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“Simple Innovations and Novel Treatment Technology

for Improved Effluent Quality- Case Studies”.


Preamble :
This presentation gives a brief overview of some simple
innovations for improving effluent quality

Innovations based on “Common Sense Approach” rather


than using any sophisticated technology

We also present some results from use of FACCO technology


for effluent treatment developed by CLRI
Driving Factors “Necessity- Mother of innovation”

• Cost Advantage
• Better Safety
• Environmental Impact – Improved Emissions
Approach for Improving Effluent Quality

• Change in Mindset
• Reduction at source
• Recycling
• Recovery
• Treatment
Tools Used

• Extensive COD Measurements


• Use of GC & GCMS
Reduction at Source - Examples

– Hydraulic effluent Load reduction :

• Use of external chilling in place of Ice

• Optimizing water used for centrifuge and filter press washing etc

• Results not only in lower volume but also Concentrated effluent easier to treat

– Organic Load reduction

• optimizing raw material usage - GCMS data of effluent streams revealed

presence of a particular raw material. Usage of this was gradually reduced

leading not only to improved effluent but also RMC reduction


Recycling and Recovery- Examples

– Recycling

• centrifuge washes

• Hydrolysis and reduction mother liquors

– Recovery

• evaporation and fractional distillation of effluent streams


Case Study
• Production of Aromatic Di Amine Sulfate from Mono Amine
• Process steps :
– Diazotization and coupling

– Iron Acid reduction

– Steam distillation

– Sulfatation
NH2 NH2
2RNH2 Diazo
R Reduction
R + RNH2
NRNH2 NH2
Effluent Details

• Liquid effluent is generated from steam distillation as well as from


isolation of product
• Effluent contains mono amine and Diamine Sulfate
• Both these contribute heavily to the organic load in effluent and also
result in yield loss
Di Amine Sulfate - Original Process Block Diagram
MA
HCl Iron
Steam Steam
SN Solu Powder CSA Water

Filter Sulphatation CF
Diazo Reduction Distillation Distillation
Press
vessel Vessel

Distillate Iron Oxide Distillate Distillate Diamine CF ML CF Wash ML


Qty: 7 KL Qty: 3 T Effluent Effluent Sulfate Effluent Effluent
Qty: 9 KL Qty: 4.5 KL Wet Cake Qty: 5 KL Qty: 6 KL
COD: 35000 COD: 8000 to COD: 35000 COD: 8000 to
10000 10000
Salt Settling &
Separation

Rec MA Effluent
Qty: 450 Kgs Qty: 6.5 KL
(For Reuse COD: 40000
After Dist)
Process Operation was modified as follows :

- Fractionation of distillate from steam distillation

- Employing steam stripping columns in place of simple


steam distillation
- Re-cycling of distillate and centrifuge washes

- Evaporation of mother liquor after sulfatation


Di Amine Sulfate Plant – Modified Process Block Diagram
MA
HCl Iron
Steam Steam
SN Solu Powder CSA Water

Diazo Filter Stripping


Reduction Column 1 Distillation Sulphatation CF
Vessel Press
Vessel

Distillate Iron Oxide Distillate Distillate CF ML CF Wash ML Di amine


Qty: 7 KL Qty: 3 T Effluent Effluent Effluent Qty: 6 KL Sulfate
Qty: 7 KL Qty: 4.5 KL Qty: 5 KL Wet Cake
COD: 45000 COD: 8000 to COD: 35000 1st 50% Effluent
Settling & 10000
Qty : 3 KL
Separation
Stripping COD: 8000 to 10000
Steam
Column 2 Recycle in Reduction
Neutralize
2nd 50% Recycled
Rec MA Effluent for Washing
Qty: 450 Kgs Qty: 6.5 KL Qty : 3 KL
(For Reuse COD: 40000 Bottom Effluent Column Top
After Dist) Qty: 8.5 KL Qty: 0.5 KL
COD: 2000 to 4000
From Stripping Fractionating CSA
Column 2Top Column Evaporation
Rec MA
Salt
Qty : 100 to 150 Kgs Recovered
(Distill & Use) Mother Liquor Di Amine
Sulphate
Bottom Effluent Column Top Settling & Effluent for Incineration Distillate Effluent Wet Cake
Qty: 6 KL Qty: 1 KL Separation Qty : 900 to 850 Kgs Qty : 4 KL Qty:25 Kgs
COD: 2000 to 4000 COD: 35000 COD: 2000 - 3500
Results
– Lower water consumption

– Higher recovery of raw material (mono amine)

– Higher product yield

– Lower hydraulic and organic load of effluent


Di Amine Sulfate Plant – Original / New Modified Process Summary
Details Old Effluent New Effluent Remarks
Qty COD Qty COD
Steam Distillation 6.0 KL 40000 6.0 KL 2000 to COD reduce due to
(1) 4000 fractionation Column

Steam Distillation 9.0 KL 35000 8.5 KL 2000 to COD reduce due to 2nd
(2) 3500 stripping Column

Distillation 4.5 KL 8000 to 0 0 Recycled in Reduction –


10000 Hydraulic & COD reduced

CF 1st ML 5.0 KL 35000 4.0 KL 2000 to COD reduce due to


2500 evaporation and product
recovery

CF Wash ML 6.0 KL 8000 to 3.0 KL 8000 to 3.0 KL washing ML recycled


10000 10000 for Product wash in CF.

Recovered MA 450 Kgs 575 Kgs

Product Yield 0.48 0.51


Factor
Treatment Efforts
• Extensive study of effluent characteristics using tools like COD
measurement, GC, GCMS etc.

• Segregation of streams for effective treatment

• Licensed FACCO technology from CLRI

• Pioneered use of FACCO . 6 FACCO units installed in group cos.

• Appointed NEERI to advise of improving aerator performance

• Installed sand filters and polishing filters before final discharge

• Continuous discharge
Primary ETP - FACCO 2 & 3 to Aeration

FACCO2 FACCO3

Cartridge Filter
A Lime
I FeSO4
R Magnafloc

N3 N4 N2 N5

Acidic 1 KL 1 KL
Effluent
From Plant

+ From FACCO 1

H2 O 2

TK1 TK2 FeSO4 Equalizing


Tank

Aeration
Secondary ETP & Final Discharge
Neutral
FACCO1
From FACCO 2/3
Effluent Alum
Cartridge Filter Sol
Lime
FeSO4
Magnafloc

Equalizing Secondary Secondary


Tank Lamella Lamella
Tank
N4
N2 N2

1 KL Sand
Filter
H2 O 2

FeSO4
Sludge Sludge
Bed Bed

PT1 PT2
Primary ETP
Effluent From Plant or FACCO2/3
Washing

Overflow
PT3
27KL Septic Tank Final
Discharge
Tank
Aeration

CETP
WHAT IS FACCO?

Fenton (reaction)
Activated
Catalytic
Carbon
Oxidation
FACCO BASICS
• Uses Hydroxy radical – second most powerful oxidizing agent for
oxidizing organics in effluent
• CLRI developed technique uses Meso porous Carbon as catalyst to
catalytically generate hydroxy radical from fenton reagents (H2O2
and FeSO4) , oxygen and water
• Use of Fenton reagents only to initiate reaction. Therefore cost
effective
FACCO
1.8 mts

Effluent + H2O2 Solu


+ FeSO4 Solu (inlet) Backwash Out

Carbon C 0.85 mts


800 Kgs
3.8 mts
Carbon B
400 Kgs 0.35 mts

Air Inlet Pebbles 0.70 mts


Effluent outlet
& Backwash In

Foundation
Monthly Average COD Results from FACCO
treatment
FACCO 1 FACCO 2/3
Month Input COD Output COD Month Input COD Output COD
Mg/lts Mg/lts Mg/lts Mg/lts
Jan 2010 38792 14979 Jan 2010 9500 5676
Feb 2010 28800 13348 Feb 2010 8028 3203
Mar 2010 24800 10082 Mar 2010 6499 2889
Apr 2010 34563 14664 Apr 2010 8310 3306
May 2010 32690 12452 May 2010 7835 3175
Jun 2010 20800 10400 Jun 2010 6040 2865
Jul 2010 30813 14441 Jul 2010 5973 2531
Aug 2010 34094 14024 Aug 2010 7392 3130
Sep 2010 36108 13955 Sep 2010 7800 3293
Oct 2010 31921 14947 Oct 2010 6640 3224
Nov 2010 34500 15580 Nov 2010 5800 2300
Dec 2010 28791 14988 Dec 2010 6359 2805
GCMS Analysis of Effluent streams before and after FACCO 1

GCMS Analysis of Effluent streams before and after FACCO 1


  GCMS AREA Units % Area
COMPOUOND NAME Before AFTER Reduction
FACCO 1 FACCO 1 in FACCO

ANILINE 58,15,000  Nil 100


PHENOL 1,64,40,000 1,36,20,000 17
ACETIC ACID PHENYL ESTER 27,63,000 97,000 96
O - TOLUIDINE 1,78,000 66,000 63
N ETHTYL ANILINE 7,27,000 73,90,000 (917)
N ETHYL N METHYL ANILINE 14,12,000 2,02,000 86
N, N 4 TRIMETHYL ANILINE 80,000 Nil  100
N, N DIETHYL ANILINE 58,39,000 9,67,000 83
4 - (DIETHYLAMINO) BENZALDEHYDE 34,78,000 1,58,000 95

2 - (ETHYLPHENYLAMIO) ETHANOL 28,41,00,000 5,67,00,000 80


       
GCMS Analysis of Effluent streams before and after FACCO 2/3
  GCMS Area units % Area Reduction
COMPOUOND NAME Before FACCO 2/3 After FACCO 2/3 in FACCO

CYNO - ETHYL ESTER ACETIC ACID 46,46,000 11,900 100


ANILINE 1,43,20,000  Nil 100
PHENOL 1,24,50,000 48,10,000 61
FLUORO ANILINE 2,98,70,000 1,15,80,000 61
M - CRESOL 6,39,00,000 2,01,50,000 68
O - TOLUIDINE 16,00,00,00,000 10,20,00,00,000 36
P - TOLUIDINE 1,95,60,000  Nil 100
DIMETHYL PHENOL 2,53,10,000 1,74,80,000 31
DIMETHYL PHENOL 2,16,40,000 25,80,000 88
P - NITRO TOLUINE 24,50,000 6,38,000 74
HYDROQUINONE OR RESORCINOL 2,77,90,000 3,04,30,000 (9)
N PROPYL ANILINE 1,01,70,000  Nil 100
2 METHYL 3 NITRO PHENOL 10,31,00,000 3,96,00,000 62
P - FLUORO 3 NITRO ANILINE 17,16,00,000 4,01,10,000 77
B - NAPHTHOL 34,74,00,000 5,83,00,000 83
3 METHYL 2 NITRO PHENOL 30,09,00,000 10,67,00,000 65
P - NITRO 2 AMINE TOLUINE 1,05,40,000 42,80,000 59

       
B /F ACC O -I (01/12/10)
CS SPE_041210 003 GCMS Analysis of Effluent streams
17.22
from different stages Scan EI+
T IC
100
2.0 0e9
%
6.61
8.93 13.2713.77
-5 T ime
4.05 6.05 8 .05 10.0 5 12.05 14.05 16.05 18.05 2 0.05 22.05 24.05 26.05 28.05
A/F ACC O -I (01/12/10)
CS SPE_041210 004 Scan EI+
T IC
100
2.0 0e9
%
6.70 10.99 17.24
-5 T ime
4.05 6.05 8 .05 10.0 5 12.05 14.05 16.05 18.05 2 0.05 22.05 24.05 26.05 28.05
AFT E R AER AT IO N (01/12/10)
CS SPE_061210 005 Scan EI+
T IC
100
2.0 0e9
%
17.80 18.82
-5 T ime
4.05 6.05 8 .05 10.0 5 12.05 14.05 16.05 18.05 2 0.05 22.05 24.05 26.05 28.05
F IN A L D IS C H AR G E (0 1 /1 2 /1 0 )
C S SPE_0 61210 006 S ca n E I+
T IC
100
2 .0 0 e 9
%

-5 T im e
4 .0 5 6 .0 5 8 .0 5 1 0 .0 5 1 2 .0 5 1 4 .0 5 1 6 .0 5 1 8 .0 5 2 0 .0 5 2 2 .0 5 2 4 .0 5 2 6 .0 5 2 8 .0 5
Observations from GCMS Data
• Substantial reduction in Area of most compounds after FACCO indicating
complete oxidation

• Increase in N ethyl aniline content most likely due to cleavage of ethanol


molecule from 2-(ethyl phenyl amino) ethanol molecule. This is classical
FACCO mechanism where hydroxy radical cleaves large organic molecules to
form smaller , more bio degradable molecules

C2H5 N C2H4OH HN C2H5

• GCMS data of stream after aeration shows substantial reduction in all areas
indicating increased biodegradability. This offers the greatest advantage.
Limitations of FACCO
• Suspended Solids or Oil present in effluent hamper COD reduction as these block
active sites on catalyst
• Is not a “Quick Fix “ solution - Proper Process control and operation is critical :
– Dosing correct quantities of reagents
– Effective air blowing
– Back Washing
– Maintaining effluent pH

– Filtration and removal of SS from effluent

• Very effective for high COD effluents -cost effectiveness reduces for low COD
effluents
• Is not a substitute for biological treatment but complements biological treatment
Concluding Remarks

• Improvement in effluent quality can often be done by simple, inexpensive means – Change in
Mindset required

• Constant and ongoing efforts needed. Drive should come from top

• Efforts to reduce organics in effluent can lead to recoveries resulting in cost advantages

• FACCO technology is versatile and works with most kinds of effluent streams. It is a relatively
inexpensive process for reducing organic load and toxins like phenols
Quotes

• “Our environment, the world in which we live and work, is a mirror of


our attitudes and expectations.”

• “ In the long term economic sustainability depends on ecological


sustainability”
THANK YOU