Journal of Cleaner Production 255 (2020) 120278

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Journal of Cleaner Production

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

Process development of sustainable biorefinery system integrated into

the existing pulping process
Ghochapon Mongkhonsiri a, Pongtorn Charoensuppanimit a, *, Amata Anantpinijwatna b,
Rafiqul Gani c, Suttichai Assabumrungrat a
a
Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn
University, Bangkok, 10330, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang, Bangkok, 10520, Thailand
c
PSE for SPEED, Skyttemosen 6, Allerod, DK 3450, Denmark

a r t i c l e i n f o a b s t r a c t

Article history: The change of paper consumption trend may jeopardize the future of pulp and paper industry. This work
Received 25 October 2019 aims to design and develop the integrated network of biochemical and biofuel productions into existing
Received in revised form pulp mills for sustainable purposes. The systematic methodology aided by computation tools is under-
27 December 2019
taken using the three-stage approach including process synthesis, design and innovation. Previously, the
Accepted 26 January 2020
optimal technologies of the biorefinery-integrated pulping processes were successfully determined in
Available online 28 January 2020
the synthesis stage providing the highest cost-effective incorporation; 48 million USD/year of profit was
Handling editor: Panos Seferlis estimated according to the integration of succinic acid and dimethyl ether productions into the soda
pulping process. Herein, the process designs of the integrated processes were performed followed by
Keywords: evaluations of the process performances and identifications of the hot spots and targets for establish-
Pulp and paper industry ments of the innovations.
Biorefinery In this work, the biomass gasification option is designed and implemented to enhance the material
Process integration and energy utilizations in the previously determined biorefinery-integrated pulping processes. Electricity
Dimethyl ether
and biofuel are produced and sold, which contributes positively to the economic and environmental
Succinic acid
impacts of these processes. The hot spots and targets are subsequently identified prior to the innovation
stage. According to this stage, the cleaner alternatives that implements the CO2 utilization via methanol
synthesis and solar cell installations are selected in order to minimize the CO2 emission. A net CO2
reduction of 42% is achieved when the cleaner alternatives are applied. Accordingly, these biorefinery-
integrated innovations are not only conducive to the enhanced sustainability of existing pulp mills but
also adaptive in response to the change of paper consumption trend.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction Moreover, the volatility of oil prices and the increase of green
product demands are impetus to the productions of bio-based
1.1. Environmental concerns chemicals and biofuels. Accordingly, the productions of these
chemicals from renewable sources have been goals for various in-
The global atmospheric CO2 has soared to a disquieting level, dustries (Fernando et al., 2006). To achieve these goals, process
which raises concerns worldwide. According to United Nations design and development of the sustainable biorefinery specifically
Framework Convention on Climate Change (UNFCC) summit, the from lignocellulosic biomass are keys to mitigate the environ-
global agreement of the climate change focuses on reducing the mental and energy shortage issues.
emissions of greenhouse gases by the transition from the
petroleum-based economy into the carbon-neutral bioeconomy. 1.2. Lignocellulosic biomass

Lignocellulosic biomass can act as the starting material trans-

* Corresponding author. formable into high-value chemicals, fuels and energy (Menon and
E-mail address: [email protected] (P. Charoensuppanimit). Rao., 2012). In addition to its desired attributes such as

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2 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

cheapness, abundance and diversity, lignocellulosic biomass typi- 1.4.1. Enhancement of pulp utilization via productions of bioplastic
cally contains 60e80% of carbohydrates and 20e25% of lignin. The precursors
carbohydrates are poly/oligosaccharides of cellulose, hemicellulose, Bioplastics produced from biomass feedstock are perceived as
starch, and inulin whereas the lignin contains a network of sustainable material unlike the conventional plastics derived from
phenolic compounds. The separation of lignin and carbohydrates petroleum (Moharir & Kumar, 2019). New biodegradable plastics
by chemical or thermal means (Pourbafrani et al., 2014) is have been developed and introduced to the market such as poly-
mandatory prior to the utilization of carbohydrates. The obtained lactic acid (PLA), polybutylene succinate (PBS), polybutylene
carbohydrates are useful since the saccharine polymers they succinate-co-butylene adipate (PBSA) (Pathak and Navneet., 2017)
contain can be transformed into numerous chemicals, for example, and poly(3-hydroxybutyrate) (PHB) (Zahari et al., 2015). The mar-
glucose, ethanol and succinic acid via the biochemical and ther- ket growth of bioplastics is reported currently at 10% and expected
mochemical conversions (Choi et al., 2015; Bhowmick et al., 2018). to increase to 25e30% by 2020 (Ashter, 2016). Nowadays, it covers
However, before the lignocellulose can be utilized especially for approximately 10e15% of the total plastic market (Ashter, 2016).
the biorefinery purposes, effective pretreatments must be per- Consequently, chemicals such as ethanol, lactic acid and succinic
formed in order to first break the lignocellulosic bonds so that acid, are increasingly required as feedstock for bioplastic pro-
lignin and cellulose can be separated afterwards. Factually, there ductions (Choi et al., 2015). Since these precursors can be attained
exists the industry that is familiar with the pretreatment and via the hydrolysis and fermentation of the readily available pulps,
fractionation of lignocellulose. Such industry is the pulp and paper the biorefinery-integrated pulping process allows the co-
manufacturing which is selected due to its effectiveness of the productions of paper and these bioplastic precursors.
pretreatment and fractionation.
1.4.2. Enhancement of utilization of black liquor and biomass waste
1.3. Pulp and paper industry and its current situation via gasification
The gasification technology has been found useful for the pulp
Pulp and paper industry represent a lignocellulosic biorefinery and paper industry. For example, it has been found that the per-
that consumes a large amount of woody biomass for pulp and paper formance of the gasification technology could overcome the per-
productions through, for example, the soda pulping process that is formance of a freshly installed Tomlinson boiler (Consonni et al.,
the focus in this work. Despite its long existence, this traditional 2009). The atmospheric and pressurized black liquor gasification
bio-system is characterized by limited innovation, high fossil fuel (BLG), known as the Chemrec technology has been utilized suc-
dependency and high emissions of greenhouse gases (Bajpai, 2015). cessfully in large scale (Lindblom and Landlv, 2007). Also, the
Regarding the product from the pulp and paper industry, ap- fluidized-bed biomass gasification has been proven reliable for
plications of its main product (paper) are divided into two main commercial use (Wilk and Hofbauer, 2016). Furthermore, since the
categories including printing and packaging. The production of gasified products can be converted into value-added chemicals,
paper as printing material has been decreasing due to the tech- technologies of liquid biofuel synthesis via catalytic reactions of the
nological advancements in electronic devices used for communi- gasified products are commercially available (Molino et al., 2018;
cation (Schroder et al., 2019). In contrast, the consumption of Yang et al., 2018; Ramirez and Rainey., 2019).
packaging paper (for example, paper board and carton) has been As seen from these enhancements, key requirements for the
increasing as observed from the high demand of parcel deliveries development of this bio-based system are: (1) the implementation
offered by online shopping (Berg and Lingqvist., 2019; Schroder of breakthrough technologies that enable the cleaner, the highly
et al., 2019). In fact, though environmentally friendly and light- efficient and the cost-effective conversions of renewable feedstock
weight, packaging paper may not be suitable in some applications into valued-added biochemicals and (2) the integration of these
especially those that require durability. technologies into existing infrastructure and utility system. As a
As such, it may be inferred that the pulp and paper industry may result, the biorefinery-integrated pulp mill is potentially attractive
not be sustainable in the long term due to, (1) the decreasing for enhancement of the long-term sustainability of the industry.
consumption of printing paper, and (2) development of new eco- Furthermore, maturity of the existing pulp and paper industry in
friendly and durable material (e.g., bioplastics) that possibly af- terms of infrastructure, facilities, logistics and operations adds
fects the utilization of paper as packaging material. benefits to the integrated system, which helps leverage the possi-
bility of lignocellulosic biorefinery closer to a commercial scale.
1.4. Sustainability enhancement of pulp and paper industry using
biorefinery framework 1.5. Systematic framework for development of biorefinery-
integrated system
Renewable sources from pulp mills include pulps (cellulose-fi-
ber), black liquor (the lignin-rich by-product) and biomass waste Various biorefinery technologies together with diverse technical
from feedstock pretreatments. In biorefinery concept, cellulosic research results in biofuel and biochemical productions are already
pulps can be hydrolyzed and fermented in order to attain diversi- available (Brodin et al., 2017; Kajaste, 2014). Such varieties lead to a
fied products (e.g. ethanol, lactic acid, succinic acid, etc.) via the largely complex network of alternatives such that the appropriate
sugar platforms (Cherubini et al., 2009). For biofuel and bioenergy processing pathways are difficult to select. Accordingly, technolo-
productions, a black liquor comprising of lignin and spent chem- gies for realistic productions of high-value products derived from
icals from pulp cooking process can be converted into a syngas (CO reasonable raw material should be systematically determined
and H2) using gasification technology. The obtained syngas could (Ha€ma€la
€inen et al., 2011).
then be efficiently burnt in a gas turbine for power generation, or Several biorefinery-related studies adopted the systematic
alternatively passed through appropriate catalysts to synthesize framework with the assistance of mathematical programming for
liquid biofuels or biochemicals (Naqvi et al., 2010). Traditionally process synthesis and design (Gassner and Mare chal, 2009;
burnt as hog fuel for steam and power generations, biomass waste Alvarado-Morales et al., 2009; Zondervan et al., 2011; Rizwan et al.,
could be gasified also to improve efficiency of energy recovery with 2015; Kongpanna et al., 2016; Schroder et al., 2019; Ghayur et al.,
positive gains in economic and environmental effects (McKendry, 2019). According to these studies, this systematic framework
2002; Wetterlund et al., 2011). coupled with the mathematical programming has been proven
 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 3

beneficial for development of a more sustainable process. 2. Methodology

The generic framework proposed by Quaglia et al. (2012) was
developed for the synthesis of a processing network (or the su- To develop the case study of biorefinery-integrated pulping
perstructure modelling) contained subparts of processing intervals. process, the systematic framework is decomposed hierarchically
A large amount of data associated with each processing interval into three stages: Synthesis (Stage I), Design (Stage II) and Inno-
such as information of mass and energy balances has been vation (Stage III). This framework is employed step by step. The
compiled from diverse sources. After the superstructure (network output from each stage is transferred to the next stage to achieve
of processing paths) generation, an optimization is carried out to the associated objective resulting in a more sustainable biorefinery
determine the optimal processing path, which is then evaluated process. To demonstrate the utilization of this systematic frame-
considering process design issues e this problem is called the work, Section 2 outlines the Synthesis and Design stages (Stages I
synthesis-design problem. Since this problem has been categorized and II) whereas the Innovation stage is outlined in Section 3.
as a decision-making type (i.e., which route is optimal?), the su-
perstructure is transformed into mathematical models that contain 2.1. Stage I: Synthesis stage
decision variables for optimization. Mixed-integer nonlinear pro-
gramming (MINLP) has been used in order to obtain the optimal Typically, problems of process synthesis, which involve a com-
pathway (processing route or path). Recently, Bertran et al. (2017) plex network of alternative technologies need computer-aided
developed the platform that involves mathematical models, tools for systematic data and model-based solution searches. Ac-
structured databases with consistent data, and the user-friendly cording to our previous work (Mongkhonsiri et al., 2018), this
interface software (Super-O). The workflow involved in this plat- methodology was proven effective in determining the optimal in-
form is illustrated in Fig. 1. tegrated process that incorporated the biorefinery technologies
As illustrated in Fig. 1, the three-stage approach (Babi et al., into the existing pulp mill. Fig. 2 illustrates the optimal pathway
2015) for sustainable process synthesis and design is applied in obtained through the superstructure optimization. Additional de-
this work. The synthesis stage was completed successfully in our tails on the problem formulation and solution for the synthesis
previous study (Mongkhonsiri et al., 2018) providing the most stage are given in our previous study (Mongkhonsiri et al., 2018).
profitable alternative ethe incorporation of succinic acid (SA) and
dimethyl ether (DME) productions into the existing pulp mill 2.2. Stage II: Design stage
appeared the most optimal. Therefore, this work targets the process
design issues of this novel biorefinery-integrated pulping process 2.2.1. Base case design
using a simulator to evaluate the performances of the integrated According to the synthesis stage, the results revealed that the
process. Sustainability evaluations including economics, energy soda pulping process with the utilization of sugarcane bagasse is
and environmental aspects representing LCA factors (Kalakul et al., the proper receptor for biorefinery-integrated technology.
2014; Khoo et al., 2019) are provided also. Based on these evalua- Furthermore, productions of succinic acid (SA) and dimethyl ether
tions, the bottlenecks for further improvements are identified. The (DME) resulted in the maximized profit compared to other alter-
third innovation stage is applied to identify alternatives that ach- natives. Thus, design of the soda pulping process integrated with
ieve the improvement targets. Thus, the aims of this paper are: (1) the SA and DME productions are undertaken.
to illustrate the application of the three-stage approach for gener- As seen in Fig. 2, the processing route of base case starts with the
ation and evaluation of the biorefinery-integrated pulping process sugarcane bagasse delivered to the soda pulping process to attain
alternatives, and (2) to propose the more sustainable alternative pulps and black liquor. The pulps are utilized in the biochemical
that make use of the versatile biorefinery framework specifically for process to synthesize SA. The black liquor and pith are processed
the improvement of soda pulping process. through the biofuel and energy production unit which produced

Fig. 1. Overview of systematic three-stage framework.

4 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

Fig. 2. Optimal pathway based on optimization of generated superstructure.

DME and electricity. Since the required tasks (e.g., black liquor technology (Whitty and Nilsson, 2001), the BLG is simulated as a
gasification (BLG), separation, fermentation, etc.), in the processing pressurized-oxygen-blown-entrained-flow reactor comprised of
route are already assigned in the synthesis stage, in the design two main sections. The upper section produces syngas from the
stage, the unit operations that can perform these tasks are selected gasification of dry solid in the black liquor and oxygen. The product
and evaluated. Rigorous process simulation is employed for this obtained after the gasification contains CO, H2, CO2, H2S, and smelt
purpose. The simulation results provide input data for the analysis (sodium-based compounds from pulping chemical). The lower
(performance criteria, cost, environmental impacts, etc.). section is the quench section where the gas products and the smelt
are cooled by the condensate from the syngas cooler. The inorganic
2.2.2. Process simulation of base case smelt could dissolve in the quench liquid and form the green liquor,
Process simulation is conducted using Aspen Plus. Mass and which is sent to the lime kiln for the regeneration of pulping
energy balances are conducted in this step, which are used for the chemicals. In this study, the black liquor fed to the gasification unit
evaluations of the process performances. In this work, the is assumed to contain only organic compounds without the inor-
biorefinery-integrated processes are simulated excluding the ganic smelt. The operating conditions of the gasifier is at 1000
C
pulping process, which was calculated in our previous work and 35 bar. The black liquor is fed with the constituents listed in
(Mongkhonsiri et al., 2018). In the biorefinery-integrated process, Table 1 (Mtunzi et al., 2012).
there are five main regions including the black liquor gasification As shown in Fig. 3, the gasifier unit is simulated using three
(Fig. 3), the gas cleaner (Rectisol technology, Fig. 4), the DME syn- reactors in Aspen Plus including DCOMP (feed decomposition using
thesis (Fig. 5), the pulp hydrolysis (Fig. 6), the SA synthesis (Fig. 7) RYIELD), PYROLYS (Pyrolysis using RGIBBS), COMBUST (Combustion
and the biomass gasification (Fig. 8). The quantities of raw material using RGIBBS). Following the literature, the smelt-free syngas
for biorefinery, e.g., pulps, pith and black liquor from the soda pulp leaves the gasifier at 217
C and 35 bar, and is cooled to about 120
C
mill are determined based on the feed rate of sugarcane bagasse of in the downstream heat exchanger (Lason et al., 2006a). The heat
100,000 tons/year which is the current production rate from the recovered in the cooler can be utilized for the process steam gen-
pulp mill in Thailand (KTIS, 2019). At this bagasse feed rate, pulps eration. Water contained in the syngas is condensed in the cooler
are produced and fed to the SA production at 30,700 tons/year and used as quench liquid for the regeneration of green liquor (not
containing 71.4%wt glucan, 22.3%wt xylan and 3%wt lignin. The included in this simulation). Chemrec technology produces a
black liquor containing 20% moisture is delivered to the BLG/DME minute level of alkali in the syngas, which helps to protect down-
unit at 21,100 tons/year. Biomass residue (bagasse pith) is fed to the stream equipment (Lindblom and Landlv, 2007). Cooled syngas
biomass gasification process at 22,800 tons/year. (35
C) is subsequently fed to the gas cleaner to remove acid gases
(CO2 and H2S), which may poison the catalyst for DME synthesis.
Syngas after the removal of condensed water is discharged with the
2.2.2.1. Black liquor gasification (BLG) region. The BLG region pro-
composition listed in Table 2. For conciseness of this article, the
duces syngas for DME production. Following the Chemrec
G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 5

Fig. 3. Process flow diagram of black liquor gasification region.

Fig. 4. Process flow diagram of gas cleaning region (Rectisol).

Fig. 5. Process flow diagram of DME synthesis region.

6 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

Fig. 6. Process flow diagram of two-step concentrated acid hydrolysis: sugar production region.

Fig. 7. Process flow diagram of SA production region.

complete details of streams (e.g., mass flow rate, temperature, highly exothermic nature of the CO2 absorption in methanol. The
pressure and component mass flow) in Fig. 3 are given in Table SM1, low operating temperature in the absorber is required to prevent
which are provided in the supplementary material. the evaporation of solvent that possibly flows out with the cleaned
gas during the absorption process.
2.2.2.2. Gas cleaning region. H2S and CO2 contained in the syngas Syngas from the gasification of black liquor is cooled to 35
C
must be removed prior to the DME synthesis. In this case, the and enters at the bottom of the absorber (C1), which is simulated
concentration of sulfur compounds in the black liquor is low using RADFRAC in Aspen Plus. The methanol with very low tem-
because sodium sulfide (Na2S) is not utilized in the soda pulping perature of 50
C (Ranke and Weiss, 1982) is introduced at the top
process. However, H2S derived from the sulfur compounds must of the column. The cleaned syngas discharged at the top of the
not be allowed to exceed 0.1 ppm to prevent the catalyst from absorber is sent to the DME synthesis with the constituents listed in
deactivation during the synthesis of DME (Lason et al., 2006b). CO2 Table 2. Since the solubility of H2S in methanol is about five times
removal is maximized in this study to maintain the catalyst activity higher than that of CO2, H2S is expected to be captured completely
by avoiding the built-up of CO2 in the recycle loop. Furthermore, the around the bottom section of the column and discharged out of the
performance of DME production in the reactor is enhanced as a column through the bottom stream. The side stream above the
result of the high partial pressures of CO and H2. Thus, the CO2 bottom stream is expected to contain rich CO2 with nearly no H2S.
content is fixed at less than 1 mol% in this study. Followed by the absorber C1, three columns including the H2S
Rectisol® (Air Products and Chemicals, Inc., 1993) is the most Concentrator (C2), the CO2 Stripper (C3) and the Solvent Regener-
widely used acid gas removal (AGR) technology utilizing methanol ator (C4) are simulated using RADFRAC (Prosim, 2015). The H2S
as a solvent for physical absorption. The acid gases are removed Concentrator (C2) had the stream of almost pure CO2 discharged at
from the syngas by physical absorption at high pressures without a the top of the column and the stream of methanol rich in H2S
chemical reaction. Therefore, the solvent can be regenerated easily discharged at the bottom. In the CO2 Stripper (C3), CO2 content was
via indirect heating. The Rectisol technology was adopted in this drastically reduced in the methanol stream using nitrogen (N2) as
work to remove both H2S and CO2. The process simulation was the stripping agent. In the solvent Regenerator (C4), the methanol
validated with Lason et al. (2006b). The Rectisol system requires residue in the gas phase is condensed, the remaining H2S and CO2
very low temperature of methanol for best performance due to the are discharged at the top of the column while methanol discharged
 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 7

Fig. 8. Process flow diagram of biomass gasification with gas turbine combined cycle region.

Table 1 1996; Ng et al., 1999). Process configuration adapted from Larson

Composition of feedstock. and Tingjin, 2003 was simulated as shown in Fig. 5. Complete de-
Black liquor Bagasse pith tails of streams (e.g., mass flow rate, temperature, pressure and
Feed flowrate (kg/h) 2530 2730
component mass flow), in Fig. 5 are givenin Table SM3, which are
LHV 12.31 12.12 provided in the supplementary material.
HHV 13.87 13.53 The reactor operates isothermally at 260
C. Results of inlet and
Proximate analysis (%) outlet streams are displayed in Table 2. The outlet gases from the
Moisture 20 20
reactor are fed into the subsequent separation region where DME
Fixed carbon 28.13 11.88
Volatile matter 40.21 85.2 product stream is purified to 99.8 wt% by removing methanol,
Ash 31.66 2.92 unconverted syngas, and water. Most of unconverted syngas is
Ultimate analysis (%) separated from the product stream by a series of flash tanks. 97% of
Ash 31.66 2.91
syngas recovered in the separation region is recycled to the DME
Carbon 36.11 49.2
Hydrogen 4.54 4.69
synthesis reactor, while the purge gas (3%) is sent to the power
Nitrogen 1 0.18 plant for energy generation. For product purifications, the first
Chlorine 0 0 distillation column is used to remove CO2 and other light gases
Sulfur 0.45 0.02 through the distillate stream. The second column is used to sepa-
Oxygen 26.24 43
rate DME product from methanol/water mixture. Finally, methanol
is purified, which is recycled to the methanol makeup stream in the
gas cleaning region.
at the bottom is recycled to the absorber (C1). Fig. 4 illustrates the
process flow diagram of the unit operations involved in the gas
cleaning process. Complete details of streams (e.g., mass flow rate, 2.2.2.4. Succinic acid production region. Pulps are utilized as feed-
temperature, pressure and component mass flow) in Fig. 4 are stock for SA production in the biorefinery-integrated design. To
given in Table SM2, which are provided in the supplementary produce pulps, sugarcane bagasse is processed using pulping
material. chemical (sodium hydroxide in Soda process) to extract lignin and
some hemicellulose from cellulose fiber. Containing mainly cellu-
2.2.2.3. DME synthesis region. The cleaned syngas from the AGR lose, pulps are hydrolyzed subsequently to glucose. SA is produced
system is heated to 240
C and pressurized to 65.7 bar prior to the by the fermentation of sugar and then purified to remove other
delivery of the syngas to the single-step DME synthesis reactor. organic acid by-products. According to our previous work
Inside the reactor, a mix of two catalysts are used: one promoting (Mongkhonsiri et al., 2018), the appropriate processing route for
the synthesis of methanol from syngas and another promoting the the production of SA contained (1) the pulp hydrolysis for the
dehydration of methanol to DME (Gogate and Vijayaraghavan, production of sugars using concentrated acid, (2) the fermentation
1992). In this work, the liquid-phase DME synthesis reactor of sugars using A. succiniciproducens strain (Datta, 1992; Lee, 2015)
(LPDME) is utilized for the DME synthesis simulated using RCSTR for the production of SA, and (3) the direct crystallization with
with the LHHW kinetic model proposed by (Graaf and Beenackers, electrodialysis as the product purification.
8 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

Table 2
Selected streams obtained from process simulation.

RAWGAS CLEANGAS RXIN RXOUT DME-PROD GASTURB FLUEGAS PULP SUGAR FERMBROTH

Mass Flow (kg/h) 2,180 1,380 5,400 5,400 642 4,590 30,400 3,690 9,000 43,300
Temperature (
C) 35 50 240 260 44 374 229 25 28 37
Pressure (bar) 33 32 66 62 10 24 1 1 1 1
Mass fraction
H2O 0 0 0 0.0039 0 0.1972 0.0683 0.0042 0.5871 0.6465
N2 0.0133 0.0208 0.1412 0.1412 0 0.0506 0.5943 0 0 0
H2 0.0411 0.0644 0.0302 0.0141 0 0.0266 0.0001 0 0 0.2487
O2 0 0 0 0 0 0 0.0252 0 0 0
NO 0 0 0 0 0 0 0.0778 0 0 0
NO2 0 0 0 0 0 0 0.0721 0 0 0
CO 0.5663 0.8798 0.5704 0.3595 0 0.2249 0.0028 0 0 0
CO2 0.3514 0.0005 0.1419 0.2460 0.0008 0.4843 0.1488 0 0 0
SO2 0 0 0 0 0 0 0 0 0 0
SO3 0 0 0 0 0 0 0 0 0 0
AR 0.0153 0.0233 0.0666 0.0666 0 0.0087 0.0100 0 0 0
H2S 0.0043 0 0 0 0 0.0001 0 0 0 0
COS 0.0003 0 0 0 0 0 0 0 0 0
CH4 0.0078 0.0112 0.0455 0.0455 0 0.0076 0.0005 0 0 0
Methanol 0 0 0 0 0 0 0 0 0 0
DME 0 0 0.0042 0.1231 0.9992 0 0 0 0 0
C2H2 0 0 0 0 0 0 0 0 0 0
C2H4 0 0 0 0 0 0 0 0 0 0
C2H6 0 0 0 0 0 0 0 0 0 0
H2SO4 0 0 0 0 0 0 0 0 0.0117 0
NH4SO4 0 0 0 0 0 0 0 0 0 0.0090

DAP 0 0 0 0 0 0 0 0 0 0.0010
NaOH 0 0 0 0 0 0 0 0 0 0.0037
Glucose 0 0 0 0 0 0 0 0 0.3004 0
Galactose 0 0 0 0 0 0 0 0 0.0006 0.0001
Mannose 0 0 0 0 0 0 0 0 0.0002 0.0000
Xylose 0 0 0 0 0 0 0 0 0.0901 0.0102
Arabinos 0 0 0 0 0 0 0 0 0.0067 0.0013
HMF 0 0 0 0 0 0 0 0 0.0004 0.0001
Furfural 0 0 0 0 0 0 0 0 0.0027 0.0006
Acetic acid 0 0 0 0 0 0 0 0 0 0.0131
Lactic acid 0 0 0 0 0 0 0 0 0 0.0027
Succinic acid 0 0 0 0 0 0 0 0 0 0.0622
Acetate 0 0 0 0 0 0 0 0.0024 0 0
Lignin 0 0 0 0 0 0 0 0.0302 0 0
Arabinan 0 0 0 0 0 0 0 0.0165 0 0
Xylan 0 0 0 0 0 0 0 0.2225 0 0
Mannan 0 0 0 0 0 0 0 0.0004 0 0
Galactan 0 0 0 0 0 0 0 0.0020 0 0
Cellulose 0 0 0 0 0 0 0 0.7085 0 0
Formic acid 0 0 0 0 0 0 0 0 0 0.0008
Ash 0 0 0 0 0 0 0 0.0133 0 0

The hydrolysis of pulps using concentrated acid is effective in et al., 2016). In the second hydrolysis tank operated at 80
C, the
breaking the crystalline structure of cellulose emore than 90% of solid product from the first stage is dewatered and soaked in a
cellulose is broken at relatively mild temperatures and atmospheric 30 wt% concentration of sulfuric acid. The dewatered material is
pressure, which is possible for enlargement to a commercial scale dried so that the acid concentration in the material rises to about
(Badger, 2002). A two-step hydrolysis of concentrated acid is 70 wt% (Badger, 2002). In this reactor model, the 95% conversion of
adopted to hydrolyze pulps to sugar before the fermentation cellulose to glucose and 88% to xylose are assumed (Kong-Win
(Wijaya et al., 2014). The flowsheet of hydrolysis process is illus- Chang et al., 2018; Hilpmann et al., 2016). Note that the acid/
trated in Fig. 6. The hydrolysis process is simulated in two reaction sugar separation is added to recycle the acid whereas the neutral-
steps including the decrystallization and the two-step hydrolysis ization process, represented by T1 and T2 (in Fig. 7), are added to
using concentrated sulfuric acid followed by the product separa- neutralize the sugar solution prior to the subsequent process of
tion. RSTOIC is used to represent the decrystallization and the hy- fermentation. The composition of sugar from acid/sugar separation
drolysis. Complete details of streams (e.g., mass flow rate, is given in Table 2. To separate sugar from sulfuric acid, this work
temperature, pressure and component mass flow) in Fig. 6 are applied the continuous ion-exclusion chromatography technique
given in Table SM4, which are provided in the supplementary (Springfield and Hester, 1999). This technology allows for more
material. than 95% recovery of sugars and 98% acid recovery.
Initially, the raw pulps with composition given in Table 2 and Sugar is equally divided for the seed fermentation and for the
the 75 wt% concentrated acid are mixed in the decrystallization direct fermentation to produce SA. The seed fermentation tank
tank at 30
C and atmospheric pressure. In the first hydrolysis tank (SEEDFERM) contains microorganism, nutrient, fermentation me-
operated at 30
C, fresh water is fed to dilute the acidic feed to 10 wt dium and other gases. The fermentation tanks are simulated using
% acid in order to minimize the degradation of sugar (Kanchanalai RSTOIC with kinetic data from literature (Lee, 2015).
 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 9

Anaerobiospirillum succiniciproducens is selected to produce SA in Before the HRSG, the duct burner illustrated as BURNER in Fig. 8 is
this case. After the fermentation, the broth is filtered to remove employed to provide heat supplementary to the gas-turbine
cells and solid waste. Then, the electrodialysis located before the exhaust heat. The duct burner is simulated using HEATER and its
evaporator and the crystallizer is used to separate sodium hy- outlet temperature of 751
C is assumed. Process details of applied
droxide for reuse as a neutralizing agent in the fermentation step. gas turbine are available in reports on black liquor gasification
Simultaneously, succinate salt is converted into SA. Substantial combined cycle in Kraft pulping process by Larson et al. (2003).
amounts of water and light by-products: e.g. acetate and formate In this work, electricity produced from the steam turbine (that
are vaporized using the evaporator. The concentrated succinate is used high pressure steam from the HRSG) is estimated using the
crystallized in the crystallizer operated at 4
C with the pH moni- assumed recovery efficiency of 30% relative to the enthalpy change
tored at 2.0 conditioned by the addition of HCl. At low tempera- of steam. Essentially, the biomass (bagasse pith and hog fuel)
tures, the solubility of SA drops to only 3% compared to other water- gasification in the power generation region is designed to
miscible by-products such as formic acid, lactic acid and acetic acid. compensate the parasitic load used in the integrated process. In
Finally, the obtained SA crystal is dried to remove moisture and case of power deficit, electricity could be imported from a grid to
enhance the product purity to 99 wt% (Morales et al., 2016). The meet the power requirement; otherwise, the electricity could be
process configuration of SA production after the hydrolysis step is exported to the grid and counted as income.
shown in Fig. 7. Complete details of streams (e.g., mass flow rate,
temperature, pressure and component mass flow) in Fig. 7 are 2.3. Evaluations of process performances
givenin Table SM4, which are provided in the supplementary
material. In this study, three scenarios of biorefinery-integrated processes
(assigned as base case) and other two scenarios (Tomlinson and
2.2.2.5. Biomass gasification with power plant region. In integrated BLGCC that did not implement the biorefinery framework) have
biorefinery designs, pith that is the biomass residue from the been established for comparative purposes. Incorporated to the
bagasse pretreatment (before the pulping step) and imported traditional pulping process, the biorefinery-related scenarios are:
biomass (purchased as supplementary hog fuel) are processed the integration of DME production only (Scenario 1), the integra-
through the biomass gasification. 20% moisture content is assumed tion of DME and SA productions with hog fuel as supplement for
to be contained in the biomass, as listed in Table 1 (Mtunzi et al., the power plant (Scenario 2), and the integration of DME and SA
2012). Though biomass dryer is not simulated, the energy con- productions with the natural gas boost for the power plant (Sce-
sumptions for biomass handling and drying are estimated at nario 3). Process evaluations are determined in terms of the process
5.6 kWh/ton of wet biomass (Consonni and Larson, 1996). Nitrogen economic, the power consumption, and the environmental impact.
obtained from the air separation unit is fed to pressurize the The operation hours per year is assumed at 8,330 h/year.
biomass feedstock in the lock hoppers at 36 bar (Blackadder et al., For economic assessment in each scenario, the profit of
1994). The pressurized oxygen/steam-blown fluidized-bed gasifier biorefinery-integrated process is estimated based on the product
operated at 950
C is selected for biomass gasification, which is sales, the raw material and chemical costs as well as the power and
simulated and represented by 4 reactors in Aspen Plus (see Fig. 8). capital costs (assumed project life of 25 years). Prices of material
DCOMP using RYIELD is initially utilized for the feed decomposi- are collected from the previous publications (Mongkhonsiri et al.,
tion. Then, RSTOIC accounts for tar formation (Ahmed et al., 2015). 2018; Larson et al., 2006a). Capital costs of the processes
After that, volatile compounds are processed by PYRO using excluding the existing pulp mill are calculated based on feedstock
RGIBBS. flowrate of each region and the capital cost data (e.g. black liquor
Char (fixed carbon) is separated and mixed with the mixture of gasification, DME synthesis, biomass gasification, power plant and
oxygen and steam for gasification in GASIFY (RGIBBS) (Kaushal and air separation plant) from publication (Larson et al., 2006a). The
Tyagi, 2017). Both product streams are mixed and fed to the cata- capital cost of SA integrated process is calculated using Aspen Plus.
lytic tar cracker (Simell et al., 1996) (simulated by CRACKER using Also, the capital cost of air separation plant (Larson et al., 2006a)
RGIBBS). Steam used as a gasifier agent is provided at a rate of 28% that provides O2 and N2 (for the gasification and gas cleaning re-
relative to the dry biomass feed rate. The oxygen flow is determined gions) is also included.
in order to achieve a specified temperature of 950
C at the exit of For the estimation of power consumption in each scenario, the
the gasification system (Larson et al., 2006a). The process simula- power requirement of the integrated process is determined using
tion of the biomass gasification and the catalytic reforming is extracted data from the literature (Larson et al., 2006a) (e.g. pulp
validated with a model proposed in Hannula and Kurkela (2012). mills and air separation plant) and the process simulation (the five
The temperature of syngas product at the expender exhaust is regions outlined in Section 2.2.2). The estimated power is compared
375
C with composition listed in Table 2. This syngas is directly with the parasitic load obtained from the biomass gasification and
utilized as fuel in the gas turbine combined cycle where high power plant region. Please note that the only discrepancy between
pressure steam is produced for electricity generation. Biomass Scenarios 2 and 3 is the types of supplement ehog fuel is supplied in
gasification combined with the power generation system shown in Scenario 2 whereas natural gas is supplied in Scenario 3. Further, the
Fig. 8 is designed based on the process configuration from the supplements are required only in these two scenarios, which led to
public report of Lason et al. (2006a). Complete details of streams the unnecessity import of electricity. However, in Scenario 1, there
(e.g., mass flow rate, temperature, pressure and component mass are no supplements provided to the gasification and power plant
flow) in Fig. 8 are given in Table SM5, which are provided in the region. Thus, extra electricity are required in these scenarios if the
supplementary material. power generated from the gasification of bagasse pith is not suffi-
The gas turbine combustor is installed before the gas turbine cient. For conventional Tomlinson boiler and BLGCC process, their
system to ensure that any residual tars are converted into light performances calculated based on extracted data (Larson et al.,
gases. The gas turbine combined cycle is designed to generate 2003) are illustrated to compare with the scenarios of integrated
electricity for the biorefinery-integrated pulp mill, or for export in biorefinery that are considered in this study.
case of excess. In this power region design, the gas turbine gener- For analysis of the environmental impact in each scenario, the
ator and the heat recovery steam generator (HRSG) operated using total CO2 emissions as well as other pollutants such as NOx, SOx and
the gas-turbine exhaust heat are simulated as shown in Fig. 8. PM 10 are estimated and assessed.
10 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

3. Results and discussion power consumptions in Scenario 2 and 3 are considerably higher
than other scenarios due to the substantial amount of energy
Integration of the biorefinery framework into the existing pulp consumed in the SA production (15.8 MW). However, Scenarios 2
mill is developed to enhance the sustainability of the integrated and 3 still appear to be superior to other scenarios from an eco-
process. Potentials for the synthesis of new value-added bio- nomic point of view.
chemicals and biofuels within the existing infrastructure of pulping In comparisons between Scenarios 2 and 3, the natural-gas-
process are evaluated to improve the efficiencies of material and boost (Scenario 3) requires far less supplement than the
energy utilizations, the profitability and environmental impact. As imported-hog-fuel (Scenario 2) due to the higher heating value of
mentioned in Section 2, after evaluation of the performances of natural gas relative to hog fuel; 9,860 tons/year of natural gas and
base case (the three scenarios), the hot spots and targets are 59,200 tons/year hog fuel are estimated. Though requiring sub-
identified. Highlighted in Sections 3.2 and 3.3, the innovations are stantially higher supplement, Scenario 2 is found not to depend on
implemented and reevaluated, which are crucial for future rec- the fossil fuel since the hog fuel is utilized. Furthermore, the power
ommendations and process improvements. surplus in Scenario 2 is higher when compared to Scenario 3 thanks
to the gasification of hog fuel, which improves the heating value by
3.1. Process evaluation transforming hog fuel into syngas. Thus, by considering both eco-
nomic and power consumption, Scenario 2 is found to be superior
3.1.1. Economic evaluation to other scenarios.
Economic assessments of the biorefinery-integrated (Scenarios
1, 2 and 3) and the conventional (Tomlinson and BLGCC) scenarios 3.1.3. Environmental impact
are given in Table 3. As seen in the table, Scenarios 1, 2 and 3 The net CO2 and other pollutant emissions (SOx, NOx and PM10)
yieldsubstantially higher profits than those of Tomlinson and are listed in Table 5. Fig. 9 illustrates comparisons of CO2 emission/
BLGCC due to the high values of SA and DME and the excess power reduction and the net CO2 associated with each scenario. The
sales. Although Scenario 1 has considerably lower profit than Sce- biorefinery-integrated processes in scenarios 2 and 3 have higher
narios 2 and 3, the profit is relatively higher in comparison with the CO2 emissions than other scenarios due to the higher power con-
Tomlinson and BLGCC. Thus, the incorporation of biorefinery sumptions in the SA productions. However, the processes discharge
framework to the existing pulp mill is found to enhance the prof- relatively less SOx, NOx and PM10 since bio-based fuel is used in lieu
itability of integrated processes. However, when compared be- of the fossil fuel. As observed in Table 5, all scenarios consume CO2
tween Scenarios 2 and 3, the estimated profits are comparable within the processes as indicated from the negative values in CO2
suggesting that other indicators (e.g. power consumption and emissions. Though consuming less CO2 compared to other sce-
environmental impact) should be assessed in order to justify the narios, Scenario 2 appear to be superior to others and has the
most superior scenario. highest profitability and the independency on fossil fuel.

3.1.2. Power consumption 3.2. Target setting

The power consumptions estimated for all scenarios are sum-
marized in Table 4. In Tomlinson scenario, a power deficit is According to the process evaluations, the designed biorefinery-
observed due to the low efficiency of energy recovery. The BLGCC, integrated processes are analyzed to define hotspots and targets
on the other hand, could generate a power surplus but it requires a based on the bottlenecks of the processes. As seen from the results,
natural gas boost indicating the dependency on the fossil fuel. The the integrated processes with the SA production (Scenarios 2 and 3)

Table 3
Economic evaluations of biorefinery-integrated scenarios, Tomlinson and BLGCC processes.

Info/Process Unit /DME/Scenario 1 DMEþSA DMEþSA (Nat.gas) Tomlinson BLGCC

Scenario 2 Scenario 3

Raw material
Bagasse ton/year 100,000 100,000 100,000 100,000 100,000
23 $/ton $/year 2,300,000 2,300,000 2,300,000 2,300,000 2,300,000
Imported biomass ton/year e 59,200 e e e
23 $/ton $/year e 1,362,000 e e e
Natural gas boost ton/year e e 9,690 e 643
37 $/ton $/year e e 358,400 e 23,800
Biochemical products
Pulp sale ton/year 30,700 e e 30,700 30,700
300 $/ton $/year 9,220,000 e e 9,220,000 9,220,000
DME ton/year 5,350 5,350 5,350 e e
680 $/ton $/year 3,640,000 3,640,000 3,640,000 e e
SA ton/year e 14,700 14,700 e e
3000 $/ton $/year e 43,980,000 43,980,000 e e
Total biochemical product sale $/year 12,900,000 47,600,000 47,600,000 9,220,000 9,220,000
Power
Power sell (þ)/buy ()** MWh 3,240 83,100 66,400 24,100 7,100
0.14 $/kWh** $/year 453,000 11,600,000 9,290,000 3,370,000 993,000
Capital cost* $/year 975,000 3,070,000 1,581,000 195,000 344,000
Chemical cost for SA production $/year e 954,000 954,000 e e
Profit $/year 9,120,000 51,600,000 51,700,000 3,350,000 7,540,000

*Based on non-fuel operating and maintenance costs with 25 years project life excluding pulp mill.
**Negative value means power deficit that the purchase of power from other sources is required.
 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 11

Table 4
Summary of power consumption of biorefinery-integrated scenarios, Tomlinson boiler and BLGCC processes.

Info/Process Unit /DME/Scenario 1 DMEþSA DMEþSA (Nat.gas) Tomlinson BLGCC

Scenario 2 Scenario 3

Raw material
Bagasse (tons/year) 100,000 100,000 100,000 100,000 100,000
Black liquor (80% DS*) (tons/year) 21,100 21,100 21,100 21,100 21,100
Pith (80% DS*) (tons/year) 22,800 22,800 22,800 22,800 22,800
Pulp (tons/year) 30,700 30,700 30,700 30,700 30,700
Imported biomass (tons/year) 0 59,200 0 0 0
Natural gas boost (tons/year) 0 0 9,680 0 643
Biochemical products
Pulp sale (tons/year) 30,700 0 0 30,700 30,700
DME (tons/year) 5,350 5,350 5,350 0 0
SA (tons/year) 0 14,700 14,700 0 0
Power
Power production (MWh) 48,500 166,000 135,000 15,300 49,700
Power use (with pulp mill) (MWh) 51,700 83,200 68,800 39,300 41,600
Power sell (þ) (MWh) 3,240 83,100 66,400 24,000 7,090
/buy ()

*DS denotes dry solid.

** Negative value means power deficit that the purchase of power from other sources is required.

Table 5
Process flow diagram of DME synthesis region.

Info/Process Unit /DME/Scenario 1 DMEþSA DMEþSA (Nat.gas) Tomlinson BLGCC

Scenario 2 Scenario 3

CO2 Emission
Process CO2 emission ton/year 82,500 299,000 232,000 48,900 70,000
CO2 from power import (TH-Grid) ton/year 2,660 e e 19,700 e
Total CO2 Emission ton/year e 1,360,000 e e e
CO2 Reduction
Grid power production replacement (TH-Grid) ton/year 39,700 136,000 111,000 12,500 40,000
Diesel replacement by DME ton/year 3,240 3,240 3,240 e e
Petro-based SA replacement ton/year e 27,700 27,700 e e
Biomass consumption ton/year 103,000 165,000 103,000 103,000 103,000
Total CO2 reduction ton/year 146,000 332,000 245,000 116,000 143,000
Net CO2 (Emission e Reduction)
Net CO2* ton/year 61,300 33,200 13,600 47,300 73,000
Pollutant Emissions
Total SOx Emission ton/year 29.7 65.9 51.0 96.5 10.3
Net SOx ton/year 185 561 468 42.9 161
Total NOx Emission ton/year 22.8 77.2 59.7 55.8 50.9
Net NOx ton/year 101 96.9 101 49.3 30.1
Total PM10 Emission ton/year 4.41 5.77 4.47 32.9 9.3
Net PM10 ton/year 124 150 48.9 19.7 33.0

* Negative value means the consumption of CO2 in the process.

cause high CO2 emissions since the processes require large amounts global attention due to its low CO2 emission, low environmental
of energy. Thus, enhancement of CO2 reduction is set as the impact and becoming continuously cheaper (IRENA, 2012; IRENA,
improvement target for the integrated SA production scenarios. 2018).
Though possessing high potential in GHG reductions as observed in According to the large CO2 emissions observed in Scenarios 1, 2
Table 5, the integrated DME process without the SA production and 3, CO2 is mainly released by the gasification of biomass and
(Scenario 1) requires imported electricity from a grid, which de- power plant. To capture CO2 in flue gas, the Rectisol process that is
pends on fossil fuel. Thus, an alternative green power is required. readily available in these scenarios could be employed (Xiang et al.,
For illustrative purposes, the summary of specified targets is shown 2019). Following the innovative design, CO2 removed at the ab-
in Fig. 10. sorption column (C2) in the existing Rectisol process is utilized for
methanol synthesis via CO2 hydrogenation (Frauzem, 2017).
Methanol produced from CO2 could be converted to DME at the
3.3. Stage III: Innovation stage DME synthesis region. Process flow diagram contained the inte-
gration of CO2 utilization is shown in Fig. 12.
3.3.1. Alternative generation
To match the established targets through process debot-
tlenecking in stage III, both scenarios of biorefinery-integrated 3.3.2. Evaluation of process alternatives
processes become more sustainable via the applications of inno- The generated alternatives based on the improvement targets
vative green technologies as depicted in Fig. 11. For Scenario 1, are evaluated in terms of economic and environmental impacts. As
electricity deficit that requires the import of electrical power could given in Table 6, utilization of electricity derived from the solar
be solved using an installation of solar cells. Solar energy has gained power could reduce the CO2 emission by 4% (2,530 tons/year) with
12 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

Fig. 9. Distributions of CO2 emission, reduction and net CO2 associated with each scenario.

profit decrease about 2% (194,000 $/year) due to the higher cost of

solar energy. Though expensive, the cost of electricity from solar
cells has fallen by almost three quarters during the period: 2010 to
2017. Furthermore, by 2020, the solar-photovoltaic system is ex-
pected to provide lower cost of energy than the fossil fuel system
(IRENA, 2018). Accordingly, the generation of electricity via solar
cells appears to be a plausible and attractive alternative.
To reduce the CO2 emission, the CO2 utilization via methanol
synthesis is implemented to produce more DME. According to the
results, the innovative process achieves the expected target of
reducing CO2 emission; 14,200 tons of CO2/year is reduced ac-
counting for 42% reduction relative to the base case of integrated SA
production (Scenario 2). However, a 0.6% profit reduction
compared to the base scenario is obtained due to the enlarged
Fig. 10. Improvement targets of biorefinery-integrated processes.
chemical, capital and utility costs stemming from the addition of a
methanol plant. For illustrative purposes, process performances of
the alternatives, based cases, conventional Tomlinson and BLGCC
are compared using the sustainability factors including the net
profit, the net CO2 reduction, the power generation and the bio-
product income which are given in the form of a radar chart in
Fig. 13.

4. Conclusions

The integration of biorefinery framework into the existing pulp

mill has been examined for the enhancement of sustainability of
the integrated process. According to the obtained results, it was
possible to improve the profitability and the efficiencies in terms of
mass and energy utilizations of each biorefinery-integrated process
with the acceptable low compromise to the environment. There-
fore, the systematic approach decomposed into three stages: syn-
thesis, design and innovation has been capable of providing the
more sustainable biorefinery-integrated process solutions.
Fig. 11. Innovation alternatives of biorefinery-integrated processes. Furthermore, according to the superstructure optimization results,
 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278 13

Fig. 12. Block diagram of integrated methanol synthesis via CO2 utilization contained in innovation alternative based on Scenario 2.

Table 6
Economic evaluations and environmental impacts of the generated alternatives compared with the base case of biorefinery-integrated scenarios based on the improved target.

Info/Process /DME/Scenario 1 DMEþSA DME (SOLAR) DMEþSA (CO2eMeOH)

Scenario 2

Raw material
Bagasse ton/year 100,000 100,000 100,000 100,000
23 $/ton $/year 2,300,000 2,300,000 2,300,000 2,300,000
Imported biomass ton/year 0 59,200 0 59,200
23 $/ton $/year 0 1,360,000 0 1,360,000
Biochemical products
Pulp sale ton/year 30,700 0 30,700 0
300 $/ton $/year 9,220,000 0 9,220,000 0
DME ton/year 5,350 5,350 5,350 31,900
680 $/ton $/year 3,640,000 3,640,000 3,640,000 21,700,000
SA ton/year 0 14,700 0 14,700
3000 $/ton $/year 0 44,400,000 0 44,400,000
Total biochemical product sale $/year 12,900,000 47,600,000 12,900,000 65,600,000
Power
Power sell/buy MWh 3,240 83,100 3,240 56,700
0.14 $/kWh $/year 453,000 11,600,000 648,000 7,940,000
Capital cost* $/year 975,000 3,070,000 195,000 4,340,000
Chemical cost $/year e 954,000 e 10,200,000
Extra utility cost $/year e e e 4,340,000
Profit $/year 9,120,000 51,600,000 8,930,000 51,200,000
CO2 Emission
Process CO2 emission ton/year 82,500 299,000 82,500 300,000
CO2 from power import (TH-Grid) ton/year 2,660 e 130 e
Total CO2 Emission ton/year 85,100 299,000 82,600 300,000
CO2 Reduction
Grid power replacement (TH-Grid) ton/year 39,700 136,000 39,700 136,000
Diesel replacement by DME ton/year 3,240 3,240 3,240 19,300
Petro-based SA replacement ton/year e 27,700 e 27,700
Biomass consumption ton/year 103,000 165,000 103,000 165,000
Total CO2 Reduction ton/year 146,000 332,000 146,000 348,000
Net CO2** ton/year ¡61,000 ¡33,000 ¡63,800 ¡47,000

*Based on non-fuel operating and maintenance costs with 25 years project life excluding pulp mill.
** Negative value means the consumption of CO2 in the process.

SA and DME productions integrated into the Soda pulping process Finally, innovation alternatives identified in response to the
have been found to be the most profitable. Although the integration targets for improvement were found to be capable of reducing the
of SA and DME productions to the pulping process resulted in the adverse impacts to the environment. The net CO2 emission ob-
required external supply of biomass, the benefit could be attained tained from the innovation alternatives revealed that the solar
due to the excess electricity for sale and the independency to fossil power could reduce the CO2 emission by 4% compared to the base
fuel. case of DME production (Scenario 1) while the obtained profit
14 G. Mongkhonsiri et al. / Journal of Cleaner Production 255 (2020) 120278

Fig. 13. Comparison of innovation alternatives and base cases for sustainability evaluation.

decreased by merely 2%. In case of the integrated SA production Air Products and Chemicals, Inc, 1993. Synthesis of DME and alternative fuels in the
liquid phase from coal-derived synthesis gas. In: Report DOE/PC/89865-T8, U.S.
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pp. 1e17.
The authors declare that they have no known competing Babi, D.K., Holtbruegge, J., Lutze, P., Gorak, A., Woodley, J.M., Gani, R., 2015. Sus-
financial interests or personal relationships that could have tainable process synthesiseintensification. Comput. Chem. Eng. 81, 218e244.
appeared to influence the work reported in this paper. Badger, P.C., 2002. Ethanol from cellulose: a general review. In: Janick, J.,
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Berg, P., Lingqvist, O., 2019. Pulp, Paper, and Packaging in the Next Decade:
Transformational Change. Paper & Forest Products Practice, Mckinsey & com-
Ghochapon Mongkhonsiri: Formal analysis, Writing - original pany. Available at: https://www.mckinsey.com/industries/paper-and-forest-
draft. Pongtorn Charoensuppanimit: Supervision, Validation, products/our-insights/pulp-paper-and-packaging-in-the-next-decade-
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Writing - review & editing. Suttichai Assabumrungrat: Concep- on superstructure optimization. Comput. Chem. Eng. 106, 892e910.
tualization, Supervision, Funding acquisition. Bhowmick, G.D., Sarmah, A.K., Sen, R., 2018. Lignocellulosic biorefinery as a model
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