Pulp and Paper Industry: Chemical Recovery

Well-to-wheel

Chapter 1

Introduction

Abstract

General introduction to pulp and paper manufacturing process and overview of chemical recovery in pulp mills (Kraft mill, Sulfite mill, Neutral sulfite pulp mill) are presented in this chapter. Significance of chemical recovery and key drivers and current trends in this area are also discussed.

Keywords

Chemical recovery; kraft mill; sulfite mill; neutral sulfite pulp mill; current trends in chemical recovery; modern recovery boiler; super combustion system

Paper is an essential commodity and has made a major contribution to the progress and development of many people. It has provided a means for people to keep written records, information, create works of art, and communicate ideas throughout the ages. In some parts of the modern world, the consumption of paper has reached an all time high, and much of it is wasteful and also unnecessary. Pulp and paper manufacturing has become one of the world’s biggest industries as a result of this excessive consumption. Global paper and board production advanced 0.8% to reach a new record level of 403 million tonnes in 2013 in-spite of the persistent drop in Europe and North America. Positive growth in packaging grades and tissue continued to counter balance the retreat in global graphic paper production. According to Annual Review of Pulp and Paper Statistics report (2014) published by RISI, China has maintained the top position for both production and demand of total paper and board over the past 5 years, with the United States remaining in second place. China accounted for 25% of global demand and 26% of world production of total paper and board in 2013. In terms of pulp production, the United States remained the top producing country. It produced 49.4 million tonnes in 2013, Canada produced 17.3 million tonnes, and China produced 17.1 million tonnes. Pulp and paper industry growth in China has been driven by strong performance in the consumer goods industry, the ready supply of raw materials, the low cost of manufacturing and labor, and the possibility of rapid expansion of the capacity.

Demand for recycled fibers is increasing as the industry continues to observe advances in recycling technology (Bajpai, 2013). Recycling rate in Europe reached 71.7% in 2012. In North America also, recycling is playing a very important role in the paper industry. Mineral fillers continue to expand as the use of virgin wood pulp declines. Other factors, such as the introduction of precipitated calcium carbonate and ground calcium carbonate, have also had a significant impact on the papermaking process. The recycling of waste paper continues to gain advantage from state legislative measures to favor ecological issues and for economic reasons within companies. Paper recycling represents the world’s second-largest source of fibrous material. This sector, is witnessing strong growth.

The pulp and paper industry produces different types of pulp. These pulp are produced both from wood and recycled material that is subsequently processed into paper. Virgin pulp production can be integrated with paper production on the same site. But standalone market virgin pulp mills also exist and standalone paper mills exist. These mills buy a mix of different type of market pulps to produce specific paper products. About 18% of all mills in the pulp and paper industry in Europe are integrated mills producing both virgin pulp and paper although different degrees of integration occur (CEPI, 2009). With the exception of few deinked market pulp mill, pulp production from recycled fibers is mostly integrated with paper production, although deinked recycled pulp is also sold to the market by many of these mills. The production of pulp and paper requires the use of power and steam. The electricity/steam consumption ratio at paper mills allows efficient use of cogeneration of heat and power (CHP) and therefore CHP is widely applied in the paper industry.

1.1 Pulp and Papermaking Processes

The main steps in pulp and paper manufacturing are: wood yard preparation, pulp manufacturing, pulp bleaching, and paper manufacturing. Pulp mills and paper mills may exist separately or as integrated operations. Paper production is a two-step process. The fibrous raw material is first converted into pulp, and the pulp is then converted into paper. The harvested wood is first processed so that the fibers are separated from the unusable fraction (lignin) of the wood. Pulp making can be done mechanically or chemically. The pulp is then bleached and further processed, depending on the type and grade of paper that is to be produced. In the paper mill, the pulp is dried and pressed to produce paper sheets. Post-use, an increasing fraction of paper and paper products is recycled. Nonrecycled paper is either incinerated or landfilled.

1.1.1 Wood Yard Operation

Wood yard operation includes raw material storage, debarking (when wood is used as raw material), chipping, chip screening, chip handling, and storage. Other processes such as depithing is used, when bagasse is used as the raw material (Biermann, 1996; Gullichsen, 2000; Gerald, 2006).

Wood is the predominant source of cellulose fiber for paper products. Other fiber sources, such as bamboo, straw, and bagasse are used in areas with limited access to forest resources, especially in developing countries. Some nonwood plants like hemp, abaca, and cotton are used for specialty applications. Wood is obtained at the mill in several forms including wood logs, chips, and sawdust. In the case of roundwood (logs), the logs are cut to manageable size and then debarked (Smook, 1992). In the pulp mills integrated with lumbering facilities, acceptable lumber wood is removed at this stage. In these facilities, any residual or waste wood from lumber processing is returned to the chipping process. In-house lumbering rejects are a significant source of wood at these facilities. The bark of those logs not suitable for lumber is usually removed mechanically using a drum debarker in order to avoid contamination of pulping operations. Log debarking is required to ensure that the pulp is free of bark and dirt. Mechanical and hydraulic bark removal methods are most commonly used. The barking drum is the most common form of mechanical debarking. Bark is removed from the logs by friction which is created from the rotating drum action as the logs rub against each other. In wet drumbarkers, water is added to the early solid steel portion of the drum in order to help loosen the bark. The remaining portion of the drum has slots to allow the removed bark to fall out while the log continues on through. In dry drumbarkers, the whole length of the drum has slots for bark removal. Dry drumbarkers are longer in length and rotate much faster compared to wet-type drumbarkers. The bark from dry drum barking can be fired directly into bark burning furnaces, whereas bark from a wet system should be collected in a water flume, dewatered, and then pressed before burning. Drumbarkers usually generate about 4–5% wood waste and cause broomed ends on the logs that produce inferior quality wood chips for pulping. They are relatively low-cost devices and require high power consumption (Russel, 2006).

Bark, may then be burned for energy production depending on the moisture content. If not burned for energy production, bark can be used for ground cover, mulch, or to produce charcoal. Wet debarking processes have substantially been abandoned by the industry. These processes produce wastewater that contains nutrients, fiber, and oxygen-consuming organic compounds such as fatty acids, resin acids, etc.

After debarking, the logs or the portions of logs are reduced to chips suitable for the pulping operations. Several designs of chippers are used. The most common one is the flywheel-type disk with a series of blades mounted radially along the face. The logs are usually fed to one side of the rotating disk at an optimum angle of about 45 degrees through a vertical directing chute. The logs can also be fed horizontally to a disk mounted at the proper angle. Usually, the horizontal feed provides better control but is found less suitable for scrap wood pieces. Off-size chips have the adverse effect on the processing and quality of pulp. A uniform chip size of typically 4 mm thick and 20 mm long in the grain direction is necessary for the quality of the pulp and for the efficiency of the processes. The chips are passed over multistage vibratory screens and the acceptable size chips are usually isolated from fines and oversized pieces. The oversized chips are rejected to a conveyor, which carries them to a rechipper. The fines are mostly burned with the bark unless special pulping facilities are available. Conventional screening mostly segregates chips only on the basis of chip length but in the recent years, the greater importance of chip thickness has been recognized and now few recently designed screens segregate according to this parameter. New design rechippers that slice the chip lengthwise to reduce thickness cause much less damage to the fibers in comparison to the old-style crushers.

Most chips are transported on belts or in pipes using an airveying system within the mill areas. Chips are readily handled by air over distances of 300–400 m. However, power consumption is high and chip damage can be quite substantial. By contrast, a belt conveyor system has a much higher initial cost. Other systems such as screw and chain conveyors are also used to move chips, but mostly for relatively short distances. Bucket elevators are being used for vertical movement.

Chip storage is widely used basically because chips are more economical to handle compared to logs. Some disadvantages are apparent like blowing of fines, airborne contamination. In the recent years, the significant loss of wood substance from chemical reactions, respiration, and microorganism activity has been quantified. It is now found that losses of 1% wood substance per month are typical. Substantial research has already been carried out to find a suitable chip preservation method, but so far, a totally effective, economical and environmentally safe method has not been developed. It makes good sense to provide a ground barrier of concrete or asphalt before building a chip pile in order to inhibit the mobility of ground organisms and to reduce dirt contamination. Chips should be stored on a first-in/first-out basis for avoiding infection of fresh chips by old chips. The ring-shaped pile facilitates the complete separation of old and new chips. Wind-blown concentrations of fines should be avoided because these fines reduce the dissipation of heat which builds up in the pile from various causes. From localized heat build up, thermal degradation, and even spontaneous combustion can result. Optimum handling of chips depends partly on pulping requirements. Loss of extractives is high for the first 2 months of outside storage, so all chips for sulfite pulping should go to storage for reducing resin problems. For some Kraft pulping operations, by-product recovery is important. Therefore fresh chips should bypass storage wherever possible for maximizing the yield.

Several reclaiming methods are in use. Older installations employ use of a belt or chain conveyor along the side of the pile, which is fed by a bulldozer that pushes chips down the side of the pile onto the conveyor. This arrangement is labor-intensive requires the use of a full-time bulldozer operator and results in damage to the chips. Modern installations work automatically, some using augers or chain conveyors on rotating platforms at the base of the pile.

With respect to a given wood source, the quality of chips is measured by uniformity of size, i.e., length and thickness and by the relative absence of contaminants. All chips 10–30 mm long and 2–5 mm thick are usually considered to be of good quality (Smook, 1992). Contaminants are considered to be:

• Oversized chips (either thickness or length)

• Pin chips (passing 3/8″ screen)

• Fines (passing 3/16″ screen)

• Bark

• Rotten wood (including burnt wood)

• Dirt and extraneous

Oversize chips represent a handling problem and are the major cause of screen rejects in chemical pulping (Smook, 1992). Size reduction of the oversize fraction is difficult to obtain without production of fines. Pin chips and particularly fines and rotten wood cause lower yields and strengths in the resultant pulps and also contribute to liquor circulation problems during cooking of chemical pulps. Bark mostly represents a dirt problem, particularly mechanical and sulfite pulping. The Kraft pulping process is much more tolerant of bark because most bark particles are soluble in the alkaline liquor.

Nonwood fibers are handled in ways specific to their composition in order to reduce degradation of the fibers and thus maximize the pulp yield. Nonwood raw materials are usually managed in bales.

1.1.2 Pulping Processes

Plant material basically consists of cellulose fibers, hemicelluloses, and lignin. Lignin is a natural binding material which holds together cellulose fibers in wood or in the stalks of plants. In the pulping process, the raw cellulose containing material, raw plant material, or recycled paper is broken down into its individual fibers, known as pulp. Pulping processes are categorized as chemical and mechanical. Different pulping processes result in pulp with specific properties suited for different applications (Casey, 1983a,b; Smook, 1992; Biermann, 1996).

1.1.2.1 Chemical pulping

Chemical pulping mainly relies on chemical reactants and heat energy to soften and dissolve the lignin in wood chips, followed by mechanical refining to separate the fibers. Major chemical pulping processes include the alkaline sulfate pulping process (Kraft pulping), acid sulfite, and semichemical pulping. Kraft pulping represents about 80% of current pulp production worldwide and almost all new construction. Kraft pulp typically produces a stronger sheet of paper or paperboard than other pulping processes. Kraft and sulfite pulps usually have higher market value and have higher costs of production compared with mechanical pulping processes. Their fiber quality is better for most purposes, with mostly less lignin or other wood constituents and proportionately more cellulose fiber and more intact fibers. Kraft and sulfite pulps can be more readily bleached to yield high brightness or whiteness that is desirable in several paper products.

1.1.2.1.1 Kraft pulping

Kraft pulping has become the dominant chemical pulping method because of the following reasons (Sixta, 2006):

• Better fiber strength compared to sulfite pulping

• Its applicability to all wood species

• Ability to efficiently recover chemical feedstocks

In the Kraft pulping process, wood chips are combined in a digester with white liquor, an aqueous solution comprising mainly sodium hydroxide and sodium sulfide, which breaks down lignin and, to a lesser extent, hemicelluloses under elevated temperature and elevated pressure, liberating the cellulose fibers (pulp). Following digestion, the resulting black liquor is separated from the pulp, called brown stock. The black liquor contains dissolved organic substances. The brown stock is treated with oxygen in the presence of sodium hydroxide to remove some of the residual lignin using the oxygen delignification process. The brown stock is then bleached, to obtain the desired strength, brightness, and purity of the final pulp product. The chemical feedstocks are recovered using the liquor cycle.

The superiority of Kraft pulping has further extended since the introduction of modified cooking technology in the beginning of 1980s. In the meantime, three generations of modified Kraft pulping processes have emerged through continuous research and development efforts. Modified continuous cooking (MCC), isothermal cooking (ITC), and Compact Cooking are examples for continuous cooking and Cold-blow, Superbatch/rapid displacement heating (RDH), and Continuous Batch Cooking (CBC), are examples of batch cooking technology. The third generation includes black liquor impregnation, partial liquor exchange, increased and profiled hydroxide ion concentration and low cooking temperature (elements of Compact Cooking), and also the controlled adjustment of all pertinent cooking conditions in that all process-related liquors are prepared outside the digester in the tank farm (as realized in CBC). Nevertheless, the potential of Kraft cooking is not exhausted by far. New generations of Kraft cooking processes are expected to be introduced, focusing on improving the pulp quality, reducing production costs by more efficient utilization of energy, further reducing the effects on the receiving water, and recovering high value-added wood by products (Marcoccia et al., 2000; Annergren and Lundqvist, 2008; McDonald, 1997).

1.1.2.1.2 Sulfite pulping

The sulfite cooking process is based on the use of aqueous sulfur dioxide and a base. Sulfite pulps are brighter and are easier to bleach but are weaker compared to Kraft pulps. Sulfite pulps are produced in several grades but bleached grades dominate production (Sixta, 2006). Yields are generally in the range of 40–50%, but tend toward the lower end of this range in bleached grades. This operation has the disadvantage of being more sensitive to species characteristics compared to the Kraft process. The sulfite process is mostly intolerant of resinous softwoods, tannin-containing hardwoods, and any furnish containing bark. Sulfite process produces bright pulp which is easy to bleach to full brightness and produces higher yield of bleached pulp. This pulp is easier to refine for papermaking applications. The base (calcium, magnesium, sodium, and ammonium) used affects the process conditions, water use, chemical and energy recovery, and properties of the pulp. The dominant sulfite pulping process is magnesium sulfite pulping and the calcium sulfite process is now being considered environmentally unacceptable for the new constructions. Use of sodium base and ammonium base in most mills have been discontinued because of higher costs. Although calcium base is relatively cheaper, the cooking chemicals cannot be recovered and are discharged. So, it is generally not used in new installations. Sulfite pulps can be easily bleached than Kraft pulps. Sulfite pulping produces fewer malodorous gases and has a higher yield than Kraft pulping. However, because of weaker fiber and poor recovery technology the sulfite process has not been competitive apart from magnesium base and has often resulted in more water effluents. Other major limitations of this process include its much higher net energy consumption than the Kraft process and also the limitations on the use of certain wood species such as pine wood which limits the raw material base. For these reasons, most major new chemical pulping investments use the Kraft