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Cover Story

TREATING INDUSTRIAL WASTEWATER:

Anaerobic Digestion
Comes of Age
Anaerobic treatment systems offer important
advantages over conventionally applied
aerobic processes for removing organic
pollutants from water-based streams FIGURE 1. This comparison shows the respective
fate of organic materials that are biodegraded under
aerobic versus anaerobic conditions. Aerobic treat-
Robbert Kleerebezem, Technical University of Delft ment requires energy input for aeration, whereas a
and Herv Macarie, Institut de Recherche pour le Dveloppement, net energy surplus is generated during anaerobic
Universit de Provence et de la Mditerrane treatment, in the form of methane-bearing biogas
that can be used to power utility boilers onsite

n the absence of molecular oxygen, wastewater constituents on anaerobic the production of byproduct methane-

I natural environments depend on


the activity of anaerobic microor-
ganisms for the biological degrada-
tion of organic substrates. In
anaerobic environments where, other
than carbon dioxide, no inorganic elec-
tron acceptors are present, the final
microbes. As a result, it is the opinion
of these authors that such systems are
not currently being applied as widely
as they could be within the global
chemical process industries (CPI).
This article aims to address some of
the lingering misconceptions associ-
rich biogas. The use of the methane for
energy generation elsewhere at the
plant allows for conservation of more
than 90% of the caloric value of the or-
ganic substrates being treated. In addi-
tion, modern anaerobic bioreactors do
not require large energy input for me-
degradation of organic compounds is ated with anaerobic wastewater treat- chanical mixing (which is required to
achieved by their conversion to ment. It provides a description of the maintain adequate aeration during aer-
gaseous methane and carbon dioxide. microbiological basis of anaerobic obic treatment).
As discussed here, wastewater-treat- biodegradation, and defines the By comparison, during aerobic
ment systems that rely on the anaero- boundary conditions required to en- treatment, most of the caloric value of
bic digestion process for the removal able anaerobic treatment. the organic substrates is dissipated as
of organic pollutants in industrial A brief discussion of the pros and non-recoverable heat. And, aerobic
wastewater streams offer important cons of todays leading anaerobic bioreactors require significant
advantages over conventionally ap- bioreactor designs is also provided, amounts of energy for aeration.
plied aerobic processes. along with some simple calculations 2. The anaerobic digestion produces
Discussed in detail below, and sum- and basic guidelines for selecting the typically five to ten times less biomass
marized in Figure 1, are several of the best bioreactor design for the waste per unit of organic substrate con-
most compelling operational advan- stream at hand. Finally, the article verted than comparable aerobic
tages and sources of cost savings asso- provides a list of organic compounds processes. Since the disposal or treat-
ciated with using anaerobic biological- that have proven to be degradable ment of waste sludge may account for
treatment systems. using anaerobic digestion, and in- 50% or more of the total waste-treat-
Despite these demonstrable perfor- cludes several tables that summarize ment costs, the ability to reduce
mance and cost-saving advantages the current status of commercial- sludge production is a major advan-
and the fact that nearly 1,600 com- scale, anaerobic-treatment systems tage of anaerobic treatment.
mercial installations are currently in throughout the global CPI. 3. All microorganisms require nutri-
operation around the world anaero- ents, such as nitrogen, phosphorus and
bic wastewater treatment still re- Primary advantages sulfur, for growth. However, many
mains something of a mystery to Listed here are some of the leading op- chemical and petrochemical waste-
many chemical process operators. erational advantages and sources of cost water streams contain relatively low
Many operators still harbor miscon- savings associated with using anaerobic levels of these nutrients.
ceptions and prejudices about the poor biological-treatment systems: If insufficient nutrient concentra-
biodegradability and presumed toxic- 1. Anaerobic treatment is in principle tions are present, additional nutrients
ity of chemical and petrochemical an energy-generating process through must be dosed into the wastewater to
56 CHEMICAL ENGINEERING WWW.CHE.COM APRIL 2003
TABLE 1. ANAEROBIC SCORECARD:
NUMBER OF SYSTEMS, BY REACTOR TYPE
Number of commercial scale reactors built in the world by January 2003 for treat-
ing different kind of industrial wastewaters and sewage*.
Type of wastewater Type of reactor (see Figure 4 for reactor types)
Low- AC Fixed- Moving- UASB EGSB Total
sustain the process. Since the amount rate bed bed number
of nutrients to be dosed is directly re-
Food and related Industries
lated to the amount of biomass
Brewery and malt 2 6 4 185 88 285
formed, the nutrient loads required
Distillery & ethanol 25 31 40 76 9 181
for anaerobic treatment systems are
Beverage 0 3 11 2 88 15 119
significantly lower than for aerobic
Sugar production 49 7 1 34 3 92
systems.
Potato processing 14 4 2 46 10 76
4. Despite the relatively low bio-
Dairy, ice-cream & cheese 12 10 10 2 27 6 67
mass production that typify most
Starch production 2 9 10 2 32 7 64
anaerobic digesters, higher biomass
Yeast production 7 8 6 25 8 54
concentrations can be achieved in
Candy / Confectionery 4 3 15 2 24
todays anaerobic bioreactors. In gen-
Citric acid production 2 3 1 1 3 5 15
eral, higher biomass concentrations
Coffee processing 7 4 1 12
enable higher volumetric treatment
Wine processing 6 1 3 1 11
capacities, thereby minimizing the re-
Fish & seafood processing 1 4 2 1 8
actor volume and footprint required.
Miscellaneous 10 22 40 5 112 25 213
Non-food industries
Heading for a breakdown
Pulp-and-paper 1 16 5 3 75 37 137
Thanks to the voracious appetites of
(Petro)chemical 3 4 43 1 20 20 91
so many types of aerobic microorgan-
Leachates 6 18 24
isms, and the robustness of the tradi-
Pharmaceutical 4 1 2 6 3 16
tional aerobic activated-sludge
Pig, cow manure & poultry 5 3 6 1 15
process, aerobic wastewater treat-
Textile 1 4 2 7
ment has long reigned as a leading
Natural rubber 3 3 6
method for managing organics-laden
Sludge & sludge liquor 1 2 1 1 5
industrial wastewater streams. The
Tobacco manufacture 4 4
activated-sludge process takes place
Tannery 3 3
in open basins, equipped with surface
Fluegas desulfurization 1 1
or submerged aeration facilities for
Electronic components 1 1
transferring molecular oxygen from
Sewage 2 1 64 67
air to the liquid phase.
Number of reactors
During respiration, aerobic microor- per type 93 167 219 24 852 244 1,599
ganisms use molecular oxygen to con- *NOTES: Low-rate reactors include CSTR, lagoons and reactors from the firm ADI-BVF. 80% of the
vert complex organic compounds into plants reported are from BVF, which offers one of the few low-rate systems commercialized as a
turnkey package, and for which statistics exist. AC = Anaerobic Contact; UASB = Upflow Anaero-
carbon dioxide, water, and large quan- bic Sludge Bed; EGSB = Expanded Granular Sludge Bed. The fixed-bed systems reported corre-
tities of residual biomass. Whereas spond for 44% to upflow anaerobic filters (UAF); 26% to downflow filters (DAF); and 30% to hybrid
reactors. UASB reactors include reverse Dorr-Oliver clarigesters. Both upflow fluidized-bed reac-
roughly 50% of the organic substrate is tors and the AnAerobics Mobilized Film Technology are classified as moving-bed reactors. They rep-
respired, the remaining 50% is con- resent, respectively, 79% and 21% of this group of reactors. The Biothane Biobed EGSB (43% of the
units) and Paques IC (57% of the units) systems conform to the expanded sludge bed class (EGSB)
verted to biomass. The low levels of of reactors. The data presented here have been compiled from the January 2003 reference list [10]
residual organic compounds that are of ADI (Canada), Biotec (Colombia), Biotecs (Brazil), Biothane (USA/Netherlands), Entec (Austria),
Global Water Engineering (ex-Enviroasia, Germany), Paques (Netherlands), Proserpol (France),
typical in aerobically treated effluent Purac (Sweden), Sinko Pantec (Japan) and older reference lists of AnAerobics (2001, USA), Applied
Technologies (1999, USA), Badger (1994, USA), Biotim (2000, Belgium), Grontmij (1998, The
often allow for direct discharge of the Netherlands) and Ondeo-Degrmont (1999, France), as well as data from the literature and the au-
treated stream to surface waters. thors files. Care has been taken not to double count units reported in different reference lists due
to commercial agreement between companies (i.e. Shinko Pantec with Badger and Grontmij;
By comparison, anaerobic microor- Biotecs with Biotim and Global Water Engineering). The data reported here correspond to treat-
ganisms convert organic compounds ment plants. This means that various units on one site have been considered as one sole reactor, un-
less the technology used changed at the occasion of a treatment expansion. As for the low-rate re-
are into biogas consisting of methane actors, the number of plants treating sewage is probably much more important than the given one.
and carbon dioxide. Only 510% of the Actually, most of these plants are designed by a large variety of local engineering companies diffi-
cult to identify, which is particularly true for Latin America.
organic compounds are converted to
biomass. Despite the lower volume of the order of 5 to 40 kg of chemical oxy- also has some limitations. For instance,
biomass produced per unit of sub- gen demand (COD) per m3 reactor per the lower biomass production per unit
strate converted, higher biomass con- day; see the box on p. 59 for more on of substrate removed is an advantage
centrations (2035 kg of dried solids COD]. Higher treatment capacities when considering the amount of sur-
per m3) can be achieved in so-called also allow for the design of compact re- plus sludge to be disposed, but becomes
high-rate anaerobic bioreactors. actors, with small footprints. a disadvantage when considering the
Since the volumetric treatment ca- time needed for startup of an anaerobic
pacity is directly related to the bio- Anaerobic limitations treatment system. If no specifically
mass concentration achieved, such While the cost and performance advan- suitable biomass is available in suffi-
high-rate bioreactors result in higher tages of anaerobic digestion, as noted cient quantities, startup of the system
volumetric treatment capacities [on above, can be compelling, this approach may require up to several months. This
CHEMICAL ENGINEERING WWW.CHE.COM APRIL2003 57
TABLE 2. A SAMPLING OF ANAEROBIC SYSTEMS, BROUGHT ONLINE,1989EARLY 2003
Commercial-scale anaerobic wastewater treatment plants built in the chemical & petrochemical industries (for a detailed list
of plants built from 1981 to 1999, see Ref. [10]).*
Reactor Year Company Industrial produc- Type Organic COD Constructor,
number of con- and tion generating of Load removal references
struction location the wastewater reactor Ton COD/d %
1 1989 K. Chemical, Dyestuff raw material UAF 4.8 80 Shinko
Hyogo, Japan (BOD5) Pantec
2 1992 Undisclosed, PET UASB 6 Enviroasia
Taiwan
3 Changzho Worldbest PET Hybrid 1.7 Biotim
Radici, China
4 BP Amoco, Cooper PTA DAF 80-85 BP Amoco
River, SC, USA (TOC)
5 1994 Baek Hwa Co. Alcohols EGSB 2.5 75** Biothane
Korea
6 1996 APR, pH liquor rayon pulp UASB 40 65** Paques
Kamalapuram, India 85 (BOD5)
7 1996 Copenor Formaldehyde, formic acid, EGSB 2.2 60** Biothane
Brazil sodium formate, polyols,
Hexamethyleneamine
8 1997 Eastman Chem. Co. Oxo - chemicals EGSB 12.5 92 Biothane1
Singapore
9 1997 Hyosung Industries Plastics EGSB 0.9 75** Biothane
Korea
10 1997 Procter & Gamble Soap / detergent Hybrid 3 70** ADI
Indonesia***
11 1999 M. Gas Chemical PTA UASB 6 75 Shinko
Okayama, Japan (BOD5) (BOD5) Pantec
12 2000 BP-Amoco Chem., PTA IC Paques
Kuantan, Malaysia
13 2000 SKW Trotsberg Metallurgi EGSB 6.7 80** Biothane
Germany
14 2000 Borsudchem Co. PU / PVC EGSB 10.7 80** Biothane
Hungary
15 2000 Reliance Industries, PTA EGSB 25.2 70** Biothane
Maharastra, India
16 2000 Sam Nam Petro- PTA Hybrid 6 75** ADI
chemicals, Korea
17 2000 PT Bakrie Kasei Corp., PTA Hybrid 18.8 75** ADI
Indonesia
18 2001 Getec, Sorbitol, manitol, food IC 7.5 80 Paques
So Gonalo, Brazil taste additives
19 2001 Yizheng Chem. Fiber PTA UAF 81.6 80** Global Water
China Engineering
20 2001 Interquisa, Canada PTA EGSB 26.3 75** Biothane
21 2002 Toray Industries PTA IC 16.8 75 Paques
Tokai, Japan
22 2002 SUT IWWT Various (13 chem. plants) EGSB 20.8 60** Biothane [13]
Singapore
23 2002 Procter & Gamble Soap / Detergent Hybrid 2.7 75** ADI
Thailand
24 2003 Celanese, Cangrejera Alcohols, derivates Hybrid 9.6 > 90** Celanese
Mexico of acetic acid, amines,
ketones and acrylates
* NOTES: The abbreviations are the same as in Table 1; PET = polyethylene terephthalate; PTA = purified terephthalic acid; PU = polyurethane;PVC
= polyvinyl chloride; TOC = total organic carbon. Plant #4 must be operated similarly to the other DAF designed by BP Amoco at three of its PTA
production facilities. The TOC removal is estimated from the one previously given for these units [10]. This plant is planned to be replaced by a UASB
system. Plants number 16 & 17 correspond to expansions of the treatment capacity of already existing anaerobic plants. The information reported in
this table comes from the same source as in Table 1, and from Yan et al. [13]. ** Design values. *** Factory closed down.

effect may become even more pro- generally longer for anaerobic systems the treatment of strongly dilute
nounced because most specific anaero- than for aerobic ones. wastestreams (those with less than 0.5
bic microorganisms are capable of de- Another point to be considered is kg of COD per m3 wastewater).
grading a limited range of substrates. that the treated effluent from an anaer- Higher concentrations of organic
This means that seeding an anaerobic obic bioreactor typically has (slightly) compounds in anaerobically treated
bioreactor for the treatment of a specific higher effluent concentrations of or- effluent also implies that some form of
type of wastewater with biomass ob- ganic materials, compared to aerobi- post-treatment such as aerobic bio-
tained from a reactor treating another cally treated effluent (0.1 to 0.5, versus logical treatment, or various types of
type of wastewater may still take up to 0.05 to 0.2, kg of COD per m3 of treated physical-chemical treatment will be
1 month. Analogously, the time re- wastewater). In general, this makes required before discharge to surface
quired to recover from a process upset is anaerobic digestion less suitable for waters. In general, anaerobic diges-
58 CHEMICAL ENGINEERING WWW.CHE.COM APRIL 2003
CHEMICAL OXYGEN DEMAND (COD)
he COD concept is a lumped concept that is used to represent the concentration and
Cover Story
T the oxidation state of organic materials that are present in a water-based stream
[1]. The COD concentration corresponds to the concentration of oxygen that is re-
quired for the full oxidation of all organic carbon into carbon dioxide and water.
The units that are typically used to describe the COD concentration of a wastewater are
tion is better-suited for removing the kg of COD per m3 of wastewater, or kg of O2 per m3 of wastewater. For solutions of a
bulk of organic materials from rela- known composition, the COD-equivalent concentration can be calculated from the stoi-
tively concentrated wastestreams chiometry of the combustion reaction of the organic compounds. Combustion of ethanol
(those containing more than 4 kg of for example can be described as:
COD per m3 of wastewater). C 2H 5OH + 3O 2 2CO 2 + 3H 2 O (1)
Still, the evident advantages pre-
dominate these potential shortcom- Consequently, to obtain COD-equivalent concentrations the conversion factors of 3
mol-O2 per mol-ethanol, or 2.09 g-O2 per g-ethanol, have to be applied. In general
ings of anaerobic wastewater treat-
terms, the combustion reaction of an organic compound containing the atoms C, H, O,
ment, as reflected by the nearly 1,600 and N (with the oxidation state of ammonia being III) can be written as:
full-scale reactors that are now in com-
4 x + y 2 z 3 v u y 3 v u
mercial service worldwide (Table 1). C x H yO xN vu +
4
O 2 x CO 2 +
2
( )
H 2 O + v NH 4+ + u v H + (2)
To date, anaerobic treatment has
evolved to become the dominant treat- and the corresponding conversion factors can be calculated.
ment method for brewery, distillery,
and numerous food-processing waste- It should be noted that lag periods Toxicity
waters, and has demonstrated great po- prior to the degradation of some an- Numerous organic and inorganic
tential for treating more-complex waste thropogenic organic by anaerobic inoc- chemicals may have either a re-
streams. Examples include sewage, ula from natural environments can be versible or irreversible toxic effect on
and wastewater produced by the chem- very long. The natural inocula contain microorganisms. Irreversible toxic
ical, petrochemical and pulp-and-paper a very limited number of microorgan- properties are generally related to the
industries. isms that can degrade these sub- presence of highly reactive functional
Still, since less than 15% of all anaer- strates, and they often need several groups, such as aldehyde, or nitro-
obic wastewater-treatment systems months of growth before measurable groups. Temporary exposure to ele-
are currently in use by such CPI facili- conversion rates are achieved. vated concentrations of some cations,
ties, a large potential expansion seems For example, for the anthropogenic organic acids or unfavorable pH val-
possible in the future. A summary of phthalic acid isomers, it has been ues generally has a reversible toxic ef-
anaerobic bioreactors constructed be- shown that the lag periods prior to fect on microorganisms.
tween 1989 and early 2003 in the CPI quantifiable degradation were in the Anaerobic processes have a notori-
is shown in Table 2. This table is an up- range of 20 to 100 days, depending on ous reputation for being very suscepti-
date of a longer compilation [10]. the origin of the inoculum and the ori- ble to process upsets as a result of in-
The implementation of anaerobic entation of the carboxylic groups on hibition by toxicants. However
wastewater treatment in chemical the benzene ring [7]. contrary to a still-common belief
and petrochemical applications has, Meanwhile, compounds that were anaerobic microorganisms, particu-
for decades, been hampered by the found to be persistent in anaerobic en- larly methanogenic Archaea, are not
presumed limited biodegradability of vironments include benzene, and sev- more susceptible to toxic compounds
numerous substrates, and the pre- eral molecules containing tertiary- than aerobic bacteria, except in the
sumed susceptibility of primarily substituted carbon or ether bonds [i.e., case of chlorinated aliphatic hydrocar-
methanogenic Archaea toward poten- methyl tert-butyl ether (MTBE), tert- bons [2]. Still, wastewaters containing
tial toxicants in petrochemical waste- amyl methyl ether (TAME), ethyl tert- elevated concentrations of potential
waters. For both limitations, commer- butyl ether (ETBE)]. It should be toxicants will require specific pre-
cial experience has demonstrated that noted, however, that several of these treatments before either anaerobic or
this is true only to a very limited ex- compounds are similarly hard to de- aerobic biological treatment. In some
tent; this is discussed further below. grade in aerobic environments. cases it was found to be possible to
It should also be noted that some treat toxic wastewater by acclimation
Target compounds compounds that are persistent in aero- of the biomass or by application of spe-
The range of compounds that have been bic environments are susceptible to cific reactor designs.
found to be degradable in methanogenic partial conversion or even complete
environments has increased enor- degradation in methanogenic environ- Environmental factors
mously during the past three decades ments. Examples include polyols (such Petrochemical and chemical waste-
(Table 4). In general, most aliphatic and as pentaerythritol, trimethylol- waters typically have a temperature
homocyclic aromatic compounds can be propane, azo-dyes, nitroaromatics and of 30 to 70C. Anaerobic digestion has
degraded in methanogenic environ- polychlorinated aromatic and aliphatic successfully been applied within two
ments, as long as they have at least one compounds, including tri-, tetra-, pen- temperature ranges: 3040C and
oxygen-containing functional group. tachlorophenol, tetrachloroethylene). 5065C. In both zones, specialized
Even some aromatic hydrocarbons, In some cases, a hybrid treatment microorganisms develop, enabling the
such as toluene and o-xylene, are com- scheme, which involves the use of both application of the process in the full
pletely fermented to methane and car- anaerobic and aerobic digestion, is re- range of wastewater temperatures
bon dioxide in an anaerobic biodegra- quired to achieve full degradation of that are typical of CPI operations.
dation system [3]. these substrates. By comparison, at elevated temper-
CHEMICAL ENGINEERING WWW.CHE.COM APRIL2003 59
TABLE 4. ORGANIC COMPOUNDS THAT ARE CANDIDATES
FOR ANAEROBIC DIGESTION
Partial list of organic compounds known to be biodegradable under
Cover Story methanogenic conditions and susceptible to be present in the effluents of chemi-
cal & petrochemical industries*.
Aromatic compounds (homocyclic & heterocyclic)
Benzene Formylbenzene (benzaldehyde) (cont.)
atures, aerobic treatment systems can methylbenzene (toluene) 4-hydroxy-3-methoxy-
suffer, due to decreased oxygen solu- 1,2-dimethylbenzene (o-xylene) benzaldehyde
bility (partly compensated by higher Carboxybenzene (benzoate) Hydroxybenzene (phenol)
oxygen mass-transfer rates), higher o, m, p-amino, chloro, iodo, methyl o-aminophenol
heat production, and the large amount & methoxybenzoate o, m, p-chloro, hydroxy, methoxy
o-nitrobenzoate & nitrophenol
of water that will be evaporated. mono, di, tri-hydroxybenzoate 2,4 -dichloro, 3,4-dichloro
Optimal conversion of organic sub- 3,5-dichlorobenzoate & 3,5-dichlorophenol
strates in anaerobic environments oc- 3-chloro,4-hydroxybenzoate pentachlorophenol
curs at around neutral pH values. 2-acetylbenzoate (acetylsalicylate) trihydroxybenzene
3,4,5-trimethoxybenzoate m, p-methylphenol (m, p-cresol)
Since acidic carbon dioxide is one of
4-hydroxy-3- methoxybenzoate 2,6-dimethoxyphenol
the end products of the anaerobic di- 4-hydroxy-3,5-dimethoxybenzaote Nitrobenzene
gestion process, a basic compound ei- o, m, p-dicarboxybenzene 3-nitrobenzene sulfonate
ther needs to be present in the waste- (phthalates) phenylacetate
water, or it needs to be dosed in, dimethyl o-phthalate & p-phthalate phenylpropenoate (cinnamate)
typically in the form of sodium hy- diethyl o-phthalate phenylpropionate (hydrocinnamate)
di-n-butyl o-phthalate 3-methoxy-4-hydroxy cinnamate
droxide or carbonate. Butylbenzyl o-phthalate 4-hydroxyphenylalanine (tyrosine)
In presence of sufficient neutralizing Formylbenzene (benzaldehyde) Benzyl alcohol
capacity (alkalinity), both gaseous car- 4-hydroxy-3,5-dimethoxy- 4-hydroxy benzyl alcohol
bon dioxide and bicarbonate will be benzaldehyde
2-furaldehyde (furfural)
formed, resulting in a strongly buffered
Aliphatic compounds
system with a pH around 7. Depending
Hydrogen cyanide Alcohols
on the oxidation state of the organic pol-
Acids C1 to C8 n-hydroxyalkanes
lutants, and the strength of the waste- & i-butanol
C1 to C18 n-carboxyalkanes
water, the biogas produced will typi- 4-aminobutyric 1-amino-2-propanol
cally contain about 30% carbon dioxide. glyoxalic & 3-methylbutanol
In order to achieve a pH around 7 at a 2-hydroxypropanoic (lactic) butylene, ethylene & propylene
3-hydroxybutanoic & propanoic glycol (diols)
carbon dioxide concentration in the bio- di, tri & polyethylene glycol
i-butyric & i-valeric
gas of 30%, roughly 40 equivalents of bi- acrylic, -methylacrylic (crotonic) (up to MW* 20,000)
carbonate per m3 of wastewater needs & 2-propenylacrylic (sorbic) glycerol (triol)
to be present in the reactor. C2 to C6 n-dicarboxyalkanes Esters
It should be noted that the actual 4-aminoadipic ethyl, methyl & vinyl acetate
cis & trans-1,2-ethylenedicarboxylic butyl, ethyl & methyl acrylate
pH inside the anaerobic reactor can be
(maleic & fumaric) methyl n-, i-butyrate & propionate
significantly different from the influ- 2-hydroxy-1,2,3-propanetricarboxylic Ethers
ent pH. Wastewaters containing high (citric) ethylene glycol monomethyl ether
concentrations of biodegradable or- Aldehydes (2-methoxyethanol)
ganic acids (>100 eq. per m3 of waste- C1 to C4 n-formylalkanes ethylene glycol monoethyl ether
water) and a low pH (~ 4), for example, 2-butenal (crotonaldehyde) (ethoxyethanol)
2-propenal (acrolein) methyl butyl ether
can be treated in a well-mixed reactor.
Amines Ketones
Treatment is possible as long as at sec-butylamine acetone
least about 40 eq. of the acids per m3 of methyl, dimethyl, ethyldimethyl methyl ethyl ketone
wastewater are neutralized. Assuming & trimethylamine
* MW: molecular weight.
that all organic acids are degraded in triethanolamine
the reactor, this will result in the for-
mation of 40 eq. bicarbonate per m3 sludge and the organic fraction of mu- Uncoupling the biomass or solid re-
wastewater and a pH around 7. nicipal solid waste. tention time (SRT) from the HRT can
The hydraulic retention time (HRT) increase the volumetric treatment ca-
Engineering aspects in CSTR-type reactor is determined by pacity of an anaerobic bioreactor treat-
Figure 4 provides a comparison of six the specific growth rate of the slowest- ing dissolved substrates. Initially, bio-
widely used bioreactor designs, and growing microorganism in the system. mass separation from the
provides optimal values for design This generally means that very high biomass-wastewater mixture in the
boundary conditions that need to be HRT values are required to achieve an CSTR-type reactor was achieved by
observed during design. A brief de- acceptable level of degradation gravitational sedimentation in an ex-
scription of each is provided here. (roughly 25 days). The high HRT val- ternal settler. During operation, set-
Continuously stirred tank reac- ues make the CSTR concept less feasi- tled biomass is fed back to the CSTR-
tors (CSTR) were the first anaerobic ble for treatment of the wastestreams type reactor, increasing the volumetric
bioreactors to be built, and are still considered here, containing primarily degradation rates in the system. This
widely used for anaerobic digestion of dissolved organic compounds at mod- approach is called the Contact
wastes with a high concentration of erate concentrations (430 kg of COD process, and is fully comparable to the
particulate matter, such as sewage per m3 of wastewater). aerobic activated-sludge process.
60 CHEMICAL ENGINEERING WWW.CHE.COM APRIL 2003
MICROBIAL ASPECTS OF ANAEROBIC DEGRADATION
n environments where inorganic electron

I acceptors are absent, microorganisms de-


pend on fermentation reactions to biode-
grade organic substrates. In these
FIGURE 2 (left). Shown here is the
stepwise degradation of organic
materials in an anaerobic or
methanogenic treatment environment
methanogenic environments, the final prod-
ucts of the fermentation reactions are
methane, carbon dioxide and ammonia.
From an energy perspective, the fermenta-
tion of organic substrates to methane and car-
bon dioxide yields much less energy for the
microorganisms than the oxidation with inor-
ganic electron acceptors (Table 3). This is the FIGURE 3. This microbial culture a
main reason why methanogenic degradation mixed, anaerobic culture enriched on
ortho-phthalate consists of at least
of organic substrates only occurs in the ab-
three different types of microorganisms:
sence of external electron acceptors. anaerobic, phthalate-oxidizing bacteria;
Furthermore, the free energy yields are di- and acetate-fermenting and CO2-reduc-
rectly coupled to the biomass yields of the mi- ing methanogenic Archaea
croorganisms. Consequently, the amount of
biomass formed per unit of organic substrate TABLE 3. ENVIRONMENTALLY IMPORTANT ELECTRON ACCEPTORS
converted is much higher in aerobic or deni- AND THEIR STANDARD REDOX POTENTIALS (E01) AND STANDARD FREE
trifying environments compared to ENERGY CHANGES (G01) FOR REDUCTION*
methanogenic environments. Since the rate of Electron couple Reaction E 01 G01
electron transfer per unit of biomass is basi- [V] [kJ/e]
cally independent of the electron acceptor [6], Mn III/Mn II manganese reduction 1.48 -142.6
the different energy yields form the basis of O2/H2O aerobic respiration 0.82 -78.7
the main differences between biological Fe III/Fe II iron reduction 0.77 -74.3
wastewater-treatment concepts for the re- NO 3-/N2 denitrification 0.75 -72.1
moval of organic compounds.
H+/H 2 proton reduction -0.41 39.9
Degradation of complex substrates in
methanogenic environments involves a complex SO 42-/HS- sulfate reduction -0.26 25.1
network of different types of microorganisms. CO2/CH4 methanogenesis -0.24 23.6
Full conversion to methane and carbon dioxide * Corrected for a biologically favorable pH of 7.0.
results from a biological chain reaction, where
one type of microorganism generates the substrate consumed by the ited number of alcohols and volatile fatty acids. In the subsequent step
subsequent organism in the chain. A schematic overview of the indi- of the chain reaction, acetogenic bacteria anaerobically oxidize al-
vidual steps in the degradation of polymeric substrates in cohols and fatty acids to the two main precursors of methane pro-
methanogenic environments is shown in Figure 2. duction; namely, acetate and molecular hydrogen. Methanogenesis
Hydrolysis of polymeric substrates (such as carbohydrates, proteins through acetate fermentation, and carbon dioxide reduction with
and fat) to the corresponding monomers is generally assumed to be molecular hydrogen, are both catalyzed by Archaea, which repre-
catalyzed by extracellular enzymes that are excreted by acidogenic sent a distinct group of microorganisms. An example of a mixed
bacteria. These acidogenic bacteria ferment the monomers to a lim- methanogenic culture degrading phthalate is shown in Figure 3.

However, the maximum biomass vides adequate mixing of the sludge- tributed to the spontaneous formation
concentration that can be achieved in water mixture to avoid preferential of large, dense biomass conglomerates
these systems is usually limited to 46 channeling in the sludge bed, and ex- in the reactor compartment. This so
kg per m3 of reactor. This relatively low cludes the need of mechanical mixing. called methanogenic granular sludge
value for the biomass concentration is Biogas is collected in the three- (shown in Figure 5) plays a key role in
the result of the poor settling charac- phase separator that is operated at a the high SRT values that can be
teristics of methanogenic sludge, partly low overpressure to increase the gas- achieved in this type of reactors.
due to biogas formation in the settler. to-liquid-exchange surface area. The Methanogenic granular sludge has a
Consequently, this technology has only sludge-water mixture flow to the set- diameter of 0.5 to 3.0 mm and a biomass
been applied on a very limited scale for tler section in the top of the reactor, concentration of approximately 100 kg
treatment of industrial wastewater where biomass is allowed to settle and dry matter per m3. Due to the absence of
containing dissolved organic com- return to the reaction compartment. inert carrier material, the density of
pounds. Nevertheless, the contact It was found in the 1970s that in such granules is slightly higher than
process remains a good option for this type of reactor, very high biomass water (~1.05 kg per m3), enabling both
wastewaters containing high concen- concentrations (on the order of 2030 good mixing in the reactor compartment
trations of suspended solids and/or fats. kg of biomass per m3 reactor) could be and good settling in the internal settler.
Upflow anaerobic sludge bed achieved with moderate-strength These characteristics make granular
(UASB) reactors [9] combine a reac- wastewaters (~5 kg of COD per m3 sludge a perfect biomass carrier. The
tion compartment with an internal set- wastewater) at low HRT-values (~10 combination of a simple construction
tler and a biogas separator. Waste- h), but very high SRT-values (~50 d). and a high volumetric treatment capac-
water is evenly distributed in the The effective uncoupling of the SRT ity has made the UASB reactor concept
bottom (reaction) section of the reactor and HRT in such systems resulted in the dominant anaerobic bioreactor type,
and flows through the sludge bed. In the higher treatment capacities. with more than 800 UASB reactors cur-
sludge bed, the organic pollutants are The high biomass concentrations in rently in use worldwide.
converted into biogas. The biogas pro- UASB-type reactors can largely be at- Expanded granular sludge bed
CHEMICAL ENGINEERING WWW.CHE.COM APRIL2003 61
Cover Story

(EGSB) reactor. A novel variation on


the UASB reactor concept is the
EGSB reactor. This is comparable to Reactor type Upflow anaerobic Hybrid Anaerobic filter
UASB reactors, except that much sludge bed (UASB) (AF)
higher liquid upflow velocities are ap- Max. biomass 25 25 15
plied: between 5 and 20 m/h, com- conc., kg/m3
pared to less than 1 m/h in UASB re- Max upflow 1 1 10
velocity, m/h
actors. To achieve this, EGSB reactors
are constructed as tall reactors with a Reactor height, m 6 6 6
limited diameter and relatively small
footprint.
The high liquid upflow velocities
can avoid preferential channeling in
the sludge bed, making wastewater
distribution in the bottom of the reac-
tor less critical. Consequently, treat-
ment capacities and biomass concen-
trations are generally higher than
Reactor type Expanded granular Contact process Continuously
those associated with UASB reactors. sludge bed (EGSB)/ stirred tank
Other bioreactor types that have fluidized-bed (FB) reactor (CSTR)
been investigated intensively use bio- Max. biomass 35/20 5 3-12% of
mass immobilized on either a stag- conc., kg/m3 influent COD
nant support material (i.e., fixed-film Max. upflow 15/30
reactors) or a mobile support mater- velocity, m/h
ial (i.e., fluidized-bed reactors). Reactor height, m 15
Both of these reactor types do not
have the hydraulic limitation encoun- FIGURE 4. Shown here is a comparison of the reactors most often used for
commercial-scale anaerobic treatment of industrial wastewater, and the optimal
tered in UASB-reactors. However, the boundary conditions for each
desired biomass quantity and quality
control is hard to achieve using these The maximum specific growth rate production. An example calculation
reactor types. Furthermore, the vol- (max) of the slowest-growing organ- for prediction of the biomass yield is
ume occupied by the carrier supports ism in the system, and shown in the box titled Sample Prob-
inside the reactor reduces the effective The maximum active biomass con- lem, on p. 63.
volume that is available for biomass centration that can be achieved in a The second step in the procedure is
formation; hence, volumetric treat- biomass-retention reactor systems the definition of the slowest-growing
ment capacities are generally lower. (all reactor types shown in Figure 4, organism in the system. For anaerobic
Hybrid reactor. A final variant except the CSTR-type reactor). bioreactors treating readily degradable
comprises a combination of the UASB The biomass yield (Yx/s) values for full soluble substrates, this is typically the
and the fixed-film reactor. In such a conversion of a wide array of organic process of acetoclastic methanogenesis,
hybrid design, biomass separation is substrates to methane and carbon or acetate fermentation to methane
not achieved using an internal settler dioxide are in the range of 0.03 to 0.12 and carbon dioxide. The maximum spe-
(as with UASB reactors), but with a kg/kg-COD removed from the waste- cific growth rate of the type of
packing material installed at the top water. The actual values depend on methanogenic organism that is nor-
of the reactor. Due to their relatively several variables, such as the type of mally dominant in methanogenic
recent commercialization, these reac- substrate, the temperature and the bioreactors, Methanosaeta, amounts to
tor types have until now found solid-retention time of the system. roughly 0.08 kg biomass per kg bio-
only limited application in anaerobic Numerous biomass yield values for mass per day at 35C. [14]. To achieve
wastewater treatment. anaerobic growth can be found in the effluent acetate concentrations in the
literature [11]. g/m3 range, this implies that the actual
Bioreactor design If no biomass yield measurements biomass growth rate in the reactor
If the substrate composition and are available, the total biomass yield should not exceed about half of the
strength of a wastestream are known, of the mixed microbial population can maximum specific growth rate, or 0.04
a basic design of a high-rate anaerobic be estimated, as long as the waste- kg per kg per day.
bioreactor can be established, with water composition is known. Estima- Then, combining the estimated bio-
relatively limited knowledge. The only tion of Yx/s is based on the concept of mass yield (Yx/s, kg/kg-COD) and the
parameters that must be known are: free energy conservation by bacteria. biomass growth rate (, kg/kg/day)
The overall biomass yield (Yx/s) value Free energy generated in a chemical with the typical biomass concentra-
for growth of the biomass (X) on the reaction catalyzed by microorganisms tions in the different types of bioreac-
substrates (S) in the wastewater is conserved and utilized for biomass tors (Figure 4) allows for the design of
62 CHEMICAL ENGINEERING WWW.CHE.COM APRIL 2003
SAMPLE PROBLEM:
ESTIMATION OF THE BIOMASS YIELD FOR ANAEROBIC BIOMASS DEGRADING ETHANOL
or estimation of the biomass yield, the stoichiometry of the energy- lationship between these two variables and GN was established:
F generating (catabolic) reaction equation needs to be derived:
2
0.16
COD 4 (5)
( ) ( )
1.8
C 2H 5OH 1.5CH 4 + 0.5CO 2 (3) G AN = 200 + 18 6 C + exp 3.8 3.6 + 0.4 C
C
GCAT = 91.6kJ reaction (4)
For ethanol, a GN value of 706 kJ per mole of biomass formed
From the stoichiometry of the chemical reaction, the standard
can be calculated.
free energy change under standard conditions can be calculated
Now, the following equation for the biomass yield can be de-
from the free energy of formation values of the reactants that can
rived as a function of GN, GCAT and the COD-equivalence val-
be found in review papers and textbooks [5,12]. Standard free en-
ues for the substrate (CODS) and biomass (CODX)
ergy change values (G0) need to be corrected for the biologically
favorable pH value of 7 (G01). G CAT
YX = (6)
Free energy generated in the catabolic reaction is invested in the S COD x
conversion of a carbon source to biomass (anabolic reaction). G AN GCAT
COD s
From an extended literature review, Heijnen [5] proposed that the
amount of free energy required for biomass formation (GN) de- Using a general molar biomass composition of CH1.8O0.5N0.2,
pends only on the carbon chain length (C) and the COD-equiva- a CODX value of 1.05 mole O2 per mole of biomass can be cal-
lence of the carbon source (COD, mol O2 per mole of carbon culated. Using this equation, the estimated biomass yield for
source) for growth. The GN value was found to be independent anaerobic growth of biomass on ethanol of 0.12 C-mol/mol, or
of the electron donor-acceptor couple. The following empirical re- 0.032 g biomass per g ethanol-COD.

FIGURE 6. This comparison shows the


hydraulic retention time required as a
function of the COD concentration to be
removed for different types of high-rate
anaerobic bioreactors. Lower limits of the
curves are set by the hdraulic operating
limits. Assumptions used are = 0.04
kg/kg/d, and Yx/s = 0.06 kg/kg COD
are capable of handling high hydraulic
loads (EGSB, fluidized-bed designs),
FIGURE 5. UASB-type anaerobic by recirculation of the reactor efflu-
reactors often produce granular biomass, ent. For an example, see Ref. [15].
such as that shown here
In other specific cases, a plug-flow
the anaerobic bioreactor. A mass bal- regime is preferred over a completely
ance for substrate over the reactor can mixed regime. A treatment system
be written as: that enables a plug-flow regime can
dS = Q ( S S) X limits of the curves are the result of readily be achieved either by placing
inf R (7)
dt V Y the hydraulic operational limit. The two or more high-rate anaerobic biore-
where: figure shows that the UASB and hy- actors in series, or by compartmental-
Q = Influent liquid flowrate, m3/d brid reactors concepts are not very at- izing the anaerobic bioreactor.
V = Reactor volume, m3 tractive for the treatment of strongly In general, a plug-flow regime is
In steady state, this equation can be dilute wastewaters, due to their lim- preferred in case of: (a) a wastewater
solved to obtain the hydraulic reten- ited hydraulic capacity. that contains a mixture of slowly and
tion time (HRT, d) required to achieve rapidly degradable substrates, or (b) a
an effluent concentration S: Flow regime wastewater that contains a substrate
The mixing regime in the reaction that gives rise to inhibition of the
( S S) Y
HRT = V = inf compartments of UASB, EGSB, hy- degradation of other substrate(s). One
Q XR (8)
brid and fluidized-bed reactor configu- particular type of wastewater that ex-
A boundary condition that needs to rations approaches completely mixed hibits both of these characteristics is
be checked for the different types of at full scale. Consequently, spatial the wastewater generated during pu-
biofilm reactors is the maximum value variations in both the substrate con- rified terephthalic acid (PTA) produc-
for the hydraulic load. Based on the centration and the biomass composi- tion. PTA wastewater consists of a
typical reactor height (h) of the reac- tion in the reactor compartments of mixture of acetate, benzoate, tereph-
tor types shown in Figure 4, the liquid these competing designs are small. thalate and para-toluate. The first two
upflow velocity (vup ,m/h) can be calcu- Still, elevated concentrations of or- are readily degradable in
lated using the following equation: ganic substrates may locally occur in methanogenic environments, whereas
reactors that are operated at low hy- the latter two are only degraded after
vup = h HRT (9)
draulic loading rates, such as UASB long lag periods and at a considerably
If the calculated liquid upflow ex- and hybrid reactors. In case of toxic lower rates. It has been demonstrated
ceeds the value shown in Figure 4, bio- but biodegradable compounds (such that pre-removal of acetate and ben-
mass washout may impede sufficient as formaldehyde) in the wastewater, zoate enables higher rates of degrada-
solids retention in the reactor. small spatial-concentration variations tion of terephthalate in the second
Figure 6 presents the HRT values may give rise to progressive toxifica- stage [ 8]. Two specific characteristics
required as a function of the COD con- tion of the sludge bed [4]. This limita- of methanogenic terephthalate ex-
centration to be removed. The lower tion can be overcome in reactors that plain this observation:
CHEMICAL ENGINEERING WWW.CHE.COM APRIL2003 63
EXAMPLE: REACTOR DESIGN TABLE 5.
s an example, the bioreactor volume required to treat a EXAMPLE WASTEWATER COMPOSITION AND FLOW

A wastewater with the composition and flow shown in Table 5 is


calculated. It is assumed that a UASB-type reactor is de-
signed, and that a COD-removal efficiency of 95% (S = 0.95)
Name
Wastewater strength
Influent flowrate
Abbr.
Sinf
Q
Unit
kg-COD/m3
m 3/d
Value
5
2,000
must be achieved. The organic material in the influent is assumed
to be fully biodegradable in methanogenic environments. The re- Biomass yield YX/S g/g-COD 0.06
quired reactor volume can then be calculated according to: Biomass growth rate d -1 0.06
Q S inf Y X
= 2000 0.95 5 0.04
S S
V = (10) steady-state biomass concentration of 25 kg/m3, as proposed for
X R 0.04 25 UASB-type reactors. The SRT can be calculated from the actual
giving a required reactor volume of 380 m3. biomass growth rate, according to:
Assuming a typical reactor height for UASB-type reactors of 6 m,
the corresponding liquid upflow velocity amounts to 1.3 m/h. SRT = 1 (11)
Thus, the maximum upflow velocity exceeds the proposed maxi- giving an SRT value of 25 days. Given that the hydraulic retention
mum value of 1 m/h shown in Figure 3. Relatively high upflow ve- time (HRT) amounts to only 4.5 hours, this means that the biomass
locities may lead to limitations in biomass retention in UASB-type needs to remain in the reactor roughly 90 times longer than the
reactors; consequently, an EGSB, fluidized-bed or fixed-film reac- liquid. Provided that the biomass is present as methanogenic gran-
tor would be preferred for this example. ular sludge (such as that shown in Figure 5, this can readily be
Another point that is useful to check is the solid-retention time achieved in UASB-type reactors, demonstrating the potential of the
(SRT) that needs to be achieved in the reactor, in order to enable a system.

Terephthalate degradation is wastewaters. Compared to aerobic cal of many CPI wastewater streams
strongly inhibited by benzoate and treatment, anaerobic treatment offers The full potential of anaerobic treat-
acetate, which both are intermedi- the following advantages: ment has only in the past two decades
ates of terephthalate degradation Lower biomass production per unit begun to be recognized. This has re-
As described above, the microorgan- of organic substrate removed sulted in the current construction rate
ism with the lowest specific growth Lower nutrient requirements, of roughly four new full-scale anaero-
rate determines the actual SRT that which is specifically important for bic treatment plants per year. Ongo-
needs to be achieved in the bioreac- chemical and petrochemical waste- ing research and engineering efforts
tor. Since terephthalate-degrading waters, which tend to be nutrient- will surely expand the reach of anaer-
biomass grows even more slowly deficient obic biological treatment in the years
than methanogens, they determine Production of a potential energy to come.
the actual SRT required source (methane-bearing biogas), Edited by Suzanne Shelley
Anaerobic biological wastewater which can often be used onsite, as Authors
treatment is, in many cases, a highly opposed to energy consumption for Robbert Kleerebezem is a re-
searcher at the Technical Univer-
attractive option for treatment of var- aeration in aerobic systems sity Delft, Kluyver Laboratory of
ious chemical and petrochemical A temperature optimum that is typi- Biotechnology, Faculty of Applied
Sciences, Julianalaan 67, 2628
BC Delft, Netherlands; Phone:
References 9. Lettinga, G., vanVelsen, A.F.M., Hobma,
S.W., de Zeeuw, W., and Klapwijk, A., Use of
+31-15-2782425; Fax: +31-15-
2782355; E-mail: r.kleerebezem
1. APHA, Standard Methods for the Examination the upflow sludge blanket (USB) reactor con- @tnw.tudelft.nl). In his current
of Water and Wastewater, 16th ed. American cept for biological wastewater treatment, es- position, Kleerebezem is work-
Public Health Assn., Washington D.C., 1985. pecially for anaerobic treatment, Biotechnol. ing on fluegas desulfurization
2. Blum, D.J.W., and Speece, R.E., A database of Bioeng., 22: 699-734, 1980. using inorganic biotechnology.
chemical toxicity to environmental bacteria 10. Macarie, H., Overview of the application of Before that, he conducted post-doctoral research
and its use in interspecies comparisons and anaerobic treatment to chemical and petro- at the University of Santiago de Compostella in
correlations, Res. J. WPCF, 63:198-207, 1991. chemical wastewaters, Water Science and Spain and at the Moscow State University. He
Technology, 42 (5-6): 201-213, 2000. holds an undergraduate chemical engineering
3. Edwards, E.A., and Grbic-Galic, D., Anaero- from Engineering College Enschede (Enschede,
bic degradation of toluene and o-xylene by a 11. Pavlostathis, S.G., and Giraldo-Gomez, E., Ki- Netherlands); and a masters degree and a doctor-
methanogenic consortium, Appl. Environ. netics of anaerobic treatment: A critical review, ate in environmental sciences from Wageningen
Microbiol., 60:313-322, 1994. Critical Rev. Environ. Control, 21:411-490, 1991. University (Wageningen, Netherlands). He has
4. Gonzalez Gil, G., Kleerebezem, R., and Let- 12. Thauer, R.K., Jungermann, K., and Decker, K., several professional publications to his name.
tinga, G., Formaldehyde toxicity in anaero- Energy conservation in chemotrophic anaero- Herv Macarie is a research
bic systems, Water Science and Technology, bic bacteria, Bacteriol. Rev., 41:100-179, 1977. officer at the Institut de
42 (5-6): 223-229, 2000. Recherche pour le Dveloppe-
13. Yan Y.G., Wong, P.C.Y., Tan, C.G., and
5. Hanselmann, K.W, Microbial energetics ap- Tang, K.F., Integrated centralized utility ment (Laboratoire de Micro-
plied to waste repositories, Experientia, services to a chemical complex on Jurong Is - biologie IRD, Universit de
47:645-687, 1991. land, Singapore, Water Science and Technol- Provence et de la Mditer-
6. Heijnen, J.J. Bioenergetics of microbial ogy, 47 (1), 15-20, 2002. rane, ESIL case 925, 163 Av-
growth, in Encyclopedia of Bioprocess Tech- enue de Luminy, 13288 Mar-
14. Zehnder, J.B., Huser, B.A., Brock, T.D., and seille cedex 09 France; Phone:
nology, M.C. Flickinger and Drew, S.W. Wuhrmann, K., Characterization of an ac-
(Eds.), John Wiley, New York, 1999. +33 (0)4 91 82 85 81; Fax: +33
etate-decarboxylating, non-hydrogen-oxidiz- (0)4 91 82 85 70; E-mail:
7. Kleerebezem, R.,Hulshoff Pol, L.W., and Let- ing methane bacterium, Arch. Microbiol., herve.macarie@esil.univ-mrs.fr).
tinga, G., Anaerobic biodegradability of ph- 124:1-11, 1980. In this position since 1994, Macarie is responsible
thalic acid isomers and related compounds. 15. Zoutberg, G.R., and Been, P.d., The Biobed for IRDs anaerobic-treatment program. From 1995
Biodegradation, 10:63-73, 1999. EGSB (Expanded Granular Sludge Bed) sys- to 2000, he was assigned as visiting professor at the
8. Kleerebezem, R., Ivalo, M., Hulshoff Pol, tem covers shortcomings of the upflow Universidad Autnoma Metropolitana-Iztapalapa
L.W., and Lettinga, G., High-rate treatment anaerobic sludge blanket reactor in the in Mexico City in the frame of a Mexican-French co-
of terephthalate in anaerobic hybrid reac- chemical industry, Water Science and Tech- operation program. He holds a biochemical engi-
tors, Biotechnol. Prog., 15: 347-357, 1999. nology, 35:183-188, 1997. neering degree and a Ph.D. in microbiology from
the Universit de Provence (Marseilles, France),
and was a post-doctorate fellow at the Biotechnol-
Acknowledgements Marc de Pijper (Biothane), Marc Eeckhaut (En- ogy Research Institute, Canadian National Re-
The authors thank Connie Smith & Graham viroasia), Haruki Ikemoto (Shinko Pantec), Bo search Council (NRCC; Montral) from June 1992
Brown (ADI), Leo Habets (Paques), Yann Hallin (Purac) and Alfredo Luna Len through April 1994. Macarie is a member of the In-
Mercier (Proserpol), Philippe Conil & Gustavo (Celanese) for sending information on the anaer- ternational Water Assn. (IWA), and participated in
Arroyave (Biotec), Richard Moosbrugger (Entec), obic reactors designed by their companies and the managing committee of IWAs Anaerobic Diges-
Gilberto Salerno (Biotecs), Dennis Korthout & for kindly answering our questions. tion working group from 19972001.

64 CHEMICAL ENGINEERING WWW.CHE.COM APRIL 2003

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