Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

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

Review

Sustainability of kraft pulp mills: Bleaching technologies and sequences

with reduced water use
A.M. Sousa a, I.S.S. Pinto b, L. Machado b, L. Gando-Ferreira a, M.J. Quina a
a
University of Coimbra, CIEPQPF, Department of Chemical Engineering, Rua Sílvio Lima, Pólo II – Pinhal de Marrocos, 3030-790 Coimbra, Portugal
b
RAIZ – Instituto de Investigação da Floresta e Papel, Quinta de São Francisco, Apartado 15, 3801-501 Eixo-Aveiro, Portugal

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

Article history: The Kraft pulp industry is a relevant industrial sector in many countries with a considerable social, eco-
Received 2 February 2023 nomic, and environmental impact. Thus, sustainability is the adequate framework to address this activity
Revised 8 May 2023 sector. This work presents a review of the literature, with a particular focus on the bleaching area and its
Accepted 21 May 2023
relevance in reducing water use. The sustainability reports of the most prominent pulp and paper com-
Available online 26 May 2023
panies were analyzed, considering their specific water utilization and the sustainability targets they have
outlined. The most industrially applied bleaching sequences were also addressed and the stages of the
Keywords:
state-of-the-art sequences were analyzed (elemental chlorine free – ECF bleaching). Moreover, in this
Sustainability
Pulp mills
review, a detailed analysis of a sequence used on an industrial scale was carried out, highlighting the
Water reduction washing steps and the measures that are taken to minimize water use. The main limitations to the min-
Bleaching imization of water use were identified, being deposit formation the major problem. Measures to over-
Elemental chlorine free come these limitations, as well as future perspectives were discussed. Due to the shortage of
freshwater nearby some pulp and paper production sites, there will continue to be great pressure in
the future to reduce water utilization, especially in the bleaching area.
Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of The Korean Society of Industrial and
Engineering Chemistry. This is an open access article under the CC BY-NC-ND license (http://creativecom-
mons.org/licenses/by-nc-nd/4.0/).

Contents

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Kraft pulp mills process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Environmental sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Bleaching technologies and the water reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Common bleaching sequence: A historic perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Most efficient bleaching technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Oxygen delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
First bleaching stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Final bleaching stages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Washing steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Industrial case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Main actions to reduce water use and its impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

https://doi.org/10.1016/j.jiec.2023.05.033
1226-086X/Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Introduction the pulp industry is intensive in energy, water, and wood, and
releases very significant quantities of atmospheric emissions, liq-
Sustainability issues are currently highly relevant to the pulp uid effluents, and solid residues. From the sustainability reports
industry. In addition to the relevance of this sector in economic of several pulp industries, it is noticeable that environmental con-
and social terms, business models must approach environmental cerns more addressed are water, forest management, biodiversity,
sustainability carefully. Nowadays, many pulp industrial plants waste, and climate issues.
and corporations periodically prepare sustainability reports, that This study intends to contribute to filling this information gap
are made available to the shareholders, stakeholders, and the gen- in the scientific literature, focusing on sustainability issues and
eral public. Many of these reports follow the Global Reporting Ini- more specifically on water use in the pulp bleaching stages. In par-
tiative (GRI) framework, to ‘‘deliver the highest level of ticular, information published in the literature in recent decades on
transparency for impacts on the economy, environment, and peo- these topics is aggregated, allowing an evolutionary view of the
ple” [21]. The sustainability reports following GRI standards dis- pulp bleaching process, what measures were taken to reduce water
play the approaches already implemented in each site and future consumption, and the impact of applying these measures. Finally, a
strategies to achieve specific goals. Common tools that have been methodology for modeling and integrated simulation of water con-
used to improve the sustainability of the pulp industry, namely sumption in bleaching will be proposed.
for developing environmental sustainability are the standard ISO
14001 (Environmental management systems), EMAS (The EU Kraft pulp mills process
Eco-Management and Audit Scheme), Ecolabel, ISO 9001 (quality
management system), ISO 45001 (Occupational health and safety The kraft process, also known as the sulfate process, allows the
management systems), ISO 50001 (energy management system), conversion of wood into pulp consisting mainly of cellulose fibers,
the UN Global Compact, circular economy framework, etc. These the main raw material for obtaining paper. A simplified scheme of
tools have made it possible to reach high standards of sustainabil- the kraft process is shown in Fig. 1. Globally, the process involves
ity that have led some pulp industries to outstanding levels. In par- the treatment of wood chips with a hot mixture (white liquor) of
ticular, some corporations have been considered eligible to water, sodium sulfide (Na2S), and sodium hydroxide (NaOH), to
integrate the Dow Jones Sustainability (DJSD) Index, which is one disintegrate lignin. After the cooking phase, the cellulose fibers
of the leading international benchmark indices for world-leading are suspended in the dark liquid (black liquor) due to the dissolu-
companies in sustainability. Some examples that can be high- tion of lignin [23]. The fiber and black liquor suspension go through
lighted in this scope are UPM-Kymmene Oyj, Canfor Pulp Products a washing process, making it possible to separate the washed pulp
Inc., Chung Hwa Pulp Corporation - Taiwan, Indah Kiat Pulp & suspension and the weak (diluted) black liquor. Weak black liquor
Paper Corp Tbk PT, and Japan Pulp and Paper Company Limited. consists of a liquid with a high organic load, resulting mainly from
However, UPM has stood out as the only company in its industry the decomposition of lignin, as well as sodium salts that allow the
sector in the Dow Jones European and World Sustainability Indices reconstitution of the main reagents that make up the white liquor.
for a decade (2012–2022). This liquid is concentrated and sent to the recovery boiler for
Even so, searching the Web of Science database with the words energy recovery from the high organic load. During the combustion
‘‘pulp mill” and ‘‘sustainability” in the title, only four results were of black liquor, a melting mass (the smelt) is formed, especially of
found, which means that the scientific community has not dis- Na2CO3. The smelt is dissolved in weak white liquor, producing
cussed this issue in depth. One of these studies is related to the green liquor. This liquid goes through a causticizing cycle, regener-
‘‘sustainability assessment of integrated forest biorefinery imple- ating NaOH and white liquor [79].
mented in the Canadian pulp and paper mills” [6]. The other study The fiber suspension is directed to the bleaching area, which
addressed the ‘‘minimization of the environmental impact of kraft normally requires several bleaching stages to achieve the desired
pulp mill effluents” [82]. This fact is unexpected, considering that brightness. In the bleaching area, the remaining lignin and chro-

Fig. 1. Overview of a conventional kraft pulp mill Ó 2008 Kvaerner Pulping [87].

59
A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

mophore groups are removed from the fibers. The target molecules the documents analyzed, the specific use of water exceeded 60 m3/
are oxidized and solubilized and these processes can occur, typi- t, since the water used in turbines and the water used in the paper
cally, in two modes: Elemental Chlorine Free (ECF) sequences, mill were accounted for in this value. In these mills, the specific
which avoid the use of molecular chlorine, replacing it with ClO2 production of effluent varied between 22 and 36 m3/t, and most
as the main bleaching agent, and Totally Chlorine Free (TCF) of the water used in the process is treated and returned to the envi-
sequences, that avoid totally the use of chlorine. In these types of ronment. Concerning the reduction of water use, some of these
sequences, the main oxidizing agents are typically oxygen perox- industries have established water use reduction targets for the
ide, oxygen, and ozone. For ECF and TCF sequences, bleaching next decade. Moreover, it is important to highlight that some of
stages are interspersed with pulp washing stages to remove solu- these industries were included in the Dow Jones Sustainability
bilized compounds [28]. Despite the recycling strategies, this area Index.
is responsible for significant freshwater utilization, and for achiev- To address environmental sustainability, it is relevant to men-
ing the removal of the chromophore groups from the fiber which tion life cycle assessment (LCA) as a valuable tool, which has been
results in a high load effluent. used for comparisons between different products and/or technolo-
gies. In recent years, some studies have been published in the con-
text of the assessment of the life cycle of various pulp and paper
Environmental sustainability products. These studies were focused on the production of raw
materials (eucalyptus), pulp production, paper production, the
Industrial growth and the high energy intensity from non- market, the potential for global warming, etc. For example, Lopes
renewable energy sources (fossil fuels) have led to consequences et al. [34] carried out an LCA study for paper production in Por-
that may compromise the needs of future generations. The pulp tuguese mills, comparing the use of heavy fuel oil or natural gas
and paper industry is one of the industrial sectors that has a rele- in the recovery cycle. Although the evaluation of the two cases
vant contribution to resource depletion (namely, wood, chemicals, did not differ in the bleaching, the pulp production step was iden-
water, and energy), producing simultaneously high loads of efflu- tified as the largest source of organic matter emission (identified as
ents. For these reasons, sustainability practices must be imple- COD). Pulp production was also identified as the major source of
mented and properly addressed, and communicated. The most adsorbable organic halogens (AOX) emissions, due to the use of
common way of reporting sustainability is the so-called ‘‘sustain- ClO2 as a bleaching agent. Pulp production makes a major contri-
ability reports”. These reports are generally published annually, bution to the eutrophication-related impact category. Samantha-
and most companies have applied the standards provided by the John [67] conducted a study related to the various stages of the
Global Report Initiative (GRI). GRI provides companies the tools paper production process in South Africa. This study does not focus
to report the impacts, creating a global common language to report on water utilization, while the bleaching area was identified as a
sustainability, helping simultaneously the companies take respon- significant contributor to the ‘‘summer smog” impact category.
sibility for mitigating the impacts. This tool can be extremely rele- Since the bleaching effluent is discharged into the sea, the impact
vant for benchmarking [22]. For the pulp and paper industry, most associated with salinization was not relevant. Two production lines
of the sustainability reports include the values of specific water were considered in this study, and the total specific use of water
use, water withdrawal, total production, energy consumption, and the specific use of bleaching water were identified. In one case,
and percentage of water devolution, among others. the uses determined were 68.8 m3/t and 34.9 m3/t, respectively,
Some of the pulp production companies were assessed to inte- and in the other case 33.2 m3/t and 16.8 m3/t. In this study, the
grate the Dow Jones Sustainability Index, which is integrated by comparison of South African and Finland mills revealed the exis-
companies that, within a given area, present the highest sustain- tence of higher impact loads in South Africa. González-García
ability scores, encouraging improvement in the implementation et al. [20] performed a study to identify which section of pulp pro-
of sustainable practices (S&P [73]. Another way of evaluating sus- duction, from the origin of raw material production, has the great-
tainability practices is related to the inclusion of ‘‘sustainable est environmental impact and the greatest potential for impact
development goals”- SDG, to be further implemented according reduction. In the case under study, pulp bleaching used a Total
to a strategic plan. Organizations that follow GRI standards gener- Chlorine Free (TCF) sequence. This study identified pulp cooking,
ally include in their annual reports the most relevant objectives for washing, and bleaching as the steps that most contribute to the
achieving sustainability in the industrial ecosystem. Often, specific production of wastewater. Ferrari et al. [17] conducted an LCA of
industrial objectives can be related to some of the 17 SDG estab- different types of paper, focusing on the emission of CO2 equiva-
lished by the United Nations (UN) in 2015 [81]. Table 1 contains lents throughout the life cycle of the products. The bleaching area
a list of the largest pulp and paper production companies that was identified as one of the operations that contributes the most to
report sustainability documents, where data related to water uti- the impact of paper, especially regarding the production of bleach-
lization was also indicated, including specific water use (water ing additives. These data are corroborated by the study by Culbert-
per air-dried (AD) ton of pulp), as well as the main SDG addressed son et al. [14], in which the LCA for the softwood pulp production
in each report. It is important to highlight that 12 out of 17 reports process is compared to the same process, integrated with lignin
analysed in the present study addressed precisely Goal 6 - Ensure extraction. In this study, it is pointed out that the consumption
availability and sustainable management of water and sanitation for of sodium chlorate to produce chlorine dioxide contributes signif-
all. Specifically, the pulp and paper industry should handle target icantly to most impact categories. The study published by Ma et al.
6.3, which is related to ‘‘improve water quality by reducing pollution, [36] approached the coupling of the life cycle assessment and the
eliminating dumping and minimizing release of hazardous chemicals assessment of the water footprint of different papers, produced
and materials, halving the proportion of untreated wastewater and from ECF pulps and C-E-H pulps (C-E-H – chlorine, alkaline extrac-
substantially increasing recycling and safe reuse globally”. tion, and hypochlorite). In this study, the water footprint is defined
Analyzing the data gathered in Table 1, it is worth mentioning as a comprehensive indicator, with geographic and temporal
that most pulp-producing industries followed GRI standards to dimensions, used to assess water pollution and its utilization in
report sustainability data. As for water use, generally, the range anthropogenic activities. The results revealed that papers produced
of specific water use (m3) per ton of pulp varies between 20 and from ECF pulps are more environmental-friendly than those pro-
50, which is in line with the recommendations of the Best Available duced from CEH pulps. In addition, it was found that water utiliza-
Techniques for the pulp and paper production industries. In two of tion and effluent generation in ECF pulps (32.7 and 27.4 m3/t,
60
A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Table 1
Sustainability data of the most relevant pulp industries.

Company, Document, year GRI Water: Specific use, targets SDG from the UN Reference
country addressed in the
report
Altri - Portugal Sustainability [61,47,50– Yes Specific water use: 22 m3/tAD; 6, 7, 8, 12, 13, and (Report [46]
51,57] 15
83% of the collected water is returned to the environment;
Target: reduce the specific water use by 50% by 2030;
Target: reduce the effluent organic load by 60% by 2030.
APRIL Group - Sustainability [61,47,50– Yes Specific production of effluents: 31.6 m3/t (integrated pulp and paper 6, 7, 8, 9, 12, and (Report
Indonesia 51,57] mill); 13 APRIL,
2020) [47]
90% of the water collected is reused;
82% of the water collected was returned to the river;
Target: reduce water use by 25% in 2030;Pulp production (excluding
energy and paper production)
increased by 8% in total water use.
Asia Pulp and Sustainability [61,47,50– Yes Specific water use: 29 m3/t (integrated pulp and paper mill); 6, 12, and 13 [2,48]
Paper Sinar 51,57]
Mas - In 2020, 13% of the water was reused;
Indonesia Roadmap vision 2030 Target: reduce the intensity of water use by 30% in 2030, compared to
2018; Achieved in 2020: 8%.
Bracell - Brazil Sustainability [61,47,50– Yes Total water use: 31.7 m3/tAD; - (Report [49]
51,57]
Effluent generation: 23.5 m3/tAD;
75% of the collected water is returned to the environment.
CENIBRA - Brazil Sustainability [61,47,50– Yes Specific water use: 38.3 m3/tAD; 6, 12, and 14 (Report
51,57] CENIBRA,
Effluent generation: 35.6 m3/tAD. 2020) [50]
CMPC - Chile Integrated [61,47,50–51,57] Yes Specific water use: 30 m3/t (integrated pulp and paper mill);Target: 6, 7, 12, 13, and (Report
reduction of water use by 25% in 2030 compared to 2018 15 CMPC,
(reference value: 30.84 m3/t). 2020) [51]
Eldorado Brasil Sustainability [61,47,50– Yes Total water withdrawal: 44.1 Mm3; 2, 6, 8, 9, 11, and (Report [52]
Celulose - 51,57] 12
3
Brazil Total effluent discharge: 37.7 Mm ;
85% of the collected water is returned to the environment;
Specific water use: 24.7 m3/tAD (gradual reduction since 2018).
International Annual Report, 2021 No 90% of the collected water is returned to the environment after - [29,53]
Paper - USA Global Citizenship, 2019 treatment;

Target: reduce water use by 25% by 2030.

Klabin - Brazil Sustainability [61,47,50– Yes Specific water use has gradually decreased from 2017 (26.65 m3/t) to 6, 7, 8, 12, and 13 (Report [54]
51,57] 2020 (23.72 m3/t) (integrated pulp and paper mill);

In 2020, effluent discharge was reduced by 3%;

Reduction of specific use by 18% (2020); Target for 2030: 30% reduction;
Integrates the ‘‘Global and Emerging Markets” list of the Dow Jones
Sustainability Index.
OJI Holdings Integrated [61,47,50–51,57] Yes Specific water withdrawal (2020): 49.3 m3/t (integrated pulp and paper 6, 12, 14, and 15 [56]
Corporation - mill);
Japan 95% of the water withdrawn is returned to the environment after
treatment;

Target for 2020: reduce water withdrawal by 6% compared to 2018;

achieved: 4.6% reduction in water withdrawal;
Reducing withdrawn water: improving operations and minimizing
water use, purifying, and treating it for reuse within the factory.
PT Toba Pulp Sustainability [61,47,50– Yes Target: 2020: freshwater use decreased by 13.36% in 2020 compared to 6, 8, and 9 (Report
Lestari - 51,57] 2019; Toba Pulp
Indonesia [60]
In 2020, freshwater was reused/recycled 4.79 times, before being
released into the environment being returned to rivers;
The management of freshwater use has improved by 9.39% compared to
2019.
SCA Pulp - Sustainability [61,47,50– Yes Water withdrawal: 63 m3/tAD, from superficial sources; 3, 6, 7, 8, 9, 11, 12, (Report
Sweden 51,57] 13, and 14 SCA, 2020)
Emissions to water: minimization (currently: 22 m3/tAD); [57]
Phosphorus emission to effluents: dropped 23 % comparing emissions in
2020 with 2014;
Virtually all used water is returned to the environment after treatment.
Stora Enso - Sustainability [61,47,50– Yes Water withdrawal: 65 m3/t (integrated pulp and paper mill); 12, 13, and 15 [58]
Finland 51,57]
Effluents: 31 m3/ t;
About 97% of withdrawn water is returned to the environment after
purification;
A decrease in pulp production in 2020 led to slight increases in specific

(continued on next page)

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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Table 1 (continued)

Company, Document, year GRI Water: Specific use, targets SDG from the UN Reference
country addressed in the
report
water consumption.
Suzano - Brazil Sustainability [61,47,50– Yes Specific use in 2020: 28.6 m3/t (1.2 m3/t reduction compared to 2019) 6, 7, 9, 12, and 13 (Report [59]
51,57] (integrated pulp and paper mill);

Target: reduction of water withdrawal in the industry by 15% in 2030;

2020 reduction totals 26.7% of the 2030 target achievement;
Target: avoid water use of more than 28.6 m3/t for 2021, optimizing
water management. Forecast to change equipment for greater water
efficiency and reuse of process water;
Part of the Dow Jones Sustainability Index.
The Navigator Sustainability Report, 2021 Yes Specific water use: 20.9 m3/t of product (integrated pulp and paper 8, 9, 12, 13, and (Report [55]
Company - mill); 15
Portugal 84% of the water collected is returned to the environment;
Achieved: 6.7% reduction in specific water use (compared to 2019);
Target: reduce specific water use by 33% by 2030 (compared to 2019)
;
The Navigator Company was awarded 3rd place by Sustainalytics,
among 81 pulp and paper mills.

UPM - Finland Corporate environmental Yes Specific water use (pulp): 32 m3/tAD (2019) and 30.7 m3/t (2020); 6, 7, 12, 13, and (Report
and societal responsibility Targets: Reduction of effluent the organic load by 40% (COD – chemical 15 UPM, 2020)
statement, 2020 oxygen demand) in liquid effluents by 2030; Achieved: 33% compared [61]
to 2008; Reduction of wastewater volume by 30% by 2030; Achieved:
10% compared to 2008;

In one of the pulp sites, the increase in washing efficiency led to a 9%

reduction in the amount of wastewater.
Veracel - Brazil Sustainability [61,47,50– Yes Specific water use: 22.2 m3/tAD. - Report [63]
51,57]

respectively) are lower than the same parameters in the produc- fuels. Globally it should be noted that although LCA is an invalu-
tion of CEH pulps (36.8 and 35.9 m3/t, respectively). Echeverria able tool for addressing environmental sustainability, in the area
et al. [16] focused on the bleaching section, by comparing a tradi- of pulp and paper industry there is room for its use in the future,
tional bleaching sequence based on the Elemental Chlorine Free namely to address issues related to water in the bleaching. In par-
(ECF) type, with a TCF sequence, using peracetic acid as the bleach- ticular, LCA could provide valuable data for deciding which is the
ing agent. The LCA demonstrated that the use of a TCF sequence best bleaching sequence from an ‘‘environmental sustainability”
with peracetic acid reduces water use by 14%, effluent production point of view.
by 16%, and the emission of AOX is eliminated. Furthermore, the
energy required is minimized as well as the amount of bleaching Bleaching technologies and the water reduction
agents. The TCF sequence with peracetic acid showed better results
than the ECF only for the three impact categories: global warming Common bleaching sequence: A historic perspective
potential, freshwater eutrophication, and resource depletion fossil
The bleaching process has undergone significant development
in the last two centuries. In the 19th century, the application of
only one chemical compound prevailed – hypochlorite. From the
late 1920 s onwards, the use of chlorine as a bleaching agent was
introduced, and multi-stage processes were developed, followed
by the application of an alkaline extraction stage to remove oxi-
dized lignin. Until the mid-1970 s, the CEH sequence (C-Chlorine,
E-Alkaline Extraction, and H-Hypochlorite) and its variants, were
the standard bleaching procedure. With the increase in production
capacity and environmental awareness, the effects of pollution
have become increasingly noticeable. Mills that used chlorine
and/or sodium hypochlorite as bleaching agents were discharging
higher and higher concentrations of polychlorinated dibenzo-p-
dioxins and furans (PCDD/F), as well as other organochlorine com-
pounds into waterways. In the mid-1960 s, the presence of these
compounds in effluents, which have toxic, mutagenic, persistent,
and carcinogenic effects, was associated with the use of elemental
chlorine [4,74]. Since then, pulp mills around the world have
Fig. 2. Evolution of the bleaching sequences [25]. phased out the use of elemental chlorine and adopted ECF bleach-
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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Table 2 following sections, the stages in which greater variations are

Modern bleaching sequences considered BAT [77]. observed on an industrial scale in Eucalyptus kraft pulp production
O/O-D-E-D-P O/O-A-D-E-D O/O-P-D-Q-PO units will be discussed in greater detail. In particular, issues such as
O/O-D-E-D O/O-Z-E-D-D O-Q-PO-DQ-PO the implementation of oxygen delignification, the replacement of
O/O-D-E-D-D O/O-A-D-P-Z-P O-Q-X-O-P/O-D-E-P-D-Paa chlorine dioxide in the first bleaching stage, and even variations
O/O-A-D-E-D-P O/O-Z-D-P O/O-Q-O-P-D-PO between the use of D or P at the end of bleaching will be addressed.
O-mP-Z-P-Z-P O/O-Q-OP-Paa/Q-PO Dhot-EOP-D-P From the analysis of Table 3, it appears that most pulp mills
A/D-EOP-D-D Dhot-PO-D D-EOP-D-D
focus on eliminating the use of elemental chlorine, except for an
Indian industrial unit, where the use of elemental chlorine and
hypochlorite is still observed. According to the literature, the water
ing sequences or sequences that eliminate chlorine (TCF use in the pulp mill is in the range of 20 and 40 m3/tAD, and the
sequences) [27]. Chemical agents such as oxygen, hydrogen perox- bleaching area is in the range of 11 and 30 m3/tAD. However, it
ide, or ozone have been introduced as bleaching agents over the is important to note that it is very difficult to establish compar-
years. Fig. 2 represents the historical evolution of the most com- isons between different processes and sequences, since many vari-
monly applied bleaching sequences. ables affect water consumption in the bleaching, such as the origin
Currently, ECF sequence-based bleaching is the dominant con- of the forest biomass, the yield of the upstream cooking process, as
cept, while several combinations can be explored. Indeed, several well as the pulp washing efficiency before bleaching. In addition,
factors must be considered in the selection, such as raw material, process conditions such as temperatures, pressures, and concentra-
type and load of chemical agents, bleaching performance, water tions of bleaching reagents have significant impacts on pulp wash
use, effluent emissions, adsorbable organic halogen load, bright- water requirements. Lastly, the quality and source of the water
ness stability, papermaking properties, operating flexibility costs used for washing also affect the water flows required in this sec-
[4]. Due to the high pollution load, the effluents generated in the tion of the mill.
process of pulp washing are treated through physical (e.g., sedi-
mentation), chemical (e.g., oxidation), and biological processes
(e.g., anaerobic digestion) [31].
The pulp and paper industry has made significant efforts to Most efficient bleaching technologies
select the best ECF sequences, considering the specific characteris-
tics of the pulp, as well as optimizing the use of chemical reagents Oxygen delignification
from an economic and environmental point of view. When the Oxygen delignification is used after cooking aiming at oxidizing
objective is to produce tissue paper, the bleaching technology is and solubilizing lignin before bleaching. It involves the reaction of
currently well established, with three-stage sequences of the D- the pulp with oxygen under alkaline conditions, followed by wash-
EPO-D type being enough to achieve a brightness of 88–90% ISO ing to recover/remove the dissolved lignin [65]. The oxygen delig-
[10]. On the other hand, for printing and writing paper grades, nification technology applied to eucalyptus kraft pulp is typically
where it is necessary to achieve high brightness with low rever- based on a two-stage system. After the first oxygen stage, the
sion, the best bleaching technology is still a matter of debate. How- amount of lignin remaining in the pulp is small (representing a
ever, the use of one or two oxygen stages (O or O/O) followed by low kappa index – an indirect measure of residual lignin content),
four stages of the D-EPO-D-D or D-EPO-D-P type is recommended which is essentially due to the presence of hexenuronic acids
to assure brightness greater than 90% ISO with reversion lower (HexA). These compounds are formed in the kraft cooking process
than 2 % ISO [10]. and are responsible for increasing the consumption of bleaching
The inclusion of alternative stages to replace chlorine dioxide chemicals, reversing the brightness of pulp, and forming oxalates
(D), such as acid hydrolysis (A or Ahot), hot chlorine dioxide (Dhot), that increase deposits and limit the closure of water circuits [70].
peracetic acid (Paa), and/or ozone (Z) in the sequences of bleaching Thus, removing HexA at the beginning of bleaching has advantages,
aims to reduce the consumption of reagents, as well as the envi- and different alternatives have been explored for this purpose.
ronmental impact (ClO2 load, effluent volume, COD emission) However, oxygen does not react with HexA, and the second stage
and allow the partial closure of the water circuit in the bleaching with oxygen has little impact on the kappa index [83]. The second
process [7]. This happens since the replacement of ClO2 by other stage significantly increases brightness, which represents an
total chlorine-free bleaching agents can allow the valorization of advantage for the overall process [12].
the filtrates in the recovery boiler. In addition, oxygen has a greater selectivity when compared to
Table 2 summarizes the modern bleaching sequences according kraft cooking, which makes it possible to preserve the pulp yield.
to the European Commission’s reference document on the best Thus, it is more advantageous to finish kraft cooking at a higher
available techniques - BAT [77]. kappa index, using oxygen as a more selective agent to complete
Currently, modern pulp and paper mills consume about 20 – delignification and achieve lower kappa numbers. Vuorinen et al.
25 m3/tAD of water in bleaching [41]. Reducing the utilization of [83] demonstrated that the yield benefit after oxygen delignifica-
fresh water is advantageous both from an environmental and eco- tion was 2 – 2.5% by stopping the cooking at a kappa index of
nomic point of view, as it reduces energy consumption and effluent 19, instead of 15.5. The same trend was observed in other studies
treatment costs. Efforts have been made to close loops of water, for applied to softwood pulps [11].
example, by integrating filtrates into recovery systems or increas- The advantages of oxygen stages are both environmental and
ing their recirculation within the bleaching area. However, a high economic. The effluent from the oxygen stage is free of chloride
closure in the water circuit can have negative effects due to the ions and can be recirculated. Thus, the installation of an oxygen
accumulation of dissolved substances and non-process elements stage considerably reduces AOX, COD, BOD, and color emissions
(NPE) in the bleaching stages and process cycles, and the later for- in the effluents, allowing their recirculation and reducing water
mation of scale deposits in pipes and equipment [28]. Thus, the utilization [8,37]. There are also savings in operating costs through
selection and use of bleaching chemicals properly are extremely the use of lower amounts of oxidizing agents (D, Z, P, etc.) since
important to minimize these problems. Table 3 contains water uti- oxygen is less expensive. The main disadvantages of oxygen com-
lization data for different bleaching sequences, including industri- pared to chlorine dioxide stages are lower reactivity and selectiv-
ally applied sequences and laboratory-tested sequences. In the ity, as well as the higher capital cost of the installation [5].
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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Table 3
State-of-the-art bleaching sequences and respective water use and effluent production.

Mill/ Pulp Sequence Water use Total Bleaching Notes Ref

country bleaching (m3/ water use effluents
tAD) (m3/tAD) (m3/tAD)
Brazil Kraft O-Dhot-(EP)-D-P 16 40 ni 6 m3/t of fresh water is used in [39]
countercurrent washing with stage jump
Brazil Kraft ECF D-(EP)-D-P Values tested in ni ni Lab-scale study; [18]
the lab: 9, 6
and 3 Washing was carried out by mixing
filtrates and distilled water;
Desired brightness is not achieved when
3 m3/t is used for washing.
Brazil Kraft ECF O-D-(EOP)-D-P ni ni ni Through a simulation study, the main [40]
conclusions are:

replacement of fresh water in the P

washer by filtrates from the EOP washer
can lead to a reduction of 219 m3/h
(freshwater reduction);
This change can lead to 74% water savings.
CENIBRA, Brazil Kraft ECF O-Ahot-(EOP)-D- 23.67 ni 9.11 Lab-scale study, using oxygen [13]
(PO) delignification before bleaching;

Effluent generation: 9.11 m3/t;

3.89 m3/t of filtrates are sent to the
washing steps of the causticizing cycle;
Washing liquid: 15.67 m3/t from white
waters; 8 m3/t from condensates;
9 m3/t reduction in effluent generation.
Compilation Kraft ECF O-D-(EO)-D-D ni ni 5.9–18.4 Volatile solids in the effluent: 26–72.7 kg/t [3]
Compilation Kraft TCF O-Z-(EO)-Z-Q-P ni ni 5.8 Volatile solids in the effluent: 44–59.6 kg/t [3]
Husum Mill of MoDo Kraft ECF Includes O, Z, P, ni ni 5 Countercurrent (Bajpai,
paper AB, Sweeden and D 2012)
[4]
India Kraft Includes C, H, and 11.0 ni ni Small mills average water use of around [78]
D 11.0 m3/t (production < 100 t/day); some
smaller mills use only H stage;
16.9
Large mills average water use of around
16.9 m3/t (production > 100 t/day).
Kymmene, Wisforest Kraft ECF O-(ZD)-(O/E)- 25 ni ni (Bajpai,
(ZD)-(EPD) 2012)
[4]
Kymmene, Wisforest Kraft TCF O-(ZQ)-(OP)-(ZP) 15 ni ni Intention to reduce the water use to (Bajpai,
10 m3/t 2012)
[4]
Louisiana Kraft TCF Q-(EOP)-P-P-P ni ni 6.76 Q stage – Chelation stage - is the only one (Bajpai,
-Pacific Corporation, that generates effluent 2012)
USA [4]
Scandinavia Kraft ECF D-(EO)-D-(PO) 30 ni ni Oxygen delignification before bleaching; [84]

High water use: lower risk of metal

scaling;
Washing equipment: wash filter, wash
presses, drum displacement, dewatering
presses;
The company is using process simulation
to apply process modifications to reduce
water use.
Stora, Gruvon Kraft ECF D-E-D-E-D ni ni 12 (Bajpai,
2012)
[4]
Union Kraft ECF O-Z-(EO)-D ni ni 9.1 Filtrates from O, Z, and (EO) flow in (Bajpai,
countercurrent, to be recovered. 2.1 m3/t 2012)
Camp Corporation, from Z stage is purged to avoid scaling; [4]
USA
D-stage filtrate is discharged to the sewer.
UPM Fray Bentos, Kraft ECF (AD)-(EOP)-D-P ni 21.5 ni [62,77]
Uruguay
Veracel, Brazil Kraft ECF A-D-(EOP)-D-P ni 22.2 ni (Report
[63,77]

ni – not indicated.

First bleaching stage many variations to account for the constraints of each industrial
As aforementioned, the core technology of ECF bleaching of unit, including raw material, etc. Currently, the starting point for
eucalyptus kraft pulp is D-(EPO)-D-D type. However, there are bleaching eucalyptus pulp is almost invariably the high content

64
A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

of HexA. These compounds are not removed during the oxygen stage guarantees lower brightness reversion, better refinability,
stage and thus, HexA reaches the first bleaching stage [83,88]. water retention, and fines.
For this reason, many state-of-the-art mills are replacing the con-
ventional first D stage (30 min, 50–70 °C) with an alternative stage
Washing steps
[41]. The removal of HexA can be accomplished through an acid
Pulp washing is a fundamental process in bleaching sequences
treatment (A), an ozone stage (Z), or by increasing temperature
that takes place in washer equipment and promotes the contact
in the D stage, Dhot (120 min, 90–95 °C). There are several ways
of the pulp suspension stream with the water stream, allowing
to combine these stages to enhance HexA removal and minimize
the dissolved components of the pulp suspension to migrate to
reagent consumption. Generally, the D stage, when operated at
the bulk of the solution. The washing stage ends with the separa-
higher temperatures, can also be an Ahot/D combination. The acid
tion of the filtrate and the washed pulp, where the consistency of
stage removes metals that can accumulate and give rise to scale,
the suspension is one of the washer design specifications. The pur-
and are responsible for the decomposition of H2O2 in later stages
pose of the washing steps is to remove NPE as well as dissolved
[88].
and/or oxidized organic matter during the bleaching stages, since
Ragnar and Lindstrom [43] reported that Dhot technology is
if they remain in the fiber line, the later bleaching stages are ham-
more efficient than Ahot/D in terms of reducing reagent consump-
pered, requiring larger amounts of reagents to achieve the same
tion, loss of yield, and amount of AOX in effluents and also increas-
brightness [69]. Thus, the washing steps also prepare the pulp in
ing brightness stability. The comparison of the sequences D-EPO-D,
the best conditions for the next bleaching stage, namely concern-
Ahot/D-EPO-D, and Dhot-EPO-D showed a total consumption of
ing temperature, pH, and composition.
ClO2 as active chlorine (including H2O2) of 4.34, 4.14, and 3.74%,
Conceptually, pulp washing is based on 5 basic concepts: dilu-
respectively. According to this study, the Ahot/D stage achieves a
tion, mixing, dehydration, diffusion, and displacement [69]. Dilu-
saving of the total active chlorine used in the sequence of about
tion consists of decreasing the concentration of NPE and organic
4.6%, while the saving in the Dhot is 13.8%.
matter in the pulp line, by mixing it with a cleaner stream. This
The effects of the Dhot or Ahot/D stages can vary considerably
allows that when separating the streams at the outlet of the
in Eucalyptus kraft pulps, which can be attributed to differences
washer, the amount of contaminants transported with the pulp is
in the composition of the raw material [44]. For similar pulps,
lower. Dehydration (as well as displacement) involves removing
D0, Ahot/D, and Dhot technologies showed a similar trend in
the water from the external pulp solution, and replacing it with
chemical consumption, with the benefits due to Dhot bleaching
cleaner water, to minimize the carry-over of the pulp. In the case
technologies being slightly more significant [10]. [42] also reported
of displacement, the water in the slurry is replaced by cleaner
that the bleaching efficiency with a Dhot stage depends signifi-
water, with the aid of a pressure difference. Diffusion is a mass
cantly on the type of wood.
transfer process, in which the NPE adsorbed on the pulp are
Regarding the application of ozone in the first stage, it can be in
removed to the liquid matrix. However, because the diffusion pro-
total chlorine dioxide replacement mode (Z/E) or partial (Z/D)
cess is slow, the operating residence time is high (
4 hours)
replacement mode [19]. Some variants may include adding an Ahot
[64,69]. At the industrial scale, several configurations of the wash-
stage before ozone. Although acid hydrolysis decreases the effi-
ing process have been studied, based on countercurrent circula-
ciency of ozone, it has been commercially proven that the intro-
tion. The simplest form is the direct countercurrent scheme, but
duction of the Ahot stage can reduce the bleaching costs of the Z/
it can also include flow splitting, associated with stage-jump coun-
EP-D-P sequence [38]. The main motivations for including ozone
tercurrent washing.
in Z/EO-D-D and Z/EO-D-P sequences have been the possibility of
As it requires high amounts of water to wash the pulp, bleach-
partially reusing the effluent, the low AOX content of the pulp,
ing is the section of the pulp mill with the highest water use, rep-
and the brightness stability [38]. However, a limited number of
resenting up to 50% of the total consumed [18,28], generating
mills have implemented Z stages due to low selectivity, which
about 65% of the effluent produced in the mill [64]. For this reason,
leads to marked degradation of cellulose and consequent loss of
it is very crucial to establish efficient washing schemes. To mini-
viscosity and yield [10]. Additionally, the low efficiency in ozone
mize the environmental impact of mills in terms of water utiliza-
production has also been an obstacle [37].
tion, fresh water has been replaced by condensates [28]. These
condensates result from the concentration process of the black
liquor, by evaporation. Its use in bleaching, as a washing liquid
Final bleaching stages
to replace fresh water, has been investigated, especially with
After the first bleaching stage, which as mentioned can be D0,
regard to pulp quality and the presence of contaminants, such as
Dhot, Ahot/D, or Z, an alkaline extraction (generally EOP) must
acetone, methanol, sulfur-based compounds, or volatile organic
be followed to remove the oxidized lignin. Regarding the final
compounds [86]. Replacing fresh water with condensate did not
stage of bleaching eucalyptus kraft pulp, it can be made up of dif-
have noticeable effects on pulp properties, such as brightness, vis-
ferent combinations, typically of the D, Dn/D, D-D, Dn-D, D-, P, or
cosity, and kappa number. It was found that the presence of vola-
D-E-D type. While the use of three final stages (after the first alka-
tile organic compounds and methanol in the condensates did not
line extraction) has been popular in the past, the current trend is to
significantly affect the COD of the filtrates [85].
use only one or two stages to minimize capital costs. The Dn/D
stage is considered just one stage, although it requires an interme-
diate wash step. Pulps bleached with only one stage have lower Industrial case study
capital costs, although they have lower brightness stability and
higher operating costs. In this section, a state-of-the-art bleaching sequence will be
Among the two-stage approaches (DD and DP), DP has been analyzed in detail. The bleaching section follows the sequence O/
considered the most interesting, since it guarantees high final O-D-E-D-D and the simplified diagram is shown in Fig. 3.
brightness and good brightness stability [15,75,76]. Final bleaching This bleaching sequence begins with two consecutive oxygen
with DP also produces pulp with better refinability and tensile delignification (O/O) stages, promoting the extension of the cook-
strength compared to DD [26]. Loureiro et al. [35] compared the ing process. This double stage of bleaching promotes an increase
effects of using D or P in the last bleaching stage of Eucalyptus in the brightness of the pulp and is followed by washing and press-
globulus kraft pulp (D-E-D-D vs. D-E-D-P), concluding that the P ing [28].
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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Fig. 3. Industrial bleaching line (case study).

The main aims of washing the oxygen delignified pulp are the AOX is avoided and problems due to scale and corrosion in the boi-
removal of organic compounds dissolved in the oxidation stage, ler are minimized. The condensates resulting from the concentra-
as well as sodium (for sodium recovery) and the chemical species tion process of liquid in evaporators can also be reused in other
that contribute to alkalinity, such as CO2– –
3 and HCO3 anions. The processes, such as washing liquid in the other bleaching stages,
removal of these species is particularly important, since this allowing the reduction of water utilization. The amount of water
stream moves to an acid stage, in which the adsorbed NPE tend to be introduced at this stage must be carefully optimized, to both
to migrate to the external solution, with the risk of precipitation achieve good washing efficiency and facilitate the concentration
of solubility-limited minerals. In the washer equipment after the process [68].
D0 stage, the objective is to remove and purge the solubilized Then, a chlorine dioxide (D0) stage is applied, where the oper-
organic compounds and NPE, to minimize the carry-over along ating pH typically ranges from 2 to 3.5. Chlorine dioxide reacts
the fiber line. Furthermore, the species that contribute to the acid- with the lignin present in the pulp, oxidizing it and giving rise to
ity of this stream need to be removed, since the presence of these chlorate (ClO-3), chlorite (ClO-2), hypochlorite (ClO-), chlorine (Cl2),
species is associated with corrosion problems in the equipment and chloride (Cl-) species. These species pass to the filtrates in
[80] and excessive use of chemicals in the alkaline stage. After the washing stages, and their concentrations are higher than the
the alkaline extraction stage, it is necessary to remove the organic recommended chlorinated species content for energy recovery.
compounds that were oxidized in D0 and dissolved in the EOP Therefore, this filtrate must be discharged as liquid effluent.
stage. The other target of this washing consists of the extractable After bleaching with chlorine dioxide, the pulp goes to an alka-
constituents of the wood, which remained in the pulp until this line extraction stage reinforced with oxygen and hydrogen perox-
stage, such as fats and resins. Most of the lignin present in the fiber ide, where the oxidized lignin is solubilized and can be removed
is degraded and removed until the alkaline extraction stage, so the from the pulp stream with a washing process. Alkaline extraction
last two ClO2 stages have the function of increasing the brightness is operated at a pH greater than 10.5. The pH in a basic range pro-
stability and attacking the residual lignin, conditioning the pulp for motes the adsorption/ion exchange of NPE on the fiber surface
the paper production process. Thus, the purpose of washing after (Fig. 4), as well as the precipitation of minerals such as calcium car-
D1 is to remove the compounds that give the pulp acidity, as well bonate (CaCO3), calcium oxalate (CaC2O4), or barite (BaSO4). For
as any organic matter that is solubilized. Lastly, the purpose of this reason, the reduction of water use in the washing steps asso-
washing after D2 is to remove chlorides to avoid corrosion prob- ciated with this stage must be done considering the restriction of
lems in the pulp line. not reaching saturation for the mentioned and similar minerals
As can be seen in Fig. 3, the pulp suspension from the oxygen [72].
delignification is washed with water or condensate and the filtrate Bleaching ends with two stages of chlorine dioxide. The objec-
continues in countercurrent to the previous washing stage up to tive is to remove the chromophore groups present in the pulp.
the digester. This stage marks the boundary between delignifica- The pH of these stages varies between 3.5 and 5, allowing for the
tion and the bleaching process itself. The washing liquid from the desorption of NPE, as well as the dissolution of some minerals.
delignification section is rich in organic compounds solubilized in The four stages of bleaching are combined with washers. White
the cooking and oxygen stages. This filtrate is typically alkaline, water from the pulp drying machine is introduced for washing
and the organic substances present have a high molecular weight after the last bleaching stage and circulates in countercurrent, to
[69]. Furthermore, this filtrate is free from chlorides or other wash all the pulp that leaves a D stage. At the end of this washing
organochlorine compounds (potentially formed in chlorine dioxide line, at the D0 washing equipment, the filtrate is removed from the
stages). For this reason, this liquid with a high organic load can be process, as acidic effluent. This effluent has high concentrations of
recirculated to the energy recovery boiler. Thus, the formation of calcium and other NPE, which are desorbed from the pulp under
these acidic conditions. Hot water or condensates from evapora-
tion are used to wash the pulp after the alkaline extraction, result-
ing in a final basic pH for this effluent, which is discharged
separately. These effluents can be treated differently to minimize
the possibility of the formation of precipitates or adsorption of
NPE on the fibers, since the combination of a high pH (from the
washing of EOP) and high concentrations of NPE in the stream to
be washed is avoided [28,64].
The selected configuration for the washing has some advan-
Fig. 4. Scaling and sorption on the fiber wall. tages over the use of direct countercurrent:

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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

 The effluent from the washing of D1 is less loaded than what Main actions to reduce water use and its impacts
would result from the EOP if direct countercurrent were used,
which increases the driving force in the washing, and, conse- Over the last few decades, the reduction of water utilization in
quently, its efficiency. pulp bleaching units has been achieved using a semi-
 Dividing the filtrate, generating two effluents, minimizes cal- countercurrent pulp washing system. In some situations, fresh
cium precipitation, as mentioned in Section 1. water is only used to clean the pulp after the last stage of bleach-
 Acid effluent and alkaline effluent can have different destina- ing. In other situations, the use of fresh water to wash the bleached
tions depending on the process needs of the mill [69,80]. pulp can be fully replaced by white water, from the pulp drying
machine, as seen in the industrial case study (section 4.3, Fig. 3).
The evolution of the bleaching sequences led to a significant Furthermore, there has been a reduction in washing flows, mini-
reduction in water use. The gradual replacement of chlorine- mizing the generation of effluents in the process [28]. However,
based bleaching reagents with oxygen-based reagents (O, P, and the reduction of water input in the bleaching sequence has led to
Z) found in TCF sequences, decreased chloride content in alkaline an increase in the concentration of organic (from wood) and inor-
filtrates. Since these filtrates are rich in organic matter and with ganic species, which end up accumulating in the process. The main
a low concentration of chlorides, the energetic recovery of the NPE that accumulate in the process are calcium (Ca), magnesium
organic load present is possible [30,69]. (Mg), potassium (K), chlorine (Cl), and barium (Ba) causing several
problems in the industrial process [80].
The most relevant organic species with the greatest contribu-
tion to the formation of precipitates is oxalate (C2O2- 4 ), which
results from the deprotonation of oxalic acid (H2C2O4). Oxalic acid
is naturally present in wood, but during the cooking and bleaching
process of the pulp, the formation of this species can occur as a
result of the oxidation and degradation reactions of lignin [32]. It
is estimated that between 250 and 500 g of oxalic acid are formed
per ton of pulp in the set of oxidizing stages [66], namely, the
stages involving chlorine dioxide and hydrogen peroxide [80].
Among the anionic inorganic species that accumulate in the pulp
production process, the sulfate ion (SO2- 4 ) and the carbonate ion
(CO2–
3 ) stand out.
The accumulation of NPE in pulp production and bleaching
plants has negative impacts not only on pulp quality but also on
mill operation [28]. The main minerals that can precipitate in a
pulp mill with reduced water use are calcium carbonate (CaCO3),
calcium oxalate (CaC2O4), and barite (BaSO4). CaCO3 tends to pre-
cipitate at pH values between 8 and 13, since the carbonate ion
is dominant, Fig. 5a, making it possible for its formation and pre-
cipitation in the oxygen delignification stages and the stages of
alkaline extraction [80]. The carbonate ion appears in the recausti-
cization cycle (associated with cooking), and is available in the pro-
cess streams for the formation of minerals. Equation (1) describes
the formation of calcium carbonate and the solubility product of
this mineral in water at 25 °C is 2.8x10-9 [71].

Ca2þ ðaqÞ þ CO2

3 ðaqÞ ! CaCO3 ðsÞ ð1Þ
In the case of calcium oxalate, the occurrence of this mineral is
possible for pH values above 3 and below 12.5. In fact, for pH
greater than 3, there is a deprotonated form of oxalate ion in the
solution, Fig. 5b. On the other hand, for pH greater than 12.5, all
the calcium is mobilized in other reactions [28]. Calcium oxalate
can precipitate in various crystalline forms, and the monohydrate
form is the most soluble. However, if the pH of the system is lower
than 4, the dihydrate form may appear, which is less soluble [24].
Thus, in the bleaching sequence, the highest probability of the
appearance of calcium oxalate precipitates occurs in the alkaline
extraction stages and the last two stages of chlorine dioxide. Pulp
transfer from acidic to alkaline stages, where sodium hydroxide
is added, is a critical point where there is a sudden change in the
pH, creating the optimal conditions for deposit formation. Thus,
it is important to ensure adequate pulp washing to avoid carry-
over of the oxalate ion along the fiber line, minimizing the proba-
bility of precipitate formation. Equation (2) describes the forma-
tion of calcium oxalate and the solubility product of this mineral
is 2.7x10-9 at 25 °C [71].
Fig. 5. Speciation of CO2– 2- 2-
3 (a), C2O4 (b), and SO4 (c) anions in aqueous solution as a
function of pH (obtained with Visual Minteq). Ca2þ ðaqÞ þ C 2 O2
4 ðaqÞ ! CaC 2 O4 ðsÞ ð2Þ

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A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Finally, BaSO4 precipitation can occur for a pH above 2. How- value. However, from the interaction with the industrial sector, the
ever, the occurrence of this mineral is less frequent, since the authors of this study understood that it may be possible to further
amount of barium in the wood is lower than that of calcium. The reduce the water consumption in the bleaching, if the reduction is
sulfate ion is present in the process, resulting from the cooking applied to strategic points. This can be achieved with process mod-
with sodium sulfate and the use of sulfuric acid to correct the pH eling and simulation, which will be detailed in section 5. Fig. 6 rep-
in the D stages. When the barite appears in the equipment, its resents the direct impacts of water closing in pulp bleaching.
removal is done using ‘‘hydro blasting” with caustic detergent Another way to minimize water use during bleaching is to min-
and chelating agents, which adds substantial costs to the operation imize the amount of NPE that goes through the fiber line as carry-
[24]. According to the literature, an approach to minimize the for- over. For this, an efficient debarking of the wood must be carried
mation of these precipitates involves the efficient debarking of the out, since the concentration of NPE in the green parts (bark, leaves,
wood, since several cations are in greater concentration in the bark branches) can be about 10 times higher than in the wood itself
than in the wood ([4]; [28]. Eq. (3) describes the formation of barite [80]. As an example, it is estimated that about 2 t/day of calcium
and the solubility product of this mineral is 1.1x10-10 at 25 °C [71]. enters a pulp mill together with the wood [24].
Fig. 5c shows the chemical speciation of SO2- 4 anions in aqueous Additionally, the utilization of peracetic acid (A) in complement
solutions as a function of pH. Thus, it can be inferred which precip- to the O/O delignification stage may have a positive effect on water
itates are more likely to form for each pH. utilization. In oxygen delignification, lignin degradation occurs
mainly, with no attack on the hexenuronic acids present in the
Ba2þ ðaqÞ þ SO2
4 ðaqÞ ! BaSO4 ðsÞ ð3Þ pulp, which contribute to its brown color. Peracetic acid can
degrade these molecules and may increase brightness before the
Mineral precipitation can also be prevented by using flocculants ClO2 stages. Thus, the amount of reagents needed for the bleaching
or chelating agents, which inhibit the nucleation and growth of itself decreases, also minimizing the amount of water needed for
mineral crystals. Another alternative involves the use of Mg(OH)2 washing [9].
as a source of alkali, since the Mg2+ ion competes with Ca2+, mini- Another possibility to reduce water utilization involves an
mizing the formation of oxalates and carbonates [28]. attempt to take advantage of the alkaline effluent generated, send-
As already mentioned, in addition to precipitation, cations can ing it to the recovery boiler. This will only be possible if the chlo-
also interact with the fiber through adsorption processes on its sur- ride content in the effluent is reduced to an acceptable level in the
face. This phenomenon is dependent on the type of ion, and the boiler. To this end, some pulp production companies have imple-
number of active sites in the fiber. In turn, the amount of active mented measures to remove chlorides from this effluent, namely
sites in the fiber is dependent on the pH in the solution phase, since through evaporation followed by electrodialysis, precipitation with
under acidic conditions, the carboxylic and phenolic groups tend to lime, acidification or desorption of HCl, and evaporation. However,
be completely protonated, minimizing the existence of active sites the efficiency of these processes is not guaranteed [28].
for adsorption. Some studies have highlighted the equilibrium of In the case of integrated pulp and paper mills, the replacement
Donnan approach to model the fiber and solution system [72]. of fresh water in bleaching with process water from paper machi-
One of the limitations of ECF-type sequences is the presence of nes, specifically clarified water, has been pointed out by some
chlorinated species in the filtrates, which hampers the recircula- authors as a measure to achieve further reductions in water use
tion of these filtrates to brown stock washing, evaporation, and [1] and industrial cases can already be found. This measure is also
recovery boiler. Nevertheless, it is possible to reuse alkaline filtrate mentioned among the guidelines of the document on the BAT).
in the brown stock given some conditions: controlled ClO2 charge Furthermore, this document indicates that measures to reduce
in the D0 stage and good washing and purge in D0 washer to water use should be applied gradually, starting with good system-
results in low chloride content in alkaline filtrate; treatment of atic water management and appropriate treatment of white water,
recovery boiler ashes and chloride purge to control its content in going through saving and replacing fresh water, with advanced
the circuit and avoid corrosion problems. In the case of TCF treatments and recirculation of white water, and concluding with
sequences, in theory, it is possible to achieve greater reductions the in-line treatment of the process water so that it can be recircu-
in water use, since the filtrates are free from chlorides and can lated. This document also indicates that there must be good stor-
be concentrated and recovered by combustion, resulting in a age capacity to minimize the impact of a possible system crash
greater amount of condensate further used as freshwater [28]. [77].
However, according to Axegård et al. [3], sequences of the TCF type In addition, guidelines are indicated on how to operate the
are less compatible to reduce water utilization, since their reagents bleaching line, to optimize water use, highlighting: i) Oxygen
are more susceptible to the accumulation of metals and organic delignification at medium consistency (10–15%) allows for higher
species. Despite this, the effluents generated in E sequences can selectivity in the bleaching [77]; ii) Use of hydrogen peroxide
be treated to remove NPE, namely, through precipitation processes under optimized conditions for bleaching residual lignin (D2 stage
with lime or lime mud or by ion exchange [33,80]. complement) [77].
Overall, the reduction in the water flow for the washing steps
will increase the concentration of NPE in processual streams,
which can have two direct consequences: scaling, which leads to Future prospects
frequent plant shutdown (higher operation costs), and sorption
on the fiber wall, reducing the fiber quality and the product added In addition to the already established BAT, emerging techniques
are pointed out, which have been studied at a laboratory or pilot
scale, and which are expected to allow additional reductions in
water utilization [77], highlighting:

 Leaching the chips with an acidic solution removes the NPE that
enters the process through the wood. Thus, it is estimated that
the amount of calcium that enters the process can be reduced
by about 70%. This measure complements the efficient debark-
Fig. 6. Negative impacts of closing the water loops in the pulp bleaching section. ing of wood.

68
A.M. Sousa, I.S.S. Pinto, L. Machado et al. Journal of Industrial and Engineering Chemistry 125 (2023) 58–70

Fig. 7. Methodology proposed by the authors to approach the water minimization in the bleaching area.

 Separation of metal ions from bleaching filtrates through a observed in the 1980 s. Furthermore, the oxygen stage allows the
purge. To this end, ‘‘kidney” technologies are used, which allow use of filtrates for the boiler, minimizing the need for water for
a selective separation of multivalent metal ions. One example is washing the subsequent stages, since these filtrates are concen-
the use of ion exchange processes. Another example involves trated and the resulting condensates can be later integrated into
adjusting the pH of acidic filtrates to the basic range, forming the washing circuits. As the main limitations to the reduction of
compounds of low solubility that can be removed by filtration water utilization, the adsorption of NPE and the precipitation of
or flotation. For the selective removal of organic compounds minerals stand out, once reducing the water flow increases the
present in alkaline filtrates, the use of ultra and nano- concentration of the different dissolved species, thus making it
filtration methods is recommended. easier to reach the saturation product for the different minerals.
The water network in the washing (associated with bleaching)
Another alternative for minimizing water use in a pulp produc- can be optimized with simulation tools, to determine the washing
tion unit involves optimizing the water distribution network for configuration that minimizes water use while simultaneously
bleaching which was studied by the authors of this review. This restricting scaling and adsorption. For the reduction of water uti-
hypothesis requires the correct mathematical modeling of the lization in the future, further research is required at the lab scale,
industrial process, so that the water network is properly optimized, to refine the implemented models, and then the scale-up is the
allowing identification of the washing configuration that allows final step to achieve full scale. LCA can generate valuable data to
the lowest water use, without inducing the adsorption of NPE decide which is the best bleaching sequence in terms of environ-
and the precipitation of minerals. Currently, process software ded- mental sustainability, and this type of study should be promoted
icated to the simulation of pulp production units does not predict in the future.
accurately the pH nor the adsorption and precipitation phenom-
ena. To this end, these simulators must be upgraded with more Declaration of Competing Interest
reliable adsorption models, for example, the Donnan equilibrium
model [45], and must be integrated with chemical speciation tools, The authors declare that they have no known competing finan-
to allow, in the future, to optimize the water network to be used. cial interests or personal relationships that could have appeared
Fig. 7 shows an example of integration between a process simula- to influence the work reported in this paper.
tor and an Excel spreadsheet where speciation calculations, pH
prediction, and Donnan equilibrium are previously predefined. Acknowledgments

Conclusions This work was carried out under the Project inpactus – innova-
tive products and technologies from eucalyptus, Project N.° 21874
In this review, the sustainability data of the most relevant pulp funded by Portugal 2020 through the European Regional Develop-
and paper mills were analyzed, with a special focus on water uti- ment Fund (ERDF) in the frame of COMPETE 2020 n°246/AXIS
lization. It was found that most companies follow the rules of the II/2017.
Green Report Initiative (GRI) in the preparation of their sustain-
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