Industrial Crops & Products 150 (2020) 112411

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Industrial Crops & Products

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Economic risk assessment using Monte Carlo simulation for the production T
of azelaic acid and pelargonic acid from vegetable oils
Gerardo Antonio De Leon Izeppia, Jean-Luc Duboisb,*, Antonin Ballec, Ana Soutelo-Mariac,d
a
Microinnova Engineering GmbH, Europapark 1, 8412, Allerheiligen bei Wildon, Austria
b
Arkema France, 420 Rue d’Estienne d’Orves, F-92705, Colombes, France
c
Arkema France, Centre de Recherche Rhône-Alpes, Rue Henri Moisson, F-69493, Pierre Bénite, France
d
Dipartamento di Scienza e Tecnologia del Farmaco, Università di Torino, Via P. Giuria 9, I-10125, Torino, Italy

ARTICLE INFO ABSTRACT

Keywords: The interest in renewable products is growing as a source of raw materials. Alongside, new process technologies
Monte Carlo (process intensification combined with continuous manufacturing) are seen as better alternatives to increase the
Azelaic acid profitability of new projects. Consequently, two Monte Carlo simulations were performed to focus the Research
Risk assessment and Development effort on areas of major impact on the development of a chemical process. Palm oil and high
Process intensification
oleic sunflower oil were used as case studies for the production of azelaic acid. It was found that process in-
tensification strategies should focus on selectivity and on the reduction of the number of processing steps.
Additionally, the use of vegetable oils with a higher quality although at higher price (about 50 % more ex-
pensive) provides a faster payback time, mostly due to a lower CAPEX and a better value of the co-products. For
specialty chemicals, the choice of the oil depends strongly on the fatty acid profile.

1. Introduction of non-edible alternative crops.

Industrial vegetable oils have gained also interest in the polymer
The discovery of petroleum in the 19th century had a tremendous industry due to their attractive fatty acid composition used as renew-
impact on our society. It has become the main source of energy and raw able building blocks precursors. Several of these compounds are already
materials for the industry. Nevertheless, it is a non-renewable material, being used as raw materials for the production of more complex end
its use has a negative effect on climate change and its decline will have products in commercial applications (Dubois, 2016a, b). 11-ami-
a great impact on our way of living. noundecanoic acid is produced from the oil of castor bean, for the
As a result, the interest in sources that could substitute fossil specialty polyamides (PA) production of Rilsan®, Pebax® and Rnew®
carbon/petroleum has increased. Nonetheless, this decision cannot be polymer ranges (Dubois, 2016a, b). Sebacic acid (DC10), also produced
made in a short period of time considering that manufacturing plants from castor oil, and its derivated diamine (DA10) are renewable
are planned to run for years and the adoption of new products can take monomers for PA6,10 (Rilsan® S) and PA 10,10 (Rilsan® T) (Dubois,
more than 20 years (Dubois, 2016a, b). 2016a, b).
Unlike petroleum, vegetable oils are renewable and their use in the The increase in the demand of renewable monomers production
chemical industry is not a novel topic. Vegetable oils can be subdivided requires effective production processes. Among the industrial processes
in edible and non-edible oils. Non-edible oils have fatty acid profiles to obtain renewable monomers, the oxidative cleavage of unsaturated
that can be useful for industrial applications. Linseed (Zuk et al., 2015) fatty acids has been considered as a greener alternative to achieve these
and castor oils (Dubois, 2014; Dubois et al., 2013) are grown because of renewable monomers (Dubois, 2018). Valuable difunctional monomers
their unique chemical properties, important for the chemical industry such as azelaic acid are being already produced by this process by
(Atabani et al., 2013). They have been used for non-edible purposes like oxidative ozonolysis and more recently by oxidative cleavage using hy-
paints (“Sarbio®”, 2019), plastics, agrochemicals (“EU Pesticides data- drogen peroxide and oxygen (Soutelo-Maria et al., 2018). Other re-
base - European Commission”, 2019) and as lubricants (Fox and newable monomers have been under investigations lately, such as the
Stachowiak, 2007). The popularity of renewable fuels has resulted in a production of dodecanedioic acid (DDDA, or DC12), through fermen-
significant investment of public and private capital for the development tation of Lauric acid ester, but the company has not been able to

⁎
Corresponding author.
E-mail address: [email protected] (J.-L. Dubois).

https://doi.org/10.1016/j.indcrop.2020.112411
Received 25 November 2019; Received in revised form 27 March 2020; Accepted 28 March 2020
Available online 23 April 2020
0926-6690/ © 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

complete its demonstration plant (Bomgardner, 2017; Latieule, 2018). • Rent

Recently, the production of Amino Dodecanoic acid ester also through • Royalties
fermentation of Lauric acid ester was piloted, but the product does not • Distribution and selling
seem to be on the market yet (“Vestamid”, 2013). • Research and development
Regardless of the high interest in renewable products, an economic
risk assessment is necessary to evaluate each project, to identify the 2.2. Monte Carlo simulation
impact of the vegetable oil choice and to identify the impact of the
technology. Typically, economic considerations are done using a deterministic
approach. This type of approach consists of input and output variables
2. Materials and methods which are constant in time. In other words, once the variables and their
values have been fixed, the result or outcome will remain constant. This
2.1. NPV type of analysis is simple and a good starting point for any analysis, but
it deviates from reality by not considering uncertainty and fluctuations
The decision to make an investment relies on the profitability of the over time. In addition, the set of data selected can severely affect the
project. There are several methodologies to evaluate projects and select result while not representing the reality or a high probability of oc-
the one which generates the biggest economic benefit, which helps currence.
management to decide which project receives funding. These types of Certain methods exist in order to evaluate the impact of uncertainty,
methodologies can also be used as filters in the early stages of a project. such as sensitivity analysis. This type of analysis measures the impact of
These methodologies can be payout period plus interest (POP), Net uncertainty, but it does not define the probability of happening.
Present Value (NPV) and discounted cash flow (DCFROR), between Monte-Carlo method, on the other hand, is a stochastic method
others (Green and Perry, 2007; Peters et al., 2003). (non-deterministic). On this method, the variable inputs come from
One of the most used methodologies is the NPV or sometimes called probabilistic distributions instead of single or fixed values. This ap-
the net present worth (NPW) (Green and Perry, 2007). The NPV is the proach leads to output variables with its own probabilistic distributions
sum of the yearly cash flow in present value terms and it can be de- and allows to evaluate the probability of certain results as can be seen
scribed with the Eq. (1). in Fig. 1.
n The Monte Carlo method consists of simple steps:
OCF
NPV =
t=0
(1 + i )t (1)
• Definition of the probabilistic distribution of the variables.
Where t represents the year, n is the number of years that the project is • Generation of the correlation between variables to shorten dis-
operational, i is the discount rate and OCF is the annual operational tribution of output variables (Supplementary Data S2).
cash flow. If the NPV is higher than 0 it means that the project generates • Generation of a series of values based on the probabilistic dis-
a return rate higher than the discount rate (Green and Perry, 2007; tribution.
Peters et al., 2003). • Generation of the deterministic output for each of the series of va-
The discount rate might be defined based on specific targets and/or lues generated.
the interest for borrowing money. For instance, a discount rate equal to • Analysis of all of the deterministic values.
the interest of borrowing money would be required to generate a po-
sitive NPV to make a profit. 2.3. Chemical process
Additionally, the NPV can be used to compare two or more projects
and the project with the highest NPV would generate the highest return 2.3.1. Industrial process / benchmark
rate (if all projects use the same discount rate). The industrial production of bi-functional monomers such as azelaic
The annual operational cash flow can be determined with Eq. (2). acid through ozonolysis is accomplished since the beginning of XXth
century by the oleochemical company Emery Oleochemicals with a plant
OCF = ANP + D (2)
in the USA (“Bio-Lubricants Product”, 2013) and Croda Sipo (“Where
Where ANP is the Annual Net Profit and D is the depreciation. The We Operate | Croda”, 2019) with a plant in China. More recently P2
ANP can be determined with Eqs. (3) and (4): Science (Foley and Yang, 2014) has invested also in the production of
the monomer azelaic acid through ozone application. However, this
ANP = AP *(1 TR) if AP > 0 (3)
process presents some disadvantages such as high energy and techno-
ANP = AP * 1 if AP < 0 (4) logic demand to produce ozone and some potential risks associated
with ozone utilization.
Where AP is the Annual Profit and TR is the tax rate. The AP is further
The application of hydrogen peroxide as the oxidant of this reaction
determined in Eq. (5):
has been industrialized in Porto Torres (“Novamont S.p.A. - Chimica
AP = Sales Expenses D (5) Vivente per la Qualità della Vita”, 2019). The investment was divided
Where Sales is the annual sales generated from the sales of the products into three phases and during phase 1, a plant capable of producing
and Expenses is the annual expenses of the plant. In the present case azelaic and pelargonic acid was installed. The maximum capacity of the
study, the following items were considered as expenses: plant has been stated to be between 32,000–40,000 tons by different
sources. The products include azelaic acid, carboxylic acids for ester-

• Raw materials ification and for the market, glycerol and other secondary products with

• Catalysts high boiling points. Based on the publicly released (Bieser et al., 2011)

• Labor costs information the general mass balance of the plant can be seen in Fig. 2.

• Utilities The reported process used high oleic acid sunflower, although the

• Maintenance and repairs company communicates a lot on the use of Cardoon oil. Nevertheless,

• Operating supplies other sources of vegetable oils could be used but different end products

• Property taxes and byproducts are to be expected.

• Financing interest The patented process (Bieser et al., 2011) has already been de-

• Insurance scribed before and it is used as the basis for the case study (Soutelo-
Maria et al., 2018). The process described in the patents has been

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Fig. 1. Comparison of a deterministic and non-deterministic approach for data analysis.

Fig. 2. General mass balance described in the integrated environmental authorization from the plant installed at Porto Torres (Bieser et al., 2011).

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Fig. 3. The chemical process for the production of azelaic and pelargonic acid from vegetable oils – Although diol esters are produced in the process, in order to
simplify the analysis they have been omitted in the mass balance, which would mean that they are recycled in the process at the step 3.

adapted to close the mass balance and can be observed in Fig. 3.

The process covers 4 main steps. In step 1, the transesterification of
the triglycerides with methanol and an inorganic base occurs to obtain
the fatty acids methyl esters (FAME) and glycerol. Crude glycerol is
extracted from the reaction medium. Step 2, dihydroxylation, com-
prises the oxidation of the double bond with H2O2 and tungsten catalyst Fig. 4. Structure of a triglyceride. R1, R2, R3 – un/saturated fatty acids con-
into the formation of methyl dihydroxy-stearate intermediates. Step 3 stitution.
involves the CeC oxidative cleavage of the intermediate formed in step
2. The reaction proceeds under 20 bars of industrial air (containing
in Table 1. At the same time, each fatty acid can lead to different re-
about 21 % oxygen) – this pressure is referred as Pmax later in the
newable products.
study. Finally, step 4 constitutes the purification process. After oxida-
tive cleavage, the organic phase contains mono and dicarboxylic acids,
the derivatives of the fatty acids present initially in step 2 such as 2.4.2. Others
methyl stearate, palmitate and still the remaining diol intermediate. Other raw materials in the analysis include hydrogen peroxide
The pelargonic acid (C9) and the lighter monocarboxylic acids (C6-C8) which is used for the dihydroxylation reaction. Methanol, which is used
can be recovered with a distillation column. The monomethyl azelate, in the transesterification process, is recovered at the end of the process
methyl palmitate, methyl stearate and the esters of methyl dihydroxy- through the hydrolysis of the methyl esters. Tungstic acid and cobalt
stearate recovered from the bottom of the distillation column are con- acetate are the catalysts used to carry out the oxidative scission of fatty
tinuously fed into a reactor with an emulsifier and then hydrolyzed into acids and to a lower extent sodium hydroxide and sulfuric acid are used
three consecutive columns filled with acid ion exchange resin. The in the transesterification process.
azelaic acid is separated by crystallization from the heavier mono-
saturated fatty acids palmitic and stearic (Soutelo-Maria et al., 2018).
2.5. Oxidative cleavage / main reaction
Products obtained with one carbon less such as acid C8 (octanoic acid)
and dicarboxylic acid DC8 (suberic acid) are the result of the dec-
These renewable products can be obtained through different reac-
arboxylation of pelargonic acid and azelaic acid, a side-reaction (loss of
tions depending on the chemical structure of the vegetable oils. The
selectivity) of the process.
total number of carbons, the presence of double bonds, ester linkages or
hydroxyl groups in the chemical structure will determine the type of
2.4. Raw materials reaction and the type of products that can be produced.
Furthermore, vegetable oils do not contain only one fatty acid but
2.4.1. Vegetable oils several of them. These different compounds lead to several coproducts
Vegetable oils are the main raw material and they represent the and byproducts during the reaction, which added to reactions yields
major expense. Vegetable oils are triglycerides (Fig. 4). Where R1, R2, lower than 100 %, demand several separation and isolation steps to
and R3 represent three different or identical fatty acids. obtain products with high purity needed for commercial and industrial
The composition of the fatty acids depends on the type of oil as seen applications such as polymers.

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Table 1
Fatty acid composition of some vegetable oils, n-position of the double bonds from the acid group ((Beare-Rogers et al., 2001)– composition in wt %.
Oil Saturated Fatty Acids Monounsaturated Fatty Acids Polyunsaturated Fatty Acids Others

16:0 18:0 20:0 22:0 16:1 n-9 18:1 n-9 20:1 n-11 22:1 n-13 18:2 n-9,12 18:3 n-9,12,15 18:1 – OH

Rapeseed 4 2 62 22 10
Palm 40.1–47.5 <1.0 <0.6 36–44 6.5–12 <0.5
Sunflower High Oleic 3–4 4–5 79–89 1–12
Sunflower High Linoleic 5.9 4.5 19.6 65.7
Soybean 10 4 0.4 0.4 23 0.3 54 7.5
Castor 1.0–2.0 4.0–9.0 85–90

Table 2
Number of moles of products/building blocks obtained from the oxidative cleavage per mole of fatty acid.
Fatty acid Carbon number, n: Azelaic Pelargonic Palmitic Steraic Others Heptanoic Caproic Malonic Propionic
carbon number acid (DC9) acid (C9:0) acid (C16:0) acid saturated acid (C7:0) acid (C6:0) acid (DC3) acid (C3:0)
insaturation (C18:0) (C20:0/C22:0)

Oleic acid C18:1 n-9 1 1 0 0 0 0 0 0 0

Linoleic acid C18:2 n-9,12 1 0 0 0 0 0 1 1 0
alpha-Linolenic acid C18:3 n-9,12,15 1 0 0 0 0 0 0 2 1
Palmitoleic acid C16:1 1 0 0 0 0 1 0 0 0
Palmitic acid C16:0 0 0 1 0 0 0 0 0 0
Stearic acid C18:0 0 0 0 1 0 0 0 0 0
Others saturated C20:0 / C22:0 0 0 0 0 1 0 0 0 0

The main reaction, which is considered in this case study, is the Sebacic acid (DC10) is a dicarboxylic acid, HOOC(CH2)8COOH, with
oxidative cleavage of unsaturated fatty acids. Oxidative scission of the a strong presence in several industries. This renewable monomer is
double bonds present in the fatty acids can be accomplished through produced industrially from ricinoleic acid, obtained from castor seeds,
the use of ozone as an oxidant (ozonolysis) or through the use of hy- and besides its similar structure to azelaic acid, it has different physi-
drogen peroxide and a tungsten-based catalyst (Soutelo-Maria et al., cochemical properties, which makes azelaic acid more convenient in
2018). The expected products without considering side reactions are certain applications like lubricants as a result of a lower melting point
shown in Table 2. as seen in Table 3. As seen in Table 3, there is a periodicity in melting
Saturated fatty acids are not expected to react during the process points. This periodicity leads to DC7, DC9 and DC11 having a similar
such as palmitic acid (C16:0) and stearic acid (C18:0), therefore they melting point compared to DC8 and DC10 which have much higher
are recovered at the end of the process. melting points.
As we can observe in Table 2. The production of azelaic acid and Recently the price of sebacic acid has been increasing due to Asian
pelargonic acid is highly dependent on the oil composition. The larger political-economic constraints related to the closure of several plants
the content of C18:2 and C18:3, the lower the production of pelargonic during winter times given past preference to burn coal for energy
acid. Higher content of C16:0, C18:0 or other high molecular weight production, contributing so to air pollution (“Chemical Industry
saturated fatty acids, reflects lower production of pelargonic acid and Impacted by Chinese EPA Crackdown – Chemceed”, 2019). As a result,
azelaic acid as there are no double bonds to oxidize. The production of the sebacic acid supply became tight and the price increased to around
these high-value monomers relies on the selection of the most appro- 5000 $/ton. The same constraint does not apply to azelaic acid, which
priate vegetable oil. is produced in China but also in the US, while most of the sebacic acid
worldwide is produced in China (with some production in India and
2.5.1. Products recently plans in Oman).
Azelaic acid and Pelargonic acid have the highest market price and Azelaic acid, although less pure than sebacic acid, has a market at a
are therefore considered as the main products of the process. higher price today, but also a much lower market share. Sebacic acid
world production might reach 100 kt/year by 2024 and the market size
2.5.1.1. Azelaic acid. One of the main products of this case study is was above 300 m USD in 2016 (“Sebacic Acid Market Size, Growth –
azelaic acid (DC9). DC9 is a linear saturated dicarboxylic acid with 9 Industry Share Report 2024”, 2019). On the other hand, azelaic acid
carbons and the following formula HOOC(CH2)7COOH. This bi- had a market size of 94 m USD in 2017 and is expected to reach 140 m
functional monomer is a renewable product and it is highly USD by 2025 (“Global Azelaic Acid Market Growth Opportunity”,
appreciated for its physicochemical properties in the cosmetic and 2019). It is reasonable to think that in the past also there was a price
pharmaceuticals (“Capchem”, 2019), electronics (Kawakami and
Sakakura, 2017), lubricants, plasticizers and in the polymer industry
Table 3
to form the Nylon-6,9 (Acton, 2013). Azelaic acid can be obtained by Physical properties of some dicarboxylic acids (Haynes, 2015).
the oxidative cleavage of oleic acid, linoleic acid, and α-linoleic acid
along with different byproducts depending on the number of Dicarboxylic acid Number of Melting Molecular Density
carbons point (°C) weight (g/mol) (g/mL)
unsaturation of the fatty acid precursor.
In some cases, raw materials can be replaced by cheaper sources, Pimelic acid (DC7) 7 106 160.17 1.28
which indirectly correlates the market prices of raw materials through Suberic acid (DC8) 8 144.0 174.20 1.27
competition and it can be used to predict the future prices of the raw Azelaic acid (DC9) 9 106.5 188.22 1.225
Sebacic acid (DC10) 10 130.8 202.25 1.208
materials. Nevertheless, in some cases, the substitution of raw materials
Undecanedioic acid 11 108-110 216.28 0.89
can be performed in limited cases due to physicochemical properties, (DC11)
which is the case of sebacic acid (DC10).

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Table 4
Physical properties of some carboxylic acids (Haynes, 2015).
Monocarboxylic acid Number of carbons Melting point (°C) Boiling Point (°C) Molecular weight (g/mol) Density (g/ml)

Enanthic acid (C7) 7 −7.5 223 130.19 0.92

Caprylic acid (C8) 8 16.3 239 144.21 0.91
Pelargonic acid (C9) 9 12.3 254.5 158.24 0.91
Capric acid (C10) 10 31.5 268.7 172.27 0.99
Undecanoic acid (C11) 11 28.6 280.0 186.30 0.891

differential and that azelaic niche markets allowed it to survive even Table 5
when sebacic acid was cheaper. Mass balance to produce 10,000 ton of azelaic acid per year (x 103 ton/year).
Sebacic acid is correlated to the price of castor oil. But azelaic acid High Oleic Palm Oil
should depend for example on animal fat, vegetable oils (US source) or Sunflower Oil processing plant
palm oil (Asian source). However, its market value is so high that it processing plant
decorrelates from the oil source. Castor has been historically about
Raw Materials / Vegetable oil 21.8 38.7
twice the price of palm oil, so indirectly there is a kind of correlation
catalysts H2O2 pure 3.02 3.45
between azelaic acid and castor oil. Tungstic acid 0.089 0.102
Cobalt acetate 0.065 0.075
2.5.1.2. Pelargonic acid. Pelargonic, a carboxylic acid with 9 carbons Methanol 0 0
Products / Azelaic acid (DC9) 10.0 10.0
and chemical formula HOOC(CH2)7CH3, is the second main product of
byproducts Suberic acid (DC8) 2.31 2.31
this case study. This monofunctional carboxylic acid can be obtained by Caproic acid (C6) 0.431 1.53
the oxidative cleavage of oleic acid, gondoic acid and erucic acid along Heptanoic (C7) 0 0
different byproducts depending on the precursor unsaturated fatty acid Caprylic acid (C8) 1.81 1.53
used (Echa, 2020). In 1995 the Mycogen Corporation introduced Pelargonic acid (C9) 7.94 6.71
Palmitic acid (C16:0) 0.833 16.3
pelargonic acid in the pesticides market with the brand name Scythe®
Stearic acid (C18:0) 1.25 1.48
and, more recently the company JADE (Jade, 2020), since then has Arachidic acid (C20:0) 0 0.480
being used as a natural herbicide (Ma et al., 2018). Alike azelaic acid, Glycerol 2.27 4.19
the replacement of pelargonic acid depends on the physicochemical Propionic acid (C3), 0.387 1.45
Malonic acid (DC3)
properties of the acids as seen in Table 4.

2.5.1.3. Others. Other products from the reaction, which have a lower
market price include glycerol. Glycerol market price has dropped since • Other products have a yield of 100 %
the expansion of renewable diesel, where glycerol is a byproduct and • Separation efficiency is 100 %
the supply is much greater than the demand. Additionally, long-chain • Transesterification reaction had a yield of 100 %
saturated fatty acids would be produced.
Other products might have a lower number of carbons due to un-
• Methanol recovery was assumed to be 100 %
desired decarboxylation, which reduces the yield and efficiency of the As seen in Table 5, two plants with a yearly production of 10 kton of
process (non-selective reaction). azelaic (DC9) and 7–8 kton of pelargonic acid (C9) per year are com-
pared. Lower C9 in the case of Palm Oil due to different ratio ( MuFA ) . It
PuFA

2.5.2. Mass balance is also seen that the plant which uses high oleic sunflower oil (H.O.S.O)
Based on the chemical process described in Fig. 3, the required is half the size of the palm oil plant (22k ton/year vs 39k ton/year). In
amount of raw materials and end-products are determined for the fol- other words, due to the composition of fatty acids in high oleic sun-
lowing vegetable oils and are shown in Table 5. The mass balance was flower oil, less raw material is required to obtain the same amount of
based with the next two vegetable oils: the desired products (DC9, C9).

• High oleic sunflower (C18:1 = 85 %, C18:2 = 5 %, C16 = 4 %, 3. Results

C18 = 6 %)
• Palm oil (C18:1 = 40.5 %, C18:2 = 10 %, C18:3 = 0.2%, C16 = 44 3.1. Economic analysis
%, C18 = 4 %)
3.1.1. Products and raw materials price distributions
The following assumptions were made for the mass balance: The goal in this section is to identify the prices distribution, based
on the historical data, corrected for inflation. The price distribution was
• A concentration of 0.51 mmoles of tungstic acid and 0.29 mmoles of fitted with several statistical laws (Normal, Log-Normal, Gamma and
cobalt acetate was used according to the number of C]C bonds Weibull) and the best fit was identified. The distribution then reflects
(double bonds) in the oil composition. geo-climatic or geopolitical parameters that affect the market prices.
• Due to the high solubility of DC3 and C3 in water, it was assumed Furthermore, it was determined if the past events that affected the
that they are not recovered and end up as wastes. prices have the same probability to occur in the future and to decide if
• The oxidative cleavage reaction has an efficiency of 80 % for the the same laws of distribution should apply, estimate the mean and the
production of azelaic acid and pelargonic acid. The side products of other statistical parameters.
this reaction consist of CO2, octanoic or caprylic acid (C8) and oc- After each distribution was fitted, the future distribution of the
tanedioic or suberic acid (DC8). That means we assume that 80 wt % prices was estimated based on the past and our own experience. Both
is C9 and the rest is CO2 and C8. The decarboxylation reaction is a the fitted distribution based on the historical price and the future dis-
serious drawback of the process as it makes the final purification of tribution of High Oleic Sunflower Oil and Palm Oil, are shown in Figs. 5
the products more complex and could impede the valorization of the and 6. The fitted distributions for the rest raw materials such s Me-
diacid as a high purity monomer. thanol and H2O2 can be found in the Supplementary Data S3.

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Fig. 5. Fitted price distribution of raw materials (historical data) taking into consideration inflation (“Palm oil - Monthly Price - Commodity Prices - Price Charts,
Data, and News – IndexMundi”, 2019, “Sunflower oil - Monthly Price - Commodity Prices - Price Charts, Data, and News – IndexMundi”, 2019).

Fig. 6. Fitted future price distribution of raw materials based on historical prices distribution laws and assuming ranges for future.

3.1.2. Correlation matrix 3.1.3. Capital costs

In addition, a correlation matrix was prepared and the correlation Capital costs are the expenditures needed to design and build a
factors between each of the parameters was estimated. In other words, chemical plant. These expenses are fixed costs and represent the highest
the dependency between the prices of each of the variables (raw ma- investment before the start-up of the plant. The determination of capital
terials prices and products) was determined. The main purpose is to costs depends on the degree of the project definition. The Association
sharpen the distribution of the final output, by restricting the range in for the Advancement of Cost Engineering (AACE) categorizes cost es-
which the individual distributions are allowed in the Monte Carlo timation in 5 classes with different ranges of accuracies, as seen in
Simulation. Table 6.
The historical data were analyzed to determine correlation coeffi- Several correlations have been proposed in the literature for cost
cients between them. A matrix of correlation coefficients was gener- estimations at the early stages of a project. Some of these correlations
ated. On a case by case basis, the correlation coefficient was adjusted to were made by Wilson, Taylor, Bridgewater, Klumpar, Petley, and
reflect the expected value for the future. The adjusted value took into Lange, between others (Tsagkari et al., 2016). These correlations vary
consideration if the values which showsome correlation are due to ca- on the information required to estimate the total capital costs and it is
sualty or if there is a true dependence between the values. For instance, possible to achieve Class 5 and Class 4 level of accuracy with these
methanol and azelaic acid are two different products for different methods.
markets and the new plant will not have an impact on the price of Due to simplicity and limited information about the plant, the
methanol. On the contrary, if the demand for acid C9 increases, it could correlation based on the work of Petley was used in the Monte Carlo
be expected that the price of C8 would increase due to a direct sub- simulation, found as one of the best identified by Mirela Tsakgari
stitution in some applications. When no correlation coefficient was (Tsagkari et al., 2016). The correlation was attained with fuzzy
available from historical data, a value was generated by expert judg- matching using different processes (Petley, 1997). The original corre-
ment. Then random values were generated with the assigned distribu- lation by Petley is:
tion laws, and the data are multiplied by a Cholesky matrix generated
from the correlation matrix in order to create correlations between the
Capital Cost (1988) = 55882Q0.44N 0.486Tmax 0.038Pmax 0.02F 0.341
m (6)
data. The generated correlation matrixes can be found in the supple- The Capital Cost is the total expenses of the processing facilities in
mentary information. US dollars in 1988, Q is the capacity in tonnes/year, Tmax is the max-
imum temperature of the process in kelvin, Pmax is the maximum

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Table 6
Cost estimation classification matrix (Tsagkari et al., 2016).
Class Degree of projection definition Usage Methodology Accuracy

5 0–2 % Conceptual screening Capacity factored or parametric models Low: −20 to – 50 %

High: +30 – +100 %
4 1–15 % Study of feasibility Equipment factored or parametric models Low: −15 to – 30 %
High: +20 – +50 %
3 10–40 % Budget authorization or control Semi-detailed unit costs Low: −10 to – 20 %
High: +10 – +30 %
2 30–70 % Budget control Detailed unit costs Low: −5 to – 15 %
High: +5 – +20 %
1 70–100 % Construction Detailed unit costs Low: −3 to – 10 %
High: +3 – +15 %

pressure in bars, N is the number of functional units, Fm is a factor for materials during the total operation of the plant are much higher. The
the material of construction. annual purchase for both vegetable oils are around 20 million $
The correlation proposed by Petley is not a grass-root investment (average value). In a period of 10 years these costs would increase up to
but rather only the cost of the processing facilities is considered. 200 million $ (10 year operation time and not considering inflation and
Additionally, the estimation is based on prices from 1988 and the lo- price variation over time) just for the vegetable oil in any case analyzed.
cation of the plant is different than the one assumed here. The corre-
lation was updated to current prices 2018 by taking consideration of the 3.1.4. Additional assumptions
inflation in 30 years. The inflation factor can be estimated with the The following assumptions were used in the simulation:
Chemical Engineering Plant Cost Indexes (CEPCI). These factors are
dimensional numbers used to bring up-to-date data from a different
period by considering inflation through time. The CEPCI for 1988 was
• Utility costs would be 10 % of the total cost of the raw materials (the
detailed energy demand is unknown at the moment)
342.5 and the CEPCI for 2018 is 603.1 (“Chemical Engineering Plant
• A total of 5 operators/shift and 5 shifts per day are needed
Cost Index”, 2019; Vatavuk, 2002). It has been estimated that the total
OSBL (Outside Battery Limits) investment is between 24–50 % of the
• The average labor cost of one operator is 60,000 $/y, giving a total
of 3.6 m $/y for the labor costs (LC). These costs are deterministic.
processing facilities (Peters et al., 2003). For this case study, it was
assumed that a factor of 40 % would be used. Additionally, it was as-
• Additionally, the following costs were determined using factors
o Operating supervision: 18 % of LC
sumed that the plant would be built in France and the appropriate re- o Laboratory charges: 18 % of LC
location factor was used. o Plant overhead: 60 % of LC
Bearing in mind the uncertainty of the original equation and the o Administration 20 % of LC
additional factors used, the final uncertainty of the method is further
increased. It has been stated that big projects are usually under-
• The following costs were determined based on the total capital costs
(TCC) and are therefore stochastic values:
estimated and under-budgeted and real cost estimations can be re- o Maintenance and repairs: 2 % of TCC
presented by a log-normal distribution (Hollmann, 2012). Therefore, in o Operating supplies: 1 % of TCC
the present analysis, it was assumed that capital investment had log- o Property taxes: 2 % of TCC
normal distribution and the following probabilities were used: P10, P90 o Insurance:2 % of TCC
values of −26 % and +118 % respectively.
The following assumptions were taken to estimate the capital cost of
• The following costs were determined based on the total product
sales (TPS)
the project: o Royalties: 3 % of TPS
o Distribution and selling: 10 % of TPS
• Number of steps: 15 • Research and development: 5 % of TPS
• Maximum temperature (Tmax ): 473.15 K • Waste treatment was not considered in the analysis
• Maximum pressure (Pmax ): 20 bar of Air, during the oxidative • The discount rate was assumed to be 10 %
cleavage step
• Tax rate equal to 35 %
• Desired output: 10,000 ton/year of azelaic acid (total capacity of the • The initial capital investment would be done in two years (year 0
plant is dependent on the oil type as seen in Table 5) and year 1) and 2/3 of the investment would be performed in the
• Fm: 1.5 first year (year 0 in the NPV) –This can be visualized on Fig. 7 (start
• Location Factor: 1.05 (Plant located in France) with decreasing the NPV)

Based on the previous information, the initial estimated cost of the

• The plant would achieve a 50 % capacity in year 2.75 % capacity in
year 3.90 % capacity in year 4 and full capacity in year 5.
processing facilities for the production plant that processes palm oil is
equal to 58 million $, which increases up to 81 million $ once the
4. Discussion
outside battery limits are considered. Contrary, the estimated cost of a
plant that uses high oleic sunflower oil is equal to 45 million $ and 63
4.1. Monte-carlo simulation
million $ with the outside battery limits. Additionally, once taken into
consideration the uncertainty of the estimation, the log-normal dis-
A Monte Carlo simulation was performed for both palm oil and high
tribution and the probabilities used, the average capital investment
oleic sunflower oil including the revenues and expenses previously
increases to 83 million $ for the high oleic sunflower plant and 106
described. A total of 3000 iterations1 were used to simulate the po-
million $ for the palm oil plant.
tential outcomes of the analysis.
The use of “higher” quality raw material with “better” composition
for the production of azelaic acid and pelargonic acid reduces the total
capital investment costs by more than 25 % (25 million $). 1
A higher number would assume much more processing time and similar
Nevertheless, it should be also considered that the price of raw conclusions would be obtained.

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

Fig. 7. Average Cumulative Cash Flow of the Monte Carlo Simulations.

Fig. 8. NPV Cumulative value. The slope of the curve at the inflexion point depends on the cumulated uncertainties (distributions of input data); and that’s where the
correlation matrix created helps to reduce the dispersion of the results (increase the slope).

The average cumulative cash flow of both vegetable oils is shown in selectivity (lower OPEX) and at the same time reduce the size of the
Fig. 7. The initial investment of palm oil is 25 % higher than the initial plant (lower CAPEX). This outcome could be used for future research
investment of high oleic sunflower oil. The main difference is due to the areas, in which the use of non-conventional processes could increase
amount of oil needed to process annually. In other words, in order to the economic success of the plant only if the selectivity of the process is
achieve the same yearly throughput of azelaic acid, the plant that increased. Additionally, if two vegetable oils have identical selectivity,
processes palm oil must have a capacity twice bigger compared to a it should not be assumed that the cheapest raw material would be the
plant that processes high oleic sunflower oil. The same outcome would best performing. A raw material with a higher price, but also with a
be expected if a higher selectivity would be achieved using other better fatty acid profile can lead to higher profits.
technologies (smaller capacity). Therefore, new processing technologies Other areas of technological improvement rely on the number of
could reduce the amount of raw materials needed by having a higher processing steps. In the scenario evaluated, it was assumed that a

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

transesterification reaction was needed before performing the scission the risks taken initially and so, the shorter the payback time the more
of the fatty acids. It would be more convenient from an investment and convincing is the investment on such a project. Additionally, the cu-
operational perspective, if the conversion of fatty acids into esters was mulative probability distribution of the NPV for both vegetable oils was
not performed and that the reaction would be carried out directly on generated, and it is shown in Fig. 8. There is 90 % probabilities of
the oil leading to the removal of several steps reducing though the making a better profit (NPV > 0) than IRR with high oleic sunflower oil
capital cost. Furthermore, fewer side-products of low value might be vs 85 % with palm oil under the current scenarios evaluated.
preferable. Lastly, a sensitivity analysis was performed to measure the impact of
Lower initial investment also reduces the payback time of the plant. uncertainty in each of the parameters analyzed. The sensitivity analysis
In the cases studied, a total of 7 years would be required to recover the is represented with a tornado plot and can be seen in Fig. 9. Through
investment using high oleic sunflower oil vs 8 years with palm oil the analysis, the lower 5 % and highest 95 % percentile of each of the
(Fig. 7). Even though on a period higher than 20 years, the cumulative values was evaluated.
cash flow of the palm oil might be higher than the high oleic sunflower The tornado plot (Fig. 9) clearly shows that the most impacting
oil-based. As the future is unpredictable, an investor takes into account variables are the azelaic acid and pelargonic acid. Moreover, capital

Fig. 9. Tornado plot for the production of azelaic from high oleic sunflower oil and palm oil.

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G.A. De Leon Izeppi, et al. Industrial Crops & Products 150 (2020) 112411

costs and vegetable oil had also a major impact on the uncertainty of Other alternatives, to improve the profitability and payback time of
NPV. In other words, in order to improve the NPV, the first focus should the project, could be retrofitting an old biodiesel plant to reduce the
be on increasing the production of azelaic acid and pelargonic acid by initial capital investment, or the purchase of FAMEs, to avoid the
improving selectivity. Additionally, the initial capital investment could transesterification step and reduce the number of processing steps (5
be reduced by improving efficiency with new processing technologies process units removed) and likewise the capital investment.
and/or using raw materials with a different fatty acid composition. In the cases studied here, although High Oleic Sunflower Oil was
Costs information in Supplementary data S1. about 50 % more expensive than Palm Oil, it leads to better economics.
For specialty chemicals, the fatty acid profile and the value generated
4.2. Process intensification and continuous manufacturing strategies by coproducts, has a high impact on the selection of the right feedstock
at the right price.
Process intensification (PI) is a growing trend in the chemical in-
dustry. Process intensification arose from the “drastic and improvement CRediT authorship contribution statement
of equipment and process efficiency” need without compromising the
desired output and still have a positive significant impact on the total Gerardo Antonio De Leon Izeppi: Formal analysis, Methodology,
plant capital and operating costs. For instance, ultrasound and micro- Writing - original draft. Jean-Luc Dubois: Conceptualization,
wave are considered as non-conventional sources of energy and fulfill Methodology, Software, Writing - review & editing, Supervision.
the requirements of these approaches (Gerven and Stankiewicz, 2009). Antonin Balle: Sofware, Visualization, Data curation, Formal analysis.
Ultrasound technology can be used in the oxidative cleavage process Ana Soutelo-Maria: Formal analysis, Investigation, Writing - original
to substantially enhance the rate of the chemical reactions and by this draft.
reducing the reaction time. By enhancing the rate of the main reaction,
the possibility of side-reactions, such as decarboxylation, is reduced and Declaration of Competing Interest
therefore the formation of co-products, such as octanoic acid should be
reduced as well. The achievement of higher monomer quality can be Currently Arkema is a producer of hydrogen peroxide. But Arkema
achieved resulting in the reduction of purification steps necessary in the is neither a producer of Azelaic acid nor Pelargonic acid which are the 2
conventional process. main products described in the publication, nor a producer of Palm oil
In the thermodynamic domain, microwaves can be key to replace and High Oleic Sunflower Oil, which are the feedstocks used in the case
conventional conduction-based heating “volumetric heating” not being studies.
limited by heat transfer surface or heat transfer coefficient (Stefanidis
et al., 2014). Acknowledgements
This type of analysis is the foundation to encourage the use of al-
ternatives technologies. Therefore, these types of analysis will give an The authors are grateful to Dr. Jean-Luc Couturier (Arkema, Centre
insight into whether there is room for non-conventional technologies de Recherche Rhône-Alpes, France) and Dr. Dirk Kirschneck
and where these technologies should focus on. Additionally, continuous (Microinnova Engineering GmbH, Austria) for the support provided
manufacturing offers better mass and heat transfers which can also during the working process.
have a positive impact on selectivity. Furthermore, continuous manu- This project has received funding from the European Union’s
facturing fully utilizes the equipment units. For example, dimensioning Horizon 2020 research and innovation program under the Marie
a batch reactor has to consider dosing the reactants, heating, cooling, Sklodowska-Curie grant agreement no.721290.
discharging, and cleaning. On the other hand, continuous manu-
facturing has dedicated equipment which can reduce reaction times and Appendix A. Supplementary data
the size of the plant.
Supplementary data associated with this article can be found, in the
5. Conclusion online version, at https://doi.org/10.1016/j.indcrop.2020.112411.

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