1. Field
This disclosure relates to treatment of wastewaters containing organic matter, phosphorus and nitrogen. In particular, the disclosure relates to utilizing sulphur compounds as the electron carrier for biological nutrient removal of wastewater treatment
2. Background
Since the discovery of activated sludge process and the introduction of the biological nutrient removal processes, the biological Phosphorus (P), Nitrogen (N) and Carbon (C) removal processes has remained the same, i.e., with electron flow from carbon to oxygen through heterotrophic carbon oxidation, as shown in
The details of this biological P, N and C removal process are as follows:
If nitrogen removal is not necessary, the biological processes can be simplified as
As the heterotrophic carbon oxidation and heterotrophic denitrification process has a very high sludge yield factor, depending on the sludge age, about 40-50% of the organic carbon in the sewage will be converted to CO2 while the rest converted to sewage sludge. The disposal of excess sludge, which often involves sludge digestion, dewatering and incineration, is not only costly, but also unwelcome by neighbours to the facility.
Since the introduction of biological phosphorus (P) removal process in 1970s, the process has relied on the electron flow from organic carbon to oxygen via an integrated P-uptake and release cycle. As the process has a high sludge yield, excess sludge disposal is required.
Sulfate Reduction Autotrophic Denitrification and Nitrification Integrated SANI Process
Making use of the sulfate ion available in the saline sewage of Hong Kong, where seawater is used for toilet flushing, the Hong Kong University of Science and Technology developed the novel Sulfate reduction Autotrophic denitrification and Nitrification Integrated (SANI) process (Lau et al., 2006; Lu et al., 2009; Wang et al., 2009) as shown in
Each liter of seawater contains about 2.7 grams of sulphate. When used with a seawater flushing system, the sulphates in seawater can be used to oxidize the organic carbon pollutants forming sulphide; while the sulphide formed can then be used to reduce nitrate to nitrogen gas through autotrophic denitrification, which can help sludge reduction. The SANI process uses sulphate-reducing bacteria to oxide and eliminate pollutants in the seawater-mixed sludge. It is noted, however, that the sulphate cannot directly reduce sludge; however, it is used as a oxidizing and reducing agent to remove organic carbon and nitrate, which in turn results in sludge reduction.
The three key biological chemical processes all produce minimal sludge as shown in the following equations:
(1) Heterotrophic Sulfate Reduction:
127.8 gCOD+192 gSO42−+55.8gH2O→68 gH2S+2.4 gSludge+244 gHCO3−
(2) Sulfide Oxidation and Autotrophic Denitrification:
124gNO3−+7.32 gHCO3−+44.54 gH2S→28 gN2+125.76 gSO42−+2.66 gSludge
(3) Autotrophic Nitrification:
18 gNH4++1.32 gCO2+62.4 gO2→0.94 gSludge+62 gNO3−+2 gH++17.64 gH2O
Limited-Oxygen Sulphur Cycle-Associated EBPR (LOS-EBPR) Process
In view of its significant environmental and financial benefits to minimize sludge production by the SANI process, research has been conducted to extend the SANI process for P-removal. The success of this biological P-removal SANI process lies with the development of the P uptake and release in the sulphur cycle. Although the oxygen and nitrate induced P-uptake and release phenomenon has been fully studied and understood, the proposed sulphur cycle involved P-uptake and release has not been extensively tested. The phenomenon is described in Sulfate Reducing Bacteria (SRB) with the PAOs.
Sewage treatment is performed using a first cycle which uses sulphur comprising at least one of sulphur and sulphur compounds to transfer electrons from organic carbon to oxygen, nitrate and nitrite. The sulphur is also used to convert phosphorus containing compounds to solid material for retention in sewage sludge. The sulphur is then used to perform denitrification of nitrogen compounds. Oxygen is used to oxidize any ammonia present to nitrate and/or nitrite.
By introducing the sulphur cycle into the carbon oxidation cycle, a Sulphur cycle-associated Denitrifying Enhanced Biological Phosphorus Removal (SD-EBPR) process is developed for biological nutrient removal (BNR) with minimal sludge production.
In terms of operation, the feed and the reaction of an aerobic sequencing batch reactor (SBR) can be combined into a single step. Moreover, to enable a more efficient operation, it is also possible to use a combination of several similar or identical biological P-removal reactors and nitrification reactors operating in parallel in order to smooth out the operations. Through the SD-EBPR process, it is possible to achieve biological nutrient removal from wastewater while at the same time minimizes sewage sludge production.
The sulphur can be derived from any convenient source. In non-limiting examples, saline sea water provides the sulphur. The saline water is either provided as part of the wastewater, for example as a saline water flush system, or is added to the wastewater during treatment. The salinity is not essential, and is only one way to provide the sulfate and/or sulphite. The sulphur can also be provided from industrial effluent such as flue gas desulphurization units.
The SD-EBPR process is shown in
The depiction of
Under anoxic condition, there is nitrate (NO3−) and nitrite (NO2−). During the process bacteria will use up the oxygen from nitrate and convert the nitrate to nitrogen gas. In this phase, bacteria consume the phosphorus from the bulk liquid. This contrasts with anaerobic processed in that, under anaerobic conditions, there is no nitrate and nitrite, and instead bacteria will release phosphorus into the bulk liquid.
Depending on the design of the reactors, apart from activated sludge/SBR process, other types of reactor designs such as granular sludge bed, attached growth biofilters, membrane biological reactors, can be used for biological P-removal. Moreover, the SD-EBPR process can be operated in many forms, such as a combination of SBR in parallel operation to enable a continuous flow condition, as shown in
The minimum sulphur content is related to the concentration of organic material in the wastewater. A minimum ratio between the organics and sulphur contents used to completely process the wastewater would be 2 g COD/1 g SO4−S or 1.5 g COD/g SO3−S, where COD is the Chemical Oxygen Demand. This ratio may change if other sulphur compounds, e.g. thiosulfate, is used. It is also possible that lower ratios can be used, such as at least 1.5 g COD/g SO4−S, or 1 g COD/g SO3−S by weight, depending on the characteristics of the wastewater being treated.
Using Other Sulphur Compounds
The SD-EBPR process, apart from sulfate, may make use of other possible sulphur oxidation and reduction processes for accomplishing the heterotrophic sulphur reduction and autotrophic sulphur oxidation processes. The key biological processes involved in the autotrophic oxidation of sulphur compounds are shown in
As compared to the conventional biological P-removal processes, the SD-EBPR process makes use of the sulphur compounds as electron carrier for the oxidation of organic carbon to carbon dioxide. As both the anaerobic sulphur-reduction and autotrophic sulphur-oxidation processes have very low sludge yield factor, the sludge production rate of the SD-EBPR process is much lower than conventional P-removal processes. It effectively minimizes the need for sludge wastage, handling and disposal requirements. This not only reduces a large amount of sewage treatment cost, but also reduces greenhouse gas emission.
Effectiveness of the SD-EBPR
As compared with conventional biological process, shown in
As compared with the SANI process, shown in
A 140-day lab-scale study was completed using synthetic sewage, confirming that the SD-EBPR system, as shown in
Set Up of the SD-EBPR Lab-Scale System
Reactor 1 was made of transparent PVC, having a total reactor volume of 5 L (4 L reaction volume and 1 L headspace). This reactor was tightly sealed and continuously operated in darkness, with mixing by a mechanical mixer, at 250 rpm. Reactor 2, packed with plastic media (specific area of 200 m2/m3), had an effective liquid volume of 4 L. In addition, a 3.5 L tank was used to collect the nitrified effluent from Reactor 2, and then pumped into Reactor 1 at the initial of anoxic reaction phase.
Reactor 1 was operated continuously under an alternating anaerobic/anoxic condition. The cycle length of this SBR (Reactor 1) was 720 min in total. The cyclic operation of this anaerobic anoxic-SBR, comprised (i) feeding of 2 L synthetic sewage (in 10 min), (ii) anaerobic reaction phase (in 310 min), (iii) setting (30 min), (iv) decanting 3.5 L of liquid (i.e., primary discharge) into Reactor 2 (in 10 min), (v) feeding of 3.5 L nitrified effluent from the collecting tank into Reactor 1 (in 10 min), (vi) anoxic reaction phase (in 230 min), (vii) settling (in 110 min), and (viii) decanting 2 L of supernatant as the final effluent (in 10 min).
Reactor 2 was intermittently operated in every 12 hours. In each operation, the cycle length of this SBR (Reactor 2) was 6 hours in total. The cyclic operation of Reactor 2 comprised (i) feeding 3.5 L of partially treated effluent from Reactor 1 into Reactor 2 (in 10 min), (ii) aerobic condition for autotrophic nitrification (in 310 min), (iii) settling (in 30 min), and (iv) decanting 3.5 L supernatant into the collecting tank (in 10 min).
After the nitrified effluent of Reactor 2 was discharged into the collecting tank, Reactor 2 and collecting tank was put aside in the idling condition of 6 hours; the nitrified effluent in the collecting tank was used by step (v) of Reactor 1 after 6 hours.
The system SRT values were estimated based on the effluent washed out solids.
Synthetic Sewage
Synthetic sewage composition was modified from a composition developed by Kuba, et al. (1993) in terms of organic carbon and phosphorus concentrations, which contained 400 mg COD/L, 20 mg P/L and 50 mg N/L. It was prepared from 0.521 g/L NaAc, 0.067 g/L K2HPO4 and 0.035 g/L KH2PO4. Appropriate amounts of nitrogen and macro minerals were added to the feed by adding 0.19 g/L NH4Cl, and 0.01 g/L EDTA (Kuba et al., 1993), and 2.0 ml/L trace mineral solution. The only organic substrate was sodium acetate. The sulphur source was provided by using 20% of real toilet flushing seawater instead of distilled water in the synthetic sewage. Seawater naturally contains sufficient ions of Mg2+, K+ and Ca2+ required for poly-P synthesis.
System Performance
When operating under the anaerobic condition, Reactor 1 performed anaerobic acetate uptake (maximum rate≈11 mg C/g VSS/h) and sulfate reduction (maximum rate≈4 mg S/g VSS/h), in concomitant with anaerobic P release (maximum rate≈6 mg P/g VSS/h). The PHA synthesized during anaerobic phase was 30±12 mg PHA-C per cycle, while the poly-S2−/S0 formed was 21±8 mg poly-S2−/S0-S per cycle. In the subsequent anoxic condition, Reactor 1 performed denitrification (maximum rate≈10 mg N/g VSS/h) and anoxic P uptake (maximum rate≈11 mg P/g VSS/h). The stored PHA and poly-S2−/S0 were completely consumed during the anoxic reaction phase. In summary, Reactor 1 achieved the volumetric rates of anaerobic acetate uptake, anaerobic sulfate reduction and anoxic nitrate consumption at 115±5.5 mg C/L/d, 48±6.9 mg S/L/d and 90 mg N/L/d, respectively. Meanwhile, the volumetric P removal rate from the bulk liquid in Reactor 1 was 7.2±3.2 mg P/L/d.
In Reactor 2, most ammonia was oxidized to nitrate, with an effluent nitrate concentration of 45 mg NO3—N/L. All of effluent nitrate was used for denitrification and anoxic P-uptake in the anoxic reaction phase of Reactor 1.
Over all, this new bioprocess has been operated for simultaneous removal of organics, nitrogen and phosphorus, exhibiting excellent performance with COD=100%, N removal >90%, and P removal >85%. The final effluent total COD, total nitrogen (TN) and total phosphorus (TP) of Reactor 1 was about 40˜60 mg COD/L, 0˜5 mg TN-N/L, and 0˜3 mg TP-P/L.
Comparing with conventional heterotrophic bacteria, both the sulphur cycle-associated bacteria and autotrophic bacteria produced much less sludge. The average MLVSS in Reactor 1 was about 3±0.5 g VSS/L. The observed yield coefficient of Reactor 1 was 0.05±0.02 g VSS/g COD. This confirmed that nearly no biological excess sludge removal from Reactor 1 was required. The settling capacity of the sludge in Reactor 1 was good, the SVI30 of this sludge was 48±5 ml/g, since a large amount of inorganic poly-P had been accumulated in the sludge and the MLVSS/MLSS ratio was as low as 0.6˜0.75 g VSS/g SS. The final effluent TSS was <40 mg SS/L.
Energy consumption and CO2 emission from a treatment plant were mainly contributed from two sources: operation and sludge disposal. As there was no excess sludge removal required, we estimated that the SD-EBPR process could reduce one-third of energy consumption and greenhouse gas emission as compared with conventional biological nutrient removal process.
It is noted that, while influent and effluent is described, it is possible to pre-treat the sewage, which is likely in some areas where intermediate settling plants are used, and to post-treat the sewage, for example to reduce bacteria levels. Therefore, “influent” and “effluent” may be intermediate connections rather than the initial inflow of sewage or the final discharge of treated waste. Additionally, further processes can be included within the system within the scope of the technique.
It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described and illustrated to explain the nature of the subject matter, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims.
Filing Document | Filing Date | Country | Kind |
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PCT/CN2014/090970 | 11/13/2014 | WO | 00 |
Number | Date | Country | |
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61962634 | Nov 2013 | US |