance is quite variable and
system (EMS), the required heat for the regeneration of the absorption vulnerable to adverse weather conditions (i.e. drought seasons) and to
liquid in DAC can be offset by the exothermic processes of green am- the volatility of international market. As such, the price of urea bulk im-
monia and urea production. Hence, this article uniquely addresses one port to Australia was 74% higher in September 2021 than the average
of the most challenging and hard-to-abate industries to pave the way price for 2020 [28]. Fig. 4 illustrates the urea price trend in Australia
for Australian manufacturers, technology providers, and investors to re- since 2007 and clearly indicates the recent peak in urea price which is
duce the reliance on fertilizer imports, transform the domestic fertilizer the second highest after the global financial crises in 2008. Fig. 4 also
industry, and strengthen Australia’s position in the regional and global shows the monthly urea imports to Australia by volume which reflects
markets. the seasonal variation in demand to synchronize with the crops and pas-
tures growth needs. Typically fertilizers importers in Australia have very
An overview of the global fertilizer market limited storage facilities close to the arrival ports capable of holding few
ship loads of fertilizers (18 to 45 kt), although smaller importers may
In 2012, the International Fertilizer Industry Association (IFIA) have storage for one or two ship loads of fertilizer (5 to 10 kt) [30]. In
stated that more than 70% of the fertilizers were consumed by China, In- contrast, importers also need to carefully consider the long lead times of
dia, and USA. China was the main producer of nitrogen- and phosphate- fertilizer products from overseas suppliers to Australia. For example the
based fertilizer, while Canada was the leading producer of potash fer- typical lead time to import urea from Middle East is 24 days and from
tilizers followed by Russia [22]. From 2010 to 2020, it is estimated Malaysia is 18 days, which may cause complications of over- or un-
that China has increased the consumption rate of nitrogenous fertiliz- dersupply if the forecasts vary substantially from actual demand [30].
ers by 75% while the production increased only by 11%. Fig. 2 shows Therefore, to limit the risks of long-term storage and to carefully man-
3
Fig. 2. The major global nitrogenous fertilizer players in the last 50 years from both (a) the production, and (b) consumption perspectives [22].
age supply/demand uncertainties, fertilizer companies and distributors pathways for fertilizer manufacturing. For example, Strike Energy plans
use a mixture of storage options coupled with high-level planning and to blend hydrogen input with green sources and use a 10 MW hydrogen
logistics. Consequently, the existing supply chain of fertilizers in Aus- electrolyzer powered by the abundant local wind energy [33].
tralian market is struggling with a number of key challenges as listed Australia has extremely high solar irradiation levels compared to the
below: global average, many potential sites for productive wind farms, poten-
tial geothermal resources in central Australia and Northern Territory
1 Traditional nitrogenous fertilizer production routes (fossil-fuel based
(NT), tidal and wave energy potential from the surrounding oceans, hy-
ammonia) already categorized as one of the most carbon-intensive
dro infrastructure and various bioenergy options. In addition to natural
industries responsible for 1.2% of the total global GHG emissions
resources, Australia has the skillset and the infrastructure to build an
[31].
economically sustainable domestic and export fertilizer industry that
2 International market volatility and increasing shipping costs.
can meet the emissions reduction targets and address concerns around
3 Strict Australian quarantine rules.
energy and food security. To promote the green pathways for urea pro-
4 Limited product storage options need high-level of liaison between
duction in Australia, three benchmarks must be established and thrived:
product imports and the dynamic market demand.
green hydrogen infrastructure, competitive advantage of green ammo-
To date, Australia has not been considered as a major player in the nia, and the carbon-neutral feedstock for green urea. The following sec-
global fertilizer market. However, Australia’s position in the interna- tions outline these benchmarks in Australia’s texture (Fig. 5).
tional market may change with several new fertilizer projects that are
coming online. For example, in 2019 Australian Potash became the first Green hydrogen
Australian manufacturer of organic sulfate of potash (SOP) where the
potash nutrient was produced from potassium-rich brine extracted from Among many hydrogen production methods and technologies [34–
Lake Wells, one of Australia’s largest salt lakes. Furthermore, the Aus- 36], two potentially viable hydrogen production routes being carefully
tralian mining company Centrex could utilize the Ardmore Phosphate considered in Australia are: (A) the blue hydrogen production via fossil
Rock Project to reduce Australian reliance on imported phosphate rock fuel cracking using either SMR of gas resources or coal gasification, but
[29]. For urea production, Derby Fertilizers and Petrochemical Com- must be integrated with carbon capture and sequestration (CCS) tech-
plex have announced plans for a AU$4.0 billion urea and complex fertil- nologies; and (B) green hydrogen production using water electrolysis
izer/petrochemical plant along with solar energy input near Derby using and must be powered by renewable energies [36]. These are the main
fracked gas sourced from the Great Sandy Desert in Western Australia two routes for a future commercial-scale clean hydrogen economy in
(WA) [29]. Perdaman Industries also has plans for a AU$4.5 billion urea Australia as illustrated in Fig. 6.
project in WA to transform natural gas into urea. A gas company named A significant amount of work has been done in recent years to quan-
Strike Energy also announced plans to build a AU$2.3 billion urea fer- tify the economic opportunities associated with the hydrogen economy.
tilizer plant called Project Haber to utilize a portion of the natural gas Australia’s abundant land and natural/renewable resources bode well
from their Greater Erregulla gas resources within the Perth basin project for the establishment of hydrogen supply chains for both domestic and
[29]. Most of the existing manufacturing plants and the announced plans international markets. Nonetheless, the main impediments to market
would continue using fossil fuels to drive fertilizer manufacturing pro- activation are a lack of supporting infrastructure and/or the high cost
cess or be utilized as a feedstock for various fertilizers. Nevertheless, of hydrogen supply. Both barriers however can be overcome through
local manufacturers are very aware and concerned about the heavy car- a series of strategic investments from both the private and public sec-
bon footprint of their fertilizer products and actively seeking alternative tors along the value chain. The CSIRO National Hydrogen Roadmap
affordable green options. This historical trend of the unsustainable fer- calculated the cost elements for each technology based on their ma-
tilizer manufacturing may change if Australia decides to track greener turity, size, and grid connectivity for the base year of 2018 [37]. Ac-
4
Fig. 3. Price movements in selected crops (left) and livestock (right) in Australia in the last 10 years [28].
AU$4.78 and AU$5.84/kgH2 for alkaline electrolysis (AE) and AU$6.08–

7.43/kgH2 for the proton exchange membrane (PEM) counterparts. At
present, Australia is far away from producing green hydrogen at an at-
tractive price compared with the blue hydrogen. However, the Gencost
report published by CSIRO in 2021–22 predicted that by 2040, the cost
of electrolyzers will fall by almost 83%, while gas-derived hydrogen cou-
pled with CCS (blue hydrogen) is predicted to slightly reduce in cost,
which means the green hydrogen would likely to expand in the market
and overtake the blue hydrogen after the year of 2030 [38]. However,
the determining parameters for green hydrogen production are pro-
foundly location-specific depending on natural resources availability,
durability, and intensity. These parameters would vary geographically
from far north Queensland (QLD) to Tasmania. Fig. 7 shows the predic-
tions of LCOH dynamics across four eastern Australian states as modeled
by Victorian Hydrogen Hub at Swinburne University [39]. In near term
Fig. 4. Australian imports of urea, by volume (left) and price (right), from Jan
(year of 2023), far north of QLD and Tasmania are the hotspots of green
2007 to Sep 2021 [32].
hydrogen production due to the abundance of renewable resources. By
2030, these two hotspots will continue to lead, but more competitive
cording to the roadmap, Australia can reduce the levelized cost of hy- hotspots will start to emerge. By 2040, the favorite hotspots will shift
drogen (LCOH) to a record AU$(1.88–2.30)/kgH2 for SMR technolo- to the coastal regions of QLD and some parts of South Australia due to
gies, and AU$(2.02–2.47)/kgH2 for black-coal gasification technologies. a combination of cheap solar resources, underlying infrastructure, and
Comparatively, the LCOH via electrolysis technologies cost between greater ports accessibility for exportation to the international markets.
5
Fig. 6. Two possible clean hydrogen production routes being considered in Aus-
tralia: A- fossil fuel cracking coupled with CCS, or B- water splitting using re-
Fig. 5. Three benchmarks for a urea production to effectively pursue green newable energy (green electricity).
pathways in Australia.
Nevertheless, green hydrogen production is one side of the story

that must be linked to the right infrastructure in transport-storage- Therefore, ammonia can be either used directly as a source of power
conversion to demonstrate appealing business models. Among several (e.g. in IC engines, turbines, and fuel cells) or as a source of hydrogen
options for hydrogen transport-storage-conversion to reach the endpoint producible via ammonia cracking. Importantly, an ammonia molecule
as presented in Fig. 8, green ammonia synthesis that utilizes the green does not contain carbon atoms and thus, has the advantage of not re-
hydrogen as a feedstock stems an appealing option, giving the wide leasing any CO2 when combusted. Ammonia is the second-most-widely
range of ammonia applications in industries, transport, and as an ex- produced chemical commodity in the world with a market value of more
portable commodity. Compared to liquid hydrogen, transporting liquid than US$60 billion. About 80% of the global ammonia production goes
ammonia for international end-users is less expensive by an order of into fertilizer products and 20% into other industrial applications. The
magnitude, which greatly enhances the business model of green ammo- conventional production route of ammonia uses ∼2% of the world’s
nia production. fossil fuel energy and generates over 420 million tons of CO2 per an-
num [19]. Ammonia is a highly toxic substance, requiring special stor-
Green ammonia age and safety measures. Hence, the industry is under mounting pres-
sure to improve production processes and develop more environmental-
In addition of being a feedstock for urea synthesis, ammonia (NH3 ) friendly products. The research in green ammonia chemistry must focus
is also being considered as a hydrogen and renewable energy carrier. on the development of greener chemical products and processes, involv-
Fig. 7. The LCOH dynamics at various hotspots across four states of Australia predicted for 2023, 2030 and 2040 [39].
6
Fig. 8. Potential pathways for the production-

transport-storage-conversion of green hydro-
gen [39].
ing waste minimization, replacement with less toxic alternatives, and an tion from those projects is likely to be higher than that of conventional
increase in renewable-powered feedstocks where possible. ways of ammonia production [40].
Ammonia production would benefit from the well-established pro- In Australia, ammonia products comprise 8.3% of a wide range of
duction and transport infrastructure including established standards and inorganic chemical manufactured where the growth forecast shows a
regulations due to the high volume of use in the agricultural industry. gloomy future in near-term [53]. However, as the energy density of
Therefore, the capital cost contributions on operating costs for many green ammonia is far higher than the green hydrogen and other forms
ammonia plants around the world are very low since they have mostly of energy carriers, a paradigm shift in renewable energy export is being
been written off due to the aging of these plants. In contrast, green am- promoted in Australia and elsewhere where the value chain of green am-
monia production is a low carbon and more environmentally benign monia production-storage-transport-conversion is prevailing [54–56]. A
chemical that predominantly offers high hydrogen content when com- recent study conducted by Johnston et al. [57] revealed that ammonia
pared to alternative fuels. However, global demand for ammonia across as an energy carrier relatively offers the lowest cost for transport. These
multiple sectors can cause scalability issues, and therefore, the cost of aspects of assessing the complete value chain of green ammonia from
green ammonia production is relatively high. production point to the end-user would certainly influence the market
From the sustainability viewpoint, feeding hydrogen generated from preferences.
water electrolysis powered by renewable sources signifies only one Globally, the current price of green ammonia is often quoted around
part of shifting ammonia production to greener pathways. However, US$600–800/tonneNH3 free on-board (FOB) compared with conven-
one must also account for the environmental impacts of the energy- tional ammonia of US$350–500/tonneNH3 FOB depending on the input
intensive air separation unit (ASU) that typically uses cryogenic methods natural gas price and the age/capacity of the production plant [58]. In
to extract pure nitrogen. Furthermore, the parasitic energy demand of 2020, green ammonia cost as a fuel was 15 to 20 times higher com-
the Haber-Bosch process itself requires more energy input that is typ- pared with liquefied natural gas (LNG), however by 2050, both are
ically derived from fossil fuels (i.e. natural gas) combustion. Fig. 9 il- predicted to be in the range of US$50–100/MWh. Renewable ammo-
lustrates the typical green ammonia production process, where the en- nia could account for up to 43% of the shipping energy mix in 2050,
ergy required for water electrolyzers is sourced from various renew- implying the use of approximately 183 Mt of renewable ammonia for
able energy options with an optional connection to the grid to main- international shipping alone, which is comparable to today’s total global
tain the process stability. However, to buffer the intermittency in re- production. From one example techno-economic analysis carried out
newable energy supply and market demand, electrolyzers capacity is by the International Renewable Energy Agency (IRENA) [58], it was
often techno-economically optimized where the excess hydrogen pro- found that for a hypothetical green ammonia plant, the likely operating
duction can be stored for later use in the ammonia production plant. cost would be around AU$500–800/tonneNH3 in 2030 based on a num-
The excess hydrogen can also be utilized in a hydrogen fuel cell to pro- ber of assumptions at a very low electricity and hydrogen prices (e.g.
vide the supplementary energy and minimize/stop the reliance on grid AU$14/MWh, and AU$1.4/kg H2 combination) with other expected
connection. capital cost items estimated for this evaluation. This is in comparison
Overall, green ammonia is widely recognized as the most essential with conventional ammonia production cost likely to be in the range of
step-forward in decarbonizing food production chain, where these en- AU$500–1000/tonneNH 3 currently for a large-scale greenfield plant, if
vironmental concerns may also help drive product innovation and tech- natural gas price is varied by ±50% from a base case price of AU$7.5/GJ
nological developments. For example, the green credentials of ammonia [58].
production can be further enhanced if renewable energy is also used to
produce the required feedstock (hydrogen and nitrogen at the nominal Green urea
pressures and temperatures) for the Haber-Bosch process. As such, the
development of new green ammonia processes is expected to initiate in- Similar to Haber-Bosch technology, the urea synthesis process (USP)
dustry growth where large international industry operators have already also typically uses fossil fuels in upholding the perfect reaction condi-
begun to focus on these technology pathways. In the last few years, a tions. To enhance the green pathway, this energy input is preferably
number of green ammonia projects have been announced around the obtained from non-fossil fuel sources. However, many research outputs
world (Table 1). However, the levelized cost of green ammonia produc- advocated for green pathways of urea synthesis in sub-optimal ways,
7
Fig. 9. Illustration of the green ammonia block diagram. Solid lines represent essential and dash lines represent optional or complementary routes.
Table 1
A list of large/commercial scale green ammonia projects around the world announced in recent years.
Project/ location Country Company Renewable source Production capacity (t/y) Electrolyzer capacity (MW) Production year Refs
Oxford/ Fukushima UK/ Japan Siemens/ FREA Wind 7–10 10 2018 [41]1
Pilbara Australia Engie & Yara Wind/Solar 720,000 1500 2030 [42]2
Western Jutland Denmark Haldor Topsoe Wind/Solar 5000 10 2022 [43]3
Porsgrunn Norway Yara & NEL Hydro 5000 5 2022 [44]4
Donaldsonville USA CF Industries – 20,000 – 2023 [45]5
Antofagasta/ Magallanes Chile Engie & Enaex Solar 700,000 1600 2030 [46]6
HNH Chile AustriaEnergy & Co. Wind/Solar 850,000 – – [47]7
AREH Australia bp & Co. Wind/Solar 9,0000,000 – 2025 [48]8
Bell Bay Australia Origin Hydro 420,000 500 2025 [49]9
Gibson Island Australia FFI & Incetic Pivot Wind/Solar – – 2023 [50]10
Sluiskil Netherland Ørsted & Yara Wind 75,000 100 2024–25 [51]11
Neom Saudi Arabia Air Products & Co. Wind/Solar – 4000 2025 [52]12
1
Pilot plant scale at 20–30 kgNH3 /d capacity.
2
Four phases project starts from only solar add-on at 10MW capacity (2023) and ends in full scale 1,500MW Green plant Ramp-up by 2030.
3
Power-to-X process consists of 12 MW existing V80–2.0 MW Vestas wind turbines and 50 MW new solar panels.
4
Nel will test their next generation electrolyzers at Yara’s existing plant in Porsgrunn.
5
Gradual reduction of CO2-e emissions, they will install new electrolysis system to generate carbon-free hydrogen to integrate with existing plant aiming for 25%
reduction in CO2-e emissions by 2030 and net-zero carbon emissions by 2050.
6
Their plan will start by 2024 with a pilot-scale plant equipped with a 36MW solar plant, 26MW electrolyzers and 18,000 tonne/y green ammonia production.
7
The project will run on 100% renewable energy to generate 150,000 ton of green hydrogen, abate 2.3 million tonneCO2 /y.
8
The project will produce around 1.6 million tonneH2 /y and abate ∼17 million tonneCO2 /y.
9
A feasibility study (AU$3.2 M) has been conducted and Front-End Engineering Design (FEED) studies (AU$6 M) are planned in 2023.
10
This project will build a 15 million tonneH2 /y of green hydrogen by 2030, and rising to 50 million tonneH2 /y in the next decade.
11
This project will develop a 100MW wind powered electrolyzer plant to generate renewable hydrogen and abate ∼100,000 tonneCO2 /y.
12
This project will produce 650 tonneH2 /d of green hydrogen to fuel ∼20,000 hydrogen buses.
but have not covered all aspects of urea production. For example, Prof. mental impacts. Lee et al. [60] approached the concept of ‘green’ urea
Yahya [22] proposed a new urea synthesis route using electromagnetic from a different angle. They proposed an integrated modeling frame-
induction and nano-catalyst at ambient conditions and called the pro- work (RCOT-P2P) to represent various stakeholders’ interests by consid-
cess ‘green’ because it requires less energy consumption for the con- ering all engineering, environmental, and economic dimensions of the
version process. Zhu et al. [59] also described their method of elec- supply chain. Kongpanna et al. [61] discussed an integrated method of
trochemical routes of urea synthesis under ambient conditions using synthesizing urea and dimethyl carbonate (DMC) using CO2 as a chem-
two-dimensional metal borides (MBenes) as a ‘green’ process. Alfian and ical feedstock at intermediate temperature (165–190 °C) and high pres-
Purwanto [4] proposed a ‘green’ multi-objective optimization method to sure (135–205 bar) range. Earlier, Yahya and co-authors [62, 63] con-
partially utilize renewable feedstock along the pathway of typical urea sidered catalytic activity of hematite (𝛼-Fe2 O3 ) nanowires under the in-
production routes to compromise between production costs and environ- fluence of magnetic field for urea synthesis as a ‘green’ pathway. In a
8
Fig. 10. Biomass resources and bioenergy facilities distribution in Australia. Source: Geoscience Australia and Bureau of Rural Sciences.
different study of capturing the CO2 and storing in a valuable chemical based CO2 source in the production line would certainly compromise
product, Koohestanian et al. [64] proposed a novel process to produce the ‘green’ label of the process. Hence, the input CO2 stream must be de-
urea by directly capturing both the CO2 and N2, which constitute the ma- rived from non-fossil fuel sources to maintain a carbon-neutral or ‘green’
jor components of the flue gasses, to produce 2856 kg/h of urea. More pathway. Therefore, all the literature mentioned above may partially
recently, Ishaq et al. [65] proposed a renewable (solar and wind) pow- contribute to lowering the carbon footprint of various urea synthesis
ered hydrogen and ammonia production, utilizing the CO2 from the flue routes, but certainly they cannot be considered as fully green pathways.
gas of a thermal power or industrial plant for the purpose of urea produc- The greatest positive impact in decarbonizing the urea synthesis which
tion. The authors modeled the integrated system using Aspen Plus and has a 40% C/N ratio must come from non-fossil fuel source of CO2 con-
claimed 44.4% and 32.2% for the energetic and exergetic efficiencies, tribution. In Australia, there are three possible routes of CO2 derivable
respectively. The authors however neither specified the concentration from non-fossil fuel sources: from biomass, a renewable methane pro-
of the CO2 in the flue gas nor the energy penalty of the capture method. duction route, or via direct CO2 capture from the atmosphere (DAC)
Later, Abbaspour and co-authors [66] proposed a 5E (energy, exergy, (Fig. 5).
economic, exergo-environmental and environmental) analysis for a co-
generation system to produce power and urea from a gas-fired power CO2 from biomass
plant. A portion of the power production used to run PEM electroly- Compared to fossil fuels, biomass would generally have much lower
sis, ASU, ammonia production, and capturing the CO2 from the exhaust net carbon footprint because it consumes atmospheric CO2 during
flue gas for urea synthesis. The authors claimed this cogeneration sys- growth and is considered as a renewable feedstock. Utilizing the CO2
tem produces 689 GWh of electricity and 10,323 million tons of urea by-product from any biomass combustion process into a downstream
at 31.8% and 53.3% for the energetic and exergetic efficiencies, respec- urea synthesis would capitalize on the process sustainability in the most
tively. efficient and carbon-neutral way. However, the greenest way of biomass
Overall, considering urea’s high solubility in water and the decom- utilization is via gasification process. In this case, the generated hydro-
position to original compounds by the end-of-life, using any fossil-fuel gen from biomass gasification can directly be used in the green ammo-
9
Fig. 11. A simple diagram of H2 and CO2 production from waste.
nia production, while the CO2 by-product would ideally be utilizable plant to capture the CO2 by-product of bioenergy or gasification plant
in a complementary urea production plant. This route marks the gen- for the purpose of urea synthesis is a very challenging task.
eration of H2 from biomass as the most practical and environmental-
friendly option. The sustainability and local availability of the raw ma- CO2 from renewable methane
terials must be tightly correlated with the economic viability of produc- Interest in methane produced from renewable sources are rising
ing H2 from biomass, though. Quantity, distribution, cost, and physico- mainly due to its low C/H2 ratio, compatibility with existing energy
chemical properties are used to evaluate the biomass feedstock’s es- infrastructure, and reliability for energy supply. Renewable methane is
sential qualities. Given the wide variations in form and composition mostly produced via three pathways: by anerobic digestion of organic
of biomass feedstocks, it is important to carefully match the feedstock matters; from gasification of biomass and subsequent methanation; and
with the appropriate conversion method. Therefore, while evaluating via the ‘so-called’ power-to-methane process [70,71]. Due to yet high
the quality and/or quantity of biomass, the three main factors that in- costs of the renewable methane produced from the second and third
fluence engineering decisions are moisture, energy, and mineral con- methods [72,73], it is most likely that they will be mainly used only for
tent. Because of the 40% oxygen composition, the energy content in energy storage or in areas/industries that are difficult to become fully
biomass is relatively low, and the yield of H2 from biomass is relatively electric and hence willing to pay premiums for renewable fuels as an
less since the hydrogen content in biomass is 6 wt% almost quarter of alternative source of energy to reduce their GHG emissions. Neverthe-
the 25 wt% hydrogen content in methane [35]. Therefore, the foremost less, if the renewable methane from these pathways is used to produce
decision-making priority in H2 production from biomass is to optimize energy, the by-product CO2 can still be captured and utilized.
the match between the feedstock, production technology, and end-use Fermentation of wastes and organic matters is the most mature and
options. Techno-economic comparisons supported by a comprehensive economical technology for production of biogas and then renewable
LCA are the only way to make rational and profitable investment deci- methane through biogas upgrading [74,75]. It is a biochemical process,
sions. Since biomass is relatively low in energy density, the economy of in which organic matters are decomposed by anaerobic microorgan-
scale must fully incorporate the cost of the transport and storage for both isms. The biogas recovered from biochemical transformation of wastes
the biomass feedstock and the product H2 toward the green ammonia in landfills is the most economically favorable option [72]. The bio-
plant or any alternative end-use option. In many cases, these features gas produced from both anerobic digesters and landfills contains be-
will make it difficult for H2 production from biomass to liberally com- tween 35 and 70% CH4 and the remaining is mostly CO2 , with a heating
pete with the common natural gas SMR technology unless supported by value of around 5–7.5 kWh/m3 depending on methane concentration
adequate regulatory mechanisms (e.g. carbon tax) that competitively fa- [72,74,76]. The biogas can be directly used to generate heat and elec-
vors sustainable H2 production systems. In this case, converting the CO2 tricity, and in that case, it is possible that the CO2 by-product is captured
waste of biomass gasification into a valuable feedstock for downstream using available technologies and fed into a downstream urea production
urea production plant will have a major positive impact. As a result, the plant. Alternatively, it can be upgraded to renewable methane for injec-
regional perspectives of biomass H2 production opportunities will differ tion into gas grid or thermo-catalytically reformed to produce renewable
greatly from Europe to North America, Asia, and the developing regions H2 with the by-product CO2 [77], the two main components required
of the world. Australia utilizes massive land for crop plantations and in green ammonia synthesis and green urea production. A schematic
natural forests, and therefore plenty of biomass/bioenergy resources as diagram of the process is presented in Fig. 11.
shown in Fig. 10, where most of these resources are utilized for electric- Considering the share of steam methane reforming (SMR) used to
ity/heat generation or biofuel synthesis [67]. Nevertheless, the biomass produce hydrogen worldwide (on average, 50%, over the last decade)
resources are highly varied in type and dispersed in location. The relia- [78–80], it is evident that there is a massive opportunity for the use of
bility and consistency of biomass resources are largely affected by water existing SMR infrastructure to convert biogas to clean hydrogen and CO2
resources and climate conditions which may increase the uncertainty of by-product. However, the production of biogas worldwide is currently
the resource forecasting over long-term. For example, the crushed outer quite low, on average, equivalent to around 10% of all available biogas
stalk of sugar cane named ‘bagasse’ was the focus of recent R&D to utilize potential [72]. In Australia, the biogas industry is emerging, with 242
this large resource that is currently under-utilized by the sugar indus- biogas plants (including landfill gas plants) reported in 2017, and was
try. Currently, some bagasse is used to generate electricity (Australia estimated to reach 90,000 biogas units at a capacity of ∼103TWh if the
has 250 MW installed capacity), while the rest is either burned or used full potential of biogas is realized [81]. Hence, Australia is in a strong
as mulch/fertilizer. Gasification could produce hydrogen from bagasse, position to benefit from renewable methane production and use in elec-
providing a competitive advantage for Australia’s sugar cane growers tricity generation, hydrogen production and other industrial processes.
who are struggling to compete in the global market [68]. Nevertheless, The Jandakot bioenergy plant and the Waste-to-Energy plant (known
due to the limited scale of distributed resources, various types of biomass as ReWaste) are two recent successful bioenergy projects operated in
have primarily been used to produce biofuels (e.g., ethanol), which are Australia [81]. A study around technoeconomic and environmental as-
primarily used as additives to automotive fuels [69]. Biomass has also sessment of biogas-to-hydrogen process showed that hydrogen can be
been used to produce decentralized electricity and heat as shown in produced at a cost of AU$0.27/kWh through steam biogas reforming
Fig. 11. Since the carbon composition would greatly vary based on the (SBR) [79], which is equivalent to around AU$9/kgH2 , higher than the
large inconsistency in biomass ingredients, optimizing a carbon capture target price of hydrogen reported nowadays [82]. Also, Hazer Group
10
Fig. 12. A schematic of Hazer process using iron-ore catalyst.
was funded by Australian Renewable Energy agency (ARENA) to build Liquid absorption and solid adsorption are the two main approaches
and operate the first commercial plant in the world to demonstrate the being used to remove bulk CO2 from the atmosphere. In such pro-
conversion of wastes to hydrogen and graphite with an obligation that cesses, adsorbents/absorbents are placed in contact with the air in such
no CO2 by-product is produced from this process (Fig. 12) [83]. ways that they react with the CO2 contained in the atmospheric air
On the other hand, biogas resources are distributed all over Aus- stream, and then in a later stage, often using high temperature heat,
tralia, hence biogas production units often have limited capacity, much the CO2 is released, and absorbents/adsorbents are regenerated and
lower than SMR capacity. This inconsistency may make the use of ex- reused. Fig. 13 illustrates a simple diagram of such systems. A Cana-
isting SMR infrastructure for the purpose of SBR processes a challeng- dian company named Carbon Engineering is a major player using liquid
ing task. This would also result in dispersed production of H2 and CO2 absorption technology for DAC system [88], while Climeworks (Switzer-
[77], which may provide opportunities for small local producers of urea land) and Global Thermostat (USA), are the two main companies with
and other products to have close accessibility to feedstock H2 and CO2 , extensive focus on adsorption-based DAC systems [89,90]. They have
the cost can increase significantly due to their limited scale of produc- the most mature DAC technologies that are used in several upcoming
tion. Therefore, the focus should probably move from the cost reduction large-scale demonstration plants worldwide [91–94]. Recently, as the
through economy of scale to the network economy where the dynamic world’s commitment to reach net-zero emissions target was reaffirmed
development of networking is expected to positively contribute to peo- [95], the level of support on RD&D activities in the area of DAC has
ple life, to the wider economic and societal ecosystem, the protection increased [96], which has led to some emerging technologies out of the
of natural resources, and to combatting climate change [84]. Alterna- fundamental research and laboratory scale testing. Table 2 presents a
tively, the biogas feedstock can be transported to a central point where summary of some major existing and upcoming projects and technolo-
available SMR facilities can be used to produce biomethane at large gies on DAC systems.
scale and hence lower the costs. In any case, comprehensive techno- The CO2 that is sourced from the atmosphere via DAC systems gen-
economic analysis is needed to assess the economic viability of possible erally provides multiple advantages. Depending on the capture method
options. used, CO2 removed from the ambient air would often have high concen-
tration and may not need further purification before being used. This
CO2 from DAC would be an important factor because the presence of impurities can re-
To meet the ambitious net-zero emissions target by 2050 as reaf- duce the efficiency of downstream processes and affect the quality/cost
firmed lately in COP26 [23], actions are needed for active CO2 removal of final products. In contrast with point-source CO2 emitters, DAC can
technologies along with sharp cut in anthropogenic GHG emissions. The be built and operated almost anywhere, making this technology a more
point-source emissions can be addressed via post-combustion and other accessible, reliable, and scalable source of CO2 for use in downstream
capture technologies. However, almost half of the global CO2 emissions applications. Such a system can generally benefit from a lower cost as-
are derived from non-point sources where most of the common carbon sociated with share of equipment and infrastructure and avoid the cost
capture technologies are ineffective [85]. Direct extraction of CO2 from and environmental impact of the long-distance CO2 transport [86]. For
ambient air using sorbents, commonly known as direct air carbon cap- urea synthesis, the use of CO2 removed from the atmosphere can sig-
ture (DAC) is considered as a key climate change mitigation technol- nificantly reduce the carbon footprint of the urea product and cut the
ogy that has the potential to achieve negative carbon emissions. DAC is emissions that are commonly associated with agricultural sector.
believed to provide multiple advantages over other technologies used However, considerable technoeconomic challenges need to be over-
for CO2 capture, including less area of land and water consumption, as come, before DAC can make a real impact on climate change and pro-
well as less limitation in terms of global deployment since it does not vide low-cost CO2 feedstock to various downstream processes such as
compete for agricultural lands and often scarce bioresources [86]. How- urea production. DAC has historically been a quite expensive technol-
ever, the removal of CO2 directly from air is inherently quite challeng- ogy [86,98], marking at its best of around US$250/tonneCO2 , relative to
ing, mainly due to the extremely low concentration of CO2 in ambient the costs for CO2 capture from point-source emissions from industries
air (∼400 ppm), where the energy demand for DAC plants is excessively that were reported to be less than US$100/tonneCO2 [86]. However, the
high (theoretically almost three times higher than the PCC counterparts) cost of CO2 capture via DAC technology is likely to decrease as the tech-
[87]. nology matures further and scales up to take steps towards commercial-
11
D. Milani, A. Kiani, N. Haque et al.
Table 2
A summary of existing DAC technologies and projects [97,98].
Investigators Technology for capture Method for regeneration Funding sources CO2 utilization/ storage
Carbon Engineering (CE) Liquid absorption using strong Calcination at ∼ 900 C Bill Gates and Murray Edwards. Fuel synthesis, Enhanced Oil
hydroxide solution Occidental Petroleum, Chevron Recovery
Technology Ventures and BHP
Climeworks Solid adsorption using amine High temperature of around 100 Investors, like Microsoft Fuel synthesis,
coated adsorbents C Greenhouse, mineralization
Global Thermostat Solid adsorption using amine High temperature and low Corning Technology, Edgar Beverage and food, synthetic
coated monoliths pressure Bronfman Jr., Georgia Tech, fuels
NRG, SRI International,
US Energy Company, and Vice
Media, US Department of
Energy and the New York State
Energy Research and
Development Authority
Skytree Adsorption using plastic resin – Car manufacturers such as Fertilizer, Greenhouse
Jaguar, Land Rover
12
Infinitree Solid sorbents High humidity Fertilizer, Greenhouse

Soletair Power Adsorption using amine sorbent – Finnish and German industrial –
partners. The energy technology
group Wärtsilä
Others: Oak Ridge National Absorption, adsorption, Synthetic Mainly use of high temperature, – Kerosene, methanol, methane,
Laboratory, Arizona State membrane, Electrochemical low pressure and high moisture diesel
University, National Energy reduction
Technology Laboratory (NETL),
Synhelion, Sunfire GmbH, CSIRO
Upcoming projects: Mainly using Climeworks and Heat, low pressure, and moisture – Sequestration, EOR, Jet fuel,
Oxy Low Carbon Ventures, Carbon Engineering technology Synthetic fuels, Methanol
Sustainable Chemistry for Climate Action 1 (2022) 100008

CarbFix, Rotterdam Jet Fuel,
Nordic Blue Crude AS,
PrometheusFuels, Synhelion &
ENI, Silicon Kingdom Holdings,
sponge mountain
Fig. 13. A schematic diagram of the mechanism for absorption/adsorption-based direct air capture.
ization. DAC technology is also quite energy intensive, not only because and used as a sustainable source of carbon for various applications such
it needs to process an enormous volume of air to produce a reasonable as urea production.
amount of CO2 , but also because of the deep regeneration requirements Australia is in a unique position to highly benefit from the emerging
for the capture agents. In order to avoid releasing more CO2 resulted interest in DAC to become one of the world leaders in this domain. The
from sorbent regeneration energy demand than captured in such sys- accessibility of low-grade lands that are not suitable for agricultural ac-
tems, the required energy should therefore come from carbon-neutral tivities and the abundance of sunlight can provide great opportunities
or renewable energy sources, hence accessibility to sufficiently low cost for low-cost deployment of enormous DAC systems that would ideally
and low carbon energy is crucial for the successful deployment of DAC be powered by solar energy. In addition, Australia has some of the most
technology. suitable sites for underground CO2 storage that can be used to store
As stated in Table 2, DAC technology should be incentivized in the CO2 that is directly removed from the atmosphere, adding to viability
short term by supportive measures from governments and investors as of DAC technology in Australia. It can be the case that only large-scale
it progresses toward maturity, to provide inexpensive and affordable DAC systems would ultimately become economically feasible, where in
CO2 for downstream storage and utilization routes. DAC combined with that case, setting up large-scale DAC systems near storage sites for both
geological storage of the CO2 product is an effective method to offset CO2 storage and utilization purposes may be more economically attrac-
large volumes of CO2 emissions from hard-to-abate sectors like aviation tive than having multiple small-scale DAC systems scaled only to the
and marine transport that are otherwise expensive to be decarbonized utilization sites. Fig. 14 shows the land use, and potential locations for
over the short term. Hence, large companies such as Microsoft have solar energy and CO2 storage sites in Australia, which indicates an ex-
already started backing DAC technologies, but further support is still cellent synergy between these factors that are crucial for low-cost de-
needed from various companies and investors around the world. Also, ployment of DAC technology [99–101]. Lastly, DAC is a technology that
the revenue that can be generated from the production of carbon-based can offset emissions from hard-to-abate industries such as transport and
products and marketing emissions-offset credits, and possibly tougher agriculture. The transport sector alone is Australia’s third largest source
policies around carbon tax will all likely make the use of DAC technolo- of GHG emissions (96 MtCO2-e per year) followed by agricultural activ-
gies even more attractive. Undoubtedly, DAC technologies are currently ities which have accounted for around 80 MtCO2-e GHG emission per
high in cost, however, it is believed that the cost will be reduced over year over the last 10 years [102,103]. DAC can therefore play a major
time and CO2 removed from the atmosphere will be gradually accepted role in reducing emissions from these industries and helping Australia
13
realize the goal of net-zero emissions by 2050. Large scale deployment

of DAC technology can also create benefits beyond the climate change
mitigation purpose for Australia, such as economic benefits from pro-
ducing and selling low carbon fuels and products, and social benefits
from creating enormous potential jobs and market from manufacturing,
installation, to the operating of DAC systems.
Nevertheless, the DAC concept is still relatively new opportunity to
Australia. The Commonwealth Scientific and Industrial Research Or-
ganization (CSIRO) has recently started developing various technolo-
gies around DAC. Airthena using Metallic Organic Frameworks (MOFs),
the Ambient CO2 Harvester (ACOHA) using amine solution, and Car-
bon AssistTM are the main technologies at a technology readiness level
(TRL) of ≤ 5 and targeting a levelized cost of carbon capture at less
than US$100/tonneCO2 [104–106]. Also, AspiraDAC joined by South-
ern Green Gas company have been recently involved into the possibility
of developing and using modular DAC systems to capture CO2 directly
from air and powered by solar energy to convert into renewable methane
for the injection into the gas wells [107,108]. Despite the current low
level of activities around DAC technologies in Australia, the rising mo-
mentum in the RD&D and more supportive measures from the Federal
and States governments are evident, hence it is quite likely that removal
of CO2 from ambient air through DAC systems would soon become a
key player in supplying sustainable and carbon-neutral feedstock CO2
to various industries that helps Australia realizing the net-zero emissions
target.
In short, each route of carbon-neutral CO2 source either from
biomass, renewable methane, or DAC has its own advantages and dis-
advantages. The choice of the right option would mostly depend on the
resource reliability, consistency, and economical factors. Table 3 sum-
marizes the main advantages and disadvantages for each carbon-neutral
CO2 feedstock.
Green urea prospect in Australia
Historical urea synthesis plants (USPs) have been mostly erected

downstream of conventional ammonia plants to utilize their excess am-
monia and a portion of the SMR CO2 by-product. Depending on the
market preferences, if the price of urea is significantly greater than the
price of ammonia, there would be an incentive to convert the excess am-
monia into urea using the recovered CO2 from the SMR process. There-
fore, the size of the urea plant is often constrained by the projected urea
demand and the capacity of the upstream ammonia facility. However,
as the market is strongly leaning towards a more affordable and sus-
tainable urea production, it might be an opportunity for an Australia
based urea production companies to innovate new business models for
such products. External factors such as increasing shipping costs and in-
ternational geopolitical tensions may also help to boost the Australian
made green urea production goal provided that well-planned govern-
ment incentive programs are active in-place. To label urea synthesis a
fully ‘green’ technology, renewable energy needs to power more than the
basic water electrolysis units for the green hydrogen process. Australian
made green urea provision not only requires a responsible utilization of
the abundant natural and renewable resources but would also necessi-
tate a comprehensive process/heat integration to synchronize and opti-
mize the performance of the green urea production line. The USP itself
may not need excessive energy input because the first stage of ammo-
nium carbamate formation (R.4) is an exothermic process. With a proper
heat integration via an advanced heat exchange network (HEN) it can
sufficiently overcome the slightly endothermic process of urea synthesis
(R.5). However, other energy-intensive processes such as ASU and the
SMR in the conventional ammonia production plant would require a
vast energy demand, where direct renewable energy input or via hydro-
Fig. 14. (A) Land classification in Australia, (B) potential locations for intensive gen fuel cells utilizing the excess green hydrogen (Fig. 9) may mitigate
solar energy©, and (C) the availability of potential CO2 storage sites in Australia the carbon footprint of this technology suit. Then, a carbon-neutral CO2
[99–101]. source would perk the urea synthesis technology to be labeled a com-
pletely ‘green’ process. In this context, for example, DAC may provide
14
Fig. 15. A conceptual design of DAC-integrated green urea synthesis plant.
15
Table 3
A comparison of the key advantages/disadvantages for the common carbon-neutral CO2 feedstock.
Carbon-neutral CO2 feedstock Pros Cons
Biomass ▪ Biomass gasification has the lowest net carbon footprint. ▪ Biomass quantity, and quality highly affected by water
▪ H2 from biomass gasification can directly contribute to the resources and climate conditions.
green ammonia synthesis. ▪ The economics highly affected by the locality, and
quantity of raw materials.
▪ Relatively lower in energy density and H2 yield.
▪ Conversion efficiency highly related to moisture, energy,
and the mineral content.
▪ High transport/storage costs.
Renewable methane ▪ Compatible with existing energy infrastructure. ▪ The biomass gasification-methanation and
▪ Wastes fermentation is a mature technology option. power-to-methane routes are costly.
▪ Landfill biochemical conversion to biogas is the most ▪ Biogas produced from either anerobic digesters or landfills
economical option. contain 35–70% CH4 only.
▪ Opportunity to use existing SMR infrastructure to convert ▪ The H2 production from renewable methane is relatively
biogas to clean H2 and CO2 by-product. higher in cost.
▪ Biogas resources are randomly distributed and often have
limited capacity.
▪ Resource inconsistency may limit the use of existing SMR
infrastructure.
▪ The dispersed production of H2 and CO2 provide
opportunities for small-scale urea production that have
close accessibility to feedstock H2 and CO2 , the production
cost may increase significantly due to the limited scale of
production.
DAC ▪ Rapidly emerging as a key climate change mitigation ▪ Relatively new technologies with low TRL.
technology. ▪ The energy demand for DAC plants is excessively high.
▪ Occupies less land area, consumes less water, and highly ▪ The levelized cost of CO2 product from DAC is 2.5–3 folds
scalable and flexible technology. higher than point-source carbon capture.
▪ High concentration CO2 product that may not need further ▪ DAC’s sustainability may be undermined if the sorbent
purification for end-users. regeneration energy demand sourced from non-renewable
▪ Integration with downstream process can lower the cost of energy sources.
shared infrastructure and carbon footprint of long-distance ▪ Erecting very large-scale DAC systems near storage sites
CO2 transport. and optimized for both CO2 storage and utilization
purposes would be more economically viable than having
multiple small-scale DAC systems scaled only for the
utilization sites.
this reliable and scalable carbon-neutral source of CO2 . Presently, the scale DAC system realizing the benchmark of producing almost pure
cost of CO2 capture via DAC is uneconomical, but it is likely that the CO2 at < US$100/tonneCO2 [106]. If Australia is able to meet the cost
DAC technologies will scale-up and mature resulting in lower cost of of green hydrogen production target in the med-long term as reported
CO2 production. Having a carbon-neutral source of CO2 (e.g., via DAC in the National Hydrogen Roadmap [37] and lower the cost of domestic
process) will certainly enhance the sustainability of the ‘green’ urea syn- green ammonia production to < US$500/tonneNH3 , there would be a
thesis. realizable opportunity to set a new benchmark of < US$1000 per ton of
Nevertheless, synchronizing and optimizing such a multi-player ori- green urea manufactured locally in Australia. This green urea produc-
entation for a common objective of maximizing the penetration of re- tion benchmark is quite consistent and compatible with the current and
newable resources at competitive costs would be a challenge. However, future trend of conventional urea imports from overseas (Fig. 4). Hence,
this challenge could be addressed more effectively using the concept of such optimized EMS for the whole superstructure can mitigate the en-
intelligent energy networks (IENs) by managing the dynamics of sup- ergy demand for those energy-intensive units and reduce the cost and
ply and demand, reliable storage systems, improved efficiencies, and carbon footprint of the ‘green’ urea technology. With increasing demand
waste heat integration/reuse [109,110]. Fig. 15 illustrates a conceptual for fertilizers in Australia and overseas, such high-level of EMS can help
integration of DAC system into the green urea technology suit using a to transform Australia and its wealth of renewable/natural resources to
smart technology selector that can intelligently distribute the energy be one of the major players in the regional fertilizer market.
for various technology blocks depending on the resource availability
and time of use. Breaking the distribution into small clusters of micro- Conclusions
units and striving for distributed optimal controls coordinating the mul-
tifunction of the energy management system (EMS) is the best way to In this article, we have reviewed the key trends of fertilizer produc-
handle such complicated systems. For example, in green ammonia pro- tion routes at the global arena with a particular focus on Australian
cess the Haber-Bosch ammonia production process is exothermic (R. 3) market. We then analyzed the local market drivers, barriers, and op-
and the highly endothermic syngas production (R. 1) process no longer portunities to emphasize on the significance of transforming urea pro-
exists, any heat/energy requirement for ASP is eliminated (slashed out duction pathway to track the green ammonia momentum. Skyrocketing
in Fig. 15) and can be redirected to another energy-intensive process. urea prices mostly influenced by external factors such as increasing ship-
In fact, both ASP (R. 3) and USP (R. 4 - R. 5) would become exothermic ping costs and international geopolitical tensions may favorably boost
and when having a proper EMS in-place, the excess heat can generate the Australian made ‘green’ urea production goal, providing an oppor-
steam that might partially be redirected to the sorbent regeneration pro- tunity for Australian manufacturers to initiate new business models for
cess in DAC. This process integration can certainly help a commercial- such products, but this goal will need effective and well-planned gov-
16
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Sustainable Chemistry for Climate Action 1 (2022) 100008

Contents lists available at ScienceDirect

Sustainable Chemistry for Climate Action

Green pathways for urea synthesis: A review from Australia’s perspective

Introduction ﬁciency of agricultural crops production. Nitrogen (N), Phosphorus (P),

AU$4.78 and AU$5.84/kgH2 for alkaline electrolysis (AE) and AU$6.08–

Nevertheless, green hydrogen production is one side of the story

Fig. 8. Potential pathways for the production-

Fig. 11. A simple diagram of H2 and CO2 production from waste.

Fig. 12. A schematic of Hazer process using iron-ore catalyst.

Inﬁnitree Solid sorbents High humidity Fertilizer, Greenhouse

Sustainable Chemistry for Climate Action 1 (2022) 100008

realize the goal of net-zero emissions by 2050. Large scale deployment

Green urea prospect in Australia

Historical urea synthesis plants (USPs) have been mostly erected

Carbon-neutral CO2 feedstock Pros Cons

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