UTILIZATION OF PAPER INDUSTRY EFFLUENT AS WATER REDUCING AGENT IN CONCRETE
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05-09-2010, 01:38 PM


UTILIZATION OF PAPER INDUSTRY EFFLUENT AS WATER REDUCING AGENT IN CONCRETE


ABSTRACT



The present paper describes the utilization of paper industry effluent as water reducing agent in concrete for its effects on various properties like slump, setting time, compressive strength etc. The properties have been compared with commercially available water reducing agents like modified lignosulphonate (MLS) and sulphonated naphthalene formaldehyde condensate (SNF). It has been observed from studies that the effluent which is a source of pollution on receiving water bodyâ„¢s aquatic ecosystem and adjacent agricultural fields, cattles etc. and can be used as an admixture in concrete to get better workability at same w/c ratio or by reducing w/c ratio at a given workability.

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1.0 INTRODUCTION

Paper industry, small and large, has expanded tremendously in the last five decades in India. These industries use wood and agricultural residues in papermaking and discharges huge volumes of highly coloured and toxic waste water (effluent) in the environment. The process dissolves the lignin present in the wood and loosens the cellulose fibre. Lignin is converted into thio and alkali lignin in Kraft process and lingo-sulphonate in Sulphite process. The fibres still contain a part of lignin and hence are coloured brown and require bleaching for making white paper. The spent liquor from Kraft process or Alkali process is either drained out or collected for recovery of chemicals, wherever chemical recovery is feasible. The paper industry consumes around 300 m3 water per ton of paper and discharge about 250 m3 of water per ton of paper. The process of pulp washing gives rise to dark brown coloured waste known as stock wash or conveniently called as black liquor. On standing, the effluent after some time has odour.

The brown colour on long standing is imparted mainly by the presence of lignin and its derivatives.
Lignin derivatives account 20% of the composition of wood. The chemical recovery is done from the black liquor which contains 90% of total lignin of the wood.


1.1 NEED FOR TECHNOLOGY TRANSFER

The colour and toxicity of the effluent from paper industry arise due to the presence of low and high molecular weight chlorinated organic compounds generated from lignin degradation products during wood cooking, conventional bleaching and alkali extraction of pulp. Although low molecular weight chlorolignins are partially removed from the effluent during anaerobic “ aerobic treatment processes, the medium and high molecular weight lignins remain unaffected and pass effluent treatment plants into receiving water bodies. The slow decomposition of these compounds releases toxic and bioaccumable chlorinated phenols, dioxins, and other mutagenic and carcinogenic compounds. Regular monitoring of pollution parameters in these effluents in respect of total suspended solids, biochemical oxygen demand, chemical oxygen demand, chlorophenols, dioxins and colour, therefore assumes paramount importance to maintain environmental safety.
The presence of characteristic brown colour of the pulp and paper mill effluents makes the receiving water bodies aesthetically unpleasant, added COD and chronic toxicity to fish and other aquatic species. The paper industry effluent generally contains various contaminants in the form of organic and inorganic chemicals. Presence of these chemicals in large quantities in the effluent impart damaging effect on the plant development including germination and seedling growth. Therefore it is extremely necessary to treat the effluent properly before releasing it in the neighbouring areas to minimize the harmful impact.
Since the paper mill effluent contains lignosulphonates which are known as water reducing agents. Thus, in view of huge cost of treatment of effluent and to avoid polluting the inland surface water and agricultural fields etc. it is worth while to utilize this value added waste effluent as a water reducing agent. In the study carried out by S.K.Agarwal,scientist ,EST Division, CBRI,Roorkee and Kiran Patel,School of building science and technology,CEPT,Ahemdabad, effluent from small and large paper mills have been taken and its effect on the physical properties like setting time, slump loss, compressive strength etc. have been studied and compared with the commercially available water reducing agents like modified lignosulphonate (MLS) and sulphonated naphthalene formaldehyde condensate (SNF).

2.0 EXPERIMENTAL WORK

The following experiments were carried out on the effluent, MLS, SNF:
a) The effect of effluent, MLS, SNF on the setting time of cement at various dosages has been studied as per BIS 4031-1988.
b) The workability of concrete mix was determined by the slump test BIS 1199-1988. The slump loss or loss of workability with time using effluent and commercial water reducing agent was measured at different time intervals.
c) The effect of effluent ,MLS ,SNF on the compressive strength of concrete at 3,7 and 28 days was determined at different w/c ratios and at different dose level.






2.1 CHARACTERISTICS OF COMMERCIALLY AVAILABLE ADMIXTURES


Sl. No. PARAMETER MLS SNF
1. COLOUR DARK BROWN DARK BROWN
2. PHYSICAL STATE LIQUID LIQUID
3. PH 4.96 4.3
4. TOTAL SOLIDS (mg/l) 382760 140585
5. TOTAL SUSPENDED SOLIDS (mg/l) 100 105
6. TOTAL DISSOLVED SOLIDS (mg/l) 382660 140480
7. CHEMICAL OXYGEN DEMAND (mg/l) 366396 230769
8. BIOCHEMICAL OXYGEN DEMAND (mg/l) 138200 116384
9. CHLORIDE (mg/l) 867 578
10. SULPHATE (mg/l) 5050 5192

2.2 CHARACTERISTCS OF PAPER MILL EFFLUENT

Sl. No. PARAMETER SPME (small paper mill effluent) LPME (large paper mill effluent)
1. COLOUR DARK BROWN LIGHT BROWN
2. PHYSICAL STATE LIQUID LIQUID
3. PH 7.81 5.85
4. TOTAL SOLIDS (mg/l) 30228 34416
5. TOTAL SUSPENDED SOLIDS (mg/l) 215 195
6. TOTAL DISSOLVED SOLIDS (mg/l) 30013 34221
7. CHEMICAL OXYGEN DEMAND (mg/l) 102561 19658
8. BIOCHEMICAL OXYGEN DEMAND (mg/l) 3015 5890
9. CHLORIDE (mg/l) 459 545
10. SULPHATE (mg/l) 810 980






2.3 EFFECT OF SPME, LPME, MLS AND SNF ON THE SETTING TIME OF CONCRETE

Sl. No. DESCRIPTION % DOSE SETTING TIME
INITIAL FINAL
1. CONTROL NIL 110 220
2. SMALL PAPER MILL EFFLUENT (SPME) 1.5 150 235
2.0 160 265
3. LARGE PEPER MILL EFFLUENT (LPME) 1.5 155 255
2.0 160 270
4.
MODIFIED LIGNOSULPHONATE (MLS) 0.2 175 290
0.5 190 310
5. SULPHONATED NAPTHALENE FORMALDEHYDE CONDENSATE (NSF) 0.6 215 330
1.2 240 355

BIS 4031 “1988 REQUIREMENTS:
1. CONSISTENCY OF CEMENT: 29%
2. INITIAL SETTING TIME: NOT LESS THAN 30 MINUTES
3. FINAL SETTING TIME: NOT MORE THAN 600 MINUTES

The table shows the effect of effluent dose and that of commercial admixtures on the setting behaviour of cement compared to control mix initial (110 mins) and final (220 mins) time, the addition of effluent dose (1.5 and 2.0) from small mill has delayed initial setting by 40 and 50 minutes, while 15 and 45 minutes delay in final setting time. In case of large paper mill effluent the delay in initial setting is 45 and 50 minutes and that of final is 35 and 50 minutes.
The addition of modified lignosulphonate (MLS) at 0.2% and 0.5% dose level, there is 65 and 80 minutes delay in initial setting time, while 70 and 90 minutes delay in the final setting time. In the case of SNF at 0.6% and 1.2% dose level, delay in initial setting time of cement (105 mins and 130 mins) and final setting (110 mins and 135 mins) has been observed
Discussion
Thus the above studies show that the addition of effluent has no remarkable effect on the setting time of cement and is well within the BIS limits (4031-1988).





2.4 WORKABILITY OF M30 CONCRETE IN TERMS OF SLUMP VALUE FOR VARIOUS W/C RATIO.

Sl. No DESCRIPTION % DOSE SLUMP VALUE (mm)
W/c RATIO
0.5 0.45 0.4
1. CONTROL NIL 30 _ _
2. SPME 1.5 70 50 30
2.0 130 65 40
3. LPME 1.5 100 90 70
2.0 140 100 80
4. MLS 0.2 - 70 30
0.5 - 95 55
5. SNF 0.6 - 80 45
1.2 - 140 75

The effect of effluent and commercial MLS and SNF on the workability of concrete is shown above.
The slump of control concrete at 0.4 and 0.45 w/c ratios was very stiff for any measured values. The slump of concrete at 0.5 w/c ratio at 2% dose level of small and large paper mill effluent increases 4.3 to 4.6 times as compared to the workability of control mix. At 0.45 w/c ratio this increase is 2.1 and 3.3 times higher when compared to control mix.
The increase in case of MLS and SNF is 3.2 and 4.7 times. However at 0.4 w/c ratio the increase in slump with the addition of effluent from small and large paper mill is 1.3 and 2.7 times and in case of MLS and SNF, it is 1.8 and 2.3 times compared to control concrete.
Discussion
The studies show that the addition of paper mill effluent and commercial super plasticizer exhibits significant improvement in the workability compared to control concrete. The slump increases with increase in dose level. The slump value of concrete with effluent is comparable to commercial super plasticizer.





2.5 LOSS OF WORKABILITY WITH TIME:

2.5.1 LOSS OF WORKABILITY OF M30 CONCRETE AT 0.5 W/C RATIO MODIFIED WITH VARIOUS ADMIXTURES

Sl. No. DESCRIPTION % DOSE SLUMP OF CONCRETE (mm)
TIME ELAPSED AFTER MIXING
5 MINS 15 MINS 30 MINS
1. CONTROL NIL 30 25 15
2. SPME 1.5 70 35 20
3. LPME 2.0 130 110 70
4. MLS 1.5 100 80 65
5. SNF 2.0 140 120 95


2.5.2 LOSS OF WORKABILITY OF M30 CONCRETE AT 0.45 W/C RATIO MODIFIED WITH VARIOUS ADMIXTURES

Sl. No. DESCRIPTION DOSE % SLUMP OF CONCRETE (mm)
TIME ELAPSED AFTER MIXING
5 mins 15 mins 30 mins
1. SPME 1.5 50 30 15
2.0 65 40 20
2. LPME 1.5 90 60 35
2.0 100 65 35
3. MLS 0.2 70 40 20
0.5 95 70 45
4. SNF 0.6 80 50 25
1.2 140 90 60

2.5.3 LOSS OF WORKABILITY OF M30 GRADE CONCRETE AT 0.4 W/C RATIO MODIFIED WITH VARIOUS ADMIXTURES


Sl. No. DESCRIPTION DOSE % SLUMP OF CONCRETE (mm)
TIME ELAPSED AFTER MIXING
5 mins 15 mins 30 mins
1. SPME 1.5 30 20 10
2.0 40 25 15
2. LPME 1.5 70 45 20
2.0 80 50 25
3. MLS 0.2 30 15 5
0.5 55 30 15
4. SNF 0.6 45 30 15
1.2 75 55 25







Control

The slump of control mix at 5 minutes was 30 mm and at 30 minutes it came down to as low as 15 mm.
The initial slump (at 5 minutes) of concrete modified with small paper mill effluent at 1.5% dose level was observed as 70mm (more than 2 times than that of control mix) and after lapse of 30 minutes it was observed as 20 mm (5mm higher than that of final value of control mix at the same w/c ratio).
At 2% dosage with LPME at same w/c ratio, the initial slump was 130mm(about 4.3 times) and with laps of 30 minutes, slump value observe was 70mm(which is twice as high as the initial slump value of control mix.
At 0.45w/c ratio and at 1.5% dosage, the slump observed was 50mm and it was reduced to 15mm after the laps of 30 minutes.
At 0.4w/c ratio, the slump value observed was same as those of control mix at 1.5% dose level.
At 10%water reduction i.e. 0.45 w/ c ratio, the slump value observed was 1.5 times as those of control mix at 1.5% dosage. However at 20% water reduction i.e. at 0.4w/c ratio, the slump observed was same as those of control mix at 1.5 dose level.
The slump value of concrete modified with SNF at 0.5w/c ratio and 2% dose was 140mm(4.67 times initial value of control mix) and after 30 minutes, the value observed was 95mm (6.67 times the final slump value of control mix).
Even with 20% water reduction i.e. at 0.4% w/c ratio, the slump value for LPME was 80mm(2.6 times the initial value) and after 30 minutes it was 25mm(more than 1.6 times the final value of the control mix) at 2% dosage
MLS at 0.5% dosage and 0.45w/c ratio had its 5 minutes and 30 minutes slump as 95mm and 45mm(about 3 times more than the control mix at 0.5w/c ratio) and with 20% water reduction i.e. at 0.4w/c ratio ,the 30minutes slump at 0.5 dose level is same as final slump of control mix
Napthalene based admixture at 1.2% dose gives initial slump as 140mm and after 30minutes it is 60mm for 0.45w/c ratio.At 0.6% dosage at the same w/c ratio,the initial and final values observed were 80mm and 25mm respectively.However for 0.4w/c ratio and 1.2% dosage the values observed for the initial and final slump were 75mm and 25mm respectively and for 0.6% dosage, they were 45 and 14mm respectively.
Discussion

The above study shows that with the use of water reduction agent the initial slump at same w/c ratio is approximately 2-5 times the initial slump of control mix.However,after 30minutes,the slump was found to be comparable to initial value of slump of control mix i.e. even after the lapse of 30minutes. Slump values observed for the concrete modified with the additives (SPME, LPME, MLS,SNF)were comparable to the initial value of the control mix.So even after the lapse of 30minutes with the addition of admixture,we get workable concrete,which was not possible for control mix.
Water reduction
One of the benefits of using reducing agent is to get better workability at the same w/c ratio or by reducing the w/c ratio at a given workability.The addition of paper mill effluent at same w/c ratio significantly improves the workability as compared to the control mix.At 0.4w/c ratio using small mill effluent (1.5% dose)is as workable as control mix at 0.5w/c ratio.
However ,at 2% dose level and 0.4w/c ratio, it shows 33% improvement in workability compared to control mix.
2.5.4 WORKABILITY OF M30 GRADE CEMENT CONCRETE AT REDUCED WATER CONTENT AT VARIOUS DOSE OF ADMIXTURES.

Sl. No DESCRIPTION %DOSE W/C RATIO SLUMP
1. CONTROL 0 0.5 30
2. SMALL MILL 1.5 0.4 30
3. MLS 0.2 0.4 30
4. SNF 0.2 0.4 45

Concrete modified with large mill effluent at 1.5 % dose level shows higher workability at 0.4 w/c ratio .
It is clear from the tables that it is possible to reduce the water content beyond 20% and still the same workability can be achieved. The recommended water reduction in BIS 9103 “ 1999 limit is 20% for normal water reducing agent. This shows that paper mill effluent shows characteristics similar to superplasticizer according to BIS limit. This water reduction is responsible for increase in compressive strength.
Similarly, the commercial admixture modified lignosulphonate at 0.2% dosage shows same slump as control mix at 0.4 w/c ratio and sulphonated naphthalene formaldehyde condensate shows 50% improvement in slump compared to control mix. Thus the commercial super plasticizer reduces water content beyond 20%.
From the above discussion, it is evident that the concrete modified with small and large mill effluent shows characteristics of the commercial superplasticizer at higher dosage level.

2.6 COMPRESSIVE STRENGTH

2.6.1 COMPRESSIVE STRENGTH OF M30 GRADE OF CEMENT CONCRETE AT 0.5 W/C RATIO WITH THE ADDITION OF VARIOUS ADMIXTURES.

Sl. No. DESCRIPTION DOSE % COMPRESSIVE STRENGTH (N/mm2)
3 DAY 7 DAY 28 DAY
1. CONTROL 0 21.8 24.2 32.89
2. SPME 1.5 22.56 27.1 33.67
2.0 26.07 30.4 36.19
3. LPME 1.5 22.89 27.56 34.5
2.0 24.0 29.55 35.1

2.6.2 COMPRESSIVE STRENGTH OF M30 GRADE CEMENT CONCRETE AT 0.45 W/C RATIO WITH THE ADDITION OF VARIOUS ADMIXTURES


Sl. No. DESCRIPTION DOSE % COMPRESSIVE STRENGTH (N/mm2)
3 DAY 7 DAY 28 DAY
1. CONTROL 0 25.8 30.4 36.5
2. SPME 1.5 26.3 31.26 38.7
2.0 26.22 32.89 36.3
3. LPME 1.5 24.45 30.96 36.3
2.0 30.22 32.60 37.04
4. MLS 0.2 24.00 15 40.3
0.5 22.11 30 39.56
5. SNF 0.6 24.45 30 36.25
1.2 26.96 55 37.63
2.6.3 COMPRESSIVE STRENGTH OF M30 GRADE CEMENT CONCRETE AT 0.4 W/C RATIO WITH THE ADDITION OF VARIOUS ADMIXTURES




Sl. No. DESCRIPTION DOSE % COMPRESSIVE STRENGTH (N/mm2)
3 DAY 7 DAY 28 DAY
1. CONTROL - 31.4 35.5 41.2
2. SPME 1.5 32.59 37.56 43.56
2.0 33.00 39.11 44.5
3. LPME 1.5 29.04 34.97 39.00
2.0 33.11 40.89 42.00
4. MLS 0.2 32.0 40.30 41.63
0.5 29.33 34.81 39.7
5. SNF 0.6 32.74 39.11 40.14
1.2 29.33 35.78 39.11

The concrete mix was designed for M30 grade.The compressive strength of the control.as well as concrete modified with various admixtures at different w/c ratios are given above.
The compressive strength of control concrete at 3,7 and 28 days at 0.5w/c ratio are 21.8,24.2 and 32.89 N/mm2 respectively.
However , when small and large paper mill effluent is added to concrete there is increase in compressive strength for all dosage percentages studied.The increase in strength at same w/c ratio of mix can be attributed to efficient compaction of concrete due to increased fluidity.
It is clear from the above table 2.6.2 that concrete modified with MLS at 0.2% dose is showing maximum 28 days strength . However, concrete modified with SNF at 1.2% dose level shows maximum 7 days strength and LPME at 2% dosage maximum 3days strength. This shows that the rate of strength gain is different for concrete modified with each admixture .Concrete modified with MLS shows low early days strength but high 28 days strength.Where as concrete modified with LPME shows high early strength , but after that the rate of strength gain is almost straight and 28 days compressive strength is not as high as other in the chart.
However the concrete modified with SPME shows steady strength gain rate,whereas concrete modified with MLS give maximum 28 days compressive strength.
However there is no significant variation between 28 days compressive strength , but the strength at 3 and 7 days vary significantly .This means that the rate of strength gain is different for each but the final effect is almost the same.
At 0.4 w/c ratio concrete modified with SPME shows maximum compressive strength at 28 days. Concrete modified with MLS at both 0.2% and 0.5% dose level shows good 28 days compressive strength, but the 3 and 7 days strength is not as high as other, as was in previous case.However in this case, the concrete modified with LPME at 2% dose level shows steady strength gain.
In all the cases discussed above, concrete modified with admixture,shows significant improvement in all the 3 ,7 and 28 days compressive strength,than that of control concrete.There is no significant variation between the various admixtures in their final measured strength for a given w/c ratio.the concrete modified with paper mill effluent both small and large mills shows quite comparable results with those of concrete modified with commercially available super plasticizers.The results found in case of large paper industry effluent have been more effective as the dissolved solids particularly the lignin content is more.
The above studies also reveal that ,with the use of all admixtures,the 28 days compressive strength shows more than 10% increase as compared to control mix, which is in accordance with BIS 9103-1999

3.0 CONCLUSION
From the above tests and the results obtained, it is seen that the paper industry effluent containing lignosulphontes can be effectively used as an admixture in concrete which is otherwise a source of pollution. The addition of effluent has no remarkable effect on the setting behaviour of cement and is well within BIS limits. Studies have shown that the addition of paper mill effluent improves the workability by increasing slump value of concrete and is comparable to commercial superplasticizers. Studies reveal that the 28 days compressive strength increases by more than 10% with the use of LPME than SPME as the lignin content is more.Thus the LPME and SPME characteristics as an admixture in concrete compare well with commercially available superplasticizers like modified lignosulphonate (MLS) and sulphonated napthalene formaldehyde condensate(SNF)used for the tests

ACKNOWLEDGEMENT
I acknowledge, with thanks, the support and guidance provided by my guide Divya S.J, senior lecturer and also Prof. K.P.Narayanan, Head of Department of Civil Engineering for the facilities provided to prepare and present the seminar and presentation.
I am also grateful to my teachers and friends for all their support and encouragement.

REFERENCE

1. Agarwal .S.K and Kiran Patel.Utilization Of Paper Industry Effluent As Water Reducing Agent In Concrete.NBM & CW April 2004Tonguep 62-68
2 Baruah B.K and Das .M . Study On Impact Of Paper Mill Effluent On Germination Behaviour And Seedling Growth Of Crop Plant,Oryza Satna.L. Pollution Research 17(1)Tonguep 65-68(1998)
3 Shetty .M.S. Concrete Technology ,Theory And Practice S.Chand & Company.
4 Sidhu .D.S. Effect Of Superplasticizers On Properties Of Cement And Concrete. NBM & CW May 2001 Tonguep 38-43


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