Estimation of dewatering intensity of the paper web in the wet
Transcription
Estimation of dewatering intensity of the paper web in the wet
Aleksandra Judasz 128573 Faculty of Chemistry Technical University of Lodz Papermaking and printing “Estimation of impact of alternative papermaking additives on paper web dewatering intensity and paper properties” Master Thesis written in Institute of Papermaking and Printing under direction of dr eng. Konrad Olejnik Lodz 2009 1 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Table of content ................................................................................................................... 2 Preface .................................................................................................................................. 4 Summary .............................................................................................................................. 5 Objectives and scope of the thesis ...................................................................................... 6 1. Theoretical introduction ....................................................................................... 7 1.1. General information and definitions concerning papermaking process, construction of paper machine and basic functions of its elements ........................ 7 1.1.1. Pulp preparation ............................................................................................ 7 1.1.2. Stock and water systems of paper machine .................................................. 8 1.1.2.1. Stock preparation ............................................................................. 9 1.1.2.2. Stock approach flow system ............................................................. 14 1.1.2.3. Short and long circulation systems ................................................... 14 1.1.3. Wet part of paper machine ............................................................................ 15 1.1.4. Press section of paper machine .................................................................... 20 1.1.5. Dry part of paper machine............................................................................. 23 1.2. Classification and characteristic of water contained in formed paper web ............. 25 1.3. Intensity of paper web dewatering and energy consumption in conventional paper making process .................................................................... 33 1.4. Dewatering phenomenon ........................................................................................ 39 1.4.1. Mechanisms of dewatering ........................................................................... 39 1.4.2.1. Kozeny-Carman equation ................................................................. 40 1.4.2.2. Hydrodynamic specific surface area assessment .............................. 42 1.4.3. Factors affecting drainage intensity .............................................................. 48 1.4.3.1. Stock preparation ............................................................................. 49 1.4.3.2. Initial solid content and fiber alignment .......................................... 49 1.4.3.3. Stock temperature ............................................................................ 50 1.4.3.4. Permeability of pulp fiber mat ......................................................... 51 1.4.3.5. Fines content .................................................................................... 52 1.4.3.6. Fiber flexibility ................................................................................ 54 1.4.4.7. Retention aids .................................................................................. 56 2. Research phase ...................................................................................................... 59 2.1. Characteristic of raw materials and alternative materials used ............................... 59 2.2. Microscopic pictures ............................................................................................... 62 2.3. Pulp preparation ...................................................................................................... 66 2.4. Methodology of analysis ......................................................................................... 67 2.4.1. Methods of pulp dewatering analysis ............................................................ 67 2.4.1.1. Schopper-Riegler freeness ................................................................ 69 2.4.1.2. Water retention value ........................................................................ 70 2.4.1.3. Rapid-Köthen number ...................................................................... 71 2.4.1.4. Hydrodynamic specific surface area ................................................. 72 2.4.1.5. FiberXPress....................................................................................... 74 2.4.2. Methods of paper sheet properties analysis .................................................. 77 3. Results and discussion .......................................................................................... 79 3.1. The influence of addition of alternative materials on pulp dewatering .................. 79 3.1.1. Dewatering in the wire section ...................................................................... 79 3.1.2. Dewatering in the press section..................................................................... 84 3.2. The influence of addition of alternative materials on paper sheet properties ......... 4. Conclusions ............................................................................................................ 157 2 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Annex 1General definition and symbol list .......................................................................... List of figures ....................................................................................................................... List of tables ......................................................................................................................... References ........................................................................................................................... 3 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Preface The main objective of this thesis is to assess factors affecting dewatering behavior of the paper web in the wet part of paper machine with a clear focus on the influence and the role of additives and fibers, and to search for alternative bio-based additives that can reduce the required drying energy without negatively affecting of paper quality. The aim is to elucidate the balance between dewatering and water retention value of different raw materials and additives used during paper production in relation to paper quality. This thesis contains description of researches carried out in order to find out what is the effect of the addition of bio-based additives in different ratios on pulp dewatering properties, water retention value and paper properties. Within Thesis the comparison of influence of additives was done and also comparison of different dewatering methods used was performed. Researches were carried out using wide range of dewatering apparatus available, inter alia, at Institute of Papermaking and Printing at the Technical University of Lodz in Poland and also abroad. Hydrodynamic specific surface area measurements were performed according to Dresden method with usage of the unique analyser, placed in Germany, at Dresden University of Technology, at Faculty of Mechanical Engineering, Professorship of Paper Technology. This cooperation was possible within European Union program called Short Term Scientific Mission during COST E54 Action with title: “Characterization of the fine structure and properties of papermaking fibres using new technologies”. Investigations in participating paper mills were carried out with coordination of Centre of Competence Paper and Board, the Netherlands, and cooperation with experts from paper mills. Analysis was also performed in the laboratory of Smurfit Kappa Roermond Papier B.V. in Roermond with the usage of new FiberXPress device, invented and developed by Voith and Smurfit Kappa. This thesis has been based on a part of a larger project performed in the framework of the projects: Briljant, ‘Susprise – Green biorefinery’, ‘Biorefinery program of Energy Transition’ as well as the ‘Fibre Raw Material program’ of KCPK in pulp and paper industry. Coordination of the project is performed by Centre of Competence Paper and Board, the Netherlands with the cooperation from Institute of Papermaking and Printing. 4 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” Summary 5 2009 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Objectives and scope of the thesis In every area of engineering, including papermaking, there is long-standing policy to improve economy of production and quality of products. Sustainable objectives including energy and raw material savings are the most important aims of every industry. The European paper and board industry also has set the challenging target to reduce energy consumption with yearly more than 2%. The Dutch Paper and Board industry has set their targets even further. With their energy transition initiative they have committed themselves to halve the energy consumption in the paper chain. Drying is the most energy consuming unit operation in papermaking. The dryer section is definitely the largest consumer of thermal energy on a paper machine as steam [1]. In the Netherlands steam is obtained by the combustion of natural gas (in CHP’s), which is directly related to the oil prices. This makes steam consumption an important parameter to reduce. The amount of drying energy required in a paper machine depends significantly on the dewatering efficiency of the paper web in the wet part of the paper machine. Most drainage on a paper machine occurs mechanically on the wire and press sections. When the dry solids content of a web after the paper machine press section is approximately 50% (1 g dry solids/g H2O) for example, the dryer section removes less than 1% water volume originally received by the forming section [1]. By changing the intensity of dewatering within the wire and press section, it is possible to influence the amount of drying energy needed and save the cost of paper production accordingly. It can be seen that a 5% increase of the consistency at the start of the drying section can result in a 20% decrease in the energy requirement for drying [29]. Thereby, an increase of 1% in web dryness before the dryer section reduces the amount of water for evaporation by approximately 4% [1, 30]. The objective of the Master Thesis is to assess the possibility of influencing the dewatering efficiency in relation to paper and board quality by changing fibers or adding different alternative additives or fibers. Research work includes processing and analysis of some hydrophobic (fibrous and/or non-fibrous) bio-based additives to enhance dewatering in reference to strength properties and choosing the most optimal. Analytical work has been done to simulate the effect of usage of different furnishes under laboratory conditions and evaluate dewatering efficiency (during web drainage and pressing). Analysis provides information about correlation between additives and raw material used, and allows to compare different dewatering methods available. 6 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 1. Theoretical introduction 1.1. General information and definitions concerning papermaking process, construction of paper machine (PM) and basic functions of its elements Papermaking is a multidisciplinary technology; all systems of pulp production, paper making and converting consist of a lot of operations and processes. The complexity of this process requires understanding of every unit processes. The aim of theoretical chapter is to provide introduction to papermaking process, construction of paper machine and basic functions of its elements. Fundamentals about water contained in formed paper web, dewatering process and factors its affecting are the subject of the following chapters. Information about dewatering intensity and its relation to energy consumption are also presented. 1.1.1. Pulp preparation Papermaking pulp is produced using wood as a primary raw material for the paper and board industry. Wood is made from cellulose fibers that are bound together by a material called lignin [2]. At present, wood provides over 90% of the world’s virgin fiber requirement, while non-wood sources (bagasse, cereal straws, bamboo, etc.) provide remainder. Approximately one-third of all paper products is recycled as secondary fiber [3]. Wood or other fibrous feedstocks are converted into a papermaking raw material in process called pulping. The purpose of these processes is to separate the fibers from the wood and to prepare them for papermaking operations. Fibers can be separated from each other, without being too damaged, chemically or mechanically. There are the following pulping types: Mechanical pulping – In these processes fibers are separated from each other by applying the mechanical energy to the wood matrix. Energy causes that the bonds between the fibers break gradually and fiber bundles, single fibers and fiber fragments are released. Lignin and also the hemicelluloses are more or less softened what eases fibers separation. The composition of wood is not changed. Chemi-mechanical pulping – In these processes only small amount of chemicals is used (and thus only a small amount of lignin is dissolved). The 7 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 pulp obtained from these processes – chemimechanical pulp – is also considered as belonging to the mechanical pulp family. Chemical pulping – In these processes fibers are separated from each other when lignin and to a large extent, also the hemicellulose is dissolved and removed. Delignification is done by using chemicals. Product of chemical pulping is called pulp. Thus, with regard to the pulping processes, the term “pulp” is collectively used for chemical, semichemical, chemimechanical, and mechanical pulps [3, 4, 5, 6]. In a pulp mill, after fibers separation, fibers are washed and screened in order to remove any remaining fiber bundles. The pulp may then be used directly to make unbleached paper, or be bleached for white paper. In an ‘integrated paper mill’ pulp may be sent directly to a paper machine section or dried and pressed into bales to be used as a raw material by paper mills worldwide [2]. Fibrous raw material which is shipped and sold (not processed into paper in the same facility) is considered as a market pulp [7]. Pulp after pulping operation is processed in different departments in order to obtain desired papermaking properties. Both chemical and mechanical pulp fibers must be mechanically treated (refined, beaten) before the fibers become suitable for papermaking. The difference is that for chemical pulp this is a separate process in the paper mill, while for mechanical pulps this happens during the mechanical pulping process itself [5]. Chemicals are added either to the stock or to the process water and for this reason it is important to define stock and water systems of the paper machine (Fig.1). 1.1.2. Stock and water systems of the paper machine It is possible to distinguish the following areas and systems as part of the entire paper mill water system: Stock preparation Stock approach flow system Short circulation Long circulation 8 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.1. Stock and water systems in the paper machine [x]. 1.1.2.1. Stock preparation When pulp is coming from integrated mill, stock preparation begins with repulping or the dilution of pulp from integrated mill operations at the pulp storage towers. When paper mill is not integrated with pulp mill, paper production begins with stock preparation, where baled pulp treatment runs. Stock preparation contains several unit operations as mechanical treatment of the stock before the machine chest. Stock preparation consists of: disintegration of pulp, defibration of pulp, refining, pulp cleaning, proportioning, and blending of the main stock components. The main stock preparation objectives are: To add additives: fillers, biocids, chemicals to pulp In non-integrated mills to pump pulp from pulp mill to the paper mill To prepare properly the pulp before passing it through the headbox Slushing operation is realized inside a special device called pulper. During slushing, water and dry pulp bales are fed into the pulper vat, and the pulper rotor creates strong 9 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 disintegration forces. As a result, a pumpable fiber slurry is received. This fiber slurry is then pumped to the pulper dump chest. Objectives of slushing are the following: to disintegrate bales into pumpable slurry by releasing fiber bonds created in the pulp dewatering and drying processes. to disintegrate the fiber slurry so that there are no visible flakes or fiber bundles. to disintegrate fiber slurry so that fibers are separated, wetted, and flexible before entering the refining stage. During slushing, heavy contaminants (e.g. wires, staplers, sand) are also removed. If there is no defibration/deflaking stage between slushing and refining, the slushing result must be better than in a system where defibration or deflaking completes slushing. Figure 2 shows a typical slushing system for dried baled pulps. Fig.2. Typical slushing system [8]. There are various terms used to describe the action in which pumpable fiber slurry is further treated so that paper pieces, fiber flakes, fiber bundles, or separated but still dry and stiff fibers are disintegrated into individual, wetted, and flexible fibers, e.g. "defibration," "defibering," "deflaking," and "disintegration". This operation completes slushing if pulper is not able to produce sufficient defibration. Commonly used terms for expressing the result or the status of fibers after this stage are degree or result of defibration, defibering, deflaking, and disintegration. The term "deflaking" is used here to describe the fiber treatment, the "deflaker" is the machine, and "disintegration degree" refers to the deflaking result. The object of deflaking is to break the remaining flakes or fiber bundles into separate, wet, flexible, and externally fibrillated fibers. The effect on pulp properties is mainly seen as 10 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 an increased tensile strength because deflaking has increased the flexibility and produced some internal fibrillation, thus improving the bonding ability of fibers. Deflaking has practically no effect on the drainage resistance of the fibers. Only a minor increase in Schopper-Riegler or decrease in freeness can be observed [8]. Refining is the next step of stock preparation. Refining or beating of pulps is the mechanical treatment and modification of fibers in water to increase surface area, flexibility and promote bonding of fibers. Refining is performed mainly to improve the bonding ability of fibers so that they can be formed into paper or board of the desired properties. Sometimes the purpose is to shorten too long fibers for a good sheet formation or to develop other pulp properties such as absorbency, porosity, or optical properties specifically for a given paper grade. During refining or beating, fibers in the presence of water are treated with metallic bars. The plates or fillings are grooved so that the bars that treat fibers and the grooves between bars allow fiber transportation through the refining machine. Term “refining” is used to describe the work accomplished with refiners on the fibers [8, 9]. Refining affects fibers in many ways and the most important effects are: - Cutting and shortening of fibers - Fines production and complete removal of parts from fiber walls, creating debris in suspension - External fibrillation, the partial removal of the fiber wall, leaving it still attached to the fiber - Internal changes in the wall structure, variously described as delamination, internal fibrillation, or swelling - Curling the fiber or straightening the fiber - Creating nodes, kinks, slip planes, microcompressions in the cell wall, or removing those from cell wall - Dissolving or leaching out colloidal material into the external liquor - Redistribution of hemicelluloses from the interior of the fiber to the exterior - Abrasion of the surface at the molecular level to produce a more gelatinous surface. Fibers after refining are collapsed (flattened) and made more flexible, and their bonding surface area is increased. The measurable fiber and sheet properties, when refining chemical pulps, can be seen as follows: 11 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Drainage resistance (water removal resistance) increases. Tensile strength, tensile stiffness, burst strength, internal bonding strength, and fracture toughness increases. Tear strength of softwood fibers might slightly improve at first, but then decreases, whereas that of hardwood fibers at first significantly increases but then decreases after prolonged refining. Air permeability, bulk, absorbency, opacity, and light scattering decreases. Brightness slightly decreases [8]. The stock is blend of several components in order to reach the desired paper properties under the most economic circumstances. Stock blending can take place continuously or in a batch system. In modern papermaking, batch blending is used only for specialty papers produced on machines with small production rates or even in discontinuous operation, applying very special furnish components, dyes or chemicals. Figure 3 shows a typical example for a continuous system. Fig.3. An example of stock blending and machine chest including sampling station [8]. The number of used pulp components depends on their availability and on the product properties desired. Accordingly, in stock preparation, the fiber furnish is determined by: Selection and proportion of the stock components Improvement and development of the fibers, i.e., beating. 12 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The consumption of fresh water in stock preparation should be very low if not zero. Fresh water is used for the dilution of chemicals and eventually as supplement water in startup situations. All fiber components are diluted to the same pre-set concentration for blending. Each pulp typically has a separate pulp chest, the proportioning chest, to ensure a constant supply at the dosage point. In an integrated mill, pulp is usually picked up at a medium-consistency storage tower by dilution with water from the main paper machine dilution header. The concentration in the pulp chest is usually adjusted to 0.2%–0,3% points higher than in the blend chest. The stock is then diluted to the blending concentration and pumped to blending via refiners or directly. The blend chest is also called “mixing chest”, because the aim of this chest is not only to create complete motion of the stock (mixing) but also to gain complete stock uniformity (blending). There are three or more components mixed in the blend chest: Primary stock component(s) Broke Recovered fiber from the saveall. Broke is paper which is discarded at any point of the manufacturing and finishing processes inside the paper mill. Broke can be divided into wet broke and dry broke. Wet broke occurs on a continuous basis as trims from the wire section, press section and partly from drying section. Dry broke occurs as trims from winders, as e.g., reel slab-offs, in the finishing room, or during breaks. Usually, all broke is repulped, cleaned, and stored in the broke system. The processed broke is blended with other components at the blend chest and thus fed back into the production process. The amount of broke dosed to the furnish depends on web breaks and the broke line capacity [8, 11]. In specialty paper or dyed paper production, the reuse of broke might be somehow limited by the required product quality or due to other reason. Depending on the paper grade and the degree of processing, the broke might be pulped and used at another time or elsewhere. However, when this broke leaves the mill, it becomes per definition "recovered paper" or secondary fibers. The blended pulp is pumped at a constant rate to the machine chest where stock preparation ends. The stock is diluted by a small concentration decrement, typically about 0.2%-0.3% [8]. 13 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 1.1.2.2. Stock approach flow system The approach flow system extends from the machine chest to the headbox lip. The main purpose is to meter and dilute the stock including blending with other components like fillers, chemicals, and additives unless not already added in stock preparation. Then, the lowconsistency stock is pumped and screened before feeding to the headbox. Stock cleaning by hydrocyclones and deaeration can be included. The main operations in the approach flow system are: Dilution to headbox consistency Removal of product and production disturbing contaminants (solids and air) Conditioning with chemicals and additives Feeding the headbox Supply of additional water for PM cross-profile control in case of a headbox dilution system. Thick stock from machine chest is typically diluted at the bottom of the wire pit. The goal of doing that is to control the basis weight cross-profile at the paper machine. Basis weight control is more efficient, the lower the solids content of the dilution water is. Headbox dilution water is usually taken directly from the wire pit. The dilution water is deaerated in a separate unit or in a separate compartment which is integrated into stock deaeration tank [8]. 1.1.2.3. Short and long circulation systems Short circulation is a compartment in which paper machine wire water is separated from the stock in web forming and filtrate, which has passed through the wire, is used for the thick stock dilution prior to entering the headbox. This water is used also as a make-up water for the beaters. Usage of white water, which contains an abundance of fibrous matter and fillers used as the raw-material, significantly influences on the total water and fresh water consumption. Losses of raw materials and additives are also decreased by white water usage. Short circulation is present in all technological systems of paper machine [8, 10, 11]. Overflow (or excess of white water) from short circulation system is directed (together with water from suction boxes and wire washing) to long circulation system. This water is used for applications such as: wire screen showers, felt sprays, seal water for vacuum pumps and for stock dilution as well. Equipment for fiber recovery and water cleaning (device called save-all) is installed in the long circulation loop. Long circulation system is usually present in technological system of the paper machine [8, 10, 12]. 14 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 During normal steady state operation of a papermaking machine, an equilibrium condition develops in the material balance of the short and long stock circulation loops. For the short circulation loop this means that the fines and filler retention of the paper web are in equilibrium with the concentration of these materials in the white water circulation; and for the long circulation this means that the fiber save-all operation, broke filler concentration, retention chemical concentration and furnish composition are stable [13]. The paper mill stock and water system within the paper machine is responsible for: Supplying paper machine with stock with quantity sufficient for the production capacity of paper machine and possible for reaching a high paper machine productivity, Supplying the stock prepared is such a way that the product at the reel meets given quality parameters, Improving process materials economy, because it increases solids recovery and recycles water fraction, Environmental impact of paper machine water management reduction and increase of environmental protection [8, 10]. 1.1.3. Wet part of paper machine The papermaking machine is essentially a dewatering, i.e., water removal, system. Dewatering can be described as a water removal from wet web during paper forming. In the papermaking art, the term machine direction (MD) refers to the direction that the sheet material travels during the manufacturing process, while the term cross direction (CD) refers to the direction across the width of the sheet which is perpendicular to the machine direction [13]. When stock is prepared accurately, it is pumped through various types of mechanical cleaning equipment to the paper machine and there paper web is formed. The term "forming" describes the dilution in the short circulation of the thick stock flow to a mix flow, the approach flow system, and the CD (cross machine direction) distribution and jet generation of the mix by the headbox, as well as the creation of a wet web by dewatering of the mix in the wire section. The term "mix" is used to denote the thick stock, after dilution with white water to a fiber concentration low enough to avoid excessive flocculation. The mix is the last link in the chain: 15 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Pulp - original fiber raw material, delivered from pulp production, Stock - treated pulp including eventual additives, Thick stock - homogenized stock, delivered from the machine chest, Mix - thick stock diluted in the short circulation and delivered to headbox and wire section. Forming denotes the overall process of paper web generating. The forming of the fiber web is the crucial stage in building up the paper sheet. During this stage, the basic structure of paper is created. The term “formation” exclusively refers to small-scale local basis weight variations in the final paper web [8]. Besides formation, the distribution of material components such as fines and fillers in the thickness direction is important. The receiving of paper web from pulp stock suspension in paper machine is called also consolidation of paper web. This process is based on dewatering of pulp stock suspension, consolidation of fibers and fines into wet paper web which after pressing and drying becomes paper web with specific structure and properties [10]. Mix is fed to wire section through headbox. Headbox is located between short circulation and wire section (Fig.4) [14]. Headbox main objective is to distribute the mix evenly in the CD of the paper machine (across the width of the wire section). This means, for example, that the flow from a pipe with a diameter of 800 mm shall be transformed into a 10 mm thick and 10 000 mm wide jet, with absolutely the same flow rate and flow direction at all points across the width, as indicated in figure 5. Fig.4. Headbox location in the paper machine [14]. 16 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.5. Feed pipe for mix and cross-section of jet from headbox (not to scale) [8]. Headbox and the approach piping other aims are the following: to stabilize pressure variations and pulsation in the infeed flow as well as any cross directional flow disturbances to produce a suitable turbulence level in the stock suspension for fibre floc dispersal to produce a stock suspension jet in the forming section with a desired consistency (typically from about 0.5 to 1.0 %), speed and direction [14]. The flow transformation by the headbox from the incoming pipe flow to the delivered plane jet takes place in mainly three steps: The cross-direction distributor makes a first distribution of the mix across the machine width. Pressure drop elements are introduced to even out the CD flow profile. A headbox nozzle generates the final jet [8]. There are the following constructions of headbox: Air-cushion headboxes - are a development of the original, completely open headboxes, where gravity was the only driving force for the outflow through the headbox nozzle. Air-cushion headboxes are now used mainly for moderate machine speeds, for the manufacture of different specialty papers, and for some kraft paper machines, which require very large jet thickness. Hydraulic headboxes were designed specifically for twin-wire forming. A main requirement was small nozzle dimensions to allow a short free jet from the headbox into the gap between the two wires. Hydraulic headboxes lack the traditional air cushion and are available either with or without an equalization 17 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 chamber. If disturbing pressure pulsations occur in the approach mix flow, it is necessary to install a separate air-cushion pulsation damper before the headbox. Multilayer headboxes - include a separate CD distribution channel for each layer and flow separation between the different layers throughout the headbox. In the headbox nozzle, separation vanes are applied, for which bending stiffness as well as thickness along the vanes is important. Especially the geometrical design of the downstream ends and the vane length in relation to nozzle length are critical parameters. The web is formed by draining water from the mix in the wire section. In this section different types of formers are used: Fourdrinier former Hybrid former Twin-wire former (also called “Gap former”) Cylinder former. Fig.6. Fourdrinier former [15]. Fourdrinier former is shown in figure 6. Fourdrinier former serves to form one-side dewatered paper web. It consists of a horizontal wire which is spread between breast roll (which is under headbox) and couch roll (which is at the end of wire section) and entire raw of dewatering elements like: forming board, table rolls, foil elements, forming boxes, which create wire-carrying section. Next section, so called suction boxes section, consists of wet suction boxes, dandy roll, and dry suction boxes and couch roll for downward dewatering. 18 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Deckles protect against mix spilling. Dewatering devices are applied below the fourdrinier wire with the objective of creating dewatering effects and also of providing means for controlling the degree of fiber flocculation in the sheet formed. Originally, all dewatering relied on gravity effects and supporting rolls were introduced only to keep the wire horizontal, while causing a minimum of friction drag [8, 10, 15]. Hybrid former is an improvement of Fourdrinier former, which was complemented with an upper wire for dewatering upward at the end of the wire section. It is a hybrid form between fourdrinier former and twin-wire former. Twin-wire former has a twin-wire forming zone (two continuous wire belts running very close together) with the stock in between. Stationary elements were mounted on both sides of the wires, initially opposing each other but later positioned in a staggered mode. The mix is trapped between two wires what allows symmetrical two-side dewatering (Fig.7) from the top and bottom of the furnish and prevents two-sidedness. Fig.7. Basic principle of two-sided dewatering [8]. This principle has the advantage of avoiding the free surface between mix and air and of increasing dewatering capacity. Since, in each direction, half the dewatering will take place through half the basis weight, dewatering capacity will in principle quadruple compared to one-sided dewatering [8]. Since the 1950s paper machines with twin-wire formers have been developed. During the 1960s, twin-wire blade formers with stationary dewatering elements were developed by Beloit (Bel Baie) and Black Clawson (Vertiforma). In pure twin-wire formers, the mix jet is delivered directly into the gap between the two wires, hence the term “gap former” [8]. The examples of twin-wire formers are shown in figure 8. Cylinder former is covered with a wire and rotates in a vat of stock. The stock is picked up onto the cylinder by applying vacuum at point where the cylinder surface exits the stock. Vacuum is drawn on the stock to drain it until a point at the top of the rotation where a continuous felt contacts the cylinder. The paper web is released from the cylinder and is 19 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 carried along on the underside of the felt. The surface then reenters the stock and the process begins again. Machines with a cylinder former are often used to make multilayer paperboard [15]. Fig.8. Examples of Twin Wire Formers [16]. 1.1.4. Press section of paper machine After forming and partly dewatering paper web tears away from the wire and is passed through to press section. On couch roll and hitch roll which are movable wire is changing the direction of movement and it is turning back towards breast roll. Wire is lead by guide rolls system and cleaned with showers [10]. The press section is the part of paper machine in which paper web is passed to nip between two press rolls or a roll and a shoe. Water is expelled from the wet web by mechanical compression and is partly absorbed by felt or fabric and partly received by voids in the roll surface. The water removal is often assisted by the application of heat to the wet web, thus increasing the temperature of the fibrous web and water contained therein [8]. The objectives of press section are: To remove a maximum amount of water from the web (further dewatering of paper web) 20 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 To thicken and make even of paper web structure To smooth the surface of paper web To ensure a sufficiently high wet strength with the press in order to enable web transferring to the dryer section without any breaks To compress paper web in order to enable the formation of strong interfiber bonds during web drying To gain exact joint of specific layers in multilayer papers [10, 14]. Construction and working of the press section is described on the basis of plain press. The plain press consists of two press rolls, felt, felt conditioning system, systems of felt guide rolls and felt stretching rolls. The press section usually consists of several presses. The paper web is transported by felt to press nip between two press rolls. The suction box removing air which is between paper web and felt should be put before press nip. Water which is drained from paper web is received outside and absorbed by felt. The felt is washed and partly dewatered during turning back. Usually the top roll is rubber-covered and bottom roll is made of granite or cast iron. Modern paper machines posses press sections with 3 to 4 nips and use new technical developments as vented nips, shoe presses or other types of wide nip presses or elevated temperature either by using steam boxes or pressing the web against a heated cylinder or roll. The paper web after the wire section is a three-phase system, it consists of solid phase – fibres and fines, liquid phase – water and gas phase – air. The felt cooperates with the paper web and is also very important in this process. During pressing specific pressure is exerted on the web due to its compression in the press nip. This pressure (compressive force) is balanced in each point of the nip by the web structure and water contained in web (water flow resistance in the fiber network), therefore by a sum of structural pressure and hydraulic pressure. The structural pressure balanced by the mechanical stiffness of the solid structure dominates as long as the web is not saturated. When the web becomes saturated, the hydraulic pressure starts to rise and water flows into the felt, where its movements are determined by the press design and roll surface structure. Hydraulic pressure is a driving force in pressing process. In the outgoing nip, there is a reverse flow from the roll structure into the felt and from the felt into the web. The reverse water flow from the felt to the web is called rewetting [8, 10, 17]. Analyzing precisely mechanism and proceedings of pressing process, it is possible to divide pressing area into four phases what can be seen in figure 9. 21 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.9. The four phases of the nip process [17]. Phase I extends from the beginning of pressing zone until the place in which paper web achieves repletion. In this area compressive pressure increases and calipers of web and felt decrease because of air removing. Minor amount of water is taken away by the air flowing out of the web very quickly and is passed by capillary forces between web and felt. At the end of this zone web is saturated but felt still contains water. In phase I there are only slight changes in web dryness. Phase II extends from the place in which web achieves repletion until the place where press pressure reaches the greatest value. This point is reached usually before the line which joins midpoints of press rolls. In this zone press pressure increases, what causes that hydraulic pressure also increases and water is drained from the web. Water is channeled to the felt because of capillary forces and then after achieving repletion by felt water is pressed outside the press zone. This water slows down bottom press roll in plain presses or is drained to special dewatering spaces in press roll in modern presses. In this process stage main part of water is removed from the web. Phase III extends from the greatest point on pressure curve in press zone to the place in which web achieves maximum dryness. This point lines up with the greatest point of structural pressure curve and simultaneously with zero point of hydraulic pressure curve. Because in this phase hydraulic pressure of felt reaches zero point earlier than paper web, water flows from the web to felt. Owing to this phenomenon paper web achieves the 22 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 maximum dryness. Within this zone felt starts to absorb not only water from the web but also water which is below the felt. Phase IV extends from the point in which web achieves maximum dryness to the end of press zone. Within this phase paper web and felt expand taking water which has not been already drained out of press area. Paper web is here rewetted. Rewetting water comes from the felt because underpressure caused by expansion is higher in the web than in felt. Moreover after expansion of web and felt water penetrates from felt to web as a result of capillary forces acting since capillary tubes in the web are smaller than in the felt and they absorb water more intensive. [8, 10, 18]. During paper web pressing paper web is thickened what casts light on the most paper properties causing increase of density, transparency and static strength properties because of increasing of fiber contact surface, but decrease of web thickness, volume, air permeability, water absorptiveness and the amount of fines. 1.1.5. Dry part of paper machine Drying is the last stage in papermaking process. Drying section is the only one part of paper machine which has remained almost unchanged since their initial development. The main objective of drying section is to remove water from the web through evaporation. This phenomenon must go ahead efficiently, economically, evenly and without impairing paper quality. Dryer section is the larger consumer of in steam energy in paper machine, typically accounting for 55% of the total machine energy cost [19]. At present drying occurs using predominantly contact drying with steam-heated cylinders method. A multicylinder dryer section consists of drying set groups having its own felting and drive systems. Cylinders are arranged in two-tier configuration and the singlefelted or single-tier configuration. Other available configurations are twin-run, tam-run, putting cylinders in the basement, arranging tier in vertical position, and using more than two tiers of cylinders. The Yankee dryer for tissue and machine-glazed paper, through-air drying for tissue, impingement and air flotation drying for coating and sack paper, and infrared drying for coating and moisture profiling are other commonly used drying methods. Despite the fact that paper web has got formed construction, it is characterized as having not enough mechanical strength. Ultimate structure of paper comes from drying process during which physicochemical processes proceed. They are following: Evaporation of water from paper web, 23 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” Creating inter-fiber bonds, Shrinking of paper web, Hydrofobization of paper web (paper becomes water-reppelent). 2009 Paper drying is always connected to air that is either the drying medium or surrounds the drying atmosphere and receives vapor from paper. Evaporation process can be divided into three stages (Fig.10): The heating phase - it includes preheating of paper web; during this stage temperature and drying rate are gradually increased and approach constant rate conditions. The constant drying rate phase - drying occurs with the constant drying rate and in constant temperature, energy input to and consumption by web are in equilibrium. Evaporation can occur on the web surface or inside the web. The inversion point between the constant and falling rate phases is the critical moisture content (CMC). The falling drying phase – it is characterized by decreasing drying rate and it has two components called the first and the second falling rate phases. In the first falling rate phase web has got constant temperature. The second falling rate phase begins after removal of all free water from the web (89-92% dryness) and temperature of the web starts to increase gradually because of the diminishing of the drying velocity [1, 10]. Fig.10. Phases of drying process [1]. 24 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The finished paper should have a moisture content 4-8%, roughly corresponding to the equilibrium moisture content of the paper under the humidity conditions at which it will be used [20]. Paper web after dryer section is very hot and needs to be cooled in order to convert it further. Paper finishing processes depend on desired paper or board grade and they occur in finishing end. The main types of finishing processes and their objectives are: Surface sizing – to improve paper strength properties like internal strength (bonding strength) or surface strength (low dusting) Pigmenting – to plug paper pores Coating – to improve the appearance and printability of the product Reeling – to render the planiform paper or board produced in a form which is easier to handle Calendering – to improve paper surface properties and printing properties and other factors related to further processing - Adjusting of paper thickness or caliper to obtain paper of desired density - Leveling the paper caliper profile to obtain smooth and even rolls at the winder - It may be used for stamping relief designs on the paper with patterned rolls Winding – to slit reel into web sections of suitable width and length for customer and wound up around cores before sending out from the mill Sheeting – to cut paper into sheets which would be suitable for further processing Roll handling – to prepare paper rolls or paperboard rolls properly to ensure that the roll arrives in the right place at the right time [14]. 1.2. Classification and characteristic of water contained in formed paper web Water plays very important role in paper forming, converting and using because of its specific properties. Process of formation and consolidation of papermaking web is dependent on properties of pulp used. One of the most important property of pulp is the distribution and the bonding degree of water in formed paper web. Water present in the web fulfils the spaces 25 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 between and inside the fibers with various distribution of sizes. When the dimension of spaces is diminishing, the degree of water bonding with fiber inside the web is increasing. Therefore the water is more difficult to remove in web consolidation process. The degree of water bonding with fibrous material is one of the most important factors influencing on paper web forming and dewatering [21]. There are several water classification systems. With reference to these systems in professional literature there are the following water categories: Sorption water Hygroscopic water Monomolecular sorption water Bound water Polimolecular sorption water Total bound water Condensation capillary water Nonfreezing bound water Adhesive capillary water Freezing bound water Inner-fibril water Retention water Inter-fibril water Semi-bound water Micro-capillary water Free water Macro-capillary water Clarified water Inaccessible water Sedimentation water Accessible water Usage of all above terms can cause a lot of misunderstandings because some of them can be treated as synonyms. This thesis shows one of the water classification systems, which was created in Institute of Papermaking and Printing at Technical University of Lodz. It takes into account factors as water distribution and bonding energy of water and fibrous material, but also puts emphasis on the role and importance of classified water categories in papermaking process. One of the advantages of above system is the relatively simple water fractions separation method. Accepting the criteria which describe the water bonding energy in papermaking pulp stocks and heading technological aspects, it is possible to divide water categories into the following (Fig.11): Clarified water, Sedimentation water o Free water Free gravity water 26 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 o Free gravity water o Gravity retention water Free press water o Retention water Semi-bound water Bound water Fig.11. General classification of water contained in fibrous materials [22]. Remaining water categories which are mentioned in scientific literature can be considered as auxiliary and used for more precisely describing of basic water categories. Very important criterion in classification of basic categories of water included in fibrous material is the importance of these water categories in technological processes and relatively simple method of quantitative determining. Introducing criterion water fraction classification into clarified and sedimentation water (Fig.12) is reasonable for form and practical sakes. Inter alia, it results from miscellaneous bonding energy of these water categories with fibrous material. Energy needed to extract clarified water from suspension equals zero but in case of sedimentation water, it is higher than zero and according to water location in pulp suspension shows diversity. Fibrous 27 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 suspension in which the amount of entire water is higher than the amount of sedimentation water creates not stable system. In this system in stable conditions spontaneous extraction of clarified water follows. Entire water is then divided into: clarified water sedimentation water. Clarified water is extracted in the way of free sedimentation above sedimentation layer of fibrous pulp suspension. It consists of water which has not got any connection with fibrous pulp. Fig.12. Extracting and measurement principle of sedimentation water content [23]. Sedimentation water accounts for water which is contained in sedimentation layer of fibrous pulp suspension. This is water, which is embedded in spaces between fibers and inside them but also in spaces between fibers and fines and inside fines. Sedimentation water content in fibrous suspension is determined according to PN EN 872-02 standard. Measurement of sedimentation water relies on placing 1dm2 of tested fibrous suspension in Imhof’s hopper and definition of the volume of fibrous suspension which gravitated after specific time and then definition of its dry matter. Sedimentation water content in tested sample is definite as the amount of water (cm3) which accrues on 1g of dry matter. It usually ranges from 100cm3/g to 500cm3/g dry matter of fibrous material, what equals 0.2-1% of consistency of pulp suspension on average 0,5%. Because of the differences in location and bonding energy of sedimentation water in pulp suspension, it can be divided into (Fig.13): o Free water 28 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 o Retention water Division into free water and retention water follows exactly during mechanical dewatering. Free water is embedded between fibers and fines and is kept by surface tension forces in fibrous material. It constitutes the main part of sedimentation water. Its content varies between 100÷500cm3/g. Because of miscellaneous size of spaces between fibrous elements and also bonding energy, free water can be divided into: Free gravity water Free press water Free gravity water is the water which can be extracted from fibrous pulp in the way of gravity dewatering on the wire. Free gravity water is extracted spontaneous during filtration of fibrous materials. After extracting of free gravity water from fibrous suspension, consistency of fibrous pulp is usually 3÷5%. This category is important in regard of papermaking industry, where gravity filtration devices are used for thickening pulp suspensions and extracting these pulps from circulating water and effluents. During gravity filtration free gravity water is distributed into: o Free gravity water o Gravity retention water Fig.13. Division of sedimentation water [24]. 29 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 1.3. 2009 Intensity of paper web dewatering and energy consumption in conventional paper making The paper making process, in general, is a rapid water removal operation in a very large scale. In conventional paper making (Fig.16), the fibers are mixed with about 100 times their weight of water and subsequently water is removed. The percentage of dry solids (ds) is called the consistency/concentration of the sheet [31]. Percentage consistency from the definition is described as the amount of given substance in relation to the amount of entire mixture and is denominated in % as a unit [32]. Consistency of the stock flow entering the paper machine headbox is typically 0.2%1.0% (2-10 g fiber per kg water). Pulp stock sheet formed that way is over 99% water by weight. Pulp is continuously sprayed onto the moving woven mesh brass or bronze cloth screen at the rear section of the headbox. The water falls through the wire screen and into drainage trays as the continuous paper sheet is pulled along. At low speeds gravity force predominates in drainage causing. At higher speeds gravity force is not enough and pumping action of the drainage elements (i.e., the table rolls or foils) need to be applied. As web proceeds down the wire a visible change occurs in appearance of the stock. At this point, when concentration of the web reaches about 2%, its surface ceases to appear mobile because it loses its liquid sheen and takes on a matte appearance. The consolidation process begins, the web is formed and drainage elements are no more effective, for water removing. Next, the sheet travels through a section of suction boxes to physically extract more water. The sheet then moves onto a couch roll which prepares it to be lifted off the wire screen. At this point, the paper sheet is barely strong enough to support its own weight (roughly 80-85% water) and is transferred to a felt. After drainage on the wire or forming section using gravitation, pulsation, or vacuum (suction), the web consistency increases to 15%-25% [1, 11, 12, 17, 33]. Fig.16. Conventional papermaking process [12]. 30 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The felt takes the continuous paper sheet on the press section. There mechanical compression removes water by passing the sheet, supported by a felt, through a series (three or four pairs) of press cylinders, leaving the sheet with 71-74% water concentration. This process removes additional free water and some capillary water. The web consistency (now called dry solids content) then increases to 33%-55% depending on the paper grade and press section design [1, 12, 31, 33]. Finally, when no more water can be removed mechanically, the web enters the dryer section where a thermal operation, i.e., evaporation, removes the remaining water, water which is within the lumen and pores of the fiber wall. The sheet is passed over 40-5- steamheated cylinders (drying section), the final consistency being about 90-95% ds. A small amount of moisture (5%-9%) remains in the paper even after the dryer section [1, 12, 33]. Relationship between energy use and the amount of water removed is very important. It is shown in figure 17. Fig.17. Final energy requirement vs amount of water removed for the three operations forming, pressing and drying in a paper mill [31]. Removal of water in papermaking process can be divided into three processes occurring in the paper machine. The bulk of the water is removed in the forming section, 31 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 using the smallest amount of energy. Drying uses by far the most energy per mt of water removed. Pressing involves squeezing water out of the voids and the cell walls. This water drains away through the felt. At normal pressing temperatures, i.e. 40-50°C, the maximum consistency after pressing is 40-50% ds, depending on the type of pulp and the density and the porosity of the sheet. Increased temperatures aid water removal by pressing because the water viscosity is lowered, fibers are softened and water surface tension is reduced. A 10°C temperature increase gives a minimum of one percent improvement in consistency [34]. The influence of the consistency on the steam demand of the drying section is shown in Table 1 [31]. It can be seen that a 5% increase of the consistency at the start of the drying section can result in a 20% decrease in the energy requirement for drying [35]. Thereby, an increase of 1% in web dryness before the dryer section reduces the amount of water for evaporation by approximately 4% [1, 37]. Drying involves evaporation of the remaining water. The fibers and water should be heated to 100°C. Since water binds chemically to fibers above a consistency of 70% ds, heat is required for desorption. The water vapor is carried away by pre-heated air. The heat for heating and evaporation is obtained from saturated low-pressure steam (3-8 bar). The steam condenses on the inside of the cylinders, transmitting its latent heat to the cylinder shell. Heat is conducted through the shell to the paper through a thin layer of dirt, rust and air. The heating efficiency depends on the conductivities of the layers and the mechanism of evaporation in the sheet [38, 39]. The minimum energy requirement for water evaporation from paper is 2,55 GJ/mt of water. In practical situations at least 0,15 GJ additional heat per mt of water evaporated is required to preheat the air and to compensate for condenser and radiative losses [35]. Values for the steam consumption of newsprint dryers in Canada range from 3,5-6,7 GJ/mt of paper, with the average value being 4,5 GJ/,mt of paper. In Sweden, the steam consumption ranges between 2,4 and 5,5 GJ/mt of paper, with an average value of 3,4 GJ/mt [40]. The consistency after the press ranged from 39% to 47% ds. Values for the Netherlands range from 1,7 to 8,0 GJ/mt of dried paper, the average being about 5 GJ/mt [41]. Minimum energy requirement for: Heating and evaporation of water, from 50°C to 100°C (GJ/mt of paper ) Increasing consistency (%ds) 40% 45% 3.25 2.63 32 (GJ/mt of water evaporated) 2.46 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” Heating of fibers from 50°C to 100°C Desorption heat Total 2009 0.07 0.07 0.07 0.02 3.34 0.02 2.72 0.02 2.55 Tab.1. Minimum energy requirement for water evaporation form paper, expressed in GJ/mt of water evaporated and GJ/mt of paper [35]. It is assumed that the final consistency of the paper is 93% ds. In the case of the energy requirement per mt of water evaporated, ingoing consistency is 45% ds [31]. According to the newest data typical paper machine uses approximately 4GJ of thermal energy per ton of paper produced as low-pressure steam. The energy consumption on a paper machine varies with the paper grade produced. On printing paper machines, the share of steam in total energy consumption is 70%-75%. For tissue machines, the share is approximately 50%. The dryer section is definitely the largest consumer of thermal energy on a paper machine as steam. Most drainage on a paper machine therefore occurs mechanically on the wire and press sections. When the dry solids content of a web after the paper machine press section is approximately 50% (1 g dry solids/g H2O) for example, the dryer section removes less than 1% water volume originally received by the forming section [1]. By changing the intensity of dewatering within the wire and press section, it is possible to influence the amount of drying energy needed and save the cost of paper production accordingly. Intensity of dewatering of the paper web in different part of paper machine is defined as a ratio between total percent of removed water in specific part of paper machine and overall cost of produced paper. Distribution of percentage removal of water is following: 97%-98% of overall amount of water is removed in wire section 1,2%-2% of overall amount of water is removed in pressing section 0,8%-1% of overall amount of water is removed in drying section [41]. This data agree with simple calculations relating to removed water. Calculations are done using the definition of consistency/concentration: Cp wp ws 100 wp w p ww where: Cp – percent consistency/concentration of suspension, [%] wp – the amount of bone dry pulp [kg] 33 100 [%] , “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 ws – the amount of suspension (what is equal with the amount of bone dry pulp and the amount of water) [kg] ww – the amount of water [kg] By transformation of above formula, it is possible to obtain formula for the amount of removed water: ww w p 100 Cp w p [kg] . If it is assumed (with reference to above data): the amount of bone dry pulp, wp = 1kg, the amount of stock, ws=100kg the amount of water in the headbox, wE=99kg consistency in the headbox: 0,5%, web consistency after the wire section: 25% web consistency after the press section: 50%, the final consistency after the drying section: 95%, The calculations, according to consistency used, are the following: The amount of water in the pulp with specific concentrations: the headbox, c p 1%: ww 1kg 100% 1kg 99kg 1% When the consistency is 1%, the pulp composition is: 1kg of bone dry pulp and 99kg of water. after the wire section, c p 25%: ww 1kg 100% 1kg 3,00kg 25% When the consistency is 25%, the pulp composition is: 1kg of bone dry pulp and 3kg of water. after the press section, c p 50%: ww 1kg 100% 1kg 1,00kg 50% When the consistency is 50%, the pulp composition is: 1kg of bone dry pulp and 1kg of water. after the drying section, c p 95%: ww 1kg 100% 1kg 0,05kg 95% 34 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 When the consistency is 95%, the pulp composition is: 1kg of bone dry pulp and 0,05kg of water. The amount of removed water, wR : in the wire section: wR 99kg 3kg 96kg in the press section: wR 3kg 1kg 2kg in the drying section: wR 1kg 0.05kg 0.95kg the percentage removal of water, C RW wR 100 [%] , wE in the wire section: C RW 96kg 100 % 96,97% 99kg in the press section: C RW 2kg 100 % 2,02% 99kg in the drying section: C RW 0,95kg 100 % 0,96% 99kg It is important to remember that the results of above calculations depend on the type of paper produced and the consistencies used. Analyze the cost of paper production in relation to paper machine it is possible to observe some characteristic distribution. Taking costs in wire section as 1 unit of value per m 3 or mt of paper, in pressing section this gauge would be 50 units and in drying section it would be 200 values [41]. Energy consumption is related to energy prices and is an important parameter to reduce. Because the drying section removes the last part of water from paper web, the amount of drying energy required depends on the dewatering intensity of the paper web in the wet part of the paper machine. Changing the dewatering intensity can reduce energy costs and bring a lot of savings. 1.4. Dewatering phenomenon Dewatering is defined as formation of a paper or board web on the wire by removing water at the paper machine wet end [2, 9] or as removal of water from wet web during formation of paper sheet [9, 42]. 35 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Dewatering is a phenomenon which is complex itself and a lot of factors influence on it. That is why, dewatering can be described from different points of view and it is possible to distinguish separately mechanisms of dewatering and models of dewatering. 1.4.1. Mechanisms of dewatering The paper web forming in the wire section is based on changing the diluted pulp stock suspension in paper web with definite structure. The structure of the paper web formed depends on the mechanism of dewatering of paper web in the paper machine wire. Dewatering process can be of two different kinds, filtration or thickening (Fig.18). Filtration type dewatering is based on successively fibers depositing flat on a wet web as the suspending water is removed. In the course of water removing, a mix with the same concentration as in the jet from the headbox is still present above the wet web. As dewatering proceed, the thickness of filter layer is built up and suspension layer over filter layer is decreased. Paper web obtained by filtration should have layer structure. This type of dewatering dominates conventional (fourdrinier) forming. Thickening type dewatering relies on progressive compressing of a fiber network. Fiber flocs which have reminded in the mix are also dewatered according to the thickening principle. During the thickening process, fibrous layer consistency increases concurrently in whole fibrous layer. Paper web obtained by thickening should have structure in which fibers order stays similar like in fiber suspension, i.e. fibers are ordered every which way. Fig.18. Dewatering through filtration (left) and thickening (right) [8]. Filtration type dewatering prevails in the initial forming stage when consistency of pulp suspension is small. When the consistency increases, possibility of fiber movement is 36 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 limited and then the thickening type dewatering takes place. It starts to take place when all free mix has been dewatered. Changing mechanism of dewatering as forming of paper web proceed is the reason that structure of paper web resolves from layered (at the bottom/wire side) into having fibers ordered every which way (at the top side) [8, 10]. 1.4.1.1. Kozeny-Carman equation Kozeny-Carman equation is based on permeability principle published by Kozeny and Carman in 1927 [43]. This principle found also application in liquid permeability method according to Robertson and Mason, published in 1949 [44]. The background of this theory is presented beneath. It is strictly related to hydrodynamic specific surface area measurement. This explanation accounts for the basis of hydrodynamic surface area measurement which will be presented and described within this Thesis. Kozeny-Carman equation stems from mathematical equations of Darcy (flow rate through a porous material with unknown porosity) and Hagen-Poiseuille (flow rate through a material with known number of circle-cylindrical pores) (Fig.19) [45, 46, 47]. Kozeny-Carman model assumes laminar flow through cylindrical pores perpendicular to the surface. Kozeny presented that the resistance to flow through packed beds of granular materials could be explained in terms of the porosity (size and number of pores), specific surface area and shape factor of the material. In the fiber network both, the porosity and the fiber orientation have effect on Kozeny factor (K). In the Darcy-equation the unknown permeability is characterized by a factor, so-called permeability factor K, which is an important parameter of the hydrodynamic specific surface area method. 37 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.19. Flow rate through a porous solid body according to Darcy (left) and Hagen-Poiseuille (right) [45] From the Darcy-equation permeability factor K [m2] is defined as: K V L , A p where: V - flow rate [ cm 3 ], s - dynamic viscosity of liquid [ g ] cm s L – distance between upper and lower screen [cm] (=height of the compressed fiber pad), A – cross section of material [m2], p - hydrostatic pressure [Pa]. Permeability factor’s influence on papermaking stock dewatering is described beneath in permeability of pulp fiber mat description. Different researches shows that Kozeny-Carman concept originally developed to predict flow through textile materials also can be used with good precision for predicting flow through papermaking fiber mats [20, 45, 46, 48]. 1.4.1.2. Hydrodynamic specific surface area measurement 38 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Hydrodynamic specific surface area assessment is based on the permeability of compressed water-swollen fibers pad. In a water-swollen fiber pad it is possible to describe internal and external surface area of a water-swollen fiber wall (Fig.20). Fig.20. Definition of internal and external surface area of a water-swollen fiber wall [46]. Internal surface area is interpreted as the surface which is not accessible for water molecules which flow along the external fiber surface. Only the external surface is in contact with the streaming/flowing water. Hydrodynamic specific surface area of fibers [ m2 ] is defined as the g surface area of fibers in a compressed water-swollen fiber pad that is accessible for streaming water molecules. The relation between Kozeny-Carman equation and hydrodynamic specific surface area is that the inner surface of cylindrical pores corresponds to the accessible fiber surface in a compressed fiber pad. Hydrodynamic specific surface area is a function of flow rate through a compressed fiber pad under defined hydrostatic pressure. Hydrostatic pressure is an expression of the fiber pad’s resistance against fluid flow. Hydrodynamic pressure gradient caused by either mechanical compaction or gravity is a driving force in drainage. Streaming resistance is determined by the pore size within the fiber pad and also by fibers surface structure, e.g. their external fibrillation. Pore size distribution cannot be measured directly, but compression forces decrease pore sizes depending on the fiber conformability (the pore structure within the fiber pad which contains mainly highly flexible fibers will be different from that of a fiber pad built from stiff and non-flexible fibers). During hydrodynamic specific surface area measurement for each compression step, hydrostatic pressure, flow rate, wire screen distance and liquid temperature is measured, and fiber pad concentration and the permeability factor K are calculated. 39 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The permeability behavior of compressed water-swollen fibers pad according to Roberston and Mason is linear for a certain range of concentration (0.07-0.15 g ) at the cm 3 given sample amount of 2.5g. Linearity can be expressed by a straight-line equation according to Kozeny and Carman: ( K c F2 )1 / 3 ( 1 1/ 3 1 1/ 3 ) Vm c F ( ) , 2 2 Sm 2 S m2 where: K – permeability factor [m2], c F - consistency of the compressed fiber pad [ S m - specific surface area [ Vm - specific volume [ g ], cm 3 m2 ], g cm 3 ], g Specific surface area S m [ m2 ] is defined as the sum (Z) of all lateral surface areas of g cylindrically shaped pores having the length L and the diameter 2r, related to sample mass m: Sm 2r L Z m cm 3 Specific volume Vm [ ] is defined as the sum (Z) of all volumes of cylindrically g shaped pores having the length L and the diameter 2, subducted from the total volume of the fiber pad A*L and related to sample mass m: Vm (A r2 Z) L m Consistency of the compressed fiber pad c F [ g ] is calculated from sample mass m cm 3 and the outer dimensions of the fiber pad A and L: cF m . A L The so-called Kozeny-Carman plot is created by putting calculated data in a chart with Value ( Kc F2 )1 / 3 versus c F . 40 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” At concentrations smaller than 0.07 2009 g , fibers can move freely under hydrostatic cm 3 pressure, and the flow rate increases with increasing pad consistency. At about 0.07 g , cm 3 fibers cannot move anymore with hydrostatic pressure, they start to find their “favorite place” under compression pressure. Flow rate decreases uniformly with increasing pad consistency. The concentration 0.15 g is the upper concentration limit for the linear area. It is due to cm 3 construction limits of the first testing apparatus. At this concentration uniform flow rate decrease continues and particles move under compression pressure. It was found that the straight-line equation can be applied also for higher fiber pad compressions. In this case flow rate decelerates because particles cannot move anymore under compression pressure and start to collapse. Total specific surface area of the fibers (not only that part of surface that is not in contact with their neighboring fibers) is calculated when the straight-line is extrapolated to the Y-axis. It is due to theoretical assumption that no fiber is in contact with their neighbors when concentration equals c F 0 g . According to the theory, all fibers are in contact with each cm 3 other and no free fiber surface is left in the fiber pad, permeability K is zero, when straightline is extrapolated to the X-axis. At this concentration the specific volume of all fibers can be calculated [46, 47, 48]. The compressions steps and correspondingly Kozeny-Carman plots are shown in figure 21. 41 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.21. Kozeny-Carman plots for unrefined softwood chemical pulp as an example of pulp with straight-line assumption between the concentration limits 0.07 g g and 0.15 3 , 3 cm cm intercept with Y-axis to calculate specific surface area and intercept with X-axis to calculate specific volume of the sample [45, 46]. 1.4.2. Factors affecting drainage intensity Dewatering is described in three models, but there are always deviations from even the best predictions. As it was mentioned earlier, there are a lot of factors determined as affecting the dewatering of pulp suspension. There are the following: 42 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Stock preparation operations, Initial solids content and fiber alignment, Stock temperature, Permeability of pulp fiber mat, Porosity, Hydrodynamic specific surface area, Fines content, Origin of fiber fines, Size and shape of particles and fines, Distribution of particle sizes within the wet web, homogeneity of paper web, Flexibility of wet-fiber/Stiffness of wet fiber Recycling of fibers, Fibers swelling, Retention aids. The influence of every factors named above on pulp dewatering is described beneath. It is important to notice that all factors are interrelated and together influence on the papermaking pulp dewatering and the final paper web appearance. 1.4.2.1. Stock preparation operations During stock preparation there are three steps which can influence on pulp dewatering. The first one is deflaking, the second one is refining and the third one is the usage of broke. Deflaking has practically no effect on the drainage resistance of the fibers. Only a minor increase in Schopper-Riegler or decrease in freeness can be observed. The second factor is refining. Refining is performed inter alia to cut fibers and to cause internal and external fibrillation of fibers. As an effect of refining, the amount of fines in stock increases. Fibers after refining are collapsed (flattened) and air permeability decreased. Fibers are made more flexible, their bonding surface area is increased and also their swollen volume increases. It influences on pulp dewatering and brings about that drainage resistance increases. As a result the pulp dewatering would be decreased [8]. Usage of broke changes properties of stock. There is almost no difference between wet broke and stock. Wet broke contains less amount of fines than stock and that is why it can bring about better dewatering properties. It can be metered into stock without limits. Dry broke differs from stock significantly. Pulps are irreversibly altered during the first drying, 43 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 which impairs some paper properties as known from paper made of recycled fibers. The properties of dry-broke pulp are different when compared to the fresh pulp used. There is no specific quality difference between dry broke and clean, unprocessed paper, e.g., unprinted printing shop waste, which is called "wastepaper" or "recovered paper" by definition. Drying of broke causes decreasing of apparent density, increasing of bulkiness and porosity and also deteriorating of strength properties. 1.4.2.2. Initial solids content and fiber alignment Dewatering results can be strongly influenced by the fibrous suspension initial solids content as well. Researches of Hubbe, Heitmann and Cole have shown that the amount of water retained in a fiber mat after gravity dewatering is directly proportional to the amount of solids present. The higher the initially solid content is, the greater is amount of water retained in a fiber mat. Increasing of solid content causes decreasing of pulp dewatering. This inspection suggests also that the resistance to flow is increasing with increasing initial consistency and approves that secondary fines have a greater relative effect than primary fine, what is discussed further within thesis. The higher solid content can be understand also as the amount of fibers in suspension, so higher consistency. The higher the consistency of pulp stock is, the higher is association between fibers and fine matter. Moreover, fibers are showing increasing tendency to entangle and forming flocs with the increasing consistency beyond a certain point. Flocculation is expected to increase the rate of dewatering by gravity [20, 53]. On the other hand, forming paper at relatively high solids content of the suspension causes that fiber alignment will be chaotic, including a high degree of out-of-plane alignment. Under these conditions more permeable wet paper mat can be created. Paper formed under such conditions shown to have a reduced resistance to dewatering [20]. 1.4.2.3. Stock temperature Paper web temperature was changed few times during the last fifty years. When analyzing of dewatering process, it may be assumed that changes in physical properties of pulp are caused because of changes in physical properties of fibers carrier, water. It was stated that increasing of stock temperature may give an increase in pulp dewatering velocity and more rapid drainage. A 10°C temperature increase gives a minimum of one percent improvement in consistency. It may be because of changes in water viscosity. Increasing of temperature will 44 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 cause decreasing of water viscosity. It will aid water removal by pressing because as water viscosity is lowered, fibers are softened and water surface tension is reduced. The ratio of force of inertia to internal frictional force (which is defined as liquid viscosity) is out of proportion high in table roll section. Here decreasing of viscosity forces may do not have any effect on pulp dewatering. But the effect of decreasing the water viscosity may affect pulp dewatering on a couch roll and in press section. In these areas the bonding forces between water and fibers are high in comparison to forces of inertia and there is considerable water flow resistance in capillary and concentrated paper structure [33, 55, 55]. 1.4.2.4. Permeability of pulp fiber mat Dewatering of pulp depends on the structure of forming mat. Form one hand, it is possible to assume that in a papermaking furnish fibres are able to slide past each other when they come into contact and they would form a relatively dense mat. On the other hand, fibres tend to stick together and not slide past each other and form more bulky, porous mat. Water will flow easily out of the second presented fibrous mat. The degree to which the furnish components tend to become packed together is expected to play significant role in determining the formed mat permeability [20]. Paper is composed of a randomly felted layer of fibres, so its complex structure has a varying degree of porosity. Paper contains as such as 70% air. Permeability and water diffusitivity are inherently related to the resistance offered by so highly porous material. Permeability is the ability of permeate (such as a liquid, gas, or vapor) to penetrate through a solid. As it was mentioned earlier, researches of Kozeny and Carman and also of Robertson and Mason present that resistance to flow in the transport channels between the fibers in the wet web could be explained in terms of the porosity (size and number of pores), specific surface area and shape factor of the material. Porosity of paper sample is the ratio of the pore volume to the total sample volume. It is the measurement of the total connecting air voids, both vertical and horizintal, that exist in paper. Pores within the cell wall can be divided arbitrary into macropores and micropores. Larger pores in the cell wall are called “macropores” and relatively smaller pores are called “micropores”. Macropores are believed to be gaps between microfibrillar lamellae which are formed in pulping by dissolution of liginn and hemicellulose from the cell wall. The micropores are spaces within the lamellae. The macropores and micropores are not well separated nodes on the pore size distribution. 45 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Pore size within the fiber pad and also fibers surface structure determine streaming resistance of penetrate. Pore size distribution cannot be measured directly, but compression forces decrease pore sizes depending on the fiber conformability. The pore structure within the fiber pad which contains mainly highly flexible fibers will be different from that of a fiber pad built from stiff and non-flexible fibers. That is why permeability of a web of previously dried fiber is higher than that for one from never-dried fiber. Changes in pore size within the fibre wall is important for the ability of molecules to diffuse in and out of the fibre wall. The higher the permeability is, the lower is the flow resistance and that is why also drainability is better. Increasing the permeability in water removal during pressing will lead to increasing of water removal by pressing. According to what is written above, in porous structure there is a relationship between the size and shape of pores and the compressive strength of a material. Drop of pressure through a porous membrane, such as the cell wall, depends on the size of the pores through the membrane. The first pores which collapse when a porous material is compressed are the largest pores in this structure. They are followed sequentially by the smallest. It may be stated that pores in the cell wall colapse from the macropores to micropores. Larger pores collapse easier that smaller one. The smaller the pores within a structure the higher is the compressive strength. It may be expected that dried-pulp are less compressive than never-dried pulp because drying causes that fiber cell wall pores are closed. The fiber swelling is also strictly related to the porous structure of fiber mat. During fiber swelling, fibers changes theirs volume and therefore the volume of pores between fibers is decreased. Because of that permeability of fiber pad is expected to be lower and drainability is decreasing. Swelling influence negatively on fiber pad permeability and dewatering [7, 43, 44, 56, 57]. Hydrodynamic specific surface area is defined as the surface area of fibers in a compressed water-swollen fiber pad that is accessible for streaming water molecules. It is related to the pore structure of fibers, because the inner surface of cylindrical pores corresponds to the accessible fiber surface in a compressed fiber pad. The higher the surface is, the higher is the water flow resistance through fiber pad and therefore the lower is fiber pad dewatering. The greater pore sizes are, the higher is the surface available for water streaming and also the higher is hydrodynamic specific surface area and dewatering is lower. Therefore, dewatering of pulps which are characterized by high specific surface area should be lower that for those characterized by relatively small hydrodynamic specific surface area. 46 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Also dewatering of pulps which have smaller pore size i.e. dried-pulp should be better than for those which have relatively higher pore size i.e. virgin or swollen pulps. 1.4.2.5. Fines content Fines is described as pulp fraction, which separated, posses inter alia low dewatering property, very high external surface (5 to 10 times higher than fiber sample with the same weight) and high swelling degree. Fines may also contain various range of well-beaten furnish (from 1% to 30%). That is why, it influences on the pulp drainage. It may be expected that different types of fines behave differently. Fines fraction has much higher external surface area per unit mass than typical fibers in suspension. In this case, the Kozeny-Carman equation can be applied to predict fines impact on dewatering. Dewatering of fines particles should be slower than of fibers because of greater frictional resistance expected, when fluid flows through bed of fines (Fig.24). However, this approach fails to predict increasing fines content effect and increasing basis weight influence on dewatering. Fig.24. Typical fiber and typical fine particle comparison. Right side of picture shows dewatering through a bed of coarse fibers in comparison with fine matter, assuming uniform packing density [20]. Fines slow drainage as it is unattached to fibers and during pulp flow fines particles can migrate within the pulp until choke-points and reduce the rate of flow through a fiber mat. This approach agrees with “choke-point” model. Secondary fines decrease dewatering to a much greater extent than primary fines [20, 50, 51, 52, 53]. 47 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The origin of fiber fines has play significant role in pulp dewatering. Primary fines compared to secondary fines, is considered as negligible to sheet bonding due to its low specific surface area and mineral particles presence in the fraction. The role of fibers origin in pulp drainage can be explained not only due to the differences in surface area. Hawes and Doshi noted that variations in stock dewatering are due to flexibility and conformability among different kinds of fines. This attitude may follow sealing model [20, 58]. The size and the shape of particles added to or present in papermaking stock also influence suspension drainage. In regard to fines, fibrillar material (mainly composed of delaminated call wall material) posses higher surface area per unit mass than fines having rounded or brick-like shapes (as e.g. parenchyma cells from the wood). That is why fibrillar material tends to cause greater reductions in dewatering rate. Secondary fibers tend to be long and slender, so it may be expected that with increasing content of secondary fibers, the mat can become very effective as a filtration medium [20, 52]. Also distribution of particle size is important. Suspensions which have particles with wide range of sizes are expected to have higher packing density. As result, smaller particles can fill in spaces which would occur within suspensions consisting only of larger particles. In effect, resistance of dewatering has been found to be larger in the case of mixtures [20]. 1.4.2.6. Fiber flexibility Fiber flexibility is also one of factors affecting dewatering. As it was mentioned describing sealing mechanism, the more flexible fibres are, the greater is the resistance to fibre mat dewatering. According to other researches, the stiffer the fibres are, the greater is the rate of dewatering. This assumption was done also, because stiffness can have impact on density of packing, so it may also affect rate of dewatering. According to researches performed rapid drainage is flavored by the presence of relatively stiff fibers. This concept was quantified using new technique for measurement of wet-fiber flexibility. Also results from researches of Hawes and Doshi put emphasis on fiber flexibility [20, 58]. Flexibility of fibres changes, the more times fibres are used and recycled. When pulp is dried and then rewetted, there is a loss of swelling and also porous structure of fiber mat is changed, most of macropores and a small part of the micropores collapsed. Paper recycling reduces the swelling of fibres and interfiber bonding and brings a lot more changes. That is why also recycling of fibres may influence fibre pulp dewatering. The problem occurs with 48 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 usage of dried market pulp and recycled fibers. The main effect of fibres recycling is loss in fibre swelling due to hornification. Hornification is a loss in swellability, water uptake and surface area, of both the long and fines fraction of a pulp. It occurs between 50% and 80% of solids content. Hornification occurs with heat application (drying) but also with water removal from pulps through wet pressing. That is why also previously dried chemical pulp is easier to press then never-dried pulp. Dried pulp has less specific surface area than the neverdried pulp and it has also lower water-holding capacity than virgin fibers. As a result, usage of recycled fibres should decrease the drainage resistance of pulp, so enhance dewatering, due to they are stiffer than and cannot absorb the same amount water as virgin fibres. It is important also to remember that different behaviour of the hornified pulp in static pressure is not because of effects brought about by changes in fibre flexibility but it is due to the closure of micropores [25, 28, 29, 51, 56, 59, 60, 61]. Loss in fibre flexibility was noted also as a result of loss in hemicellulose. Loss in hemicellulose was determined qualitatively and considered as an indicator for loss in fibre flexibility, although these researches were not conclusive [60]. Absorbed water changes the fibre flexibility, so fibre swelling itself has an impact on pulp dewatering as well. Swelling is the ability for liquids absorbing by solid with the simultaneously increasing of solid size, without changes in solid uniformity and with decreasing of internal cohesion. Water is presented in the wet web in capillary voids between the fibres and in the porous structure of the fibre wall. Water infiltration to fibres interior has a great technological impact during paper production, because absorbed water changes the fibre flexibility and plasticity. Water plasticizes hemicellulose and to a lesser extent than lignin. Swollen fibres become more resistant for cutting during refining. The closure of the fibre wall pores upon drying deswells the fibre surface. Fibres swelling affects not only drainage on wire section, but also wet pressing of fibrous web. In a pressure controlled situations solid content after pressing is limited by the rate at which water can be removed from the cell wall. There is a negative correlation between the degree of swelling and the solids content after pressing. When pressure is exacted on fibre mat, stresses are concentrated at the contact areas between the fibres, especially at the fibres crossing. High local pressure removes water from the fibres at these points but water still fulfils some of the voids between the fibres at a solid content corresponding to fibre saturation point. As a consequence, the solids content varies along the fibre length and the swelling is inhomogeneous. Press performance can be improved by pulp deswelling. Removal of swelling water is slower 49 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 process than the removal of water form interstices between the fibres. In limited impulse pressure presses, the solid content obtained after pressing is related to the pulp swelling. Expelling of swelling water appears to be a limiting factor for the attainment of a high solid content after press section. That is why solids content after the press section is predicted with the usage of Water Retention Value. Increased fibre swelling may facilitate the formation of dense, impermeable fibrous layer. In flow controlled pressing the dewatering of such pulp is expected to decrease [11, 56, 60, 61]. 1.4.2.7. Addition of retention aids To improve pulp dewatering papermakers strive for achieving as high as possible degree of so-called fine flocculation, i.e. precipitation of fine fraction on the surface of fibers with the minimal flocculation of fibers themselves. The degree of flocculation chiefly affects pulp dewatering. Fibrous material in papermaking suspension (in water system) exhibits negative charge on its surface. This charge is a result of sorption of hydroxide ions from water or from dissociation of carboxyl group present on the fiber surface. The charged particles affect the distribution of ions in the surrounding interfacial region, resulting in an electrostatic double layer around each particle (inner Stern layer and outer diffuse layer). Electrostatic double layer consists of adsorptive layer (layer which adheres to the fiber surface, it posses positive charge) and diffusive layer (layer which extent into water phase, it posses the advantage of positive charge). Positive charge which exists in the surrounding of fiber compensates the negative charge of fiber in static conditions. On the border line of adsorptive and diffusive layer there is so-called electrokinetic potential or potential zeta. This is one of the crucial factors in papermaking agglomeration or dispersion. Maximal fibers flocculation can be reached when zeta potential is approaching or equals zero. Electrokinetic potential data allows to predict how a furnish is likely to respond to the addition of cationic or anionic additives. The presence of negative electrokinetic potential of fiber in solution causes fibers repulsion and in case of other particles present in water phase, they remain in stable dispersion. The surface charge can be reduced with the usage of papermaker's alum or other more effective retention aids. The main aim of retention aids is to increase the amount of fibers, fiber fines and fillers retained on wire of papermaking machine. Retention aids settle on the surface of fibers and fines and neutralize negative charge of fibrous materials. The repulsion of fibrous materials is weakened and as a result agglomeration of fines, its 50 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 adsorption onto the fiber surface and flocculation of fibrous material follow. The retention of fines is increased and that is why the drainability of pulp is improved. Molecular weight and charge density of a retention polymer are the most important factors impacting the mechanism of their action. Early retention aid systems were singlecomponent products, most often based on acrylamide chemistry, alum, starch, polyamines, polyethyleneimines (PEI). Dual-component systems used later were based on combinations of cationic polymers and anionic inorganic microparticles. Today, multi-component systems, were long-chain formation aids in conjunction with dual component systems is used, are applied. It was stated that additives characterized by the highest ability to create flocs bring about the highest change in drainability. Retention aids act according to the following mechanisms (Fig.25): charge neutralization patch formation bridging flocculation complex flocculation network flocculation Fig.25. Schematic illustration of: a) charge neutralization, b) patch formation, c) bridging flocculation [69] In papermaking industry chemicals are commonly used in order to improve water removal on the papermaking machine. Cationic additives were described as chemicals which increase drainage on the wire section but also they may improve the pressability of a fiber pad [60]. 51 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 When the amount of retention agent is established, it is important to keep in mind that it does not only increase retention and pulp dewatering, but also that this addition can cause deteriorating of formation and strength properties of paper. Tendency to maximal dewatering of papermaking suspension should not cause excessive impairment of paper web formation [10, 53, 54, 63, 64, 65, 66, 67, 68]. 2. Research phase This part describes materials and additives used and methods applied to find out what are the changes brought about with the addition of alternative pulps and what is the behavior of pulp during dewatering. Because the additives influence on both, pulp and paper properties, the impact of alternative materials will be distinguished and described separately. This chapter includes also description of methodology used to perform tested properties. 2.1. Characterization of raw materials and alternative materials used There were two pulps which were considered as reference pulps: Recovered pulp - Pure recovered paper coming from production of fluting was used to produce the first reference pulp. Recovered paper (Fig.26) was produced by Smurfit Kappa Roermond Papier. It was made of 60% of OCC and 40% of Mixed Office Waste. The recovered paper has 93% of dryness. Virgin bleached mixed pulp from hardwood and softwood was used to produce the second reference pulp. The virgin pulp was coming from production of transfer papers for screen and digital sublimation printing applications. It was characterized as having freeness of 30°SR. Before preparation of pulp with alternative materials, virgin pulp was supplied in a form of pulp cookies (Fig.27). Before pulps preparation, the reference pulps were stored and conditioned according to TAPPI T402 [70, 71]. 52 Fig.26. Recovered paper used to produce Fig.27. Virgin bleached mixed pulp used to the first reference pulp – recovered pulp. produce the second reference pulp – mixed pulp. Cellulose fiber is potentially the most sustainable papermaking biomaterial available. This raw material may be not enough for future paper production. That is why paper and board industry is considering other raw materials as useful in papermaking. Preferable alternative materials are considered as that they might replace conventional raw materials, but are cheaper; might enhance dewatering or might improve paper or board quality. The papermaking industry faces also challenge to decrease the amount of energy used, what may mean that at the same time these alternative additives should help to reach that aim. As an alternative material for reference pulps 5 different commonly available hydrophobic (fibrous and/or non-fibrous) substances (Fig.28–Fig.32) coming from the collaborating (bio-based) industries were used: Apple pulp Betacal - is one of the by-products of sugar industry, it consists mainly of CaO and MgO and organic matter, Beer fines Sawdust with diameter 100µm Sawdust with diameter 320 µm Alternative materials were supplied by three Dutch companies. Information about chemical composition, dryness, availability and prices of these additives were collected from companies and sorted in Tab.2. Before pulps preparation, alternative materials were stored in a laboratory of paper mill in containers (when they were solids) or kept refrigerated to prevent degradation (in case of wet samples). 53 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Alternative materials are characterized by different origin, shape and size of particles. These factors influence on pulp dewatering behavior. Because of that they may cause problems and influence diversely on paper machine runnability and general paper production. Due to variety of raw materials, the dewatering process can be fully characterized and different method results are expected. The described features of alternative materials may also have impact on paper sheet properties. It is important to remember that usage of such an alternative raw materials is worth considering when taking into account the desired pulp and paper properties. Alternative materials were added to reference pulp in proportion of 5%, 10% and 15% in reference to bone dry reference pulps. The way of pulp preparation is described in point 2.3. Tab.2. Available information about alternative materials. Additive Cellulose [g/kg] Hemicellulose [g/kg] Lignin [g/kg] Ash [g/kg] Apple pulp Betacal - - - 43 Beer fines 220 480 60 Sawdust C100 Sawdust C320 450-550 100-200 250-300 474 214 246 The solid content [%] 38 64 seasonality Availability [ton/year] 1500 100.000 dry 22-27 continuously produced by 4 months, available all year continuously 5 92 continuously 200 2 92 continuously 200 * also depending on transport (high moisture content) Fig.28. Apple pulp. 54 500.000 (100.000 dry) Price per dry ton [€] 5-10 20 120 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.29. Betacal. Fig.31. Sawdust with diameter 100µm. Fig.30. Beer fines. Fig.32. Sawdust with diameter 320 µm. 2.2. Microscopic pictures Different composition of pulps with alternative materials as addition is visible on microscopic pictures. Microscopic pictures were taken at Dresden University of Technology, in Germany during STSM program. 55 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” Fig.33. Typical recovered pulp. 2009 Fig.34. Eucalyptus vessel in recovered pulp. Fig. 36. Birch vessel in recovered pulp. Fig.35. Poplar vessel in recovered pulp. As it is possible to see from figures 33 to 36, recovered pulp contains a big variety of particles. Figure 33 demonstrates a typical microscopic picture for recovered pulp. Figure 34 shows a eucalyptus vessel present in recovered pulp. Figure 35 identifies a poplar vessel from recovered pulp. Figure 36 presents a birch vessel in recovered pulp. This means that the recovered pulp itself is produced from different raw materials. 56 Fig.38. Recovered pulp with apple pulp piece. Fig.37. Recovered pulp with apple pulp. Figures 37 and 38 identify recovered pulp with addition of apple pulp. In these pictures it is possible to notice apple pulp pieces and liquid dirt agglomerates from impurities of the pulp. Fig.40. Recovered pulp with betacal seen Fig.39. Recovered pulp with betacal. under polarised light. Figures 39 and 40 depict betacal addition. Also after disintegration, betacal particles are still much bigger than the normal size of filler particles. Alternative material particles are partly kept with dirts coming from recovered pulp and part of them is free (Fig.39). Figure 40 indicates recovered pulp with betacal addition visible under polarised light. Betacal particles contain sugar which can be seen as white spots in polarised light. Smaller particles which are composed of minerals CaO and MgO are not visible in the microscopic pictures. 57 Fig.41. Beer fines particle. Fig.42. Recovered pulp with beer fines. Fig.43. Recovered pulp with addition of Fig.44. Recovered pulp with beer fines. beer fines. Eucalyptus vessel comes from recovered pulp. Figures 41 to 44 display recovered pulp with addition of beer fines. The big aggregate in figure 41 is a particle ensemble from the skin of the cereal used for the bear production (epidermis cells). Figure 42 shows the structure of beer fines. Dirts presented in microscopic picture seem to be smoother and connected differently than in recovered pulp. Figures 43 and 44 confirm that different raw materials were used to produce recovered pulp. Eucalyptus vessels are visible in both pictures. 58 Fig.46. Recovered pulp with sawdust C100. Fig.45. Recovered pulp with sawdust C100. Figures 45 and 46 demonstrate recovered pulp with addition of sawdust with diameter 100µm. Dark spots visible on both pictures may be from sawdust. Fig.47. Recovered pulp with sawdust C320. Fig.48. Recovered pulp with sawdust C320. Figures 47 and 48 indicate the presence of sawdust with diameter 320 µm in recovered pulp. The big particle in figure 47 is a typical shive (wood fibres still connected via ray-cells) which may come either from sawdust C320 or from recovered pulp. Figure 48 depicts big dark spots which may certify the presence of sawdust. 2.3. Pulp preparation Pulp samples were prepared with the addition of 5%, 10% and 15% of alternative materials in relation to bone dry reference pulp. Altogether, 32 different pulp samples were prepared for 59 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 testing. Any way of pretreatment was not used to change the size and shape of alternative materials particles. Samples can be divided into pulp samples which were prepared and measured almost immediately after preparation and into pulp samples which were prepared and measured after at least two hours after preparation. This time was used for pulp swelling. Pulp samples were used to perform definite researches and after that paper sheets with addition of alternative materials were made. Fig.49. Desintegrator. Fig.50. Prepared pulps placed in containers and left for swelling. 2.4. Methodology of analysis 60 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Since alternative materials influence of pulp properties and also on paper sheets appearance, the methods of analysis of these two effects are separated into: Methods of pulp dewatering analysis, Methods of paper sheet properties analysis. In order to study the effect of alternative materials addition on pulp properties, the tests were performed using non-standardized methods. Information about the methodology of pulp properties analysis and techniques used to collect data is described beneath in point 2.4.1. The impact of alternative materials on pulp dewatering process in wire section and on ability of pulp to being dewatered in press section is also separated. 2.4.1. Methods of pulp dewatering analysis Due to there is no standard method, which describes dewatering property of papermaking pulp according to one norm, the following measurements were chosen to investigate and fully describe dewatering of pulp stock with the usage of alternative pulps: Schopper-Riegler freeness, Water Retention Value method, Rapid-Köthen number, Hydrodynamic specific surface area according to Dresden method, FiberXPress. The impact which alternative materials have on pulp dewatering in the wire section and in the press section is also separated. The effect of additives on dewatering in the wire section was tested using: Freeness test for both types of pulps after disintegration, Freeness test for both types of pulps after disintegration and 2h of swelling, Rapid-Köthen number measurement for both types of pulps with addition of alternative materials after disintegration, Hydrodynamic specific surface area measurement for recovered pulp with alternative materials addition after disintegration, Hydrodynamic specific surface area measurement for recovered pulp with alternative materials addition after disintegration and 2h of swelling, The effect of alternative additives on pulp dewatering in the press section was tested using: Water Retention Value measurement for both types of pulps after disintegration, 61 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Water retention Value measurement for both types of pulps after disintegration and 2h of swelling, FiberXPress test for both types of pulps after disintegration and 2h of swelling. . Researches were carried out using wide range of dewatering apparatus available. Schopper-Riegler freeness, Water Retention Value and Rapid-Köthen number tests were performed at Institute of Papermaking and Printing (IPIP) at the Technical University of Lodz (TUL) in Poland. Hydrodynamic specific surface area measurements were performed according to Dresden method with usage of the unique analyser, placed in Germany, at Dresden University of Technology, at Faculty of Mechanical Engineering, Professorship of Paper Technology. This cooperation was possible within European Union program called Short Term Scientific Mission (STSM) during COST E54 Action with title: “Characterization of the fine structure and properties of papermaking fibres using new technologies”. Analysis with the usage of new FiberXPress device, invented and developed by Voith and Smurfit Kappa, was performed in the laboratory of Smurfit Kappa Roermond Papier B.V. in Roermond, the Netherlands. Investigations in participating paper mill were conducted with coordination of Centre of Competence Paper and Board, the Netherlands, and cooperation with experts from paper mills. Since there is no information about the above methods in standards, some information and method description to present and to make possible by one to be acquainted with the methods are needed. 2.4.1.1. Schopper-Riegler freeness Schopper-Riegler tester is the most known instrument which uses the method of filter cake creating to measure the dewatering possibility of the pulp. The Schopper-Riegler value (°SR) is a measurement of the rate at which a diluted pulp suspension may be dewatered. It is specified according to Zellchemig Merkblatt V/7/61. The standards for this measurement are also: ISO 5267/1, SCAN C19 M3, BS 6035/1. The industry uses a freeness measurement to characterize the drainage capability of a pulp on the paper machines. Earlier Schopper-Riegler device was used only to measure pulp beating degree because there was a correlation between freeness values and a target level of 62 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 pulp refining. Freeness is a measure of how quickly water is able to drain from a fibre furnish sample. The measurement is based on pouring 1000ml of fibrous suspension with the concentration of 0,2% (2g bone dry pulp with 998ml of water) to metal container with a built wire. Pulp is dewatered on the wire with 100cm2 surface and filtrate is collected to calibrated cylinder. Freeness is determined as the total volume of water discharged from a side orifice of a specific configuration while the pulp suspension drains freely under gravity. Freeness is given in Schopper-Riegler [°SR] degrees as a unit. 10ml of water discharged from device equals 1°SR. The devices are designed so that an operator can judge the speed of dewatering by observing the volume of liquid collected in a graduated cylinder [69, 72, 73, 74, 75, 76]. The test measurements were performed according to the Zellcheming Merkblatt V/7/61. The device used is shown in figure 51. The test were carried out two or three (in case when the difference between results was more than 1°SR) times for each sample and the average value was calculated. Results of freeness were mass corrected. Fig. 51. Schopper-Riegler tester. 2.4.1.2. Water Retention Value Water Retention Value (WRV) is a result of centrifugal test and is expressed as the ratio of mass (weight) of water retained after centrifugation under specified conditions by a wet pulp sample to the oven-dry mass (weight) of the same pulp sample. Water Retention Value accounts for the amount of retention water which is present in fiber after subjecting wet fibrous sample to a certain amount of centrifugal force. Centrifugal force is a mean of separating water from the fiber material [28, 78, 79]. 63 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Water retention value is based on an empirical convention, which means that the final result is dependent on the conditions in testing. There are two methods used to define WRV: TAPPI Useful Methods UM 256 – in this method sample is centrifuged at 900g for 30min. SCAN-C 102 XE standard proposal – in this method sample is centrifuged at 3000g for 15min. The difference is these two ways of test performance in significant. Scan method is preferable because the higher gravitational field removes more inter-fiber water. This test is less sensitive to the inter-fiber pore geometry [21, 29, 30, 79, 80, 81]. The result from the Water Retention Value test allows to calculate nominal dryness of paper web. This is the dryness which corresponds to the amount of retained water in the paper web and the dryness can be used to assess the dewatering intensity of industrial press sections. The dryness was calculated with the help of WRV Calculator, application invented and used at Institute of Papermaking and Printing. 2.4.1.3. Rapid-Köthen number Rapid-Köthen number (RK number) (drainage time) is described as a time, which takes a volume of 6l of aqueous fiber slurry to drain in the Rapid-Köthen handsheet former from 8l to 2l under atmospheric pressure. Applied drainage pressure equals 100 kPa (atmosphere). Drainage time stopped 2l above the screen. The schematic illustration of the method is shown in figure 53. The method is was performed according to description from old Zellcheming Technical Leaflet ZCH V/7/61 [72, 82]. Test was performed only for pulps after disintegration. Test was repeated twice for each pulp sample and the average from the results was calculated. 64 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.53. Illustration of Rapid- Köthen number method [82]. 2.4.1.4. Hydrodynamic specific surface area Hydrodynamic specific surface area measurement is based on permeability principle published by Kozeny and Carman. The method is described in details in theoretical part of the thesis in point 1.4.2.2. After similar pulp preparation as described in point. 2.3. the following activities were carried out in order to conduct the hydrodynamic specific surface area test: Placing the pulp either directly after disintegration or after swelling into a dilution tank and filling the tank up to a volume of 10 liters Taking of the proper amount of pulp corresponding to approximately 2 g bone-dry material from the dilution tank for performing the hydrodynamic specific surface area test Using the same volume of pulp for exact determination of consistency in the dilution tank Simplified testing principle is shown in figure 54. Scheme of the testing device and the device itself as it is used at Dresden University of Technology is presented in figure 55. The measurement principle is based on compression of pulp between two wire screens from which one is moving with a piston and the other is fixed. The measurement is performed in few steps (Fig.56). 65 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.54. Simplified testing principle [45]. Firstly, dewatering and compression parts of tank are put together. Water is poured into the device and it covers the lower screen (1). Earlier prepared pulp is inserted and ready for drainage (2). Pulp is being dewatered by gravity (3). When drainage is finished, all thickened fiber material is placed only in the compression part (4). The compression part is moved to the main device and measurement can start (5). Initially, when the piston is moving downwards, the system is still without hydrostatic pressure (6). Start of compression is visible and begins when the piston is moving further downwards and causes sealing between upper screen and vessel wall (7). Only now the main device container is filled with water. The overflow system of the main container and the adjustable water outlet (flow rate measurement) determines the constant hydrostatic pressure drop. The sample is compressed stepwise, and for each resulting fiber pad concentration, position of the upper screen, flow rate and temperature are measured. Additionally to the common procedure to determine specific surface area, compressibility of pulp can be measured. After performing the six compression steps, the fibre pad is further condensed by driving the upper piston downwards as far as possible (8). From the position of the upper piston, the fibre pad concentration is determined, which is corresponding to the compressibility of the pulp sample at compression pressure of 1.56 kPa [45, 46]. 66 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.55. Scheme of the testing device and the device itself as it is used at Dresden University of Technology [45]. During pulps with alternative materials testing, six pressure steps were taken. Also compressibility of these pulps were tested. This measurement was applied only for recovered pulp with additives. One measurement was taken for one pulp sample. No tests with virgin pulp and additives were performed. All researches were carried out according to method description. The difference between the method description and tests performance was in pulp samples preparation. The pulp preparation of all samples was a little different than it is done usually with hydrodynamic specific surface area method. Normally, samples are swollen and after that they are disintegrated and deaerated (during deaeration dewatered pulp settles), as air bubbles in pulp prevent water from streaming through the pad. Swelling prevents fibers from being too damaged and cut. Within the researches for Short Term Scientific Mission which were used within this Thesis, the way of investigation was changed to be comparable with the sample preparation applied on other dewatering tests within the Thesis. Pulp preparation was done according to what is written in point 2.3. Recovered paper was cut into pieces and because of that fibers were already more damaged. Pulps were also not deaerated. 67 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.56. Measurement steps [45]. 2.4.1.5. FiberXPress The new FiberXPress test unit (Fig.57) was developed by Voith Paper Automation. This device analyzes stock which is usually taken from the mixing chest and gives results in view of stock water removal capability in the press section. That is why FiberXPress can be used as a method for estimation of pulp dewatering. Test of stock is explored by closing stock into sample chamber (2) where it is pressurized up to 10MPa by pneumatic cylinder (1). The required pressure is built up with compressed air (4) in the upper chamber of FiberXPress. Water which is pressed out of the stock passes a wire, which holds back fibers and fines. The screen ensures also a lateral flow towards the small syringe (diameter 1mm) through which the water flows and is drained into the weighting scale dish underneath the chamber (5, 6). After the pressing process, fibers are collected in so-called pellet. The pellet is taken out of the device and dried in an oven. After drying the mass balance is derived. Stock dewatering performance is assessed by analyzing the dried fibers and the extracted water. Fig.57. The FiberXPress test unit [83]. 68 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 FiberXPress measurement (Fig.58) is controlled from and recorded with a MS Exel spreadsheet with embedded VBA code. This device is moreover equipped with computer aided control of the pressure transducer (3) which allows for the stimulation of arbitrary pressure profiles over time and potentiometric displacement transducer (8) which allows for the thickness measurements during the pressing process. Owing to that information about compressibility and spring-back behavior of furnish can be achieved. The pressing chamber can be also heated by heating clamp (7). Conditions of FiberXPress working simulate mechanical dewatering of the mix in a press. The device was designed taking into account most of the factors influencing on the maximum dry content possible to achieve at the exit of the press section. It enables one-site visualization of dry content development as function of time, and analyzes the effects of varying pressing duration, nip pressure and temperature. The effects of using a different furnish can be also simulated with the FiberXPress under laboratory conditions and evaluated. According to inventors, FiberXPress tool is much more advanced than conventional test methods, based e.g. on water retention capacity of freeness. The test parameters are controlled more precisely and can be varied over a wide range. This enables a better approximation to the papermaking process, with more conclusive results accordingly [83, 84, 85, 86]. Fig.58. Photo of FiberXPress in a typical measurement setup (left) and turned for filling (right). The numbers are reffered to in the text [84]. 69 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The test performance was not different form the typical measurement performance. The test conditions were established simultaneously with the researches carried out for the method evaluation [87]. The chosen conditions were accepted as the best conditions that time allowing for the highest possible dryness achieving and they are the following: Pressure 9MPa, Time 980s, Basis weight 2500 g , m2 Pulp consistency 4%, Temperature 21°C. One measurement for every pulp sample was taken. The result was calculated and given directly by a computer program. The result can be interpreted as a dryness of paper web undergoing through ideal press section. Within the thesis this result will be compared with the result from WRV test. 2.4.2. Methods of paper properties analysis After pulps preparation and dewatering tests performance, remaining parts of pulps were used to made paper hand sheets. The assumed basis weight was 110 g what equals around 3,5g m2 per sheet (OD weight). The hand sheets were prepared according to TAPPI T205 standard [88]. The paper sheets were performed with the usage of Rapid-Köthen sheet former (Fig.59). Fig. 59. Rapid-Köthen sheet former used during investigation. 70 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 To define properties of paper sheets, the following structural-dimensional and strength tests were carried out in the same laboratory at Roermond: Basis weight [g/m2] – according to Thickness [mm] – according to Air permeance [ml/min] – according to ISO 5636/3 Breaking strength [kN/m] – according to Breaking length [m] – according to Elongation [%] – according to Stiffness [kN/m] – according to Bursting strength [kPa] – according to Span Compressive Test (SCT) [kN/m] – according to Paper sheets tests were performed according to TAPPI T220 standard [89]. The following devices were used during the investigation: Fig.60. Caliper gauge. Fig.61. Air permeance Fig.62. Bursting strength tester. tester. 71 Fig.63. Tensile strength tester. Fig.64. Compression strength tester. 3. Results and discussion In chapter 3 results from all pulp and paper tests are presented. Data were collected and sorted in tables (Tab.3 – Tab.10). Tables are presented in Appendix at the end of the Thesis. Results of all tests are presented on graphs. Graphs are sorted in turn of the method description and alternative material used. The trend lines normally visible on graphs can lead to some relationships which cannot exist or are not possible to achieve in reality. That is why graphs are released with measurement point results which are connected to show what the changes of pulp behavior with alternative pulp proportion (5%, 10% and 15%) are and to avoid misunderstandings. 3.1. The influence of addition of alternative materials on pulp properties 3.1.1. Dewatering in the wire section 72 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.65. Freeness as a function of alternative material proportion for all non-swollen pulps made of recovered paper. Fig.66. Freeness as a function of alternative material proportion for all non-swollen pulps made of bleached mixed virgin pulp. 73 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.67. Freeness as a function of alternative material proportion for all swollen pulps made of recovered paper. 74 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.68. Freeness as a function of alternative material proportion for all swollen pulps made of bleached mixed virgin pulp. Figure 65 displays the relationship between freeness values tested after disintegration for pulps made of recovered paper and alternative materials. Figure 66 identifies similar relationship but for alternative materials added to bleached mixed virgin pulp. Figure 67 points out the relationship between freeness values tested after disintegration and 2h of swelling for pulps made of recovered pulp and alternative materials. Figure 68 shows similar relationship but for bleached mixed virgin pulp and additives. Diversions in pulp behaviour depend on the shape and size of particles of alternative material added. Because of that, results of measurements seem to be spread and the changes brought about by alternative materials addition have not always visible tendency. For both types of non-swollen pulps (Fig.65, Fig.66) all alternative materials addition causes decreasing of pulp freeness or that the values of freeness fluctuate. The highest changes are provoked by sawdust C100, C320 and betacal. This additives are expected to improve pulp dewatering. In case of swollen pulps (Fig.67, Fig.68), alternative materials addition brings about mostly freeness increase, so they are expceted to deteriorate the dewatering of papermaking pulp, especially when using apple pulp and beer fines. When looking at swollen pulps, the greatest changes in pulp dewatering may be also caused by addition of sawdust C320, C100 and betacal. The alternative materials cause that pulp behaviour when using bleached mixed virgin pulp is similar to recovered pulp. In relation to virgin pulp, the greater changes in pulp dewatering behaviour are provoked by betacal addition. Usage of apple pulp and sawdust with diameter 100µm also brings freeness diminishing on. The relation between freeness results and hydrodynamic specific surface area results is very strong. Both of them depend on each other. The relationships between hydrodynamic specific surface area and the proprotion of alternative material used for all alternative material types are shown in turn in next figures. Figure 69 points out specific surface area as a function of alternative pulp proportion for all alternative non-swollen pulps. Figure 70 indicates similar relationship but for swollen pulps. Both graphs depict that the proportion and the type of alternative pulp used cause different changes in recovered pulp. Apple pulp is the alternative pulp which increase hydrodynamic specific surface area. Apple pulp brings about an increase in value with 75 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 proportion of 5% and 10% for both types of pulp. Addition of 15% changes the tendency. Alternative pulps which decrease hydrodynamic specific surface area are: betacal, sawdust with diameter 100 µm and sawdust with diameter 320 µm. Alternative pulp such as beer fines can be treated as an additive which does not have significant effect on pulp behavior when hydrodynamic specific surface area is compared. Fig.69. Hydrodynamic specific surface area as a function of alternative pulp proportion for all alternative non-swollen pulps. 76 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.70. Hydrodynamic specific surface area as a function of alternative pulp proportion for all alternative swollen pulps. 3.1.2. Dewatering in the press section Figure 71 demonstrates the relationship between compressibility of pulp and the usage of alternative materials for all alternative non-swollen pulps. Figure 71 displays that all alternative pulps added to recovered pulp changes its compressibility. Only usage of some of additives shows that it is possible to achieve higher consistency than without adding this material. 77 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.71. Compressibility as a function of alternative pulp proportion for all alternative nonswollen pulps. Alternative pulps such as betacal, apple pulp and sawdust with diameter 100µm have the highest influence on pulp compressibility in case of non-swollen pulp. It means that usage of these additives may allow achieving higher consistency than for recovered pulp itself in the same conditions as with recovered pulp. The above additives can be added to paper but only to some extent. The behaviour of betacal and apple pulp seems to be similar; the curves are following almost the same direction. These alternative additives are the best compressed with addition of 5% and 15%. Values of compressibility of recovered pulp with 10% additions are much worse than with remaining proportions, but still better than with recovered pulp itself. Compressibility comparisons of apple pulp and betacal usage are presented correspondingly in figures 78 and 97 and described underneath the graphs. The addition of sawdust with diameter 100µm to recovered pulp in non-swollen state of pulp causes that pulp is better compressed than pure recovered pulp with addition of 5% and 10% in relation to bone dry recovered pulp. Addition of 15% proportion of sawdust causes that compressibility of recovered pulp with this alternative material is worse than for recovered 78 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 pulp. The difference between swollen and non-swollen pulp with sawdust C100 addition is shown in figure 141 and described beneath the graph. Alternative pulp such as sawdust with diameter 320 µm causes no effect on pulp compressibility. The lines show that maximal possible consistency does not change significantly. It may mean that the addition of this pulp is neither here nor there for recovered pulp or that this alternative material causes that recovered pulp with its addition is not good compressible. The comparison between swollen and non-swollen pulp with sawdust C320 is shown in figure 155 and described beneath the graph. Usage of beer fines as an alternative additive shows that this additive decreases the consistency when the amount is higher than 5%. Addition may cause the changes of fiber and the shape of air-containing pores. The comparison between swollen and non-swollen pulp with this additive is illustrated in figure 122 and described beneath the graph. Fig.72. Compressibility as a function of alternative pulp proportion for all alternative swollen pulps. Figure 72 points out that the behavior of non-swollen recovered pulp with alternative pulps does not vary so much as for swollen pulps. The highest consistency is possible to get using betacal, what is similar as for non-swollen pulp. Also beer fines addition for swollen pulp gives similar results as for non-swollen one. This additive decreases the consistency when the amount of additive used is higher than 5%. Addition of remaining additives sawdust with 79 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 diameter 100µm and 320 µm samples and apple pulp, causes that recovered pulp is less compressible. Figures 72 and 74 display the relationship between dryness achieved by usage of FiberXPress device and alternative material proportion for both types of reference pulps with additives. In case of recovered pulp, the highest dryness is possible to reach by using betacal as an alternative additive. Betacal addition in all proportion gives increase in dryness. The usage of 15% of betacal gives the highest dryness among applying of all additives in different ratios. Usage of sawdust C320 gives also rise in dryness as in case of betacal. The tendencies for both alternative materials have ascending order. Usage of sawdust C100 is limited. 5% proportion in relation to bone dry recovered pulp allow achieving higher dryness, than with remaining proportions. Higher ratios than 5% cause dryness decreasing compared to 5%, but the values are still higher than for recovered pulp itself. It may mean that applying of sawdust C100 may bring pulp dewatering improvement. Apple pulp and beer fines usage bring about dryness decreasing. Apple pulp added to recovered pulp in proportion higher than 5% causes that dryness is diminished compared to reference pulp. Beer fines addition causes that dryness values fluctuate, but all of them are lower than initial value for recovered pulp. 80 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.73. Dryness achieved by usage of FiberXPress device as a fucntion of alternative material proportion for recovered pulp. Similar behavior is shown for virgin bleached mixed pulp as a reference pulp (Fig.74). Apple pulp added with all proportions causes that pulp dryness falls down. In case of beer fines, 5% proportion in relation to bone dry reference pulp gives dryness decreasing, 10% proportion usage causes that dryness values are approaching values for recovered pulp, and 15% proportion brings about final dryness diminishing. Dryness values reached with different beer fines usage seem to fluctuate, similarly as for recovered pulp, and it can be stated generally that the more additive is used, the lower is the possible achieved dryness for both types of pulps. In case of virgin bleached mixed pulp the highest dryness can be also reached by addition of betacal. The highest dryness is achieved when proportion of 5% of betacal is used. The higher amounts of this mineral additive cause dryness decreasing. 10% addition of betacal brings about that dryness approaches to the dryness of reference pulp and 15% addition causes that dryness is lower than for reference pulp. For both sawdust types, dryness values are lower with addition of alternative materials than value for reference pulp. Sawdust C320 gives better result than sawdust C100. Sawdust samples added to paper are themselves having very high dry content. It may mean also that from the mixture of recovered or virgin pulp with sawdust, even after rewetting, it is not possible to extract more water. 81 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 The comparison between pulp types with different alternative material and the amount of material used is shown in points 3.1.3.1 to 3.1.3.5 and described beneath the graphs. Fig.78. Dryness achieved by usage of FiberXPress device as a fucntion of alternative material proportion for virigin bleached mixed pulp. 3.2. The influence of addition of alternative materials on paper properties All graphs are shown as a relationship between tested property and the proportion of alternative material used. Graphs are divided into graphs showing the alternative materials impact on reference pulp and on virgin bleached mixed pulp. 82 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig. 50. Thickness index as a function of alternative materials proportion for recovered pulp. Figures 150 and 151 show the relationship between thickness index and the proportion of alternative materials used. Both figures display similar relationships. In case of recovered pulp, thickness index can be increased by the usage of apple pulp, beer fines and sawdust with diameter 320µm. Application of betacal and sawdust with diamter 100µm does not change thickness index significantly compared to the reference pulps. In case of virgin bleached mixed pulp, the addition of apple pulp and beer fines and also sawdust C320 show the greatest changes as well. In case of both pulps, sawdust C320 brings about that thickness index ratches correspondingly to the increase of this raw material proportions. Generaly, the usage of apple pulp and beer fines causes similar changes, the curves have almost the same shapes. In case of recovered pulp, the additives seem to be useful until 10%, but 15% proportion brings about thickness index decreases. In case of virgin bleached mixed pulp, 5% proportion decreases the thickness index, but the more materials are used, the higher is the thickness index. Usage of apple pulp and beer fines causes that pieces of these alternative materials were still visible in paper sheets by the naked eye (Fig. –Fig. ). This may cause errors in paper thickness measurements. The thickness value given by the caliper gauge could give the thickness of the alternative material particles present in paper sheets plane instead of thickness of paper sheet. 83 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Because of that only sawdust with diamter 320µm can be considered as a material which can increase thickness index. Betacal addition with 5% proportion in relation to bone dry recovered pulp causes that thickness index increases a little, but the more material is used, the lower is the thickness index. Inverse relationship is shown in case of virgin bleached mixed pulp. 5% proportion brings about that thickness index increases a little, but the more additive is used, the higher is the thickness index. Sawdust with diameter 100µm application with 5% proportion in relation to both reference pulps brings about that thickness index decreases. The more this additive is used, the higher is the thickness index. It may mean that the usage of this alternative pulp is worth considering only then more than 5% proportion in relation to bone dry pulp is applied. Fig.151. Thickness index as a function of alternative materials proportion for virgin bleached mixed pulp. 84 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.152. Air permeance as a function of alternative materials proportion for recovered pulp. Fig.153. Air permeance as a function of alternative materials proportion for virgin bleached mixed pulp. 85 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Figures 152 and 153 displays the relationship between the air permenace and the proportion of alternative materials used. Accorging to the apperance of paper sheets with the usage of apple pulp and beer fines, it is expected that the results do not show any real tendencies. The results presented on graphs may be not considered, because the particles of alternative materials are visible in sheet plane and may cause wrong interpretations of results. Sawdust with diameter 320µm seem to be applicable to both types of pulps with all proportions. Sawdust C320 addition causes that the air permeance is increased the most. Sawdust with diameter 100µm added to recovered pulp until 10% and to virgin bleached mixed pulp in all proportions also cause that air permeance is increased. Application of betacal to recovered pulp causes that air permeance is also increased with all proportion used. The higher changes are brought by addition of 5%. In case of virgin bleached recovered pulp, betacal can be applied until 10%, because than it increases the air permeance. 15% proportion seems to be too much and decreases the flow of air on the paper structure. It may be expected that these additives may be used in production of papers where higher air permeance is needed, as for dust-absorbing packagings or filter papers. Fig.154. Breaking length as a function of alternative material proportion for recovered pulp. 86 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.155. Breaking length as a function of alternative materials proportion for virgin bleached mixed pulp. Fig.156. Burst factor as a function of alternative material proportion for recovered pulp. 87 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.157. Burst factor as a function of alternative materials proportion for virgin bleached mixed pulp. Fig.158. Short Span Compression Test as a function of alternative material proportion for recovered pulp. 88 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.159. Short Span Compression Test as a function of alternative materials proportion for virgin bleached mixed pulp. Figures 154 and 159 displays the relationship between strength properties of paper and the proportion of alternative materials used. All figures show that the strength properties of paper are deteriorated when alternative materials are applied. The strength properties were expected to decrease in case of apple pulp and beer fines addition, because the particles of these materials were visible on paper surface. Sawdust C320 addition could have been expected to give similar results and it did. The usage of betacal and sawdust C100 causes that these alternative materials were present in the paper matrix, they were not visible in the paper structure, so they might have acted possitive on paper strength properties until some point (as fillers do). Unfortunately, also these materials caused falling down of the strength properties: breaking length, bursting strength (presented as burst factor) and SCT. 89 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 3.2.1. Pictures of paper sheets Fig.160. Paper sheet made of 100% Fig.161. Paper sheet made of 100% virgin recovered pulp. bleached mixed pulp. Fig.162. Paper sheet made Fig.163. Paper sheet made Fig.164. Paper sheet made of recovered pulp with 5% of recovered pulp with of recovered pulp with addition of apple pulp. 10% addition of apple 15% addition of apple pulp. pulp. Fig.165. Paper sheet made Fig.166. Paper sheet made Fig.167. Paper sheet made of virgin bleached mixed of virgin bleached mixed of virgin bleached mixed pulp with 5% addition of pulp with 10% addition of pulp with 15% addition of apple pulp. apple pulp. apple pulp. 90 Fig.168. Paper sheet made Fig.169. Paper sheet made Fig.170. Paper sheet made of recovered pulp with 5% of recovered pulp with of recovered pulp with addition of betacal. 10% addition of betacal. 15% addition of betacal. Fig.171. Paper sheet made Fig.172. Paper sheet made Fig.173. Paper sheet made of virgin bleached mixed of virgin bleached mixed of virgin bleached mixed pulp with 5% addition of pulp with 10% addition of pulp with 15% addition of betacal. betacal. betacal. Fig.174. Paper sheet made Fig.175. Paper sheet made Fig.176. Paper sheet made of recovered pulp with 5% of recovered pulp with of recovered pulp with addition of beer fines. 10% 15% addition fines. of beer fines. 91 addition of beer Fig.177. Paper sheet made Fig.178. Paper sheet made Fig.179. Paper sheet made of virgin bleached mixed of virgin bleached mixed of virgin bleached mixed pulp with 5% addition of pulp with 10% addition of pulp with 15% addition of beer fines. beer fines. beer fines. Fig.180. Paper sheet made Fig.181. Paper sheet made Fig.182. Paper sheet made of recovered pulp with 5% of recovered pulp with of recovered pulp with addition of sawdust C100. 10% addition of sawdust 15% addition of sawdust C100. C100. Fig.183. Paper sheet made Fig.184. Paper sheet made Fig.185. Paper sheet made of virgin bleached mixed of virgin bleached mixed of virgin bleached mixed pulp with 5% addition of pulp with 10% addition of pulp with 15% addition of sawdust C100. sawdust C100. sawdust C100. 92 Fig.186. Paper sheet made Fig.187. Paper sheet made Fig.188. Paper sheet made of recovered pulp with 5% of recovered pulp with of recovered pulp with addition of sawdust C320. 10% addition of sawdust 15% addition of sawdust C320. C320. Fig.189. Paper sheet made Fig.190. Paper sheet made Fig.191. Paper sheet made of virgin bleached mixed of virgin bleached mixed of virgin bleached mixed pulp with 5% addition of pulp with 5% addition of pulp with 15% addition of sawdust C320. sawdust C320. sawdust C320. 93 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 4. Conclusions Beer fines No effect can be seen from S-R value for recovered pulp with addition of non-swollen beer fines. C100 Filtration – S-R Permeation – specific surface area C320 Plug the screen by particles – increases S-R, drainage goes slower (spec.surf.area goes down = freeness goes up) –this is for swollen pulp. First it cause plugging of wire, but when we add more, water flow is similar and it come back to the initial value. Drainability is faster (what we can see from S-R plot) Measurement should start when fibers cannot move any more. Dewatering time with smaller volume (2ml) and the same hydrodynamic pressure is similar as for higher volume (5ml). It means that dewatering is less intensive. 94 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” Annex 1 2009 List of abbreviations CHP – natural gas Combined Heat and Power System. This type of system takes the waste heat from the burning of fossil fuels and applies it to power another process. For example, a basic CHP system might generate electricity needed in a particular industrial setting. The excess heat and steam produced from this process can be harnessed to fulfil other industrial applications, including space heating, water heating, and powering industrial boilers. [38,39] MP – paper machine List of figures Fig.1. Stock and water systems in the paper machine [x]. ......................................................... 9 Fig.2. Typical slushing system [8]. ............................................................................................ 10 Fig.3. An example of stock blending and machine chest including sampling station [8]. ......... 12 Fig.4. Headbox location in the paper machine [14]. .................................................................. 16 Fig.5. Feed pipe for mix and cross-section of jet from headbox (not to scale) [8]. ................... 17 Fig.6. Fourdrinier former [15]. ................................................................................................... 18 Fig.7. Basic principle of two-sided dewatering [8]. ................................................................... 19 Fig.8. Examples of Twin Wire Formers [16]. ............................................................................ 20 Fig.9. The four phases of the nip process [17]. .......................................................................... 22 Fig.10. Phases of drying process [1]. ......................................................................................... 24 Fig.11. General classification of water contained in fibrous materials [22]. ............................. 27 Fig.12. Extracting and measurement principle of sedimentation water content [23]................. 28 Fig.13. Division of sedimentation water [24]. ........................................................................... 29 Fig.14. Influence of radial acceleration on water content in pulp [25]. .................................... 30 95 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.15. Model classification of water contained in papermaking fibrous pulps a) sedimentation, b) gravity dewatering, c) conventional pressing d) extreme conditions of pressing [24]. .............................................................................................................................. 32 Fig.16. Conventional papermaking process [12]. ...................................................................... 34 Fig.17. Final energy requirement vs amount of water removed for the three operations forming, pressing and drying in a paper mill [31]. ................................................................................... 35 Fig.18. Dewatering through filtration (left) and thickening (right) [8]. ..................................... 40 Fig.19. Flow rate through a porous solid body according to Darcy (left) and Hagen-Poiseuille (right) [45] .............................................................................................. 41 Fig.20. Definition of internal and external surface area of a water-swollen fiber wall [46]. ..... 42 Fig.21. Kozeny-Carman plots for unrefined softwood chemical pulp as an example of pulp with straight-line assumption between the concentration limits 0.07 and 0.15 g cm 3 g , intercept with Y-axis to calculate specific surface area and intercept cm 3 with X-axis to calculate specific volume of the sample [45, 46]. .............................................. 45 Fig.28. Typical fiber and typical fine particle comparison. Right side of picture shows dewatering through a bed of coarse fibers in comparison with fine matter, assuming uniform packing density [20]. .................................................................................... 53 Fig.25. Schematic illustration of: a) charge neutralization, b) patch formation, c) bridging flocculation [69] ...................................................................................................... 58 Fig.26. Recovered paper used to produce the first reference pulp – recovered pulp. ............... 59 Fig.27. Virgin bleached mixed pulp used to produce the second reference pulp – mixed pulp. 59 Fig.28. Apple pulp. .................................................................................................................... 60 Fig.29. Betacal. .......................................................................................................................... 60 Fig.30. Beer fines. ..................................................................................................................... 60 Fig.31. Sawdust with diameter 100µm. ..................................................................................... 60 Fig.32. Sawdust with diameter 320 µm. .................................................................................... 61 Fig.33. Typical recovered pulp. ................................................................................................ 61 Fig.34. Eucalyptus vessel in recovered pulp. ............................................................................ 61 Fig.35. Poplar vessel in recovered pulp. ................................................................................... 62 Fig. 36. Birch vessel in recovered pulp. .................................................................................... 62 Fig.37. Recovered pulp with apple pulp. .................................................................................. 62 Fig.38. Recovered pulp with apple pulp piece. ......................................................................... 62 96 “Estimation of dewatering intensity of the paper web in the wet part of paper machine and selection of alternative additives to improve dewatering intensity” 2009 Fig.39. Recovered pulp with betacal. ........................................................................................ 63 Fig.40. Recovered pulp with betacal seen under polarised light. .............................................. 63 Fig.41. Beer fines particle. ........................................................................................................ 63 Fig.42. Recovered pulp with beer fines. .................................................................................... 63 Fig.43. Recovered pulp with addition of beer fines. Eucalyptus vessel comes from recovered pulp. ................................................................................................................. 64 Fig.44. Recovered pulp with beer fines. .................................................................................... 64 Fig.45. Recovered pulp with sawdust C100. ............................................................................. 64 Fig.46. Recovered pulp with sawdust C100. ............................................................................. 64 Fig.47. Recovered pulp with sawdust C320. ............................................................................. 65 Fig.48. Recovered pulp with sawdust C320. ............................................................................. 65 Fig.49. Desintegrator. ................................................................................................................ 66 Fig.50. Prepared pulps placed in containers and left for swelling. ........................................... 66 Fig. 51. Schopper-Riegler tester. ............................................................................................... 69 Fig.52. Modified Schopper-Riegler freeness tester [77]. .......................................................... 69 Fig.53. Illustration of Rapid- Köthen number method [82]. ..................................................... 71 Fig.54. Simplified testing principle [45]. .................................................................................. 72 Fig.55. Scheme of the testing device and the device itself as it is used at Dresden University of Technology [45]. .............................................................................. 73 Fig.56. Measurement steps [45]. ............................................................................................... 74 Fig.57. The FiberXPress test unit [83]. ..................................................................................... 74 Fig.58. Photo of FiberXPress in a typical measurement setup (left) and turned for filling (right). The numbers are reffered to in the text [84]. ............................... 75 List of tables Tab.1. Minimum energy requirement for water evaporation form paper, expressed in GJ/mt of water evaporated and GJ/mt of paper [34]. It is assumed that the final consistency of the paper is 93% ds. 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