双催化层固定床甲烷化反应器CFD模拟

温度分布直接影响着固定床甲烷化反应器的甲烷产量和设备安全性。以年产12.75亿立方煤制天然气绝热甲烷化反应器为研究对象,在建立真实设备三维模型的基础上,利用ANSYS-CFX有限元数值模拟的方法,建立多孔介质内化学反应、热交换与质量传递的气-固两相反应器模型,获得了双段固定床甲烷化反应器内部温度、压力、速度场的分布规律及甲烷产率分布。对不同床层结构对应的特征场分布进行了探索,分析了床层结构对各特征场分布的影响,确定了床层结构优化方案,MCR催化剂床层出口处支撑延长的结构更有利于温度场沿反应器径向的均匀分布和甲烷质量分数的提高。对反应器入口温度、空速、压力对特征参数分布的影响进行了研究,提出了针对本工艺的允许入口参数波动范围。     

甲烷化固定床反应器床层反应过程与场分布数值模拟

以甲烷化固定床反应器床层为研究对象,使用CFD软件编写CEL语言,将甲烷化反应以源项的形式添加到模拟过程中,对比多孔介质模型与填充球床模型模拟的准确性,选择填充球床模型进行模拟,获得了床层的速度场、组分浓度以及温度场分布。研究结果表明:与填充球床模型比较,由于多孔介质模型简化了内部的孔隙结构,使用其对固定床反应器进行模拟时存在较大误差,其中出口温度模拟值比实测值低13.6%;固定床的壁效应使近壁面处10%的圆环面积上通过20%的质量流量,进而显著影响床层内部场的分布;床层内部轴向温升显著,从250℃ 升高到 685℃,同时径向温度分布不均,变化范围在20～40℃内波动。     

固定床甲烷化反应器的最新研究进展

面对我国的资源现状,我国正大力推进煤制天然气的发展,煤制天然气的关键技术是甲烷化技术,甲烷化反应器则是甲烷化过程的主要设备,因此有必要关注甲烷化反应器的研究进展。目前甲烷化反应器主要为固定床反应器,本文着重介绍固定床甲烷化反应器的近期研究。通过对甲烷化反应催化剂、甲烷化工艺及甲烷化设备三方面对甲烷化反应器研究进展进行分析并提出对甲烷化反应器的研究展望。     

流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。     

合成气甲烷化工艺技术研究进展

合成气完全甲烷化技术是煤制天然气特有的技术,按照反应器类型,合成气甲烷化工艺可以分为绝热固定床、等温固定床、流化床和浆态床等工艺,其中绝热固定床甲烷化工艺成熟并广泛应用于煤制天然气项目。本文介绍了多种绝热固定床甲烷化工艺,并比较了5种高温绝热固定床甲烷化工艺的流程、技术特点和应用情况。随着研究工作的不断深入,国内绝热固定床甲烷化技术达到了国际技术同类水平,具备了工业化应用条件,但还需在节能降耗、提高催化剂寿命方面加大研究力度。还概述了等温固定床、流化床和浆态床甲烷化工艺,分析了等温固定床、流化床和浆态床甲烷化工艺存在的问题,并指出了后续研究重点,等温固定床工艺应在反应温度控制和反应器开发方面深入研究,流化床甲烷化工艺研究重点放在开发高强度催化剂和工程化放大方面,浆态床甲烷化工艺需要重点研究解决CO转化率较低和催化剂损耗严重的问题。     

甲烷化反应器及配套工艺技术开发

以甲烷化反应器及配套工艺技术作为研究对象,对绝热固定床反应器、等温床反应器、立式多段串联冷激固定床反应器、浆态床反应器、流化床反应器及工艺进行了详细技术分析,并对甲烷化技术的选用提出一定建议。     

变床层高度固定床反应器的分析

在分子筛催化剂苯气相乙基化制乙苯过程开发中,根据该反应过程的特点,提出了变床层高度固定床反应器的构想。利用催化剂失活动力学模型,通过模拟计算,对常规固定床反应器和变床层高度固定床反应器的性能进行比较,结果表明后者对延长反应器操作周期和改善反应选择性均有显著作用。上述分析已在300吨乙苯/年中试反应器的运转中得到证实。     

合成气完全甲烷化固定床反应器数值模拟

以煤制天然气为背景,研究了反应器高径比、进料温度、操作压力、空速、原料气组成对高温甲烷化反应器内部温度和浓度分布的影响。通过建立固定床反应器拟均相二维模型,模拟合成气完全甲烷化过程,采用MATLAB进行数值求解,并与工业侧线试验数据进行对比。结果表明,高径比为2~3时有助于减小热损,可以控制床层热点温度在700℃以下;进料温度升高到400℃,加快了反应速率,导致热点温度过高,接近800℃;操作压力不适宜,直接影响CO的加氢效果;空速由4000提高到16000 h?1时,床层热点显著向反应器出口移动;原料气氢碳比(H2/(3CO+4CO2))增大到2,促进CO转化,而水气比由0.19增加到0.4,可以有效控制床层温升,热点温度在650℃左右。相关研究结果为反应器设计和工艺参数的优化提供了依据。     

甲烷化催化剂在高碳焦炉煤气制LNG项目中的应用

介绍了新疆某焦化厂高碳焦炉煤气制液化天然气(LNG)装置的概况及甲烷化工艺流程,重点分析了甲烷化催化剂在近3年间的运行情况。运行数据显示：甲烷化催化剂经过长周期运行,催化剂性能保持良好,甲烷化工段出口未检出CO和CO₂,各反应器床层压差保持在初始值附近,未明显上升,且催化剂还具有较好的裂解功能。     

流化床甲烷化基础与应用最新进展

由于CO甲烷化的快速表面反应、强放热特性,相比固定床,采用小颗粒催化剂的流化床甲烷化技术在反应活性和催化剂稳定性方面具有明显的技术优势。从高耐磨催化剂、流化床反应器及其创新、短流程两段甲烷化技术构建及其验证等方面总结了流化床甲烷化技术开发的最新进展。优化催化剂前体制备方法、调变催化剂组成可获得具有较高骨架强度和均匀性的催化剂一次微粒,进而通过优化的喷雾造粒工艺和填充黏结剂,制备出具有可调变粒度分布、高强度和高球形度的流化床用粉末催化剂,但其黏结剂的添加明显影响催化剂的低温活性。通过改性如Al₂O₃和FCC催化剂的球形颗粒,进而负载活性组分,开发了制备高活性、磨损指数小于1.5的流化床甲烷化Ni基催化剂的另一种技术方法。实验室研究证实了流化床甲烷化反应速率极快,在分布板上数毫米处即可实现可能的最高转化率,且在转化率和催化剂稳定性方面明显优于固定床,不仅由于流态化催化剂床层温度均匀,而且催化剂在床层内不停循环,加快了颗粒表面的更新。增大空速和表观气速,流化床的催化剂床层膨胀,反应气体与催化剂颗粒表面间的有效接触面积增加,使得流化床甲烷化对空速和表观气速的可调范围大。操作在更高气速条件的输送床甲烷化避免了操作气速的上限限制,可大幅降低反应器尺寸,有效提高单位截面的原料气负荷能力。输送床甲烷化可采用高热导率的催化剂颗粒传递反应热,相对于气体移热效率高、能力大。流化床甲烷化已在生物废弃物利用和焦炉煤气甲烷化方面开展了侧线示范,形成了相对多段绝热固定床工艺更简单的短流程两段甲烷化新工艺。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究

建立了测定地球化学样品中包括As、Cr、Ge、V等18种微量、痕量元素的ICP-MS方法。地化试样用HF-HNO3混酸分解后,以1 1 HNO3溶解干渣。由于制样不使用盐酸,避免了Cl对As、Cr、Ge、V的质谱干扰。用国家一级地球化学标准物质GBW 07309制备溶液优化仪器工作参数,并用于校准。方法测定限(6s)为:0.007~6.4μg/g,精密度(RSD%,n=12)为:29%~9.4%,经过国家一级地球化学标准物质的分析验证,结果与标准值吻合。方法已应用于国土资源调查的试样分析。