Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H(2)O(2) addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H(2)O(2) and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Microwave enhanced advanced oxidation treatment of dairy manure

Abstract

The microwave enhanced advanced oxidation process (MW-AOP) was used to treat dairy manure in a continuous-flow 915?MHz microwave wastewater treatment system. The treatment efficiency increased with an increase in temperature, as well as hydrogen peroxide dosage. The settling property was also improved in all treated sets, regardless of temperature applied. The system operated at temperatures >100?°C had a much higher soluble chemical oxygen demand than at temperatures <100?°C. The highest soluble carbonaceous compounds, orthophosphate and ammonia were obtained at 110?°C and 0.6%H₂O₂ per % of total solids content. The process should be operated at higher temperatures and higher hydrogen peroxide dosages for maximizing solids disintegration, nutrient release and energy efficiency. An energy fingerprint correlating the cumulative energy consumption and temperature rise was developed. The results demonstrated that the custom designed MW-AOP system is suitable for the effective treatment of dairy manure. The system can readily be scaled up and integrated into a dairy farm manure treatment and resource recovery system.     

Treating solid dairy manure using microwave-enhanced advanced oxidation process

The microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) was used to treat separated solid dairy manure for nutrient release and solids reduction. The MW/H₂O₂-AOP was conducted at a microwave temperature of 120°C for 10 minutes, and at three pH conditions of 3.5, 7.3 and 12. The hydrogen peroxide dosage at approximately 2 mL per 1% TS for a 30 mL sample was used in this study, reflecting a range of 0.53–0.75 g H₂O₂/g dry sludge. The results indicated that substantial quantities of nutrients could be released into the solution at pH of 3.5. However, at neutral and basic conditions only volatile fatty acids and soluble chemical oxygen demand could be released. The analyses on orthophosphate, soluble chemical oxygen demands and volatile fatty acids were re-examined for dairy manure. It was found that the orthophosphate concentration for untreated samples at a higher % total solids (TS) was suppressed and lesser than actual. To overcome this difficulty, the initial orthophosphate concentration had to be measured at 0.5% TS.     

Treatment of dairy manure using the microwave enhanced advanced oxidation process under a continuous mode operation

The microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) was used to treat dairy manure for solubilization of nutrients and organic matters. This study investigated the effectiveness of the MW/H₂O₂-AOP under a continuous mode of operation, and compared the results to those of batch operations. The main factors affecting solubilization by the MW/H₂O₂-AOP were heating temperature and hydrogen peroxide dosage. Soluble chemical oxygen demand (SCOD) and volatile fatty acids (VFA) increased with an increase of microwave (MW) heating temperature; very high concentrations were obtained at 90°C. Insignificant amounts of ammonia and reducing sugars were released in all runs. An acidic pH condition was required for phosphorus solubilisation from dairy manure. The best yield was obtained at 90°C with an acid dosage of 1.0 %; about 92 % of total phosphorus and 90 % of total chemical oxygen demand were in the soluble forms. The MW/H₂O₂-AOP operated in a continuous operation mode showed pronounced synergistic effects between hydrogen peroxide and microwave irradiation when compared to a batch system under similar operating conditions, resulting in much better yields.     

Microwave Pretreatment for Enhancement of Phosphorus Release from Dairy Manure

Both the advanced oxidation process (AOP) using a combination of hydrogen peroxide addition and microwave heating (H₂O₂/microwave), and the microwave heating process were used for solubilization of phosphorus from liquid dairy manure. About 80% of total phosphate was released into the solution at a microwave heating time of 5 min at 170°C. With an addition of H₂O₂, more than 81% of total phosphate could be released over a reaction period of 49 h at ambient temperature. The AOP process could achieve up to 85% of total phosphate release at 120°C. The results indicated that both the microwave, and the AOP processes could effectively release phosphate from liquid dairy manure. These processes could serve as pretreatments for phosphorus recovery from animal wastes, and could be combined with the struvite crystallization process to provide a new approach in treating animal wastes.     

Treatment of dairy manure using the microwave enhanced advanced oxidation process under a continuous mode operation

The microwave enhanced advanced oxidation process (MW/H(2)O(2)-AOP) was used to treat dairy manure for solubilization of nutrients and organic matters. This study investigated the effectiveness of the MW/H(2)O(2)-AOP under a continuous mode of operation, and compared the results to those of batch operations. The main factors affecting solubilization by the MW/H(2)O(2)-AOP were heating temperature and hydrogen peroxide dosage. Soluble chemical oxygen demand (SCOD) and volatile fatty acids (VFA) increased with an increase of microwave (MW) heating temperature; very high concentrations were obtained at 90°C. Insignificant amounts of ammonia and reducing sugars were released in all runs. An acidic pH condition was required for phosphorus solubilisation from dairy manure. The best yield was obtained at 90°C with an acid dosage of 1.0 %; about 92 % of total phosphorus and 90 % of total chemical oxygen demand were in the soluble forms. The MW/H(2)O(2)-AOP operated in a continuous operation mode showed pronounced synergistic effects between hydrogen peroxide and microwave irradiation when compared to a batch system under similar operating conditions, resulting in much better yields.     

Nutrient release from fish silage using microwave-enhanced advanced oxidation process

The microwave-enhanced advanced oxidation process was used to treat fish silage for nutrient release and solids reduction prior to its use as a fertilizer for greenhouse operations. Fifteen sets of experiments with varying hydrogen peroxide dosages and treatment temperatures were conducted to evaluate the effectiveness of the process on the solubilization of fertilizer constituents. It was found that up to 26% of total Kjeldahl nitrogen could be released as ammonia with 6% hydrogen peroxide dosage at 170°C. An increase of nitrate/nitrite concentration was observed with higher hydrogen peroxide dosage and higher microwave temperature; the highest concentration of 10.2 mg L^{? 1} nitrates/nitrites was achieved at at 170°C and 6% H₂O₂ dosage. Up to 20 ± 9.5% of total chemical oxygen demand was reduced at temperatures between 120 and 170°C. Large quantities of volatile fatty acids were generated at lower temperatures, corresponding to an increase in soluble chemical oxygen demand, but not at higher temperatures. The treatment of fish silage using the microwave-enhanced advanced oxidation process appears to be promising.     

Microwave pretreatment for enhancement of phosphorus release from dairy manure

Both the advanced oxidation process (AOP) using a combination of hydrogen peroxide addition and microwave heating (H2O2/microwave), and the microwave heating process were used for solubilization of phosphorus from liquid dairy manure. About 80% of total phosphate was released into the solution at a microwave heating time of 5 min at 170 degrees C. With an addition of H2O2, more than 81% of total phosphate could be released over a reaction period of 49 h at ambient temperature. The AOP process could achieve up to 85% of total phosphate release at 120 degrees C. The results indicated that both the microwave, and the AOP processes could effectively release phosphate from liquid dairy manure. These processes could serve as pretreatments for phosphorus recovery from animal wastes, and could be combined with the struvite crystallization process to provide a new approach in treating animal wastes.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

Microwave treatment of dairy manure for resource recovery: Reaction kinetics and energy analysis

A newly designed continuous-flow 915 MHz microwave wastewater treatment system was used to demonstrate the effectiveness of the microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) for treating dairy manure. After the treatment, about 84% of total phosphorus and 45% of total chemical oxygen demand were solubilized with the highest H₂O₂ dosage (0.4% H₂O₂ per %TS). The reaction kinetics of soluble chemical oxygen demand revealed activation energy to be in the range of 5–22 kJ mole^?1. The energy required by the processes was approximately 0.16 kWh per liter of dairy manure heated. A higher H₂O₂ dosage used in the system had a better process performance in terms of solids solubilization, reaction kinetics, and energy consumption. Cost-benefit analysis for a farm-scale MW/H₂O₂-AOP treatment system was also presented. The results obtained from this study would provide the basic knowledge for designing an effective farm-scale dairy manure treatment system.     

Solubilization of blood meal to be used as a liquid fertilizer

The solubilization of blood meal by means of the microwave-hydrogen peroxide enhanced advanced-oxidation process (MW/H(2)O(2)-AOP) was studied. It was found that over the treatment temperature range of 60 to 120 degrees C, solids particle reduction, ammonia and orthophosphate production could be achieved by this process. Large protein molecules were broken down into intermediate compounds with low molecule weights, ammonia and nitrate. Intermediate compounds, such as peptides and amino acids, can also be easily converted to nitrogenous nutrients for plant growth by bacteria. Soluble nitrogen content increased with an increase in microwave heating temperature when acid was added; significant amounts of ammonia were obtained at higher temperatures. Nitrate decreased in concentration with an increase of treatment temperature. Orthophosphate concentrations increased after the advanced-oxidation process (AOP) treatments, with and without acid addition; but were more pronounced with acid addition. Maximum solubility of chemical oxygen demand (COD) occurred at 80 degrees C. Without the addition of acid, soluble COD decreased due to protein denaturation and coagulation out of the solution.     

Effects of acidifying reagents on microwave treatment of dairy manure

Dairy manure, acidified using organic acids (acetic, oxalic, and citric acid) were treated with microwave enhanced advanced oxidation process (MW/H₂O₂-AOP). The effect of a mixture of oxalic acid and commonly used mineral acids (sulfuric and hydrochloric acid) on MW/H₂O₂-AOP was also examined. Substantial amounts of phosphorus were released under MW/H₂O₂-AOP, regardless of organic acid or mineral acid used. All three organic acids were good acidifying reagents; however, only oxalic acid could remove free calcium ion in the solution, and improve settleability of dairy manure. The MW/H₂O₂-AOP and calcium removal process could be combined into a single-stage process, which could release phosphate, solubilize solids and remove calcium from dairy manure at the same time. A mixture of oxalic acid and mineral acid produced the maximum volume of clear supernatant and had an ideal molar ratio of calcium to magnesium for effective struvite (magnesium ammonium phosphate) crystallization process. A single-stage MW/H₂O₂-AOP would simplify the process and reduce mineral acid consumption compared to a two-stage operation. The results of a pilot scale study demonstrate that MW/H₂O₂-AOP is effective in treating manure and recovering resource from dairy farms.     

微波辅助双氧水氧化降解水中磺胺二甲嘧啶

采用微波辐照技术辅助双氧水氧化降解水中磺胺二甲嘧啶（SM2）,研究了微波辅助双氧水氧化降解水中SM2的影响因素。结果表明,单纯使用微波辐照并不能显著降解SM2,而微波辐照可显著促进双氧水对SM2的氧化作用,提高SM2的降解率。在初始浓度为50 mg/L,微波功率为900 W,加入0.25 mL质量分数为30%的双氧水,pH值为4的条件下辐照6 min,SM2的降解率可达96.5%,COD去除率为72%。     

Dairy Manure Treatment,Digestion and Nutrient Recovery as a Phosphate Fertilizer

A combined approach of biological treatment, solids digestion and nutrient recovery was tested on dairy manure. A sequencing batch reactor (SBR) was operated in three modes, in order to optimize nutrient (nitrogen and phosphorus) removals. The highest average removal efficiencies of 91% for NH₄-N, 59% for PO₄-P and 80% for total chemical oxygen demand (COD) were achieved. Staining experiments suggested the coexistence of glycogen and phosphorus accumulating organisms. Anaerobic digestion of wasted bio-solids was able to produce a PO₄-P concentration of 70 mgL^?1 in the supernatant. A pilot-scale experiment, designed to recover phosphorus in the supernatant as struvite (magnesium ammonium phosphate), was able to remove 82% of soluble PO₄-P.     

Seasonal and Spatial Variations of Ammonia Emissions from an Open-Lot Dairy Operation

Abstract

There is a need for a robust and accurate technique to measure ammonia (NH₃) emissions from animal feeding operations (AFOs) to obtain emission inventories and to develop abatement strategies. Two consecutive seasonal studies were conducted to measure NH₃ emissions from an open-lot dairy in central Texas in July and December of 2005. Data including NH₃ concentrations were collected and NH₃ emission fluxes (EFls), emission rates (ERs), and emission factors (EFs) were calculated for the open-lot dairy. A protocol using flux chambers (FCs) was used to determine these NH₃ emissions from the open-lot dairy. NH₃ concentration measurements were made using chemiluminescence-based analyzers. The ground-level area sources (GLAS) including open lots (cows on earthen corrals), separated solids, primary and secondary lagoons, and milking parlors were sampled to estimate NH₃ emissions. The seasonal NH₃ EFs were 11.6 ± 7.1 kg-NH₃ yr^-1head^-1 for the summer and 6.2 ± 3.7 kg-NH₃ yr^-1head^-1 for the winter season. The estimated annual NH₃ EF was 9.4 ± 5.7 kg-NH₃ yr^-1head^-1 for this open-lot dairy. The estimated NH₃ EF for winter was nearly 47% lower than summer EF. Primary and secondary lagoons (～37) and open-lot corrals (～63%) in summer, and open-lot corrals (～95%) in winter were the highest contributors to NH₃ emissions for the open-lot dairy. These EF estimates using the FC protocol and real-time analyzer were lower than many previously reported EFs estimated based on nitrogen mass balance and nitrogen content in manure. The difference between the overall emissions from each season was due to ambient temperature variations and loading rates of manure on GLAS. There was spatial variation of NH₃ emission from the open-lot earthen corrals due to variable animal density within feeding and shaded and dry divisions of the open lot. This spatial variability was attributed to dispirit manure loading within these areas.     

Overcoming challenges to struvite recovery from anaerobically digested dairy manure

Recovering struvite from dairy manure has consistently posed problems for researchers. This study separated solids from anaerobically digested dairy manure using a filtration system. Filtrate was rich in free magnesium (160 to 423 mg/L), ammonium (320 to 1800 mg N/L) and orthophosphate (93 to 332 mg P/L). High concentrations of free calcium (128 to 361 mg/L) and alkalinity (3309 to 6567 mg/L as CaCO3), however, may hinder struvite precipitation. Batch precipitation tests were conducted to identify and overcome factors that interfere with struvite formation. Precipitation tests at pH 9 identified calcium and ionic strength as most probable interferences. Calcium addition did not significantly change phosphorus removal efficiency, but decreased struvite purity because of formation of calcium phosphates when Ca:P activity ratio was greater than 0.5 to 1. Batch tests demonstrated effective calcium removal from anaerobically digested dairy manure through precipitation of calcium carbonate at pH 9 to 10 while retaining magnesium and orthophosphate, lessening hindrance to struvite formation.     

微波诱导鳞片石墨-H2O2催化氧化处理甲基紫废水

研究微波诱导鳞片石墨-H₂O ₂催化氧化处理甲基紫废水工艺,探讨各种因素的协同作用及对废水脱色效果的影响,并采用SEM、EDX、XRD和FTIR对新鲜及使用6次后的鳞片石墨进行表征。结果表明,微波诱导鳞片石墨-H₂O₂能高效快速降解废水中的甲基紫;在50 mL初始pH为3,质量浓度为10 mg/L的甲基紫废水中, H₂O₂用量1 mL/L,鳞片石墨 3 g/L,微波输出功率259 W,微波辐射时间9 min的最佳处理工艺条件下,甲基紫脱色率达到了98.80%;微波、鳞片石墨、H₂O₂体系对甲基紫废水降解效果明显,产生协同效应。紫外-可见光谱分析表明,废水中甲基紫结构被破坏,但仍含有少量苯环等小分子。动力学研究表明,脱色反应符合一级反应动力学规律,反应速率常数k为0.42613 min^-1,反应半衰期t_1/2为1.626 min。     

掺Al-TiO2改性膨润土去除微污染水中COD和NH4-N

采用掺Al-TiO2作为改性剂制备改性膨润土,考察了微波辐射功率、辐射时间、TiO2改性剂用量、铝盐掺杂量、pH值对微污染水中COD和NH4-N去除效果的影响。实验表明,微波辐射功率为460 W,辐射时间为8 min,TiO2改性剂用量为1.3 mmol/g,铝盐掺杂量为0.2 mmol/g为最佳制备条件。pH值为6.0,改性膨润土投加量为40 mg/L,沉淀时间为30min时,对微污染水中初始浓度15 mg/L的COD和5 mg/L的NH4-N去除率分别达到92%和59%以上。     

超声波协同H_2O_2处理养殖场污水

为了有效地改善养猪场污水的质量,以H2O2为药剂,对污水进行了水浴加热和超声波辅助的对比实验,考察了超声波发生器输出端电流强度、处理时间、H2O2用量对污水的COD、氨气及颜色的影响,并进行正交实验优化。结果表明,超声波协同H2O2处理养殖污水是一种切实可行的方法,超声波协同H2O2处理污水的最佳工艺条件:电流0.7 A、处理时间2 min、H2O2用量3%,在此条件下降低COD量可达95%以上,氨氮的含量可降至14~15 mg/L,氨臭味大大得到了改善,并将原污水由黑色变为浅黄色。