Patent Grant
8444861
The present invention relates in general to the treatment of organic waste material, such as sludge resulting from sewage treatment facilities, animal waste, or industrial organic waste. More specifically, the invention relates to a process and apparatus for treating organic waste materials by the combination of microwave irradiation and oxidants such as hydrogen peroxide or ozone as a form of advanced oxidation process (AOP). The invention functions to solubilize organic solids through hydrolysis, resulting in soluble compounds available for recovery or further processing, as well as providing microbicidal activity, breaking down organic molecules, and reducing the mass of residual solid matter.
The disposal of organic waste materials such as sewage sludge, animal manure, food processing waste, and the like, presents both environment and public health concerns.
The production of large volumes of sludge as an end-product from wastewater treatment processes poses one of the biggest challenges to the wastewater treatment industry. The handling and disposal of sludge residuals has significant social, environmental, and economic implications. Treatment and disposal of sewage sludge from wastewater treatment plants can account for over half of the total cost of wastewater treatment plant construction and operation. Currently, residual sludge is commonly digested, incinerated, deposited in landfills, or used as fertilizer through agricultural land application of the residual biosolids.
In current wastewater treatment processes, toxic heavy metals become concentrated in the residual sludge. There may also be dangerous levels pathogenic organisms present in the residuals. For these reasons there are increasing concerns that land application of sludge residuals may be harmful to the environment and to public health. Under such social, environmental and economic pressures, significant effort has been invested in developing new methods of treating wastewater and wastewater sludges that result in smaller amounts of residual requiring disposal.
Anaerobic digestion is a very common solids reduction and stabilization technology, but is relatively inefficient due to the low biodegradability of the sludge. This poor biodegradability is particularly evident in the case of digesting secondary or waste activated sludge. The benefit of anaerobic digestion is that the methanogenesis stage of the process results in the production of methane (biogas) which can be used as an energy source. To improve the efficiency of the anaerobic digestion process, many techniques which enhance the biodegradability of these sludges have been developed in recent years.
The anaerobic degradation of particulate organics is considered to be a sequence of three steps: hydrolysis, acidogenesis, and methanogenesis. Among these, biological hydrolysis of the particulate organics has been considered to be the rate limiting step.
Many of the techniques recently developed to improve the biodegradability of sludges therefore focus on improving hydrolysis by other means. The processes most focused on are chemical oxidation disintegration by ozone, mechanical disintegration by various methods, and thermal or thermal/chemical disintegration. These techniques include those discussed in the following references:
Most of these prior processes operate either with large amount of chemical dosage or under high temperature and pressure conditions or both. Energy consumptions are typically large for many of these processes.
There remains a need for a cost-effective process to achieve solid waste disintegration, nutrient solubilization and pathogen destruction.
The foregoing examples of the related art and limitations related thereto are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings.
The following embodiments of the present invention and aspects thereof are described and illustrated in conjunction with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements to the existing art.
The present invention relates to a process and apparatus for treating slurries of organic solids. A slurry of organic solids is admixed with hydrogen peroxide, followed by exposure to microwave irradiation resulting in the heating of the mixture and enhanced hydrolysis of the organic solids. The treated slurry of organic solids can then be further treated in a variety of downstream processes, including solid separation, digestion and fermentation. The supernatant portion of the treated slurry of organic solids can subsequently be used beneficially as a source from which to recover valuable compounds such as nutrients (for example nitrogen, phosphate, potassium, magnesium, calcium) or industrial organic compounds (such as acetic acid, propionic acid, butyric acid), or as a source of readily biodegradable organic compounds for supplementing a biological wastewater treatment process, digester or fermenter. The treatment process also results in the conversion of a significant portion of volatile solids to soluble organic compounds, thus leaving reduced amounts of sludge solids for further treatment and disposal and increasing the rate at which the waste can be stabilized in downstream treatment processes.
The process can also be used, for example, as a side stream process, treating a portion of return activated sludge in an activated sludge treatment process. This would result in a significant reduction in overall process sludge yield, and produce a supernatant stream suitable for nutrient removal or recovery through a variety of known processes (chemical precipitation, ion exchange or struvite recovery for example). This would also provide a source of readily biodegradable organic compounds, comprised primarily of volatile fatty acids (such as acetic acid, propionic acid and butyric acid) which can be used to improve biological nutrient removal processes such as denitrification and enhanced biological phosphorus removal. Reintroduction of the treated effluent from the AOP at strategic points in a wastewater treatment could lead to significant improvements in denitrification rates as well as biological phosphorus removal rates.
The term “slurry of organic solids” is used herein to refer generally to waste materials such as sewage sludge, animal manure, food processing waste and the like. The term “supernatant” is used herein to refer generally to a liquid wastewater solution separated from such a slurry, by means such as gravity sedimentation, floatation, filtration, centrifugation or the like.
Slurries to be treated using the current invention can have a suspended solids content in the range of 0.05% to 30%, while most typical slurries that are anticipated to be of commercial interest will typically have suspended solids content in the range of 0.1 to 15%. Below this range of solids content the energy and chemical requirements are likely to become uneconomical, and above these solids ranges, the slurries become difficult to convey using fluid pumping equipment and efficient mixing of the oxidant in the slurry becomes difficult due to the elevated viscosity of the slurry.
Peroxide dosage rates found to be effective in treating the slurries is a minimum of 0.03% H2O2 by volume in the admixed slurry, or 0.3 g of H2O2 per litre of admixed slurry. Below this dosage rate the enhancement of thermal hydrolysis by microwave irradiation alone is not significantly improved. 30% hydrogen peroxide solution has been found to be a suitable source of hydrogen peroxide for the process.
It has been shown that Ozone can be used in place of hydrogen peroxide as a source of oxidant for the current process, however in embodiments tested to date, hydrogen peroxide has been shown to be more effective.
For the treatment of secondary sewage sludge slurries, it has been found that pH adjustment is of some but little benefit to the process in terms of its ability to solubilize chemical oxygen demand, and reduce suspended solids levels. In this case operation in the pH range of 6 to 7 has been found to be optimal.
For the treatment of certain slurries, such as dairy manure, it has been found that acidification of the slurry to a pH as low as 2, using a strong acid, such as sulfuric acid, either before or after treatment with the current invention significantly improves the solubilization of the slurry through acid hydrolysis.
Microwave irradiation at a frequency of 2450 MHz has been used to raise the temperature of the admixed slurry at a rate of 5-50° C. per minute to the target temperature, and thereafter maintain the temperature for a period of 0-15 minutes, and preferably 5 minutes.
Treatment temperatures in the microwave chamber of at least 50° C. are required to achieve effective solubilization of the slurry. Treatment temperatures up to 200° C. have been evaluated, and generally increased temperature results in increased solubilization for a given oxidant dose. It has also been found that the solubilization reaction is generally complete within a treatment time of 5 minutes in a batch reactor. Exposure to microwave radiation for longer periods of time was not found to improve the degree of solubilization of the slurries tested to date. Certain other types of slurries could however benefit from longer durations of treatment if they contain organic material that is more resistant to oxidation and thermal hydrolysis.
In slurries tested to date, the current invention has been capable of converting up to 100% of the insoluble Chemical Oxygen Demand (“COD”), and phosphorus, to soluble COD, and ortho-phosphate respectively. At the same time significant portions of total nitrogen are converted to ammonia, and a large fraction of nutrients present in solid form are converted to soluble form. The process also results in the destruction of up to 100% of volatile suspended solids.
The apparatus for carrying out the process could be either a batch process or a continuous flow process.
The batch process apparatus consists of a reaction vessel in which organic solid slurry is first introduced and mixed with hydrogen peroxide solution (either mixed in a common conduit before entering the reaction vessel, or introduced into the vessel through separate conduits and mixed within the vessel. The admixed slurry is then irradiated with microwave energy as required to obtain the desired temperature profile. The contents of the vessel are then discharged using either a pump or the pressure built up within the vessel. The contents can be passed through a heat exchanger to preheat the untreated slurry. Treated slurry can then be further treated by solid/liquid separation before being passed on to further treatment or recovery processes.
The continuous flow process consists of admixing the organic solid slurry with hydrogen peroxide in a mixing vessel or conduit, and then exposing the admixture to microwave irradiation in a flow through vessel or conduit enclosed within a microwave irradiation chamber. The treated slurry is continuously pumped into the mixing vessel through to the irradiation chamber and out. Once again, the treated waste can be passed through a heat exchanger countercurrently with the fresh slurry of organic solids to preheat the slurry before it is introduced to the mixing vessel. Treated slurry can then be further treated by solid/liquid separation before being passed on to further treatment or recovery processes.
Many processes could be used to further treat the treated slurry after treatment with the current invention. Because a large portion of the COD in the slurry has been converted to soluble form by the process, the remaining solids portion of the slurry contains a significantly reduced non-inert fraction. Further treatment of the solids fraction will therefore result in relatively minor further breakdown of any remaining non-inerts. It will therefore be beneficial in many cases to separate the treated slurry into a solids containing fraction and a liquid fraction through solid-liquid separation using a variety of known methods.
The liquid fraction thus formed can then be treated in a variety of available high rate anaerobic processes (such as fixed film bioreactors, upflow anaerobic sludge blanket reactors, hybrid suspended/attached growth bioreactor) to generate biogas for recovery.
The elevated soluble nutrient content of the liquid fraction also presents an opportunity for nutrient recovery, through crystallization of struvite, struvite analogs, calcium phosphate, or the like. Several reactor designs for this purpose exist.
The liquid fraction also contains elevated concentrations of volatile fatty acids, (primarily acetic, propionic and butyric acids) which can either be used directly in solution, or could be recovered through distillation, solvent extraction or other liquid/liquid separation processes.
In certain cases it may not be practical to separate the solid and liquid fractions of the treated slurry, but further treatment may still be desirable. In this case the soluble nature of the majority of the organic compounds will allow such digestion or fermentation processes to be designed with significantly reduced retention times. In some cases, the reduced solids content of the treated slurry may allow further treatment to occur in a fixed film bioreactor, upflow anaerobic sludge blanket reactor, or hybrid suspended/attached growth bioreactor rather than a traditional fermenter or digester design.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following detailed descriptions.
Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive
Throughout the following description specific details are set forth in order to provide a more thorough understanding to persons skilled in the art. However, well known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
Hereinafter, preferred embodiments of the present invention are described with reference to the accompanying drawings. However, the present invention is not limited thereto.
An apparatus according to the present invention and a process of treating a slurry of organic solids with the apparatus is described.
As shown in
Hydrogen peroxide solution storage tank 3 is connected to microwave/hydrogen peroxide reactor system 1 via hydrogen peroxide solution supply conduit 5 and conduit 5 is equipped with pump 4 for supplying hydrogen peroxide solution.
Microwave/hydrogen peroxide reactor system 1 is connected to solid-liquid separation tank 7 via conduit 6.
Optional solid-liquid separation tank 7 is connected to further treatment vessel 12 via conduit 8 for feeding treated slurry of organic solids. Solid-liquid separation tank 7 is also connected to optional product recovery system 10 via conduit 9 for recovery of nutrients, minerals or organic compounds.
Product recovery system 10 is connected to further treatment vessel 12 via conduit 19 for feeding the liquid fraction of the treated slurry after recovery of nutrients, minerals or organic compounds. Conduit 11 for recovered products (nutrients, minerals or organic compounds) or for direct use of a portion of the liquid stream in conduit 9 is also connected to product recovery system 10.
Further treatment vessel 12 is connected to solid-liquid separation system 14 via conduit 13 for drawing further treated slurry. Further treatment vessel 12 has vent 20 for recovery of biogas in the case of anaerobic process.
Conduit 16 for dewatered solids and conduit 15 for liquid effluent are connected to solid-liquid separation system 14. Conduit 16 can optionally branch into two conduits; one, i.e. conduit 17, is for disposing of residual solids, and the other, i.e. conduit 18 is for returning solids to further treatment vessel 12.
Hereinafter, workings of the apparatus according to the present embodiment are described.
Slurry comprising organic solids suspended in water is introduced into microwave/hydrogen peroxide reactor system 1 via conduit 2 and is admixed with hydrogen peroxide and subsequently exposed to microwave irradiation. Pump 4 works to supply hydrogen peroxide solution from the solution storage tank 3 to microwave/hydrogen peroxide reactor system 1 via conduit 5. The admixed slurry may preferably be treated for 5 minutes for maintaining temperature within the range of 50 to 200 degree Celsius. The combinations of hydrogen peroxide dosage amount and heating temperature vary depending on the target treatment results. With temperature lower than 50 degree Celsius, organic solids are not sufficiently disintegrated for enhancing solids solubilization to a satisfactory degree. Higher temperature or larger amount of hydrogen peroxide dosage has been shown to be unnecessary and uneconomical.
The slurry of organic solids treated by the microwave/hydrogen peroxide reactor system is then optionally sent to solid-liquid separation system 7 via conduit 6 and separated into solids containing component and a liquid component. The solid containing component can then optionally be sent to further treatment vessel 12 via conduit 8 and anaerobically digested by microorganisms. The supernatant rich in nutrients (phosphorus and nitrogen) is introduced into the crystallization reactor 10 via conduit 9 for recovery. After recovery, the nutrient pellets (struvite or other phosphate compounds) are separated and harvested from supernatant via conduit 11. The remaining supernatant rich in soluble COD is introduced into anaerobic digestion tank 12 via conduit 19.
The digested slurry of organic solids in anaerobic digestion tank 12 is discharged from conduit 13 and separated into solid component and liquid component in solid-liquid separation tank 14. The liquid component is discharged from conduit 15 for wastewater and solid component is discharged from conduit 16 for thickened solid waste. The solid component in conduit 16 is discharged via conduit 17 for disposal. If deemed necessary, part of the solid component is returned to anaerobic digestion tank 12 through conduit 18 for further digestion. Meanwhile, the digester biogas in anaerobic digestion tank 12 is recovered from vent 20.
With the above described treatment combination of hydrogen peroxide and microwave irradiation, organic solids are disintegrated to a high degree (up to 100 percent). Hydrogen peroxide is one of the most powerful oxidizers. Through microwave irradiation, hydrogen peroxide can be converted into highly reactive hydroxyl radicals that possess a higher oxidation potential than the hydrogen peroxide itself. Hardly soluble substances in the slurry of organic solids, such as fibers and cell walls, can be converted to readily biodegradable COD in the soluble form. This disintegration of organic solids can greatly enhance the biological hydrolysis rate in anaerobic digestion process. As a result, the anaerobic digestion time could be shortened, digested biogas yield could have a significant increase, and solid waste to be finally disposed could be reduced.
In addition, nutrients (phosphorus and nitrogen) in the slurry of organic solids is efficiently released by the above described treatment combination of hydrogen peroxide and microwave irradiation. Phosphorus and nitrogen are converted and solubilized in the forms of ortho-phosphate and ammonia for direct recovery through crystallization reactor. The nutrient pellet recovered in the forms of struvite, struvite analogs or other phosphate compounds is a valuable end-product.
According to the present invention, it is possible to treat a slurry of organic solids in a cost-effective manner and to recover the energy and resource, i.e. digested biogas, soluble organic compounds and nutrient pellets.
In the present embodiment, AOP treated slurry of organic solids is introduced to an anaerobic digestion tank. However, AOP treated slurry of organic solids may be introduced to a fermentation reactor. The fermentation product, such as acetate, can be used as a substrate material for many industrial applications.
It should be said that it will likely be familiar to someone skilled in the art that:
Secondary aerobic sludge was obtained from the pilot-plant wastewater treatment facilities located at the University of British Columbia (UBC) campus. A set of twelve experiments were performed in order to investigate the effects of various hydrogen peroxide concentrations in the MW/H2O2-AOP. Experiments were carried out at temperatures of 60, 80, 100 and 120° C. Various concentrations of hydrogen peroxide were tested with the objective of improving the degree of COD, nutrient and metal solubilization from sewage sludge. Either 1 mL or 2 mL of hydrogen peroxide (30 wt %) was added to sludge to make up a total volume of 30 mL for each microwave sample.
A closed-vessel microwave digestion system (Ethos TC Digestion Labstation 5000, Milestone Inc., U.S.A.) with a maximum output of 1000 W was used in this study. The system operates at 2450 MHz and consists of dual independent magnetrons with a rotating microwave diffuser for homogeneous microwave distribution. The microwave digestion system, using an independent system controller, provides real-time temperature control. The heating time was kept constant at 5 minutes for all experiments at the pre-determined heating temperatures. The ramp times were varied with respect to temperature in order to maintain a uniform rate of heating (increase of ca. 20° C. per minute of heating) up to the desired experimental temperatures.
As shown in
TABLE 1 and TABLE 2 list the soluble concentrations of nutrients, metals and COD after AOP treatment. Ammonia concentrations ranged from 1.2-108 mg N/L, while ortho-phosphate concentrations ranged from 27.5-75.6 mg P/L. The measured concentrations of soluble ammonia, ortho-phosphate, and magnesium were used to determine the Mg:NH3:PO4 molar ratio. From our results, ammonia was determined to be the limiting nutrient without any hydrogen peroxide addition in the microwave process. In all cases, magnesium was non-limiting, indicating for this treatment process that theoretically, no magnesium addition is required for struvite crystallization. Magnesium, calcium and potassium concentrations ranged from 18.3-40.0 mg/L, 9.9-31.2 mg/L, and 63.7-83.1 mg/L respectively.
As described above, the process of the present invention, in which microwave irradiation and hydrogen peroxide is combined, is highly effective not only in solubilization of carbon for acetate or methane production, but also in solubilization of nutrients for crystallization of fertilizer products, such as struvite.
While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope.
| Filing Document | Filing Date | Country | Kind | 371c Date |
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| PCT/CA2006/001327 | 8/11/2006 | WO | 00 | 3/19/2009 |
| Publishing Document | Publishing Date | Country | Kind |
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| WO2008/017137 | 2/14/2008 | WO | A |
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| Number | Date | Country | |
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| 20100044306 A1 | Feb 2010 | US |
