Journal of Cleaner Production 377 (2022) 134537

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review and environmental footprint assessment of various formalin

production pathways
Jan Puhar , Damjan Krajnc , Lidija Čuček , Annamaria Vujanović *
Faculty of Chemistry and Chemical Engineering, University of Maribor, Maribor, Slovenia

A R T I C L E I N F O A B S T R A C T

Handling Editor: Kathleen Aviso Formalin is among the most important commodity chemicals, used mainly as a precursor to a wide range of
value-added products. Currently, formalin is widely produced from methanol derived from natural gas, however
Keywords: a transition from fossil-based production to sustainable feedstocks and pathways is crucial. This study evaluates
High production volume chemicals the environmental impacts of selected promising formalin production technologies to shape a pathway towards
Formalin
more sustainable production of key chemicals. Among the investigated production routes are through methane
Formalin production
steam reforming of other fossil and renewable sources, hydrogenation of CO2, and direct conversion of methane,
Production pathways
Environmental impact assessment syngas or CO2. to formalin. A comparative Life Cycle Assessment (LCA) is performed for seven different formalin
synthesis routes with higher readiness levels. Technologies utilizing waste CO2 and biogas from manure as
feedstocks show the most promising results, reducing greenhouse gas footprint by roughly 60% compared to the
conventional pathway. Results show that a key contribution to the environmental impact mitigation was the
unburdening effect due to the use of waste and product’s substitution. With this study, a more comprehensive
outlook focusing on the environmental sustainability of formalin production is provided. Environmental per­
formance and readiness levels of formalin production technologies utilizing renewable or waste feedstocks
indicate that such pathways could be applied to industrial scale in the future.

shown that such materials could be produced in a circular manner, by

1. Introduction
Formalin is an essential precursor to produce value-added chemicals
such as resins and plastics (Reuss et al., 2000). With plastic consumption
increasing every year and with its further growth expected (Borrelle et al.,
2020), this production sector of the chemical industry presents a significant
environmental burden. To tackle these issues, it is important to systemat­
ically consider the value chains of plastic materials, which include pro­
duction of formalin as a precursor. Formalin is mainly used in the synthesis
of three important thermoset plastic resins: phenol-formaldehyde, ure­
a-formaldehyde, and melamine-formaldehyde, which are produced in the
amounts of around 80 • 106 t/y in total, of which 40 • 106 t/y is
urea-formaldehyde, 21 • 106 t/y is melamine-formaldehyde, and 16 • 106
t/y is phenol-formaldehyde (The Essential Chemical Industry, 2017).
By selecting greener production pathways for formalin, more sus­
tainable production of formalin-based resins could be achieved,
addressing the objective to develop a circular economy for these plastic
materials (Santander et al., 2020). Simulation of more sustainable al­
ternatives for the production of melamine-formaldehyde resin fibres has
considering raw materials sourced from either renewables or waste
(Vujanović et al., 2021). However, potentially viable production path­
ways still remain unexplored, particularly in the case of formalin
production.
Formalin is the most commonly stored and distributed as an aqueous
solution of formaldehyde, containing around 37 wt% formaldehyde in
water (PubChem, 2019). Production of formalin has been increasing
globally and will likely continue to increase due to the rising demand for
wood-based panels, which is one of its chief products (IHS Markit,
2019). The global consumption of formalin is projected to increase at an
average annual rate of approximately 6.1% between 2020 and 2024
(TechNavio, 2020).
Formalin can be produced from a range of raw materials, including
natural gas, coal, biomass, and other carbon-based sources. Its most
common production process involves steam reforming of natural gas,
followed by methanol synthesis from the produced syngas, and finally
formalin synthesis from methanol and oxygen. There are currently two
main routes to produce formalin on an industrial scale: oxidation-
dehydrogenation using a silver catalyst which can involve either

* Corresponding author.
E-mail addresses: jan.puhar@student.um.si (J. Puhar), damjan.krajnc@um.si (D. Krajnc), lidija.cucek@um.si (L. Čuček), annamaria.vujanovic@um.si
(A. Vujanović).

https://doi.org/10.1016/j.jclepro.2022.134537
Received 15 March 2022; Received in revised form 1 October 2022; Accepted 2 October 2022
Available online 5 October 2022
0959-6526/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
J. Puhar et al.
Abbreviations
ADP Abiotic depletion potential
AP Acidification potential
CAMERE Carbon dioxide hydrogenation to form Methanol via a
Reverse-water-gas-shift reaction
CML Centrum voor Milieukunde Leiden (Institute of
Environmental Sciences Leiden)
DCB Dichlorobenzene
DEA Diethanolamine
EP Eutrophication potential
GHG Greenhouse gas
GWP Global warming potential
HTP Human toxicity potential
complete or incomplete methanol conversion, and the direct oxidation
of methanol to formaldehyde using a selective metal oxide catalyst
(Thrane et al., 2021).
More than 90% of the formalin production in the world is realized by
the natural gas reforming via methanol synthesis route (Bertau et al.,
2014). However, alternative production pathways have gained rele­
vance in recent years due to the pressure on the chemical industry to
reduce its environmental burden. Rising crude oil prices and advances in
formalin gasification and synthesis technologies have led, especially in
China, to a shift in production to the synthesis of coal-based methanol
and further formalin synthesis (Li and Broadstock, 2021). As a result,
technological innovation has triggered increased attention towards
alternative raw materials, such as bio-based resources or waste mate­
rials. Such resources could contribute towards mitigation of environ­
mental burdens and support the transition towards circular economy.
Methanol, which is required to produce formalin by most conven­
tional pathways, can also be obtained using different production path­
ways and with a vast number of feedstocks. While natural gas-based
production pathways are most common, there has been a significant
increase in research of more renewable pathways (Roode-Gutzmer et al.,
2019), such as conversion of wind power to methanol (Bos et al., 2020),
utilization of renewably produced hydrogen (Cifre and Badr, 2007), and
the utilization of biogas (Entesari et al., 2020). Companies around the
world are already using new and innovative sources to synthesize
methanol, with syngas or liquid fuels being produced from sources such
as waste black liquor (Häggström, 2011), crude glycerine (Van Benne­
kom et al., 2012), CO2 emissions (Hobson and Márquez, 2018), and solar
energy (Steinfeld and Lehmann, 2019).
Factors such as resource availability have an important effect on
choosing production pathways. In the example of China, which produces
most of the methanol in the world (Su et al., 2013), there is an abun­
dance of coal, which has caused the methanol industry to shift to
coal-based production pathways. To consider the impacts of resource
extraction, transport, and production, a systematic comparison of the
different options is required.
Life Cycle Assessment (LCA) is a widely recognized method for
assessing environmental impacts of products and services. LCA and life
cycle thinking has thus far been beneficial in the field of sustainable
plastics as a tool for estimating the most environmentally friendly
strategies on a policy level (Tamburini et al., 2021). Despite the global
scale of formalin production and the relevance of formalin as a product,
to the knowledge of the authors, there has been no comprehensive
comparative LCA studies performed regarding different synthesis routes
of formalin (Riaz et al., 2013).
Several research works have been published on the LCA of methanol
production. Comparative LCA was performed for coal-based methanol
and electricity co-production and natural gas reforming process (Sli­
winska et al., 2017). The concept of hierarchical attribution
2
Journal of Cleaner Production 377 (2022) 134537
ILCD International Reference Life Cycle Data
LCA Life Cycle Assessment
LCI Life Cycle Inventory
MDEA Methyl diethanolamine
MEA Monoethanolamine
MER Melamine etherified resin
MSR Methane steam reforming
MSW Municipal solid waste
NADH Nicotinamide adenine dinucleotide cofactor
POP Photochemical oxidation potential
RWGS Reverse water-gas shift
SOEC Solid oxide electrolysis cell
TRL Technology Readiness Level
WGS Water-gas shift
management has been utilized to evaluate the carbon footprint of
coal-to-methanol chain (Qin et al., 2016). The authors discussed
detailed greenhouse gas (GHG) generation during the methanol pro­
duction process, providing a systematized method for identification of
related direct and indirect emissions. The life cycle environmental per­
formance of various fuels such as liquefied natural gas, methanol, and
bio-methanol has been compared (Brynolf et al., 2014). The environ­
mental impacts of methanol production has been analysed, where the
study considered sugarcane bagasse and Brazilian conditions as raw
material (Reno et al., 2011). Methanol production routes have been
compared based on a cradle-to-gate LCA, where global warming po­
tential (GWP) and energy demand were discussed (Kajaste et al., 2018).
When considering both operating costs and the impact of GWP, meth­
anol produced by gasification of wood biomass was recognized as the
best performing technology.
Environmental aspects should be considered when designing
different production routes for the sustainable production of chemicals,
especially those produced in larger quantities. Research has already
shown that coal coking technology causes lower environmental harm
than coal gasification (Li et al., 2018a). Other processes, such as CO2
electrolysis, have shown great promise regarding their yield efficiency,
mild operating conditions and lower environmental impact (Patel et al.,
2016). One of the most promising alternatives is methanol production
by hydrogenation of captured CO2, which has been developed to a
readiness level appropriate for higher scale implementation (Álvarez
et al., 2017). However, despite the presence of new technologies with
the potential to replace current practice, there is insufficient research
comparing the current industrial state and alternative technologies
(Al-Kalbani et al., 2016).
To the best of the authors’ knowledge, there was no comprehensive
environmental analysis performed yet evaluating different processing
routes for formalin production from different feedstocks. This study
therefore brings a review into currently available formalin production
technologies, complementing LCA with Technology Readiness Level
(TRL) analysis to offer a well-rounded comparison when making de­
cisions among different technologies. The objectives of this paper are to
investigate environmental performance of formalin production from
different synthesis routes and to understand the sustainability of the
formalin production technologies. To make a balanced comparison
among the formalin production pathways, only technologies with a
moderately high TRL are investigated. In this way, realistic input-output
data is considered for technologies at or above pilot scale. The
comparative assessment was carried out using seven environmental
impact categories to identify the possible impacts of formalin produc­
tion: GHG footprint, eutrophication potential (EP), human toxicity po­
tential (HTP), potential for abiotic depletion of fossil fuels (ADP),
acidification potential (AP), photochemical oxidation potential (POP),
and eco-costs. OpenLCA software with the integrated database
J. Puhar et al.
Ecoinvent 3.6 (Ecoinvent V3.6, 2019) and other was used for the envi­
ronmental analysis.
2. Review of formalin production pathways
This section briefly describes the formalin production pathways and
classifies them in three categories: (1) Formalin synthesis via syngas
conversion, (2) Alternative formalin synthesis routes from methanol
produced by hydrogenation of CO2, (3) Direct conversion to formalin.
2.1. Formalin synthesis via syngas conversion
Syngas conversion to methanol and further to formalin is currently
the standard process used to produce formalin industrially. In the first
step of the process, syngas is converted to methanol, which is later pu­
rified by removing water and other impurities. In the next step, form­
aldehyde is produced from methanol and air, where the leading
industrial reaction pathway today is the Formox process, where formalin
is synthesised by conversion over a metal oxide catalyst (Rellán-Piñeiro
and Lopez, 2015). The syngas used as feedstock can be obtained from
various carbon-based sources, the most common of which is natural gas.
The production pathways described in this section are presented in
Fig. 1.
2.1.1. Formalin produced via steam reforming of natural gas
Currently, the majority of formalin is produced via the natural gas
reforming route. The process consists of: (1) methane steam reforming
(MSR), (2) methanol synthesis from syngas, and (3) formalin synthesis.
The MSR reaction, which generates syngas by the reaction of
methane and high-pressure steam, is presented in Eq. (1). The syngas is
mainly composed of H2, CO and CO2. To increase the H2 content in the
syngas, the water-gas shift (WGS) reaction occurs, as shown in Eq. (2).
CH4 + H2 O → CO + 3H2
CO + H2 O ↔ 3H2 + CO2
In the second part of the process, methanol is formed according to the
equilibrium reactions shown in Eqs. (3)–(5).
CO2 + 3H2 ↔ CH3 OH + H2 O
CO2 + H2 ↔ CO + H2 O
Fig. 1. Formalin production pathways via conversion of syngas.
Journal of Cleaner Production 377 (2022) 134537
CO + 2H2 ↔ CH3 OH (5)
Finally, formalin is synthesised from methanol and oxygen by the
combination of partial oxidation and dehydrogenation of methanol
(Millar and Collins, 2017). Eq. (6) represents the formalin synthesis
reaction.
2CH3 OH + 0.5O2 → 2CH2 Ο + H2 O + H2 (6)
2.1.2. Syngas produced via gasification of biomass, combustible waste or
coal
Syngas may be produced from bio-based sources such as wood
biomass and various other carbonaceous feedstocks, such as municipal
solid waste (MSW) or coal. In the case of biomass gasification, the first
part of the process consists of feedstock delivery, weighing and prepa­
ration by drying and preheating. The dry biomass is then gasified by
partial oxidation and pyrolysis, and the resulting raw syngas is purified
by quenching and acid gas separation (Cifre and Badr, 2007). The
simplified biomass gasification process is shown in Eq. (7). It should be
noted that glucose is used to represent wood biomass, however actual
biomass composition is more complex due to its complex structure and
composition.
C6 H12 O6 + O2 + Н 2 O → CO + CO2 + H2 (7)
Coal-based syngas is mainly produced by two methods: coal gasifi­
cation and coal coking (Li et al., 2018a). During gasification, the coal is
blown through with oxygen and steam, as shown in Eq. (8). Addition­
ally, the oxidation reaction shown in Eq. (9) takes place in the gasifier,
resulting in a gaseous mixture of CO, CO2, H2 and water vapour.
Alternatively, the coal coking process refers to heating the coal inside an
oven, where the main difference to the gasification process is seen in the
raw syngas composition. The gas is also named coke oven gas, and
contains mainly CO2, H2 and CH4. To purify the coke oven gas, steam
reforming is used to convert the methane into additional CO and H2.
(1)
3C + O2 + H2 O → H2 + 3CO (8)
(2)
C + O2 ↔ CO2 (9)
Syngas from waste can be produced also from the organic content of
MSW, which consists of combustible components such as non-recyclable
(3) plastics, cardboard and other materials. The waste is gasified to produce
syngas, which is later purified, removing the contents of salts, HCl and
(4) H2S. The high-temperature gasifier enables a high selectivity of CO and
3
J. Puhar et al. Journal of Cleaner Production 377 (2022) 134537

H2 in the resulting gas and avoids CH4 formation, resulting in syngas sources range from organic waste such as manure, sewage sludge,
composition that is more suitable for future use in methanol production agricultural residues, organic fraction of MSW and other. Purification of
(Iaquaniello et al., 2017). biogas to remove contaminants such as H2S is also conducted to ensure
For all the pathways described, methanol and formalin are syn­ its quality for future use (Mulu et al., 2021). To produce syngas, the MSR
thesised after syngas has been formed. The synthesis occurs in the same method similar to natural gas reforming is used. This method is desirable
manner as the natural gas-based process, which is referred to in Eqs. (3)– as WGS produces additional H2, which results in syngas composition
(6). that is more beneficial for further processing (Vita et al., 2018). In the
following steps, methanol and formalin are synthesised from syngas as
2.1.3. Syngas produced via gasification of black liquor described in Eqs. (3)–(6).
Black liquor is formed during the Kraft pulping process by converting
wood into wood pulp, which is the dominant method for producing
2.2. Alternative formalin synthesis routes from methanol produced by
paper. During the Kraft process, wood chips are treated by a white liquor
hydrogenation of CO2
solution containing sodium hydroxide and sodium sulfide, which pro­
duces black liquor as the by-product. The black liquor contains organic
To obtain methanol used in formalin production, an alternative to
matter from wood and is usually gasified in the paper mill to recover
the conventional routes may be the hydrogenation of CO2. The CO2 used
energy by producing heat and/or electricity (Magdeldin and Järvinen,
can be obtained by physical or chemical absorption to capture CO2 from
2020). However, it can also be used as a gasification feedstock to pro­
flue gases. A solvent, usually amine-based, such as diethanolamine
duce biofuels such as methanol. Due to black liquor being sourced from
(DEA), methyl diethanolamine (MDEA) or monoethanolamine (MEA)
wood and due to its liquid state, it presents a practical option for use in
(Vega et al., 2018) is used to obtain a liquid phase containing mainly
chemical industry. It offers the additional advantage of containing a very
CO2 after absorption. The CO2-rich stream is introduced to an acid gas
small amount of methane in the resulting syngas (IEA Bioenergy, 2007).
stripper, where desorption occurs and purified gaseous CO2 is obtained.
Gasification of the black liquor, which burns in a manner similar to
Technologies where CO2 is used to produce methanol and further
heavy oil, occurs in a pressurised reactor, and the generated gas is
formalin are presented in Fig. 2.
cleaned to remove smelt, ash and H2S. The resulting syngas contains
mostly H2, CO and CO2. In the following steps, methanol and formalin
2.2.1. Formalin produced via methanol from CO2 capture
are synthesised from syngas as described in Eqs. (3)–(6).
Formalin is alternatively produced by the catalytic hydrogenation of
CO2, a process which can be sourced fully from renewable or waste
2.1.4. Syngas produced via biogas
sources if hydrogen is produced by one of the greener pathways such as
Another bio-based process which can be used to produce syngas is
electrolysis of water. The CO2 required for the reaction is usually sup­
biogas. Biogas is obtained via anaerobic digestion, where organic matter
plied from flue gases of fossil-fuel power plants and factories (Cifre and
is decomposed by microorganisms in the absence of oxygen and is
Badr, 2007). Once it is separated from the bulk gas stream, methanol is
converted to a gaseous mixture of methane, CO2, water, and other trace
produced by mixing CO2 with H2 in the stoichiometric ratio according to
compounds, which are largely dependent on the biogas source. These
Eqs. (3)–(5). Finally, analogous to the syngas-based process, methanol

Fig. 2. Alternative formalin production pathways.

4
J. Puhar et al.
and oxygen are used to produce formalin.
2.2.2. CAMERE conversion process of CO2 to methanol
Aside from the direct hydrogenation of CO2 process described in
section 2.2.1, the CAMERE process (CO2 hydrogenation to form meth­
anol via a reverse WGS (RWGS) reaction) presents an alternative
pathway to produce methanol from CO2. The process employs a RWGS
reaction to partially convert CO2 to CO and water. The water in the
solution is then removed by a flash separator, which is beneficial for
resulting in higher methanol content during the methanol synthesis
(Araya et al., 2020). The gaseous mixture of CO, CO2 and H2 is then fed
to the methanol synthesis reactor, where methanol is formed according
to reactions specified in Eqs. (3)–(5). The RWGS occurs at temperatures
above 600 ◦ C and up to 800 ◦ C (Park et al., 2004) and is shown in Eq.
(10). Catalyst selection is critical for this reaction, as the RWGS is
required to effectively convert CO2 to CO and to remain stable at tem­
peratures up to 800 ◦ C. Research has shown that ZnAl2O4 is among the
efficient catalysts that could be used to produce methanol with the
CAMERE technology (Aničić et al., 2014).
CO2 + H2 → CΟ + H2 O (10)
2.2.3. Electrocatalytic reduction of CO2 to methanol
Methanol may be produced from CO2 via electrocatalytic reduction,
a method which attracts interest due to its ability to be performed under
ambient conditions. Two electrocatalytic pathways of methanol pro­
duction are described in this section: the direct electrocatalytic con­
version of CO2 and water to methanol and the electrocatalytic
conversion of CO2 and water to syngas.
During the direct electrocatalytic conversion of CO2 to methanol,
electricity is supplied to establish a potential between electrodes and
reducing CO2 to other value chemicals. The products of this electro­
chemical reduction depend on catalyst materials and the reaction me­
dium. To obtain methanol from CO2 and water, metal compounds such
as oxidized copper, either in the form of Cu2O cubes or oxidized copper
foil, are selected for the cathode, while platinum is commonly used for
the anode. For the reaction medium, the electrochemical reduction of
CO2 most often requires an aqueous solution of inorganic salts con­
taining Cl− , HCO−3 or OH− anions, which offer high conductivity and are
beneficial for product selectivity (Albo et al., 2015). The overall reaction
of the electrode system is presented in Eq. (11). The individual cathode
and anode reactions are presented in Eqs. (12) and (13).
CO2 + 2H2 Ο ↔ CH3 OH + 1.5O2 (11)
CO2 + 6H+ + 6e− ↔ CH3 OH + H2 O (12)
3H2 O ↔ 1.5O2 + 6H+ + 6e− (13)
However, the described process has so far not been carried out effi­
ciently regarding the methanol yield, and therefore it is unlikely to be
applicable in practice without additional research of the process
mechanism (Albo et al., 2015).
A method more likely to be used is electrolysis of CO2 and water to
form syngas, which can then be used to produce methanol by known
reactions, specified in Eqs. (3)–(5). To perform water electrolysis, water
and CO2 input flows are used alongside a solid oxide electrolysis cell
(SOEC). Similar to the CO2 capture and hydrogenation method
described in section 2.2.1, CO2 is first captured from flue gas by chem­
ical absorption with amine solvents. It is heated to the SOEC operating
temperature of 800 ◦ C, where together with water, syngas consisting of
CO, CO2 and H2O is produced (Al-Kalbani et al., 2016). Three separate
reactions occur inside the SOEC: water electrolysis and CO2 electrolysis
as shown in the cathode reactions in Eqs. (14) and (15), as well as the
WGS reaction (Eq. (2)).
H2 O + 2e− ↔ H2 + O2− (14)
5
Journal of Cleaner Production 377 (2022) 134537
CO2 + 2e− ↔ CO + O2− (15)
2−
The anode reaction is shown in Eq. (16). O oxygen ions are
transported through a solid oxide electrolyte, and O2 gas is generated by
oxidation.
2O2− ↔ O2 + 4e− (16)
The overall reaction is shown in Eq. (17). Along with it, the WGS
takes place, increasing the amount of H2 in the resulting syngas.
CO2 + Н 2 O ↔ CO + H2 + O2 (17)
In the following steps of the process, methanol is produced from
syngas and later purified, and formalin is produced from methanol and
air as specified in Eq. (6).
2.2.4. Conversion of CO2 to methanol by alternative means
Additional methods to perform reduction of CO2 to methanol, such as
photocatalytic or enzymatic methods, have received experimental
attention. One of the promising technologies is photocatalytic reduction
of CO2 using UV light irradiation (Ali et al., 2015). The process uses
semiconductor materials such as TiO2, ZnO, and ZnS as well as reducing
substances like H2O, H2, CH4 and alcohols. While the operating condi­
tions of this process are rather mild, the downside is a substantial energy
demand to convert CO2 to methanol. The process of photocatalytic
conversion of CO2 is still far from practical applications, particularly due
to a complicated mechanism and inefficient product selectivity (Kar­
amian and Sharifnia, 2016), and will therefore require significant im­
provements in catalyst modification or other areas before it can be
performed at the industrial level.
The biological conversion to methanol offers the benefit of being
carried out at ambient conditions (Patel et al., 2016). The proposed
method utilizes CH4 and CO2 as feedstocks to produce methanol by
enzymatic reactions. There is potential for this technology to be utilized
for biogas conversion, as biogas is comprised of a mixture of gaseous
CH4 and CO2.
2.3. Direct conversion of various precursors to formalin
Several reaction mechanisms to produce formalin from precursors
other than methanol have been proposed, mainly focusing on feedstocks
such as CO2, syngas and methane which could be converted directly to
formalin. The majority of research on direct conversion to formalin is
still far from practical applications, however the technologies in this
section offer vital opportunities in transitioning towards more sustain­
able production of formalin at lower cost and energy demands (Heim
et al., 2017).
2.3.1. Direct conversion of CO2 to formalin
Formalin has been produced by a stoichiometric reduction of CO2,
where the reducing agent used was the zirconium metallocene complex
[Cp2Zr(H)(Cl)]n (Heim et al., 2017), as shown in Eq. (18). Formalin is
also formed when CO2 is inserted in the Si–H bonds of a decomposed
silyl formate molecule (Sun and Wang, 2021), shown in Eq. (19). Format
dehydrogenase and formaldehyde dehydrogenase enzymes coupled
with the nicotinamide adenine dinucleotide (NADH) co-factor also
reduce CO2 to formalin with the enzymatic reaction occurring at 37 ◦ C as
shown in Eq. (20).
2Cp2 Zr(H)Cl + CO2 → [Cp2 (Cl)Zr]2 O + CH2 O (18)
3NC11 H12 –SiC7 H8 O2 → N3 Si3 C51 H54 O3 + 3CH2 O (19)
CO2 + 2NАDH + 2H+ ↔ CH2 O + 2NАD+ + H2 O (20)
2.3.2. Direct conversion of syngas to formalin
Formalin conversion directly from syngas has been successfully
J. Puhar et al. Journal of Cleaner Production 377 (2022) 134537

carried out as hydrogenation of CO in the aqueous phase, where a
selectivity of 100% and conversion of 19% were achieved (Bahmanpour
et al., 2015). By using a selective Ru–Ni/Al2O3 catalyst, the reaction
equilibrium was pushed towards formalin as the major product in
aqueous solution. For the formalin to stabilise, methanediol (CH4O2)
was formed as the main product in the resulting aqueous solution of
formalin.
2.3.3. Direct oxidation of methane to formalin
Formalin formation has also been studied using the direct oxidation
of methane at temperatures between 600 and 770 ◦ C and in the presence
of a surface containing SiO2. The process mechanism involves initiation
by formation of free radicals on the solid surface and chain propagation
in the gas phase (Bobrova et al., 2007). With the surface oxygen indi­
cated by Os, methyl radicals are first formed from methane, and con­
verted to formalin in the secondary interaction with Os (De Vekki and
Marakaev, 2009), as shown in Eqs. (21) and (22):
CH4 + Os → CH3 + HOs (21)
CH3 + Os → CH2 O + 0.5H2 (22)
3. Environmental footprint analysis
The LCA study was performed in four steps according to the ISO
14040 series standards (International Organization for Standardization,
2006a, b): goal and scope definition, inventory analysis, impact assess­
ment and interpretation. This study aims to compare the life cycle im­
pacts of formalin produced from different resources and using
alternative technologies on a cradle-to-gate basis. The final use of
formalin as a chemical is excluded from the evaluation due to the
various possible end uses.
The Ecoinvent database version 3.6 (Ecoinvent V3.6, 2019) with
allocation at the point of the substitution system model was taken,
meaning that impacts of waste burdens are shared between its producers
and its subsequent users benefitting from waste treatment products
(Ecoinvent Association, 2021).
In the study, operational CO2 emissions from bio-derived fuels are
considered to be zero, as they captured from the atmosphere during
feedstock growth (Gilbert et al., 2018). The LCA included production of
raw materials and formalin while did not include the construction,
distribution, and use.
In the Life cycle inventory (LCI) phase of LCA, the inputs and outputs
of the production system are quantified. In the case of formalin pro­
duction from captured CO2, hydrogen is produced by steam reforming of
natural gas, a process which was taken from the Ecoinvent database. LCI
for electricity consumption for the processes is assumed to be coming
from the Slovenian electricity mix (Statistical Office of the Republic of
Slovenia, 2021). Also, the LCI for natural gas production and transport
processes was based on the Slovenian natural gas basket (Ministry of
Infrastructure of Republic of Slovenia, 2019). Inventories for
country-specific natural gas production processes were obtained from
Ecoinvent database with estimated transport distances to the case re­
finery location (assumed to be Kočevje, Slovenia).
hydrogenation have reached a readiness level that shows they could be
utilized for methanol production on a higher scale. Other technologies
such as biogas utilization have been developed up to pilot-scale capacity
and could be viable options in the future. On the other hand, technol­
ogies such as electrocatalytic reduction of CO2 or various pathways for
direct conversion of precursors to formalin are at very low maturity
levels, and they clearly require further research to increase production
capacity.
Table 1 shows the studied formalin production technologies and
their respective TRLs. Descriptions of TRLs are taken from guidelines
available in the literature (Buchner et al., 2019), where levels 1–3
represent technologies in the proof of concept stage, levels 4–6 represent
proof of principle, and levels 7–9 represent proof of performance. Of the
11 technologies where TRL was assessed, 6 technologies (T1-T6) which
have a moderately high TRL were further analysed in this study to
evaluate their environmental impacts. The evaluation was conducted for
technologies which operate on a comparable scale and can provide
sufficient and realistic data for accurate LCA analysis.
The different production routes have been assessed for all process
stages of formalin from cradle to gate of the factory. Screening was
performed to only include technologies with TRL above 6 for further
analysis, by excluding laboratory-scale systems due to insufficient data
for environmental assessment. Out of the 11 production routes of
formalin technologies listed in Table 1, seven were reviewed, including
both emerging and conventional technologies:
(1) Case A: Formalin produced via steam reforming of natural gas
(T1);
(2) Case B: Formalin produced via gasification of wood biomass (T2);
(3) Case C: Formalin produced via gasification of coal (T2);
(4) Case D: Formalin produced via gasification of black liquor (T3);
(5) Case E: Formalin produced via biogas utilization (T6);
(6) Case F: Formalin produced via CO2 capture technology and hy­
drogenation of CO2 (T4);
(7) Case G: Formalin produced via the CAMERE process (T5).
3.2. Definition of the functional unit and system boundaries
The functional unit provides a reference unit for the system. In this
study, the functional unit considered was defined as 1 t of produced
formalin. The seven formalin production routes were assessed within the
system boundaries "cradle-to-gate", including raw materials extraction,
methanol synthesis and final formalin production. The study considered
all the relevant raw materials, energy, utilities (e.g., electricity, steam,
Table 1
Technology readiness levels of previously investigated formalin production
technologies.
Technology Name TRL Description
Natural gas reforming T1 9 Actual system proven through
Biomass or coal T2 9 successful operation in a commercial
gasification setting
Black liquor gasification T3 9
Hydrogenation of CO2 T4 8–9

3.1. Goal and scope definition CAMERE process T5 6–7 Pilot-scale system demonstrated in
Biogas utilization T6 6 relevant laboratory environment

An important variable to consider when assessing the sustainability Electrocatalytic T7 3–4 Proof-of-concept validated through
of technologies is their maturity level, which is related to the viability of reduction experiment or analysis
a given technology to be implemented into a full-scale operation. This Photocatalytic or T8 3
enzymatic reduction
can be expressed via the technology readiness level (TRL), which has
CO2 to formalin (direct) T9 2–3
been researched by the authors in previous work (Puhar et al., 2021).
The study investigated available formalin production technologies and Syngas to formalin T10 2–3 Technology concept and/or
assigned TRLs according to standardized guidelines. It was found that (direct) application formulated
while the MSR pathway is the most common one for formalin produc­ Methane to formalin T11 2–3
(direct)
tion, alternatives such as black liquor gasification and CO2

6
J. Puhar et al. Journal of Cleaner Production 377 (2022) 134537

water), auxiliary chemicals, and emissions involved in each stage. The
use of formalin and waste treatment was not considered. The direct
wastewater emission has not been considered because it was assumed
that each production facility has its own on-site wastewater treatment
system. For the simplification, infrastructure, facilities, and labour were
not included in the system boundary. Enzymes were also not considered
since their amount is minimal when considering the overall inputs and
outputs of systems.
4. Footprint analysis of formalin production pathways
In this section, inventory data for the different formalin production
pathways is presented. LCA evaluation was conducted by using the CML
midpoint method (CML - Department of Industrial Ecology, 2016). The
selected impact categories considered are GHG footprint, ADP, EP, HTP,
AP, and POP. Additionally, the single-score metric of eco-costs was
evaluated at the endpoint level.
GHG footprint reflects global warming and climate change and is
expressed with the amount of CO2 and other GHG emissions (mass of
CO2 equivalents). ADP represents the potential depletion (or exhaus­
tion) of non-renewable fossil resources from the estimated world re­
serves and is measured in MJ. EP estimates the potential to cause over-
fertilization of water and soil, which causes growing of biomass. HTP
reflects the potential harm of a unit of chemical released into the envi­
ronment, quantified in 1,4-dichlorobenzene (DCB) equivalents. AP es­
timates the potential of chemicals such as SO2 and NOx to contribute to
deposition of acid. POP estimates the potential for creation of photo­
chemical smog. Finally, eco-costs are defined as the monetary value for
prevention of environmental pollution, and are comprised of impact
categories for human health, ecotoxicity, resource depletion and global
warming (Sustainability Impact Metrics, 2021).
The LCI data for the relevant inputs and outputs from the production
of 1 t formalin is shown in Table 2 for the seven cases considered (Case A
– Case G). Inventory data for the methanol production step was obtained
from a distinct source in each of the seven cases representing different
production pathways, where the sources are described in detail for each
case below. Inventory data for the production of formalin from methanol
was obtained from a previous study by the authors (Vujanović et al.,
2021), where several production pathways for melamine etherified resin
(MER) fibres were simulated. Data for both the methanol production and
formalin production steps was adjusted to fit the needs of 1 t formalin
production and to generate the inventory for the comparative LCA of
formalin production. OpenLCA software with integrated databases
Ecoinvent (Ecoinvent V3.6, 2019), GaBi (GaBi Software System, 2020),
Soca (Ciroth and Eisfeldt, 2016), and ILCD (International Reference Life
Cycle Data) (ILCD Handbook, 2010) has been applied to perform LCA
models.
For Case A, where formalin is produced via the natural gas pathway,
the material mass flows for methanol production are obtained from a
study which compared the environmental and economic performances
of different methanol production routes (Li et al., 2018b). The LCI data
was assumed from the paper, where inputs and outputs for methanol
production from natural gas are specified. For formalin production in
the second part of the process, the LCI data is obtained from a simulated
process for formalin synthesis, which is described in detail in previous
work (Vujanović et al., 2021). The required compression electricity and
heating and cooling energy is also calculated. The data for compressed
air is obtained from average air blower’s electricity consumption.
For Case B, a wood-based methanol process was sourced from the
Ecoinvent database (Ecoinvent V3.6, 2019), which covers pre-treatment
and gasification of wood biomass to obtain syngas, and subsequently
methanol synthesis. Methanol production includes the estimation of
catalyst use, even though the amount is minimal when compared to the
overall inputs and outputs of the system. The catalyst selected for the
methanol synthesis was Cu/ZnO/Al2O3 due to be one of the most
commercially available catalyst for methanol production (Puig-Gamero
et al., 2018). For the consumption of catalysts, it is assumed that the
44.5 t Cu/ZnO/Al2O3 (Van-Dal and Bouallou, 2013) are renewed once a
year. A typical wood-based biomass uptake area is estimated at a slightly
conservative level at about 150–200 km. In this study, the average
one-way transport distance of wood biomass to the conversion plant is
estimated to be 150 km by truck (50% load, 16–32 metric ton). Similar
to Case A and other selected formalin production pathways, the LCI data
for production of formalin from methanol was obtained from the
simulated process.
Formalin production via coal gasification (Case C) is a similar pro­
cess to biomass gasification, with the main difference represented by the
mining, processing, and transportation of coal. The LCI data is partially
based on a recent study (Liu et al., 2020), where a simulated process for
the extraction and gasification of coal and subsequent methanol syn­
thesis was presented. Input and output data for raw coal, fuel coal, and
electricity during the extraction process was provided.

Table 2
Life Cycle Inventory analysis for formalin produced via different pathways.
Parameter Case A Case B Case C Case D Case E Case F Case G Unit

Inputs
Compressed air 304.97 317.57 315.26 295.29 315.26 315.25 295.29 m3
Water 6.58 0.78 0.80 0.80 1.00 0.81 0.80 t
Electricity 982.43 18.38 459.57 47.33 878.53 1333.76 637.43 MJ
Steam 0.27 0.27 2.06 0.27 0.36 3.97 0.27 t
Natural gas 278.28 / / / / / / m3
Wood chips / 1.52 / / / / / t
Hard coal / / 0.76 / / / / t
Fuel gas / / 128.46 / / / / MJ
Bark / / / 0.18 / / / t
Fuel biomass / / / 0.34 / / / t
Pulp wood / / / 1.21 / / / t
Biogas / / / / 384.57 / / m3
Captured CO2 / / / / / 0.67 0.78 t
DEA / / / / / 0.62 0.77 g
Hydrogen / / / / / 85.48 85.48 kg
Outputs
Pulp / / / 0.93 / / / t
CO / / 0.26 / 49.04 / / kg
Ash / 12.19 71.72 / / / / kg
Carbon dioxide 57.73 58.16 59.42 58.16 69.99 58.16 58.16 kg
Nitrogen oxides 5.81 5.86 5.81 5.81 5.81 5.81 5.81 kg
Wastewater 2.42 2.38 2.45 12.16 2.58 2.69 2.43 t
Formalin (product) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 t

7
J. Puhar et al.
The LCI data for formalin production from black liquor (Case D) is
based on a study which proposes a pulp mill, where black liquor is ob­
tained during pulp production (Carvalho et al., 2018). The black liquor
is further gasified and converted into methanol. For the inputs of
pulpwood, electricity, bark and biomass (both used as fuel), and outputs
of produced pulp and wastewater, the readers are referred to the paper.
For LCI of formalin production via biogas (Case E), the reference was
a proposed system which consists of a series of simulated methanol
production processes, among them methanol from biogas (Clausen et al.,
2010). Mass flows of biogas and steam inputs as well as water and syngas
outputs were specified. Data for required heating energy and compres­
sion electricity was also stated. The first part of the process, the anaer­
obic digestion and conversion of waste to biogas was assumed from
databases.
LCI for formalin produced by CO2 capture (Case F) is based on
simulation data from a study on a methanol production plant via CO2
hydrogenation (Van-Dal and Bouallou, 2013). The simulated process
includes CO2 capture by DEA absorption and subsequent hydrogenation
of CO2 to methanol. Hydrogen is assumed to be produced by steam
reforming of natural gas, where the Slovenian electricity mix (Statistical
Office of the Republic of Slovenia, 2021) is used. The LCI data for
hydrogen production via natural gas is obtained from the Ecoinvent
database. The compression and transport of hydrogen are excluded from
the data set.
The LCI data of formalin produced via the CAMERE process (Case G)
are obtained from a study of simulated methanol production plant from
CO2 using the CAMERE process (Aničić et al., 2014), which is described
in more detail in section 2.2.2. The data specified was mass flows of CO2
and H2 as well as heating energy and electricity. Pure methanol is ob­
tained in the proposed process. The CO2 used in LCI is assumed to be
captured CO2 from flue gas of a coal-fired power plant (Vujanović et al.,
2021).
5. Results and discussion
This section presents the results of environmental analysis for GHG
footprint, EP, HTP, ADP, AP, POP, and eco-costs. Fig. 3 shows the results
for GHG footprint for production of 1 t of formalin by the considered
production pathways. GHG footprints are shown for the following con­
tributions to the footprint: main feedstock, electricity, steam (as hot
utility), output emissions, and other. The main feedstock contribution
Fig. 3. Global warming potential for different formalin production pathways.
8
Journal of Cleaner Production 377 (2022) 134537
represents the key raw material used in each respective case: natural gas
in Case A, wood chips in Case B, hard coal in Case C, pulpwood in Case
D, a mixture of liquid cattle manure, liquid swine manure, solid cattle
manure and sewage sludge in Case E, and captured CO2 in both Cases F
and G. The cases E-G show the unburdening effect of the main feedstock
due to avoided emissions, and the total impact is defined as a sum of
burdening and unburdening effects (Kravanja and Čuček, 2013). The
category “Other” combines contributions of various other chemicals,
fuels, and transport demands for the processes.
Results show that the highest GHG footprints are obtained in Cases A
and C, which are the only cases utilizing fossil sources as main feed­
stocks. The Case C contributed to 987 kg CO2 eq./t formalin, which is by
far the highest value among all the cases. GHG footprint is reduced by
41% when utilizing natural gas, and up to 79% when utilizing renewable
and waste feedstocks. These two cases show that majority of footprint is
due to utility demand of processes, particularly due to high electricity
demand in Case A and high contributions of coal mining and gasification
operations in Case C.
When considering Case B, where methanol is obtained by gasifica­
tion of wood biomass, GHG footprint is reduced by 28% compared to
Case A and by 58% compared to Case C. The reduction is attributed to
the use of a wood-based methanol production process with lower
emissions from electricity consumed. Wood used in gasification is
considered as a carbon-neutral feedstock due to its embodied biogenic
carbon being returned to the atmosphere upon gasification. Because of
this, no unburdening effects are considered in this case.
Case D, where black liquor is gasified to produce methanol, further
reduces GHG footprint for around 47% compared to Case A and 69%
compared to Case C. The process is highly energy efficient in terms of
electricity and steam demand. The largest contribution comes from
emissions from treatment of pulp sludge as a part of the overall process.
The feedstock for this process is considered as the pulpwood entering the
pulp mill, which produces black liquor as a by-product. The utilization
of black liquor was not considered as an unburdening effect, as this
material should not be discharged into the environment but rather
gasified and electricity and/or heat could be produced in recovery
boilers (Naqvi et al., 2010). It is worth noting that in the event of black
liquor leakage, a significant hazard to the environment would be caused
due to its toxicity and poisoning effect on aquatic ecosystems (Sari et al.,
2015).
Case E, which utilizes biogas for formalin production, is among the
J. Puhar et al.
least environmentally burdensome cases, with a 59% reduction in GHG
footprint compared to Case A and 76% reduction compared to Case C. A
significant contributor to the low environmental impacts is the unbur­
dening effect of the main feedstock, which is considered as a combina­
tion of liquid swine manure, liquid and solid cattle manure and sewage
sludge. The GHG footprint of manure is negative mainly due to avoided
methane emissions by considering 10-days storage period in average.
This causes a total unburdening effect of − 142 kg CO2 eq./t formalin and
results in a reduced overall figure for Case E.
Cases F and G, which utilize different methanol production pathways
from CO2 (direct CO2 hydrogenation in Case F and CAMERE in Case G),
also include unburdening effects, which are obtained by capturing CO2
from flue gases, thus avoiding CO2 emissions to the atmosphere. Case F
reduces GHG footprint by 37% compared to Case A and by 64%
compared to Case C, while Case G has the lowest GHG footprint obtained
in the study, with respective reductions of 63% and 79%. The difference
in results between the two processes is mainly related to the lower de­
mand for hot utilities in the CAMERE method (Case G). The contribution
of impacts in the “Other” category is notable in these two cases, and it is
Fig. 4. Environmental impacts for different formalin production pathways.
9
Journal of Cleaner Production 377 (2022) 134537
mainly represented by the demand for hydrogen, a feedstock which is
unique to these two cases.
Results for the impact categories EP, HTP, ADP, AP, and POP are
presented in Fig. 4. For better representation, some of the scales have
been modified to fit the graph. For example, the observed ADP value
presented in 10 MJ units must be multiplied by a factor of 10 to obtain
the actual calculated value.
The results for the selected impact categories show that low utility
demands in Case B and the use of wood rather than fossil-based re­
sources cause this to be among the least environmentally burdensome
cases, as can be seen in the low impact values of POP, which is reduced
by 69% compared to Case A, as well as HTP, which is reduced by 58%
compared to Case A. However, the case shows a slight increase in AP
when compared to Case A, which is attributed to NOx, SO2 and ammonia
emissions during plywood production. The differences among the cases
for the category of AP are fairly small, as around 55% of this impact is
caused by NOx outputs from the formalin production process, a value
which is shared among all cases producing 1 ton of formalin.
Case C unsurprisingly shows highest results in the categories of AP
J. Puhar et al.
and ADP, where its demand for steam and utilization of hard coal as a
non-renewable feedstock are main contributors. Similarly, its high HTP
and EP result values are obtained due to a higher demand for hard coal
and lignite mining. Case A also shows high results in the HTP category
mainly due to emissions caused by the natural gas extraction and pro­
cessing phase.
Case D, which utilizes black liquor gasification, results in significant
reductions from an environmental standpoint, yielding the lowest value
in AP (reduced by 24% compared to Case A) as well as ADP (reduced by
61% compared to Case A), which is mainly attributed to the process
utilizing pulpwood as main feedstock, as well as fuel biomass for process
heating. However, this process also has the highest EP among all cases
(increased by 19% compared to Case A), which is attributed to treatment
of waste pulp sludge.
Case E, which utilizes biogas, has among the lowest results in most
selected environmental impact categories with around 34% reductions
in EP and HTP, and 77% reduction in ADP compared to Case A, mainly
due to low utility demands and use of natural feedstocks. However, it is
notable for its increase in POP when compared to other cases. The result
is attributed to direct impacts of the process output emissions, where a
small amount of syngas is purged from the process, causing the
embodied CO to contribute to photochemical oxidation potential.
Cases F and G, which both utilize captured CO2, are noted for their
unburdening effect in the category of POP, which is due to capturing
CO2 from flue gases that would otherwise be released into the atmo­
sphere. Results also show that Cases F and G rank relatively high in the
category of ADP (higher than for all Cases except Case C). The impacts in
both cases are clearly caused by the demand for hydrogen, which is
produced from natural gas.
In addition to GHG footprint and potential environmental impacts,
formalin production is also evaluated using the eco-costs method. The
impact metric is shown in Fig. 5, broken down into its four core cate­
gories: eco-costs of carbon footprint, resource depletion, eco-toxicity
and human health.
Results show that eco-costs are highest for Case C at over 120 EUR/t
formalin, which is driven mainly by eco-costs of carbon footprint from
fossil fuel use. The next highest eco-cost burden is yielded by Case A,
where natural gas demand is the main contributor towards the impact
category results. These two cases rank as by far the most environmen­
tally burdensome among the alternatives, similar to their results in
categories such as GHG footprint and HTP. The remaining cases show
promising results toward mitigating environmental impacts, particu­
larly Cases E and G, which benefit from unburdening effects of biogas
and captured CO2 utilization. Case E, where biogas from manure is used,
reduces total eco-costs by 65% compared to Case A (natural gas) and by
71% compared to case C (coal). Despite also using captured CO2 as the
main feedstock, eco-costs of Case F are notably higher due to its greater
Fig. 5. Eco-costs of formalin production pathways.
10
Journal of Cleaner Production 377 (2022) 134537
demand for electricity and related increase in the eco-costs of eco-
toxicity.
6. Conclusions
In this paper, the environmental performance of seven different
production pathways for formalin having higher TRL values were
investigated: natural gas, biomass gasification, coal gasification, black
liquor gasification, biogas utilization, CO2 hydrogenation, and CAMERE
process. Seven environmental impact metrics were used to conduct the
LCA assessment of the production of 1 t formalin: GHG footprint, EP,
HTP, ADP, AP, POP, and eco-costs.
In comparison to the conventional fossil-based pathways of formalin
production from natural gas and coal (Cases A and C), the analysed
alternative pathways were shown to be beneficial from an environ­
mental standpoint, as they resulted in reduced GHG footprint. Aside
from the reduced contributions of feedstock sources, they also show a
reduced utility demand, which leads to their improved environmental
performance.
Several formalin production pathways are notable for their envi­
ronmental unburdening effects. In Case E, which utilizes biogas pro­
duced by anaerobic digestion of manures and sewage sludge, GHG
footprint is reduced due to the unburdening effect of avoiding methane
emissions during manure storage. In Cases F and G, which both utilize
CO2 capture technology, unburdening effects are caused by removing
CO2 emissions from flue gas. These unburdening effects result in Case G
yielding the lowest GHG footprint value among all cases. Similarly, Case
E also reduces GHG footprint significantly due to these effects. For the
wood gasification pathway, unburdening effects were considered
regarding carbon-neutral nature of wood. Also, the black liquor process
brings some unburdening as utilities could be produced by further
valorization of the waste black liquor.
Accounting for unburdening effects is a key step towards under­
standing the cumulative environmental impact of a process. In the
present study unburdening offers additional insight into the pathways
that should be prioritized when selecting among alternatives. The results
indicate that pathways which utilize renewable and waste sources and
particularly pathways with unburdening environmental effects should
be prioritized over traditional natural routes.
Results obtained for the environmental impact categories of EP, HTP,
ADP, AP, and POP also reflect the benefits of utilizing renewable and
waste sources in chemical production processes. Values for HTP are the
highest in Cases A and C which utilize natural gas and coal and are
reduced by up to 58% when considering the alternative cases, owing
largely to the reduced demand for fossil fuels. ADP category results
reflect the importance of considering more sustainable hydrogen pro­
duction pathways when producing methanol by CO2 hydrogenation
J. Puhar et al.
processes. Due to hydrogen being produced by reforming of natural gas,
Cases F and G yield relatively high results in ADP and AP. Conversely,
the figures in the category of POP are lowest for Cases F and G, where
their capturing and utilization of waste CO2 unburdens the environment
from smog that would otherwise pollute the atmosphere. When
considering the impact categories of EP, HTP, ADP, and AP, Case E
which utilizes biogas is shown to be among the most environmentally
beneficial, validating biogas as a viable option to replace natural gas in
such production processes. Similar insight into the case studies was
found when assessing the endpoint impact category of eco-costs, where
Case E yielded the lowest environmental impacts, while cases utilizing
fossil-based feedstocks were highly burdensome to the environment.
The dependence of our everyday lives on chemical industry products
and concerns over current fossil-based production routes has led to
increased attention on sustainability. One such product with a rapidly
increasing global demand is formalin, commonly used in the plastics and
resins industry. Given that the majority of the world’s formalin is
currently produced by the conventional natural gas route, cleaner pro­
duction pathways should be given more attention. As shown in this
study, production routes based on renewable or waste sources offer
lower environmental burdens and a high enough readiness level for
large-scale viability. This paper therefore presents an important step
towards transforming the current unsustainable practice in formalin
production.
The results of this study are influenced by the quality of the data used
and the limitations imposed by the methodology used. In addition to the
data used from the simulations specified in the LCI section, secondary
data from the Ecoinvent database was used. The method used in the
assessment reflects the production systems as defined in the corre­
sponding reference production systems. In a sense, this imposes a clear
limitation and limits the results to the technologies, efficiency factors,
raw materials and geographical locations used in the assessment.
In future work, further avenues for utilizing waste feedstocks should
be explored in order to not only mitigate environmental impacts, but
also unburden the environment and transition towards sustainable
production. Research should include comparative environmental impact
assessment of pathways producing other important bulk chemicals and
products such as hydrogen, ammonia, fuels and plastic materials and
other.
CRediT authorship contribution statement
Jan Puhar: Investigation, Writing – original draft, Writing – review
& editing, Data curation, Visualization. Damjan Krajnc: Conceptuali­
zation, Investigation, Writing – original draft, Data curation. Lidija
Čuček: Writing – review & editing, Supervision. Annamaria
Vujanović: Conceptualization, Writing – review & editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors would like to acknowledge financial support from the
Ministry of Education, Science and Sport of Republic of Slovenia (project
No. 5442-1/2018/106) and the Slovenian Research Agency (research
core fundings No. P2-0412 and P2-0421 and projects J7-3149 and N2-
0138).
11
Journal of Cleaner Production 377 (2022) 134537
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