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I

P 05406
80

A COMPARISON OF TREATMENTS FOR HIGH STRENGTH

DISTILLERY SLOPS
FROM THE SUGAR CANE INDUSTRY
HPctor M . Poggi-Varaldo, Associate Professor

Center of Advanced Studies and Research,


CINVESTAV del I P N , Dept. of Biotechnology and Bioengineering
MCxico D.F., MCxico
INTRODUCTION
The industrial activity is the main contributor to the water pollution in h4exiCo. The sugar cane
processing industry is the major wastewater generation source with nearly 6OTo of the total discharges' (Figure 1 ) . T h e distillery slops from alcohol manufacture based on molasses fermentation
account for a n important amount of the organic load of these emissions.
T h e distillery slops, known as vinasses, can be very aggressii e to rhe environment N hen improperly
managed. They have low pH and high contents of suspended and dissol\.ed organic matter and
nutrients. On the average, each liter of alcohol distilled generates 12 l o 14 liters of vinasses. The
potential en\:ironmental impact of a distillery manufacturing 5 0 0 m' alcohol/d.ay is equivalent to that
of a city of 200,000 inhabitants.' In 1989, about 1,500,000 m3 of \inasses were discharged in Mesico
in parallel to a production of 115,000 ni3 of alcohol.'*4
Recycling and resource recovery from vinasses is a very dynamic area of research.' Current experiments in the CINVESTAV in reusing/recycling vinasses for alcohol fermenration or single cell protein
synthesis show promise (V. Lopez-Mercado and M. de-la-Torre, private communication, CINVESTAV, 1992). Although reuse and recycle could alleviate the vinasses' pollurion problem in the future,

i--r-iDISTILLERY

SUGARCANE 62 0%

Alcohol

Vinaase

Aneeroblc EffluenI

O T H E R S 19.0%

CHEMICAL 2.1%
PULP AND PAP 10.0%

TOTAL:

Tapwater

Aerobic Etfluent

ONE BILLION M3/YR

LEACHATE

Figure 1. Industrial wastewater discharges in


hfexico-contributions of industrial sectors.

Figure 2.

Experimental design flowsheet.

47th Purdue fndusirial lVus/e Conference Proceedings, 1992 Lewis Publishers, Inc.. Chelsea, Michigan 481 18.

Prinred in U.S.A.
789

47TH PURDUE UNIVERSITY INDUSTRIAL WASTE

790

Table I .

CONFERENCE PROCEEDINGS

Reactor Characteristics
~~

Total
Volume
(L)
A n a er o b i c

I.luidized
Ikd

Carrier

Work
Volume
FBED
(L)

1011

300

\,e r o b ic
1-1uidized
tkd

2.65

Exchange
Resin

Hydra u I
Retent
Time
(Day)
3.6

Temperature
(C)
35 & 25

120

7.2

Active
Carbon

1.5

1
2

23

ilieir treatment is and \ \ i l l continue to be necessary. Among the menu of processes available, biologitreatment of the sugar industry effluents seems to provide both a sound degree of pollution
irbatement and resourcelenergy recovery o p p o r ~ u n i t i e s . ~Furthermore,
-~
effective full scale applicalions v e r e implemented since rhe early 8Os.3~*

c.:ll

I n 1987, the government-ouned company AZUCAR S . A . a n d three h4exican higher education


~ ~ i s t i t u t i o n(Center
s
for Advanced Studies and Research-CINVESTAV, National Autonomous Uni\.crsity of i\lIexico-U.N.A.M, and the State University of San Luis Potosi-U.A.S.L.P) with the cooper;tiion of the Mexican sugarcane mill Alianza Popular launched a pilot scale experiment I O test the
\,inasses treatability and the actual potential for resource and energy recovery using a combination of
Iiigh-rate anaerobic and aerobic processes.
This paper reports some results form the experiments conducted in the context of this Pilot Project.
I h e objectives of this particular \vork uere:
1. to determine the performance of series anaerobic-aerobic treatment of vinasses;
2. to examine the feasibility of anaerobic treatment of vinasses followed by irrigation.

MATERIALS A N D METHODS
b;sperimental Design

Figure 2 summarizes the experimental program. Raw vinasses \vere treated in a pilot scale Anaerobic Fluidized BED reactor (ANFBED). The anaerobic effluent from this stage was fed to a bench scale
Aerobic Fluidized BED reactor (AEFBED). Lysimeters containing soil of the region received other
portions of the anaerobic effluent at hydraulic rates 5 and 10 cm/\sk. Two control lysimeters ere
irr-igated with tap water and raw vinasses at 10 cm/wk (see Table 11). Irrigation tests lasted six months.
The ANFBED operated at 35C a n d hydraulic retention times ( H R T ) of 1,2,3, and 4 days during
the first campaign; in the second campaign the A N F B E D run at 2 5 C (psychrophilic or sub-optimal
icrnperature range) and H R T of 3.6 a n d 7.2 days (Table I). The A E F B E D worked at 23C, in the
I-;rnge of 1 to 4 days HRT. Both the A E F B E D a n d the lysimeters received anaerobic effluent from the
x c o n d campaign.
17:iperimental Set-up

Table I shows the main characteristics of the fluidized bed reactors. The ANFBED has a tall column
(1.30 m diameter and 4 m height with a n expansion chamber at the top. I t contained ion exchange resin
(\pent) of 700 pm average diameter as carrier for biological grolvth. The AEFBED was a tall glass
Table 11.

Lysimeters

Type of Influent

Hydraulic Rate
(cm/wk)
~

Anaerobic Effluent
Anaerobic Effluent
Raw Vinasses
T a p Water
I cngth = 1.5 m; Diameter = 0.1 m ; Material = PVC.

10
5
10
IO

I
HECTOR M. POGGI-VARALDO

Table 111.

791

Raw Vinasse Characterization

Parameter

Average Value

Temperature, C
PH
Total Alkalinity, mg/L C a C 0 3
Chemical Oxygen Demand, mg/L 0,
Volatile Organic Acids, m g / L acetic
Total Kjeldahl Nitrogen, mg,/L N
Ammonia Nitrogen, mg/L N
Sulfate, mg/L SO,

27
4.3
2250
69400
10820
1600
150
3 100

column 1.65 m height by 0.05 m diameter. I t had a shorter concentric internal glass column 0.50 cni
height by 0.03 c m diameter, which allo\ved the reactor to w o r k in recirculating fluidized bed mode. I t
contained 1 liter granular activated carbon (GAC) 500 pm alerage a s carrier.
The lysimeters were slim plastic columns (polyvin)~l-chloridepipe) 1 . S m height by 0.1 m diameter.
They had lateral outlets equally spaced 0.15 cm and bottom trays for leachate collection. More
detailed descriptions of the reactors and lysimeters dimensions, lay-outs, appurtenances, a n d start-up
can be found elsewhere.1*13
Analyses

All the analyses followed Sraridard A4eihods except \,olatile organic acids, which were determined
by direct titration,15 and methane in biogas, N hich was estimated by 3 simplified syringe (Orsat-based)
method. l 6
Climatological and Soil Characteristics

The sugarcane mill Alianza Popular is located at 21 97 41 latitude North and 99 23 00


longitude, 320 m above sea le\,el, in a temperate/subtropicaI region belonging to the state San Luis
.Potosi, 34exico. During the experimental period, the average mean, rhe average maximum, and the
average minimum temperatures \\ere 17C, 29C, and 16C respectively. The average precipitation
was 181 /month,
the average evaporation rate was 126 m m / m o n t h .
The soil for the lysimeters came from a sugarcane field nearby the mill. I t has a loamy-clay soil,
with high content of organic matter, relatively high p H . Cores of 1.5 m depth \\ere sampled and
transferred to the lysimeters with the least disturbance as possible. In this w o r k , three strata of soil
were defined and analyzed: top (0 to 30 cm depth), middle (30 cm to 90 cm depth), a n d bottom (90 cm
to 150 cm depth).
RESULTS A N D DISCUSSION
Raw Vinasse Characterization

Table I11 shows a typical average analysis of the raw vinasses treated in this s t ~ d y . ~It. has
~ a high
strength effluent, corrosive, with a high content in volatile organic acids due to fermentation during
the storage. T h e organic matter concentration fluctuated in a range from as low as 25,000 up t o near
100,000 mg 0 2 / L C O D . The [total COD]/[total N] ratio was approximately 44. This value was judged
sufficient for anaerobic treatment.I8
Although sulphate concentration was high, the COD/sulphate ratio was around 22, well above the
10 to 12 threshold value below which methanogenesis impairment by sulphide toxicity can be
expected. l 9 Therefore, no special provisions to remove sulphides from the recirculating effluent flow
of the ANFBED \vere undertaken.
Anaerobic Fluidized Bed Reactor (ANFBED) Performance

Figure 3 shows the results o f the first campaign for the A N F B E D in terms of C O D removal
efficiency, unit removal rate, and biogas productivity as functions of the organic loading rate. During
this period, the reactor operated at 35C. The C O D reduction \vas between 65 and 7 5 % o n total COD
basis; it slightly decreased with the increase in loading rate. The biogas productivity reached a
maximum of 8 m3/m3*day. The unit removal rate followed a slight curved hyperbola. I t fitted
Convertis model very well (Figure 4). Convertis model is a semi-empirical kinetic relationship

..
792

47TH PURDUE UNIVERSITY INDUSTRIAL WASTE CONFERENCE PROCEEDINGS

ut

0
0

10
PO
33
ORGANIC L O R O I f G ( K G COD FEO/M3 DRY)

45

Figure 3. Anaerobic treatment of vinasses in mesophilic conditions- pilot scale fluidized bed reactor (ANFBED) performance.

between the u n i t removal rate a n d loading rate, based on a n analogy of the \lichaelis-h?enten model
for enzymatic catalysis.20 The ANFBED shouted some acidogenic excursions at loading rates near 38
kg COD/m3-day, which was estimated as the maximum intensity limit for the process in the conditions
of the experiment.
The ANFBED operated for a second season at sub-optimal temperature of 25C. Figure 5 depicts
the average results of this period.The organic matter removal efficiency reached 62% on total C O D
basis at a loading rate around 10 kg COD/m3-day. When accelerated u p to 17 kg COD/m3*day
loading rate, the reactor showed acidogenic upsets resulting in a poorer COD removal (47% average).
T h e reactor recovered from these excursions with alkalinity addition a n d loading rate a d j ~ s t m e n t s . ' ~

0.15 -

0
0

0
0
Y

1
RflTE=207XLR/(285tLR)

?O.lO

E
v

..

0.00

0.04

I/LR (m3 doy/kgCOD

0.08

n. I2

fed)

Figure 4. Anaerobic treatment of vinasses in mesophilic conditions- ANFBED results fitted a


saturation kinetic model.

I
HECTOR M. POGGI-VARALDO

/lo

TEMPERflTURE = 25 C

793

v
Ia

BpH

* Ya

!-

6 . -

z
3

2
0

17.2

9.64
L G A D l NG RATE

( kg

COD/m3 d a y )

Figure 5. Anaerobic treatment of vinasses at sub-optimal temperature (25'C)-AKFBED average


result s.
Aerobic Fluidized Bed Recfor (AEFBED) Performance

T h e A E F B E D was started-up and acclimated to increasing concentration of the anaerobic effluent


in four stages (Table IV). Figure 6 portrays the performance of the AEFBED during the acclimation
periods in terms of C O D and colour removal. The COD reduction was above 85% (on total C O D
basis) for all the stages. The overall C O D removal of the series ANFBED-AEFBED reached 96Vo
when the A E F B E D was fed dilute anaerobic effluent (stages 2 a n d 3). These results compared
favorably to those reported by Yang et al.".who found that a series Upflow anaerobic sludge blanketTable IV.

Aerobic Fluidized Bed Start-up Semysinthetic Wastewater Formulation and Operation

Molasses, g / L
Anaerobic Effluent, L / L
T a p Water, L / L
Ammonium Phosphate, g/L
Hydraulic Retention Time, Day
Time, Day

Stage
1

Stage
2

Stage
3

3
0.3
0.7
0.5
4
10

2
0.6
0.4
0.5
4

0.1
0.9
1
a2

10

150

40

Figure 6 .

10

cm

INFLUENT

e LOROIN; R R T E

Aerobic treatment of the anaerobic effluent in the AEFBED -acclimation results.

Stage
4
1

0.8
0.2
0.5
4
10

794

4 7 P~
U R~
D U E UNIVERSITY INDUSTRIAL WASTE C O N F E R E N C E P R O C E E D I N G S

Entrapped Aerobic Fixed Bed reactors achieved 97% soluble COD removal treating a sugarcane mil
wastewater (no vinasses in it). The color removal (reported as luminance increase) reached 85 or mor(
when the influent to the AEFBED contained between 3010 to 60% of anaerobic effluent by volume
However, during the stage 4 , when the anaerobic effluent in the feed was 80% by volume, the ~ 0 1 0 ~
reduction fell dramatically (Figure 6). No attempt to determine the relative effects of biodegradation.
adsorption on the G A C , and bioregeneration of the carrier G A C on color removal was made.
Whether adsorption and bioregeneration of the carrier were the main mechanisms of color removal
a n d were outcompeted by the high loading rate of dissolved coloured substances in the influent o f
stage 4 (and during the subsequent steady states) deserves further research.
The AEFBED removed nearly 50% of the total C O D during the steady states (fed 100% anaerobic
effluent). Figure 7 shows that the C O D reduction was almost independent of the loading rate, in a
ikide range going from 3 to 35 kg COD/m3*day. N o appreciable color removal was detected. The
reactor liquor was aerobic in the range of loading rates experimented.
Although the combined ANFBED-AEFBED process showed higher C O D removals than either o n e ~ final
stage anaerobic (ANFBED) or one-stage aerobic (rotating biological contactor) t r e a t n ~ e n t ,the
effluent did not meet the criteria for direct discharge into water bodies. Further treatment for colour
a n d the recalcitrant C O D removal should be necessary. A combination of physico-chemical treatmeni
(including membrane separation) and innovative biotechnological processes could accomplish the
desired pollution r e d ~ c t i o n . ~The
~ . ~economic
~
feasibility of such more complex approaches i:
questionable.
Irrigation Results
Figure Sa presents the a\'erage results of organic matter loading (espressed on surface are basis) a n d
remo\.al (in decimal 0 to 1 range) in the lysimeters. A comparison between lysimeters 1 a n d 2
(anaerobic effluent at 10 and 5 cm/wk respectively) showed a higher C O D remo\al for the lysimeter 2 .
The concentration of C O D in the bottom leachate was almost proportional to the organic loading
(Figure 8b). The lysimeter 3 irrigated with raw vinasses averaged a C O D removal comparable to thar
in lysimeter 2 but the dynamic performance showed a remarkable deterioration of C O D reduction i n
the last two months (down to 60%, data not shoiGn).
The overall C O D removal of the anaerobic pretreatment followed by irrigation at 5 cm/\\.k
(ANFBED + 5 cm/wk anaerobic effluent irrigation, Figure 9) was the highest of the four alternatives. With the caution due to the impact in some physico-chemical characteristics of the soil (as
discussed below) this combination seemed to be the most recommendable.
The effects of anaerobic effluent a n d vinasses application on the soil are discussed here in terms of
the variation with time and depth profile of the following parameters: organic matter content,
electrical conductivity and sodium adsorption ratio (SAR) of the soil extracts, and sodium a n d
calcium ions concentrations (Figures 10 to 12). The bar denominated SOIL stands for the results of
non-irrigated soil (or time zero). The other bars represent the results of lysimeters 1 to 4 (see Table 11)
at the end of six months irrigation period.

m
m

u
o

1103

c
c

o
a

STER@Y STATES REFBEO

Figure 7 .

Aerobic treatment of the anaerobic effluent in the AEFBED-steady state average results.

HECTOR M. POGGI-VARALDO

795

LYSIMETER IRRIGATION TESTS


COD LOADING AND REMOVAL

' I

LOADING
RATE
(kgC 0D/m2.d )

I I I

0 COD REMOVAL
4

LYS 1

LYS2

LYS3

COD CONCENTRATION
IN LEACHATES

10000

8000

fl

6000

LEACHATE
COD (mg/L)

4000

2000
0
LYS 1

LYS2

LYS3

Figure 8. Lysimeter irrigation tests: &-COD removal efficiency and loading rate; 8b-COD concentration in lysimeter leachates. Key: Lys 1: anaerobic effluent at 10 cm/uk: Lys 2: anaerobic
effluent at 5 cm/wk; Lys 3: raw vinasses at 10 cm/wk.

Irrigation with anaerobic effluent and vinasses at 10 cm/wk increased significantly the organic
matter content of the t o p and intermediate layers (Figure 10). Interestingly, the lysimeter 2 (anaerobic
effluent at 5 c m / w k ) showed the highest organic matter increase at the bottom. The electrical conductivity of the t o p layer was not practically affected (Figure 1 la). However, this parameter increased
significantly in the intermediate and bottom strata, especially for the lysimeters receiving anaerobic
effluent at 10 cm/\vk a n d raw vinasses. In all cases, the electrical conductivity values of the t o p layers
were below the recommended 4 to 5 mS/cm maximum."
Figure I I b shows a n outstanding increase in the SAR ratio, singularly in the lysimeters irrigated
with anaerobic effluent. This effect was accompanied by an increase of o n e unit of p H (data not
shown). T h e SARs were nearly three- to four-fold the maximum recommended value." Sodium
accumulation and calcium washout suggested sodium (and potassium, data not shown) exchange by
calcium, especially in the top layer (Figures 12a a n d b). This exchange acted synergistically to increase
the experimental SARs. Sweeney and G r a t reported
~ ~ ~
similar increases in soil pH and monovalent
cation concentrations in soils irrigated with anaerobically pretreated molasses stillage.
I t is well kn0u.n that high values of SAR are associated to decrease of the soil permeability and
sodium toxicity to crops." The S A R results suggested that the hydraulic rate of the anaerobic effluent
should be set considering the monovalent cation loading, in addition to the conventional organic
matter a n d nutrient loading rite ria.^' The anaerobic effluent should be applied onto land at rates
lower than 5 cm/\vk. The use of strategies combining effluent dilution, intermittent irrigation (one
every other or t\vo years), calcium supplementation, a n d drainage would minimize long term detrimental impact on soil properties and crop yields.'

4 7 PURDUE
~ ~
UNIVERSITY INDUSTRIAL WASTE CONFERENCE PROCEEDINGS

796

IRRIGATION
5 cm/wk

10 cdwk

RPJAEROB I C EFFLUENT

..

I L I

1 0 cm/wk
V I I-IASSES

ULU

>

0
UJ

LT

0
0
J
J

0:

LL

>

-,

! i

' J I fi6S';t

Figure 9 .

TREfiT!.lEIL'TS

Overall COD removal of the four alternatives.

On the other hand, the lysimeter receiving \inasses had a normal pH of 7.7 and the distribution of
sodium and calcium \\'as not so disrupted as compared to that in the soil before irrigation. The SAK
values \vere below the maximum recommended level of 9 (Figures 1 l b and 12a and b). These results
substantiated the findings of Tauk a n d Medeiros16 who reported increases in calcium and magnesium
concentration in the t o p layer of a soil irrigated with a single dose of 80 m3/ha of ra\v \#inasses
(equivalent to a 500 m3/ha*year or 0.2 cm/wk).

CONCLUSIONS
1. The anaerobic treatment of vinasses a t 35C in a fluidized bed process was reliable and

efficient, reaching 70% C O D removal a n d 8 m3/m3.day biogas productivity. The intensity limit for the process was approximately 38 kg COD/m3-day loading rate, beyond
\vhich acidogenic excursions impaired the reactor performance.
6

0.15

W SOIL
~VINASE

0.6
AVERAGE DEVM (m)

12

0ANAJZREFFL@lOcmhv aANAEREFFL@Scmhut
TAP WATER

Figure 10. Organic matter contents profile in lysimeters. Key: SOIL: results in soil before irrigation.
The other results were obtained after 6 months of irrigation with the corresponding influents.

HECTOR M. POGGI-VARALDO

79 7

E: t
0.1s

0.6
AVERAGE DEPTH (m)

1.2

a is

@.6

L2

AVERAGE DEPTH (m)

Figure 11. Conductivity and S A R profiles in lysimeters; Ila-Electrical conductivity in the extract;
llb-SAR in the extract. See Key in Fig. 10.

2. The performance of the A N F B E D at sub-optimal temperature (25C) was dependable at


loading rates near 10 kg COD/m3.day. It removed approximately 60Vo of the incoming
C O D a n d the biogas productivity attained 4 m3/m3.day. At 17 kg COD/m3*day the
reactor showed acidogenic upsets.
3. The aerobic fluidized bed reactor removed more than 85% of incoming colour and
organic matter when fed dilute anaerobic effluent (30% to 60% by volume) during the
acclimation stages. At the time of receiving whole anaerobic effluent, the reactor did not
accomplish any colour reduction. The C O D reduction was SO%, almost independent of
the loading rate in Ihe range of 3 to 35 kg COD/m3.day.
4. The effluent from the series ANFBED-AEFBED would need further treatment for
discharging into water bodies.
5 . The lysimeter irrigated with anaerobic effluent at 5 cm/wk showed the highest organic
load removal (near 90% C O D reduction). However, the S A R reached very high values,
sodium and potassium exchanged for calcium in the soil matrix, and the soil p H
increased up to 9. The load of monovalent cations seemed to be the limiting factor of the
irrigation rate.
6. The lysimeters irrigated with anaerobic effluent 10 cm/wk a n d raw vinasse exhibited
organic matter accumulation and electrical conductivity increase, as well as inferior
C O D removal.

798

4 7 PURDUE
~ ~
UNIVERSITY INDUSTRIAL WASTE CONFERENCE PROCEEDINGS

so

0.1s
loo

0.6

..1

1.i

AVERAGE DEPTH (m)

a 1s

a6

L2

AVERAGE DEPTH (m)

Figure 12. Cation profiles in lysimeter. 12a-Calcium concentration; 12b-Sodium concentration. See
Key in Fig. 10.

The series anaerobic-aerobic treatment did not produce an effluent quality for discharging in \\rater
bodies. On the other hand, anaerobic treatment followed by irrigation at I O U rates could be a feasible
alternative for vinasse treatment a n d disposal, provided close monitoring a n d irrigation strategies
(combining anaerobic effluent dilution, calcium supplementation, intermittent irrigation and drainage) are adopted to mitigate adverse impacts on soil structure a n d fertility.
ACKNOWLEDGMENTS

Financial support from the CINVESTAV, the Project TAEK-CIEA, and A Z U C A R S.A. is gratefully acknowledged. The authors thank Dr. Fernando Esparza-Garcia, Head of the Dept. of Biotechnol. and Bioeng., CINVESTAV, for his continued support a n d understanding. The authors are
indebted to Prof. Carmen Duran-de-Bazua, Faculty of Chemistry, UNA!vI, \ f r . Luis E. Zedillo, (at
that time Director of R&D, IMPA, AZUCAR S.A.), Prof. A . Noyola, UNA\I, a n d Dr. S. Gonzalez,
U N A M for their consistent help a n d encouragement; Dr. Pedro Medellin, Director of UASLP and
staff of the UASLP for their significant contribution with soil analysis; and the managers and staff of
the sugarcane mill Alianza Popular for logistics and laboratory support.
LIST OF ABBREVIATIONS

ANFBED

Anaerobic fluidized bed reactor

AEFBED

Aerobic fluidized bed reactor

HECTOR M. POGGI-VARALDO

COD

Chemical oxygen demand

CAC

Granular activated carbon

HR

Hydraulic rate

HRT

Hydraulic retention time

LR

Loading rate

LYS

Lysimeter

VOA

Volatile organic acids

SAR

Sodium adsorption ratio

799

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h4ex. Ing. Sanit. y Amb., Mexico D.F., Mexico (in Spanish) (1982).
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(1989).
3. Duran-de-Bazua, C.; h4.A. Cabrero, and H . M . Poggi. Vinasses Biological Treatment by Anaerobic and Aerobic Processes: Laboratory and Pilot-plant Tests, Bioresour. Techno/., 35( 1):87-93
(1991).
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Anaerobic and Aerobic Treatments, CINVESTAV-UNAM-UASLP, Mexico D.F., h4exico
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UNIVERSITY INDUSTRIAL WASTE CONFERENCE PROCEEDINGS

23. Rao, A.V.S.P., J . Karthikeyan, and L. lyengar. Removal of Color from Distillery Wastewater,
Proceedings, 44th Pirrdue Industrial Wasre Conference, Lewis Publishers, Chelsea, MI ( 1 990.
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