Chemical Process Technology (II)

Pulp and Paper

Introduction:
Raw materials for the pulp and paper industry can be classified as fibrous and nonfibrous. Wood is account for fibrous raw material. Wood contains cellulose, hemi cellulose, and lignin and extractives. Cellulose is crystalline material hemi cellulose is amorphous material. Cellulose links with hydrogen bonding if the amount of cellulose is more than the paper will be strong. Lignin is the binding material cellulose are fibers, lignin bond these fibers, so in pulp making we remove lignin. Wood is converted into pulp by mechanical, chemical, or semichemical processes. Sulfite and kraft (sulfate) are the common chemical processes, and neutral sulfite is the principal semichemical process (NSSC). The following table summarizes the conditions utilized with the various pulping processes.

Nonfibrous raw materials include the chemicals used for the preparation of pulping liquors and bleaching solutions and the various additions to the fiber during the papermaking process. For pulping and bleaching, these raw materials include sulfur, lime, limestone, caustic soda, salt cake, soda ash, hydrogen peroxide, chlorine, sodium chlorate, and magnesium hydroxide. For papermaking, they include rosin, starch, alum, kaolin clay, titanium dioxide, dyestuffs, and numerous other specialty chemicals.

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Wood Preparation:
Measurement and purchase of wood on a weight basis are practiced, and are desirable because weight is directly related to fiber content. The outer most layer of the wood is called the bark. The bark of trees contains relatively little fiber and much strongly colored nonfibrous material, the fiber preset in bark is of poor quality. The nonfibrous material usually will appear as dark-colored dirt specks in the finished paper (0.3-0.5 tolerance is allowed in the pulp making step). Bark doesnt dissolve in chemicals due to this consumption of chemicals also increase. Therefore bark should be removed as thoroughly as possible.

Debarking:
Debarking usually is done in several types of barkers. Drum barker, where the bark is removed by the rubbing action of logs against each other in a large rotating drum. Hydraulic barkers using high-pressure water jets are excellent for large logs. Mechanical knife barkers are becoming more common and are used extensively in smaller operations because of their relatively low capital cost. Also they have found widespread use in sawmills to debark logs prior to sawing so that the wood wastes can be used to produce pulp. Wood used in producing groundwood or mechanical pulp requires no further preparation after debarking, but that used in the other chemical processes must first be chipped into small pieces.

Pulp
Pulp consists of wood or other lignocellulosic material that broken down physically and or chemically such that discreet fibers are librated and can be dispersed in water and reform into a web.

Mechanical Pulping:
Mechanical pulping, as the name implies, involves mainly a grinding and abrading action on wood to produce a mechanical pulp. Stone groundwood pulping (SGW): Modern mechanical pulping includes stone groundwood pulping (SGW), in which bolts of wood are pressed against a revolving grindstone. Refiner mechanical pulping (RMP): In mechanical pulping chips are passed between single- or double-rotating plates of a vertical-disc attrition mill. Pressure to the grinder (PGW): Developments in stone grinding include application of pressure to the grinder (PGW) and control of temperature.

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Chemical Pulping:
The objective of chemical pulping is to solubilize and remove the lignin portion of wood so that very little mechanical treatment is necessary to fiberize the wood.

Kraft Process:
The kraft (sulfate) process uses a mixture of sodium hydroxide and sodium sulfide as the active chemical. The word kraft means good strength, now is mainly used to describe this process, as this process produces the strongest pulp. We can use all types of wood in this process. Digester: The pulping (cooking) process traditionally was performed on a batch basis in a large pressure vessel called a digester. There are four steps in digestes. 1. 2. 3. 4. Pre steaming Liquor impregnation Cooking Washing

Digesters are cylindrical in shape with a dome at the top and a cone at the bottom. The chips are admitted through a large valve at the top, and at the end of the cook they are blown from the bottom through a valve to a large blow tank. During the cook the liquor is heated by circulation through a steam heat exchanger, which also avoids the dilution of the cooling liquor that would occur from heating by direct injection of steam. The development of the continuous digester significantly facilitated the use of kraft pulping. Chips are admitted continuously at the top through a special high-pressure feeder, and the cooked pulp is withdrawn continuously from the bottom through a special blow unit. Because of the high alkali charge, the chemicals must be recovered and reused. The yield of pulp is only about 45 percent of the original wood weight, and the organic residues must be eliminated. After being cooked in the digester, the pulp is washed in a countercurrent rotary vacuum washer system using three or four stages. The pulp then is ready for bleaching or for use in papers such as grocery bags, wrapping paper where the brown color is not objectionable.

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Recovery In kraft process:
The separated liquor, which is very dark, is known as black liquor. It is concentrated in multieffect evaporators to 60-65 percent solids. By controlling the amount of excess air admitted to the furnace and the temperatures, the organics in the liquor can be burned. The inorganics collect on the bottom of the furnace as a molten smelt of Na2CO3 and Na2S. Sodium sulfate is added to the liquor as makeup and is reduced to Na2S by carbon. After dissolving in water, this mixture (called green liquor) is reacted with slaked lime: Na2C03 + Ca (OH) 2 2NaOH + CaCO3

The Na2S does not react with the lime, so the resultant mixture of NaOH and Na 2S (called white liquor) can be reused to pulp more wood. The CaCO3 sludge is filtered off, burned in a lime kiln, and reused. The kraft process has had a serious problem with air pollution due to the production of hydrogen sulfide, mercaptans.

Sulfite Process:
The sulfite process uses a cooking liquor of sulfurous acid and a salt of the acid. Although calcium was the most widely used base at one time, it has been supplanted by sodium, magnesium, and ammonia. Lignin will react with the bisulfite ion (HSO3-) under acidic conditions to form lignosulfonates that are soluble in water. Regardless of the base used, the initial step is the burning of sulfur to produce sulfur dioxide (SO2). The air supply to the burner must be carefully controlled, as too much air will enhance the formation of sulfur trioxide (SO3) and subsequent production of sulfuric acid Prepared By: Syed Saad Ahmed (B.E 3rd Year) CHEMICAL ENGINEERING

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(H2S04), which is very undesirable. The SO2 gas must be absorbed in water and reacted with the proper base ( MgOH etc) to form the cooking liquor (Mg(SO3)2). The pulp produce y this process is used to form Tissue, newspaper, drying paper etc.

Semi Chemical Pulping:

The NSSC process is one in which wood chips, usually from hardwoods, are cooked with Na2SO3 liquor buffered with either, NaHCO3, Na2CO3 or NaOH to maintain a slightly alkaline pH during the cook. Unbleached pulp from hardwoods cooked to a yield of about 75 percent is widely used for the corrugating medium. Although bleachable pulps can be produced by this process, they require large quantities of bleaching chemicals, and the waste liquors are difficult to recover. 50% chemical recover is sodium sulfate it ca e used I the recovery of Kraft process.

Bleaching of Wood Pulp:

The color of unbleached pulp ranges from cream for the sulfite process to dark brown for the kraft process. Although about 75-90 percent of the lignin has been removed by the pulping process, the remainder, along with other colored degradation products, must be removed by bleaching. Although it is possible to improve the brightness (whiteness) of the pulp in one stage, the economical achievement of high brightness requires the use of several stages. Current practice uses combinations of chlorination with elemental chlorine, alkaline extraction with sodium hydroxide, and various oxidative stages using sodium or calcium hypochlorite, chlorine dioxide, or hydrogen peroxide. The pulp is washed between each stage to remove solubilized impurities. The greater the number of stages, the higher the quality of the final pulp but at increased cost. Sulfite pulps are much easier to bleach and usually use only the three- or four-stage sequences, whereas kraft pulps require additional stages.

Recycling:
The basic means of recycling is minimizing waste. Worldwide, approximately 38 percent of wastepaper is recycled. The majority of recycled paper (about 75%) is used with no attempt to remove inks, dyes, or pigments from the paper. The resultant pulp is of rather poor color and quality, and is used primarily as filler stock in paperboard. The steps in the recycling process are: Re-pulping Screening Deinking Bleaching Refining Deinked grades of wastepaper require special techniques and equipment to remove inks, coatings, adhesives. The process may involve a number of combinations of washing, flotation, dispersion, screening, and the use of cyclone cleaners.

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Stock Preparation:
Stock preparation in a paper mill includes all intermediate operations between preparation of the pulp and the final papermaking process. It can be subdivided into Preparation of the furnish Beating or refining. Furnish is the name for the water slurry of fiber and other chemicals that goes to the paper machine. Beating or refining refers to the mechanical treatment given to the furnish to develop the strength properties of the pulp. In order to enhance the bonding capability of the fibers, it is necessary to mechanically beat or refine them in equipment such as beaters, jordans, or disc refiners. This treatment of the pulp slurry at about 3-6 percent consistency is done by passing the pulp between the two rotating surfaces of the refiner. These surfaces contain metal bars and operate at very close clearances. As the fibers pass between the bars, they are made more flexible, and a larger surface for bonding is developed by the mechanical action. This refining increases the degree of interfiber bonding in the final sheet of paper. As additional refining is performed, properties such as tensile strength, fold, and density are increased while tear resistance, opacity, thickness, and dimensional stability are decreased. Thus, the proper refining conditions must be selected to bring out the desired properties The paper industry is a large user of chemicals because relatively small quantities of additives can materially change the properties of paper. The use of 1-2 percent rosin size (resin is the sizing material) and 2-3 percent alum [AI2 (SO4)3] will greatly increase the resistance of paper to penetration by water or ink. Pigments such as kaolin clay, calcium carbonate, and titanium dioxide are added in amounts up to 15 percent to increase opacity and give a better printing surface.

Papermaking Process:
From the wet end of the machine, the wet sheet is conveyed by woolen felts through a series of roll-type presses for further water removal, increasing the consistency to about 35 percent. The sheet then is threaded through the dryer section, consisting of a long series of steam-heated cast iron cylinders that reduce the moisture content to approximately 5 percent, which is about the equilibrium moisture content for cellulosic fibers at 40-50 percent relative humidity.

The paper surface is brought to a high finish by passage through the calenders or through supercalenders. Prepared By: Syed Saad Ahmed (B.E 3rd Year) CHEMICAL ENGINEERING