Hydrogen sulfide gas treatment by a chemical-biological process: chemical absorption and biological oxidation steps

In order to remove high concentrations of hydrogen sulfide (H2S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H2S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H2S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe2+ concentrations, pH, and glucose concentrations on Fe2+ oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H2S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass-transfer was verified as the rate-determining step in the chemical reaction through model validation. The Fe2+ production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35 degrees C in which more than 90% Fe3+ formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe2+ oxidation and the growth of T. ferrooxidans CP9.     

The Use of Nahcolite Ore and Bag Filters For Sulfur Dioxide Emission Control

This paper describes some technical and economic aspects of the nahcolite ore injection process for the simultaneous removal of fly ash and sulfur oxides from stack gases. The process is capable of removing greater than 99% of the particulate matter and greater than 70% of the sulfur oxides present in such gases. In the process, nahcolite ore, a naturally occurring material containing 70 to 90% sodium bicarbonate, is ground to 90% passing through —200 mesh screens. Approximately 20% of the ground ore is used to precoat the filter bags in a baghouse filter while the remainder of the material is fed into the flue gas Just ahead of the baghouse. The flue gas is drawn through the baghouse by induced draft fans and sent up the stack. Most of the SO₂ and practically all of the fly ash in the flue gas can be removed as the gas passes through the filter bags. The spent nahcolite ore and fly ash are collected and conveyed to waste disposal as landfill, or alternatively processed for insolubilization by coprecipitation prior to landfilling. The technical feasibility of the process has been demonstrated in both bench scale and pilot scale engineering studies. Economic analyses performed for the cases of plants located in the midwest and southwest indicate lower capital costs for the nahcolite injection process when compared to wet scrubbing. On an annual cost basis, the nahcolite ore Injection process is comparable in cost to wet scrubbing for the case of the southwestern power plant, and somewhat more expensive for the case of the midwestern plant.     

One-dimensional model for biogeochemical interactions and permeability reduction in soils during leachate permeation

This paper uses the findings from a column study to develop a reactive model for exploring the interactions occurring in leachate-contaminated soils. The changes occurring in the concentrations of acetic acid, sulphate, suspended and attached biomass, Fe(II), Mn(II), calcium, carbonate ions, and pH in the column are assessed. The mathematical model considers geochemical equilibrium, kinetic biodegradation, precipitation-dissolution reactions, bacterial and substrate transport, and permeability reduction arising from bacterial growth and gas production. A two-step sequential operator splitting method is used to solve the coupled transport and biogeochemical reaction equations. The model gives satisfactory fits to experimental data and the simulations show that the transport of metals in soil is controlled by multiple competing biotic and abiotic reactions. These findings suggest that bioaccumulation and gas formation, compared to chemical precipitation, have a larger influence on hydraulic conductivity reduction.     

An efficient venturi scrubber system to remove submicron particles in exhaust gas

An efficient venturi scrubber system making use of heterogeneous nucleation and condensational growth of particles was designed and tested to remove fine particles from the exhaust of a local scrubber where residual SiH4 gas was abated and lots of fine SiO2 particles were generated. In front of the venturi scrubber, normal-temperature fine-water mist mixes with high-temperature exhaust gas to cool it to the saturation temperature, allowing submicron particles to grow into micron sizes. The grown particles are then scrubbed efficiently in the venturi scrubber. Test results show that the present venturi scrubber system is effective for removing submicron particles. For SiO2 particles greater than 0.1microm, the removal efficiency is greater than 80-90%, depending on particle concentration. The corresponding pressure drop is relatively low. For example, the pressure drop of the venturi scrubber is approximately 15.4 +/- 2.4 cm H2O when the liquid-to-gas ratio is 1.50 L/m3. A theoretical calculation has been conducted to simulate particle growth process and the removal efficiency of the venturi scrubber. The theoretical results agree with the experimental data reasonably well when SiO2 particle diameter is greater than 0.1 microm.     

垃圾渗滤液烟气脱硫体系的实验研究

利用垃圾渗滤液中较高的碱度吸收二氧化硫是垃圾渗滤液湿法烟气脱硫工艺的第一阶段。试验证明 ,垃圾渗滤液可高效吸收二氧化硫 (去除率可达 90 %以上 ) ;同时垃圾渗滤液中氨氮浓度由 133mmol L降至 78mmol L。实验结果证实了所建立的垃圾渗滤液烟气脱硫体系的互补性     

Hydrogen Sulfide Gas Treatment by a Chemical‐Biological Process: Chemical Absorption and Biological Oxidation Steps

In order to remove high concentrations of hydrogen sulfide (H₂S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H₂S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H₂S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe^2 + concentrations, pH, and glucose concentrations on Fe^2 + oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H₂S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass‐transfer was verified as the rate‐determining step in the chemical reaction through model validation. The Fe^2 + production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35°C in which more than 90% Fe^3 + formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe^2 + oxidation and the growth of T. ferrooxidans CP9.     

聚环氧琥珀酸合成及中试研究

聚环氧琥珀酸（PESA）是一种国际上公认的绿色阻垢剂。实验分析PESA合成过程中的主要工艺参数,如,反应体系pH、温度和时间,对产品阻垢性能的影响,借助中试实验平台,对正交实验结果进行验证和修正。实验结果表明,环氧化过程pH对中间体ESA产率影响显著;聚合反应过程中,体系的温度和反应时间存在关联性。根据自主开发的双反应釜及其反应控制技术,实现了中试规模的PESA化学合成过程温度等反应条件的精确控制,反应副产物减少,中间体ESA纯度高,可达90%以上,系统合成的最终产物PESA 20 mg/L时阻垢性能可达到90%以上,产品具备了较高的阻垢性能水平。     

PCDD/PCDF reduction by the co-combustion process

A novel process, termed the co-combustion process, has been developed and designed to utilise the thermal treatment of municipal solid waste (MSW) in cement clinker production and reduce PCDD/PCDF emissions. To test the conceptual design; detailed engineering design of the process and equipment was performed and a pilot plant was constructed to treat up to 40 tonnes MSW per day. The novel process features included several units external to the main traditional cement rotary kiln: an external calcinations unit in which the hot gas calcined the limestone thus making significant energy savings for this chemical reaction; the lime generated was used in a second chamber to act as a giant acid gas scrubber to remove SOx and particularly HCl (a source of chloride); an external rotary kiln and secondary combustion unit capable of producing a hot gas at 1200 degrees C; a gas cooler to simulate a boiler turbogenerator set for electricity generation; the incorporation of some of the bottom ash, calcined lime and dust collector solids into the cement clinker. A PCDD/PCDF inventory has been completed for the entire process and measured PCDD/PCDF emissions were 0.001 ng I-TEQ/Nm(3) on average which is 1% of the best practical means [Hong Kong Environmental Protection Department, 2001. A guidance note on the best practicable means for incinerators (municipal waste incineration), BPM12/1] MSW incineration emission limit values.     

Catalytic NOx reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx- and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively.     

固化/稳定化处理污泥填埋气液转化模式

固化/稳定化污泥进行填埋产生填埋气,产气规律是指导填埋气收集处理系统设计的重要依据。通过构建大型填埋柱模拟填埋实验,研究不同固化材料添加量污泥气液转化规律。实验结果表明,原泥和固化污泥产气规律分为2种类型:前期产气速率呈线性增加,达到最大速率后产气速率呈指数降低。低添加量的固化污泥,产气分3个阶段,分别为产气抑制期、增长期和衰减期。高添加量固化污泥,产气只有一个阶段,产气速率随着时间推移逐渐减小,产气量很小。固化污泥降解过程就是有机质含量降低,气体产量、含水率增加相互转化过程,达到固化材料添加量25%时,水分和气体产生量均很小,降解受到很强抑制,产气150 d左右稳定,产气量很小,无需单独设置气体收集系统。     

PM10, PM2.5 and PM1.0—Emissions from industrial plants—Results from measurement programmes in Germany

Emission measurement programmes were carried out at industrial plants in several regions of Germany to determine the fine dust in the waste gases; the PM₁₀, PM_2.5 and PM_1.0 fractions were sampled using a cascade impactor technique. The installations tested included plants used for: combustion (brown coal, heavy fuel oil, wood), cement production, glass production, asphalt mixing, and processing plants for natural stones and sand, ceramics, metallurgy, chemical production, spray painting, wood processing/chip drying, poultry farming and waste treatment. In addition waste gas samples were taken from small-scale combustion units, like domestic stoves, firing lignite briquettes or wood.In total 303 individual measurement results were obtained during 106 different measurement campaigns. In the study it was found that in more than 70% of the individual emission measurement results from industrial plants and domestic stoves the PM₁₀ portion amounted to more than 90% and the PM_2.5 portion between 50% and 90% of the total PM (particulate matter) emission. For thermal industrial processes the PM_1.0 portion constituted between 20% and 60% of the total PM emission.Typical particle size distributions for different processes were presented as cumulative frequency distributions and as frequency distributions. The particle size distributions determined for the different plant types show interesting similarities and differences depending on whether the processes are thermal, mechanical, chemical or mixed. Consequently, for the groups of plant investigated, a major finding of this study has been that the particle size distribution is a characteristic of the industrial process. Attempts to correlate particle size distributions of different plants to different gas cleaning technologies did not lead to usable results.     

NaOH预处理对玉米秸秆固态厌氧消化的影响

实验主要研究了NaOH预处理对玉米秸秆厌氧消化产气量和产气效率的影响。采用质量分数分别为1.0%、2.5%、5.0%和7.5%NaOH溶液对玉米秸秆进行24 h浸泡和未浸泡等预处理,测定其厌氧消化过程中各指标的变化。结果表明,经质量分数为5.0%NaOH浸泡24 h后,玉米秸秆木质素降解率最大,为38.67%;厌氧发酵累积产气量为226.75L/kg VS,与未经碱处理实验组相比提高了38.5%。该结果提示,5.0%NaOH溶液浸泡24 h后可使玉米秸秆厌氧消化的产气量和产气效率显著提高。     

Mobile measurement of methane and hydrogen sulfide at natural gas production site fence lines in the Texas Barnett Shale

Production of natural gas from shale formations is bringing drilling and production operations to regions of the United States that have seen little or no similar activity in the past, which has generated considerable interest in potential environmental impacts. This study focused on the Barnett Shale Fort Worth Basin in Texas, which saw the number of gas-producing wells grow from 726 in 2001 to 15,870 in 2011. This study aimed to measure fence line concentrations of methane and hydrogen sulfide at natural gas production sites (wells, liquid storage tanks, and associated equipment) in the four core counties of the Barnett Shale (Denton, Johnson, Tarrant, and Wise). A mobile measurement survey was conducted in the vicinity of 4788 wells near 401 lease sites, representing 35% of gas production volume, 31% of wells, and 38% of condensate production volume in the four-county core area. Methane and hydrogen sulfide concentrations were measured using a Picarro G2204 cavity ring-down spectrometer (CRDS). Since the research team did not have access to lease site interiors, measurements were made by driving on roads on the exterior of the lease sites. Over 150 hr of data were collected from March to July 2012. During two sets of drive-by measurements, it was found that 66 sites (16.5%) had methane concentrations >3 parts per million (ppm) just beyond the fence line. Thirty-two lease sites (8.0%) had hydrogen sulfide concentrations >4.7 parts per billion (ppb) (odor recognition threshold) just beyond the fence line. Measured concentrations generally did not correlate well with site characteristics (natural gas production volume, number of wells, or condensate production). t tests showed that for two counties, methane concentrations for dry sites were higher than those for wet sites. Follow-up study is recommended to provide more information at sites identified with high levels of methane and hydrogen sulfide.

Implications:Information regarding air emissions from shale gas production is important given the recent increase in number of wells in various regions in the United States. Methane, the primary natural gas constituent, is a greenhouse gas; hydrogen sulfide, which can be present in gas condensate, is an odor-causing compound. This study surveyed wells representing one-third of the natural gas production volume in the Texas Barnett Shale and identified the percent of sites that warrant further study due to their fence line methane and hydrogen sulfide concentrations.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Catalytic NO(chi) reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NO(chi)- and CO-emissions are reduced by 90% and 20% to about 50 mg/N m3 andbelow 10 mg/N m3, respectively.     

Compositions and greenhouse gas emission factors of flared and vented gas in the Western Canadian Sedimentary Basin

A significant obstacle in evaluating mitigation strategies for flaring and venting in the upstream oil and gas industry is the lack of publicly available data on the chemical composition of the gas. This information is required to determine the economic value of the gas, infrastructure and processing requirements, and potential emissions or emissions credits, all of which have significant impact on the economics of such strategies. This paper describes a method for estimating the composition of solution gas being flared and vented at individual facilities, and presents results derived for Alberta, Canada, which sits at the heart of the Western Canadian Sedimentary Basin. Using large amounts of raw data obtained through the Alberta Energy Resources Conservation Board, a relational database was created and specialized queries were developed to link production stream data, raw gas samples, and geography to create production-linked gas composition profiles for approximately half of the currently active facilities. These were used to create composition maps for the entire region, to which the remaining facilities with unknown compositions were geographically linked. The derived data were used to compute a range of solution gas composition profiles and greenhouse gas emission factors, providing new insight into flaring and venting in the region and enabling informed analysis of future management and mitigation strategies.

Implications: Accurate and transparent determination of environmental impacts of flaring and venting of gas associated with oil production, and potential benefits of mitigation, is severely hampered by the lack of publicly available gas composition data. In jurisdictions within the Western Canadian Sedimentary Basin, frameworks exist for regulating and trading carbon offset credits but current potential for mitigation is limited by a lack of standardized methods for calculating CO₂ equivalent emissions. The composition and emission factor data derived in this paper will be useful to industry, regulators, policy researchers, and entrepreneurs seeking statistically significant and openly available data necessary to manage and mitigate upstream flaring and venting activity and estimate greenhouse gas impacts.     

Gas production and migration in landfills and geological materials.

Landfill gas, originating from the anaerobic biodegradation of the organic content of waste, consists mainly of methane and carbon dioxide, with traces of volatile organic compounds. Pressure, concentration and temperature gradients that develop within the landfill result in gas emissions to the atmosphere and in lateral migration through the surrounding soils. Environmental and safety issues associated with the landfill gas require control of off-site gas migration. The numerical model TOUGH2-LGM (Transport of Unsaturated Groundwater and Heat-Landfill Gas Migration) has been developed to simulate landfill gas production and migration processes within and beyond landfill boundaries. The model is derived from the general non-isothermal multiphase flow simulator TOUGH2, to which a new equation of state module is added. It simulates the migration of five components in partially saturated media: four fluid components (water, atmospheric air, methane and carbon dioxide) and one energy component (heat). The four fluid components are present in both the gas and liquid phases. The model incorporates gas-liquid partitioning of all fluid components by means of dissolution and volatilization. In addition to advection in the gas and liquid phase, multi-component diffusion is simulated in the gas phase. The landfill gas production rate is proportional to the organic substrate and is modeled as an exponentially decreasing function of time. The model is applied to the Montreal's CESM landfill site, which is located in a former limestone rock quarry. Existing data were used to characterize hydraulic properties of the waste and the limestone. Gas recovery data at the site were used to define the gas production model. Simulations in one and two dimensions are presented to investigate gas production and migration in the landfill, and in the surrounding limestone. The effects of a gas recovery well and landfill cover on gas migration are also discussed.     

Gas permeability of biochar-amended clay: potential alternative landfill final cover material

Compacted biochar-amended clay (BAC) has been proposed as an alternative landfill final cover material in this study. Biochar has long been proposed to promote crop growth, mitigate odor emission, and promote methane oxidation in field soils. However, previous studies showed that soil-gas permeability was increased upon biochar application, which will promote landfill gas emission. The objective of the present study is to investigate the possibility of using compacted BAC as an alternative material in landfill final cover by evaluating its gas permeability. BAC samples were prepared by mixing 425-μm-sieved peanut shell biochar with kaolin clay in different ratios (0, 5, 10, and 15 %, w/w) and compacting at different degrees of compactions (DOC) (80, 85, and 90 %) with an optimum water content of 35 %. The gas permeability of the BACs was measured by flexible wall gas permeameter and the microstructure of the BACs was analyzed by SEM with energy-dispersive x-ray spectroscopy (EDX). The results show that the effects of biochar content on BAC gas permeability is highly dependent on the DOC. At high DOC (90 %), the gas permeability of BAC decreases with increasing biochar content due to the combined effect of the clay aggregation and the inhibition of biochar in the gas flow. However, at low DOC (80 %), biochar incorporation has no effects on gas permeability because it no longer acts as a filling material to the retard gas flow. The results from the present study imply that compacted BAC can be used as an alternative final cover material with decreased gas permeability when compared with clay.     

The role of mechanical and biological treatment in reducing methane emissions from landfill disposal of municipal solid waste in the United Kingdom

In Europe, the European Union Landfill Directive aims to reduce the negative environmental impacts of landfilling. This is mainly to be achieved by reducing the quantity of organic matter deposited, through measures such as the separate collection and recycling of the organic waste stream or pretreatment of residual wastes before landfilling. Other than incineration or other thermal processes, mechanical biological treatment is playing an increasingly important role. This study was conducted to seek the benefits of municipal solid waste (MSW) pretreatment, as well as the differences in methane production from the landfilling of untreated and mechanically/biologically treated (MBT) MSW using GasSim simulation. Results demonstrated that methane production rates vary significantly among waste fractions. Those that contribute most to methane generation (organic material and potentially reusable or recyclable material) could be targeted and treated before landfilling. The statistic relationship from the first phase of the study indicated that to match the increasingly stringent landfill waste organic content allowance, local councils should prioritize the reduction/sorting of certain targeted fractions, such as paper, card, green waste, and other putrescibles from MSW. Moreover, mechanical treatment alone produces organic-rich waste called mechanically sorted organic residues (MSORs), which can be viewed as an organic content concentration process. Mechanically and biologically pretreated waste, on the other hand, differs significantly from untreated MSW and MSORs. This work demonstrated that if efficient mechanical-biological treatment is used, considerable reductions in biological activity, landfill gas production, and energy content/total organic carbon could be achieved. Using GasSim, reductions in methane production of >74% have been simulated if a 90% organic content reduction can be achieved during biological treatment on MSORs. A 50-60% organic content reduction by following biological treatment can turn MSOR properties only into normal MSW equivalent though considerably less volume.     

Treatment of N,N-dimethylacetamide waste gas by a trickle-bed air biofilter.

The system performance of a trickle-bed air biofilter (TBAB) for treating N,N-dimethylacetamide (DMAC) waste gas was investigated under different gas flow rates and influent concentrations. In the pseudo-steady-state conditions, the DMAC elimination capacity increased but the removal efficiency decreased as the influent loading increased. More than 90% and 80% DMAC removal efficiencies are achieved for influent loadings below 20.2 and 34.5 g DMAC/m3/h, respectively. The TBAB appears to be an effective treatment process for controlling DMAC emission with low-to-medium loadings and the effectiveness could be maintained over a long-period operation.