南海天然气水合物地热学研究

Through generalizing the thermal field characteristics in gas hydrates distribution area in the world, the favorable thermal conditions for gas hydrates in the South China Sea are analyzed firstly. On the basis of above analysis, focused on the gas hydrates stability zone (GHSZ), the dissertation initiated the gas hydrates studies with geothermal methods in the South China Sea which will provide useful information for gas hydrates resource exploration and evaluation in the future. On the basis of study on hydrates phase equilibrium and the GHSZ affecting factors, the potential planar distribution of gas hydrates is determined by studying the temperature and pressure conditions in the sea bottom with different water depth, and the thickness of GHSZ is attained by solving the hydrates phase boundary curve equation and geothermal gradient curve equation. The result shows that, if the chemical composition of hydrocarbons contains methane only and the salt content of water is 3.5%, hydrates can form and keep stable at sea bottom at water depth not less than 550m, and the thickness of GHSZ is more than 200m in Xisha Through, Southeastern area of Dongsha Islands, Southwestern basin of Taiwan Island, northern area of Nansha Trough. The GHSZ is thicker with heat flow, geothermal gradient, and thermal conductivity decreasing, and with water depth increasing. Geothermal field simulating also attains the base of GHSZ in Xisha through, which is less than the depth of BSR. Although the present T-P conditions is not the most favorable for gas hydrates through 6Ma history, gas hydrates are still profitable in Xisha Through, Southeastern area of Dongsha Islands, Southwestern basin of Taiwan Island, Luzon Trough and northern area of Nansha Trough by systemic study on the sedimentary and structural characteristics, the conditions of T-P and natural gas source, considering geochemical and geophysical indications found in the South China Sea.

富硫流体的成因与硫酸盐还原作用研究

Origins of H_2S, thiols, thiophenes in natural gases and sulphur-enriched oils are complicated and thus some debates exist on them. The post-doctoral research is based upon oil- and gas-field data. Cases for study include Triassic Jianglingjiang Formation natural gases, Wolonghe Field, Sichuan Basin, Paleozoic oils and bitumen, Central Tarim, gases reserviored nearby Carboniferious - Ordovician unconformity, Hetianhe Field, Tarim Basin and sulphur-enriched oils in Tertiary reserviors in Jinxian Sag, Bohai Bay Basin. We have carried out analyses on the oils and gases for chemistry, δ~(13)C, δ~(34)S, and molecular composition of biomarkers, analyzed authigenetic pyrite forδ~(34)S, formation water for chemistry and δD and δ~(18)O along with petroleum system and burial history analyses, The aims are to assess the origins of the H2S and authigenetic pyrite, to discuss the possibility of reduced sulphur incorporation into hydrocarbons and to determine the mechanisms of hydrocarbon secondary alteration in the above four cases by comparison. The research shows that the reduced sulphur in the four cases is the result of thermochemical and biological sulphate reduction., TSR and BSR, respectively. No evidence indicates an origin of decomposition of organic matter or mantle - derived H2S in the cases. Elevated H_2S contents (up to 32%) in the Triassic Jialingjiang Formation are considered to result from TSR while relatively low H_2S (up to 2000ppm) in the Hetianhe Field resulted from BSR. However, it is not the case for the Central Tarim where relatively low H2S but abundant authigenetic pyrite occurr. Part of the H_2S in the Central Tarim reservoirs has reacted with iron released from clay minerals to precipitate pyrite. Thus, reduced sulphur δ~(34)S and reservoir temperatures rather than the H2S amount are reliable parameters to distinguish between TSR and BSR. TSR in Sichuan Basin Triassic Jialingjiang Formation and Central Tarim Paleozoic reservoirs are showed to take place at more than 125℃. the H2S and authigenetic pyrite have δ~(34)S close to parent anhydrite. In contrast, BSR in the reservoirs near the Carboniferous - Ordovician unconformity in the Hetianhe Field and in the Tertiary in the Jinxian Sag took place at temperatures less than 80℃with sulphide δ~(34)S as light as -24.9‰ and -12.5‰, anhydrite δ~(34)S as heavy as +26‰and +3 5-+40‰, respectively. Chemistry and isotopic composition of the natural gases change as the result of sulphate reduction. It has been observed that relative composition of light hydrocarbon gases is changed along with a rise in H_2S and CO_2. TSR in the Triassic Jialingjiang Formation and BSR in the Hetianhe Field result in a greater degree of preferential depletion of methane than larger molecular hydrocarbon gases. As TSR or BSR proceeds, hydrocarbon gases evolved to heavier carbon isotope as the result of kinetic isotopic fractionation, i.e., selective anaerobic oxidation of ~(12)C. Using the model of residual methane (Whiticar, 1999) to describe the relationship among the proportion of methane oxidation, isotopic shift and fraction factor, about 30% methane is calculated to have been oxidized during BSR in the western part of the Hetianhe Field. From the above, it can be concluded that in the area where H_2S is abundant, empiricalδ~(13)C -Ro relationships do not work. Sulphate reduction results in a rise in sulphur content, gravity and viscosity of an oil as well as changes in δ~(13)C and δ~(34)S. On special conditions, the reduced sulphur from sulphates might be incorporated into oils, i.e., the increasing sulphur is derived from secondarily reduced sulphur. A positive correlative relationship exists between sulphur content and δ~(34)S in the oils in Paleozoic reservoirs in Central Tarim, indicating that enhanced sulphur is ~(34)S-enriched, originated from TSR. The Jinxian oil with the highest sulphur content has the lightest δ~(34)S, suggesting part of the sulphur in the oil is ~(34)S-depleted, originated from BSR. In the Jinxian oil with increasing sulphur content, asphaltenes shows higher content and more negative δ~(13)C, and saturates shows evidence of biodegradetion and a decreasing content and a positive δ~(13)C shift. Thus, asphaltenes have δ~(13)C values closer to saturates. All the above indicate that the reduced sulphur has been incorporated into biodegradated saturates to generate new asphaltenes with relatively light δ~(13)C of saturates. Thiols and thiophenes in natural gases in the Triassic Jialingjiang Formation may result from reaction of H_2S with hydrocarbon. In the Jialingjiang Formation hydrocarbon gases are dominated by methane thus have a high dryness coefficient and thiols are showed to be positively related to H_2S content, suggesting that the thiols may result from H_2S reaction with short chain hydrocarbons. In contrast, high thiophenes occur in wet gases in Jurassic reservoirs with their source rock from sulphur - depleted type I kerogen, indicating that thiophenes may be a product of reaction of H2S with longer chain hydrocarbons.

微功耗海底地震仪的研制

Our motherland has large area of maritime space. Searching and developing ocean becomes more and more important. So Ocean Bottom Seismometer (OBS) as an absolutely necessary equipment can be used in many oceanic fields. OBS not only is an important instrument for discovering structure of lithosphere of ocean bottom, but also plays a main role of oceanic geophysical exploration. The paper introduces my relational work. The MCI micro-power broad frequency seismometer was developed independently. Its power dissipation is less than 300mW. It has some merits including miniature volumeN light mass and cheap price. It is an ideal device not only for the collection high-resolution natural seismic data, but also for the fields of seismic sounding and engineering seismology. Many new high technique were applied to develop this instrument including over-sampling A/D converter, high performance 32bit Micro Process Unit and Flash memory with smart-media interface. Base on the achievement, I have accomplished the showpiece of OBS, which is applied to the deepwater oil and gas geophysical exploration. Because of micro-power dissipation, the seismograph and the sonar releaser can be integrated into a sphere cabin. By this means, the instrument's frequency of resonance and frequency of couple are improved obviously. The data acquisition system of OBS is improved from MCI seismometer. The capacity of flash memory is enlarge from 1G bytes to 8G bytes. The advance MPU in data acquisition system is used to integrate other function modules such as sonar, GPS, compass and digital transmitter.

天然有机质与多环芳烃相互作用的荧光光谱学研究—以苝、菲和蒽为例

自然界水体（如地下水、湖泊、河流及海洋）中的天然有机质（NOM）因具有显著的生态及环境功能而受到人们的广泛关注。NOM作为全球碳循环的主要组成部分，是水体中异养型微生物生长所需碳及能量的重要来源。此外，NOM对湖泊生态系统中的多种物理、化学过程具有不同程度的影响：NOM中的有机酸对淡水体系的酸度具有控制作用而且对酸沉降有一定的缓冲作用；NOM通过减弱可见光及紫外线照射从而影响淡水系统的光化学环境，这一方面降低了水体中自养生物的繁衍速度，同时保护水生生物免受有害的紫外线辐射。更为重要的是，NOM能够影响环境中污染物的命运，比如重金属离子和疏水性有机污染物与天然有机质结合后，其迁移途径、溶解度、生物可利用性及毒性受到明显的控制，这样其对环境中生物的危害性减弱。多环芳烃（PAHs）是一类对环境危害极大的疏水性有机污染物，多数PAHs对有机体具有毒性和致癌性而被美国环保署（EPA）列为优先处理的污染物。因此，确定NOM-PAHs反应的强弱，即PAHs在NOM中的分配系数（Kdoc）以及NOM的物化特性对Kdoc的影响对于预测PAHs毒性和生物可利用性大小、了解NOM-PAHs相互作用的机理及确立污染预测模型具有十分重大的意义。前人的研究结果表明，多环芳烃与天然有机质相互作用的分配系数Kdoc的与PAHs的疏水度（即Kow大小）、NOM的物化特性（如芳香度、脂肪碳含量、分子量及极性等）和水化学参数（pH、离子强度等）有很大的相关性。然而，许多学者在NOM的物化特性对分配系数的影响方面存有较大分歧。前人在研究天然有机质与多环芳烃之间的相互作用时所用的NOM多为腐殖质，即水体NOM中的疏水性组分，而其中的亲水性组分与PAHs的结合作用文献中却鲜见提及，因此人们对其结合作用的特性如反应机理和结合作用强弱等的了解十分有限。 本论文利用XAD树脂分离技术把红枫湖水体中天然有机质分成了疏水性酸、碱、中性物质和亲水性酸、碱、中性物质等六种有机组分。同时运用元素分析、有机碳分析仪、紫外－可见分光光度，高效液相体积排阻色谱、三维荧光光谱和荧光偏振技术等现代分析方法，对各有机组分的物理、化学特性进行了表征。荧光光谱技术被用于研究水化学参数对腐殖质荧光特性和分子构型的影响以及测定Amherst腐殖酸（Amherst HA）、垃圾渗滤液富里酸（LF FA）和红枫湖NOM有机组分与多环芳烃苝、菲和蒽的结合系数（分配系数、条件稳定常数）并探讨了影响分配系数的各种因素和NOM与多环芳烃相互作用的机理。本论文的获得的主要结果如下： 1. 在水化学参数对腐殖质荧光特性及分子构型的影响方面： 在NOM与PAHs相互作用过程中，腐殖质的分子构型起着关键性的作用，而其分子构型又受到其本身的浓度、溶液的pH和离子强度等水化学参数的影响。本论文运用三维荧光光谱和荧光偏振技术研究了水化学参数对腐殖质荧光特性的影响，并由此推断其分子构型变化情况。实验结果表明随着腐殖质浓度、溶液的pH和离子强度的改变，腐殖质荧光特性（如荧光强度、荧光峰位和荧光偏振值等）出现不同程度的变化，揭示了腐殖质分子构型的改变。因此，本实验结果有利于深入了解腐殖质的分子构型及其对吸附PAHs的重要影响，对理解NOM的环境行为具有一定的理论价值。 2. 运用荧光猝灭滴定法研究Amherst HA和红枫湖NOM有机组分对多环芳烃苝、菲和蒽的吸附作用，结果表明NOM对多环芳烃的吸附能力与其中芳香结构单元有很强的相关性，logKdoc值与NOM在280 nm处的摩尔吸收（ε280）和分子量有线性度较高的正比关系，而C/H原子比值对不饱和碳含量（芳香度）并没有很好的指示作用。同时，脂肪碳（0－50 ppm）中的聚亚甲基碳对吸附PAHs也有很大的贡献，而有机组分的极性与分配系数有明显的负相关性。不同种类的多环芳烃与NOM有机组分的结合能力有很大的差异，这取决于不同PAHs的疏水度大小。本研究结果有利于弥合前人在NOM物化特性对PAHs吸附能力的影响方面的分歧，揭示了NOM的组成和结构在与PAHs等疏水性有机污染物相互作用方面的重要影响。 3. 在结合机理方面，苝与NOM有机组分结合的Stern－Volmer图具有较高的线性度，这表明其结合机理以疏水反应（或分配）为主，而菲和蒽与有机组分相互作用的吸附等温线显示较多的非线性特征表明极性反应为主要反应机理，结合过程以吸附为主。在红枫湖NOM有机组分中，疏水性组分显示对PAHs较高的结合能力，同时疏水性组分与PAHs相互作用的吸附等温线具有较高的线性度。这一结果揭示了不同种类的PAHs和各NOM有机组分之间结合机理的差异，加深了人们对NOM与PAHs相互作用机理的认识。 4. 前人在研究pH、离子强度等水化学参数对分配系数的影响方面得到的结果多有矛盾之处，同时，对实验结果的解释也不尽相同。本实验结果表明分配系数随pH增加而下降；离子强度对分配系数的影响比较复杂，就总体趋势而言，增加离子强度有利于对PAHs吸附能力的提高，这一结果初步揭示了水化学参数对PAHs分配系数的影响，丰富了人们对其影响机理的认识。 5. 运用荧光偏振技术测定了蒽与Amherst HA、LF FA和红枫湖NOM有机组分的条件稳定常数，结果如下：随着NOM浓度增加，蒽的荧光偏振值不断下降，这表明蒽的分子构型由平面线性向圆柱状转变。在所有NOM样品中，土壤源的Amherst HA与蒽结合的条件稳定常数最大（pH 4时logK=5.6，pH 6时 logK=5.4）；就NOM有机组分而言，疏水性组分的logK变化范围在pH 6时为（4.4－5.2），而亲水性组分为（4.3－4.8），这表明疏水性组分具有相对较高的蒽吸附能力。实验结果有利于了解PAHs与NOM相互作用前后的分子构型变化情况，揭示了不同的NOM有机组分在吸附PAHs过程中的差异。

Column switching-back flushing technique for the analysis of aromatic compounds in gasoline

A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was less than or equal to3% RSD for real gasoline samples. (C) 2002 Elsevier Science B.V. All rights reserved.

High-throughput screening of HZSM-5 supported metal-oxides catalysts for the coupling of methane with CO to benzene and naphthalene

High-throughput screening of HZSM-5 supported metal-oxides catalysts were carried out for the coupling reaction of methane with CO to aromatics in a multi-stream reactor system. Zn/HZSM-5 and Mo/HZSM-5 were observed to be rather effective for the catalytic formation of aromatics from the coupling reaction of methane with CO. Temperature-programmed reaction has further proven the efficiency of the coupling of methane and CO over Zn/HZSM-5 catalyst. The results were also validated in a conventional fixed-bed reactor coupled with GC. The results propose that the coupling methane with CO toward benzene and naphthalene can be catalyzed by Zn/HZSM-5 at 500 ° C. Both methane and CO are needed for the formation of reactive coke on the catalyst, and the reactive coke may be the initial product in the producing of hydrocarbons. © 2005 Elsevier B.V. All rights reserved.

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/gamma-Al2O3 catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba0.5Sr0.5Co0.8Fe0.2O3 which has an oxygen permeation flux around 11.5 ml/cm(2) min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/gamma-Al2O3 in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91-93% and a H-2 selectivity of 95-97% have been achieved. (c) 2005 Elsevier B.V. All rights reserved.

Gas phase catalytic partial oxidation of toluene in a microchannel reactor

Gas phase partial oxidation of toluene over V/Ti oxide catalysts has been successfully performed in a microchannel reactor, which provides very good mass and heat transfer conditions. With the elimination of hot spots, which are known as the most negative factors for partial oxidation of hydrocarbons, steady and uniform reaction conditions can be achieved in the catalyst bed by using, the microreactor. Since the best performance of the catalysts might be exploited, the selectivity of partial oxidation products of toluene has remarkably increased compared to the traditional packed fixed-bed reactor, even without the bother of modifying the catalysts, diluting the reactants or catalysts with inert contents to avoid hot spots or improve the diffusion and mixing. Furthermore, in virtue of its inherent safety features, when using pure oxygen as oxidant, the reactions were handled safety within the explosion limits in the microreactor. With TiO2 carried V2O5 as catalysts, the total selectivity of benzaldehyde and benzoic acid reaches around 60%, and the toluene conversion is about 10%. The conversion can go up without violent decline of selectivity, unlike most fixed bed reactors. Space time yield of 3.12 kg h(-1) L-1 calculated on the basis of the channel volume has been achieved. The influence of operating conditions has been investigated in detail in the microreactor. (c) 2005 Elsevier B.V. All rights reserved.

Uniformly carbon-covered alumina and its surface characteristics

Uniformly carbon-covered alumina (CCA) was prepared via the carbonization of sucrose highly dispersed on the alumina surface. The CCA samples were characterized by XRD, XPS, DTA-TG, UV Raman, nitrogen adsorption experiments at 77 K, and rhodamine B (RB) adsorption in aqueous media. UV Raman spectra indicated that the carbon species formed were probably conjugated olefinic or polycyclic aromatic hydrocarbons, which can be considered molecular subunits of a graphitic plane. The N(2) adsorption isotherms, pore size distributions, and XPS results indicated that carbon was uniformly dispersed on the alumina surface in the as-prepared CCA. The carbon coverage and number of carbon layers in CCA could be controlled by the tuning of the sucrose content in the precursor and impregnation times. RB adsorption isotherms suggested that the monolayer adsorption capacity of RB on alumina increased drastically for the sample with uniformly dispersed carbon. The as-prepared CCA possessed the texture of alumina and the surface properties of carbon or both carbon and alumina depending on the carbon coverage.

New route for light olefins production from chloromethane over HSAPO-34 molecular sieve

HSAPO-34 molecular sieve was employed in chloromethane conversion and showed high performance in activity and selectivity in production of light olefins. Our detailed IR investigation allowed the identification of the active sites and the adsorbed species and demonstrated that the conversion started from 350 degrees C with alkoxy group as the intermediate. The fixed-bed catalytic testing evidenced that in the range of 350-500 degrees C, 70-80% of chloromethane was transferred to ethylene, propylene and butenes. Increasing reaction temperature favors the conversion and enhances the yield of lighter olefins. A very important reversible phenomenon, the breaking of Al-O-P bonds upon adsorption of HCl, a main product of reaction to generate a large amount of P-OH groups and the recovery of Al-O-P upon removal of HCI was revealed. (c) 2005 Elsevier B.V. All rights reserved.