Anaerobic Industrial Wastewater Treatment;

Perspectives for Closing Water and Resource Cycles.

Jules B. van Lier

Wageningen University, Sub-department of Environmental Technology, P.O.Box 8129, 6700 EV
Wageningen, The Netherlands &
Lettinga Associates Foundation (LeAF), P.O.Box 500, 6700 AM Wageningen, The Netherlands,
[email protected]

Introduction
Decades of developments and implementations in the field of high-rate anaerobic wastewater
treatment have put the technology at a competitive level. With respect to sustainability and cost-
effectiveness, anaerobic treatment has a much better score than many alternatives. Particularly,
the energy conservation aspect, i.e. avoiding the loss of energy for destruction of organic matter,
while energy is reclaimed from the organic waste constituents in the form of biogas, was an
important driving force in the development of such systems. At present, other advantages such as
the extremely low production of excess sludge and the system compactness are important
selection criteria. Compared to conventional aerobic treatment systems, the most striking
advantages of high-rate anaerobic wastewater treatment are:

1. Reduction of excess sludge production up to 90%

2. Excess sludge has a market value
3. No use of fossil fuels for treatment, saving ± 1 kWh/kg COD removed
4. Production of energy in the form of methane gas at a theoretical value of 3.8 kWh/kg
COD removed (assuming 100% treatment efficiency, and 100% conversion to
electricity).
5. Up to 90% reduction in space requirement
6. High applicable COD loading rates reaching 20-35 kg COD.m-3 reactor volume.day-1
7. No or very little use of chemicals
8. Rapid start-up (< 1 week), using granular anaerobic sludge as seed material
9. Anaerobic sludge can be stored unfed; reactors can be operated during agricultural
campaigns only (e.g. 4 months per year in the sugar industry)
10. Plain technology with high treatment efficiencies
11. High rate systems facilitate water recycling in factories (towards closed loops)

The ever rising energy prices and the overall concern on global warming puts again the attention
on the traditional advantages as mentioned under points 3 and 4. On the other hand, for economic
reasons, point 1 is more and more decisive in choosing for anaerobic high-rate systems,
particularly when incineration of excess sludge /biowaste is the only option at costs of 400-450 €
/ ton. The compactness of the system can be illustrated by a full-scale example where, an
anaerobic reactor with a 6 m diameter and a height of 25 m, can treat up to 25 tons of COD daily,
producing 7000 m3 methane (assuming 80% CH4 recovery), with a usable energy potential of 1-
1.5 MW at an assumed 30-50% energy conversion efficiency. The produced sludge, which is less
than 1 ton/day in the above example, is not a waste product, but is marketed as seed sludge for
new reactors. Such compactness makes the system suitable for implementation on the industry
premises or sometimes even inside the factory buildings. The latter is of particular interest in
densely populated areas and for those industries aiming to use anaerobic treatment as the first
step in a treatment for reclaiming process water.

Reactor Technology
Key to the worldwide interest in anaerobic treatment is the development of high-rate reactor
systems allowing for an extreme uncoupling of the solid retention time from the hydraulic
retention time. This uncoupling can be achieved by various ways of sludge retention, such as
sedimentation, immobilization on a fixed matrix or moving carrier material, and granulation
High-rate systems can be divided in suspended growth and attached-growth processes including
expanded/fluidized bed reactors and fixed-film processes. In suspended growth systems bacterial
sludge is present as flocs or granules, whereas in attached growth systems micro-organisms are
adhered to a moving a fixed medium. In an expanded/fluidized bed reactor, suspended carrier
media (such as sand or porous inorganic particles) are used to develop an attached film. Fixed
film processes rely on the bacteria attaching to a fixed media, like rocks, plastic rings, modular
cross-flow media, etc. Some systems, such as the anaerobic hybrid process, combine suspended-
and attached-growth processes in a single reactor to utilize the advantages of both types of
biomass.

(1981- 2004, N=1902) (1998 - 2004, N= 519)

EGSB
IC 17%
12% AF
8% IC
34% LAGOON 4%
CSTR
8% *
HYBRID 2%
CSTR 2%
EGSB 7%
AF 1%
LAGOON 5% FB 1%
HYBRID 3%
UASB
55% FB 2%
*
UASB
36%

Super high rate based: 21% Super high rate based: 52%
Granular sludge based: 76% Granular sludge based: 88%

Figure 1. Implemented anaerobic technologies for industrial wastewater pictured for the
period 1981-2004 ( left) and the period 1998-2004 (right). UASB: upflow anaerobic sludge
blanket; EGSB: expanded granular sludge bed; Hybrid: combined system with sludge bed at
the bottom section and a filter in top; IC: internal circulation reactor; type of EGSB system
with biogas-driven hydrodynamics AF: anaerobic filter; FB: fluidized bed reactor; CSTR:
continuous stirred tank reactor.
The upflow anaerobic sludge bed (UASB) reactor technology is considered a breakthrough in the
development and application of anaerobic high-rate technology for industrial wastewater. After
the initial first trials in the seventies, the system became rapidly popular in particularly the agro-
food sector. The worldwide applied technologies, implemented between 1980 and 2005 are
depicted in Figure 1. The right graph shows the relative number of the same technologies in the
time frame 1998-2005. Figure 1 indicates that the granular sludge based technologies (UASB,
IC, EGSB) dominated the market in the passed decades. This is confirmed by the newly installed
systems in the most recent period. Interestingly, competitive technologies like anaerobic filters of
hybrid systems were not able to be consolidating in the market. But also the super high rate
technology of Fluidized Bed (FB) almost vanished, most likely due to technology problems in
various full scale systems. An interesting observation in Figure 1 is the increasing popularity of
the super high rate reactors EGSB and IC. At present the major Dutch constructors (Paques and
Biothane) sell more IC and EGSB reactors than conventional UASB systems. Most likely, the
vast growing experiences and the higher availability of the indispensable seed material for these
systems, i.e. methanogenic granular sludge, have lead to the success of the super high-rate
reactors.
Biogas

Effluent

Recycle
2

Sludge bed

Influent

1. Sludge/water mixture
2. Settled sludge

Figure 2. Paques IC reactor (left) and Biothane EGSB reactor (right), inoculated with
granular sludge. Applicable loading rates: 15-45 kg COD/m3.day.

In addition to the anaerobic reactor technology, there is an increasing experience in pre- and post
treatment systems, safe-guarding stable operation and guaranteeing the contracted effluent
discharge criteria. Effluents containing fatty, oily and greasy compounds (FOG), such as dairy,
are in some cases pre-treated to such extent that all FOG and suspended solids are removed from
the wastewater prior to feeding it to the super high-rate system. However, in other situations, the
resulting treatment train becomes so complex that decisions are made to apply conventional
CSTR systems that treat the entire flow in a single step. Even with relatively simple wastewater
flows like those coming from the beer brewery process, adequate pre- and post- treatment is
essential for the success of the system. In some cases the actual anaerobic reactor volume is only
20-25% of the totally installed wastewater treatment volume for brewery effluents. Novel
developments in anaerobic reactor technology are directed to integrated multifunctional
bioreactors, such as sequencing batch reactors (SBR) and a simplification of the treatment trains.

End-of-the-pipe-treatment
Recent surveys showed a total registered number of over 2000 anaerobic reactor systems for the
end-of-the-pipe treatment of various types of industrial wastewater worldwide. This number is
much higher when all reactor systems are added that are constructed by local suppliers.
Generally, anaerobic high-rate treatment is applied for wastewaters coming from food processing
industries such as, sugar, potato, distilleries, wineries, fruit juices, starch, beer and soft drinks,
etc. Table 1 gives an overview of application in the most important industrial sectors.

Table 1. Application of anaerobic technology to industrial wastewater

Industrial sector Wastewater
Agro-food industry Sugar, potato, starch, yeast, pectin, citric acid, cannery, confectionary,
fruit, vegetables, dairy, bakery
Beverage Beer, malting, soft drinks, wine, fruit juices, coffee
Alcohol distillery Can juice, cane molasses, beet molasses, grape wine, grain, fruit
Pulp & paper industry Recycle paper, mechanical pulp, NSSC, sulphite pulp, straw, bagasse
Miscellaneous Chemical, pharmaceutical, sludge liquor, landfill leachate, acid mine
water, municipal sewage

The number of anaerobic applications in the non-food sector is rapidly growing. Common
examples are the paper mills and the chemical wastewaters, such as those containing
formaldehyde, benzaldehydes, terephthalates, etc. Especially the chemical industries are difficult
to enter with anaerobic technology, owing to the general prejudices against biological treatment
in general and anaerobic treatment in particular. However, most of the reactors listed in Table 2
perform better than expected and the number of chemical applications is steadily growing.

Table 2. Anaerobic treatment in chemical industries.

Wastewater Reactor type Loading (ton COD Number
COD/day) removal of reactors
Poly ethylene therephthalate UASB, 1.7 - 6 N.A. 2
(PET) Hybrid
Purified therephthalic acid UASB, IC 6 - 81 75 – 85% 9
(PTA) EGSB,
Hybrid, UAF
Pure Chemicals (formaldehyde, EGSB, 2 -10 60 - 90% 8
alcohols, organic acids, amines, Hybrid
etc.)

Others (Metallurgic, soaps, pH UASB, UAF, 2 - 40 75 – 95% 5

liquor, dyestuff, plastics, etc.) EGSB, IC,
Hybrid
N.A.: not available
With regard to the chemical compounds it is of interest to mention that certain compounds, such
as poly chloro aromatics and poly nitro aromatics as well as the azo-dye linkages can only be
degraded when a reducing (anaerobic) step is introduced in the treatment line. Anaerobics are
then complementary to aerobics for achieving full treatment. With the ongoing research and full-
scale applications in chemical industries the application potential of anaerobic treatment in this
sector is rapidly growing. As such, anaerobic high-rate treatment has become a matured
technology.

Despite the many advantages of anaerobic wastewater treatment, the global market share of
anaerobic reactors in the total treatment capacity is still very low. The latter can be ascribed to a
general lack of knowledge, the ‘fear of the unknown’, prejudice, and a possible bad image in the
past. However, the fact that in densely populated countries like the Netherlands, the major part of
the agro-food processing wastewater is treated by anaerobic reactor systems indicates that these
prejudices are based on perception rather than on verifiable facts. Encouraging, in this respect, is
that companies that have selected an anaerobic system for effluent treatment, which has been
constructed by recognized suppliers, will stick to the technology for all factories belonging to the
company. A good example is the brewery and beverage sector.

Zero-effluent-discharge
Reduction in industrial water consumption is generally achieved by good housekeeping and
redesigning the process water loops. Benefits to the companies include cost savings resulting
from e.g. less tax, less energy consumption, and less costs for wastewater treatment. Also
environmental improvement (green label), increased throughput, and risk and liability reduction
may result from optimized process water cycles. In clean industrial production processes, water
use reduction is essential.

fresh water
1000 m3/d
product
evaporation
1000 ton/d H2S
1000 m3/d removal
sulphur
steam 0.2 ton/d
industry 80 ton/d
biogas

anaerobic aerobic
treatment treatment
waste paper effluent

1050 ton/d 4000 m3/d

Excess sludge
1 ton/d
55°C 30 °C

Figure 3. ‘Zero-discharge’ cardboard and packaging industry of the Smurfit Kappa Group in
Zülpich, Germany.
After good housekeeping, a generally warm and more concentrated process water stream is left
that can be more easily treated by anaerobic high-rate reactors. Particularly when the treated
warm effluent is recovered for reuse, concomitant energy conservation is experienced that goes
far beyond the energy production from the anaerobic system itself. An interesting example is the
pulp and paper industry where ‘zero-effluent-discharge’ already can be achieved in the cardboard
and packaging paper manufacturers. Compared to an open system that consumes 10 m3 of water
per ton of paper produced, the closed system saves 1045 MJ.ton-1, assuming a fresh water
temperature of 10°C and an effluent of 35°C. The surplus energy of the anaerobic system adds
another 200 MJ.ton-1, bringing down the energy costs considerably. In this case, the role of the
anaerobic reactor is more than a treatment system: its cost-effectiveness leads to a more rapid
implementation of the zero-discharge approach with all its benefits for the industry. With regard
to the closed paper mill, it must be noted that in addition to COD removal, the anaerobic reactor
also eliminates sulphate as sulphide from the process water cycle, reducing the smell inside the
factory. And in fact, the anaerobic reactor is the only place for an efficient sulphur bleed at zero
costs. The anaerobic-aerobic treatment concept in closed water loops is already applied at
various full-scale situations (Figure 3).

Although not yet feasible in many industries, the zero-discharge approach is now being
researched for various types of industries (e.g. white paper, textile). Also here, anaerobic reactor
systems can be considered as a crucial step in closing the cycles. The next step will be the agro-
industrial production lines that are subjected to more stringent hygienic standards. However,
reuse of treated water for low-grade applications, such as washing and transportation has been
applied for several decades (Figure 4).

factory
beet sugar
beet washing sugar refining cristallization
and chipping

200 m3/h

mud polishing • low water volumes for washing&

thickener
pond beet transportation
• short HRT’s in the production process
• reduced extracted COD-loads
UASB • more energy efficient

aerobic river
sec.
Sedimentation polishing clarifier
pond N-removal

Figure 4. Implementing anaerobic high-rate technology for optimising internal water loops in
sugar beet processing industries.
Anaerobic treatment using the sulfur cycle: recovery of inorganic resources
A complete other field of application of anaerobic treatment is the use of the sulphur cycle in
environmental technology. Sulphur has the interesting property to accept or donate a different
number of electrons and thus can be reduced or (partially) oxidised, depending on the reactor
conditions. SO2- containing flue gas can be transformed in S-free gas by a sequence of an
anaerobic and micro-aerophilic reactor. While in the first reactor sulphide is produced, in the
latter biological sulphur is formed together with alkaline (OH-) that on its turn is reused to scrub
the SO2 from the flue gas. The similar strategy is also used for the desulphurization of biogas
from anaerobic reactors where the H2S is entrapped in a slightly alkaline scrubbing liquid and the
alkalinity is recovered in the subsequent sulphide oxidation step, according to:

H2Sgas + OH- → HS-aq + H2O

HS- + ½ O2 → S0 + OH-

The resulting technology does not consume chemicals, while the produced biological sulphur can
be marketed (Figure 5).

Figure 4. Biogas desulphurization unit combining an alkaline scrubber with a partial

oxidation of HS- and alkalinity recovery.

At present the technology is also used for natural gas desulphurization at large scale, e.g. at the
AMOC natural gas refinery in Alexandria, Egypt, producing 50 ton elemental sulphur per day
(Paques, personal communication). The S-cycle can also be used to (selectively) recover heavy
metals from wastewater streams (Figure 5). An interesting full-scale example recovers both the
waste zinc and the sulphur to be reused as raw oar and sulphuric acid in the metal industry. Lens
& Hulshoff Pol (2000) made an overview of the current state on the S-technology.

metal
influent lime treatment effluent
recovery
(metals in
ppb-range)
H2S
MeS
for reuse clean
bioreactor gypsum

Figure 5. Biological metal recovery applying the S-cycle in anaerobic technology.