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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-
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
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
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.