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Biochemical Engineering Journal 194 (2023) 108864

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Biochemical Engineering Journal


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

Food waste valorization applying the biorefinery concept in the Colombian


context: Pre-feasibility analysis of the organic kitchen food
waste processing
Mariana Ortiz-Sanchez, Juan Camilo Solarte-Toro, Carlos Ariel Cardona Alzate *
Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química, Universidad Nacional de Colombia sede Manizales, Caldas, Manizales Zip Code:
170003, Colombia

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

Keywords: Food waste has been profiled as a potential source of added-value products and energy vectors. Nevertheless, the
Food waste non-standard composition of food waste has been a bottleneck in proposing different biorefinery configurations.
Poly-lactic acid This paper aims to analyze organic kitchen food waste (OKFW) as a source of valuable products by applying the
Fermentable sugars
biorefinery concept. A compositional model was proposed considering seven food groups and the consumption
Process Design
Bioethanol
trends in Colombia. Biogas and fermentable sugars were produced experimentally. Sugars were considered as
Simulation feedstock for simulating two scenarios for producing bioethanol and polylactic acid. Finally, a techno-economic
assessment was done. As a result, the liquid hot water treatment increases the crystallinity index by 30%,
obtaining a fermentable sugar yield of 0.37 kg/kg of dry OKFW. The exhausted solid after saccharification
produced 0.42 m3 of biogas/kg of exhausted OKFW. Ethanol and polylactic acid yields were 0.14 kg/kg of dry
OKFW and 0.12 kg/kg of dry OKFW. Biogas use in cogeneration units can provide 13.49% and 4.29% of the total
plant energy demand. Sugars concentration and downstream processing were the highest energy-demanding
sections in the proposed scenarios. In conclusion, OKFW is a promising feedstock to produce added-value
products in Colombia. However, biorefineries should be optimized to be robust regardless of the OKFW
composition but considering the most representative fractions.

1. Introduction small-scale processes and household activities. According to the FAO,


Food Waste is a residue generated by retailers, food service providers,
Commercial, residential solid or semi-solid (household), and green and consumers links of the Food Value Chain [5]. The high variability in
waste produced at municipal level is denominated municipal solid waste the FW composition has raised several issues. In economic terms, FW
(MSW) [1]. The MSW composition differs according to the production represents economic losses at any stage of the food value
socio-economic and cultural context. However, the Food and Agricul­ chain [6]. In environmental terms, the degradation of these residues
ture Organization of the United Nations (FAO) has estimated a per capita contributes to the pollution of natural resources such as water, air, and
production rate of 0.3–0.74 kg of MSW/person/day worldwide [2]. In soil because of greenhouse gas emissions (e.g., CO2, CH4) and waste
2018, 292.4 million tons of MSW were reported worldwide [3]. Food streams with a high organic load (e.g., high chemical and biological
and green waste has the highest compositional share in the MSW oxygen demand) [7]. Finally, FW is related to social problems since the
composition and represent the 44% [4]. This fraction comes from FW production rate can be analyzed as an indirect indicator of the

Abbreviations: ABTS+, Cation-radical discoloration; C, Cereals; CapEx, Capital Expenditure; CEPCI, Chemical Engineering Plant Cost Index; CH4, Methane; CO2,
Carbon dioxide; DNP, National Planning Department; DNS, 3,5-dinitrosalicylic acid; DP, Dairy products; DPPH, α, α-Difenil-β-picrilhidracilo; FAO, Food and Agri­
culture Organization of the United Nations; FBGU, Fungal Beta Glucanase Units; FS, Fish and eggs; FV, Fruits and vegetables; FW, Food Waste; GAE, Gallic acid
equivalent; GF, Food Groups; H2S, Hydrogen sulfide; LHW, Liquid Hot Water pretreatment; MP, Meat products; MSW, Municipal solid waste; NPV, Net present value;
NRTL, Non-Random Two Liquid; O2, Oxygen; OCP, Oily crops and pulses; OpEx, Operational Expenditures; PLA, Polylactic acid; PMI, Process Mass Intensity index;
PolyNRTL, Poly-Non-Random Two Liquid; OKFW, Organic Kitchen Food Waste; RT, Roots and tubers; SnO, Tin(II) oxide; TPC, Total Phenolic Compounds; UASB,
Upflow anaerobic sludge blanket; VT, Volatile solids; XRD, X-ray diffraction.
* Correspondence to: Universidad Nacional de Colombia, Sede Manizales, Zip Code: 170003, Caldas, Manizales, Colombia.
E-mail addresses: mortizs@unal.edu.co (M. Ortiz-Sanchez), jcsolartet@unal.edu.co (J.C. Solarte-Toro), ccardonaal@unal.edu.co (C.A.C. Alzate).

https://doi.org/10.1016/j.bej.2023.108864
Received 4 October 2022; Received in revised form 7 February 2023; Accepted 19 February 2023
Available online 24 February 2023
1369-703X/© 2023 Published by Elsevier B.V.
M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

existing food inequality, food access, and production systems in­ yields, specific energy consumption, self-generation index) and eco­
efficiencies worldwide [8]. Several authors studied how to reduce the nomic metrics (e.g., net present value – NPV, payback period).
amount of FW produced by implementing governmental policies and
other valorization alternatives [9]. Nevertheless, these attempts to 2.1. Experimental procedures
reduce FW have not achieved the expected results since an integral effort
must be done to overcome technical, economic, environmental, and 2.1.1. Raw material: composition model of organic kitchen food waste
social bottlenecks [10]. Indeed, context-based policies and solutions A composition model was proposed to establish the OKFW constit­
should be proposed since FW generation causes are different in all uents. The FW composition model was proposed following a mathe­
countries and regions due to cultural aspects. matical expression involving seven Groups of Food (GF) proposed by
FW examples are Organic Kitchen Food Waste (OKFW) and any FAO [19] (Dairy products – DP, Fish and eggs – FS, Meat products – MP,
organic waste discarded in a supermarket (e.g., peel, seeds, ripened Fruits and vegetables – FV, Oily crops and pulses – OCP, Roots and tu­
fruits, vegetables, bones, blood, meat, and expired processed foods) bers – RT and Cereals – C). Eq. 1 presents the mathematic expression of
[11]. An annual OKFW production of 32 kg/person in Colombia has FW model:
been estimated. Traditional disposal methods are incineration and
landfill. Some alternatives that have been implemented to add value ∑
7
FW CompModel = ai GF i (1)
OKFW are the production of animal feed and composting. [12]. How­ i=1
ever, Colombian regulations do not allow the implementation of these
alternatives in large-scale facilities. The versatility of the OKFW chem­ The food groups share of the composition model was defined from
ical composition allows proposing pathways to obtain a portfolio of reports of government entities. The report of the National Planning
products from biotechnological, catalytic, and physical processes [13]. Department (DNP) on "Food loss and waste generated in Colombia" was
Trends for the recovery of OKFW are guided to the production of biogas, considered to define the share of the seven food groups [20]. Eq. 2 shows
ethanol, butanol, volatile fatty acids, and hydrogen [14]. Other valori­ the mathematical expression of the composition model with the share of
zation pathways, such as bacterial cellulose [15], 2, 3-butanediol [16], each food group:
and polylactic acid [17] have been addressed. However, the OKFW Model = 0%(DP) + 1%(FS) + 3%(MP) + 62%(FV) + 1%(OCP)
non-standardized OKFW chemical composition generates a disadvan­
tage in the production process since a quality control must be done for + 25%(RT) + 8%(C) (2)
the products (i.e., the process always needs to guarantee the quality and The most representative foods were defined according to the basic
quantity of the products). Therefore, designing robust processes with a family basket of Colombia for each group. From this, Databases reported
high technological readiness level is an option for the valorization of by government entities on consumption statistics (including imported
OKFW. On the other hand, the integral valorization of the raw material foods) were used [21]. Eqs. 3 to 8 present the foods of the basic family
must be considered to mitigate the issues related to the bad disposal of basket and the share considered for each group:
OKFW. Then, the biorefinery concept achieves to take advantage of the
raw material fractions to obtain different types of products seeking FS1% = 20%(fish bone) + 80%(egg shells) (3)
economic, environmental, and social pre-feasibility in any context [18].
MP3% = 50%(beef bone) + 45%(chicken bone) + 5%(meat waste) (4)
OKFW valorization proposals involving processes addressed to
generate products with high commercialization potential, such as bio­
FV 62% = 20%(tomato peel) + 16%(onion peel) + 10%(bean residues)
fuels and bioplastics, under the biorefinery concept are needed. How­
ever, few studies have focused on analyzing the economic pre-feasibility + 1%(pumpkin peel) + 4%(lettuce residues)
of OKFW to these products by considering experimental information and + 3%(cabbage residues) + 1%(beetroot peel)
simulation tools simultaneously. In this way, this study aims to evaluate
+ 1%(celery residues) + 10%(citric peel and seed)
the techno-economic prefeasibility of two biorefineries scenarios
addressed to produce ethanol, polylactic acid, and biogas as main + 5%(banana peel) + 5%(mango peel and seed)
products. The prefeasibility analysis was based on experimental data + 5%(guava seeds) + 5%(tree tomato peel and pulp)
such as chemical composition, total and volatile solids content, raw + 4%(spent blackberry pulp)
material pretreatment, enzymatic hydrolysis, and biogas production.
These data were used as input in the simulation and analysis of the + 3%(passion fruit peel and pulp) + 1%(strawberry residues)
proposed biorefineries. + 3%(avocado peel and seed) + 1%(papaya peel and seed)
+ 1%(apple residues) + 1%(lulo peel and pulp)
2. Methodology (5)

The techno-economic assessment of the OKFW-based biorefineries OCP1% = 100%(used vegetable oil) (6)
was done following three steps. The first step involved experimental
procedures. Then, the raw material (i.e., OKFW) was characterized to RT 25% = 60%(patato peel) + 30%(cassava peel) + 10%(carrot peel) (7)
determine the cellulose, hemicellulose, lignin, extractives, ash, starch,
and moisture content based on standard methods reported in the open C8% = 100%(rice) (8)
literature. Then, the fermentable sugars and biogas production was
carried out at laboratory scale. Liquid Hot Water (LHW) pretreatment 2.1.2. Raw material conditioning
was performed to assess the effect on fermentable sugars and biogas The OKFW composition was handmade in the laboratory based on
production yields. The second step was related to the design of two the composition model. Thus, the raw material (OKFW) was not sub­
biorefineries. The first process is addressed to produce ethanol and jected to a decomposition process in a kitchen for days, avoiding mi­
biogas, while the second process is addressed to produce polylactic acid croorganisms contamination and degradation. Instead, the OKFW was
and biogas. Experimental yields, kinetic models, and open literature dried in an electric oven at 40 ◦ C overnight until reaching a constant
information were used as input data to simulate the biorefineries in moisture content (< 10%). An electric oven was employed to avoid
Aspen Plus v9.0 and calculate the mass and energy balances. The third contact between the OKFW samples and circulating air to minimize
step was guided to assess the techno-economic performance of the sample contamination. The moisture content was controlled by using a
proposed biorefineries by estimating mass and energy indicators (e.g., Shimadzu Moisture Balance MOC-120 H. Then, the samples were milled

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M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

to a particle size of 0.42 mm (i.e., 40 ASTM Mesh) in a blade mill (Gy­ 2.1.6. Biogas production
ratory mill SR200 Gusseisen, Redsch GmbH, Germany). Finally, the Biogas production was performed after the pretreatment and enzy­
samples were stored until use in a vacuum bag. The above-described matic hydrolysis procedure. The standard VDI 4630 was used to eval­
process was done to avoid possible raw material decomposition by uate the biogas production potential [35]. This assay considered an
microorganism action, components ripening, and oxidation. Then, the inoculum-to-substrate ratio of 0.4 on a volatile solids basis in a batch
OKFW chemical composition change over time was not considered in process. The sludge from an upflow anaerobic sludge blanket (UASB)
this study. reactor was used as inoculum in the biogas production assays. The
sludge was acquired in a wastewater treatment plant of a coffee pro­
2.1.3. Chemical characterization cessing company located in Chinchiná, Caldas (4◦ 59′ 21.555′′ N and 75◦
The OKFW samples were analyzed in terms of chemical composition 36′ 31.716′′ W). The anaerobic digestion assay involved micronutrients
(extractives, cellulose, hemicellulose, lignin, pectin, fats, starch, and and macronutrients to ensure biogas production (see dosage in Table 1).
ash), and total and volatile solids. For the OKFW chemical composition, The composition of these solutions are presented in Table 1 [36]. Biogas
the extractives content was determined in water and ethanol [22]. The production was done by triplicate. Gas production was measured by the
cellulose and hemicellulose contents were determined by implementing volumetric displacement method [37]. Water was used to measure the
the chlorination method reported by Rowell et al., [23]. Kraft lignin was biogas volume. Water was changed daily to avoid carbon dioxide solu­
found following the TAPPI-T-222 om-02 [24]. The total pectin content bilization and inaccurate data registration. Biogas composition (carbon
was found by applying the method reported by Yu et al. [25], [24]. The dioxide (CO2), methane (CH4), oxygen (O2), and hydrogen sulfide (H2S))
fat content was quantified by Soxhlet extraction with n-hexane for 24 h was recorded using a portable gas analyzer (Gasboard-3200 L). The
[26]. The starch content was calculated by precipitation with barium biogas production yields were reported considering as normal condi­
hydroxide according to Von Asboth [27]. Finally, the ash content was tions (i.e., T = 273.15 K and P = 1 atm).
estimated by applying the NREL/TP-510–42622 standard [28]. Total
and volatile solids were measured following the ASTM E1756–08 and 2.2. OKFW-based biorefineries: design, simulation and evaluation
2540 G standard method.
In accordance with the aim of this study, two biorefineries were
2.1.4. Liquid hot water (LHW) pretreatment proposed to evaluate alternative pathways to upgrade OKFW from a
Dried and grounded raw material was pretreated with hot water in a techno-economic point of view. The conceptual design of the bio­
shaker incubator (Binder BD 115, SK-O330). The operating conditions refineries was done based on the hierarchy, sequencing, and integration
were solid-liquid ratio 1:10, 80 ◦ C, 200 rpm for 2 h. The effective vol­ concepts. Then, the simulation of the proposed biorefineries was
ume of the pretreatment process was 300 mL. The pretreatment mixture executed using experimental results and kinetics from previous assays
was vacuum filtered to separate liquid and solid fractions. The liquid and the open literature. Finally, the technical and economic assessment
fraction was characterized in terms of fermentable sugars, total phenolic was done by estimating mass, energy, and economic indicators.
compounds (TPC), and total antioxidant activity (TAA). The 3,5-dinitro­
salicylic acid (DNS) method was used to determine the fermentable 2.2.1. Conceptual design and processes description
sugar content, TPC was measured with the Singleton Folin-Ciocalteu Biorefineries simulation using OKFW as raw material was performed
colorimetric method [23] with modifications [29]. TAA was deter­ using experimental results from the LHW pretreatment, enzymatic hy­
mined using the DPPH ((2,2-diphenyl-1-picrylhydrazyl) discoloration drolysis, and biogas production. After these stages, the liquid fraction
method. DPPH was performed by the method described by Marinova resulting of the saccharification process was used to produce ethanol
et al. [30], Molyneux et al. [31], and Brand-Williams et al. [32]. On the and polylactic acid. These products were proposed as alternatives to
other hand, the solid fraction was dried and weighted to estimate the non-renewable plastics and fossil fuels, respectively. The first bio­
solid gravimetric recovery (i.e., the ratio between the weight of the refinery produces ethanol and biogas (scenario 1). The first biorefinery
pretreated solid and the initial weight of the sample). In addition, the is composed of five areas (i) raw materials storage, (ii) raw materials
crystallinity index was measured from x-ray diffraction (XRD) before conditioning, (iii) enzymatic hydrolysis, (iv) ethanol production, and (v)
and after the pretreatment stage. The equipment used was a RIGAKU biogas production (see Fig. 1). Meanwhile, the second biorefinery pro­
MINIFLEX II diffractometer with monochromatic Cu-Kα radiation. Segal duces polylactic acid and biogas (scenario 2). This biorefinery is
et al. [33] defined the operating conditions to determine the crystallinity composed of six areas (i) raw materials storage, (ii) raw material con­
index. ditioning, (iii) enzymatic hydrolysis, (iv) lactic acid production, (v)
polylactic acid production, and (vi) biogas production (see Fig. 2).
2.1.5. Enzymatic hydrolysis OKFW conditioning is carried out by cutting the raw material using a
After LHW pretreatment, the OKFW enzymatic hydrolysis was car­ double-shaft shredder machine. Then, OKFW is dried to ensure a mois­
ried out with the remaining solid. A commercial enzyme cocktail (Vis­ ture content of less than 10% in an industrial dryer at 65 ◦ C. Afterward,
cozyme L, Novozymes) was used to hydrolyze cellulose, hemicellulose, the raw material is grounded to standardize the particle size throughout
and pectin. The enzyme activity of the cocktail was 100 FBG/g (Fungal
Beta-Glucanase). The saccharification process was performed in a Table 1
500 mL Erlenmeyer flask. The effective reaction volume of the enzy­ Macro and micronutrients considered in the digestion.
matic hydrolysis process was 250 mL. The operating conditions were pH Macronutrients (3 mL Amount Micronutrients (0.1 mL per Amount
3.5 with 0.05 M sodium citrate buffer, 55 ◦ C, solid-liquid ratio 1:20 w/v, per 100 mL of (g/L) 100 mL of digestion) (g/L)
enzyme concentration of 0.08 mL/g of dry raw material, and 150 rpm. digestion)
These operating conditions were established as reported by Molina- Ammonium chloride 34 Iron(II) chloride tetrahydrate 2.00
Peñate et al. [34]. The enzymatic hydrolysis was executed for 72 h to Zinc chloride 0.05
guarantee carbohydrate depolymerization. Enzymatic hydrolysis pro­ Ammonium molybdate 0.05
cess was done in triplicate. Solid and liquid fractions were separated Sodium chloride 10 Ethylenediaminetetraacetic 0.50
acid
through vacuum filtration. Exhausted solid samples were used to mea­ Aluminum chloride 0.05
sure the crystallinity index, total solids, and volatile solids after the Magnesium chloride 10 Cobalt(II) chloride hexahydrate 0.05
enzymatic hydrolysis process. hexahydrate Boric acid 0.05
Calcium chloride 5 Hydrochloric acid 1 mL
dihydrate Yeast extract 1.00

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M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

Fig. 1. The flow block diagram of ethanol production (scenario 1).

Fig. 2. The flow block diagram of polylactic acid production (scenario 2).

the process. The pretreatment stage consists of feeding the raw material hand, the pretreated solid is sent to the saccharification stage. The
to a jacketed and agitated tank. The operating conditions are the same as OKFW enzymatic hydrolysis is carried out in an agitated jacketed tank.
defined in the experimental section. Then, the liquor is filtered. The Sodium citrate buffer is previously prepared and stored in a tank. The
liquid fraction is concentrated in a flash at 60 ◦ C and 0.8 bar to obtain operating conditions are those mentioned in the experimental section (i.
liquor rich in polyphenols (60% phenolic compounds). On the other e., temperature, enzyme loading, and solid to liquid ratio). The

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M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

saccharification residence time will be set according to the experimental and Seavey et al. [41] were considered for the lactic acid and polylactic
results to avoid oversizing the required equipment in this section. Then, acid production, respectively.
a temperature increase is done in the same tank to denature the enzyme.
The enzymatic hydrolysis mixture is filtered. The liquid phase is fed to 2.2.3. Techno-economic assessment of biorefineries
the ethanol or lactic acid production areas. The solid is fed to the The technical evaluation of biorefineries scenarios was based on
anaerobic digestion area. At the beginning of the anaerobic digestion mass and energy indicators. The mass indicators evaluated were the
process, the inoculum is added to start the biogas production process. product yield and process mass intensity index (PMI) described by Ruiz-
Then, no more inoculum is added since the anaerobic digester can Mercado [42]. The product yield is the ratio between the output product
degrade new organic feedstocks (i.e., the consortium of microorganisms flow and the input raw material flow (i.e., ethanol, polylactic acid,
is adapted to the operating conditions and substrate). Biogas production biogas, and OKFW). The process mass intensity index is the ratio be­
uses a jacketed and stirred bioreactor to maintain mesophilic conditions. tween the total raw materials input flow (i.e., OKFW, water, enzymes,
The residence time was defined according to the experimental tests. dodecanol, etc.) and the total product output flow (i.e., ethanol, poly­
Next, moisture is removed from biogas using a chiller. Instead, the lactic acid, biogas). These indicators are estimated to calculate how
digestate is dried to ensure a moisture content of less than 50% for much the raw material is upgraded to the desired products. The energy
obtaining a secondary product (i.e., fertilizer). indicators considered were the overall energy efficiency and
Ethanol production used Zymomonas mobilis to upgrade C6 sugars. self-generation index. The overall energy efficiency is the ratio between
The fermentable sugars concentration was increased up to 130 g/L. The the heating, cooling, and energy content of the output streams and the
operating conditions are 33 ◦ C and 30 h. The liquor is autoclaved and total mass input flow. Finally, the self-generation index is the ratio be­
filtered. The liquid fraction is fed to a distillation unit. The first distil­ tween the energy produced by the combustion of an energy vector (i.e.,
lation column obtains a concentration between 50% and 55% w/w of biogas) in a cogeneration unit and the heating and cooling process
ethanol. In the second column, the azeotropic point is reached (95.6% requirements.
w/w). Then, the mixture is dehydrated in a molecular sieves unit until The economic evaluation of the proposed biorefineries was achieved
reaching a concentration of 99.7%. On the other hand, polylactic acid by considering a detailed economic assessment [43]. This assessment
production begins by obtaining lactic acid by sugars fermentation with considers the basic conceptual design and aspects of detailed engineer­
Lactobacillus casei and subsequent catalytic upgrading with SnO. First, ing to improve the Capital Expenditures (CapEx) estimation for
the fermentable sugars concentration was increased up to 110 g/L. decreasing uncertainty. This analysis was done in US dollars, the project
Fermentation conditions are 42 ◦ C and 48 h. The fermentable sugars life was fixed at 20 years, and the economic context of Colombia was
conversion is 80%. Next, the separation and purification of lactic acid considered. The tax rate and interest rate were 35% and 9.4%, respec­
are carried out by precipitation with calcium hydroxide (90 ◦ C). The tively. The straight-line depreciation method was applied. The salvage
solution is filtered, mixed with sulfuric acid, and filtered again to value was 0%. The equipment costs were determined using the software
remove calcium sulfate and impurities. The lactic acid liquor is sent to a Aspen Process Economic Analyzer v.9.0. The baseline year to perform
liquid-liquid extraction column fed with dodecanol to remove other the equipment costs was 2015 (CEPCI2015 = 557). Then, the Chemical
impurities. Lactic acid is fed to a distillation column until reaching a Engineering Plant Cost Index (CEPCI) was used to bring equipment cost
concentration of 80% w/w. The purified lactic acid is fed to an oligo­ to current cost (CEPCI2021: 708). The estimation of the raw materials,
merization reactor to generate low molecular weight polylactic acid. operating, utility, general, and administrative costs was done using
The vapors generated in the reactor are fed to a distillation column to methods explained by Sinnott and Towler (i.e., maintenance 6%, fixed
separate the non-reacting lactic acid. Afterward, this stream is sent to charges 3%, plant overhead 1.5% and general administrative costs 0.6%
the oligomerization reactor. The catalyst used in this reactor is tin oxide of the fixed capital cost) [44]. The raw material price, utility costs, labor
(SnO). The operating conditions are 0.53 bar and 60 ◦ C. Then, the liquor costs, and product price costs were calculated based on the market price.
is fed to a reactor to produce lactide at 200 ◦ C and 1 bar. Lactide is 8000 h of work was considered in the year. Three shifts per day was
purified in two vacuum distillation columns and sent to the polymeri­ considered in the plant to guarantee a continuous operation. In the case
zation reactor. Waster and non-reacting lactic acid are removed in the of the biogas production unit, the price of the inoculum was assumed as
first and second distillation columns, respectively. The polymerization the cost of transportation. Indeed, the assumed cost was 0.2 USD/ton of
reactor operates at 200 ◦ C and 1 bar. Finally, the polylactic acid pro­ anaerobic sludge supplied by a wastewater treatment plant located at a
duced is separated on a filter. 20 km of distance. In the anaerobic digestion process, the inoculum must
be supplied for the first six months of running the plant [44]. In this
2.2.2. Simulation procedure period, the anaerobic digestion process stabilizes and the inoculum
The simulation of the proposed biorefineries was done using the autogenerates. For this reason, the cost of inoculum is considered only
Aspen Plus V.9.0 software (Aspen Technology, Inc., Houston, USA). The for this time period. Operational Expenditures (OpEx) was defined with
processing scale for the two biorefinery scenarios was 44.5 ton/h of annual operation, utility, raw materials, and maintenance costs, while
OKFW (corresponding to 1% of the FW generated in Colombia). The the Capital Expenditures (CaPex) was defined considering the total
simulations were done using the Non-Random Two Liquids (NRTL) and capital investment for each area of the proposed biorefineries.
Hayden-O′ Connell equation of state (EoS) to model the liquid and vapor
phases in the simulation. In the case of the polylactic acid simulation, 3. Results and discussion
the PolyNRTL was used to model the polymerization reactions. The
thermodynamic properties reported by the National Research Energy 3.1. Experimental results
Laboratory (NREL) were used to introduce components such as cellu­
lose, hemicellulose, starch, lignin, enzymes, and microorganisms. OKFW is composed of organic fractions such as carbohydrates, pro­
Properties such as free energy of formation (DGSFRM) and enthalpy of teins, fibers (i.e., cellulose, hemicellulose, and lignin), lipids, and traces
combustion (HCOM) were estimated based on the correlation reported of inorganic components such as ash [45]. The OKFW composition de­
by Peduzzi et al., [38] OKFW conditioning, LHW pretreatment, enzy­ pends on the origin and consumption trends. Nevertheless, similarities
matic hydrolysis, and biogas production were simulated based on can be found in the open literature. the OKFW chemical characterization
experimental results. Then, RYield and RStoic aspen models were used results obtained in this work are compared with other reports in the
to find mass and energy balances. Ethanol production was simulated open literature (see Table 2). The values provided in Table 2 are on dry
considering the aspen models and kinetics reported by Quintero et al. basis. Cellulose and starch are the main compounds in OKFW samples
[39]. On the other hand, the kinetic model reported by Lin et al. [40] (about 45% of raw material on a dry basis). These results demonstrate

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Table 2 Table 3
OKFW chemical composition based on the proposed composition model and Experimental results of the LHW pretreatment, saccharification, and anaerobic
comparison with other literature reports. digestion of OKFW.
Item This Dinner shop Kitchen Organic Liquid Hot Water Pretreatment
work food waste waste [49] municipal solid
Item Units Value
(%) [48] waste [50]
Solid gravimetric recovery % w/w 57.02
Moisture 83.15 75.90 80.30 N.R.
± 4.7
Extractives* 20.92 42.30 59.80 56.20
Fermentable sugar g/L 0.59
± 0.65
concentration ± 0.05
Starch* 25.77 7.06 N.R. N.R.
TPC mg GAE/g of raw OKFW 133
± 0.34
± 14.57
Cellulose* 19.71 10.26 N.R. 46.30
DPPH mMTrox/g of raw OKFW 8
± 2.67
EC50/mL 5
Hemicellulose 5.12 36.50
Crystallinity index before % 58.3
* ± 0.29
pretreatment
Lignin* 13.69 0.80 N.R.
Crystallinity index after % 17.5
± 0.34
pretreatment
Fats* 6.34 3.10 15.70 15.60
Enzymatic hydrolysis
± 0.40
Item Units Value
Protein* N.A. 3.90 21.80 N.R.
Solid gravimetric recovery % w/w 40.96
Pectin* 5.23 N.R. N.R. 4.30
± 2.01
± 0.57
Yield g fermentable sugar/g of 0.65
Ash* 3.23 1.25 1.90 1.90
pretreated OKFW ± 0.04
± 0.03
Concentration g fermentable sugars/L 64.23 g/L
* Crystallinity index after % 12.13
Values given on a dry basis. N.A.: No Applied; N.R.: No reported
saccharfication
Biogas production
the OKFW potential to obtain high-value products and energy vectors Item Units Value
since these components can produce the C6 sugars platform. Caldeira Total solids of OKFW g/100 g of exhausted* OKFW 21.67
et al. [46] defines possible valorization pathways for obtaining enzymes, ± 0.29
Volatile solids of OKFW g/100 g of exhausted* OKFW 20.54
polyunsaturated fatty acids, collagen, bioactive compounds, polymers,
± 0.32
and proteins. Pour et al. [47] analyzed different transformation routes Total solids of sludge g/100 g of sludge 4.70
(e.g., thermochemical, chemical, and biotechnological) of FW for pro­ ± 0.57
ducing different energy vectors such as syngas, bio-oil, biochar, bio­ Volatile solids of sludge g/100 g of sludge 4.23
diesel, and biogas. The OKFW extractives content was 20.92% on a dry ± 0.53
Time Days 17
basis. This raw material fraction contains compounds such as soluble
Biogas volume produced mL/80 mL of digestion 147 ± 1.65
sugars, resins, tannins, pigments, and phenolic compounds. Biogas yield Nm3/kg of VS of exhausted 0.41
The chemical composition obtained in this work is similar to those OKFW ± 0.12
presented in Table 2. However, FW is characterized and studied based Methane content % 56.31
± 2.36
on a specific waste generated in a particular sector (e.g., kitchen, dinner
Carbon dioxide content % 43.69
shop, or canteen) and location (e.g., restaurants). The high variation of ± 1.59
the FW residues is the most important limiting factor for a global Hydrogen sulfide content ppm 58 ± 1.98
valuation of FW since process design is based on raw material compo­ *
Exhausted OKFW: remaining solid after the pretreatment and enzymatic
sition. For this reason, proposing a composition model that fits the food
hydrolysis process.
consumption trends of a region would allow defining contextualized
transformation routes since the uncertainty grade of the FW chemical
pretreatment liquor in terms of antioxidant capacity resulted in 5 EC50/
composition will be decreased. In terms of moisture, the OKFW ranges
mL and 8 mMTrox/g of dry OKFW. Like the TPC, the antioxidant ca­
between of 60–80%. The extracts content is between 35% and 60%. The
pacity proves the potential of the OKFW extracts to be valued [56]. The
starch content is between 7% and 40%. On the other hand, the fiber
crystallinity index of the sample before and after the pretreatment stage
content (cellulose, hemicellulose, and lignin) is between 20% and 60%.
was 17.5% and 58.3%, respectively. Several studies have reported a high
The complete characterization of OKFW allows for elucidating the
content of bioactive compounds present in FW from fruits and vegeta­
transformation routes, potential raw material fractions, and possible
bles [57]. Nevertheless, the applications of OKFW extracts are limited
products portfolio. The physical conversion for OKFW involves using
due to the raw material origin (e.g., antioxidants from OKFW can have
pectin, flavonoid, starch, and fats [51]. The products obtained can be
resistance as food additives from consumers). An alternative is to use
represented in food and organic molecules [52]. Biotechnological con­
these bioactive compounds in thermosetting plastics and biomaterials
version is related to all fermentations, and saccharification routes [53].
[58]. Regarding the crystallinity index, the cellulose crystalline struc­
Cellulose, hemicellulose, starch, and pectin fractions are used in OKFW
ture makes raw material conversion difficult for added-value products
[54]. For these, the products type to be obtained are food, organic
obtaining [59]. Cellulose limits the conversion of OKFW since this raw
molecules, biofuels, and biomaterials [55].
material has higher amounts of this structural polymer than hemicel­
Table 3 reports the experimental results of the pretreatment, enzy­
lulose, and lignin. This statement is because glucan in hemicellulose is
matic hydrolysis, and anaerobic digestion.
an amorphous polymer. In this sense, an increase in the crystallinity
The solid gravimetric recovery of the LHW process was 57.02
index after a pretreatment evidences the high removal of amorphous
± 4.7% w/w. Then, almost 50% of the initial raw material was degraded
glucan fraction. Then, the pretreatment process has a high effect on the
to soluble components (e.g., sugars, and phenolic compounds). The
OKFW matrix.
fermentable sugars concentration in the LHW hydrolysate was 0.59
The solid gravimetric recovery of the saccharification process was
± 0.05 g/L. Then, a fermentable sugars productivity of 0.29 g of
40.96 ± 2.01% w/w. The fermentable sugars concentration reached was
fermentable sugars/L/h was obtained. On the other hand, TPC was 133
64.08 g/L after 72 h. The global enzymatic hydrolysis yield was 0.65
± 14.57 mg GAE/g of dry raw OKFW. This result demonstrates the
± 0.04 g of fermentable sugar/g of dry OKFW. The saccharification
presence of phenolic compounds in the liquor. Characterization of the
process concluded at 30 h since the fermentable sugars concentration

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M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

did not vary more than 10% after this time. Then, a productivity of 3.2. Technical indicators
2.14 g of fermentable sugars/L/h was obtained. Molina-Peñate et al.
[34] reported a fermentable sugar yield of 0.37 g/g of OKFW without Mass indicators were estimated based on the mass balances of the
raw material pretreatment using the same operating conditions. proposed biorefinery configurations. The first assessed indicator was the
Therefore, the LHW pretreatment increases the fermentable sugars yield product yield. Ethanol production yield was 0.14 kg ethanol/kg of dry
after enzymatic hydrolysis. OKFW. On the other hand, PLA production yield was 0.12 kg PLA/kg of
On the other hand, Taheri et al. [60] analyzed the influence of pre­ dry OKFW. Then, the PLA production yield was lower than in the case of
treatments different (e.g., hydrothermolysis, sonolysis, electrochemical ethanol. This difference between the product yields can be explained
oxidation, sono-electrochemical oxidation, and solid-liquid fat extrac­ considering the conversion pathways of each bioproduct. Indeed, sugars
tion) on the production of fermentable sugars, obtaining the extraction conversion to ethanol have a maximum conversion yield of 0.51 kg/kg
of fats with hexane as the best pretreatment before enzymatic hydroly­ glucose (i.e., theoretical value). Nevertheless, total glucose conversion is
sis. In addition, the hydrothermolysis pretreatment showed lower yields not reached in the fermentation process since different restrictions
than the control assay (raw material without pretreatment). This related sugars conversion are present. The maximum sugars conversion
behavior is because the hydrothermolysis pretreatment (high pressure to ethanol was 0.42 kg/kg glucose (i.e., a conversion efficiency of 82%).
and high temperature <120 ◦ C) does not effectively disrupt the cellu­ Another contributing factor the ethanol production yield is related to the
lose, hemicellulose, and lignin structure of the raw material [61]. ethanol recovery from the fermentation broth. This recovery was 90%,
However, the high yields obtained in this work are attributed to the use losing 10% of the product in waste streams of the stripping and rectifi­
of the enzyme cocktail with the potential to degrade cellulose, hemi­ cation columns. On the other hand, the PLA production process involves
cellulose, and other structural carbohydrates (pectin). Additionally, the the lactic acid production, purification, and polymerization stages.
LHW pretreatment allowed obtaining a high removal of the amorphous Glucose conversion for producing lactic acid is higher than the conver­
fraction of the raw material, leaving the biomass more accessible to sion reported for producing ethanol. The lactic acid yield is 0.80 kg/kg
enzymatic attack. These results have the same trend as reported by of glucose [40]. Then, more lactic acid is produced using the same initial
Mahmoodi et [62] and Hafid et al. [63]. The crystallinity index of the concentration of fermentable sugars. Nevertheless, the lactic acid re­
exhausted solid after the saccharification stage was 12.13%. Then, most covery is poor compared with the ethanol recovery from the fermenta­
of the amorphous fraction of OKFW has been removed. tion broth. Indeed, 55% of the lactic acid is recovered in the simulation
The total and volatile solids content of exhausted OKFW (i.e., after since there are several product losses during the precipitation, solubi­
pretreatment and enzymatic hydrolysis) were 21.67 ± 0.29 g/100 g of lization, and distillation steps [68]. All these processing stages are
raw material and 20.54 ± 0.32 g/100 g of raw material, respectively required since the PLA production process cannot be performed if a high
(see Table 3). The total and volatile solids content of the sludge was impurities concentration is present in the lactic acid stream. The PLA
4.70 ± 0.57 g/100 g of sludge and 4.23 g/100 g of sludge, respectively. production process has a high conversion and purification performance.
The volume of the anaerobic fermentation was 80 mL. Fig. 3 shows the The PLA yield after the simulation procedure was 0.75 kg/kg of lactic
biogas production in 17 days of fermentation. The cumulative biogas acid.
curve was stopped since low volumes of biogas were registered daily at Ethanol production seems to be the best alternative from the mass
the end of the process. Therefore, most of the raw material was digested. performance point of view since more amount of product is obtained
The volume of biogas produced was 147 mL. The biogas yield was 0.42 after OKFW processing. Nevertheless, several aspects must be consid­
Nm3/kg of VS exhausted OKFW with methane, carbon dioxide, and ered before proposing ethanol production as an alternative to upgrade
hydrogen sulfide content of 56.31%, 43.69%, and 58 ppm, respectively. OKFW in Colombia. For instance, ethanol production is restricted to
The content of fruits and vegetables present in the FW provides a sugar mills. Instead, PLA production is a most feasible option since large
high content of nutrients (i.e., vitamins, minerals, etc.), improving amounts of raw material are available and production is not restricted
methane production performance [64]. The results obtained in this work by the government. Regarding to the biogas yield, this value was the
after the previous stages are similar to those reported in the literature same obtained in the experimental section since the experimental data
[65]. Zhang et al. [66] report results of 0.435 Nm3/kg of VS of FW from was used to perform the simulations. Then, a biogas production yield of
San Francisco with a methane content of 73%. In this study, the con­ 0.42 m3/kg of OKFW was obtained (i.e., a yield of 0.38 kg biogas/kg of
ditioning of the raw material was grinding, and the digestion time was dry OKFW). The global yield of the first biorefinery (i.e., ethanol +
less than 10 days. This indicates that the previous stages analyzed in this biogas) was 0.52 kg of products/kg of dry OKFW. Meanwhile, the total
work (including enzymatic hydrolysis) manage to increase the expected yield of the second biorefinery (PLA + biogas) was 0.50 kg of product/
biogas yield. In this sense, these stages manage to solubilize the residual kg of dry OKFW. Finally, the production capacity of the proposed bio­
fractions of the raw material (mainly protein). Scherzinger et al. [67] refineries were 1329 m3/day of ethanol and 900 kg/day of PLA.
report that FW pretreatment plays a dominant role in anaerobic diges­ The process mass intensity (PMI) index was estimated for the both
tion processes as it breaks down the cellular structure of foods by sol­ biorefineries. This index is defined as the required raw material mass to
ubilizing the organic fraction. produce 1 kg of products [44]. The first biorefinery gives a PMI index of
11.48 kg of raw materials/kg of product (i.e., ethanol), while the second
biorefinery gives a PMI value of 14.12 kg of raw materials/kg of product
(i.e., polylactic acid). These values were estimated avoiding the process
water consumption in both processes as stated by Tobiszewski et al.,
[69]. Then, the raw materials involved to make this estimation were the
mass flow of OKFW and supplies (e.g., sludge, enzymes, solvents). The
PMI must tend to 1 to consider a process with a high mass efficiency (i.e.,
raw materials are upgraded into the desired products avoiding waste
stream generation). The calculated PMI values agree with the reported
values for chemical processes (i.e., PMI < 30) since bulk chemicals
production have a relative low mass efficiency. These results suggest
that the second process (i.e., polylactic acid production) involves more
inputs (e.g., sulfuric acid, dodecanol, calcium hydroxide). Then, the first
biorefinery has a better mass performance.
Fig. 3. Biogas production of OKFW. The energy performance evaluation was done by considering the

7
M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

specific energy consumption and self-generation index as indicators. The g., solvents, acids, bases, catalysts) to produce the desired product.
second biorefinery (i.e., PLA production) has a higher energy con­ Moreover, process conditions affect the OpEx due to power and thermal
sumption than the first biorefinery (i.e., ethanol production). Indeed, the requirements depends on the operating conditions and equipment
specific energy consumption of the second biorefinery was 411.76 GJ/ number. Indeed, the CapEx in the polylactic acid production stage is less
ton of OKFW. Meanwhile, the specific energy consumption of the first than in the lactic acid stage (approximately 38% less).
process was 131.16 GJ/ton of OKFW. The high energy consumption of For scenario 1, the minimum processing scale for economic viability
the second biorefinery is attributed to the high number of operations is 30.5 ton/h (NPV of 20 years). On the other hand, the minimum scale
required to produce the desired product (i.e., lactic acid production, for scenario 2 was 10.5 ton/h. At the lower scales, the two biorefinery
lactic acid recovery, lactide production, PLA production and recovery). scenarios do not present economic viability (see, Fig. 4(a)). The payback
Moreover, the PLA production process has a high energy demand since period presents a decreasing trend as the processing scale increases in
several vacuum operations are performed. On the other hand, the first both scenarios. In scenario 2, the payback period for the analyzed scales
process obtained a lower specific energy consumption since few unit is earlier than scenario 1. This behavior is attributed to the differences in
operations are involved compared with the second biorefinery. The the market price of the products. These results are favorable in the
specific energy consumption was estimated considering the sugars Colombian context using 10% of the OKFW generated in the country
concentration in the two proposed scenarios. Sugars concentration has a (base case). In fact, the other processing scales analyzed (higher than the
high influence on the final results since a lot of energy is required for base case) cover up to 35% of the generation of OKFW in the country.
water evaporation. Indeed, the sugars concentration step contributes
35.67% and 21.05% of the total energy consumption, respectively. 4. Conclusion
These results are similar to those reported by Quintero et al., [70]. These
authors evaluated the influence of the sugars concentration on the Organic Kitchen Food Waste (OKFW) is a promising raw material for
ethanol production process. As results, more than 40% of the total en­ obtaining fermentable sugars and biogas since experimental yields of
ergy demand was contributed by this process. Regarding the 0.37 kg/kg of dry OKFW on dry basis and 0.42 m3/kg of OKFW on dry
self-generation index, biogas production can be used as an energy vec­ basis were obtained. This feedstock contains structural polymers such as
tor. Indeed, biogas could provide 13.51% and 4.29% of the total energy starch, pectin, cellulose, hemicellulose, and lignin that increases
demand of the proposed biorefineries after cogeneration. Then, external fermentable sugars yields and promoted a fast biogas production in
energy sources (i.e., fossil fuels) are required. anaerobic digestion. Liquid hot water treatment improves enzymatic
digestibility since the crystallinity index of the raw material after pre­
3.3. Economic results treatment was higher. Nevertheless, efforts to disrupt glucan-based
oligomers are needed to increase fermentable sugars production in
The economic analysis of the two scenarios was performed by this stage. OKFW has several advantages respect to other biomass
changing the processing scale. Fig. 4 shows the results of the economic sources such as defined logistics, availability, and productivity. Never­
analysis of the two OKFW-based biorefineries. theless, the chemical composition standardization limits the use of
In the ethanol and polylactic acid production scenarios, the proposed OKFW. Then, new strategies to solve this issue should be proposed, but
processing scale (i.e., 44.5 ton/day) presents economic feasibility at 16 based on models covering the gastronomic culture of each country or
and 9 years, respectively. For scenario 1, the payback period is later region. These strategies could involve statistical analysis of the
despite presenting a higher NPV. One of the reasons is the lower ethanol composition overtime and consumption trends analysis based on eco­
market price compared to the polylactic acid price. Scenario 2 presents nomic aspects to be used as the basis for any analysis. Regarding to the
higher investments in terms of CapEx and OpEx. The high cost of CapEx OKFW biorefining, polylactic acid is a promising product from a theo­
is because the lactic acid production and separation stage must be retical point of view since high product yields were obtained (i.e.,
included in the polylactic acid processing unit. The polylactic acid OpEx 0.12 kg PLA/kg of dry OKFW). Moreover, this production process is a
is related to the operating costs associated to the OKFW upgrading feasible option as a brownfield process because of existing plants in
process. The polylactic acid production process has a higher OpEx than Colombia can assume several of the capital investment costs. On the
the ethanol production since the first process requires more supplies (e. other hand, energy vectors production is only feasible if all the

Fig. 4. Economic assessment (a) Scenario 1; (b) Scenario 2.

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M. Ortiz-Sanchez et al. Biochemical Engineering Journal 194 (2023) 108864

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