Investigation of Nitrogen-Bearing Species in Catalytic Steam Gasification of Poultry Litter

Abstract

The production of broiler chickens has become one of the largest sectors in U.S. agriculture, and the growing demand for poultry has led to an annual production growth rate of 5%. With increased demand for poultry, litter management has become a major challenge in the agriculture industry. Although the catalytic steam gasification has been accepted as a possible and feasible method for litter management, concern has been expressed about the presence of nitrogen and phosphorus containing species in the fuel gas and/or in the final solid residue. The possible release of phosphorus as phosphine gas in the fuel gas can have an adverse impact on the environment. Similarly, possible release of ammonia from the nitrogen containing species is also not acceptable. Hence, under partial U.S. Department of Agriculture support, a study was conducted to examine the fate and the environmental impact of the nitrogen- and phosphorus-containing species released during catalytic steam gasification of poultry litter. From various preliminary tests, it was concluded that most (～100%) of the phosphorus would remain in the residue, and some (20–70%) of the nitrogen would end up as ammonia in the fuel gas. The effects of temperature, catalyst loading, and type of catalyst on ammonia liberation were studied in a muffled furnace setup at atmospheric pressure. The fraction of nitrogen released as ammonia was found to decrease with an increase in temperature during pyrolysis and steam gasification. It also decreased with an increase in catalyst loading.     

Preliminary economic analysis of poultry litter gasification option with a simple transportation model

Several environmental issues are related to the disposal of poultry litter. In an effort to provide a more environmentally friendly alternative than landfill disposal or spreading as a soil amendment, work has been carried out previously at the University of Tennessee Space Institute (UTSI). This past UTSI work was concentrated on developing a catalytic steam gasification concept to produce energy from poultry litter. In the past UTSI studies, preliminary design and economics for a stationary, centralized gasification plant capable of processing approximately 100 ton/day of poultry litter were developed. However, in this preliminary design the economic impact of transporting litter to a centralized gasification plant location was not addressed. To determine the preliminary impact of transporting the poultry litter on the overall economics of this energy conversion plant design, a simple transportation model was developed. This model was used in conjunction with the earlier plant design prepared at UTSI to determine the economic feasibility of a centralized, stationary poultry litter gasification plant. To do so, major variables such as traveling distance, plant feed rate (or capacity), fluctuations in the sales price of the product gas (that means value of the energy), population density of poultry farms, impact of tipping fees, and cost of litter were varied. The study showed that for plant with a capacity of 1000 ton/day to be able to withstand several changes in economic conditions and sustain itself, the poultry farm density would need to be approximately 0.3 houses/mi2. Smaller plants would need either a higher energy price or some kind of subsidy to be economically feasible.     

生物质气化过程催化剂应用研究进展

生物质气化技术已在国内外得到广泛的开发和运用,但由于燃气品位较差,焦油较多,限制了生物质气化气的进一步利用。在生物质气化过程中应用催化剂是一种有效的提升燃气质量和催化裂解焦油的方法,近年来已引起了国内外的广泛注意。本文对国内外生物质催化气化及相关研究进展进行了综合评述,分析了催化剂对减少生物质气化焦油的生成和改进燃料气品质的作用结果, 提出了进一步的研究方向。     

Woody biomass and RPF gasification using reforming catalyst and calcium oxide

This study focused on steam gasification and reforming of waste biomass using a reforming catalyst. The purpose of the study was to evaluate the durability of a commercial Ni reforming catalyst and the effect of CaO on the reforming behavior, and to clarify detailed factors of catalytic performance, as well as the effect of operating parameters on the characteristics of produced gas composition. Moreover, catalyst regeneration was carried out and the behavior of catalytic activity based on gas composition was investigated. Using a fluidized bed gasifier and a fixed bed reformer, gasification and reforming of waste biomass were carried out. Commercial Ni-based catalyst and calcined limestone (CaO) were applied to the reforming reaction. Temperature of the gasifier and reformer was almost 1023 K. Ratio of steam to carbon in the feedstock [mol mol⁻¹] and equivalence ratio (i.e., ratio of actual to theoretical amount of oxygen) [-] were set at about 2 and 0.3, respectively. The feed rate of the feedstock into the bench-scale gasifier was almost 15 kg h⁻¹. The results of waste biomass gasification confirmed the improvement in H₂ composition by the CO₂ absorption reaction using the reforming catalyst and CaO. In addition, CaO proved to be especially effective in decreasing the tar concentration in the case of woody biomass gasification. Catalytic activity was maintained by means of catalyst regeneration processing by hydrogen reduction after air oxidation when woody biomass was used as feedstock.     

The Use of Combined-Cycle Power Systems in Nonpolluting Central Stations

The body of information presented in this paper is directed to power engineers oncerned with reducing pollution from future electric utility power stations. An Air Pollution Control Office sponsored study of advanced-cycle power systems and methods of desulfurizing fuels investigated a large number of conventional and nonconventional power systems for use by electric utilities. These systems included current and advanced steam systems, steam systems with topping and bottoming cycles, closed-cycle gas turbines, and open-cycle gas turbines alone and combined with steam systems. Also considered were various methods for desulfurizing coal and residual oil, such as mechanical and chemical separation, hydrodesulfurization and gasification followed by gas clean up. The major conclusion of this study is that the most effective and economical means of reducing objectionable effluents from future fossil-fueled power stations appears to be gasification of high-sulfur fuel to produce a low-heating-value fuel gas for use in a combined gas turbine and steam (COGAS) power system. Recent and prospective advances in military and commercial aircraft gas turbine technology, particularly in the area of high-temperature operation, can be applied to industrial gas turbines to yield the high-performance, low-cost, and long-lifetime characteristics desired for base-load power generation.

A COGAS pilot plant burning gasified coal should be built at the earliest possible time. Experience gained in the pilot plant could allow introduction of commercial sized stations within this decade.     

UASB-SBR组合工艺处理畜禽养殖废水的研究

近年来,随着中国畜禽养殖业的快速发展,落后的养殖模式和污染防治设施,使畜禽养殖污染日趋严重,畜禽养殖污染已居农业污染源之首,已成为中国环境污染的重要因素,对环境质量乃至人体健康都会产生不良影响。文中采用UASB—SBR组合工艺处理畜禽养殖废水,通过试验探讨SBR反应器启动方法及最佳运行模式,同时研究UASB反应器的启动方法。结果表明,SBR运行的最佳模式为进水0.5 h、反应8 h、沉淀1 h、出水0.5 h、闲置14 h。经过一段时间的启动,UASB和SBR反应器均成功启动,UASB—SBR组合工艺在处理畜禽养殖废水时可获得稳定的处理效果,COD、氨氮、总磷等出水水质均达到《畜禽养殖业污染物排放标准》(GB18596-2001)要求,为畜禽养殖废水处理的工程化应用提供了参考依据。     

浅析某厂化学镀镍线的主要污染物及处理措施

某厂化学镀镍线产生的主要污染物为大气污染、水污染和固体废物污染。其中大气污染物主要为硫酸雾。水污染物为总镍、总铜、化学需氧量、悬浮物、总磷、氨氮等。固废废弃物均为危险废物,包括废包装材料、酸性废液、含镍废液。该文分析了化学镀镍线产生的废气、废水和固体废物的主要来源,并提出了防止污染的对策。     

Reduction of nitrogen excretion and emission in poultry: A review for organic poultry

Organic poultry is an alternative to conventional poultry which is rapidly developing as a response to customers' demand for better food and a cleaner environment. Although organic poultry manure can partially be utilized by organic horticultural producers, litter accumulation as well as excessive nitrogen still remains a challenge to maintain environment pureness, animal, and human health. Compared to conventional poultry, diet formulation without nitrogen overloading in organic poultry is even more complicated due to specific standards and regulations which limit the application of some supplements and imposes specific criteria to the ingredients in use. This is especially valid for methionine provision which supplementation as a crystalline form is only temporarily allowed. This review is focused on the utilization of various protein sources in the preparation of a diet composed of 100% organic ingredients which meet the avian physiology need for methionine, while avoiding protein overload. The potential to use unconventional protein sources such as invertebrates and microbial proteins to achieve optimal amino acid provision is also discussed.     

水葫芦对滇池底泥氮磷营养盐释放的影响

为了探讨水葫芦对富营养湖泊底泥氮磷营养盐释放的影响，通过原位采集滇池柱状底泥，以蒸馏水为上覆水，进行了25d的室内静态模拟实验。实验比较了水葫芦处理组和空白对照组底泥氨氮（NH4-N）、硝态氮（NO3^-N）、溶解性总氮（DTN）、正磷酸盐（PO4^3--P）等的释放特征。结果表明，与对照组相比，水葫芦处理组上覆水溶解氧、pH显著性降低，而PO4^3-P浓度显著性升高；在实验前2d，水葫芦处理组上覆水NH4^＋N和DTN浓度显著性高于对照组，而在5～25d时，其显著性低于对照组。根据上覆水营养盐浓度、水葫芦植株吸收营养盐总量，推算底泥氮磷营养盐释放的平均速率，表明水葫芦加速了滇池底泥氮、磷营养盐的释放速率，处理组氮、磷释放速率分别为对照组的5．3～170．2和1．5～21．6倍。     

Prediction of Flue Gas Composition of an Incinerator Based on a Nonequilibrium-Reaction Approach

A nonequilibrium-reaetion model is developed to predict the flue gas composition of an incinerator for solid waste combustion and gasification. The model may also be effectively utilized to predict the composition of exit gas from the primary chamber of an incinerator where invariably substoichiometrie combustion conditions exist The model assumes that the drying and pyrolysis of waste occurs in sequence followed by combustion of devolatilized gas and residue separately. The model is applied to the combustion of pine wood, and the flue gas compositions are computed as a function of operating parameters such as temperature (1100 to 1500 K), initial moisture content (0 to 40 percent), and percentage excess air (up to 100 percent). The model is extended to include substoichiometric combustion (to simulate the gasification process without steam injection) to compare its predictions with the available experimental data. The general agreement of theory and experiment is good.     

A laboratory study of microalgae-based ammonia gas mitigation with potential application for improving air quality in animal production operations

Ammonia gas emission is a major concern in concentrated animal production operations. It not only reduces the manure value as fertilizer due to nitrogen loss, but also has considerable environmental consequences for both animals and ecosystem. In this work, a microalgae culture system was developed as an ammonia gas bioscrubber to reduce ammonia gas emission. The green algae Scenedesmus dimorphus was grown in a flat-panel photobioreactor aerated with ammonia-laden air. A continuous culture was performed at different operational conditions including dilution rate (D = 0.05, 0.1, 0.2, and 0.3 day^?1), ammonia gas loading rate (9.4, 19.3, 28.9, 39.9, 55.6 mg/L-day), and medium pH (5, 6, 7, and 8). The alga culture at 0.1 day^?1 dilution rate, 39.9 mg/L-day ammonia gas loading rate, and pH 7 resulted in the highest cell density and biomass productivity. In order to provide a wide spectrum evaluation of the algae-based ammonia mitigation system, four parameters were determined, including ammonia removal rate, overall ammonia gas removal efficiency, cellular ammonia consumption rate, and cell yield based on ammonia input. Depending on the operational conditions used, the maximum values of those four evaluative parameters were 50.92 ± 2.91 mg/L-day of ammonia removal rate, 94.90 ± 1.87% of ammonia removal efficiency, 0.0597 ± 0.0024 g NH₃/g cell-day of cellular ammonia consumption rate, and 19.40 ± 2.52 g cell/g NH₃ of cell yield based on ammonia. It was also found that the majority of nitrogen in the ammonia gas was assimilated by the algal cells. At D = 0.1 day^?1, 39.9 mg/L-day of ammonia gas loading rate and pH 7, algal biomass assimilated 98.6% of nitrogen contained in the ammonia gas input, with less than 5% of inlet ammonia gas was exhausted after the algal treatment.

Implications: This study demonstrated the effectiveness of using microalgae for mitigating ammonia gas emission from animal production operations. The results enabled us to better understand the mechanisms of ammonia assimilation by microalgae, the engineering design parameters for the process scale up, and the economic viability of the system. Eventually, it will lead to a novel, alternative method for mitigating ammonia gas emission from concentrated animal operations while producing biomass as high-quality feed ingredient.     

Dynamics of water soluble phosphorus from surface applied broiler litter

Deionized water is routinely used as an extractant to determine soluble phosphorus (P) in broiler litter, but under N.E. Georgia conditions this technique may underestimate the hazard of P loss in runoff because the alkalinity of the broiler litter-water suspension limits the solubility of P compounds that may be solubilized after being spread on acidic field conditions. In this study under controlled conditions we measured soluble P in thatch and top soil after applying untreated broiler litter, residue of broiler litter after water extraction (WER), or residue of broiler litter after extraction with a 2-(N-morpholino) ethanesulfonic acid (MES) buffer at pH 6 (BER). During the 60 d incubation, the WER released 18 % more Total Dissolved P (TDP) than was determined through a conventional water extraction procedure, whereas the BER released 28 % less TDP than the WER, which reflects the greater amount of TDP removed from the broiler litter by the buffer at pH 6.0. However, the total amount of TDP extracted by the MES buffer, which includes that removed at the initial extraction plus that released during the incubation, was 30 % greater than the total amount of TDP extracted with water from the untreated litter plus the TDP extracted with water from the WER during the incubation. This result suggests the need to fine-tune the solid: liquid ratio and shaking time when the MES buffer is used.     

Gas reforming and tar decomposition performance of nickel oxide (NiO)/SBA-15 catalyst in gasification of woody biomass

In the gasification of biomass, it is necessary to limit the amount of by-product tar and increase the yields of hydrogen (H₂) and carbon monoxide (CO) (syngas). Therefore, we conducted gasification and reforming experiments on woody biomass using an electric tubular furnace, to evaluate the gas reforming and tar decomposition performance of a NiO/SBA-15 catalyst. As a result, we found that this catalyst is effective for H₂ production. It is believed that the increase in H₂ volume due to the catalyst occurs through a steam reforming reaction involving hydrocarbons, including methane (CH₄), and the water-gas shift reaction. With respect to the influence of the gasifying agent on the reforming effect of the catalyst, the amount of generated carbon dioxide (CO₂) and hydrogen (H₂) increases because the shift reaction is promoted by supplying steam. On the other hand, it was inferred that the shift reaction rarely occurred because it approaches equilibrium by supplying O₂. Furthermore, it is suggested that light aromatic hydrocarbons are decomposed by the catalyst.

Implications: The mesoporous silica catalyst NiO/SBA-15 was highly effective for H₂ production and decomposition of light aromatic compounds in the gasification of woody biomass. In the catalyst reaction, supplying steam promoted H₂ production. From thermodynamic analysis and discussion, it was also inferred that supplying O₂ might prevent the water gas shift reaction. The results are useful for designing a process needed for rich H₂ production and gas refining process for further use of syngas.     

Removal of nitrogenous compounds by catalytic wet air oxidation. Kinetic study

Aqueous wastes containing organic pollutants can be efficiently treated by wet air oxidation (WAO), i.e. oxidation by molecular oxygen in the liquid phase, under high temperature (200-325 degrees C) and pressure (up to 150 bar). However, organic nitrogen can be relatively resistant to oxidation and can be harmful to the environment. In the course of treatment, organic nitrogen (N-Org) is converted into ammonia (NH(3)), while organic carbon (C-Org) is converted mainly into carbon dioxide (CO(2)). This can be done without catalysts. In the presence of Mn/Ce composite oxides, it is possible to transform ammonia into molecular nitrogen at a temperature close to 260 degrees C. The direct conversion of organic nitrogen into molecular nitrogen also can be achieved using the same catalyst. This paper discusses the results obtained during the treatment of nitrogenous compounds like aniline, nitrophenol, beta-alanine and ammonia. Laboratory investigations were conducted in a stirred batch reactor with Mn/Ce composite oxides as catalysts. Very limited amounts of nitrites and nitrates were observed with amines, but more significant quantities were found with nitro-compounds. The kinetics of oxidation of ammonia, organic compounds, and more particularly aniline, were investigated. The treatment of a real waste (process wastewater) was also investigated. The dependence of the transformation rate on various parameters (amount of catalyst, temperature, etc.) was established. The rates of oxidation are described by first-order kinetic laws with respect to the various nitrogen species (aniline, NH(3)). Several parallel pathways are considered for the transformation of organic nitrogen, amongst which is an interaction with the catalyst surface. The orders with respect to oxygen and catalyst are established.     

Removal of ammonia solutions used in catalytic wet oxidation processes

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

Optimal loading rates and economic analyses for anaerobic digestion of poultry waste

Four combinations of litter and carcasses from broiler chickens were examined utilizing a thermophilic, stirred-tank digester of demonstration size of approximately 10,000 gal. Under computed optimal loading rates, litter with paper bedding had the highest daily production of methane over an 8-day retention period. The greatest methane production per lb of volatile solids was achieved over 10 days with litter and paper bedding combined with carcasses. This research found that sufficient poultry litter is generated within 20 mi (32 km) of Moorefield, WV, to support a commercial-sized digester operation. However, anaerobic digestion of poultry waste cannot be financially supported by methane production alone. To be financially viable, anaerobic digestion requires a disposal fee for poultry waste and/or the sale of the digested solid effluent as an organic fertilizer to retail markets.     

Low NOx,High Efficiency Multistaged Burner: Fuel Oil Results

A multistaged combustion burner designed for in-furnace NO_x control and high combustion efficiency is being evaluated for high nitrogen content fuel and waste incineration application in a 0.6 MW package boiler simulator. A low NO_x precombustion chamber burner has been reduced in size by approximately a factor of two (from 600 to 250 ms first-stage residence time) and coupled with (1) air staging, resulting in a three-stage configuration, and (2) natural gas fuel staging, yielding up to four stolchlometric zones. Natural gas, doped with ammonia to yield a 5.8 percent fuel nitrogen content, and distillate fuel oil, doped with pyridine to yield a 2 percent fuel nitrogen content, were used to simulate high nitrogen content fuel/waste mixtures. The multistaged burner reduced NO emissions by 85 percent from emission levels from a conventional unstaged burner mounted on a commercial package bollerTA minimum NO emission level of 110 ppm was achieved in the fuel oil tests, from a level of 765 ppm for conventional firing. This is compared with a 160 ppm minimum NO level achieved in gaseous fuel tests, from an uncontrolled level of 1000 ppm. Boiler fuel staging, or reburnlng, appears to be superior to air staging for high combustion efficiency due to its minimal fuel-rich core and second flame front in the boiler.