ALKALINE PULPING, WASHING, SCREENING AND CLEANING PRINCIPLES

Alkaline pulping fundamentals

 Alkaline Pulping is the separation of fibers from raw materials by dissolution of lignin Alkali attacks cellulose/hemicellulose & lignin. The attack is faster on lignin than carbohydrates. As pulping reaction proceeds lignin concentration decrease More carbohydrate fraction is attacked leading to pulp degradation & reduction in strength properties. Complete removal of lignin during pulping is not attempted It would give a highly degraded pulp unsuitable for paper making. Pulping to a target kappa number is attempted where the attack on carbohydrate function is minimal. Further removal of lignin is attempted during bleaching with more selective bleaching agents

 Carbohydrates in the alkaline liquor are attacked by peeling reaction. Removal of end glucose unit by breakdown of 1,4 glucoside/xyloside linkage This is due to active aldehydic group present in one end unit of cellulose chain. Removal of one unit, generates another active end unit and removal process continues till such time a stopping reaction take place in which the active aldehydic group is converted to non reactive group. This take place when about 300 glucose units have been removed

Plot of alkali concentration vs. time

Removal of lignin during pine kraft cooks

Change of alkali concentration, lignin & hemicellulose removal as a function of cooking time

Effect of Temperature
Rate of reaction varies with temperature and time. The extent of reaction - kdt = H The rate of reaction follows Arrehenious equation k = Ae-Ea/RT ln k = ln A Ea /RT ln k100 = ln A = Ea/373R ln k/k100 = ln kr = Ea /R[1/373 1/T ] At Ea = 32 kcal mole, kr = relative rate constant ln kr = - 16113/T + 43.2 The values of kr has been evaluated at different temperatures. H factor has been defined as H = krdt = Extent of reaction

H factor

It is a useful parameter It can indicate the change in reaction time if there is a small change in the cooking temperature

Chip Impregnation
The pulping liquor must be uniformly distributed in the chip before cooking temperature is reached. The transport of the liquid is through diffusion, because the chips are pre steamed & the cavities are full with water. Diffusion is a slow process Diffusion improves by raising the temperature, or increasing impregnation time or increasing hydraulic pressure At pH 13 or above, the rate of diffusion is same in all the directions, longitudinal, radial or tangential directions

 So chip thickness is the controlling factor for chip impregnation. But as the cooking liquor enters the chips, it reacts and pH drops. If the pH drops below 12 the rate of diffusion drops sharply and liquor may not be able to reach the center of the chips. So thinner (3-6 mm) chips are preferred. Increase of temperature by 10oC nearly doubles (2.2) the rate of delignification but rate of impregnation increases by 2% (dependent upon temperature in oK). Hard wood require 4mm and soft woods 7mm thick chips.

Chip Damage
Chipping damages the fibers at the ends. Many fibers are cut and are shortened by chipper knife. But most damaging effect is due to wedge shaped blade causing localized distortions of the wood structure. The damaged parts are more susceptible to acid hydrolyses than alkaline liquors. Sulphite pulps give 15% reduction in strength where as in kraft process the reduction is minimal. Crushing parallel to fiber axis is more detrimental than perpendicular to the grain.

Active alkali=NaOH+Na2S Effective alkali=NaOH+1/2Na2S Sulphidity=NaOH/(NaOH+Na2S)d All quantities expressed as Na2O

Pulping Variables
Alkali (NaOH + Na2 S) dose : 16% in case of softwoods and 12% in case of hardwood expressed as Na2O Unbleached screened yield 50-55% However pulp yield depends upon the chemical composition of raw material i.e. hollocellulose content

Pattern of chemical consumption

The results are of a study with soda pulping of spruce with 19% alkali as Na2O. 12.5% was consumed in pulping wood to give lignin content of 2.8% based on wood and at a yield of 44%. Out of 12.5%, 2.3-3.0% was consumed for dissolution of lignin 1.3% was consumed for hydrolysis of formyl and acetyl groups. Of the remaining 8.2-8.9% most of it was neutralized by acidic degradation products of carbohydrates but a small part was retained on the pulp by absorption

 About 20% is used for attacking lignin 70-75% for attacking carbohydrates and neutralization of degradation products 3-4% residual alkali is maintained to prevent re-precipitation of dissolved lignin on fibers. Since the alkali concentration is high and reduces with reaction time. So sufficient alkali must be added so that a minimum residual alkali concentration of 6-8 gpl is maintained to prevent precipitation of lignin

 During the initial part of the cook, i.e. raising of temperature carbohydrates are attacked. Lignin starts getting attacked at 1300C Rate of reaction increases with increase in temperature. By splitting alkali charge i.e lower alkali charge at the beginning second dose added near the cooking temperature some alkali charge at the end of the cook Pulp of lower kappa number, high viscosity and improved yield can be obtained.

Wood to liquor ratio

Wood liquor ratio of about 3.5-4.1 for soft woods, 2.8 for hard woods is maintained A lower bath ratio is preferred It reduces steam demand in evaporation section of the chemical recovery Lowering the bath ratio increases alkali concentration rate of delignification degradation of cellulose

Effect of chemical to wood ratio on chemical consumption and pulp yield

The brightness of bleached pulp (CEHDED) as a function of the effective alkali during the cook

Kappa number and yield for the different charges of effective alkali and different times of maximum temperature (1700C) in cooking

Summary of impact of increased effective alkali charge on pulp quality

Xylan content is reduced Glucomannan content is increased. Brightness of unbleached pulp increased. Longer beating time is required to reach given breaking length or drainage resistance Maximum breaking length is reduced. Tear factor at a given breaking length is increased.

Effect of sulphidity on pulp composition and yield

Effect of sulphidity during kraft pulping of southern yellow pine

Influence of sulphide charge on strength-yield relationship (constant EA 15% on wood as Na2O)

Influence of effective alkali and sulphide charges on pulp

Kraft Pulp Modification

Modifications for improving pulp yield. Major reduction is loss of hemicelluloses and some dissolution of cellulose. This loss is by peeling reaction involving the active end unit containing aldehyde group. Modification of aldehydic group by oxidation to carboxylic or reduction to hydroxy OH the peeling reaction will stop dissolution of carbohydrate fraction reduces, giving higher pulp yield. This is done by using polysulphide or anthraquinine where the CHO group is partially converted to COOH reducing peeling reaction giving an improvement in yield of 3-5%

Mechanism of anthraquinone action

Effect of yield on strength properties

Effect of anthaquinone on mixed southern hardwoods

Alkaline Digester Systems

Two types of digesters :Batch & Continuous. Batch digesters are low cost, easy to operate and maintain responds well to raw material variation gives a pulp with high quality variations have low energy efficiency, give a weaker pulp due to hot blow emits higher amount of odourous mercaptan Continuous digesters give pulp of consistent & superior quality (stronger pulp) Give low emissions and has high energy efficiency but are expensive.

Batch digestor
Batch digesters are spherical or cylindrical shape, direct heating or in directly heating type, stationary or tumbling type. A stationary cylindrical digester with indirectly heating is used at many places. In indirect heating, heating of liquor is done outside the digester using heat exchangers Heated liquor is circulated in digester giving uniform temperature and liquor composition In direct heating type steam gets condensed diluting the pulping liquor. Tumbling action do not give uniform temperature profile in the digester giving a non uniform cooking

Batch digestion system- stationary, cylindrical and indirect heating type

 Chips are added from top along with hot black liquor When full, lid is closed, heating is done by circulating hot liquor through heat exchangers Before reaching to a cooking temperature of 165-170 oC, digester is vented for a short time to allow air in the chips to escape Air acts as a barrier to heat transfer and also gives false pressure. The temperature (165-1700C) in the digester corresponds to saturated steam pressure 67kg/cm2 If air is there in the digester the temperature is lower

Blow Tank
After cooking the chips, the digester is blown by connecting to blow tank at 1 atm pressure The feed is tangentially at the top, which feeds the cooked chips into the blow tank and gives circular motion. Because of centrifugal forces the gases are separated from chips & liquor, which falls under gravity and collects in the blow tank

Flat bottom blow tank with side entering

Cone bottom blow tank

Condenser system
Hot vapors pass through a condenser where these are cooled giving condensate containing dissolved organics imparting high BOD Non condensable gasses escape to the atmosphere which contains mercaptans responsible for odor. The hot gases are cooled in the condenser system giving only hot water. This heat is not recovered. Energy requirements are high or energy efficiency is low. Blowing is done at 1650C, the fibers are soft and some rupture in the internal structure take place, lowering the strength properties

Surface condenser system

Jet condenser system

Cold blow in a batch digester

In this process, after the cooking is over, the heat of the black liquor is used to heat the white liquor and raising the temperature of the digester Some steam is needed to raise temperature of digestor to cooking temperature and maintaining cooking temperature during cooking period Cold black liquor from the previous cook is pumped in to the digestor to displace the hot black liquor Energy (steam) requirements are lower by 40% Temperature of the chips goes down below 1000C, atmospheric blowing using air compressor is done Damage to the chips is reduced,vapours are greatly reduced requiring small condenser system significantly reduced emissions of non condensable gases mercaptans, sulphides etc

Cold blow in a batch digester

Low energy cooking sequence

RDH Process
After the cooking is over, the black liquor at 130-140oC is pumped in to the digester Displaced black liquor is collected in the tank Cold black liquor at 70-80oC is fed to the digester, hot black liquor of 130-140oC is displaced Displaced liquor is collected in another tank which is used for heating of chips and liquor Temperature of chips now falls to 80-90oC Digester is now blown at 80-90oC using air blow

 For the new batch the chips along with hot black liquor is added This liquor is displaced by hot black liquor at 130 140oC to which white liquor is added This raises temperature of chips to130- 140oC This liquor is then replaced by black liquor at 150-160oC along with steam to raise temperature of the digester to cooking temperature The process has high steam economy, low TRS emissions and gives a stronger pulp with a lower kappa number The pulp kappa number is lower due to in digester washing (displacement) which reduces the bleach chemical demand

Wash Loss in a pulp mill

Reducing wash loss by installing a press at the end of a washing

Pulp Washing
Blown pulp is screened to remove uncooked/ undercooked chips, knots etc. from pulp suspension Pulp is washed to remove dissolved solids particularly black liquor which contains dissolved lignin and will contribute towards residual lignin content kappa number of pulp This will enhance the bleach chemical requirements in bleaching, increasing bleach chemical costs, degrade pulp and increase environment pollution Direct counter current washing (4-5 stages) is generally used

Washing Principles
The principle of washing is displacement A pulp mat is formed on the washing equipment The mat contains black liquor. This liquor is displaced by wash liquor and washes pulp Ideally wash liquor required for washing must be equal to liquor present with pulp In real system because of turbulence and movement of organics due to diffusion mixing at interface take place, more wash liquor is needed to wash the pulp than present with washed pulp DF is equal to difference in outgoing liquor and incoming liquor with pulp or difference in wash liquor used and liquor with outgoing pulp

 Increasing DF will improve the washing but this additional water will have to be evaporated in the chemical recovery Low values of DF are preferred 2.2-2.4 Washing improved by increasing number of wash equipment Washing efficiency is ratio of dissolved solids removed to actually present with pulp. It is expressed as ratio or as percent Dissolved solids contain two components: inorganic sodium and organics carbohydrates, lignin etc expressed as COD Both quantities are used in estimating washing efficiency

 In the first case by estimating sodium content in washed and unwashed pulp This gives good results when washing efficiencies are moderate Sodium is present in two forms free and bound Free sodium can be removed by washing , bound sodium remain attached with pulp (0.5 1.0 meq/g) Other approach is to measure COD of liquor accompanying washed and unwashed pulp COD is a measure of organic content Washing efficiency of an equipment/system can be expressed by two methods

Washing means adding wash liquor and removing/displacing equal volume of the dirty liquor with the unwashed pulp If the pulp suspension is diluted by adding wash liquor, concentration of dissolved solids in the pulp is reduced indicating washing. In this case no dissolved has been removed and thus no washing DR gives correct results only when inlet and outlet pulp consistencies in wash equipment s same

Nordon Method

 W = Liquor weight of inlet pulp / Liquor weight of out going liquor R = Wash Liquor used / Liquor with outgoing washed pulp Values of both W and R are always greater than 1 If more than one wash equipments are used in series (Direct counter current washing) each equipment will have a value of R represented as R1, R2, R3 etc These values may be same or different. Each wash equipment has E value as E1, E2 EN Identical wash equipments E1, E2 EN will be same Wash Yield = Y = 1 - (W-1)/[ WR1E1R2E2 .RnEn 1] This equation can be used to know what will be the effect on washing if the number of wash equipments are changed, a change in DF, change of inlet/out CY or a wash equipment is replaced by other wash equipment or a different wash equipment is added to the existing set of wash equipments

 A single washing step will include adding wash liquor in the pulp mixing it and removing the equivalent volume of liquor from pulp The same process is repeated a number of times A curve is plotted between dissolved solids in the pulp as a function of number of washing stages This curve is used to evaluate the E value of particular equipment E value is defined as the number of washing steps needed to give the same wash result as obtained from a given wash equipment The E value depends upon inlet and outlet pulp consistencies E values of some of equipments are given in Table

E value of different wash equipments

Filter equivalent
Filter equivalent = E value of equipment/ E value of filter Filter equivalent indicates that the washing efficiency of a equipment will be equal to that obtained from such number of filters Filter equivalent of radial washer is 2 indicating that it will give the same wash result as obtained from 2 vacuum fillers Examples -- Single/double stage vacuum filter, Radial washer (Atmospheric diffuser), Pressurized diffuser, Wash press, Belt washer, Displacement washing in Kamyr digester or in batch digesters etc

Screening & Cleaning Principles

Pulp contains two types of impurities dissolved solids which are removed by washing and the other suspended solids shives, sand etc which are removed by screening & cleaning For screening of the pulp, screens with circular/ slotted perforations are used If there is a sizeable difference in the sizes of fibers & impurities, these can be separated by screening Fibers being small are able to pass through screen opening and bigger under cooked material like knots are retained as done in case of Johnson screen Johnson screen is an example of positive screening when the separation is taking place based on difference in size of fibers and impurities.

 Fibers & shives have similar fiber dimension Both pass through or retained on screen plate Major difference is to pass or retain on screen plate Screening is a statistical process. A high probability for fibers to pass through screen Impurity has a low probability to pass through and it is retained on the screen plate and is rejected. Pulp slurry is divided into accepts and rejects In accepts there is lower amount of impurities in comparison to inlet pulp So the pulp has become clean

 One of major parameter influencing screening operation is difference in flexibility of fiber & impurity A shive is a group or bundle of fiber, has higher stiffness It can not easily bend, flexibility is small A screen plate is a cylinder shell with holes The pulp stock is rotated

 Fibers and shives align themselves with rotary flow Water flow through the perforations, fibers being flexible, bend easily and pass through perforations where as shives are stiff, do not bend easily and are not able to pass through the perforations of screen plate and are thus retained on screen plate. So accept fraction will have lower proportion of shives, giving a clean pulp.

 Two parameters are used to describe a screen

Screened Efficiency (%) = Impurities

removed/ Impurities originally present

Over screening reject rate (%) =

Weight of Pulp rejected/ Initial weight of pulp Usual values of screening efficiency are 7080% and over screening is 10-30%. Screening efficiency increases with decreasing size of the perforations and cleanliness of pulp Value is higher at higher value of Reject rate but total amount of pulp rejected is increased

Hydraulic load vs. pulp consistency

Capacity of the screen depends flow rate (hydraulic load) across the screen plate Increasing pulp consistency decreases flow rate

Kraft pulp fluidization energy vs. pulp consistency

For screening, pulp fibers must be present as individual fibres or as separated fibers at the time it reaches screen plate Above 0.5% Cy, fibers start forming net works, strength of networks increasing with Cy So these net works are to be broken by providing agitational energy fiberizing energy.

 For screening, pulp fibers must be present as individual fibres or as separated fibers when these reach screen plate Above 0.5% Cy, fibers start forming net works, strength of networks increasing with Cy So these net works are to be broken by providing agitational energy fiberizing energy This energy increases with Cy. Above 4% Cy fiberizing energy starts rising sharply and agitational energy may not be sufficient to break networks. Above 4% Cy, the flow rate becomes small, so capacity becomes small This indicates operating consistency range of screens as 1-4%.

Time for reflocculation vs. pulp consistency

Time of re-flocculation decreases with pulp consistency. This time should be greater than the time required to reach the screen plate from the point of agitation of pulp

Impact of operational parameters

Raising the pulp temperature may make the impurity more flexible and reduce the screening efficiency Screens work with screening efficiency on a percentage basis The purity of the accept will be directly influenced by the amount of debris in the inject If pressure drop increases, a large portion of small impurities will be forced through the openings of screen plate thus lowering the screening efficiency If the inject flow rate is constant and the pressure drop across the screen starts to increase, indicating that the inlet consistency has increased or screen plate has started to plug

Types
Flat screens Rotary Screens Centrifugal Screens Pressure Screens commonly used MC Screens becoming popular Pressure screens are compact (small size), require unattended operation and have high capacity Screens work at lower consistency and hence require pumping of large volumes of water Pressure screens are used as coarse and fine screen as well as knotter screens depending upon size and type of perforation MC screens work at medium consistency, do not require lowering of consistency and require much water handling

Pressure Screen

Examples of flow patterns in pressure screen

Sweeping foil keeps pressure screen plate open

Combination of screens
Screening in more stages Double screening

Double screening give high cleanliness but yield is quite low. Reject screening give high pulp yield but cleanliness has decreased as compared to a single screen

Mixing of accepts of different purity

Cascade coupling in two stages

Reject screening in two stages

Cascading of screens, the accept from a secondary screen is mixed with inject of the first screen, This will improve the cleanliness of the pulp from screening system

Optimum screening system

Centricleaners

 Centricleaners (centrifugal cleaners) are used to remove heavier matter like sand from pulp suspension Inverted centricleaners are used to remove lighter impurities. The use of centricleaners has declined as these works at very low consistency 0.5-1.0% and is considered to be expensive in operation due to pumping of very large quantities of water