REPORT ON PULP AND PAPER INDUSTRY WASTES AND ITS TREATMENT

SUBMITTED TO Mr. PAWAN KUMAR MANDAPAKA

SUBMITTED BY PRAMOD J (R080210023) JIMMY ABU SAJAN (R080210015) RAJALESHMI SUBBIAH (R080210024) ARPIT KHANNA (R080210007)

S.N0.

CONTENTS

PAGE NO.

1 2 3 4 5 6 7 8 9 10 11 12

INTRODUCTION SOURCES OF WASTE PULPING PROCESSES PULP PROCESSING PAPER MAKING AIR POLLUTION WATER POLLUTION SOLID WASTES TREATMENT COLOUR REMOVAL MINAS REFERENCES

3 5 7 10 11 13 16 23 28 40 42 43

PULP AND PAPER INDUSTRY INTRODUCTION :

Today pulp and paper industry in India is one of the largest industries due to tremendous expansion during the last few decades. Manfacture of paper from pulp is a water-intensive industry.

It involves: (a) Conversion of raw material into pulp by digestion with various chemicals (b) Conversion of pulp into paper

A mill which carries out these functions under the same roof is called an Integrated mill. Raw material used in this industry is mainly cellulose, which is obtained from wood, rags,old paper,hemp,wheat and rice stalks, bamboo,esparto grass,bagasse etc. Chemicals used in the pulpjng process are sodium hydroxide, sodium sulphate,calcium bisulphite and sodium sulphite etc. On the basis of the nature of the raw material, different pulping processes are used such as mechanical, chemical ,semichemical etc.

Large and Small Paper Mills : There are small and big paper mills producing varieties of paper for a number of uses from different types of raw materials. Printing, writing, kraft ,tissue, currency, newsprint, packaging and wrapping straw and paperboards as well as bleached paper are produced by this industry.

Primarily because of the constraints of large investments necessary for setting up of large integrated pulp and paper mills, and the reduced availability of bamboo which is main raw material for the paper industry in India, small scale paper mills have come up in recent years utilisting agricultural residues besides waste paper, as raw material.

This renewable resource which is claimed to be in abundance in several parts of the country, stimulated the growth of small paper mills with capacities ranging between 3 and 3o tone per day spread all over the country.All mills making upto 10,000 tonne per annum of paper,boards etc are classified under small paper mills.

Based on the installed capacity, the paper mills are classified into 5 categories as shown below:

Category
I II III IV V

Capacity (TPA)
20000 + 10000 20000 5000 10000 2000 5000 upto 2000

Categories I and II fall under large mills while the other three categories are termed small mills.

The Government of India is also encouraging entrepreneurs for setting up small paper mills primarily based on agricultural residues. In turn, it saves the primary forest resources and encourages regional development. In view of the small scale production and the inherent nature of agricultural residues being poor in quality compared to forest wood or bamboo, there is a risk of small paper mills not being competitive with the existing or new integrated large mills. To promote unhindered growth of small paper mills, import of second hand machinery is permitted and several concessions are given to the mills by the Government.

SOURCES OF WASTES AND POLLUTION Process of Manufacture :

Raw Materials: Conventional raw material for small paper industry is constituted of rice and wheat straw, bagasse, jute, cotton rags, different types of grasses, waste paper, purchased pulp and occasionally gunny and hessian. All these have proved to be good for paper making and are used by almost all the mills in various combinations. Composition of raw materials used in paper industry is given in Table.

Composition of raw materials used in paper industry

Raw materials Cellulose Pentosan Lignin Alcohol benzene extractables Bamboo Rice straw 57.0 51.0 14.0 22.0 28.4 29.0 20.0 15.0 13.0 25.0 13.4 13.0 19.2 11.0 14.1 25 12 22.5 23.3 21.0 11.0 6.0 18.0 24.9 27.3 23.2 26.0 30.9 2.0 4.0 2.1 4.4 1.0 1.0 1.0 3.0 6.0 4.3 3.4 1.0 2.0 11.0 33.0 2.7 2.0 3.0 3.0 4.0 1.0 1.8 0.8 1.0 0.4 1-0.3 0.03 1-1.5 4-8 1.6 0.9 1-15 0.29 Ash Silica (SiO2)

Bhutang grass 39.3 Khagre grass Jute S tick) Jute Sial hemp Bagasse Sal Salai Casuarina Pine Eucalyptus 36.5 56.0 70.0 77.0 50.0 56.0 50.7 56.7 61.0 54.0

Chemical Requirements : Sodium hydroxide, lime chlorine, hypochlorite and sulphites are the normally used chemicals in paper industry. Sodium hydroxide requirement essentially for agricultural residue based industry varies with raw materials. About 5-10% of NaOH is required per tonne of raw material. However when bagasse is used, the requirement for alkali would be as high as 12% of the raw material used. Lime is used as supplement to NaOH. In board mills, only lime is used as cooking chemical, Chlorine and calcium hypochlorinte are bleaching chemicals and are required only when bleached products are made. The quantity used is highly varying and depends not only on the raw material used but also on the final product made. Sizing chemicals such as alum, starch, talc, rosin and acid are also used. Dyes are used for making coloured paper.

Water Requirements : Paper industrys existence lies on water supply. All the process in paper making require constant supply of water. Though paper machine water is recyled to a varying extent, total intake of water per tonne of paper is very large. It is estimated that for an agricultural residue based paper mill, for processing, the requirement is 200 to 350 cubic metre per tonne of paper made. However, for units using waste paper, it varies from 100 to 150 cubic metre per tonne. Besides water consumption for steam generation and domestic purpose is also to be accounted for Quality tolerance for water in paper mills is given in Table.

Quality tolerance for water in paper industry

Kraft unbleached paper ISI Colour Turbidity pH 100@ 100@ Kraft bleached paper Nordell TAPPI NCASI SIS 15 15 0.2 0.1 100 100 150 10-80 5-25 6.5-8.0 20-150 15 25 Nordelt TAPPI 5 5 0.1 0.05 5 25 75

Total Alkalinity (CaCO3) Hardness (CaCO3) Dissolved solids Chloride Iron Manganese COD BOD Total chlorine 1.0 0.5 residual 200

200

5-200

100 0.25 0.1 2.0

100

500 200 1.0 0.5

50-500 10-150 0.5 0.3 0-12 0-5

250 75 0.1 0.05

Colour as Hazen units and turbidity on silica scale. In other cases,these two are expressed

as units, standard colour units and mg/l, respectively.

Pulping process in paper industry :

The main pulping processes that are normally employed in paper industry include : (i) (ii) (iii) Chemical process Chemo mechanical process Mechanical process (hydro-pulping)

Chemical Process : This involves digestion of raw material like agricultural residues gunny, jute etc at high temperature and pressure in the presence of chemicals like sodium hydroxide and/ or lime. Specially designed spherical digesters with capacity argound 25 cu m are employed for this purpose. The rotary digester provides necessary mixing and efficient heating of the raw material. Steam is used for heating. Steam pressure is maintained between 5 and 6 kg/cm2. The temperature of the digesting material will be around 1500C. About 1.21.5 tonne of steam are required for each tonne of raw material digested. Chemicals are added in solution along with raw material prior to cooking. Digestion time of 2.5 to 5 hours is provided for proper cooking. A ratio of raw material to water of 1 to 3.3-4.0 is maintained before digestion starts.

Two processes are used : (a) Kraft or Sulphate Process: The cellulosic materials after chipping to proper size are cooked in caustic soda, sodium sulphide mixture under temperature and pressure. This process dissolves the fibre binding materials such as the lignins and loosens the cellulosic fibres. The spent liquor known as black liquor is recovered for chemicals and the pulp is washed and bleached before it is made into paper

(b) Sulphite Process: In the sulphite process the cooker liquor consists of calcium or magnesium bisulphite and sulphurous acid. Where calcium salt is used the spent cooker liquor is not utilised for recovery of chemicals.

Chemo-mechanical pulping : As the name suggests, the process makes use of both chemical and mechanical processes in series. The raw material is soaked in 3-5% caustic soda solution at 900C for 15 to 30 minutes. Acid sulphites are also employed as pulping chemical in a few cases. The soaked material is then subjected to drastic mechanical treatment to separate fibres.

Mechanical Process : For waste paper and recycled paper and recycled paper hydro-pulping is adopted Hydropulping unit comprises of a high speed rotating disc which chops the paper to fibre in presence of steam and moisture. The pulp yield is estimated to be 70-80%. Size of the hydro pulper varies with the plant size.

Pulp Processing
Pulp washing: Chemically digested pulp is discharged into a blow pit or on a perforated floor where part of the black liquor (BL) also known as spent liquor drains out. In some mills the cooked materials is directly taken for washing in pouchers where washing is done by vacuum rotary drum. The washing continues for 2-3 hours and is in series if more than one poucher is used. The pulp wash is one of the major sources of wastewater besides black liquor. The drained out black liquor joins the pulp wash water before leaving the unit. The wastewater leaving this section is very strong initially and weak in final stages of washing.

Beater, centri-cleaner, thickener: Pulp from poucher is dumped to beater either directly or through storing chest depending on the operation schedule. Pulp is beaten to separate fibres and remove adhering dirt, chemicals and colour. Some mills employ washing along with beating thus creating a source of wastewater. From beater, the pulp is screened and then taken to centri cleaner for removal of heavy inorganic particles (mostly sand) It is then pumped to thickener where water is sucked by rotary drums and discharged as wastewater. The pulp in this section still contains some colour but can be used to make boards and unbleached paper.

Bleaching: The process is adopted in mills where bleached paper is produced. After thickening the pulp is subjected to chlorination. Chlorine requirement is reported to be 120 kg/day, in a 2000 TPA plant but it generally varies with the type of raw material used. If straw is the major raw material, the chlorine requirement will be high. After chlorination the pulp is subjected to alkali extraction, only under special circumstances popularly known as caustic extraction. This is followed by calcium hypochlorite treatment. Hypochlorite required is about half the quantity of chlorine. The pulp is white and the yield is about 30-35% of raw material used. These three steps together contribute bleach plant wastewater . In small mills, only calcium hypochlorite or bleaching powder is used and the conventional steps are not usually followed.

10

Paper Making:
Blending conditioning and stock preparation: Blending provides required pulp to water ratio before sending it to the paper machine. Further conditioning by chemicals such as alum, rosin talc and acid to suit the requirements of final paper quality and addition of dyes to make coloured paper are also adopted.

Paper Machine : This consists of a moving wire mesh and rotary driers. Steam is used in driers to drive away moisture from the sheet of paper formed on the wire mesh and picked up by the driers. The wastewater generated in this section is known as white water and is recycled in the process to the extent of 80% for pulp washing in the poucher in most of the mills. Finished product is cut to size and ready for marketing. The moisture content of finished paper varies from 2-8% by weight with an average value of 4.5%. A generalized flow sheet adopted for making paper in small mills depicting sources of wastes is given in Fig on next page.

11

GENERALISED FLOW SHEET ADOPTED FOR MAKING PAPER IN SMALL MILLS

DEPICTING SOURCESD OF WASTES

12

AIR POLLTION :
Air Pollution from Paper Plants; Particulates: Predominantly chipper house pulp washing paper machine, caustic extraction Chemical recovery power plant coal handling and disposal sections have various sizes of particulate pollution to a considerable degree. Apart from this certain mills have cyclones and electrostatics precipitator in the recovery sections which reduces air pollution to the desired level. Large sized particles are removed by setting as solid wastes and some times reused in the process i.e. coal dust fine fibre etc.

Sulphur Dioxide: Sulphur compounds are used for working wood material for manufacture of paper hence major pulping processes emit sulphur dioxide. Sulphur dioxide is emitted at the blow tank, evaporators recovery furnance lime kiln sulphitation tower etc. In addition sulpur dioxide emission stake place at the power boilers either under normal operation or during periods of auxillary fuel operation. It is estimated that about 35 to 50 ibs of sulphur bearing compounds are emitted per tonne of pulp. Sulphur dioxide pollution is mostly controlled by scrubbing sulphur dioxide through the solution of alkali. Some items such as sulphur compounds are converted into sulphur and recovered in developed countries.

Carbon Monoxide : Power plants in India are mostly based on coal. Coal-based power plants invariably emit carbon monoxide. However carbon monoxide emissions depend upon type of coal used and firing time required for the carbon monoxide. The pollution restricted to initial firing hence generally no controlled by using bnetter quality of coal. Methyl mercaptans, hydrogen sulphides, methyl sulphides, methyl suylphides methyl disulphides are emitted in the recovery and evaporating and cooking sections. To a greater extent these can be controlled by process control and control of gugitive emissions. Whereever air pollution control equipments like scrubber or electrostatic precipitators are used most of these air pollutants are kept at a low level. However much depends on good housekeeping.

13

Chlorine. : Chlorine, chlorine dioxide and various compounds of chlorine are used for bleaching pulp. During process of bleaching chlorine, always finds its way into the environment. Wherever control equipment like exhaust and vacum cleaners are used considerable reduction of chlorine pollution is achieved. Most of the mills do not have any control equipment for this. However some mills have blowers which reduce chlorine level in the work room environment. Chlorine control is also achieved by scrubbing chlorine through alkaline solution.

Cause : Air pollution is due to release of gaseous omissions into atmosphere, which occurs mainly from two sources in small paper mills viz.

(i) (ii)

Digesters. Steam boilers.

The third source could be the captive power generation facilities provided in the mills.

In agricultural residue-based mills, after the raw material digestion with caustic soda and/or lime is completed, the pressure in the digester is released after the digester attains a temperature of about 900C. During the process about 1.4 tonnes of steam per tonne of pulp escape containing volatile organics released during digestion process. The escaping gases have characteristics odour and cause aesthetic pollution problemsThe pollution is mostly confined to the sorroundings of the mill, intermittent due to batch process adopted and can be felt at the time of digester gas release. Coal is the commonly used fuel for generating steam required in all the small paper mills, it is reported that about 3.4 tonnes of coal is required per tonne of paper made in agricultural residue based mills and the corresponding coal requirement in waste paper based mills is 1.5 tonne per tonne of paper. In all these boilers coal lumps of 2.5-5.0 cm diameter are fired. Very few boilers use powdered coal. Besides coal, paddy husk diesel oil, etc. are also used in a very few mills. Indian coals are reported to contain 0.5-0.8% sulphur. Since the quantity of steam generation is small the steam boilers are not provided with any air cleaning equipment in these mills.

14

In a study conducted by NEERI on air pollution problems from steam boilers, it is observed that a boiler plant producing 57 tones stem per hour, and provided with an electro static precipitator preciptator (ESP) would release the following quantities of pollutants. The ESP is reported to be working with 80% efficiency . Suspended particulate matter Sulphur dioxide SO2 Oxides of nitrogen, NOx 620-1030 mg/N cubic metre 360-390 mg/N cubic metre 90-120 mg/N cubic metre

15

WATER POLLUTION FROM PAPER MILLS Wastewater Generation :

Sources of Wastewater : As identified earlier, in agricultural residue based units, the wastewater is released from the following sections :

(i) (ii) (iii) (iv) (v) (vi)

Black liquor from cooking section. Pulp wash water from pouchers. Beater section specially when rags are used. Bleaching section Thickener Paper machine.

Waste paper based mills generate wastewaters from section iv, v, and vi only as no chemical pulping adopted.

Blacking liquor is the most polluting among the different streams. Black liquor is not segregated, and it ends up in pulp washing wastewater. Thus pulp washing section contributes nearly 80% of the total pollution load.Further flow and composition of pulp wash wastewater will be highly varying because the operations are carried out in batches. Only in a very few mills counter current washing using two stages is adopted. Paper machine wastewater is least polluting among all the sections but contributes appreciable amounts of suspended solids. In most of the mills, paper machine wastewater either as such or after fibre recovery, is used in pulp washing beaters, etc..

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Water Pollution
Big Paper Mills : Considerable work has been carried out by the CPHERI on the characteristics of various pulp and paper mill effluents. Extensive work on the volumes and characteristics of effluents from the different sections of a large pulp and paper mill has been worked out and the flow and characteristics are given in table.

Characteristics of wastewater from pulp and paper mills

Chipper* house

Digester house

Pulp

Chemical Pulp

Paper

Combine-

washing recovery

Bleaching machin d waste e

Flow m3/tonne colour

20-60

5-10

20-40

140-180

40-90

240-30

Muddy

Dark Brown

Dark brown 8.5-9.6 14002500

Light brown 7.0-9.0 12702800 400-760

Brown

Whitish Brown

pH Total solids Suspended solids COD

6.4-8.0 540-900

9.0-10.0 1000-2500

6.0-9.0 21002900 140-220

5.3-8.1 8501250 490-

6.5 12002000 350-

240-520

140-190

350-

175-450

1850- 220

9001700

320-610

550-790

520780

600-750

BOD

30-50

300-360

230-480

90-180

125-155

100160

110

This represents conditions where bamboos are carried by water before chipping. Water is sprinkled on the bamboo stacks before chipping the quantity of wastewater will be very low (2-8 m3/tonne of paper) and the wastewater characteristics will be fairly high.

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Water Pollutants: The main pollution constituents in pulp and paper mill wastewater are suspended solids, colour foam, inorganic such as sodium carbonate, bicarbonate chlorides and sulphates toxic chemicals such as mercaptans and inorganic sulphides, mercury if caustic chlorine plant forms a part of pulp and paper mills, BOD and COD.

The wastewater when discharged untreated will damage the water course and the colour in water persists for a long distance since lignin is not readly biologically degraded As paper industry being scattered all over the country, it may be said that no river is spared from pollution due to the discharge of these wastewater.

Another important pollutant (that is yet to be assessed) in pulp and paper industry is mercury. This is so because some of the mills make their own caustic and chlorine in mercury cells and it has been reported that about 0.25 kg of mercury is lost per tonne of caustic made. Further some organic mercury compounds such as phenyl mercuric acetate (50-100 ppm of dry weight of pulp) methoxy ethyl mercury and pyridyl mercury salts are being used as slimicides on paper machines which finally find their way into the effluent. In sweden it is reported that about 25 tonnes of mercury salts are used per annum.

18

Small Paper Mill : The data given in previous Table indicate that the combined wastewater will have alkaline pH with high BOD and COD values. The BOD load contributed per tonne of unbleached paper will be 1.56 kg and this may go up to 160 kg if bleached paper is made. The BOD load from small mills will be 3 times the pollution load discharged from bigger mills with chemical recovery systems.

Similarly, the suspended solid concentration is 2120 mg/l of which 40% will be inorganic solids (848 mg/l). The combined wastewater will not be fit for irrigation in view of high sodium and BOD (780 mg/l) content. The wastewater requires treatment before it can be discharged into water course.

Another objectional constituent will be lignin as it imparts colours and COD to the receiving body of water (derived from pulping of straw and gunny or ropes). Normally 90-95% of the lignin present in the straw is removed during digestion with caustic and this quantity ends up in the pulp washing wastes. Assuming that on an average 90% of the lignin present (in straw pulping along will be of the order of 3090 mg/l. Gunny, ropes and rags contain lower percentage of lignin as compared to straw. Therefore the combined wastewater will have lignin concentration in the range of 750 to 850 mg/l. The quantity of lignin alone will exert a COD of 1350 to 1530 mg/l.

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Characteristics of Effluents :
Waste paper and/or purchased pulp based mills the flow and characteristics of combined wastewater indicate that although there is variation in the flow of the combined wastewater the minimum and maximum values respectively are 0.6 and 1.5 times the average flow. There is also variation in the characteristics of the wastewater and is mainly due to the different practices adopted for fibre recovery and extent of recycle of both recovered fibre and water. On an average for each tonne of paper made 107 28.4 cu.m of wastewater is generated containing 58 + 10.7 kg of suspended solids 20 + 10.5 kg of BOD and 70 + 15.2 kg of COD respectively.

The proportion of agricultural residue to waste paper used varies appreciably in all the agricultural residue and waste paper based mills. Even in the same mill, depending on the raw material availability season, type of paper made, the proportions vary even within a week. Hence wastewater flow and characteristics are found to vary. It is not possible to generalise the flow and pollution loads contributed per tonne of paper made from these mills.

Since most of the small paper mills are located in agricultural areas and some of them are using the combined wastewater for crop irrigation the SAR and per cent sodium values in the combined wastewater are high in mills where unbleached paper is made using soda pulping. Leaving a few high values the SAR ranged between 3.5 and 7.6. If the ratio of calcium to sodium can be increased in the combined wastewater from small paper mills, then it can be used fro irrigation after suitable dilution to keep the total dissolved solids and BOD in the ranges recommended for irrigation waters.

BOD rate constant for black liquor and combined wastewater after settling compares with that of domestic wastewater. The non biodogradable fraction of COD is high and is mainly due to the lignin in black liquor. In case of combined settled wastewater 70% of the nonbiodegradable COD is due to lignin and the remaining due to suspended solids, etc. Hence it can be concluded that the COD due to lignin cannot be removed even after biological treatment. The only alternative method is to remove colour vis-a-vis lignin by chemical treatment.

20

Standards for Discharge of Effluents : The choice of methods for treatment of wastewater dpends on the quality requirements for final disposal. The treated effluent will have to be discharged either into sewers, if available or surface waters. It can also be applied on land for agricultural utilisation. Pollution Control Boards have prescribed tolerance limits for industrial effluents for discharge into the three above mentioned media. These are shown in table.

Tolerance limits for industrial effluent discharged

Inland water BOD 5 days at 100(30) 200C COD pH Suspended solids Total 250 5.59.0 100 dissolved

surface Municipal sewer

Marine outfall

500a 5.59.0 600b 2100*

500 5.59.0 2100 30

solids (in organic) Temperature, 0C Oil and grease Phenolic compounds Cyanides Sulphides Fluorides Total chlorine Insecticides Arsenic Cadmium Absent 0.2 2.0 0.2 2.0 2.0 residual 1.0 2.0 48 10 1.0 45 100 5.0

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Chromium (hexavalent) Copper Lead Mercury Nickel Selenium Zinc Chlorides Boron Sulphates Per cent sodium Ammoniacal nitrogen (N) Radioactive materials Alpha emitters/c Beta emitters/c

0.1

2.0

600 2 1000 60

3.6 0.1 0.01 3.00 0.05 5.0 50

3.0 1.0 2 15 600* 2* 1000* 60 50

107 106

107 106

109 108

ab*

Subject to relation or tightening by local authority. Relaxable to 750 by the local authority. These requirements shall apply only where after treatment the sewage is disposed of land

for irrigation.

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SOLID WASTES :
Solid Waste : Tracing back to unit operations in paper manufacture following units have serious problems of solid wastes disposal.

Chipper House : Wood is reduced in cutters to desirable size of 20mm to 23 mm here during this process lot of floating settleable material results which can be easily recovered by screening and grit chamber. Recovered material is dried and used as fuel/land filling.

Pulp Washing: During pulp washing in centri cleaners lot of undigested/digested pulp is part of effluent. This can be recovered by inclined screen of suitable mesh size. This screen is called side hill screen. Pulp thus recovered can be reused/redigested.

Flow Machine : Paper machine is the final stage of paper production where pulp along with sizing material is dried and converted into desired shape, size and weight small fibres are always escaping in paper machine effluent. Generally fibre is recovered by an all vibrating screen. Recovered fibre is used for making paper and thus greater economy is achieved in paper making.

Hypochlorite Preparation and Floor washing sludge, Caustic Chlorine : These three sections constitute a major solid waste problem for all paper mills. I am sludge has considerable amount of silica hence burining of this lime sludge for recovery of lime is not techincally and economically feasible. Moreover lime recovery is not practised because lime is cheap. Hence lime is disposed off on land for filling up low lying areas. However efforts are being made for economical burning of lime and alterantive use of lime as fertilizer etc.

Coal Ash : Indian coal contains 10 to 40% ash hence wherever coal is used as fule in the power plants problem of coal ash disposal requires immediate attention. Some of the mills have constructed type S shaped channels which carry coal ash along with treated effluent upto water course where ultimately it is disposed off.

23

Solid waste generation :

Solid wastes are generated from the following operations : (i) (ii) (iii) (iv) Raw material handling Rejects from screening and centri cleaners Primary and secondary sludged from wastewater treatment system Coal or boiler ash from steam generation.

Estimates for the solid waste generation are based on information given by the mills and the data collected from various sources available.

Agricultural residue based mills :

(a) Raw material handling (i) Rice and wheat straw @ 5-10% of raw material handled is lost as rejects. Solid waste generated 139278 kg/t paper Average 210 kg/t paper (ii) Bagasse @ 1015% of raw material handled is lost as rejects. Solid waste generated 440660 kg/t paper Average 550 kg/t paper

(b)

Primary and secondary treatment of wastewater Suspended solids load in wastewater 155 kg/t paper BOD load in wastewater 175 kg/t paper

(i)

Primary setting @ 75% suspended solids removal solids in Primary sludge = Say 155 0.75 116.25 kg 116 kg/t paper

(ii)

Biological solids generation @ 0.5 kg per kg BOD removed and 90% BOD removal expected. Excess biological solids = 24 175 0-9 0.5 79 kg/t paper

(iii)

Suspended solids remaining in the primary clarified effluent going to secondary biological treatment and assuming about 66% of them settle along with secondary studge. Solids in the sludge = Sa 39 0.66 25.7 kg/t paper 26 kg/t paper

Total primary and biological solids generation 220 kg/t paper

(c)

Steam generation Ash content of Indian coal is approximately 40%

(i)

Coal requirement for digesters for steam generation 1.8 2.0 t/t paper

(ii)

Coal requirement for paper macine driers and also a small fraction for hydro pulpers (for steam generation) Total coal requirement say 1.4 1.5 t/t paper 3.2 3.5 t/t paper 3.35 t/t paper

Coal or boiler ash generated 0.4 3.35 t/t paper = Say 1.34 t/t paper 1.3 t/t paper

Total solid waste generation (i) Raw material handling (a) (b) Straw, jute, etc Bagasse 210 kg/t paper 550 kg/t paper

(ii)

Primary clarification

116 kg/t paper

(iii)

Secondary clarification including biological sludge 105 kg/t paper

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(iv)

Coal or boiler ash

1300 kg/t paper

Total solid waste generated (a) (b) When straw, jute is used When bagasse is used 1731 kg/t paper (25% organics) 2071 kg/t paper (37% organics)

Waste paper Based Mills

(a)

Raw Material handling Waste paper @ 1-2% of raw material handled in lost as solid waste Solid waste generated 46 kg/t paper

(b)

Primary clarification (i) Suspended solids in combined wastewater (ii) 58 kg/t paper Primary setting 80% suspended solids removal 58 0.8 = 46.4 kg/t paper say 46 kg/t paper

Secondary treatment utilises aerated lagoon or stabilisation pond and hence there will be no sludge generation.

(c)

Steam generation 1.4 1.5 t/t paper 1.45 0.4 = 58 kg/t paper

Coal requirement Coal or boiler ash

Total solid waste generation (i) (ii) (iii) Raw material handling Primary setting Boiler ash 46 kg/t paper 46 kg/t paper 58 kg/t paper 150 kg/t paper (61% organic solids)

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Pollutional Effects The pollutional effects of discharging waste water from a paper mill are: 1. Oxygen depletion in the receiving body of water 2. Presence of undesirable colour, odour and taste in the water 3. Reduced photosynthesis 4. Formation of blanket of suspended solids settling at the bottom of the receiving body of water 5. The death of fish 6. Toxicity added to the aquatic life due to the formation of

mercaptans,pentachlorophenol etc.

27

TREATMENT FOR THE WASTE WATER

5 Various unit operations in seewage treatment plant and their appicability for pulp and paper mill effluent treatment.

Unit

Applicability for treatment of pulp and paper mill effluent

Screens- coarse screens

the floating and coarse materials from chipper house and pulp mill can be removed in this operation.

Grit chamber

Useful for grit removal from chipper houses, floor washings etc.

Primary settling tanks

For removal of readily settleable solids such as fibre. For efficient removal of suspended matter mechanically scrapped clarifiers with or without addition of chemicals should be employed. This treatment is the minimum essential requirement before discharge of the effluent. The settled sludge requires only dewatering before disposal.

Biological treatment in the form For biological treatment will require addition of N and P of trickling filter or activated (30D : N.P. as 1995:1) sludge followed setting tank. Sludge disester Secondary sludge requires digestion before disposal. Since its volume will be much less compared to the primary sludge, the primary and secondary sludges can be mixed together and simply lagooned or dewatered without digestion. The primary and secondary sludge can be dried before disposal. The land requirements will be very high and hence mechanically dewatering is preferable. Sludge drying beds For drying and dewatering primary and secondary sludges. by secondary

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Treatment for Mills Using Agricultural Residues as Raw materials : The unit
process involved in the treatment of wastewater from agricultural residue based paper mills are: (i) (ii) (iii) (iv) Equalisation of flow from pulp wash section. Primary clarification for combined wastewater Secondary biological treatment. Sludge drying beds or lagoons for primary sludge depedning on the availability of land

Equalisation for Pulp Wash Wastewater : Pulp washing section accounts for about 2025% of total wastewater and contributes around 70-80% of pollution load from small paper mills using agricultural residues as raw materials. These wastewaters are discharged intermittently since in most of the mills. washing of pulp is done in batches using pouchers. Normally two pouchers are employed and operated in series and this generate two washes. The period of washing is more or less same in both but the quantity of water used varies appreciably and thus the first wash water is more concentrated than the second wash water. The flow variation has been observed to be fairly wide since the minimum and maximum values respectively are 0.15 and 2.3 times the average flow. Discharge of these washes to the main wastewater stream (on an intermittent basis) as is being practised will alter the

composition of the combined wastewater appreciably. This necessitates provision of equilisation to the pulp washes and discharge at a constant rate into the main sewer.

Two alternatives can be considered for this purpose-

Alternative 1 : It evisages flow equalisation for the first pulp wash wastewater. This wastewater is generated at a rate of 12.5 cu.m/tonne of paper made and is discharged at a rate of 1.56 cu m/batch in 8 batches of 2 hours each per day. The discharge rate is fairly uniform during the 2 hours of washing period.

Capacity of equalisation tank to be provide works out to Adding 25% extra volume including free board to meet any sarge discharge

1.0 cm m/t paper

0.25 cm m/t paper

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Total volume of equalisation tank Rate of pumping of wastewater from the equalisation tank into sewer

1.25 cm m/t paper

0.52 cu m/t for 24 hours

Therefore two equalisation tanks are to be provided to facilitate cleaning and maintenance.

Alternative 2 : It envisages flow equalisation of the entire pulp wash wastewater (2 washes). The total pulp wash wastewater is generated at a rate of 50 cu m/tonne of paper and is discharged at a rate of 6.25 cu m/batch in 8 batches of 2 hours each per day. As stated above, the flow rate of wastewater is fairly uniform during the 2 hour washing period.

Capacity of equalisation tank to be provide works out to Adding 25% extra volume including free board to meet any sarge discharge Total volume of equalisation tank Rate of pumping of wastewater from the equalisation tank into sewer

4.0 cm m/t paper

1.0 cm m/t paper 5.00 cm m/t paper

2.08 cu m/t for 24 hours

Therefore, two equalisation tanks are to be provided to facilitate cleaning and maintenance. Pumps of suitable capacity have to be provided one each for the two tanks and one as a stand-by.

Primary clarifier and sludge Drying : If secondary treatment like activated sludge, oxidation ditch or rotating biological disc is used as suggested, the excess secondary biological sludge should be added to the combined wastewater before primary settling such that the settled sludge can be filtered on drying bed. The combined primary and secondary sludges do not require biological stabilisation. The dried sludge can be disposed off by burning in an incinerator or dumping in open pits in a controlled manner.

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The treatment alternatives suggested are shown in Figs for agricultural based mills and for waste paper based mills. The wastewater is practically devoid of nitrogen and phosphorus. Hence, nutrients will have to be supplemented to biological treatment process. For anaerobic system BOD : N.P. should be 100 : 2.5 : 0.5 and the corresponding ratio for aerobic system is 100 : 5 : 1,

The treatment alternatives are detailed below.

Treatment Alternative 1 : The primary clarified effluent is proposed to be treated in an anaerobic lagoon after proper seeding and acclimatisation. The lagoon will have a deterntion time of 20 days. The anaerobic effluent will be subsequently treated in an aerated lagoon with a detentiontime of 4 days. The effluent leaving the aerated lagoon will be passed through a polishing pond with a detention time of 2-3 days before discharge or use on land for agriculture. Anaerobic treatment prior to aerated lago in will reduce foaming problems . Treatment Alternative II ;Effluent from primary clarifier will be treated in an acrated lagoon with a detention time of 6 days. The lagoon effluent will be taken through a polishing pond with 3-5 days detention time before final discharge or use on land for irrigation after suitable correction for SAR and total dissolved solids.

Surface aeration of pulp will washtes generate considerable foam which most often covers the entire surface of the aeration tanks and thus prevents or reduce oxygenation of the medium. It is observed that in square type of aeration basin or tank, the form formed is very stable and does not dispense or break away easily. On the other hand, it is noticed that in rectangular taks with length to breadth ratio equal to or greater than 2 to 1. although foam formation takes place, the foam stability is less and breaks away at a faster rate, i.e. more easily. Further spacing of aerators in the basin and the rotation in clockwise and anti clockwise direction for alternate aerators will also help in reducing the foam accumulation as well as breaking away of foam formed. With these arrangements and addition of anti forming agents, it is likely that acrated lagon can be used as a method of treatment. However this system is likely to create a problem of foam which should be kept in mind.

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Treatment Alternative III : Oxidation ditch operated on extended aeration principle with high MLSS (4000-5000 mg/l) can be used to obtain high degree of BOD removal. High MLSS in the system will help in destabilisation of foam. Although foam formation can not be eliminated, it is observed in one of the mills, where this system is used, that foam breaks away as the mixed liquid flows in the channel and the liquid surface is more or less free from foam. The mixed liquor after secondary clarification will have low BOD. In place of oxidation ditch a diffused aeration activated sludge system can also be used on the same principle. In this system, foam does form but because of diffused aeration, the oxygenation of the liquid in the tank will not be affected vis-a-vis biological purification. However foam control from a physical point of view will be required. A secondary settling tank is also necessary.

Treatment Alternative IV : Combined effluent without equalisation and primary settling is proposed to be treated in anaerobic lagoon after proper seeding and acclanatisation. The lagoon will have deterntion time of 25 days. The effluent from anaerobic lagoon will be subsequently treated in aerated lagoon with a detention time of 4 days followed by polishing pond with 4 days detention time.

Treatment Alternative V : Same as alternative II excepot that the polishing pond is replaced by settling tank.

Treatment Alternative VI : Rotating biological contractor (RBC) can be successfully used for the treatment of the settled combined wastewater from paper mills. This has been domonstrated in the USA and other places. Actual design data used for treating pulp and paper mill waste by RBC are not readily available. No foam problem will exist in RBC treatment as there is no liquid and air mixing through agitation. Thus RBC may be considered as a package plant for the treatment of the wastewater. A secondary clarifier is required to remove the biological solids which can be collected and sent to the inlet of primary clarifier and removed along with primary sludge. The design data available for

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domestic sewage treatment by RBC can be used for treatment plant design for pulp and paper mill wastes. Over 90% BOD reduction can be expected.

TREATMENT 1 AND TREATMENT 2

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TREATMENT 3,4,5

WASTE WATER TREATMENT ALTERNATIVE FOR AGRICULTURAL RESIDUE BASE3D PAPER MILLS 34

Treatment For Mills Using waste paper and Purchased pulp as Raw Material

Treatment of wastewater from mills using waste paper and purchased pulp may be carried out in the following processes :

1.Fibres should be recovered and recycle of recovered fibre and water to the maximum possible extent to be adopted. The dissolved air floatation system is found suitable for recovery of fibre from white water. After fibre recovery this water is recycled to the pulp section for pump washing.

2.Primary clarification of the combined wastewater before or after fibre recovery is essential for which rectangular or circular clarifiers can be used.

3.Primary sludge can be dried on sludge drying beds or lagooned depending on the availability of land.

4.The effluent from primary clarifier needs to be further treated either in a stabilisation pond or in an aerated lagoon (1/2 day detention time) if land is a limiting factor. The treated effluent will then meet the permissible effluent standards.

5.Primary clarified effluent can be used on land for crop irrigation.

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WATEWATER TREATMENT ALTERNATIVES FOR WASTES PAPER AND PURCHASED PULP-PAPER MILLS

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Treatment Methods for Small Mills

Treatment Alternative 1 : The suggested flow sheet for treatment alternative I, although similar to alternative II, differs from it in two ways. In this case, it is proposed to segregate about 50% of black liquor from straw and 20% fromrag digesters. The segregated black liquor is proposed to be stored in a lagoon and discharged into rivers during monsoon. Other wastewaters (about m3/tonne of paper) after primary clarification are proposed to be treated in an aerated lagoon instead of activated sludge. Nutrient addition is needed in this case in the same proportion. Detention period in the lagoon will be 5 days. The aerated lagoon will be provided with a silting chamber to prevent escape of solids in the effluent. Normally no excess sludge is expected from aerated lagoon. Primary sludge will be disposed of into the sludge lagoons. Effluent of aerated lagoon is expected to have a BOD of 30 mg/l and suspended solids of 80 mg/l and is fit for discharge into inland surface waters except for COD and colour.

Treatment Alternative II : In this alternative, it is proposed to use the combined waste, resulting after segregation of black liquor as suggested in alternatives I, on land for agricultural utilisation. The combined wastewater (about 200 m3/tonne of paper) will be taken through a clarifier to remove the settleable solids. The clarified wastewater after mixing with calcium sulphate (Gypsum) to bring down the per cent sodium below 60, will be used on land for irrigation. Depending on the type of soil, crop grown and the climatic conmditions, a dose of 54 to 108 m 3 of wastewater can be applied on land per hectare per day. It is of importance to mention that the studies carried out so far by NEERI, on agricultural utilisation of pulp mill wastes, have indicated that several kharif and rabi crops (except 3 varieties of grass and groundnut) have responded favourably when irrigated with pulp mill effluent as such or diluted with plain water. Continued use of the wastewater on land is likely to create ground water pollution due to percolation of the adsorbed colour. This is a drawback for this method of disposal.

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TREATMENT ALTERNATIVES 1 AND 2 For Small Paper Mills

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COLOUR REMOVAL
Presence of colour and its effect : Kraft pulp mills discharge dark brown coloured wastes. The colour is due to lignin and its derivatives. Only a small fraction of the total lignin of the wood processed comes out in the waste. Although lignin and its derivatives present in the waste are not toxic to human beings, animals and aquatic life, they create aesthetic pollution. Since they are not readily biodegradable when present in water, they also reduce the utility of the water and increase the cost of its treatment. In the manufacture of 1 tonne of bleached paper from bamboo, as much as 40-50 kg of lignin will be discharged into waste. In case of straw, used in small mills, as much at 225 kg of lignin per tonne of paper will be discharged into the waste. The high value is because no chemical recovery is adopted in small mills.

Studies on biological degradation of lignin revealed that : 1.There are only a limited number of micro organisms capable of degarding lignin-higher organisms like fungi are more capable than bacteria. 2.Biological decomposition is extremely slow and incomplete. 3.There seems to be of not much scope for removal of lignin in the existing biological waste treatment methods.

Methods for Colour Removal :

Lime treatment : Among the chemical methods employing precipitation or coagulation, massive lime treatment for colour removal has been found to be technically and economically feasible. This method besides achieving over 90% colour removal also result in 20-40% reductin in BOD from the coloured pulp will wastes. In India, some mills are presently establishing the massive lime treatment for colour removal. Lime recovery is an essential part of this process. A modified lime treatment for colour removal using only 1000 mg/l CaO for the total unclarified kraft pulp and paper mill waste with lime recovery system has a great promise as this method also helps in the removal and disposal of the suspended solids in the combind waste.

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Activated carbon treatment : Activated carbon treatment for colour removal from raw waste water may not prove economcial. However activated carbon treatment preceded by massive lime treatment will yield effluents that can be reused in the mill. Such a combination will make activated carbon treatment an econoic proposition.

Microlime carbon sequence : A Microlime carbon sequence for removal of 90% colour and 40% TOC from clarified wastewater of unbleached kraft mill, has been shown to yield reuseable water at a relatively low cost compared to massive or minilime activated carbon treatment.

Soils : Soils as a medium for colour removal can be used sussessfully provided the right type of soil and adequate land are available. This method of disposal of coloured pulp mill wastes will be most suited for Indian conditions. The land requirement will be high in most cases. Colour removal in waste from small mills where black liquor is not recovered, will pose serious problems and prove uneconomical. In such cases, it is desirable to segregate the small volume of strong black liquor and store it in lagoons before discharge into weater courses in the monsoon. The remaining coloured wastes can be used on land or treated by coagulation. This aspect has to be given a serious consideration before locating the mills.

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Minimal National Standards (MINAS)

The Minimal National Standards for pulp and paper mill effluent have been evolved after looking into practical difficulties, limitations, techno-economic feasibility and economic impact on the industry.

The basic considerations that went into the development of the minimal national standards were therefore as follows : Characteristics of effluent from small pulp and paper mills without chemical recovery systems. Achievability and techno-economic feasibility of various wastewater treatment alternatives. Maintained ratio of annualised cost to the turnover of the industry.

The MINAS limits for effluents from small pulp and paper industries after considering the above mentioned aspects have been evolved as presented in Table

MINAS for small pulp and paper industry

Parameter
pH Suspended solids Biochemical oxygen demand

Concentration
6.0 9.0 100 mg/1 50 mg/l

The implementation of above prescribed limits will be made in a phased manner. In the first instance, the BOD and suspended solids of treated effluent should be reduced by 90% of the total BOD and SS load in the effluent.

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REFERENCES
1. Chapter 20 of Environmental Pollution and Control in Chemical Process Industries By S.C.Bhatia

2. Chapter 11 of Industrial Waste Water Treatment By A.D.Patwardhan 3. www.cpcb.gov.in

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