USOO5798043A

United States Patent [19] [11] Patent Number: 5,798,043

Khudenko [45] Date of Patent: Aug. 25, 1998

[54] CONTROL OF ANAEROBIC WASTEWATER [57] ABSTRACT

TREATMENT
A method of controlling wastewater treatment in multi step
[75] Inventor: Boris Mikhailovich Khudenko. system comprising at least one anaerobic step and at least
Atlanta. Ga. one carbon dioxide stripping step by a combination of
(1) recuperable abiotic species and carbon dioxide
[73] Assignee: Khudenko Engineering, Inc.. Atlanta. stripping. wherein the recuperable species can be metal
Ga. ions such as calcium and iron. the said species are
charged in the treatment system and form soluble
[21] Appl. No.: 982,030 carbonates maintaining the carbonic acid equilibrium
and pH in anaerobic process steps and recuperated and
[22] Filed: Dec. 1, 1997 retained in the system as insoluble carbonates or
hydroxides formed in the carbon dioxide stripping step.
[51] im. (:1.6 ...................................................... .. cozr 3/30
and
[52] US. Cl. ........................ .. 210/603; 210/605; 210/614; (2) conditioning the sludge by cultivating methanogens in
210/630; 210/631 the sludge in a dedicated process zone called sludge
[58] Field of Search ................................... .. 210/603. 605. conditioner. and recycling the conditioned sludge in the
210/610. 614. 625. 630. 631. 623 reactor. wherein the volatile fatty acids are rapidly
consumed by thus provided methanogens.
[56] References Cited
Dramatic reduction in reagent requirements for pH and other
U.S. PATENT DOCUMENTS purposes is achieved. The system can be controlled using
excess reagent content and excess conditioned sludge sup
3,047,492 7/1962 Gambrel ................................ .. 210/625
4,029,575 6/1977 Bykowski et a1. . 210/625 ply. In extreme situations. simple automatic control can be
4,614,587 9/1986 Andersson et a1. 210/603 used. The process can be automated using a diiferential pH
5,075,007 12/1991 Morper et a1. 210/614 metering. wherein one pH meter is reading pH in the carbon
5,094,852 3/1992 Davis et a]. 210/614 dioxide stripping reactor. and another pH meter measures
5,185,079 2/1993 Dague 210/603 pH in a portion of water with carbon dioxide stripped. The
5,500,123 3/1996 Snvastava 210/603 level of pH in a water portion with depleted carbon dioxide
5,587,079 12/1996 Rowley et al. .. 210/605 indicates whether carbon dioxide needs to be additionally
5,630,942 5/1997 Steiner ........ .. 210/603
stripped or the recycle rate from the stripping step should be
5,651,891 7/1997 Molop et al. 210/625
5,670,047 9/1997 Burlee ................................... .. 210/614
increased. and/or the conditioned sludge recycle needs to be
increased.
Primary Examiner-Christopher Upton 14 Claims, 1 Drawing Sheet

L r. \
100 h
 5.798.043
1 2
CONTROL OF ANAEROBIC WASTEWATER degradable substances. thus increasing BOD. This increases
TREATMENT the organics removal in the entire system (or per cent COD
reduction) and. respectively. boosts the oxygen demand for
FIELD OF INVENTION wastewater treatment.
In free standing anaerobic reactors. and anaerobic zones
The invention belongs to biological wastewater treatment or stages in coupled and combined systems. pH in the
systems having multiple biological treatment zones. anaerobic reaction zone can substantially change during
particularly. anaerobic systems. a single-stage racetrack and treatment. VFA and carbon dioxide formed in anaerobic
recycle systems with facultative. anoxic and aerobic zones. digestion tend to reduce pH. Wastes with low total nitrogen
and multistage anaerobic-aerobic coupled and combined or other source of intrinsic alkalinity. such as predominantly
systems. carbohydrate waste. tend to lose alkalinity reserve and
become acidic. Waste with high nitrogen content. such as
BACKGROUND protein containing waste. can result in high alkalinity and pH
Advantages of anaerobic treatment are well established. It due to ammonia formation. VFA are at least partially con
can be used as a free standing biological process comprising sumed by methanogens in the methanogenic phase of the
at least an anaerobic reactor a sludge separator. and sludge anaerobic reactions. However. in rapid systems and systems
recycle means. So called anaerobic zones. or sections. are with substantial variations in the in?uent strength and ?ow
often included in aerobic activated sludge processes for rate. residual VFA concentrations are high. In present
either suppressing the ?lamentous growth. or for biological systems. pH is most often controlled by systematic addition
phosphorus removal. Such anaerobic zones have a short of reagents. The reagent feed increases the capital and
hydraulic and biomass retention time and can accommodate operating costs of the system. The total salt content of the
only acidogenic phase of anaerobic processes. which is e?luent increases. thus making its reuse and disposal more
performed by facultative organisms. Accordingly. a more di?icult. Due to slow growth of methanogenic organisms.
appropriate name for these zones is a facultative zone. organics removal and VFA accumulation in anaerobic treat
Anaerobic stages are also included in the coupled and 25 ment stages is often di?icult to control. The process control
combined anaerobic-aerobic multistage systems. In coupled is especially di?icult under variable in?uent ?ow rates and
systems. anaerobic stages are the same as in the free concentrations. At reduced process ef?ciency pH can be low.
standing anaerobic systems. All anaerobic effluent is clari and odorous volatile organics and hydrogen sul?de can be
?ed in the biomass separation means. and there is no sludge present in the digestion gas. Treatment of such gases prior to
transfer downstream and respective sludge return upstream. 30 their use is required.
Only waste sludge from the downstream stage (usually VFA and carbon dioxide in wastewater with large intrinsic
aerobic) is fed in the anaerobic stage for stabilization. alkalinity. for example. with high protein content. are neu
Combined multistage systems have a partial biomass tralized by the alkalies. such as ammonia. formed in the
exchange between stages. US. Pat. No. 5.514.278 presents digestion process. If the in?uent contains substantial quan
an example of combined multistage processes. a counter?ow 35 tity of sodium acetate. the intrinsic alkalinity is due to
process. This patent is made a part of the present invention sodium ions. Other forms of intrinsic alkalinity are also
by inclusion. In counter?ow systems. anaerobic. anoxic. possible. Digestion of the protein rich biological sludges
aerobic. and/or polishing stages have biomass separation usually results in pH within a neutral range. Anaerobic
devices for a portion of the total ?ow discharged from the treatment of some industrial waste. for example. seafood
stage. The balance of the ?ow is transferred to a downstream processing. results in very high ammonia release and exces
stage as mixed liquor. There is also a return of separated sively high pH needing neutralization by an acid.
biomass within each stage and to upstream stages. The Sometimes. ammonia gas can also be present in the diges
biomass return to the upstream zones is greater than the ?ow tion gases. Waste neutralization with alkalies and acids is
of the excess biomass. Therefore. in contrast to coupled expensive and complex. Automatic controls for neutralizing
multistage systems. combined systems have biomass trans 45 anaerobic reactors are not reliable. Several grams of alkalies
fer and exchange between and among the process stages. per liter can often be required for neutralization. thus
This process arrangement provides additional ?exibility. increasing the total dissolved solids in the e?luent and
dynamic stability and ef?ciency. rendering the effluent less valuable for reuse or discharge.
In all described anaerobic and facultative zones the in?u US. Pat. Nos. 5.514.277 and 5.616.241 teach a method
ent organics are subjected to the acidogenic transformations. 50 and apparatus for controlling VFA in anaerobic processes.
Volatile fatty acids (FVA) and carbon dioxide are formed in These patents are made a part of the present invention by
the acidogenic phase. If the intrinsic alkalinity is not su?i inclusion. The anaerobic process is improved by providing
cient for neutralization. pH in the anaerobic zone decreases. a sludge conditioner which is fed with at least a portion of
In presence of VFA. sul?des and odorous volatile organics the sludge separated from the anaerobic mixed liquor in the
can form and escape to the digestion gas. 55 biomass separator. In this sludge. organic particulates and
Methanogens are absent in the facultative zone of the acidogenic organisms are anaerobically digested and the
activated sludge process and acidi?cation is the only bio conditioned sludge becomes enriched with methanogens.
logical process in this zone. Formation of VFA and carbon The sludge rich in methanogens is fed in the reactor. and
dioxide causes pH reduction. Low strength waste usually methanogens rapidly consume the VFA. Controllable feed of
treated in the activated sludge process with facultative zones the conditioned sludge in the anaerobic reactor regulates
do not cause signi?cant pH reductions. Normally. pH control acidity due to VFA. This method provides a reliable bio
is not required. COD is not signi?cantly reduced in facul logical control of acidity due to organic acids in the anaero
tative anaerobic zones. The ultimate organics degradation bic system.
occurs in anoxic. and. more important. aerobic zones. US. Pat. No. 4.722.741 describes a method of acidity
Moreover. the portion of the in?uent COD which is not reduction in anaerobic processes for converting the biomass
removable in conventional aerobic processes is at least into methane in a phase separation system comprising an
partially converted to fatty acids and other aerobically acetogenic reactor. carbon dioxide stripping and methano
 5.798.043
3 4
genic reactor. The pH control is assumed to occur through ment is provided comprising the step of providing at least
stripping the excess carbon dioxide before the methanogenic one recuperable abiotic control specie to at least one of the
stage. However. this patent also teaches that the content of said zones in the said multi zone system. Further steps
carbon dioxide in the methanogenic stage needs to be comprise separating at least a portion of the said biomass
increased by the use of elevated pressure and high carbon from the said multi zone system. digesting the said separated
dioxide solubility. About 20 years earlier. S. V. Yakovlev and biomass to produce digested biomass. and feeding at least a
A. S. Pogosian (“Intensi?cation of digestors by enriching the portion of the said digested biomass in at least one zone of
reaction mass with carbon dioxide”. Vodosnabzhenie i Sam' the said multi zone system. The operation mode of at least
tamaya Tekhnika. No. 3. 1967. Moscow) have shown that one zone in the said multi zone system is selected from a
enriching the digestion media with carbon dioxide increases group comprising batch operation. continuous operation.
the methane yields. and the loss of carbon dioxide reduces and combinations thereof
the efficiency of Waste treatment. Therefore. teachings of the An alternative formulation of this principles can be as
US. Pat. No. 4.722.741 are contradictory and in con?ict follows. In a biological treatment of wastewater conducted
with other publications. with biomass in a multi zone system comprising at least one
The US. Pat. No. 4.415.453 presents a further improve biological zone and at least one abiotic zone the improve
ment of alkalinity control in anaerobic processes. In a ment is provided comprising steps of separating at least a
coupled anaerobic-aerobic process. an alkali is added in the portion of the said biomass from the said multi zone system.
anaerobic reactor. A magnesium oxide and sodium hydrox digesting the said separated biomass to produce digested
ide were used as alkalinic reagents. and sodium formate was biomass. and feeding at least a portion of the said digested
used as. what is called here the intrinsic alkalinity. After 20 biomass in at least one zone of the said multi zone system.
separating the bulk of biomass in the anaerobic stage. the and further providing a step of providing at least one
clari?ed anaerobic e?luent is fed in the activated sludge recuperable abiotic control specie to at least one zone of the
process. Dissolved carbon dioxide is stripped in the aeration said multi zone system. The operation mode of at least one
tank and soluble magnesium. or sodium carbonates and zone in the said multi zone system is selected from a group
bicarbonates are formed. Recycling a portion of the content 25 comprising batch operation. continuous operation. and com
of the aerobic reactor in the anaerobic stage could reduce the binations thereof
alkali requirements by 50% to 75%. Nonetheless. the The said wastewater is selected from a group consisting of
required dosages of magnesium oxide (from 1 to 4 g/l) are Water. wastewater. aqueous industrial. agricultural and pro
high. It is assumed in this patent that a magnesium carbonate duction materials. industrial. agricultural and production
is formed and precipitated in the aeration tank. It is well gases. polluted air. gaseous and ventilation emissions. solid
known that magnesium hardness cannot be noticeably waste. materials of plant. animal. or fossil origin. and solid
removed by forming magnesium carbonates at pH equal to industrial. agricultural or production streams. and combina
or less than 8.5 (normally. the upper pH limit for the tions thereof The said zones in the said multi zone system are
activated sludge process). It is well established that magne selected from a group comprising obligate anaerobic zone.
sium forms poorly soluble hydroxides at pH=10.5. This is 35
facultative anaerobic zone. anoxic treatment zone. aerobic
the usual operational regime for removing magnesium treatment zone. obligate aerobic zone. abiotic treatment
hardness. but biological treatment systems cannot be oper zone. and combinations thereof. The said abiotic zone can be
ated at this regime. Additionally. magnesium tends to form combined with at least one said biological zone selected
very dit?cult struvite (MgNH4PO4) scale in anaerobic pro from the group comprising an obligate anaerobic zone.
cesses. facultative anaerobic zone. anoxic treatment zone. aerobic
treatment zone. and obligate aerobic zone. The connection
OBJECTIVES of the said zones in the said multi zone system is selected
Accordingly. an objective of the present invention is to from a group consisting of sequential treatment zones.
control pH and alkalinity in anaerobic and facultative stages parallel treatment zones. parallel-sequential treatment zones.
and process zones of the wastewater treatment system treatment zones in a racetrack arrangement. and treatment
without systematic feed of reagents. zones with recirculating the said wastewater and the said
sludges among and between the said treatment zones. The
Another objective is to controllably increase organics
said biomass in the said zones of the said multi zone system
reduction in anaerobic zones and to etfect organics reduction
in facultative zones.
is composed of organisms selected from the group compris
50
ing obligate aerobic. facultative aerobic. anoxic. facultative
Yet another objective is to reduce the oxygen demand for anaerobic. and obligate anaerobic microorganisms. and mix
wastewater treatment in activated sludge system with func tures thereof.
tional zones for biological nutrient removal and to increase
the upper limit of the in?uent concentrations treatable in
The said recuperable abiotic control specie is selected
such systems. 55
from the group comprising calcium. magnesium. iron.
nickel. cobalt. manganese. zinc. aluminum. cesium. and
Additional objective is to produce clean odorless diges combinations thereof The method of introducing the said
tion gas with very low emissions of hydrogen sul?de. recuperable abiotic control species is selected from the
volatile organics. and ammonia. Increasing the methane group comprising zero-valent metals. salts. metal oxides.
content in the digestion gas is also an objective. metal hydroxides. organometallic compounds. and combi
Other objectives of the present invention will become nations thereof.
clear from the ensuing description.
DRAWINGS
SUMMARY OF INVENTION FIG. 1 is a ?owchart of anaerobic process with sludge
In a biological treatment of wastewater conducted with a 65 conditioning.
biomass in a multi zone system comprising at least one FIG. 2 is a ?owchart of anaerobic treatment with an
biological zone and at least one abiotic zone the improve abiotic control zone.
 5.798.043
5 6
FIG. 3 is a ?owchart of a single-stage race track system bicarbonates are lost with the e?luent from the system.
with multiple zones. although the recycled portion will help in reducing the alkali
FIGS. 4A to 4E are charts of a batch treatment system requirements. Disadvantages of this approach were pre
with abiotic process control. sented in the previously discussed teachings of the U.S. Pat.
No. 4.415.453. Accordingly. a new and more bene?cial
DETAILED DESCRIPTION OF INVENTION method of abiotic process control is needed. Calcium and
iron will form very poorly soluble carbonates and their loss
FIG. 1 illustrates anaerobic process with a sludge condi will be measured in milligrams. or in a fraction of a
tioner as described in the US. Pat. Nos. 5.514.277 and milligram per liter. Therefore. these are recuperable species
5.616.241. The system comprises an in?uent line 1. an forming insoluble carbonates at acceptable pH (less than
anaerobic reactor 2. a line 3 for transferring the mixed liquor 8.5) and are easily available and economical for providing
in a biomass separator 4. an effluent line 5. a sludge recycle the alkalinity and pH control. The precipitation of the added
line 6 leading to a sludge conditioner 7 and further to the calcium and/or iron carbonates will occur in the abiotic
reactor 2. The sludge conditioner 7 is fed with the separated zone. and the carbonate precipitates will largely embed in
biomass via line 6. where the biomass and other particulate the biomass so that little scaling will occur. In the reactor. the
organics are digested and proportion and the absolute mass precipitated materials are dissolved. the carbonates are con
of methanogenic organisms in the biomass increase. The verted into bicarbonates. and the alkalinity reserve is used
conditioned sludge enriched with methanogens fed into the for pH control. Blending calcium and iron reduces the risk
reactor 2 via line 6 takes part in consuming VFA. This of scaling. Other recuperable species can include zinc.
provides the biological means for increasing the treatment 20 nickel. cobalt. manganese. cesium. Through a thorough
e?iciency and for controlling pH and alkalinity deviations screening. a skillful in art can ?nd additional recuperable
due to VFA. High treatment e?iciency in the system of FIG. species. It is known that using mixtures of several
1 is achieved at a lesser reactor volume than needed for the coagulants. for example iron and aluminum salts. expands
conventional contact process. Moreover. the reactor-sludge the pH range where these salts precipitate and fonn ?ocks.
conditioner system can provide the dynamic process control 25 Similarly. the use of magnesium together with other coagu
and an excess of methanogens above the equilibrium estab lating ions. for example. aluminum. iron. zinc. can trigger
lished in conventional continuous growth reactors. the pos magnesium precipitation at pH values much lower than 10.5
sibilities not available in the contact process. Additional typical for the removal of magnesium hardness. Therefore.
variants and advantages of this operational mode are pre magnesium blended with other ions can sometimes also be
sented in US. Pat. Nos. 5.514.277 and 5.616.241. 30 recuperated in the abiotic zone. Such blending will also
Besides the previously described advantages. the reactor reduce the risk of struvite scaling due to lowering the
conditioner system can provide biological-abiotic alkalinity magnesium concentration and binding of phosphates by
and pH control in the reactor. Nitrogen provided in the other recuperable species. particularly by iron. Blending
reactor is consumed by rapidly growing acidogenic micro other metals. for example iron and calcium. can also reduce
organisms. When these organisms are transferred in the 35 the risk of calcium carbonate scaling in the treatment
sludge conditioner. a large fraction of these organisms dies system. Moreover. calcium improves the ferrous hydroxide
oif thus releasing organic substrate and ammonia. An precipitation and iron recuperation in an abiotic zone.
organic substrate is used for methanogenic growth. while a Therefore. blending several recuperable species produces
large portion of nitrogen remains in the solution. unexpected and very bene?cial synergistic effects.
Accordingly. pH and alkalinity of the conditioned sludge Another group of unexpected bene?ts is related to the
increase. The contents of the sludge conditioner have an abiotic oxidation-reduction processes. For example. ferrous
increased concentration of ammonia resulting in pH greatm ions in the anaerobic mixed liquor aerated in the abiotic zone
than 7. and reaching 8.5-9. Recycle of this sludge in the can be oxidized to ferric ions. Ferric hydroxide can be
reactor provides alkalinity and pH control. In addition to the recuperated at much lower pH than either fm'rous carbonate
biological consumption of VFA by the conditioned sludge. or ferrous hydroxide. Return of ferric forms in the anaerobic
recycling of nitrogen species within the reactor-conditioner reactor helps to oxidize and otherwise treat toxic and recal
system is an unexpected bene?t. Moreover. at strongly citrant organics. including many halogenated organics.
methanogenic ORP. the excess ammonia reacts with carbon Reduction of ferric forms to ferrous in the anaerobic reactor
dioxide to form methane and water (as in methane produc also provides additional alkalinity. Iron and some other
tion from hydrogen and carbon dioxide) and nitrogen. 50 recuperable species produce an additional unexpected and
Ammonia-carbon dioxide (or carbonates) reaction can occur bene?cial result. In an anaerobic reactor. iron binds sul?des.
in both. the reactor and the sludge conditioner. This is thus eliminating the hydrogen sul?de in the digestion gas. In
another new and unexpected phenomena and advantage of aerated abiotic zones. iron sul?de is oxidized forming
the anaerobic reactor with a sludge conditioner. It is now soluble sulfates and insoluble iron forms. Sulfates are dis
possible to control alkalinity and pH in anaerobic processes 55 charged with the ef?uent. while insoluble iron forms are
with the lack of alkalinity and with the excess of alkalinity recuperated to be used as an oxidation agents (reduction of
due to ammonia. ferric to ferrous forms). as an alkalinity carrier. as a
FIG. 2 shows an anaerobic system with an abiotic zone coagulant. and as a precipitating agent for sul?des and
comprising an in?uent line 1. an anaerobic reactor 2. a phosphates. Manganese. copper. magnesium and other ions
mixed liquor line 3 leading to an abiotic zone 8 and further can catalyze iron oxidation in aerated abiotic zones directly
to a biomass separator 4. an effluent line 5. a mixed liquor and through pH Increase. This is one more bene?t of using
recycle line 9. and a separate biomass recycle line 6. The blends of recuperable abiotic species.
in?uent treatment in the anaerobic reactor is accompanied Yet another unexpected bene?t is in producing digestion
by the biomass growth and mixed liquor formation. Strip gases with signi?cantly increased methane percentage. The
ping carbon dioxide with air or other gas free of carbon 65 bulk of the recuperable species returned in the anaerobic
dioxide in the abiotic zone 8 results in pH rise and formation reactor is carbonates and hydroxides. These carbonates and
of bicarbonates and carbonates. Soluble carbonates and hydroxides react with the anaerobically generated carbon
 5.798.043
7 8
dioxide to produce soluble nonvolatile bicarbonates. The system shown in FIG. 3 is operated as follows.
Simultaneously. pH in the aerobic reactor increases and the Wastewater is fed in zone 2A via line 1. Mixed liquor is
proportion of carbon dioxide to bicarbonates rapidly circulated in this zone via line 11. and the conditioned sludge
decreases. For example. at pH=7.5. the mole ratio of carbon is fed through line 12. In zone 2A. oxygen is rapidly
dioxide to bicarbonates is 0.08 to 0.92. whereas at pH=7 . this depleted and nitrites and nitrates are reduced to form mainly
ratio is 0.19 to 0.81. Therefore. operating the anaerobic nitrogen. The hydrolysis of organic particulates and anaero
process with elevated pH results in much higher methane bic acidification of the influent waste may also start in this
content in the gas. More than 90% and often more than 95% zone. After the mixed liquor is transferred in zone 23.
methane gas can be produced. This is the commercial quality organics are acidi?ed and. with the participation of metha
gas which can be sold to utilities. Since pH is controlled at nogens provided from the sludge conditioner. at least par
a high level by recuperable abiotic species. the cost of such tially converted to methane. During anoxic and anaerobic
control is low. After the initial charging. the need in replen treatment. the wastewater pH declines due to generation of
ishing the recuperable abiotic species is very low. VFA and carbon dioxide. Depending on the supply of the
The recuperable ions can be introduced in the system as conditioned sludge. VFA can be consumed at least partially
salts. metal oxides. metal hydroxides. organometallic com by the methanogens. Upon transferring the mixed liquor in
pounds. Zinc. aluminum. iron. nickel. cobalt can be intro
duced as zero-valent metals. Additional bene?ts of zero
the aerobic zone 2C. it undergoes aerobic biological
valent metals are described in the US. Pat. No. 5.348.629 polishing. and the carbon dioxide accumulated in the
which is made a part of this invention by inclusion. A further anaerobic zone 28 is stripped during the wastewater aera
improvement can be provided by using ferric salts for tion. After complete VFA consumption and carbon dioxide
striking zero-valent metals to trigger the rapid dissolution 20 stripping in anaerobic and aerobic zones 23 and 2C. the
and activation of zero-valence metals. Moderate oxygen wastewater pH rises. Sludge separated in the biomass sepa
ation of water in the abiotic zones increases the rate of rator 4 is conditioned in the sludge conditioner 7 and
zero-valent metal dissolution and the rates of destruction of becomes enriched with methanogens. The separated water is
recalcitrant and toxic organics. Ferric ions are not toxic and. discharged via effluent line 5. All features related to the use
by themselves and upon reaction with metallic iron. they 25 of recuperable abiotic species separately or in conjunction
will introduce additional quantity of recuperable iron spe with the sludge conditioning described above while discuss
cies. In an anaerobic zone. ferric ions will be reduced to ing FIGS. 1 and 2. are applicable for the system shown in
ferrous ions and some organics will be electrochemically FIG. 3 and will not be repeated. In the system of FIG. 3. the
treated. including recalcitrant and toxic organics. Besides function of the aerated abiotic zone is combined with the
being a recuperable abiotic specie in the process of concern. 30 function of the aerobic treatment in zone 2C. The pH range
such as iron and other ions. are also beneficial for dewater in zones 2A. 2B. and 2C depends on the initial wastewater
ing the excess sludge. for biomass separation in anaerobic composition and the design parameters of the system. It can
processes. for phosphorus control. and for control of sul be controlled most conveniently by the recycle rates of
?des. This is additional unexpected bene?t of the new wastewater and conditioned sludge. Increasing the recycle
process. Losses of the recuperable abiotic species occur with 35 rates reduces the range of pH change in zones 2A. 2B. and
the waste sludge and as a residual dissolved matter with the 2C. Further control can be provided by adding the recuper
eftluent. These losses are very low. The replenishment able abiotic species to any point in the treatment system. but
quantity of the recuperable abiotic species is only 1A000 to V25 the e?luent line 5 and the discharge line for the excess sludge
of the alkali required for neutralization in the once-through (not shown). The conversion of the recuperable species into
system. This is also a great reduction as compared with the bicarbonates in the anaerobic zones and into carbonates and
US. Pat. No. 4.415.453 (by an additional factor of 10 to hydroxides in aerobic zones has already been described.
250). Additionally. reduced ions (ferrous) will be oxidized in the
FIG. 3 shows a race track treatment system comprising an aerobic zone (ferric). In the anaerobic zone. reductions of
in?uent line 1. an anoxic treatment zone 2A with the transfer ferric ions can produce very powerful oxidations for many
line 3A leading to the anaerobic treatment zone 28 followed 45 toxic and recalcitrant organics. including halogenated com
by another transfer line 3B leading to an aerobic treatment pounds. This is another unexpected advantage of using iron
zone 2C with the ?rst outlet line 11 conveying the circulating as a recoverable abiotic specie. singly or in combination
?ow to the anoxic zone 2A and the second outlet line 3C with other species.
leading to a biomass separator 4 and further to the e?luent Race track systems are commonly used for treating low to
line 5. the biomass separator has a line 12 connected to a 50 moderately concentrated wastewater. An unexpected and
sludge conditioner 7 and further leading to the anoxic zone very valuable advantage of the improved system shown in
2A. Many variants of this system are possible. For example. FIG. 3 is in that it can be used from low to highly concen
the line 12 can connect to zones 2B. or 2C. Zones 2A. 2B. trated wastewater and for anaerobic-aerobic sludge diges
and 2C can be separate reservoirs (tanks. or reactors of any tion. This is achieved by the use of recuperable abiotic
kind). or they can be functional zones without de?ned 55 species for alkalinity control. Further. this is achieved by
borders in a single oval or circular tank as in the oxidation significantly reducing COD in anaerobic. and. to a lesser
ditch treatment system. or they can be accommodated in the extent. in anoxic zones 2B and 2A. For any wastewater
conventional corridor type aeration tanks. Number of zones strength. COD reduction in zones 2A and 23 via anaerobic
can also vary. For example. zones 2A and 213 can be mechanisms greatly reduces the oxygen requirements and
combined into a single denitri?cation-anaerobic zone. Other cost of aeration in the system overall. Sludges and concen
functional zones can be added. Using the present teachings. trated waste can be biologically heated in aerobic zones. In
skillful in art can design various systems. Note that the usual this and other embodiments. besides the gravity separators.
order of functional zones in biological nutrient removal a ?lter press. a belt ?lter. a centrifuge. a dissolved gas
systems is anaerobic-anoxic-aerobic. By providing the (including air) ?otation. or other means can be used as
appropriate sludge and wastewater transfer means. this 65 sludge separators. The sludge separation can be conducted in
sequence and other common modi?cations can also be used more than one step. for example. with a gravity separator or
with the present invention. a ?lter in the second separation step. When iron or other
 5 .798.043
10
specie with a variable valency is used. the sludge mass is called the ?ll-strip and react-strip steps. Upon completion of
additionally signi?cantly reduced due to oxidation by the the react-strip step. mixing is terminated. and the settling
ferric ions. Moreover. in all described process modi?cations. step is conducted. After settling. the decanting step is
the excess sludge wasted from the biological treatment conducted by discharging the top treated and clari?ed layer
system is already coagulated. Therefore. the added recuper of liquid. After that the entire cycles of process steps.
able abiotic species will be also coagulants in the sludge including ?ll-strip. react-strip. settle. and decant steps. are
treatment at no additional cost. This are also unexpected repeated.
bene?ts of this invention. Optionally. a volume of the reactor at the bottom can be
For concentrated wastewater. a multistage system with assigned as a sludge conditioner and a fraction of this
coupled or combined stages. including the system with a volume can be engaged in each cycle. Alternatively. multiple
sludge exchange between the anaerobic and aerobic stages sludge conditioning sections can be used and each section
can be preferable. Sludge exchange can be organized as can be employed on a rotation basis with the ?rst. second.
shown in the US Pat. No. 5.514.278. which is made a part and following cycles. Recuperable abiotic species can be
of this invention by inclusion. In line with the present added to the batch reactor. During the treatment cycle the
teaching. skillful in art can design alternative con?gurations 15 recuperable abiotic species will change from the dissolved to
of the process with the sludge exchange between and among precipitated form at the end of the treatment step.
stages in a multistage processes. A portion of the mixed Accordingly. these species will be settled and retained in the
liquor from upstream stages is transferred to a downstream reactor during the decant and discharge steps. All features
stage directly. and the balance of the flow passes through the related to the use of recuperable abiotic species separately or
biomass separator. The quantity of sludge allowed down in conjunction with the sludge conditioning described above
stream and the additional sludge grown in the downstream while discussing FIGS. 1 and 2. are applicable for the system
sections are recycled upstream. Therefore. the sludge shown in FIGS. 4A to 4B and will not be repeated.
recycle exceeds the excess sludge ?ow. Transferring the All embodiments described herein can be combined as
biomass downstream results in substantial sludge and waste needed for a particular application. Many other combina
water recycle between stages. Accordingly. the required 25 tions can also be designed in the spirit and letter of these
concentration of the recuperable species in the circulating teachings.
?ows is substantially reduced. and the mass of these species In all embodiments described herein. digestion gas is
in the system is also reduced. In conventional multistage generated in the anaerobic process stage. This gas can be
systems. including one described in the U.S. Pat. No. made odorless by providing sul?cient amounts of methano
4.415.453. no controllable transfer of sludge downstream is 30 gens with the conditioned sludge. and sufficient amounts of
allowed and only the excess sludge generated in the down the recuperable abiotic control species. Gas can be produced
stream stages is recycled to the upstream stages. wi?i high methane and low carbon dioxide contents. Such a
Accordingly. the recycle ?ow between stages is small and gas can be collected and utilized. if economical.
the required concentration of the recuperable species must Alternatively. this gas can be destroyed. for example. by
be high. If magnesium alone is used at high concentrations. 35 combustion on a ?are.
it can reach toxic levels. struvite will be readily formed. and The use of recuperable abiotic control species singly or
losses of magnesium with the e?luent will be large. All together with the sludge conditioning affords a simple and
features related to the use of recuperable abiotic species reliable dynamic process control system. Using an excess of
separately or in conjunction with the sludge conditioning the recuperable abiotic control species will result in con
described above while discussing FIGS. 1 and 2. are appli tinuously recycling a fraction of these species in carbonate
cable for the system shown in FIG. 3 and will not be form between the anaerobic and abiotic (or aerobic) zones.
repeated. It is understood that the multistage systems may Carbonates will support the higher limit pH in the anaerobic
have separate abiotic zones. or abiotic functions can be zone all the time but during the maximum loading rate on the
combined with biological functions in biological treatment system. when the excess of carbonate form of the recuper
zones. 45 able abiotic species will be spent. Therefore. alkalinity loss
FIGS. 4A to 4E illustrate the use of the present method in due to carbon dioxide will be controlled without any
a batch mode. The batch system consists of at least one instrumentation. on/o? or the variable rate operation of
reactor 2 with optional sludge conditioning sections 7. the metering pumps. If the alkalinity loss due to carbon dioxide
means for ?lling the in?uent and discharging the effluent. persists. the recycle rate between the anaerobic and abiotic
mixing means. means for stripping carbon dioxide. and feed 50 zones should be temporarily increased. The use of the sludge
means for the recuperable abiotic species. Only the reactor conditioning for dynamic controls should also include the
and sludge conditioning zones are shown in FIGS. 4A to 4E. excessive conditioned sludge recycle so that the need in the
Other means are familiar to those skillful in art and are not VFA consumption by methanogens is always satis?ed. If
discussed here. The system is operated as follows. After the alkalinity loss due to VFA persists. the recycle rate of the
start up and accumulation of biomass in the reactor 2. 55 conditioned sludge should be temporarily increased. In
wastewater is ?lled in the reactor from the level of the settled extreme situations. the needs in increasing the recycle of the
biomass to the operable level and the treatment step pro conditioned sludge or the recuperable abiotic species is
ceeds over the required time. Simultaneously. carbon diox detennined in the following sequence. The pH of the waste
ide is at least periodically stripped from the reactor and the water in the anaerobic reactor is continuously monitored.
content of the reactor is mixed by a mechanical mixer. water When pH reading is at the lower set point. the conditioned
jets. or gaslifts. including airlifts. or otherwise. The same sludge recycle is increased. If the observed pH does not
airlifts used for mixing can be used for carbon dioxide increase. the pH drop is. probably. not attributable to VFA
stripping. In such a case. the abiotic zone is the internal and the conditioned sludge recycle is returned to the normal
volume of the Such arrangement of the abiotic zone rate. The recycle of the recuperable abiotic species is than
can be used in other systems described herein or designed 65 increased and pH change is observed. If pH rises above the
later. A special air stripping. or other means can also be lower set point. the system is run at the increased recycle of
provided. More appropriately. these process steps should be the recuperable abiotic species and is periodically probed for
 5 .79 8.043
11 12
the possible return of this recycle to the normal setting. If from the said multi step system. digesting the said separated
after the return pH does not decrease below the lower set biomass to produce digested biomass. and feeding at least a
point. the normal setting remains. If the return causes pH to portion of the said digested biomass in at least one step of
drop. the increased recycle is continued. If pH keeps declin the said multi step system.
ing at the increased recycle of the recuperable abiotic 3. The method as claimed in claim 2. and further provid
species. recycle of the conditioned sludge is increased again. ing steps of pH measurement in the said anaerobic step.
Periodically. the system is probed for normal settings of both varying the rate of feeding the said digested biomass in at
recycles. least one step in the said multi step system. and varying the
recycle rate of the said insoluble carbonates from the said at
The completeness of carbon dioxide stripping and con least one carbon dioxide stripping step to the said at least one
version of carbonic acid species to carbonates can be anaerobic step.
checked by measuring pH in the bulk volume of the abiotic 4. The medtod as claimed in claim 3. and further provid
zone and in a portion of the same liquid added with a strong ing steps of di?erential pH measurement and controlling
alkali. preferably Ca(OH)2. If addition of Ca(OH)2 does not e?iciency of the said at least one step of carbon dioxide
rise pH. not all bicarbonates are converted to carbonates in stripping.
the abiotic zone. Accordingly. the rate of aeration should be 5. The method as claimed in claim 1. wherein the said
increased. Periodically probing the lime-added sample for wastewater is selected from the group comprising water.
pH and monitoring the pH in the bulk and correcting the air wastewater. aqueous industrial. agricultural and production
?ow rate provides the control of the abiotic zone used for the materials. industrial. agricultural and production gases. pol
recuperation of the abiotic species. luted air. gaseous vent emissions. solid waste. materials of
The pH probes in the anaerobic and abiotic zones can be plant. animal. or fossil origin. and solid industrial. agricul
used together with other probes. for example. a probe for tural or production streams. and combinations thereof.
carbon dioxide. ORP. temperature. ?ow meters. and others. 6. The method as claimed in claim 1. wherein the opera
Therefore. the pH measurement can be used to control the tion mode of at least one step in the said multi step system
carbon dioxide stripping. addition of the recuperable abiotic is selected from the group comprising batch operation.
species. and recycle of wastewater and sludges in various 25 continuous operation. and combinations thereof.
systems described here or designed in accordance with these 7. The method as claimed in claim 6. wherein the said
teachings. batch operation mode comprises steps of ?lling-stripping.
reacting-stripping. settling. and decanting the said wastewa
EXAMPLES I61‘.
A full scale three-stage anaerobic-aerobic system with a 8. The method as claimed in claim 7. and further provid
sludge conditioner at a pharmaceutical plant was charged ing a step of sludge conditioning.
with lime (dry calcium oxide charged in the anaerobic stage) 9. The method as claimed in claim 1. wherein the said
during a three-month start up period to control pH and was carbon dioxide stripping step is combined with at least one
operated for two more years without any alkali addition. step of the said multi step system selected from the group
Calcium was functioning as a recuperable abiotic specie. No 35 comprising an obligate anaerobic se facultative anaerobic
calcium carbonate scaling was detected in the system. step. anoxic treatment step. aerobic treatment step and
obligate aerobic step. and combinations thereof.
Computational analyses of anaerobic-aerobic counter?ow 10. The method as claimed in claim 1. wherein the
system for treatment of carbohydrate wastewater with very arrangement of the said steps in the said multi step system
low intrinsic alkalinity showed that calcium and calcium is selected from a group comprising sequential treatment
iron combination can be used as recuperable abiotic species steps parallel treatment steps. parallel-sequential treatment
with very low replenishment requirements. mainly for losses steps. treatment steps in a race track arrangement. and
of these species with wasted sludge. The required concen treatment steps with recirculating the said wastewater and
tration of recuperable species is inversely proportional to the the said biomass among and between the said steps. and
recycle rate of the wastewater and mixed liquor combined. combinations thereof.
It will therefore be understood by those skilled in the art 45 11. The method as claimed in claim 1. wherein the said
that particular embodiments of the invention here presented biomass in the said steps of the said multi step system is
are by way of illustration only. and are meant to be in no way composed of organisms selected from the group comprising
restrictive; therefore numerous changes and modi?cations obligate aerobic. facultative aerobic. anoxic. facultative
may be made. and the full use of equivalents resorted to. anaerobic. and obligate anaerobic microorganisms. and mix
without departing from the spirit and the scope of the tures thereof.
invention as outlined in the appended claims. 12. The method as claimed in claim 1. wherein the said
What is claimed is: recuperable abiotic control specie is selected from the group
1. In a method for controlling treatment of wastewater comprising calcium. magnesium. zinc. aluminum. iron.
conducted with biomass in a multi step system comprising nickel. cobalt. manganese. cesium. and combinations
at least one anaerobic treatment step and at least one carbon thereof.
dioxide stripping step. wherein the said wastewater and the 13. The method as claimed in claim 12. wherein the said
said biomass are sequentially treated in the said at least one recuperable abiotic control specie is selected from the goup
anaerobic treatment step and the said at least one carbon comprising zero-valent metals. salts. metal oxides. metal
dioxide stripping step the improvement is provided com hydroxides. organometallic compounds. and combinations
prising the step of charging at least one recuperable abiotic thereof.
control specie to at least one step in the said multi step 14. The method as claimed in claim 1. wherein digestion
system. whereby the said abiotic control species form gas is generated in the said anaerobic step. and further
insoluble carbonates or hydroxides in the said at least one providing steps selected from a group comprising discharg
carbon dioxide stripping step and at least partially convert ing the said digestion gas to the atmosphere. utilizing the
into soluble bicarbonates in the said at least one anaerobic said digestion gas. combusting the said digestion gas for
step. 65 elimination. and combinations thereof.
2. The method as claimed in claim 1. and further provid
ing steps of separating at least a portion of the said biomass *****