Professional Documents
Culture Documents
P 05406
80
DISTILLERY SLOPS
FROM THE SUGAR CANE INDUSTRY
HPctor M . Poggi-Varaldo, Associate Professor
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
LEACHATE
Figure 2.
47th Purdue fndusirial lVus/e Conference Proceedings, 1992 Lewis Publishers, Inc.. Chelsea, Michigan 481 18.
Prinred in U.S.A.
789
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
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
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
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
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
0.08
n. I2
fed)
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 )
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
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
Figure 7 .
Aerobic treatment of the anaerobic effluent in the AEFBED-steady state average results.
HECTOR M. POGGI-VARALDO
795
' 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
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
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.
798
4 7 PURDUE
~ ~
UNIVERSITY INDUSTRIAL WASTE CONFERENCE PROCEEDINGS
so
0.1s
loo
0.6
..1
1.i
a 1s
a6
L2
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
AEFBED
HECTOR M. POGGI-VARALDO
COD
CAC
HR
Hydraulic rate
HRT
LR
Loading rate
LYS
Lysimeter
VOA
SAR
799
REFERENCES
1. Espino de la O., E . Bi-national Symp. on Wastewater Treatment and Reuse U.S.A.-Mexico, SOC.
h4ex. Ing. Sanit. y Amb., Mexico D.F., Mexico (in Spanish) (1982).
2 . Tauk, S.31. Vinasses: waste or by-product?, Ciencia Hoje (Brazil), 9(54):68-72 (in Portuguese)
(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).
4. Zedillo, L.E. Internal Report, Institute for Sugar Production (IhiiP.4), Azucar S.A., Mexico
D . F . , hlexico (in Spanish) (1990).
5 . Chiesa, S . C . , and J.F. Manning. Resource a n d Energy Recovery Options for Fermentation
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( i n Spanish) (1988).
7. Poggi-Varaldo, H . M . , and C. Duran-de-Bazua. The Sugarcane Industry Effluents as Renewable
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Facrory: A Case Study of Comparison Between Anaerobic Technologies, Water Sei. Techno/.
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Hawaii, Water Sei. Techno/. 22(9): 13 1-140 (1990).
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(1987).
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CINVESTAV and UASLP, S.L.P., Mexico (in Spanish) (1989).
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14. Sfandard Methods for the Examination of Water and Wastewater, 16th edition, Amer. Public
Health Assoc., Washington, DC, 1985.
15. DiLallo, R., and O . E . Albertson. Volatile Fatty Acids by Direct Titration, J . Water Pollut.
Control f e d . , 33:356-365 (1961).
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Monitoring, CINVESTAV del IPN, Mexico D.F., Mexico (in Spanish) (1987).
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McGraw-Hill, 2nd. edition, 1979.
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fumigatus, Agric. Biol. Chem., 5 1 :3339-3345 (1988).
I
800
4 7 PURDUE
~ ~
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.
24. Sweeney, D.W., and D.A. Graetz. Chemical a n d Decomposition Characteristics of Anaerobic
Digester Effluents Applied to Soil, J . Environ. Qual., 17:309-3 13 (1988).
25. Crites, R.W., E.L. Meyer, and R.G. Smith. Land Treatment of Municipal \Yastewater, Process
Design h4anua1, EPA 625/1-81-013, U.S.E.P.A., Cincinnati, O H , 1981.
26. T a u k , S . M , and Medeiros. Nutrientes e atividade enzimatica em latossolo Vermehlo-Amarelo
textura media, tratado corn vinhaqa, sob cultura de milho, Ecletica Quim. 14:83-94 (Sa0 Paulo,
Brazil; in Portuguese) (1989).