基于水合物技术的沼气配送工艺研究

以十二烷基硫酸钠(SDS)作为促进剂,开展水合物技术配送沼气的工艺研究,考察了沼气水合物的制备、存储稳定性及分解释放等。结果表明,以浓度为0.03%(v/v)的SDS溶液为工作液,沼气水合物具有接近理论值的储气效果,单位储气量可达170 V/V,制备水合物的最优条件为温度1~3℃,压力3.0~3.5 MPa。沼气水合物在略低于0℃的条件下显示出良好的稳定性。温度越低,压力越高,越有利于沼气水合物的存储,但储运成本增加;在短距离配送中,温度略低于0℃的封闭体系即可满足储运要求。常压敞开条件下,沼气水合物可迅速分解释放,25℃时的释放时间为12 min。沼气水合物分解后的工作液可以回用,且对水合物的制备有促进作用。     

不同表面活性剂对甲烷水合物生成的影响

为探究表面活性剂对于水合物生成的促进机理,文章选取了阴离子表面活性剂十二烷基硫酸钠(SDS),阳离子表面活性剂十二烷基三甲基溴化铵(DTAB)和非离子表面活性剂脂肪醇聚氧乙烯醚(AEO)进行甲烷水合物的生成实验。测试了表面活性剂的特性(如临界胶束浓度)、表面活性剂溶液在反应釜内表面的润湿性对水合物生成过程的影响,并对DTAB进行搅拌增强实验。实验结果表明:以DTAB和AEO为促进剂时,促进机理为胶束作用,水合物在反应釜底部生成;以SDS为促进剂时,水合物在气/液/固三相交界处开始生成,由于形成多孔结构的水合物,可以利用毛细作用不断的促使反应液与气体保持接触,从而使其对水合物生长的促进效果更佳。     

多模态显影栓塞微球制备及体外显影实验

【摘要】 目的 开发一种具备X线/CT/MR下多模态显影能力的明胶栓塞微球。方法 采用乳化交联法制备单一携载固态纳米Fe3O4颗粒的明胶栓塞微球,光学显微镜观察微球形态、粒径、分散度;热重分析法检测微球内Fe3O4纳米颗粒载药量;X线、CT、MR检测评估多模态显影能力;利用兔心血及人血管内皮细胞行微球溶血试验及体外细胞毒性试验;观察微球弹性、溶胀特点及消毒方法。结果 最优化微球合成条件为Fe3O4与明胶质量比为2 ∶ 1。该微球外观圆整、分散性好、成球率高（最高77.0%）、载药率高（最高73.27%）、粒径适中为（199.78±142.90） μm,具备X线/CT/MR下多模态显影能力,最优化微球CT值最高可达（1 028.0±69.5） Hu（浓度25 mg/ml）,MR T2值下降约50%（浓度4 mg/ml）。溶血试验及细胞毒性试验溶血率及吸光值与对照组相比,差异无统计学意义（P＞0.05）。微球在酸性溶液中表现出溶胀特性,在无水乙醇中无溶胀现象。结论 以固态Fe3O4纳米颗粒为显影材料,明胶为聚合物材料,采用乳化交联法可成功制备载药量高、形态规则、表面光滑、不易聚集、X线/CT/MR下多模态显影能力更强、生物安全性高、消毒方便的栓塞微球。
     

聚胺水基钻井液中天然气水合物生成过程实验研究

实验采用定容压力搜索法测量了聚胺钻井液在3℃ ~ 13℃范围内甲烷水合物的三相平衡条件。定容条件下考察了在初始压力分别为8 MPa、10 MPa、12 MPa条件下聚胺钻井液中甲烷水合物的生成过程。结果表明,聚胺钻井液对甲烷水合物生成的热力学抑制作用并不明显。同时,提高反应的初始压力会显著缩短水合物的生成时间、增加水合物的生成总量、增大反应初期生长速率以及水合物生长的不均匀性。强化聚胺钻井液的传热传质速率并降低钻探时的井下压力有利于抑制钻井液中水合物的生成。     

羧甲基纤维素钠对CH4水合物形成过程的影响

羧甲基纤维素钠（CMC-Na）是水基钻井液中的重要组分,为研究CMC-Na对天然气水合物热力学和动力学的影响,实验测量了质量浓度介于0.5%～1.5%的CMC-Na溶液中甲烷水合物的相平衡条件,以及275.2 K、6 MPa的初始条件下CMC-Na溶液中甲烷水合物的形成过程。研究结果表明,CMC-Na对甲烷水合物的热力学稳定性具有微弱的抑制作用,相同压力下相平衡温度降低了0.1～0.2 K。CMC-Na溶液中形成的甲烷水合物为Ⅰ型,水合物数为5.84～5.90。在CMC-Na溶液中,甲烷水合物形成所需的诱导时间大大缩短,表明CMC-Na对甲烷水合物的形成过程具有促进作用。在CMC-Na溶液中水合物生成所需气体消耗量呈阶段式增长。水合物转化率低于35%的情况下,已经生成的水合物没有对搅拌器叶片形成持续附着进而卡住搅拌器。因此,CMC-Na对甲烷水合物的热力学稳定性具有一定的负面影响,对水合物的形成具有一定的促进作用。另外,CMC-Na能够降低水合物生成过程中搅拌扭矩的波动,对维持搅拌的正常运行具有重要作用。     

甲烷化学链重整制备合成气技术中的钙钛矿型载氧体制备及动力学特性

采用燃烧法、微乳液法、共沉淀法和溶胶-凝胶法4种方法制备钙钛矿型氧化物La Fe O3作为载氧体用于甲烷化学链重整制备合成气过程,利用X射线衍射(XRD)、扫描电镜(SEM)、H2程序升温还原(H2-TPR)、比表面积分析(BET)等技术对载氧体进行表征,在固定床反应装置上考察4种方法制备的La Fe O3与甲烷的反应性能,寻求适用于甲烷化学链重整过程载氧体的最佳制备方法,然后通过H2-TPR的多速率升温过程探讨La Fe O3的还原动力学。结果表明,4种方法制备得到的载氧体均形成钙钛矿结构,溶胶-凝胶法和燃烧法制备的La Fe O3纯度和结晶度均更好,无杂相生成;从CH4转化率、n(H2)/n(CO)、CO和H2选择性等方面综合考虑,燃烧法制备得到的载氧体反应性能最好,用于甲烷化学链重整制备合成气的生成效果最好。H2-TPR的动力学计算表明,La Fe O3载氧体的低温吸附氧还原活化能为97.001 k J/mol,高温晶格氧还原活化能为30.388 k J/mol。     

水溶性Fe_3O_4/Au纳米复合粒子制备及性能研究

本文针对可用作MRI/CT双模式成像分子探针的Fe3O4/Au纳米粒子制备方法存在工艺繁琐,工业扩大化后能耗大等缺点,发展了一种绿色、简便的可控自组装工艺,分析了纳米复合材料的微观结构特征,研究了材料的等离子体共振特性和磁学特征。结果表明:(1)发展的层层自组装方法可以使磁性纳米粒子Fe3O4与具有高X射线吸收的Au粒子组装在一起,两者结合牢固,长时间超声振荡后仍然没有脱落;(2)中心核为Fe3O4纳米团簇的结构特征使复合粒子具有高饱和磁化强度,克服了以往报道的Fe3O4/Au复合纳米粒子磁化强度低的缺点;(3)金粒子均匀分布在Fe3O4纳米团簇表面,因为粒子间距缩短增强了粒子间的耦合作用,使得等离子体共振谱发生了宽化和红移。     

等离子体辅助甲烷燃烧的主要反应路径/通道

通过实验和模拟的方法,对等离子体辅助甲烷燃烧主要基元反应进行了研究.实验测量了等离子体辅助甲烷燃烧火焰不同位置的发射光谱图,得到了参与该过程的重要组分;模拟过程中,基于密度泛函理论,研究了甲烷燃烧反应中O_2+H→OH+O、CH_4+OH/O/H→CH_3+H_2O/OH/H_2、CH_3+O→CH_2O+H、CH_2O+OH/O/H→CO+H_2O/(H+H_2O)/(H+H_2)等几个重要基元反应,在B3LYP/6-311++G**水平找到了各反应可能的反应路径/通道,并进行分析.在此基础上,对比分析了放电等离子体作用下各反应路径/通道的变化,结果表明,在研究等离子体辅助甲烷燃烧机理时,应基于甲烷燃烧机理进行完善,通过加入*2HO(v)、O(1D)、CH_4(v)等激发态组分,并对一些基元反应进行拆分或合并,重新计算各反应活化能;生成的激发态组分会提升反应势能面,降低活化能,加速反应进程;在CH_2O与O/OH/H的反应中,放电等离子体可将生成的HCO直接分解,降低了HCO对H原子的消耗,同时还会释放一个H原子,有利于燃烧反应的进行.     

铁基载氧体的还原特性研究

采用热重分析仪和质谱仪联用对使用机械混合法制备Fe2O3和Al2O3载体的还原反应过程进行研究。还原反应中使用3种10%还原气体(CH4,H2,CO),氧化反应中使用5%氧气以避免较大的温升。从载体的还原失重曲线中可明显地看出铁基载体的还原过程分为3个阶段,且反应速率各不相同。还原的3个阶段中第一阶段的反应速率最快,且燃料能够完全被氧化生成CO2,随着反应进行速率降低,燃料不完全转化程度增加。通过XRD(X射线衍射)分析各个还原阶段的产物,发现与以前认识的载氧体活性相与惰性相不同,Al2O3在反应过程中会参与反应,生成新的化合物FeAl2O4,而此化合物不稳定能够进一步分解,被还原成Fe。3种还原气体中,H2的还原反应速率最快,并且无积碳,而CH4的还原反应中存在较为严重的积碳现象。     

铁矿石作为氧载体在熔融盐中催化甲烷燃烧

熔融盐循环热载体无烟燃烧技术（noneflame combustion technology using thermal cyclic carrier of molten salt,NFCT）不会向大气中排放有害气体,是一种清洁燃烧技术。利用XRD、SEM和TG等分析手段对催化剂的性能进行了表征。在质量比为1：1的Na2CO3和K2CO3熔融盐中研究了Fe2O3中的晶格氧对甲烷的催化燃烧性能。铁矿石在熔融盐中分别与甲烷和空气发生反应,用XRD分析生成物表明,作为铁矿石主要成分的Fe2O3可以在熔融盐中失去和恢复晶格氧,这些品格氧可以用来催化氧化甲烷。TG分析结果表明,铁矿石被甲烷还原分为两个阶段,第一个阶段从550℃开始,680℃结束,Fe2O3被还原成Fe3O4,第二个阶段从850℃开始至1050℃结束,第一个阶段生成的Fe3O4在这一阶段大部分被还原成了FeO。被甲烷还原的铁矿石在TG试验中与空气反应时,只出现一个明显的增重段,从350℃开始直到反应温度的上限1100℃,增重速率较快的区间是400～850℃。从燃烧产物的气相色谱分析结果可以看出,甲烷在熔融盐中绝大部分被氧化成了CO2和H2O。因此,铁矿石可以作为氧载体在熔融盐中催化甲烷燃烧。     

Efficient promotion of methane hydrate formation and elimination of foam generation using fluorinated surfactants

Methane hydrate preparation is an effective method to store and transport methane. In promoters to facilitate methane hydrate formation, homogeneous surfactant solutions, sodium dodecyl sulfate (SDS) in particular, are more favorable than heterogeneous particles, thanks to their faster reaction rate, more storage capacity, and higher stability. Foaming, however, could not be avoided during hydrate dissociation with the presence of SDS. This paper investigated the ability of five fluorinated surfactants: potassium perfluorobutane sulfonate (PBS), potassium perfluorohexyl sulfonate (PHS), potassium perfluorooctane sulfonate (POS), ammonium perfluorooctane sulfonate (AOS), and tetraethylammonium perfluorooctyl sulfonate (TOS) to promote methane hydrate formation. It was found that both PBS and PHS achieve a storage capacity of 150 (V/V, the volume of methane that can be stored by one volume of water) within 30 min, more than that of SDS. Cationic ions and the carbon chain length were then discussed on their effects during the formation. It was concluded that PBS, PHS, and POS produced no foam during hydrate dissociation, making them promising promoters in large-scale application.     

Optimization of a fluidized bed reactor for methane decomposition over Fe/Al2O3 catalysts: Activity and regeneration studies

Catalytic methane decomposition was investigated over 40 wt% Fe/Al₂O₃ catalyst in fluidized bed reactor (FLBR). After optimization of FLBR conditions in terms of catalyst bulk density, particle size, minimum fluidization velocity, and the catalyst bed height, the catalyst activity and stability tests were conducted by comparison with a fixed bed reactor (FBR). Although a similar stable methane conversion was obtained over both reactors, the pressure drop during 35 min operation of FBR was 9 times higher than that of FLBR, which indicated the possibility of continuous operation of methane decomposition process over FLBR. Further, the influence of the space velocity, feed dilution and regeneration on catalysts reactivity was studied in FLBR to conclude that a reaction condition of 12 L/g_cat∙h, feed of 20%H₂–80%CH₄ and CO₂-regeneration of deactivated catalysts may be favourable for operating methane decomposition in FLBR continually and effectively to provide stable hydrogen.     

Production of hydrogen by methane catalytic decomposition over Ni–Cu–Fe/Al2O3 catalyst

Catalysts with high nickel concentrations 75%Ni–12%Cu/Al₂O₃, 70%Ni–10%Cu–10%Fe/Al₂O₃ were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al₂O₃ catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.     

热激励的CO_2置换CH_4水合物的实验研究

CO_2置换CH_4水合物具有在开采天然气水合物的同时储藏CO_2的功能.天然气水合物因其可燃烧、燃烧后污染小、储量巨大等特点被认为是未来最有可能的能源替代品,但CO_2置换天然气水合物存在反应周期长、置换速率低的缺点.提出了一种借助CO_2水合物生成热量激励CH_4水合物分解的方法,在低温、高压的纯水体系中,研究了温度为275.15 K,置换压力分别为2.3、2.5、2.8、3.0 MPa时有热激励和无热激励两种置换反应的区别.研究结果表明,有热激励的置换反应,由于提供了额外的热量,使CH_4水合物更易分解,从而加速了置换反应的发生,提高了置换速率.     

末次冰期以来珠江口盆地深水区天然气水合物稳定带演化

珠江口盆地深水区具备优良的天然气水合物成藏条件,是南海重要的天然气水合物资源勘探区。利用CSMHYD软件模拟预测了天然气水合物相平衡条件下,现今珠江口盆地的天然气水合物稳定带厚度分布和末次冰期以来水合物稳定带厚度的演化特征,同时讨论了晚更新世冰期以来海平面、底水温度对该区天然气水合物稳定带变化的影响,以及水合物分解对环境的影响。结果表明：（1）水深超过600 m的海域具备形成天然气水合物的温压条件;水合物稳定带平均厚度245 m,其中南部稳定带的最大厚度超过330 m,是有利的水合物勘探区;（2）中层水团温度上升很可能是新仙女木末期珠江口盆地深水区天然气水合物分解的主要诱发因素;（3）B/A暖期到YD冷期结束时水合物稳定带面积减少约0.65×10⁴ km²,分解释放的甲烷量约0.38×10¹³ m³,折算成总碳量约为1.9 Gt。     

Formation enhancement of methane hydrate for natural gas transport and storage

Methane hydrate is considered an excellent way of transporting and storing natural gas in large quantities. However, when methane hydrate is formed artificially, water/gas ratio is relatively low due to a slow reaction rate between water and methane gas. The major objective of this study is to investigate the mechanics of methane hydrate formation and to explore possible means for rapid production of hydrates and increasing its water/gas ratio. It is found that methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 8 K or above. In addition, water injection appears to be more effective in hydrate formation compared to gas injection or using a magnetic stirrer. It also gives higher water/gas ratios of 3–4 times for the methane hydrate through a nozzle at the same level of subcooling temperature, when compared to gas injection cases.     

Preparation of activated carbon supported Fe–Al2O3 catalyst and its application for hydrogen production by catalytic methane decomposition

Activated carbon (AC) supported Fe–Al₂O₃ catalysts were prepared by impregnation method and used for catalytic methane decomposition to hydrogen. The XRD and H₂-TPR results showed that ferric nitrate on AC support was directly reduced to Fe metal by the reducibility of carbon at 870 °C. The loading amount and Fe/Al₂O₃ weight ratio affect the textural properties and catalytic methane decomposition. The surface area and pore volume of the catalyst decrease with the loading of Fe and Al₂O₃. Mesopores with size of about 4.5 nm can be formed at the loading of 20–60% and promote the catalytic activity and stability. The mesopores formation is thought that Fe accelerates burning off of carbon wall and enlarging pore sizes during the pretreatment. When the Fe/Al₂O₃ ratio is 16/24 to 24/16 at the loading of 40%, the resultant catalysts show narrow mesopore distributions and relative high methane conversion. Al₂O₃ as the promoter can improve catalytic activity and shorten transitional period of AC supported Fe catalyst.     

Production of syngas from carbon dioxide reforming of methane by using LaNixFe1−xO3 perovskite type catalysts

A series of bulk and supported LaNixFe1-xO3 catalysts were synthesized, characterized and studied for dry reforming of methane (DRM) reaction. The catalysts were synthesized using sol-gel, incipient wetness impregnation (IWI) and co-precipitation methods. The catalysts were characterized by BET, XRD, FE-SEM, H2-TPR, and FTIR spectroscopy. A specific type of perovskite phase was obtained while changing the ratio of Ni to Fe for the synthesis of LaNixFe1-xO3 perovskite catalyst. The addition of supports increased the dispersion of perovskite phase, surface area and pore volume of the bulk perovskite catalysts. The support silica destroyed the perovskite features of the catalysts at higher calcinations temperature. The most active catalyst was found to be 40LaNi0.75Fe0.25O3/SiO2 calcined at 973 K for the DRM reaction with ratio of CH4:CO2:N2 as 1:1:2. The highest conversion corresponded to the catalyst calcined at 1073 K. However, the highest products yields and selectivity obtained while the catalyst was calcined at 773 K for 1 h. Thus, the choice of Ni to Fe ratio, support, method of synthesis and catalyst calcination temperature were crucial factors while synthesizing and designing a perovskite catalyst for dry reforming of methane reaction.     

The evaluation of autothermal methane reforming for hydrogen production over Ni/CeO2 catalysts

Nanocrystalline Ni/CeO₂ catalysts with various loadings of Ni (10, 15, 20, and 25%) were synthesised by a facile solvent deficient precipitation method for methane autothermal reforming process. The characterisation techniques such as XRD, BET, TPH, H₂-TPR were carried out on fresh and spent samples to investigate the catalytic properties of the Ni/CeO₂. On the basis of characterisation results, the 20% Ni/CeO₂ performs the best activity among the catalysts with different Ni contents. The optimal reaction conditions for autothermal methane reforming has been investigated by evaluating the effect of reaction parameters including the reactivity temperature, the gas hourly space velocity (GHSV) and H₂O/CH₄ (S/C) and O₂/CH₄ (O/C) molar ratios. The stability of 20 wt% Ni/CeO₂ catalyst at 700 °C is examined for 20 h on-stream reaction. It reveals that the methane conversion starts a graduate decrease trend from the second 10 h, which is found to be because of the sintering of Ni nanoparticles by TPH and BET analysis.     

Hydrogen production by radio frequency plasma stimulation in methane hydrate at atmospheric pressure

Methane hydrate, formed by injecting methane into 100 g of shaved ice at a pressure of 7 MPa and reactor temperature of 0 °C, was decomposed by applying 27.12 MHz radio frequency plasma in order to produce hydrogen. The process involved the stimulation of plasma in the methane hydrate with a variable input power at atmospheric pressure. It was observed that production of CH₄ is optimal at a slow rate of CH₄ release from the methane hydrate, as analyzed by in light of the steam methane reforming (SMR) and the methane cracking reaction (MCR) processes in accordance with the content of gas production. In comparison with the steam methane reforming (SMR), it was found that methane-cracking reaction (MCR) was dominant in conversion of CH₄ into hydrogen. An H₂ content of 55% in gas production was obtained from conversion of 40% of CH₄ at an input power of 150 W. The results clearly show that hydrogen can be directly produced from methane hydrate by the in-liquid plasma method.