SCR performance on a hydrogen reformer furnace

In late 1993, Air Products and Chemicals, Inc. began operating a new steam-methane reformer at the Tosco Refining Co.'s Avon refinery in Martinez, CA, to provide hydrogen and steam to the refinery under a long-term supply agreement. The hydrogen plant--owned, operated, and maintained by Air Products--includes a selective catalytic reduction (SCR) unit on the reformer-furnace flue gas for environmental control. SCR is a commercially proven process capable of abating emissions of nitrogen oxides (NOx) to extremely low levels; however, documented experience in a refinery setting has been limited. This paper discusses performance of the SCR, primarily during its first two years of operation; it incorporates theory and prior research findings sufficient to understand the relationship between key system variables and SCR performance. Test results demonstrate that NOx, ammonia (NH3) slip, and carbon monoxide (CO) emissions are in compliance with permit limits. NOx removal efficiency is nearly linear with the inlet NH3:NOx molar ratio up to almost 90% NOx conversion, where ammonia slip begins to rise steeply. The stoichiometric reaction ratio of NH3 to NOx is close to the theoretical 1.0. Catalyst life is estimated at four years, in line with published figures for SCR catalysts in clean-gas service.     

Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology

Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

Effect of NOx control processes on mercury speciation in utility flue gas

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NOx control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NOx control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH3, has been evaluated. The influence of NH3 on fly ash Hg reactions also is being investigated.     

Thermodynamic behaviour of sodium and calcium based sorbents in the emission control of waste incinerators

The dry treatment of flue gas produced by incineration processes is discussed thermodynamically. The study investigates the theoretical limits achieved by sodium and calcium based sorbents in the removal of the pollutant species HCl, NOx and SO2. Calculations were performed varying the temperature and the molar ratio between the amount of the injected alkaline sorbent and the content of the pollutant gaseous species in the flue gas. Results show that sodium cation based sorbents are more efficient than calcium based ones in the whole investigated temperature range (100-600 degrees C). The higher effectiveness of sodium based sorbents is particularly remarkable towards hydrogen chloride, whose concentration can always be reduced below the values set by the environmental regulations. Possible improvements in the treatment efficiency of combustion fumes obtainable with sodium based sorbents can be mainly summarised in a lower concentration of HCl in the treated gas and in a partial reduction of NOx concentration.     

用活性填料催化氧化-硝酸吸收法脱除氮氧化物的研究

为了提高硝酸吸收氮氧化物的效率，对活性填料催化氧化-硝酸吸收NOx进行了研究。结果表明：活性填料能明显提高NOx的吸收效率；当NOx中NO2体积百分含量增加，其吸收效率增加；随进气浓度和液气比的增大，NOx吸收效率增加；随NO2浓度的增加，NO的吸收效率先增加后减少，在NO／NO2为3时，NO吸收效率最高；随NO的增加NO2的吸收效率先增加后减少，在NO／NO2为0．6～1之间，NO2的吸收效果较好。     

A fungal vapor-phase bioreactor for the removal of nitric oxide from waste gas streams.

Ground-level O3 formation is becoming a major concern in many cities due to recent tightening of O3 regulations. To control O3 formation, more efficient treatment processes for O3 precursors, such as NOx and volatile organic compounds (VOCs), are needed. One promising new technology for removing both NOx and VOCs from off-gas streams is biofiltration, a simple process whereby contaminated air is passed through a biologically active packed bed. In this study, a toluene-degrading fungal bioreactor was used to treat an aerobic gas stream contaminated with NO. The fungal bioreactor removed 93% of the inlet 250-ppmv NO at an empty bed contact time (EBCT) of 1 min when supplied with 90 g/m3/hr toluene. The presence of NH4+ concentrations greater than 0.4 mg NH3/g dry packing medium, however, resulted in poor NO removal. The bioreactor achieved a maximum toluene elimination capacity of 270 g/m3/hr and maintained greater than 95% toluene removal efficiencies over the 175-day study period.     

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.     

NOx Removal with Combined Selective Catalytic Reduction and Selective Noncatalytic Reduction: Pilot-Scale Test Results

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NO_x) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium- and titanium-based composite honeycomb catalyst and enhanced urea (NH₂CONH₂) were used with a natural-gas-fired furnace at a NO_x concentration of 110 ppm. Changes in SNCR chemical injection temperature and stoichiometry led to varying levels of post-furnace ammonia (NH₃), which acts as the reductant feed to the downstream SCR catalyst. The urea-based chemical could routinely achieve SNCR plus SCR total NO_x reductions of 85 percent with less than 3 ppm NH₃ slip at reductant/NO_x stoichiometries ranging from about 1.5 to 2.5 and SCR space velocities of 18,000 to 32,000 h^?1. This pilot-scale research has shown that SNCR and SCR can be integrated to achieve high NO_x removal. SNCR provides high temperature reduction of NO_x followed by further removal of NO_x and minimization of NH₃ slip by a significantly downsized (high-space velocity) SCR.     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Control of diesel gaseous and particulate emissions with a tube-type wet electrostatic precipitator

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NOx) from diesel exhaust emissions. The concentration of ozone (O3) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O3 analyzer were used for quantifying the inlet and outlet concentrations of CO and NOx (nitric oxide [NO] + nitrogen dioxide [NO2]), and O3 in the diesel exhaust stream. The wESP was capable of removing approximately 67-86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NOx concentration in diesel exhaust. The O3 concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

好氧反硝化去除低浓度NO_x的动力学模型研究

在好氧条件下,对利用生物滴滤塔（bio-trickling filter,BTF）反硝化净化废气中NOx的过程进行了理论模型探讨,并用实验结果进行了验证。在分析NOx在BTF内传质以及生物降解过程的基础上,建立了NOx在气相和生物膜相的质量守恒方程,结合Fick定律和好氧条件下的Monod微生物反应动力学方程,最终得到了NOx在BTF中＂吸附-微生物降解＂过程的动力学方程。模型计算值与实验结果表明,BTF中好氧反硝化过程为一级反应过程,利用该模型可以较好地模拟进口浓度、停留时间等因素对出口浓度的影响,对实际应用具有指导意义。     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Simulation modeling for nitrogen removal and experimental estimation of mass fractions of microbial groups in single-sludge system

Nitrification-denitrification in a single-sludge nitrogen removal system (SSNRS; with a sufficient carbon source for denitrification) was performed. With an increase in the mixed liquor recycle ratio (R(m)) from 1 to 2, the total nitrogen (TN) removal efficiency at a lower volumetric loading rate (VLR=0.21 NH(4)(+)-N m(-3) d(-1)) increased, but the TN removal efficiency at a higher VLR (0.35 kg NH(4)(+)-N m(-3) d(-1)) decreased. A kinetic model that accounts for the mass fractions of Nitrosomonas, Nitrobacter, nitrate reducer and nitrite reducer (f(n1), f(n2), f(dn1), and f(dn2)) in the SSNRS and an experimental approach for the estimation of the mass fractions of nitrogen-related microbial groups are also proposed. The estimated f(dn1) plus f(dn2) (0.65-0.83) was significantly larger than the f(n1) plus f(n2) (0.28-0.32); the f(n1) (0.21-0.26) was larger than the f(n2) (0.05-0.07); and the f(dn1) (0.32-0.45) varied slightly with the f(dn2) (0.33-0.38). At the lower VLR, the f(dn1) plus f(dn2) increased with increasing R(m); however at the higher VLR, the f(dn1) plus f(dn2) did not increase with increasing R(m). By using the kinetic model, the calculated residual NH(4)(+)-N and NO(2)(-)-N in the anoxic reactor and NO(2)(-)-N and NO(3)(-)-N in the aerobic reactor were in fairly good agreement with the experimental data; the calculated NO(3)(-)-N in the anoxic reactor was over-estimated and the calculated NH(4)(+)-N in the aerobic reactor was under-estimated.     

尿素/三乙醇胺吸收烟气NO_x的实验研究

以尿素作为吸收液,与NOx反应生成N2和CO2,脱除烟气中的氮氧化物。以一套双级串连的填料塔为主体反应器,分别对气速、液气比、反应物浓度、添加剂浓度和反应温度等参数对尿素溶液吸收NOx反应的影响进行了实验研究,获得了优化实验工况,研究结果显示,在气速为0.1 m/s、液气比为16 L/m3、三乙醇胺为0.01%（质量比）、尿素浓度为13%（质量比）工况下,反应温度为30~70℃,脱硝总效率可达50%以上,且随着NOx体积分数增加而提高。     

Regenerative thermal oxidation of airborne N, N-dimethylformamide and its associated nitrogen oxides formation characteristics

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NOx) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m x 0.14 m x 1 m (L x W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (ts) of 1.5 min, a superficial gas velocity (Ug) of 0.39 m/sec (evaluated at an influent air temperature of around 30 degrees C) and preset maximum destruction temperatures (Ts) of 750-950 degrees C, no NOx was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N x m3. The "NOx-N formation/DMF-N destruction" mass ratios were in the range 0.76-1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO, formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NOx formation ratios were in the range 0.75-0.96. The TRE decreased as Ug increased but was invariant with Ts. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Investigation of gas production and entrapment in granular iron medium

A method for measuring gas entrapment in granular iron (Fe0) was developed and used to estimate the impact of gas production on porosity loss during the treatment of a high NO3- groundwater (up to approximately 10 mM). Over the 400-d study period the trapped gas in laboratory columns was small, with a maximum measured at 1.3% pore volume. Low levels of dissolved H2(g) were measured (up to 0.07+/-0.02 M). Free moving gas bubbles were not observed. Thus, porosity loss, which was determined by tracer tests to be 25-30%, is not accounted for by residual gas trapped in the iron. The removal of aqueous species (i.e., NO3-, Ca, and carbonate alkalinity) indicates that mineral precipitation contributed more significantly to porosity loss than did the trapped gases. Using the stoichiometric reactions between Fe0 and NO3-, an average corrosion rate of 1.7 mmol kg-1 d-1 was derived for the test granular iron. This rate is 10 times greater than Fe0 oxidation by H2O alone, based on H2 gas production. NO3- ion rather than H2O was the major oxidant in the groundwater in the absence of molecular O2. The N-mass balance [e.g., N2g and NH4+ and NO3-] suggests that abiotic reduction of NO3- dominated at the start of Fe0 treatment, whereas N2 production became more important once the microbial activity began. These laboratory results closely predict N2 gas production in a separated large column experiment that was operated for approximately 2 yr in the field, where a maximum of approximately 600 ml d-1 gas volumes was detected, of which 99.5% (v/v) was N2. We conclude that NO3- suppressed the production of H2(g) by competing with water for Fe0 oxidation, especially at the beginning of water treatment when Fe0 is highly reactive. Depends on the groundwater composition, gas venting may be necessary in maintaining PRB performance in the field.     

络合吸收结合生物转化去除氮氧化物技术

介绍了络合吸收结合生物转化处理NOx 技术的基本原理和目前的研究进展情况 ,并分析了该技术处理氮氧化物存在的问题和未来发展方向     

Quantifying NOx for industrial combustion processes

The objectives of this paper are to (1) identify the problems with many of the units that are used to report and regulate NOx, (2) show how to properly correct NOx measurements for oxygen-enhanced combustion, and (3) recommend a preferred type of NOx unit. The current variety of NOx units make comparisons difficult and can cause considerable confusion. NOx may be measured on a wet or dry basis, but it is commonly reported on a dry basis. The reported NOx may differ from the actual measurements, which may be converted to a specific O2 basis level. Nearly all of the measured NOx from industrial combustion systems is in the form of NO, which is converted to NO2 in the atmosphere. However, when given on a mass basis, the measured NO is commonly reported as NO2 for regulatory purposes, but may be reported as NO, NO2, or simply NOx in technical papers. Some existing regulations may penalize combustion technologies with higher efficiencies and lower flue gas volumes, such as oxygen-enhanced combustion. Confusion may occur when applying some of the "conventional" NOx units to oxygen-enhanced processes. A better unit is the mass of NOx generated per unit of production, which also incorporates the overall process efficiency into the emissions. That unit does not penalize more efficient processes that may generate more NOx on a volume basis, but less NOx on a production basis.     

H2O2溶液同时脱硫脱硝实验研究

二氧化硫和氮氧化物是电厂产生的主要大气污染物,研究焦点越来越集中在在一个反应器内实现同时脱硫脱硝。实验以H2O溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,实验结果表明：H2O浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱除率影响显著,pH、氧含量对脱硝率影响不大。在整个实验范围内脱硫效率总是保持在98．5％以上,脱硝效率最高达到67．4％。