KRAFTS PROCESS FOR PULP AND PAPER INDUSTRY

RAW MATERIALS :
Raw Materials Requirements per tonne of
paper (in kgs)
Cellulosic Raw Material (Wood) 2500-3000
Cooking Chemicals (as Na2S) 70-90
Caustic Soda 20-35
Chlorine 100-160
Lime 70-100

Assuming 1 tonnes of product

Chipper bin: -
 Chips are fed in this device.
 Cut logs are conveyed to the chipper where rotary disks with heavy knives reduce the wood to size 2-5cm flat chips.
 Size reduction is done to maximize penetration of process chemicals.

Digester (10 atm and 150-200 degree C ) (25 – 30 m tall)

 Cooking time is about one and a half hours at 170°C.
 To avoid mechanical weakening of fibres, digested chips are cooled with recycled black liquor.
 Temperature is maintained at 140-180°C and pressure at about 10 atm.
 Bottom temperature is maintained at 65°C.

1. Input
Wood = 2500 kg
White liquor =90 kgs ( NaOH = 30 kg, Na2S = 60 kg )
 Water =
2. Output
Black liquor – 15% solids (by wt. 10% organic chemicals (45% lignin), 5% inorganic chemicals) + water
Unbleached pulp
Unused white liquor(Recycled to digestor)
Screens: -
 Pulp is screened so as to remove wood knots and undigested residues.

BLACK LIQUOR
The black liquid remaining after digestion of timber in
a chemical pulping process. Black liquor contains the
spent cookery chemicals, lignin, resins and other non-cellulose
constituents in solution

Bleaching Plant (Treatment of cellulosic fibre with chemicals to

increase brightness and stability)
1. Input
Unbleached pulp
A)Cl2
B)NaOH
C)ClO2
D)NaOH
E)ClO2
(A and B complete delignification)
(Bleached pulp is obtained by further treatment with Cl2 and ClO2)
Follows CEDED stages
2. Output
Bleached Pulp
 Conditions for Bleaching Plant:

Symbol Concentration of pH Consistency* Temperature Time (h)

agent (%) (%) (°C)

Chlorine (Cl2) C 2.5–8 2 3 20–60 0.5–1.5

Sodium hydroxide (NaOH) E 1.5–4.2 11 10–12 <80 1–2

Chlorine dioxide (ClO2) D Approx. 1 0–6 10–12 60–75 2–5

Multiple effect Evaporator ( 4 atm at one end and 0.8-1 atm )

1. Input
Black liquor – Organic materials, water, lignin

2. Output
Conc. Black liquor (35% water) + steam

Recovery Boiler(10000C)
1. Input
Conc. Black liquor (65-80% solids)
Water

2. Output
Smelt + Steam
Dissolving Tank
1. Input
Smelt
NaOH
2. Output
Green liquor (Na2S and Na2CO3)
Slaker
1. Input
Green liquor
Ca(OH)2

2. Output
White liquor (sent to digester)
CaCO3
Lime Kiln (CaO recovery)
CaCO3 --------------> CaO + CO2
KRAFT PROCESS DESCRIPTION:

 The Kraft pulping process involves the digesting of wood chips at elevated temperature and pressure in "white liquor", which is a water
solution of sodium sulfide and sodium hydroxide.

 The white liquor chemically dissolves the lignin that binds the cellulose fibers together.

 There are 2 types of digester systems, batch and continuous. Most Kraft pulping is done in batch digesters.

 In a batch digester, when cooking is complete, the contents of the digester are transferred to an atmospheric tank usually referred to as a
blow tank.

 The entire contents of the blow tank are sent to pulp washers, where the spent cooking liquor is separated from the pulp.

 The pulp then proceeds through various stages of washing, and possibly bleaching, after which it is pressed and dried into the finished
product. The "blow" of the digester does not apply to continuous digester systems.

 The balance of the Kraft process is designed to recover the cooking chemicals and heat. Spent cooking liquor and the pulp wash water are
combined to form a weak black liquor which is concentrated in a multiple-effect evaporator system to about 55 percent solids.

 The black liquor is then further concentrated to 65 percent solids in a direct-contact evaporator, by bringing the liquor into contact with the
flue gases from the recovery furnace(boiler), or in an indirect-contact concentrator. The strong black liquor is then fired in a recovery
furnace(boiler).

 Combustion of the organics dissolved in the black liquor provides heat for generating process steam and for converting sodium sulfate to
sodium sulfide.

 Inorganic chemicals present in the black liquor collect as a molten smelt at the bottom of the furnace.
  The smelt is dissolved in water to form green liquor, which is transferred to a causticizing tank where quicklime (calcium oxide) is added to
convert the solution back to white liquor for return to the digester system.

 A lime mud precipitates from the causticizing tank, after which it is calcined in a lime kiln to regenerate quicklime.
 For process heating, for driving equipment, for providing electric power, etc., many mills need more steam than can be provided by the
recovery furnace alone. Thus, conventional industrial boilers that burn coal, oil, natural gas, or bark and wood are commonly used.

Pollutants , Their Sources ,Their Hazards & Their Treatment Methods:

AIR POLLUTANTS:

 PM (40µg/m3 annual permissible limit)

 Particulate emissions from the kraft process occur largely from the recovery furnace, the lime kiln and the smelt dissolving tank.

 It consists of microscopically small solid particles or liquid droplets suspended in the air.

 The smaller the particles, the deeper they can penetrate into the respiratory system and the more hazardous they are to breathe.

 Recent studies indicate that PM can have the following effects on our bodies:

Hazards:

 PM pollution can cause lung irritation, which leads to increased permeability in lung tissue.

 PM aggravates the severity of chronic lung diseases, causing rapid loss of airway function.

 PM causes inflammation of lung tissue, resulting in the release of chemicals that can impact heart function.

 PM causes changes in blood chemistry that can result in clots that may lead to heart attacks.
 PM can increase susceptibility to viral and bacterial pathogens leading to pneumonia in vulnerable persons who are unable to clear these
infections.

Treatment Methods:

 Particulate control is provided on recovery furnaces in a variety of ways.

 In mills an electrostatic precipitator (ESP) is employed after the direct-contact evaporator, for an overall particulate control efficiency of from
85 to more than 99 percent.

 Scrubbers may be added at existing mills after a precipitator or a venturi scrubber to supplement older and less efficient primary particulate
control devices.

 Particulate control on lime kilns is generally accomplished by scrubbers.

 Electrostatic precipitators have been used in a few mills.

 Smelt dissolving tanks usually are controlled by mesh pads, but scrubbers can provide further control.

 SOx (50µg/m3 annual permissible limit)

 Sulfur dioxide is emitted mainly from oxidation of reduced sulfur compounds in the recovery
furnace.

 Sulfur dioxide (SO2) is generally considered the major pollutant of concern from sulfite pulp
mills.
  A major SO2 source is the digester and blow pit (dump tank) system.

 Sulfur dioxide is present in the intermittent digester relief gases, as well as in the gases given off at the end of the cook
when the digester contents are discharged into the blow pit.

 The quantity of sulfur dioxide evolved and emitted to the atmosphere in these gas streams depends on the pH of the cooking liquor, the
pressure at which the digester contents are discharged, and the effectiveness of the absorption systems employed for SO2 recovery.

 Scrubbers can be installed that reduce SO2 from this source by as much
as 99 percent.

Hazards:

Health effects
 Sulfur dioxide affects the respiratory system, particularly lung function, and can irritate the eyes.

 Sulfur dioxide irritates the respiratory tract and increases the risk of tract infections. It causes coughing, mucus secretion and aggravates
conditions such as asthma and chronic bronchitis.

Environmental effects
When sulfur dioxide combines with water and air, it forms sulfuric acid, which is the main component of acid rain. Acid rain can:

 cause deforestation
 acidify waterways to the detriment of aquatic life
 corrode building materials and paints.

In Queensland, there is less heavy industry than in Europe or North America, where the potential for forming acid rain from sulfur dioxide emissions
is higher. Our weather conditions and low sulfur content of fuels reduce the potential for acid rain.
  CO (4mg/m3 in 1 hr permissible limit)
Potential sources of carbon monoxide emissions from the kraft process include the recovery
furnace and lime kilns.

Hazards :

Health Effects

 Breathing CO can cause headache, dizziness, vomiting, and nausea. If CO levels are high enough, you may become
unconscious or die.

 Exposure to moderate and high levels of CO over long periods of time has also been linked with increased risk of heart
disease.

 People who survive severe CO poisoning may suffer long-term health problems.

 Scientists are not sure what the health effects are when a person is exposed to low levels of CO over a long period of
time.

 Better tracking of CO poisoning and exposure can help us learn about the effects of long-term exposures to low levels
of CO.

Environmental effects:
 Carbon monoxide reacts with other pollutants in the air to form potentially harmful ground level ozone.

 This occurs close to the site of emission.

 It does not have any significant environmental effects at a global level.

  NOx (40µg/m3 annual permissible limit)

Some nitrogen oxides also are emitted from the recovery furnace and lime kilns, although
amounts are relatively small.

Hazards:
Health Effects

 NOx mainly impacts on respiratory conditions causing inflammation of the airways at high levels.

 Long term exposure can decrease lung function, increase the risk of respiratory conditions and increases the response to allergens.

 NOx also contributes to the formation of fine particles (PM) and ground level ozone, both of which are associated with adverse health
effects.

The effect of nitrogen dioxide on ecosystems

 High levels of NOx can have a negative effect on vegetation, including leaf damage and reduced growth.

 It can make vegetation more susceptible to disease and frost damage. A study of the effect of nitrogen dioxide and ammonia (NH3) on the
habitat of Epping Forest has revealed that pollution is likely to be significantly influencing ecosystem health in the forest.

 The study demonstrated that local traffic emissions contribute substantially to exceeding the critical levels and critical loads in the area.

 The critical level for the protection of vegetation is 30 µg/m3 measured as an annual average.
  NOx also reacts with other pollutants in the presence of sunlight to form ozone which can damage vegetation at high concentrations.

 CO2 Emissions (50 µg/m3 annual permissible limit)

 The pulp and paper industry is the 4th largest emitter of greenhouse gases.

 The paper industry contributes 9% of total carbon dioxide emissions from manufacturing.

Hazards:

 Acute high-level CO2 exposure in the presence of low-level O2 can produce significant persistent adverse health effects including
headaches, attacks of vertigo, poor memory and ability to concentrate, difficulty sleeping, tinnitus, double vision, photophobia, loss of
eye movement, visual field defects, enlargement of blind spots, deficient dark adaptation, and personality changes.
 Prolonged low-level CO2 exposure (<3%) in the presence of normal O2 can produce relatively benign short-term effects in healthy, young
adults.
 One effect, alterations in bone metabolism and related blood calcium concentrations, however, may have potentially longer-lasting
adverse effects in both healthy and sensitive populations.

 The bone and calcium alterations in animals have been associated with renal calcification at CO 2 concentrations ranging from 0.3 to
15%. Other benign effects of CO2 exposure in healthy study subjects may have more immediate

ClO2 permissible limit

The United States Environmental Protection Agency has set a maximum level of 0.8 mg/L for chlorine dioxide in drinking
water. The Occupational Safety and Health Administration (OSHA), an agency of the United States Department of Labor, has set an 8-
hour permissible exposure limit of 0.1 ppm in air (0.3 mg/m3) for people working with chlorine dioxide.
WATER POLLUTANTS:

Waste water Pollutants

Wood preparation for pulping Solid, BOD, color

Chip digester and liquor evaporator High strength BOD, reduced Sulphur
compounds, organic compounds (very low)

Post pulping process High amount of waste water including SS and

BOD
Bleaching BOD, color, chlorinated compounds
Paper making and coating Solid, BOD, color

 In the production of approximately 3 000 000 t/a of paper products the Industry uses some
130 million m3/n of water.

 The waste water produced is high both in organic material (200

to 17 000 mg/C COD) and inorganic material (500 to 13 000 mg/f TDS).
In modern four- and five-stage bleach plants the waste-water volume
is 30 - 40 m3/t pulp.
Bleach waste waters are not normally recovered and become the major pollution source
of most pulp and paper mills,

 Color

The colour pollution arising from a modern conventional pulp mill principally originates
from the first alkali stage of the bleaching process due to the lignins. tannins and
hemicelluloses present from the wood processing.

Bleach Plant Waste-water Analysis:

Parameter Concentration

COD 1400 mg/l

pH 2.8

For 1 ton / day production = water intake 35000 m3/ day (approx.) = 35 m3/ ton SWI

Waste Water Quality Discharged:

COD SS TDS
259 227 2760
 Treatment of Waste Water Generated
In most processes involved in this industry, high volume of water is consumed, and this water must be of high quality. The effluents generated as a
result of paper and paste production contain are highly contaminated with up to 250 different compounds. Some of these are of natural origin, from
the wood (lignin, tannins, etc.), whereas others, such as phenols, dioxins, and furans, are synthetic and are incorporated into the effluent during the
manufacturing and cellulose paste bleaching processes.
There are two opposing strategies for avoiding the environmental impact of discharging these effluents directly into the environment:
1.The simplest option involves treating the effluents appropriately and discharging the treated flow into the environment. This is an “Open Cycle”
system.
2.However, the more sustainable and, in most cases, cheaper alternative involves treating the effluents in order to recover the water for reuse. This
latter alternative has two main objectives: to minimize both the water used and the liquid waste generated. This management model is known as a
“closed cycle” or, alternatively, a zero-waste system.

Treatment of water (open cycle)

In this case, the objective of treatment is to reduce the contamination in effluents to such a degree that they can be discharged complying with
discharge requirements and avoiding any environmental impact.

The effluents to be treated tend to have high pH values and a high content of organic matter, solids in suspension, organo-halogenated compounds
(AOX), nitrogen, and phosphorus, amongst other contaminants.

A satisfactory treatment of such effluents would involve stages such as homogenization and neutralization of the pH, coagulation/flocculation prior
to decantation, and, finally, elimination of the organic matter using a biological process (anaerobic or aerobic) or by advanced oxidation. After these
steps, the effluent can be discharged into the environment.
TREATMENT PROCESS
The type of treatment selected depends on the size of particles present in the wastewater. In practice, treatment efficiency also depends on particle
size.
Step 1. Physio-Chemical Treatment: The physio-chemical process consists of coagulation, flocculation and sedimentation stages.

-Coagulation(or rapid mixing )

It refers to destabilization or neutralization of the negative charges contained in the wastewater by the addition of a coagulant applied during
rapid mixing and a very short contact time.The quantity of coagulant applied during coagulation depends on the quality of water.

-The most commonly used coagulants are ferric chloride ,ferric sulfate ,aluminium sulfate , aluminium polychloride, sodium aluminate
mixtures of organic and inorganic compounds.
Flocculation( or slow mixing )
-In this stage, previously formed flocs group together, increasing in volume and density, allowing them to be sedimented.

-During the flocculation stage, chemicals referred to as flocculants are applied (assisted flocculation). These products allow flocs to come together
and adhere, increasing their size and density. Flocculants can be classified by their nature (mineral or organic), their origin (synthetic or natural) or
their electric charge (anionic, cationic or non-ionic).

Sedimentation
-This is the stage of floc removal by solid - liquid separation. For this, low, medium and high rate settlers are commonly used The rate is determined
by the speed at which water and sludge are produced by the system.

Step 2: pH Neutralization
Pulp and paper industry is responsible for large discharge of highly polluted effluents, which often be treated by biological treatment process. For
biological treatment system, pH is an important environmental factor that can influence the activity of microorganisms. The Kraft Process produces
alkaline waste water.
-Industrial plants use a batch neutralization system to treat their chemical waste products. Acid-base reactions are among the most common used in
water conditioning systems

- Commercially available acids and bases can be used, but often the chemicals wastes from the plant are used for neutralization.

Step 3:Anaerobic Digestion

Anaerobic digestion is particularly suited to organic material, and is commonly used biological
process used for treatment of waste water. It can greatly reduce the amount of organic matter
which might otherwise be destined to be dumped at sea, dumped in landfills, or burnt
in incinerators.

-Pulp and paper mills generate large amounts of waste organic matter that may be converted to
renewable energy in form of methane. Chemical oxygen demand (COD) removal rates in full-scale
reactors range between 30 and 90%, and methane yields are 0.30–0.40 m3 kg−1 COD removed.
Highest COD removal rates are achieved with condensate streams from chemical pulping (75–90%).
Process:

1. In the anaerobic digestion process the organic matter is broken down by microorganisms in the absence of oxygen and
lead to the formation of digestate and biogas which mainly consist of methane and carbon dioxide.

2. This digestate which is the decomposed substrate resulting from biogas production can be used as a bio-fertilizer.
3. It is known to be a complex fermentation process brought about by the symbiotic association of different types of
bacteria. The products produced by one group of bacteria serve as the substrates for the next group. The principal
reaction sequences can be classified into four major groups involving the following,

• Hydrolysis:

-In this stage large organic polymers such as starches, cellulose, proteins and fats are broken down into sugars, amino
acids, glycerol and long chain fatty acids.

-While some products from hydrolysis such as hydrogen and acetate may be used by the methanogens in the anaerobic
digestion process, the majority of the molecules, which are still relatively large, must be further converted to small
molecules like acetic acid, so that they may be used to produce methane.

• Fermentation: . In this step, the organics are converted by acid-forming bacteria to higher organic acids such as
propionic acid and butyric acid and to acetic acid, hydrogen and carbon dioxide.

• Dehydrogenation: The hydrogen gas formed in the previous step can be regarded as a waste product; however, it can
be consumed by methane-producing bacteria functioning as hydrogen-scavenging bacteria and converted into methane

• Methanogenesis: In the final reaction, methane is produced by methanogenic bacteria. These bacteria are capable of
metabolizing formic acid, acetic acid, methanol, carbon monoxide, and carbon dioxide and hydrogen to methane.

4. . The methanogenic step is the point at which the organic pollution load, in terms of COD and BOD is significantly
reduced by the anaerobic process.

Step 4:Aerobic Digestion using Activated Sludge Plant

-In activated sludge process wastewater containing organic matter is aerated in an aeration basin in
which micro-organisms metabolize the suspended and soluble organic matter. Part of organic matter is
synthesized into new cells and part is oxidized to CO2 and water to derive energy. In activated sludge
systems the new cells formed in the reaction are removed from the liquid stream in the form of a
flocculent sludge in settling tanks. A part of this settled biomass, described as activated sludge is
returned to the aeration tank and the remaining forms waste or excess sludge.

Why the Anaerobic-Aerobic Treatment?

The benefits of anaerobic wastewater treatment can be harnessed to the fullest only when combined with aerobic-
treatment. This is because in most cases anaerobic treatment alone does not provide an effluent of sufficient quality
for release into surface waters. In addition to economic benefits that directly impact the mills, combined anaerobic-
aerobic treatment can prevent substantial amounts of greenhouse gas emissions.

-Cost reduction by removing parts of the COD anaerobically

-Waste sludge production

Aerobic wastewater treatment in pulp and paper mills generates between 0.4 and 1.0 tons biosludge per ton COD reduced. The amount of sludge
produced during anaerobic treatment of mill wastewater on a full-scale is only about 0.02 tons per ton COD reduced. There is a decrease in the
overall sludge production by two thirds if anaerobic treatment precedes the activated sludge process.

- Nutrient recovery
Macro-nutrients have become an increasingly important cost factor in wastewater treatment. If biosludge is
anaerobically digested the remaining digestate contains large amounts of released ammonia and phosphate that can
be recycled into the activated sludge process.

- Reduced space requirement

Aerobic treatment requires a relatively large surface area within a mill mainly due to the aeration tanks and settling
basins. Modern reactors have an even smaller footprint due to higher applicable organic loading rates and a larger
height-to-diameter ratio, compared to older reactors.The space requirement for combined anaerobic-aerobic treatment
in pulp and paper mills half that of aerobic treatment alone.
 Tertiary Treatment

1. Denitrification
All forms of nitrogen in wastewater effluents are potentially harmful. Plants can utilize inorganic forms as nutrients; ammonia can be utilized by certain
bacteria as an energy source with the result that oxygen is depleted in the depleted in aquatic system. That’s why denitrification is necessary.
This is essentially a modification of activated sludge process and is specifically geared to the removal of nitrogen. In nitrification, the waste is thoroughly
treated in the aeration chamber when NH 4+ is converted by bacteria to nitrate ions. This usually involves longer detention times than those for
conventional activated sludge process, and F/M ratio is maintained around 0.3. During nitrification, bacteria such as nitromonas and nitrobacter
catabolize ammonia to nitrite and nitrates.

Suggestions
1. Recycling of water within the P&P industry is an increasingly common solution because it allows facilities to reuse water and also
recover excess pulp fibers that have escaped in the wastewater, providing the industry with a high economic incentive to recycle its
waste streams.Membrane technologies such as microfiltration, ultrafiltration, and nanofiltration are the most effective strategies for
treating water to a level where it can be utilized in the beginning of a process.
2. Employing a careful choice of the chemicals added to treatment water also makes recycling easier. Using ozone instead of chlorine, for
instance, eliminates long-term residual and makes the wastewater less caustic to the membranes.
3. While cogeneration of biogas from wastewater anaerobic digester processes for generating electricity and steam is an economical, long-
term solution that is increasingly being pursued in the municipal sector, this approach has been relatively slow to gain traction in the
P&P industry, mainly because of the high capital costs associated with implementation.
Anaerobic digester processes are rarely used in the P&P industry, More frequently, energy recovery initiatives are based on
taking dewatered solids produced from primary or secondary clarification and burning the material in wood-fired boilers for the
production of steam, which powers most P&P mill processes.
It contains sulfur and odorous compounds. If burnt, increases the pollutant gases. Therefore, anaerobic treatment is important. It
generates biogas which is much cleaner fuel and can be used for energy recovery.