A sulfur removal and disposal process through H2S adsorption and regeneration: Ammonia leaching regeneration

An iron oxide solid sponge H₂S adsorbent works by reacting H₂S and turning ferric oxide into ferric sulfide. The ferric sulfide will be converted back into ferric oxide and elemental sulfur when contacting oxygen or air. This study investigates the leaching of elemental sulfur from the solid sponge using anhydrous liquid ammonia as solvent. The leaching treatment expectedly results in effective regeneration of the adsorbent, which is able to lead to a sulfur removal and recovery process suitable for handling the small and mid-sized sulfur production cases, i.e., those less than 10 ton/day sulfur. The leaching does not significantly impair the physical properties, including the adsorbent pellet strength. The adsorption–regeneration (or leaching) cycle could be repeated at least three times. The cumulative sulfur loading can achieve as high as 50% (w/w), three times greater than that in the one-time use. The wash-off in leaching and the spent adsorbent can be made into slurry that is to be injected into underground formations such as depleted oil wells. It is anticipated that this underground injection is safer and more efficient than acid gas injection.     

An experimental study for H2S and CO2 removal via caustic scrubbing system

In this study, removal of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) from simulated syngas has been studied on one column scrubbing system. Gas flow rate as a measure of gas residence time and superficial gas velocity, gas composition, inlet H₂S load, flow modes (countercurrent and cocurrent) and packing geometry were the parameters in the design and/or operation of an acid gas scrubber system. Better H₂S scrubbing efficiencies have been obtained in countercurrent flow mode than that of cocurrent flow mode. When accordingly designed, static mixer with its superior performance on H₂S removal overweighed to structured packings. The coexistence of CO₂ and H₂S has been shown to increase the sodium hydroxide (NaOH) consumption along the scrubber column thereby decreasing the H₂S removal efficiency at higher H₂S loads. The gas residence time as changing with the gas velocity was found to be more dominant on acid gas removal efficiency than the effect of superficial gas velocity within the experimented range. A gas residence times of equal or above 3 s were seemed to be closer to the optimum point.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.     

下坪渗滤液处理厂含氨尾气处理试验研究

对下坪垃圾填埋场含氨尾气的处理进行了研究.研究结果显示,采用硫酸吸收含氨尾气,吸收效率可达98%以上.吸收产生的硫酸铵产品符合<肥料、土壤调理剂-硫酸铵标准>(GB535-1995).     

Stable and eco-friendly solid acids as alternative to sulfuric acid in the liquid phase nitration of toluene

Liquid-phase nitration of toluene was carried out using a silica supported Cs salt of phosphomolybdic acid (Cs_2.5H_0.5PMoO₄₀) as catalyst with dilute nitric acid under mild conditions. The Cs_2.5H_0.5PMoO₄₀ particles with Keggin-type structure were well dispersed on the surface of silica, and the catalysts exhibited strong acidity, which may be responsible for the high catalytic nitration activity. The effects of various parameters on nitration were tested, which included reaction temperature, reaction time, catalyst amount and reactants ratio. Under suitable conditions, the nitrations gave high toluene conversion (99.6%) and good mono-nitration selectivity. Compared to the conventional process, there was no other organic solvent or sulfuric acid used in the reaction system, which made it more environment-friendly. Moreover, the supported catalyst was proven to have excellent stability in the nitration process.     

Anaerobic co-digestion of fat,oil, and grease (FOG): A review of gas production and process limitations

The addition of readily available high strength organic wastes such as fats, oils, and grease (FOG) from restaurant grease abatement devices may substantially increase biogas production from anaerobic digesters at wastewater treatment facilities. This FOG addition may provide greater economic incentives for the use of excess biogas to generate electricity, thermal, or mechanical energy. Co-digestion of FOG with municipal biosolids at a rate of 10–30% FOG by volume of total digester feed caused a 30–80% increase in digester gas production in two full scale wastewater biosolids anaerobic digesters (Bailey, 2007, Muller et al., 2010). Laboratory and pilot scale anaerobic digesters have shown even larger increases in gas production. However, anaerobic digestion of high lipid wastes has been reported to cause inhibition of acetoclastic and methanogenic bacteria, substrate, and product transport limitation, sludge flotation, digester foaming, blockages of pipes and pumps, and clogging of gas collection and handling systems. This paper reviews the scientific literature on biogas production, inhibition, and optimal reactor configurations, and will highlight future research needed to improve the gas production and overall efficiency of anaerobic co-digestion of FOG with biosolids from municipal wastewater treatment.     

Failure of a heat exchanger generated by an excess of SO2 and H2S in the Sulfur Recovery Unit of a petroleum refinery

The aim of this work is to investigate the level of damage to the heat exchanger in a Sulfur Recovery Unit (SRU) of a petroleum refinery. The by-products of oil refining are submitted to special treatment in order to meet technical specifications of corrosivity, sulfur content, acidity, formation of pollutant compounds, and color alteration. Sulfur is removed from the by-products in the form of H₂S, which is an acid gas that is sent to the SRU for sulfur production. The gases in the SRU are H₂S, CO₂, SO₂, and SO₃, which are corrosive to the mild steel equipment. The Unit is frequently forced to paralyze its activities due to the corrosion of its heat exchangers and pressure vessels, and the acid gas load is burnt causing the release of SO_x into the atmosphere. The above occurs when generalized corrosion damages SRU equipment. The importance of this work is to emphasize that the leakage of acid gas and sulfur into the atmosphere is a direct result of corrosion, which causes economical and environmental damage. This study may be used to improve the control of The Claus Process and to minimize corrosion damage. The SRU does not, at present, carry out any corrosion prevention methods. The corrosion of mild steel is controlled by correct air admission to oxide H₂S, and to produce SO₂, which is the reagent in the reaction of sulfur production.     

Biotrickling filters for biogas sweetening: Oxygen transfer improvement for a reliable operation

An industrial-scale biotrickling filter for the removal of high concentrations of H₂S is described in this work. The system has been operating at H₂S inlet concentrations between 1000 and 3000 ppm_v at acidic conditions. A decrease of pH from 2.6 to 1.8 did not affect the biological activity inside the biofilter while reducing the water make-up consumption up to 75%. The current oxygen supply system, based on direct injection of air to the liquid phase, has demonstrated to be inefficient for a long-term operation leading to elemental sulfur accumulation in the packing material (i.e. promoting clogging episodes). The present study demonstrates it is possible to partially remove (40.3%) the deposited elemental sulfur by bio-oxidation when biogas is not fed. In normal operation conditions, the implementation of an aeration system based on jet-venturi devices has shown quite promising results in terms of oxygen transfer efficiency and robustness. Such improvement of oxygen transfer was translated in a better conversion of H₂S to sulfate, which increased around 17%, prolonging the lifespan operation at low-pressure drop.     

不同pH值下含铁矿物对硫酸侵蚀混凝土的影响研究

硫酸侵蚀为混凝土耐久性损伤的一个重要方面.在硫酸盐侵蚀过程中,含铁矿物等侵蚀产物不断形成,导致混凝土材料形成不同程度的腐蚀.为研究不同pH值环境下含铁矿物对混凝土结构腐蚀的影响,在实验室配置了pH值为2.0、3.0和4.0的稀硫酸溶液,结合不同洗刷作用方式来模拟酸雨环境,采用室内长期浸泡试验方法对混凝土试件进行不同程度...     

New method for acrylic acid recovery from industrial waste water via esterification with 2-ethyl hexanol

Acrylic acid (AA) is an important component for the production of acrylate polymer. In a typical acrylic manufacturing unit, waste water contains AA in a range of 4–15 wt.% contributes to the high values of chemical oxygen demand. Due to the toxicity of AA to the aquatic organism, this wastewater should be treated before it is discharged to the environment. The waste water could be evaporated before sending to the incineration which was neither economic feasible nor environmental friendly. Esterification of wastewater containing carboxylic acid with alcohol could be a promising method to recover the acid by converting it to ester while purifying the wastewater. In the present study, recovery of AA via esterification with 2-ethyl hexanol (2EH) was investigated. The model industrial wastewater with various concentration of AA (10–100% w/w) was reacted with 2EH to produce 2-ethyl hexyl acrylate (2EHA) in the setups with total reflux and continuously water removal. These Amberlyst-15 (ion exchange resin) catalyzed reactions were carried out under the mass transfer resistance free region. The performance of both systems was compared. The yield for the reactions of the AA solutions with the AA concentrations of 30–80% was enhanced significantly when the reactions were carried out using the second setup. The kinetic data of the esterification of dilute AA was well described by the Eley–Rideal (ER) kinetic model incorporated with a correction factor to consider the catalyst fouling effect and pseudo-homogeneous (PH) kinetic model for the AA polymerization. The findings have shown the potential of recovering AA from the waste water stream via esterification. The concentrated AA solutions or larger amount of inhibitor should be adopted to prevent the catalyst fouling by the deposition of poly-acrylic acid on the catalyst surface.     

Removal of H2S by co-immobilized bacteria and fungi biocatalysts in a bio-trickling filter

Biological control of odor gases has gained more attention in recent years. In this study, removal performance of a vertical bio-trickling filter inoculated with bacteria and fungi was studied. Bacteria and fungi were isolated from activated sludge in a sewage treatment plant. By adopting “three step immobilization method”, the bio-trickling filter could degrade pollutant immediately once hydrogen sulfide (H₂S) passed. The optimal empty bed resident time was 20 s. The optimal elimination capacity was about 60 g H₂S m^?3 h^?1 with removal efficiency of 95%. And the maximum elimination capacity was 170 g H₂S m^?3 h^?1. Pressure drop was ranged between 5 and 15 mm H₂O per bed over the whole operation. Removal efficiency was not affected obviously after terminating nutrient supply. The bio-trickling filter could recover back after shut down H₂S gaseous and liquid supplies simultaneously. Microbial community structure in the bio-trickling filter was not changed significantly.Combining bacteria and fungi would be a better choice for inoculation into a bio-trickling filter because of the quickly degradation of H₂S and rapid recovery under shut-down experiment. This is the first study attempting to combine bacteria and fungi for removal of H₂S in a bio-trickling filter.     

Decomposition and oxidation of sodium 3,5,6-trichloropyridin-2-ol in sub- and supercritical water

Sodium 3,5,6-trichloropyridin-2-ol (STCP) is a necessary precursor compound for the production of chlorpyrifos and triclopyr, which are extensively used as pesticide and herbicide, respectively. In the process of STCP production, however, large amount of wastewater containing STCP is discharged, which causes increasingly environmental concerns. Therefore, it is of great significance to develop a rapid and effective method for the disposal of containing STCP contaminants. In this work, the thermal decomposition of STCP in sub- and supercritical water was investigated using a continuous tubular reactor. While STCP was stable below 280 °C, it could be effectively decomposed at elevated temperature. FT-IR spectra of the decomposition products indicated that the pyridine ring structure in the STCP molecule was stable even at temperatures up to 400 °C. The decomposition reaction was mainly caused by the substitution of Cl groups in the STCP molecule with OH groups, resulting in polyhydroxylated pyridines as the major decomposition product. Moreover, high pressure favored the substitution reaction. To completely decompose STCP into non-toxic or low toxic compounds, supercritical water oxidation (SCWO) was employed to evaluate the oxidation of STCP using H₂O₂ as an oxidant. It was found that STCP could be completely oxidized to H₂O, CO₂ and corresponding inorganic ammonium salts with an oxidation rate of 99%.     

Mesoporous simonkolleite–TiO2 nanostructured composite for simultaneous photocatalytic hydrogen production and dye decontamination

In the present work, mesoporous simonkolleite–TiO₂ composite was prepared with sol–gel method. The composite photocatalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and Raman spectroscopy. Also, surface area and particle size were analyzed using BET equation. The photocatalytic hydrogen production with simultaneous decolorization of Remazole Red (F3B) dye was investigated over TiO₂ and simonkolleite–TiO₂ composite under UV–vis light irradiation. It was worthy to be noted that the rate of hydrogen production over simonkolleite–TiO₂ is higher that produced over TiO₂. The maximum amount of photocatalytic-produced hydrogen was 2.1 mmol and 3.3 mmol within 240 min using TiO₂ and simonkolleite–TiO₂ composite, respectively. The specific production rate of hydrogen from photocatalytic conversion of dye was calculated. Improvement of apparent quantum yield (22.07%) after 5 h was achieved upon addition of simonkolleite to TiO₂. This high apparent quantum yield proves that the system proposed in this study could be a hopeful approach toward using sunlight energy as outlook energy source. The obtained results suggested that a new process for H₂ production from wastewater could be achieved. The process also provides a method for degradation of organic pollutants with simultaneous H₂ production.     

Safety evaluation of different acids in high-density polyethylene container loading

To reduce costs, high-purity chemical suppliers wash and reuse HDPE containers collected from users. To determine the lifetime of a container, the appearance of that container and the manufacturer's recommendations for its lifetime are generally considered. Guidelines for determining the lifetime of an HDPE container have not been clearly defined. The lack of these specifications may result in the leakage of high-purity chemicals in the storage, transportation and use of HDPE containers. To understand the effects of using high-purity chemicals (sulfuric acid (H₂SO₄) and nitric acid (HNO₃)) on HDPE, this study revealed its effects by mechanical and thermal performance tests. According to the mechanical properties test results, the ductility and tensile strength of HDPE soaked H₂SO₄ and HNO₃ decreased. HDPE immersed in HNO₃ exhibited the lowest thermal stability by thermal performance testing. In summary, the degradation of HDPE is affected by storage conditions. For this study, HDPE only needs 60 days of immersion in HNO_3, and its ductility and tensile strength will decline obviously. This study shows that when these containers are used for long-term storage of high purity chemicals, the mechanical properties (including ductility, ductility, and tensile strength) of HDPE containers tend to decrease. To decrease accidental leakage of chemicals due to aging of HDPE, comprehensive and approved regulations should be established for the loading, transport, and storage of HDPE containers.     

Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and GC/MS

Thermal degradation of triacetone triperoxide (TATP) was studied using differential scanning calorimetry (DSC) and gas chromatography/mass spectrometry (GC/MS). TATP, a potential explosive material, is powerful organic peroxide (OP) that can be synthesized by available chemicals, such as acetone and hydrogen peroxide in the laboratory or industries. The thermokinetic parameters, such as exothermic onset temperature (T₀) and heat of decomposition (ΔH_d), were determined by DSC tests. The gas products from thermal degradation of TATP were identified using GC/MS technique.In this study, H₂O₂ was mixed with propanone (acetone) and H₂SO₄ catalysis that produced TATP. The T₀ of TATP was determined to be 40 °C and E_a was calculated to be 65 kJ/mol. A thermal decomposition peak of H₂O₂ was analyzed by DSC and two thermal decomposition peaks of H₂O₂/propanone were determined. Therefore, H₂O₂/propanone mixture was applied to mix acid that was discovered a thermal decomposition peak (as TATP) in this study. According to risk assessment and analysis methodologies, risk assessment of TATP for the environmental and human safety issue was evaluated as 2-level of hazard probability rating (P) and 6-level of severity of consequences ratings (S). Therefore, the result of risk assessment is 12-point and was evaluated as “Undesirable” that should be enforced the effect of control method to reduce the risk.     

Technologies for the abatement of sulphide compounds from gaseous streams: a comparative overview

The techniques that may be applied to the removal of sulphide compounds from gases are briefly described and discussed. Scrubbing and adsorption on solids allow the recovery of sulphur either as such (H₂S or sulphide organics) or, after oxidation, as elemental sulphur or SO₂. This is actually a good choice when the concentration is high enough for sulphur recovery. When sulphur concentration is very low, techniques such as thermal and catalytic combustion, oxidative scrubbing and biofiltration might be preferable to attain deodorization. However, combustion converts sulphur into SO₂, while oxidative scrubbing gives rise to sulphate-containing solutions. Biofiltration mineralizes sulphur in a natural environmental friendly way, without producing secondary contaminants.     

Hydrogen sulphide removal from landfill gas

Control of odours should be considered to be a fundamental issue in order to site, design and manage sanitary landfills. With regard to construction and demolition (C&;D) debris, landfilling was the mainly adopted solution in many European Countries; in particular, gypsum drywalls can produce high concentrations of hydrogen sulphide (H₂S) in landfill gas ranging from 7 ppm to 100 ppm. In some cases also dangerous concentrations until to 12,000 ppm were detected. In this paper H₂S removal efficiency in a lab-scale vertical packed scrubber was investigated. Hydrogen sulphide abatement was evaluated for inlet H₂S concentrations of 1000–100–10 ppm, adjusting scrubbing liquid pH in the range 9–12.5 by means of caustic soda (NaOH 2N solution). Moreover, best operating conditions for the system were defined as well as H₂S abatement along the tower and liquid recirculation effectiveness in case of inlet H₂S concentration of 10 ppm (typical odour concentration). Results showed that pH of 11.5 in scrubbing liquid could be considered the best value for removal of different inlet H₂S concentrations, also taking into account parasitical consumption of NaOH due to CO₂ absorption. Moreover, in case of continuous working of the system at H₂S concentration of 10 ppm, strong removal efficiency was already obtained with a packed bed height of about 70 cm. Significant performances were ensured after 1 h of constant activity, consuming about 3 ml of soda per cubic meter of polluted air. Subsequently liquid blowdown was necessary.     

造纸污水处理厌氧系统沼气综合利用

目前厌氧系统已广泛应用于造纸废水处理,厌氧处理系统过程中产生大量的沼气,而沼气的热值很高,很有利用的价值,而本文结合笔者曾编制的某造纸废水处理厌氧技术改造环评探讨造纸污水处理厌氧系统沼气综合利用技术。该项目的实施,既减少了造纸废水的出水浓度,又提高了节能环保效益。     

活性白土废水治理的实验研究

活性自土生产过程中产生大量的含微细白土颗粒的强酸性废水,处理效果一直不佳.实验改进白土生产工艺,通过粒度控制,从根本上减少白土生产过程中超细白土颗粒的产生,循环利用硫酸和洗涤水以减少成本和对环境的污染.并对影响活性自土质量的主要生产工艺条件进行了比较系统的试验研究,确定了最佳工艺条件.成功地制备了脱色率92.88%,过滤速度21.27mL/mim的高效植物油活性白土.     

A thermal hazard risk evaluation of emulsion polymerisation and vinyl acetate monomers in the latex manufacturing process

Latex is extensively used in industrial products. However, completing some processes at scale leads to unacceptable levels of risk that need to be quantified and mitigated. Systemic risks must be eliminated wherever possible, and safety takes priority over efficiency and quality. To assess the process risks accurately, four raw materials were examined in this study: polyvinyl acetate (PVA), latex process-initiator-ammonium persulfate (APS) and hydrogen peroxide (H₂O₂), and vinyl acetate monomer (VAM). The physicochemical composition of the PVA latex process was determined via calorimeters, including differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). The calorimetry results showed that the protective colloid was a critical component in the polymerisation reaction. In addition, when adding initiators to the system, it is vital to observe the normal ratio of materials and keep the stirring system operating. The scenario system also simulated the effects of shutting down various inhibitory programs, including the build-up of free radicals that could result in a runaway reaction when the initiator was added in excess. On the other hand, the result of the risk matrix displayed as a medium level, indicating that although the probability of an accident is low, the resulting severity is at disaster level. As a result, this study provides process safety engineers with a reliable frame of reference for assessing the potential dangers in the PVA latex manufacturing process.