WO1993012044A1

WO1993012044A1 - Biological process for removing bod and nitrogen from wastewater

Info

Publication number: WO1993012044A1
Application number: PCT/DK1992/000381
Authority: WO
Inventors: Marshall L. Spector
Original assignee: I Krueger Systems As
Current assignee: I Krueger Systems As
Priority date: 1991-12-16
Filing date: 1992-12-16
Publication date: 1993-06-24
Anticipated expiration: 1994-06-16
Also published as: EP0618885A1; US5182021A; DE69211014D1; AU3255893A; AU659527B2; ATE138355T1; EP0618885B1

Abstract

A process for attaining concurrent biological nitrification and denitrification in an activated sludge treatment plant comprises aerating a mixed liquor in a first zone to attain nitrification of ammonia values to NOx, transferring the mixed liquor to a settling zone where activated sludge is allowed to settle from the mixed liquor, transferring at least a portion of the sludge to an anaerobic sludge holding zone where it is held for a period of at least 4 hours and returning the aged sludge from the sludge holding zone to the first zone for mixing with influent wastewater. By holding the sludge in the sludge holding zone for a prolonged period, a culture of organisms is developped which exhibits oxygen respiration in the presence of NOx. When returned to the first zone where nitrification is achieved, these organisms utilize the NOx being formed as an electron acceptor to metabolize sorbed BOD and to discharge the respiratory block. The result is concurrent biological nitrification and denitrification in the first zone. Improved biological removal of phosphorus and improved sludge properties are also obtainable.

Description

&

BIOLOGICAL PROCESS FOR REMOVING BOD AND NITROGEN FROM WASTEWATER

The present invention relates to processes for biologically removing BOD and nitrogen from wastewater by an activated sludge process comprising

(1) aerating a mixture of wastewater and activated sludge in a first zone;

(2) transferring the mixture thus treated to a separation zone in which activated sludge is separated from the treated water;

(3) transferring at least part of the separated activated sludge to a sludge holding zone maintained under anaerobic conditions and holding the activated sludge in the sludge holding zone for a period of time sufficient to effect complete nitrification;

(4) returning at least part of the activated sludge thus treated to the first zone.

The eutrophication of lakes, rivers and other water resources is receiving worldwide attention. The presence in the environment of nutrients, such as phosphate and nitrogen, is one of the primary causes of eutrophication. These nutrients promote unwanted growth of algae and other aquatic plants.

The eutrophication of our lakes and rivers has led to increased demands for nutrient control in wastewater treatment plants. Governmental agencies have enacted increasingly stringent regulations controlling the amount of nutrients which can be discharged into receiving waters. Since conventional treatment processes remove only small amounts of nitrogen and phosphate, wastewater treatment plants will be required to change or modify their processes to meet these increasingly stringent regulations. Unfortunately, the technology to achieve the required removal efficiencies is lagging behind regulatory requirements.

One approach for accomplishing nutrient removal is biological treatment in a modified activated sludge system without chemical addition. Numerous biological nutrient removal processes have been developed. These biological nutrient removal processes typically use a single sludge configuration in which the organic matter of the influent is used as the carbon and energy source for nitrogen and phosphate removal. This allows for a lower operation cost in comparison to multiple sludge systems and other physical-chemical systems.

In such biological systems, removal of nitrogen from wastewater is conventionally done by first nitrifying (converting ammonia to nitrite and nitrate, NO ) and then denitrifying (reducing NO to N₂) the wastewater. The process of nitrification is carried out in an aerobic environment by autotrophic organisms which derive energy for growth by oxidizing ammonia nitrogen values to NO . The energy produced is then utilized to produce protein material from inorganic components in the wastewater, such as l- O, C0₂ and NH₃. Denitrifica¬ tion is typically carried out in an oxygen-less environment by heterotrophic organisms which utilize NO A in the absence of oxygen as an electron acceptor for oxidation of sorbed organic compounds.

One biological nutrient removal process which is commonly used is known as the Bardenpho Process. The Bardenpho Process consists of an initial anaerobic contact zone followed by four alternating stages of anoxic and aerobic conditions. In the anaerobic zone, all of the raw wastewater is mixed with the return sludge. The anaerobic conditions in the initial contact zone are necessary to effect phosphate removal. The first anoxic zone follows the anaerobic zone. Nitrates and nitrites (NO ) are supplied to the anoxic zone by recycling nitrified mixed liquor from the following aerobic zone. The organic material in the raw wastewater is used as a carbon source- by the denitrifying bacteria^' in the. first anoxic zone to reduce NO to elemental nitrogen or nitrous oxide. The first aerobic (oxic) zone is followed by a second anoxic zone where any remaining NO in the mixed liquor is reduced by the endogenous respiration of the activated sludge. The final stage is aerobic where the mixed liquor is reaerated before reaching the final clarifier. The dissolved oxygen of the wastewater effluent is increased to prevent further denitrification in the clarifier and to prevent the release of phosphates to the liquid in the clarifier.

The Bardenpho Process is capable of achieving a high percentage of nitrogen compound removal as well as phosphate removal. However, the Bardenpho Process requires substantially larger tank volumes than conventional activated sludge systems which means higher capital outlays. Additionally, the Bardenpho System relies on endogenous respiration in the second anoxic reactor which is a relatively slow process. Thus, its use is limited to small plants.

Another biological nutrient removal process which is frequently used

2 2 is known in the industry as the A 0 Process. The A 0 process consists of three treatment zones - anaerobic, anoxic and aerobic.

The wastewater and return sludge are mixed in the first treatment zone which is maintained under anaerobic conditions to promote phosphate removal. The anaerobic zone is followed by an anoxic zone.

The third treatment zone is an aerobic zone where nitrification of the mixed liquor is achieved. The nitrified mixed liquor is recycled back to the anoxic zone where the nitrate and nitrite are reduced to elemental nitrogen and/or nitrous oxide by denitrifying organisms. 2 The A 0 system has a high rate of nitrogen removal and requires total tank volume comparable to that of conventional activated sludge systems. Thus, the A 0 system is a cost effective system for

2 nutrient removal. However, the A 0 system requires a relatively high mixed liquor recycle rate in order to achieve high nitrogen removal efficiency.

US-A-4488967 describes a process in which a mixture of wastewater and activated sludge is maintained under anaerobic conditions in a first zone before it is transferred to a second zone wherein it is maintained under aerobic conditions by being aerated. The aerated mixture is transferred to a settling zone in which activated sludge is separated from the treated water. Part of the separated activated sludge is transferred to a holding zone in which it is held under non-aeration conditions for a period of time sufficient to reduce any nitrates and/or nitrites contained therein before it is recycled to the first zone and mixed with incoming wastewater.

Reports of denitrification in the presence of oxygen by different species of bacteria have been published over the last years. However, almost all the work done this far has been in the laboratory with cultures of a few species of bacteria. General explanations of this phenomenon have been suggested, one of which is to the effect that during the metabolism of the bacteria some compounds are produced which inhibit oxidase, i.e. the oxygen respiration.

The object of the invention is to provide a process of the type defined above which is suitable for use in full scale plants and wherein a concurrent biological nitrification and denitrification (CBND) is effected.

The process of the invention is characterized in holding the separated activated sludge in the holding zone for a period of at least 4 hours after complete nitrification of the sludge.

Surprisingly, it has been found that by holding the sludge to be recycled to the first zone for such a prolonged period of time the wastewater will be subjected to both a nitrification and a denitrification when present in said first zone. The mechanism of such concurrent biological nitrification and denitrification is not known, but it is specul ted that the prolonged holding of the return sludge in the holding zone promotes a selection of bacteria which in the presence of NO Λ* produce oxidase inhibitors. When present in the first (aerobic) zone the bacteria having their oxygen respiration blocked are forced to use NO as electron acceptor and thus cause denitrification.

Thus, in the process of the invention ammonia nitrogen values in the wastewater are oxidized to NO in the first (aerobic) zone while NO are concurrently reduced to nitrogen and/or nitrous oxides.

Concurrent biological nitrification and denitrification in a single zone greatly reduces capital outlays for plants for the biological removal of BOD and nitrogen from wastewater as well as the operational costs of such plants.

s mentioned above, the return sludge is held in the holding zone for at least 4 hours after complete denitrification of the return sludge. Experiments have shown that a holding time of from 4 to 20 hours ordinarily is sufficient to obtain concurrent biological nitrification and denitrification.

The sludge holding zone is preferably partitioned into two or more distinct sections in order to approximate plug flow in the sludge holding zone and thus to ensure that all parts of the sludge are maintained in the sludge holding zone for a prolonged period of time.

In some cases it may be desirable to stir the return sludge in the holding zone. However, the stirring should be effected in such a manner that the sludge is maintained under anaerobic conditions.

It may also be desirable to adjust the pH of the sludge in the sludge holding zone. Thus, the pH of the sludge in the holding zone should preferably be between 5 and 8.5.

The anaerobically conditioned sludge is mixed with the influent wastewater in the first zone which is preferably aerated to such an extent that the concentration of dissolved oxygen (D.O.) is between 1 and 3 ppm.

if desired in order to obtain a particularly efficient removal of nitrogen, the process of the invention may also comprise a separate treatment in an anoxic zone. Such an anoxic treatment may be effected prior to or subsequent to the treatment in the aerobic zone.

The process of the invention may be modified so as to effect not only nitrogen removal, but also phosphate removal and sludge bulking control .

Thus, in a preferred embodiment of the invention the return sludge from the holding zone is mixed with wastewater in a zone which is maintained under anaerobic conditions before the mixed liquor is introduced into the aerobic zone. If subjected to such an initial treatment under anaerobic conditions phosphate storing bacteria get preferential access to BOD in the incoming wastewater.

Compared to the well-known Phostrip method this embodiment of the invention presents the advantage that no chemicals have to be added and that the sludge should not be subjected to further treatments before it is mixed with the incoming wastewater. As a result, the process tends to favor selection of these organisms to the disad- vantage of other species of organisms. These organisms have been found to effect both phosphate removal and the production of a non-bulking sludge. By holding the sludge in the anaerobic zone for a prolonged period of time this selection is improved.

If desired, in order to obtain a particularly efficient removal of nitrogen, the latter embodiment of the process of the invention may also comprise a separate treatment in an anoxic zone. Such an anoxic treatment may be effected prior to or subsequent to the treatment in the aerobic zone.

The production of non-bulking sludge may be further improved by dividing the anaerobic and/or the aerobic zone into hydraulically distinct sections so as to promote plug flow through these zones.

Preferred embodiments of the present invention is shown in the following detailed description with reference to the drawings, where

Figure 1 is a schematic diagram illustrating one embodiment of the present invention.

Figure 2 is a schematic diagram illustrating an alternative embodi¬ ment of the present invention.

Referring now to the drawings, and particularly to Figure I, a modified activated sludge wastewater treatment system is shown therein and indicated generally by the numeral 10. The wastewater treatment system includes a secondary treatment zone indicated generally at 12, a final clarifier 14, and a sludge holding tank 16. The secondary treatment zone 12 comprises an anaerobic first stage A followed by an aerobic stage B. The anaerobic stage A and aerobic stage B are preferably partitioned into two or more cells in order to approximate plug flow of liquid. It has been found that by provision of physically partitioned sections of the hydraulic equivalent thereof, there is better assurance of achieving freedom from filamentous growth and selection of a biomass in zone A capable of effecting CBND and better assurance of removal of NO and phos¬ phates in zone B. In the embodiment shown, the anaerobic stage is divided into two distinct cells Al and A2. The aerobic stage is divided into four distinct cells B1-B4.

Wastewater to be treated enters anaerobic stage A through line 18 where it is mixed with return activated sludge from the sludge holding tank 16 which enters through line 20. Typically, wastewater is settled sewage from a primary sedimentation tank or clarifier (not shown), but primary sedimentation is not necessary. The influ¬ ent wastewater initially enters cell Al where it is stirred and admixed with recycled sludge to form a mixed liquor.

After anaerobic treatment, the mixed liquor is transferred to the aerobic zone B where the mixed liquor is aerated. Oxygen-containing gas such as air is admitted into each cell B1-B4 in a manner well- known to those skilled in the art. For example, compressed air may be admitted into each cell (B1-B4) by spargers 26. Alternatively, the secondary treatment area 12 may be provided with mechanical aerators instead of, or in addition to spargers.

In the aerobic zone B, the mixed liquor is aerated under conditions sufficient to oxidize BOD and to convert ammonia (NH₃) present in the wastewater to NO . The N0_χ so produced is concurrently reduced by "aerobic denitrifiers" as will be hereinafter described.

To achieve almost complete nitrification, the sludge age within the system should be about 1.5 days at 30^βC and 10 days at 10°C. Sludge age is defined as the weight of MLSS in zone B divided by the weight of MLSS wasted per day. Further, the dissolved oxygen concentration should preferably be maintained between about 1 to 3 ppm, although nitrification may be attained at D.O. levels as low as 0.5 ppm. Lower dissolved oxygen concentrations retard or inhibit ammonia oxidation, while higher D.O. concentrations retard the extent of concurrent biological nitrification and denitrification (CBND) in the secondary treatment area.

After aeration, the mixed liquor passes from the aerobic zone B to a clarifier 14. The sludge in the mixed liquor settles to the bottom of the clarifier 14 thereby forming a clear supernatant in the top of the clarifier 14 and a dense sludge layer 15 in the bottom. The supernatant is discharged either to further treatment or directly to receiving waters through line 22. Activated sludge concentrated in sludge layer 15 on the bottom of the clarifier 14 is transferred to a sludge holding tank 16 through line 24 where the sludge is held in the substantial absence of added oxygen for a prolonged period. A holding period of approximately 4 hours to 20 hours after complete definitrification of the sludge 15. If the sludge is held fewer than 4 hours, the extent of CBND is reduced. If held more than 20 hours, excessive expense is incurred for unnecessary storage capacity. The minimum of 4 hours in the holding tank may be diminished by the nominal sludge residence time in the clarifier, provided that the sludge in the clarifier is free of NO A and is not re-exposed to oxygen in transit from the clarifier 14 to the holding tank 16.

In order to prevent sludge from "bypassing" the sludge holding zone, it is preferred that the sludge holding zone is divided by parti- tions into two or more sections to approximate plug flow conditions. This arrangement will prevent sludge from exiting too quickly and will assure that the sludge is sufficiently conditioned prior to its return to the mainstream.

By holding the sludge for a prolonged period under anaerobic condi¬ tions, a bio ass is developed which exhibits an oxygen respiration block in the presence of NO . These organisms appear to have deve- loped a survival mechanism that enables them to utilize NO as an electron acceptor, even in the presence of high levels of dissolved oxygen. A possible explanation is that nitrite reduction enzymes in these organisms are activated by the prolonged anaerobic storage period and remain active during several hours of aerobic conditions. When these organisms are returned to the aerobic zone B, where nitrification is being attained, they utilize NO as an electron acceptor to metabolize sorbed BOD. The result is that concurrent biological nitrification and denitrification is achieved in the aerobic zone B, even under air saturation conditions.

A high degree of nitrogen removal may require a following anoxic denitrification zone, cf. Figure 2 - Cl and C2, or an anoxic zone before the aeration zone with recycling of nitrified mixed liquor. Total retention times for this process are much lower than for the Bardenpho process, and removal efficiencies are much higher than for conventional A/0 processes.

Several examples, using the method of the present invention are set out below. These examples are illustrative of the present invention and are not means to be limiting.

EXAMPLE 1

Two laboratory units were operated as shown in Figure 1 over a period of two weeks. The dissolved oxygen concentration in Unit 1 was maintained at approximately 8 ppm (close to air saturation). The dissolved oxygen concentration in Unit 2 was maintained at approxi¬ mately 2 ppm. The results are reported in Table 1 below.

TABLE 1

Unit 1 Unit 2

Influent

SB0D5 (mg/1) TKN (mg/1) NO_χ-N (mg/1)

NH3-N (mg/1) Total P (mg/1)

Operating Conditions Volume (liters) D.O. In Aerobic Zone (mg/1) Total HRT (minutes) Anaerobic HRT (minutes) Aerobic HRT (minutes) Clarifier HRT (minutes) Sludge Holding Period (minutes) Sludge Recycle (% of influent) MLSS (mg/1)

Effluent

SBOD (mg/1) NH₃-N (mg/1) NO_χ-N (mg/1)

Total P (mg/1) Protein Nitrogen Missing Nitrogen

It will be seen from Table 1 that Unit 1 removed approximately 17.2 ppm of nitrogen from the influent. The missing nitrogen in Unit 1, which is believed to be removed by CBND, was 15.3 ppm. Missing nitrogen is the nitrogen removed that cannot be accounted for by protein nitrogen, effluent nitrogen or NO reduced during settling in the clarifier. Unit 2 removed approximately 19.7 ppm of nitrogen, of which 16.7% is considered missing nitrogen removed by CBND. The total phosphate removed was 48% for Unit 1, and 81.6% for Unit 2.

EXAMPLE 2

A laboratory unit was run in accordance with the conditions of this invention as outlined in Figure 1, except the anaerobic sludge holding was omitted. Average values for two weeks of operation are reported in Table 2. TABLE 2

Infl uent

SB0D5 (mg/1 ) 96 TKN (mg/1 ) 14.0 NO_χ-N (mg/1 ) 0 NH3-N (mg/1 ) 12.9 Total P (mg/1 ) 7.1

Operating Conditions

Volume (liters) 2.0

D.O. In Aerobic Zone (mg/1) 8.0

Total HRT (minutes) 240

Anaerobic HRT (minutes) 42 Aerobic HRT (minutes) 110

Clarifier HRT (minutes) 68

Sludge Recycle (% of influent) 43%

MLSS (mg/1) 2819

Effluent

SB0D (mg/1) <5 NH₃-N (mg/1) .39 NO_χ-N (mg/1) 6.0 Total P (mg/1) .7 Protein Nitrogen 4.5 Missing Nitrogen 3.1

In this test, the unit without a prolonged sludge holding zone removed approximately 9.4 ppm of nitrogen. In units 1 and 2 of Example 1, total nitrogen removed was 17.2 ppm and 19.7 ppm respec¬ tively. The missing nitrogen (which is removed by CBND) was only 3.0, compared to 17.2 and .16.7 in Units 1 and 2 of Example 1. This illustrates the effectiveness of prolonged sludge holding in promo¬ ting CBND.

EXAMPLE 3

Example 3 illustrates the process shown in Figure 2 wherein an anoxic trim zone follows the aerobic zone. As discussed herein •=* • before the anoxic zone tends to trim both the nitrogen and phosphate and effectively reduces these nutrient levels to a relatively low level.

Two laboratory units were operated as described in Example 1, except that the duration of the sludge holding was reduced from 1167 to 1047 minutes and the mixed liquor was held and gently stirred in the anoxic zone for a period of 120 minutes. The mixed liquor of the anoxic zone was sampled at various time periods indicated in Table 3. Results of the filtrate analysis from the anoxic zone are shown in Table 3.

TABLE 3

Nitrite ppm Nitrate ppm N0_χ ppm Ammonia ppm Phosphate ppm Unit 1 Unit 2 Unit 1 Unit 2 Unit 1 Unit 2 Unit 1 Unit 2 Unit 1 Unit

End of aeration .65 2.17 1.4 .88 2.05 3.05 .5 1.4 3.1

15 min. 1.19 1.00 2.19 .4 1.9

30 .85 1.06 1.91 .2 1.1

60 .51 1.13 1.64 .3 0

120 19 .24 .67 1.22 .87 1.46 .28 .2 0

The above data indicates that the total nitrogen is trimmed signifi¬ cantly and the phosphate in the filtrate is reduced to less than the limit of detection. The data suggests that an anoxic retention time of 60 min. will be sufficient to remove virtually all soluble phosphate and to reduce total nitrogen to less than 2.0 ppm.

The process of the present invention has several significant advan¬ tages over prior art activated sludge treatment systems. First, because nitrification and denitrification is carried out in a single reactor, the present invention reduces the total pumping capacity required for transporting the wastewater and further, the use of a single reactor results in a tremendous savings in terms of capital outlays needed to construct or modify a treatment plant to preactice the present invention. Further, the present invention has extremely low operating costs since neither chemicals nor denitrification filters are needed to attain extremely low levels of phosphate and nitrogen in the effluent. Further, the process of the present invention produces a compact, dense sludge which settles rapidl in the final clarifier. As a result, fewer operational difficulties, such as sludge loss over the weir, are encountered, and greater operational stability is realized.

The present invention may, of course, be carried out in other specific ways than those set forth without departing from the spirit and essential characteristics of the invention. The present embodi¬ ments are, therefore, to be considered in all respects as illustra¬ tive and not restrictive and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein.

Claims

C l a i s

1. A process for biologically removing BOD and nitrogen from wastewater in an activated sludge process comprising

(1) aerating a mixture of wastewater and activated sludge in a first zone;

(4) returning at least part of the activated sludge thus treated to the first zone

c h a r a c t e r i z e d in

holding the separated activated sludge in the holding zone for a period of at least 4 hours after complete denitrification of the sludge.

2. A process according to claim 1, c h a r a c t e r i z e d in holding the separated activated sludge in the holding zone for a period of between 4 and 20 hours after complete denitrification of the sludge.

3. A process according to claim 1 or 2, c h a r a c t e r i z e d in maintaining the concentration of dissolved oxygen in the first zone between 1 and 3 ppm.

4. A process according to any of the preceding claims, c h a r ¬ a c t e r i z e d in using a sludge holding zone partitioned into two or more distinct sections.

5. A process according to any of claims 1-4, c h a r a c - t e r i z e d in stirring the sludge in the sludge holding zone.

6. A process according to any of the preceding claims, c h a r ¬ a c t e r i z e d in adjusting the pH of the sludge in the sludge holding zone at a value of between 5 and 8.5.

7. A process according to any of the preceding claims, c h a r ¬ a c t e r i z e d in

(a) mixing wastewater with returned activated sludge in a contact zone maintained under anaerobic conditions; and

(b) transferring the mixture in the anaerobic contact zone to said first zone.

8. A process according to any of the preceding claims, c h a r ¬ a c t e r i z e d in

(a) transferring the mixture in the first zone to an anoxic zone; and

(b) transferring the mixture in the anoxic zone to the separation zone.

9. A process according to claim 7, c h a r a c t e r i z e d in

(a) transferring the mixture in the anaerobic contact zone to an anoxic zone;

(b) transferring the mixture in the anoxic zone to the first zone; and

(c) recycl ng part of the mixture in the first zone to the anoxic zone.

10. A process according to any of the preceding claims 1-6, c h a r a c t e r i z e d in

(a) mixing wastewater with returned active sludge in an anoxic zone;

(b) transferring the mixture from the anoxic zone to the first zone;

(c) recycling part of the mixture in the first zone to the anoxic zone.