Simulation study of hydrogen sulfide removal in underground gas storage converted from the multilayered sour gas field

A simulation study was carried out to investigate the temporal evolution of H_(2)S in the Huangcaoxia underground gas storage (UGS), which is converted from a depleted sulfur-containing gas field. Based on the rock and fluid properties of the Huangcaoxia gas field, a multilayered model was built. The upper layer Jia-2 contains a high concentration of H_(2)S (27.2 g/m^(3)), and the lower layer Jia-1 contains a low concentration of H_(2)S (14.0 mg/m^(3)). There is also a low-permeability interlayer between Jia-1 and Jia-2. The multi-component fluid characterizations for Jia-1 and Jia-2 were implemented separately using the Peng-Robinson equation of state in order to perform the compositional simulation. The H_(2)S concentration gradually increased in a single cycle and peaked at the end of the production season. The peak H_(2)S concentration in each cycle showed a decreasing trend when the recovery factor (RF) of the gas field was lower than 70%. When the RF was above 70%, the peak H_(2)S concentration increased first and then decreased. A higher reservoir RF, a higher maximum working pressure, and a higher working gas ratio will lead to a higher H_(2)S removal efficiency. Similar to developing multi-layered petroleum fields, the operation of multilayered gas storage can also be divided into multi-layer commingled operation and independent operation for different layers. When the two layers are combined to build the storage, the sweet gas produced from Jia-1 can spontaneously mix with the sour gas produced from Jia-2 within the wellbore, which can significantly reduce the overall H_(2)S concentration in the wellstream. When the working gas volume is set constant, the allocation ratio between the two layers has little effect on the H_(2)S removal. After nine cycles, the produced gas’s H_(2)S concentration can be lowered to 20 mg/m^(3). Our study recommends combining the Jia-2 and Jia-1 layers to build the Huangcaoxia underground gas storage. This plan can quickly reduce the H_(2)S concentration of the produced gas to 20 mg/m^(3), thus meeting the gas export standards as well as the HSE (Health, Safety, and Environment) requirements in the field. This study helps the engineers understand the H_(2)S removal for sulfur-containing UGS as well as provides technical guidelines for converting other multilayered sour gas fields into underground storage sites.

Hydrogen sulfide enhances adult neurogenesis in a mouse model of Parkinson's disease

Hydrogen sulfide(H_2S) is regarded to be a protectant against diseases of the central nervous system and cardiovascular system.However, the mechanism by which H_2S elicits neuroprotective effects in the progression of Parkinson's disease(PD) remains unclear.To investigate the role of H_2S in delaying the pathological process of PD, we used the most common sodium hydrosulfide(Na HS) as an H_2S donor and established a mouse model of PD induced by 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine/probenecid(MPTP/p) in the present study.Our results show that H_2S reduced neuronal loss during the progression of PD.Notably, we found that H_2S exhibited protective effects on dopaminergic neurons.Excitingly, H_2S also increased the proliferation of neural stem cells in the subventricular zone.Next, we evaluated whether the neuroprotective effects of H_2S on dopaminergic neurons in PD are dependent on adult nerve regeneration by treating primary adult neural stem cells cultured ex vivo with 1-methyl-4-phenylpyridine.Our results show that H_2S could prevent nerve injury induced by 1-methyl-4-phenylpyridine, promote the growth of neurospheres, and promote neurogenesis by regulating Akt/glycogen synthase kinase-3β/β-catenin pathways in adult neural stem cells.These findings confirm that H_2S can increase neurogenesis in an adult mouse model of PD by regulating the Akt/glycogen synthase kinase-3β/β-catenin signaling pathway.This study was approved by the Animal Care and Use Committee of Nanjing Medical University, China(IACUC Approval No.1601153-3).

Intelligent polymeric hydrogen sulfide delivery systems for therapeutic applications

Hydrogen sulfide(H_(2)S)plays an important role in regulating various pathological processes such as protecting mammalian cell from harmful injuries,promoting tissue regeneration,and regulating the process of various diseases caused by physiological disorders.Studies have revealed that the physiological effects of H_(2)S are highly associated with its concentrations.At relatively low concentration,H_(2)S shows beneficial functions.However,long-time and high-dose donation of H_(2)S would inhibit regular biological process,resulting in cell dysfunction and apoptosis.To regulate the dosage of H_(2)S delivery for precision medicine,H_(2)S delivery systems with intelligent characteristics were developed and a variety of biocompatibility polymers have been utilized to establish intelligent polymeric H_(2)S delivery systems,with the abilities to specifically target the lesions,smartly respond to pathological microenvironments,as well as real-timely monitor H_(2)S delivery and lesion conditions by incorporating imaging-capable moieties.In this review,we focus on the design,preparation,and therapeutic applications of intelligent polymeric H_(2)S delivery systems in cardiovascular therapy,inflammatory therapy,tissue regenerative therapy,cancer therapy and bacteria-associated therapy.Strategies for precise H_(2)S therapies especially imaging-guided H_(2)S theranostics are highlighted.Since H_(2)S donors with stimuli-responsive characters are vital components for establishing intelligent H_(2)S delivery systems,the development of H_(2)S donors is also briefly introduced.

One-pot solvothermal synthesis of hierarchical Co-doped NiO microspheres with enhanced hydrogen sulfide sensing performances

In this study we report,for the first time,the synthesis of Co-doped NiO microspheres assembled by two-dimension nanosheets using a facile solvothermal method.The H 2 S gas-sensing performance of the as-prepared samples was systematically investigated.The result demonstrates that the Co–NiO sensor with Co/Ni molar ratio of 1%(1%Co–NiO)exhibits high response(12.9)and rapid response speed(110 s)to 20×10^(−6) H_(2)S at 200℃ in comparison with the pure NiO sensor.Moreover,excellent selectivity,repeatability,and stability were achieved.The sensing mechanism illustrates that the superior gas-sensing properties can be attributed to two factors.(1)The hierarchical microspherical construction with an ultrahigh specific surface area of 163.1 m^(2)g^(−1) provides adequate active sites for H_(2)S gas adsorption,porous structures,and an interlayer gap that accelerates the diffusion of H_(2)S gas,resulting in improved sensitivity and response speed of the sensor.(2)Co-doping results in a decrease in the particle sizes(ca.4 nm)and increase in the number of adsorbed ionized oxygen species,which improves sensitivity and selectivity.Therefore,this study provides a facile approach for the synthesis of hierarchical Co–NiO microspheres with enhanced H_(2)S gas-sensing performance.

Investigation of oxy-fuel combustion for methane and acid gas in a diffusion flame

Co-combustion of methane(CH4)and acid gas(AG)is required to sustain the temperature in Claus reaction furnace.In this study,oxy-fuel combustion of methane and acid gas has been experimentally studied in a diffusion flame.Three equivalence ratios(ER=1.0,1.5,2.0)and CH_(4)-addition ratios(CH_(4)/AG=0.3,0.5,0.7)were examined and the flame was interpreted by analyzing the distributions of the temperature and species concentration along central axial.CH_(4)-AG diffusion flame could be classified into three sections namely initial reaction,oxidation and complex reaction sections.Competitive oxidation of CH_(4)and H_(2)S was noted in the first section wherein H_(2)S was preferred and both were mainly proceeding decomposition and partial oxidation.SO_(2)was formed at oxidation section together with obvious presence of H2 and CO.However,H2 and CO were inclined to be sustained under fuel rich condition in the complex reaction section.Reducing ER and increasing CH4/AG contributed to higher temperature,H_(2)S and CH_(4)oxidation and CO_(2)reactivity.Hence a growing trend for CH_(4)and AG to convert into H_(2),CO and SO_(2)could be witnessed.And this factor enhanced the generation of CS2 and COS in the flame inner core by interactions of CH4 and CO_(2)with sulfur species.COS was formed through the interactions of CO and CO_(2)with sulfur species.The CS_(2)production directly relied on reaction of CH_(4)with sulfur species.The concentration of COS was greater than CS_(2)since CS_(2)was probably inhibited due to the presence of H_(2).COS and CS_(2)could be consumed by further oxidation or other complex reactions.

Comparison of Perovskite Systems Based on AFeO_(3)(A=Ce,La,Y)in CO_(2) Hydrogenation to CO

CO_(2) is the most cost-eff ective and abundant carbon resource,while the reverse water-gas reaction(rWGS)is one of the most eff ective methods of CO_(2) utilization.This work presents a comparative study of rWGS activity for perovskite systems based on AFeO_(3)(where A=Ce,La,Y).These systems were synthesized by solution combustion synthesis(SCS)with diff erent ratios of fuel(glycine)and oxidizer(φ),diff erent amounts of NH 4 NO_(3),and the addition of alumina or silica as supports.Various techniques,including X-ray diff raction analysis,thermogravimetric analysis,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy,energy-dispersive X-ray spectroscopy,N 2-physisorption,H_(2) temper-ature-programmed reduction,temperature-programmed desorption of H_(2) and CO_(2),Raman spectroscopy,and in situ FTIR,were used to relate the physicochemical properties with the catalytic performance of the obtained composites.Each specifi c perovskite-containing system(either bulk or supported)has its own optimalφand NH_(4) NO_(3) amount to achieve the highest yield and dispersion of the perovskite phase.Among all synthesized systems,bulk SCS-derived La-Fe-O systems showed the highest resistance to reducing environments and the easiest hydrogen desorption,outperforming La-Fe-O produced by solgel combustion(SGC).CO_(2) conversion into CO at 600°C for bulk ferrite systems,depending on the A-cation type and preparation method,follows the order La(SGC)<Y<Ce<La(SCS).The diff erences in properties between La-Fe-O obtained by the SCS and SGC methods can be attributed to diff erent ratios of oxygen and lanthanum vacancy contributions,hydroxyl coverage,morphology,and free iron oxide presence.In situ FTIR data revealed that CO_(2) hydrogenation occurs through formates generated under reaction conditions on the bulk system based on La-Fe-O,obtained by the SCS method.γ-Al_(2)O_(3) improves the dispersion of CeFeO_(3) and LaFeO_(3) phases,the specifi c surface area,and the quantity of adsorbed H_(2) and CO_(2).This led to a signifi cant increase in CO_(2) conversion for supported CeFeO_(3) but not for the La-based system compared to bulk and SiO_(2)-supported perovskite catalysts.However,adding alumina increased the activity per mass for both Ce-and La-based perovskite systems,reducing the amount of rare-earth components in the catalyst and thereby lowering the cost without substantially compromising stability.

Selective and self-validating breath-level detection of hydrogen sulfide in humid air by gold nanoparticle-functionalized nanotube arrays

We demonstrate the selective detection of hydrogen sulfide at breath concentration levels under humid airflow,using a self-validating 64-channel sensor array based on semiconducting single-walled carbon nanotubes(sc-SWCNTs).The reproducible sensor fabrication process is based on a multiplexed and controlled dielectrophoretic deposition of sc-SWCNTs.The sensing area is functionalized with gold nanoparticles to address the detection at room temperature by exploiting the affinity between gold and sulfur atoms of the gas.Sensing devices functionalized with an optimized distribution of nanoparticles show a sensitivity of 0.122%/part per billion(ppb)and a calculated limit of detection(LOD)of 3 ppb.Beyond the self-validation,our sensors show increased stability and higher response levels compared to some commercially available electrochemical sensors.The cross-sensitivity to breath gases NH3 and NO is addressed demonstrating the high selectivity to H2S.Finally,mathematical models of sensors’electrical characteristics and sensing responses are developed to enhance the differentiation capabilities of the platform to be used in breath analysis applications.

Cr_(2)S_(3)催化H_(2)S分解制氢的活性与动力学研究

目的将H_(2)S分解制氢既能解决废气污染问题,又能实现其资源化的高值利用。制备中低温段高效稳定的H_(2)S分解催化剂,掌握其催化动力学行为,有助于构建硫化学链促进的H_(2)S高效分解的新工艺。方法采用溶液燃烧法制备了Cr_(2)S_(3)催化剂,通过XRD、BET和SEM/EDS等方法表征了催化剂组成和结构,同时通过实验考查其在H_(2)S催化分解制氢中的催化性能、稳定性以及反应动力学,并研究了制备时燃料比例对催化剂性能的影响。结果在φ(H_(2)S)=5%,气体空速(GHSV)=24000 h^(−1)的反应条件下,Cr_(2)S_(3)-T1.50具有最高的H2S转化率,在800℃时可达16.01%,并且无其他副反应;反应动力学分析表明,Cr_(2)S_(3)-T1.50催化H_(2)S分解的表观活化能为50.7 kJ/mol。结论溶液燃烧法制备出的Cr_(2)S_(3)催化剂在400~800℃具有极好的活性和稳定性,能够极大地降低H_(2)S分解的表观活化能。

Numerical Study of the Threshold Intensity Dependence on Wavelength in Laser Spark Ignition of Molecular Hydrogen Combustion

A numerical investigation of laser wavelength dependence on the threshold intensity of spark ignition in molecular hydrogen over a wide pressure range is presented. A modified electron cascade model (Gamal et al., 1993) is applied under the experimental conditions that carried out by Phuoc (2000) to determine the threshold intensity dependence on gas pressure for spark ignition in hydrogen combustion using two laser wavelengths namely;1064 nm and 532 nm. The model involves the solution of the time dependent Boltzmann equation for the electron energy distribution function (EEDF) and a set of rate equations that describe the change of the formed excited molecules population. The model takes into account most of the physical processes that expected to occur in the interaction region. The results showed good agreement between the calculated thresholds for spark ignition and those measured ones for both wavelengths, where the threshold intensities corresponding to the short wavelength (532 nm) are found to be higher than those calculated for the longer one (1064 nm). This result indicates the depletion of the high density of low energy electrons generated through multi-photon ionization at the short wavelength via electron diffusion and vibrational excitation. The study of the EEDF and its parameters (viz, the temporal evolution of: the electron density, ionization rate electron mean energy, …) revealed the important role played by each physical process to the spark ignition as a function of both laser wavelength and gas pressure. More over the study of the time variation of the EEDF explains the characteristics of the ignited spark at the two wavelengths for the tested pressure values.

A multi-parameter-induced activation of gas therapeutic platform to remarkably amplify photodynamic therapy efficacy

Gas therapy(GT)combined with photodynamic therapy(PDT)is an effective strategy to compensate for the PDT limitation caused by the hypoxic tumor microenvironment,which can greatly improve PDT efficacy.The uncontrolled leakage of gas molecules during delivery seriously hinders its practical biological application.Herein,we report a multifunction nanomedicine that enables precise gas therapy(including carbon monoxide(CO)release and H_(2)S depletion)using a multi-parameter-induced activation gas release strategy,enlarging the PDT efficacy.This nanomedicine uses a disulfide bond to covalently link a photosensitizer with the CO donor 3-hydroxyflavone(3-HF).The disulfide bond can be specifically consumed in H_(2)S-rich tumor areas,releasing the CO donor(3-HF),and also depleting H_(2)S.More importantly,the photo-controlled production of^(1)O_(2)can induce 3-HF precise release of CO in the tumor location.Such H_(2)S,light,and^(1)O_(2)multi-parameter-induced activation of gas release strategy ensures the accuracy of GT to amplify PDT efficiency.As expected,in vitro and in vivo investigations show that GT makes up for the PDT limitation,exhibiting the highest tumor therapeutic effect.This multi-parameter-activated design strategy provides a new way to improve the precision and efficacy of multimodal synergistic therapy of tumors.

H_(2)S-releasing adhesive hydrogel as oral radioprotectant for gastrointestinal tract radioprotection

Radiation damage can cause a series of gastrointestinal(GI)tract diseases.The development of safe and effective GI tract radioprotectants still remains a great challenge clinically.Here,we firstly report an oral radioprotectant Gel@GYY that integrates a porous gelatin-based(Gel)hydrogel and a pH-responsive hydrogen sulfide(H2S)donor GYY4137(morpholin-4-ium 4 methoxyphenyl(morpholino)phosphinodithioate).Gel@GYY has a remarkable adhesion ability and long retention time,which not only enables responsive release of low-dose H2S in stomach and subsequently sustained release of H2S in the whole intestinal tract especially in the colon,but also ensures a close contact between H2S and GI tract.The released H2S can effectively scavenge free radicals induced by X-ray radiation,reduce lipid peroxidation level,repair DNA damage and recover vital superoxide dismutase and glutathione peroxidase activities.Meanwhile,the released H2S inhibits radiation-induced activation of nuclear factorκB(NF-κB),thus reducing inflammatory cytokines levels in GI tract.After treatment,Gel@GYY displays efficient excretion from mice body due to its biodegradability.This work provides a new insight for therapeutic application of intelligent H2S-releasing oral delivery system and potential alternative to clinical GI physical damage protectant.

硫化氢焚烧裂解废硫酸工艺改进

硫化氢焚烧裂解废硫酸装置因硫化氢气量及浓度降低,造成焚烧炉温度下降,导致废酸裂解不完全,无法保障烷基化废酸裂解的正常运行。经工艺改进优化,使用硫化氢气体与异辛烷干气混烧或硫化氢气体与硫黄混烧补充热量,满足了烷基化废酸裂解的需要,达到了治理污染、含硫资源循环利用的目的。

无线硫化氢监测系统在高含硫气田的应用

高含硫气田天然气净化装置在高负荷下长周期运行,设备逐渐老化,管道产生腐蚀,传统的固定式硫化氢报警仪无法及时针对新漏点实时监测,新兴的无线监测技术以其高效的安装速度、低廉的安装成本,在高含硫气田中获得了越来越广泛的应用。在某天然气净化厂,以无线硫化氢报警仪、无线网关和智能天线、GDS系统为基础,建立了一套无线硫化氢监测系统,实现对硫化氢泄漏高风险区域的实时监控,有效保障了净化厂长期安全稳定生产。

440 t/h燃煤锅炉低氮燃烧模式下水冷壁高温腐蚀分析

分别采用X射线荧光光谱、X射线衍射光谱、电镜扫描和能谱分析等方法,对某440t/h燃煤锅炉下层燃烧器附近水冷壁区域收集的腐蚀层进行详细表征,分析并讨论腐蚀产物的形成和痕量元素富集特点。结果表明:腐蚀内层主要含有FeS_(2)、Fe_(2)O_(3)、PbS和ZnS,但Pb比Zn富集程度高;腐蚀外层以ZnS、PbS、GaS、Fe_(1-x)S和Zn_(1.0)Al_(1.04)S_(2.13)为主,还含有少量Ga、Se、Bi等元素,但Zn与Ga元素富集程度显著高于内层;腐蚀层中Pb、Zn、Ga、Se、Ge、As、Bi、Th、Sn、Sb等元素主要通过气化-冷凝和黏附的未燃尽碳颗粒释放析出的方式到达管壁,部分元素仍存在二次气化现象并扩散至腐蚀层深处,以进一步增大腐蚀裂纹尺度。基体铁的氧化和硫化反应同时发生并相互竞争,靠近基体侧腐蚀层先发生裂缝后逐渐开始破碎。黄铁矿向外转移中会释放气态硫并生成多种晶型的磁黄铁矿,这说明气态硫在腐蚀过程中扮演重要作用。此外,沉积层中微细颗粒和气态痕量元素可能会向基体侧移动与扩散渗透,增加腐蚀内部应力进而加剧腐蚀。

高含硫化氢气田集输系统硫化亚铁形成机理及风险控制

普光气田是国内已投入开发的最大的整装海相气田,硫化氢含量15%,二氧化碳含量10%。地面集输系统采用了"全湿气加热保温混输"工艺,天然气中含有饱和水和游离水,易产生硫化亚铁,并附着在内壁。在工艺检修、作业过程中,若与空气接触,就可能引发硫化亚铁自燃,给气田的安全生产带来严重隐患。在设计上,选用抗硫耐腐蚀材料、容器内壁防腐涂层;在生产过程中,采用了碱洗、清洗、钝化、微正压隔氧、润湿等措施,消除了硫化亚铁产生的危险因素,确保了安全生产。

改炼高硫原油典型炼油装置危险性分析及对策研究

近年来,国内炼油装置越来越多地改炼进口高硫油,对原有炼油装置的安全性能提出了挑战。本文以延迟焦化装置为例,在分析典型炼油装置在原料含硫量提高后存在的主要危险因素的基础上,从原料变化入手,通过对国内各炼化企业几年来的检修记录调查、重点单位现场勘查等,探讨了原有炼油装置在原油含硫量增高情况下的安全适应性,并提出了针对腐蚀、硫化氢泄露、硫化亚铁自燃3个主要危险因素的安全防范及处理措施。

氧化铝厂硫化氢废气燃烧法处理研究

用燃烧法处理氧化铝厂的硫化氢废气 ,H2 S转化SO2 的转化率接近 10 0 % ,H2 S燃烧过程热量可自求平衡 ,H2 S经燃烧后用氧化铝厂赤泥附液吸收 ,SO2 吸收效率大于 98% ,当H2 S浓度低于 4 3%时直接用赤泥附液吸收 ,H2 S吸收效率达 90 2 % ,排气浓度达到大气污染物综合排放二级标准 (GB16 92 7 1996 )。

低氮燃烧模式下燃煤锅炉水冷壁沉积物与腐蚀层成分分析

低氮燃烧改造后煤粉炉内最上层燃烧器同燃尽风喷口之间区域水冷壁附近的还原性气氛变强,管壁发生硫化型高温腐蚀的风险骤增。以一台330 MW四角切圆煤粉锅炉为对象,取样收集炉内多处水冷壁区域进行了灰渣与腐蚀层元素与矿物相表征,分析炉内水冷壁结焦的原因以及管壁高温腐蚀机制。结果表明,不同位置水冷壁所黏附熔渣中Si和Al元素均主要以莫来石(Al_(6)Si_(2)O_(13))和硅线石(Al_(2)SiO_(5))形式存在,提高了灰颗粒的熔融温度;而Fe元素主要以Fe_(2)O_(3)存在,其富集度显著高于碱金属或碱土金属。B层和F层燃烧器水冷壁所在高度区域黏附层状沉积物中高度富集S、Zn元素及少量Pb元素,Zn元素质量分数高达20%,主要以PbS、ZnS和ZnAl_(1.04)S_(2.13)的形式存在。F层燃烧器高度收集灰渣表面所附着的浮灰中仍含有约7%未燃尽碳,说明该区域旋转气流存在刷墙行为;灰样由Si、Al、Fe、C、S和Zn元素构成,主要以莫来石、赤铁矿、硫化物形式存在。管壁硫化氢腐蚀层以Fe_(1-x)S、Fe_(7)S_(8)、Fe_(9)S_(10)和Fe_(3)O_(4)为主,还含有少量PbS和PbO_(1.57)。腐蚀层中Fe_(1-x)S存在多种晶型结构,可能源于当地不同的H_(2)S分压和温度。黏附灰渣中的含Zn和Pb组分主要通过气化-冷凝和所黏附未燃尽碳颗粒释放析出2种方式富集,而富硅铝酸盐和富铁颗粒则主要是通过惯性撞击和热泳沉积的方式发生黏附。

火驱尾气中H_2S与O_2化学反应热力学研究

为了研究火驱尾气回注过程中H2S与O2的化学反应趋势,判断尾气回注工艺的安全性,运用化学反应热力学模型计算了给定组分中的H2S与O2化学反应参数,分析温度对反应过程的影响,进一步确定二者的反应边界条件及爆炸极限范围。研究结果表明,现场工况条件下火驱尾气中H2S与O2发生缓慢的氧化反应,主要产物为SO2与H2O,但随着温度的升高,反应自发程度减小。同时,根据混合物爆炸极限计算可知,火驱尾气在现场回注条件下无爆炸风险。

常温下铁的硫化产物自燃性

含硫油品储运过程中H2S腐蚀产物是常温下硫铁化合物的主要来源,以H2S与铁粉反应制备的硫铁化合物来模拟设备内H2S的腐蚀产物,利用自然氧化的方法测定了硫化反应产物的一次氧化升温和二次氧化升温,考察了铁粉含水量对硫化反应及硫化反应产物自燃性的影响,采用XRD和SEM手段对硫化反应产物进行了表征。结果表明:H2S与铁粉的硫化反应产物为FeS,呈微小颗粒状,覆盖在铁粉表面;硫化反应产物具有自燃性,一次氧化升温最高达到87℃;未被完全氧化的硫化反应产物密封放置一段时间后自燃性明显增加,其二次氧化升温速率最高超过39℃/min;铁粉中含有适量的水可以增加硫化反应速率,提高硫化反应产物的自燃性。