Pulp and Paper Industry: Emerging Waste Water Treatment Technologies

Pulp and Paper Industry

Emerging Wastewater Treatment Technologies

Pratima Bajpai

Pulp and Paper Consultant, Kanpur, India

Table of Contents

Cover image

Title page

Copyright

List of Figures

List of Tables

Preface

Acknowledgments

Chapter 1. Introduction

Chapter 2. The Pulp and Paper Industry

2.1. Global Pulp and Paper Industry

2.2. Pulp and Paper Manufacturing Processes

2.3. Wood Handling and Debarking

2.4. Pulping Technologies

2.5. Washing of Pulp

2.6. Screening of Pulp

2.7. Pulp Bleaching/Brightening

2.8. Chemical Recovery

2.9. Stock Preparation and Papermaking

Chapter 3. Best Available Techniques

Chapter 4. Water Usage in the Pulp and Paper Processes

Chapter 5. Reduction of Water Consumption in Pulp and Paper Mills

5.1. Water Conservation in Pulp Mills

5.2. Modification of Pulping and Bleaching Processes

5.3. Separation of Process and Nonprocess Waters

5.4. Process Modification

5.5. Improvement in Quality and Management of Paper Machine Wastewater

5.6. System Closure

5.7. Integration of Water Systems/Use of Pinch Technology

Chapter 6. External Treatment Technologies Used for Pulp and Paper Mill Effluents

6.1. Primary Treatment

6.2. Secondary Treatment

6.3. Tertiary Treatment of Wastewater

6.4. Comparison of the Treatment Efficiencies for Different Wastewater Treatments

Chapter 7. Emerging Technologies for Wastewater Treatment

7.1. Advanced Oxidation Processes

7.2. Treatment With Microorganisms and Enzymes

7.3. Sequential Biotreatment (Anaerobic and Aerobic)

7.4. Internal Circulation Reactor

7.5. FlooBed Process

7.6. Membrane Processes

7.7. Other Techniques

Chapter 8. Examples of Full-Scale Installations

Chapter 9. Future Perspectives

Glossary of Terms

Index

Copyright

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List of Figures

Figure 1.1 Relationship between forest products industry and water cycle. 2

Figure 1.2 Grade-specific effluent volume in the German paper industry. 3

Figure 2.1 Flow diagram for the pulp and paper production process. 13

Figure 5.1 Dissolved air flotation clarifier. 65

Figure 6.1 Water flows in the pulp and papermaking process. 72

Figure 6.2 An aerated lagoon system. 76

Figure 6.3 Activated sludge wastewater treatment. 78

Figure 6.4 Internal circulation (IC) reactor. 84

Figure 6.5 Upflow anaerobic sludge blanket reactor. 84

Figure 6.6 Biothane advanced upflow anaerobic sludge blanket reactor. 85

Figure 6.7 Schematic diagram of expanded granular sludge blanket (EGSB) reactor. 85

Figure 6.8 Biobed advanced expanded granular sludge blanket (EGSB) reactor. 86

Figure 6.9 Biobed DUO high-rate anaerobic expanded granular sludge blanket (EGSB) process for the treatment of industrial wastewater. 86

Figure 7.1 Reactions involved in advanced oxidation processes. 98

Figure 7.2 Advanced oxidation process (AOP) as pretreatment of biological system. 100

Figure 7.3 Advanced oxidation process (AOP) as posttreatment of biological system. 101

Figure 7.4 Decomposition of ozone in water. 103

Figure 7.5 Film layer purifying chamber process. 111

Figure 7.6 Torricelli apparatus. 111

Figure 7.7 Countercurrent bubble column. 112

Figure 7.8 Otto apparatus. 112

Figure 7.9 Percent COD reduction in case of different effluents. 114

Figure 7.10 FlooBed moving bed biofilm reactor (MBBR). 145

Figure 7.11 FlooBed biofilm-activated sludge (BAS). 146

Figure 7.12 FlooDaf microflotation. 147

Figure 7.13 Schematic of a submerged membrane bioreactor. 149

Figure 7.14 Memthane. Anaerobic Membrane Bio-Reactor. 150

List of Tables

Table 1.1 Wastewater generated in raw material preparation, pulping and bleaching operations. 4

Table 1.2 Wastewater generated in stock preparation/papermaking, utilities, and chemical recovery. 5

Table 1.3 Driving forces for recycling and reducing freshwater consumption. 6

Table 1.4 Water conservation principles. 6

Table 2.1 Contribution to the process water pollution by different raw materials. 19

Table 3.1 General measures for reducing environmental effects. 32

Table 3.2 Best available techniques for reducing emissions to water and reducing water consumption in the EU. 33

Table 3.3 Best Available Techniques (BAT) emission levels for different pulp and paper processes. 33

Table 3.4 Information regarding emission levels of various pollutants. 34

Table 4.1 Water consumption in the mills with best available techniques (BAT). 39

Table 4.2 Total water management. 39

Table 4.3 Average specific water consumption in large wood-based pulp and paper mills. 42

Table 4.4 Average water consumption in different pulp and paper mills. 43

Table 4.5 Water consumption in US pulp and paper mills. 44

Table 4.6 Freshwater consumed by different processes in bleached kraft mills. 44

Table 4.7 Freshwater consumed in fiber line in bleached kraft mills. 44

Table 4.8 Freshwater consumed in pulp machine in bleached kraft mills. 45

Table 4.9 Freshwater consumed in chemical recovery in bleached kraft mills. 45

Table 4.10 Discharge of water pollutants in CEPI (Confederation of European Paper Industries) countries. 45

Table 4.11 Effluent benchmarking of Indian pulp and paper mills. 47

Table 4.12 Water consumption in large-scale Indian mills. 47

Table 4.13 Water consumption in medium-scale Indian mills. 47

Table 4.14 Water consumption in small-scale Indian mills. 47

Table 4.15 Cluster rule (bleach plant effluent discharge). 48

Table 4.16 Emission standards in the Indian pulp and paper industry. 49

Table 4.17 Standards formulated. 50

Table 4.18 Proposed water consumption standards. 51

Table 4.19 Proposed wastewater discharge standards. 51

Table 5.1 Measure to reduce freshwater consumption and the corresponding wastewater volume per ton of product. 56

Table 5.2 Water conservation measures in pulp mills. 57

Table 5.3 Low-cost improvements. 57

Table 5.4 Design stage procedures for reducing water consumption. 57

Table 5.5 Main features of the recycle loops in unbleached kraft mills. 58

Table 5.6 Recycling loops observed in market bleached kraft mills. 59

Table 5.7 Process modification for reducing water consumption. 62

Table 6.1 Typical constituents in process water streams. 73

Table 6.2 External wastewater treatment for pulp and paper mill effluents. 74

Table 6.3 Advantages of using moving bed biofilm reactors (MBBR). 80

Table 6.4 Advantages of anaerobic treatment in comparison to aerobic treatment. 83

Table 6.5 Example of removal efficiencies for different wastewater treatments. 89

Table 7.1 Emerging technologies for wastewater treatment. 94

Table 7.2 Advanced oxidation processes. 94

Table 7.3 Mechanism of advanced oxidation process. 96

Table 7.4 Types of advanced oxidation processes. 97

Table 7.5 Electrochemical oxidation potential (EOP) for some common oxidizing agents. 98

Table 7.6 Compounds oxidized by hydroxyl radicals. 100

Table 7.7 Factors affecting ozonation performance. 103

Table 7.8 Chemicals oxidized by ozone. 106

Table 7.9 Benefits of using ozone to treat wastewater. 109

Table 7.10 Disadvantages of using ozone to treat wastewater. 109

Table 7.11 Examples of advanced oxidation processes applied to the oxidation of effluents from pulp and paper industries. 114

Table 7.12 Features of FlooBed process. 146

Table 7.13 Membrane types. 149

Table 7.14 Main advantages and disadvantages of membrane bioreactor (MBR) technology. 153

Preface

Water is one of the key components of papermaking; the production of paper is unthinkable without water. Paper producers, being one of the most important industrial water consumers, are challenged to reduce their impact on water resources. Competent decision-making by top authorities delivered significant progress in reducing the water consumption in the paper industry. Due to its high competence in closing water circuits, the paper industry presently counts among the most advanced industrial sectors regarding water efficiency. New processes and other technological developments have reduced freshwater consumption over the years. This progress has been stimulated by stern demands from environmental authorities and also the desire of many companies to be considered environmentally friendly. Several strategies—basic conservation and water reuse and water recycling—provide a systematic approach to water resource management. Implementation of these stages not only requires increased financial investment, but also increased better utilization of water resources. The ultimate objective for pulp and paper companies is to have effluent-free factories with no negative impact on the environment. The traditional water treatment technologies that are used in the paper industry are not able to remove recalcitrant contaminants, so advanced water treatment technologies are being included in industrial wastewater treatment chains for improving water biodegradability and its final quality. This book discusses various measures being adopted by the pulp and paper industry to reduce water consumption, discusses treatment techniques to treat wastewater to recover it for reuse, and examines in great depth the emerging technologies for treatment of effluents and also presents few examples of full-scale installations.

Acknowledgments

Some excerpts taken from Bajpai P. (2008). Water Recovery in Pulp and Paper Making, PIRA Technology Report, Smithers Pira, UK, with kind permission from Smithers Pira, UK, the worldwide authority on the packaging, print, and paper supply chains.

Some excerpts taken from Bajpai P. (2010). Environmentally Friendly Production of Pulp and Paper John Wiley & Sons (2010) with kind permission from John Wiley & Sons Inc., Hoboken, NJ, USA, Copyright 2010, John Wiley & Sons, Inc.

Some excerpts taken from Hermosilla D, Merayo N, Gascó A, Blanco A. (2015). The application of advanced oxidation technologies to the treatment of effluents from the pulp and paper industry: a review. Environ Sci Pollut Res, 22:168–191. DOI: 10.1007/s11356-014-3516-1, with kind permission from Springer Science+Business Media, Germany.

Chapter 1

Introduction

Abstract

Large amounts of water and energy in the form of steam and electricity are required for paper manufacturing. The process is water-use intensive relative to most other industries, but the amount of water consumed represents a small fraction of the overall water used. There have been significant improvements in both water use and effluent quality in the pulp and paper industry. While environmental effects of treated effluents are sometimes observed, aquatic communities are usually not altered by well-treated mill effluents. The general introduction on the use of water in the pulp and paper industry is presented in this chapter.

Keywords

Effluent quality; Environmental effects; Pulp and paper industry; Water consumption; Water use

The pulp and paper industry uses a lot of water in its processes. Large amounts of water and energy in the form of steam and electricity other than the raw materials are necessary for paper manufacturing. Water is required for several purposes in a pulp or paper mill. It is used to carry fibers and chemicals, to cool process equipment, for cleaning, and for many other purposes. Water is also essential for developing the chemical bonds between cellulose fibers, which give paper its strength. Frost & Sullivan published market insight research, which has shown that about 85% of the water that the pulp and paper industry consumes is only used for processing, ultimately producing large volumes of contaminated wastewater (Ravi, 2002). Therefore, the most important environmental concerns in the pulp and paper industry are the contaminant emission to water and air and also high energy consumption. Moreover, the wastes and residuals resulted by production are increasingly affecting the environmental concerns (Hynninen, 1998).

According to Ramezani et al. (2011), there is a close relationship between the forest products industry and water cycle (Fig. 1.1). Water is a vital and important source in pulp, paper, and paperboard manufacturing. A large amount of water required in the factories is supplied by surface water resources such as lakes and rivers, and the remaining is fed by water wells, with the depth ranging from very shallow to more than 1000  m.

Development of new processes and other technical improvements have decreased the freshwater consumption over the years. This progress has been stimulated by harsher demands from environmental authorities and a wish by many companies to be regarded as environmentally friendly. The ultimate goal for the pulp and paper industry has been an effluent-free factory with no negative impact on the environment. This type of factory does not exist and is probably a utopia, but with advanced water management and recycling of different process streams, there are operational paper mills demonstrating very low freshwater consumption.

Industrial wastewater streams pose a serious threat to human life, plants, and animals, and to the ecosystems of the bodies of water they enter. One of the main causes of surface water and groundwater contamination is industrial discharge from textile, pulp and paper, pharmaceutical, and other chemical industries. Environmental regulatory requirements have become tougher because of increased awareness of the human health and ecological risks associated with the environmental contaminants. As a result of legislation, a lack of water resources, and greater customer demands, the world’s pulp and paper industry must find ways to reduce water consumption.

Figure 1.1  Relationship between forest products industry and water cycle. Reproduced with permission NCASI, 2009. Water Profile of the United States Forest Products Industry. Technical Bulletin No. 0960. National Council for Air and Stream Improvement, Inc., Research Triangle Park, NC.

The pulp and paper industry is ranked as the world’s third largest consumer of water and is consequently producing high amounts of wastewaters (Sevimli, 2005). High water consumption often goes hand in hand with high energy consumption, since more pumping and treating is needed (Sdguide Org, 2008).

Process water is needed for several process stages, including raw materials preparation (e.g., wood chip washing), cooking, pulp washing, screening, bleaching, transportation, dilution, and formation (Sappi, 2012). The amount is very much dependent on the type of process and chemicals that are used in the process (Ince et al., 2011; Fontanier et al., 2006). The consumption levels can vary from mill to mill because of both general and process-related reasons, such as paper grades produced, raw materials used, and plant structure. Furthermore, local boundary conditions, such as requirements on wastewater discharge, have an impact on the consumption level. According to Jung and Kappen (2014), high specific effluent volumes occur particularly in the production of specialty paper grades (Fig. 1.2). These mills are often faced with structural handicaps, which cause increased specific effluent volumes: smaller paper machines, frequent grade changes, low production rates, and often very high quality requirements on the final product. The lowest water requirements can be found in mills that produce packaging papers, such as corrugated base paper or board. Some of these mills have already managed to close their water circuits completely, resulting in a zero effluent production.

Figure 1.2  Grade-specific effluent volume in the German paper industry. Reproduced with permission Jung, H., Kappen, J., 2014. Water in the paper industry. Professional Papermaking, 11–13.

The discharged water effluents can contain significant amounts of toxic substances, which can cause death to the living organisms in receiving waters and affect the terrestrial ecosystems negatively. The effluents can also cause thermal impact, slime growth, scum formation, and loss of aesthetic beauty in the environment (Pokhrel and Viraraghavan, 2004; Ali and Sreekrishnan, 2001; Zhao et al., 2014; Bajpai and Bajpai, 1997; Zhu et al., 2012; BREF, 2015; Buyukkamaci and Koken, 2010; Mauchauffee et al., 2012; Scott and Ollis, 1995; Thompson et al., 2001; Riffat, 2013; Ranade, 2014; Spellman, 2014; Blanco et al., 2016; Ince et al., 2011; Hermosilla et al., 2010; Fatta-Kassinos et al., 2016). Considerable volumes of cooling water are also used because of the high energy intensity of the processes. This water is normally not contaminated and does not affect the environment negatively if not reused as process water or discharged to small recipients where temperature increase is a limiting factor (Sdguide Org, 2008).

In the early stages of industrial papermaking, paper was produced with high specific water consumption. When industrial papermaking began 200  years ago, water consumption was around 500  m³/ton of paper. The paper industry has improved its processes in the last few decades for economic and ecological reasons and, as a result, has been able to reduce its water consumption significantly. This was only possible because of the increasing closure of in-mill water circuits and consistent reuse of clarified process water by former freshwater consumers. Some pulp and paper mills are located near major waterways and have access to a large, uninterrupted supply of water. After using the water for pulp and paper production, the mills discharge the used water into the waterways as waste. The industry now faces tremendous environmental, political, and economic pressure to reduce the volume and toxicity of its industrial wastewater. As a result, the availability of fresh uncontaminated water is reducing at an alarming rate, and in industrialized countries, recovery and reuse of treated effluent has become a necessity, even in homes. The only way to reduce effluent is to replace freshwater with already used white water, treated or untreated. The reuse of process water is, in most cases, possible without any treatment, and this kind of recycling is routine in all pulp and paper mills. Pulp and paper operations are very much dependent on the use and responsible management of water resources. Depending on the process, the important sources of contamination from the different process steps are: raw material preparation, pulping, pulp washing, screening, bleaching, papermaking, and coating operations (Tables 1.1–1.2). Water is used in all major process stages and paper machines (for example, pulp slurry dilution and fabric showers). Water is also used for process cooling, materials transport, general facilities operations, equipment cleaning, and to produce steam for use in processes and onsite power generation (UPM-Kymmene, 2011). There are important definitions to note regarding the use and fate of water at pulp and paper mills (Malmberg et al., 2010). The forest products industry in the US withdraws the majority of its water from surface water sources and 14% from groundwater sources (Flinders, 2009). Although the industry is a large user of freshwater, it consumes a small amount of the water that it uses. A study by the National Council of the Pulp and Paper Industry for Air and Stream Improvement (NCASI) on the water profile of the US forest products industry concluded that 88% of the water used is returned directly to surface waters after treatment, about 11% is converted to water vapor and released during the manufacturing process, and 1% is passed on to products or solid residuals (Wiegand et al., 2011; Flinders, 2009). Furthermore, there have been significant industry performance improvements, which have shown 69% reduction in the average treated effluent flow volume in the pulp and paper mills in the US since 1959 (NCASI, 2013). Over the past three decades, the quality of effluents has improved markedly through in-process measures and ongoing refinement of wastewater treatment operations (AF&PA, 2008). As a result, several extensive studies on treated effluents have shown that there is not much concern regarding the compatibility of these effluents with healthy aquatic systems (Flinders, 2009).

Table 1.1

Wastewater generated in raw material preparation, pulping and bleaching operations.

Based on Nesaratnam, S., 1998. Effluent Treatment. Pira Environment Guide Series, Pira International, UK, p. 72; Gavrilescu, M., Teodosiu, C., Gavrilescu, D., Lupu, L., 2008. Strategies and practices for sustainable use of water in industrial papermaking processes. Engineering in Life Sciences 8 (2), 99–124.

Table 1.2

Wastewater generated in stock preparation/papermaking, utilities, and chemical recovery.

Based on Nesaratnam, S., 1998. Effluent Treatment. Pira Environment Guide Series, Pira International, UK, p. 72; Gavrilescu, M., Teodosiu, C., Gavrilescu, D., Lupu, L., 2008. Strategies and practices for sustainable use of water in industrial papermaking processes. Engineering in Life Sciences 8 (2), 99–124.

For the last several years, the pulp and paper industry has been working to reduce its freshwater consumption and its wastewater output. Reuse is an important approach for reducing wastewater generation and freshwater consumption. The pulp and paper industry in the US and other parts of world has reduced water consumption per ton of products significantly in the past 20–30  years. According to a survey by the NCASI, the water consumption per ton of product was reduced by 34.5% between 1975 and 1988 (Chandra, 1997). Water consumption by the pulp and paper industry is highly variable. It is affected by production conditions such as frequent grade changes, equipment used, and water management monitoring practices. However, there are opportunities to reduce water usage. The benefits of optimal water management include (Pacheco, 2003):

• lower costs for water and equipment

• a safer water supply

• compliance with environmental regulations

• better relationships with public authorities and organizations, communities, and mill staff

Table 1.3 shows the driving forces for recycling and reducing freshwater consumption.

Table 1.4 shows water conservation principles. Three stages—basic conservation, water reuse, and water recycling—offer a systematic approach to water resource management. Implementing these three stages involves increased financial investment and the greater utilization of water resources. The ultimate goal for pulp and paper companies is to have effluent-free factories with no negative environmental impact. The traditional water treatment technologies that are used in paper mills are not able to remove recalcitrant contaminants. Therefore, advanced water treatment technologies are being included in industrial wastewater treatment chains for improving water biodegradability or its final quality (Parsons and Williams, 2004; Oller et al., 2011; Merayo et al., 2013; Hermosilla et al., 2015). This book discusses various measures being adopted by the pulp and paper industry to reduce water consumption, deals with treatment techniques to treat wastewater to recover it for reuse, examines emerging technologies for treatment of effluents, and presents examples of full-scale installations.

Table 1.3

Driving forces for recycling and reducing freshwater consumption.

Legislation and permission in respect to either freshwater consumption or effluent discharge

Cost

Freshwater pumping and its treatment

Effluent treatment and possibly the cost of effluent discharge

Material savings

Fibers

Fines

Filler

Energy savings on freshwater pumping and on heating and treatment

Freshwater availability

Based on Bajpai, P., 2008. Water Recovery in Pulp and Paper Making. Pira Technology Report, Pira International, UK.

Table 1.4

Water conservation principles.

Reuse of water close to its point of generation

Use of lowest quality water, which is still acceptable for a particular application

Have sufficient water storage capacity

Development of a flexible water system, which allows reuse of two or more types of process water at various application points

Treatment of water or dilution with freshwater as necessary

Based on homepages.wmich.edu/.../mill-water-conservation.pdf.

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