共查询到20条相似文献，搜索用时 415 毫秒
1.
The reaction between methane and oxygen over platinum and rhodium surfaces in metalcoated ceramic monoliths can be made to produce mostly hydrogen and carbon monoxide (greater than 90% selectivity for both) with almost complete conversion of methane and oxygen at reaction times as short as 10(-3) seconds. This process has great promise for conversion of abundant natural gas into liquid products such as methanol and hydrocarbons, which can be easily transported from remote locations. Rhodium was considerably superior to platinum in producing more H(2) and less H(2)O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces. 相似文献
2.
Acetic acid is an important petrochemical that is currently produced from methane (or coal) in a three-step process based on carbonylation of methanol. We report a direct, selective, oxidative condensation of two methane molecules to acetic acid at 180 degrees C in liquid sulfuric acid. Carbon-13 isotopic labeling studies show that both carbons of acetic acid originate from methane. The reaction is catalyzed by palladium, and the results are consistent with the reaction occurring by tandem catalysis, involving methane C-H activation to generate Pd-CH3 species, followed by efficient oxidative carbonylation with methanol, generated in situ from methane, to produce acetic acid. 相似文献
3.
RA Periana DJ Taube S Gamble H Taube T Satoh H Fujii 《Science (New York, N.Y.)》1998,280(5363):560-564
Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product. 相似文献
4.
Shemansky DE Stewart AI West RA Esposito LW Hallett JT Liu X 《Science (New York, N.Y.)》2005,308(5724):978-982
The Cassini Ultraviolet Imaging Spectrometer (UVIS) observed the extinction of photons from two stars by the atmosphere of Titan during the Titan flyby. Six species were identified and measured: methane, acetylene, ethylene, ethane, diacetylene, and hydrogen cyanide. The observations cover altitudes from 450 to 1600 kilometers above the surface. A mesopause is inferred from extraction of the temperature structure of methane, located at 615 km with a temperature minimum of 114 kelvin. The asymptotic kinetic temperature at the top of the atmosphere determined from this experiment is 151 kelvin. The higher order hydrocarbons and hydrogen cyanide peak sharply in abundance and are undetectable below altitudes ranging from 750 to 600 km, leaving methane as the only identifiable carbonaceous molecule in this experiment below 600 km. 相似文献
5.
Hunt JM 《Science (New York, N.Y.)》1984,226(4680):1265-1270
Light hydrocarbons (containing from 1 to 14 carbon atoms) are formed from disseminated organic matter in sediments at the parts-per-billion level by biological and low-temperature (< 50 degrees C) chemical reactions and at the parts-permillion level by high-temperature (> 50 degrees C) cracking reactions. The cooler reactions produce mainly branched hydrocarbons, whereas the hotter reactions yield more straight chains. Hydrocarbon generation zones in the subsurface can be recognized on the basis of hydrocarbon distribution patterns. Hydrocarbons with tertiary carbon atoms form at lower temperatures than those with quaternary carbons. Methane and ethane migrate vertically through fine-grained shales by diffusion and solution, whereas many of the C(3+) hydrocarbons show little or no vertical migration. Concentrations of light hydrocarbons, including methane, in fine-grained source rocks decrease to low values in deep, high-temperature (>200 degrees C) sediments. This decrease may be one reason why no economic accumulation of gas has been found to date deeper than 8.2 kilometers (27,000 feet). 相似文献
6.
Zhong D Franke JH Podiyanachari SK Blömker T Zhang H Kehr G Erker G Fuchs H Chi L 《Science (New York, N.Y.)》2011,334(6053):213-216
In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation. 相似文献
7.
In a small-scale reaction, vanadium-dependent nitrogenase has previously been shown to catalyze reductive catenation of carbon monoxide (CO) to ethylene, ethane, propylene, and propane. Here, we report the identification of additional hydrocarbon products [α-butylene, n-butane, and methane (CH(4))] in a scaled-up reaction featuring 20 milligrams of vanadium-iron protein, the catalytic component of vanadium nitrogenase. Additionally, we show that the more common molybdenum-dependent nitrogenase can generate the same hydrocarbons from CO, although CH(4) was not detected. The identification of CO as a substrate for both molybdenum- and vanadium-nitrogenases strengthens the hypothesis that CO reduction is an evolutionary relic of the function of the nitrogenase family. Moreover, the comparison between the CO-reducing capacities of the two nitrogenases suggests that the identity of heterometal at the active cofactor site affects the efficiency and product distribution of this reaction. 相似文献
8.
Chang S Kvenvolden K Lawless J Ponnamperuma C Kaplan IR 《Science (New York, N.Y.)》1971,171(3970):474-477
Total carbon in the Apollo 12 sample 12023 fines was 110 micrograms per gram of sample with a carbon isotopic abundance delta(13)C (relative to the Pee Dee belemnite standard) of +12 per mil. Hydrolysis of the fines with deuterium chloride yielded undeuterated methane along with deuterated hydrocarbons, thus confirming the presence of 7 to 21 micrograms of carbon per gram of sample as carbide and about 2 micrograms of carbon per gram of sample as indigenous methane. After vacuum pyrolysis of the fines to 1100 degrees C the following gases were detected in the relative abundance: carbon monoxide carbon dioxide methane. Variations of the delta(13)C value with the pyrolysis temperature indicated the presence of carbon with more than one range of isotopic values. The observed delta(13)C value of +14 per mil for lunar carbide is much higher than that of carbide in meteorites. These results suggest that lunar carbide is either indigenous to the moon or a meteoritic contribution that has been highly fractionated isotopically. 相似文献
9.
Alkenes and alcohols are among the most abundant and commonly used organic feedstock in industrial processes. We report a selective catalytic alkylation reaction of alkenes with alcohols that forms a carbon-carbon bond between vinyl carbon-hydrogen (C-H) and carbon-hydroxy centers with the concomitant loss of water. The cationic ruthenium complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4)(-) (Cy, cyclohexyl) catalyzes the alkylation in solution within 2 to 8 hours at temperatures ranging from 75° to 110°C and tolerates a broad range of substrate functionality, including amines and carbonyls. Preliminary mechanistic studies are inconsistent with Friedel-Crafts-type electrophilic activation of the alcohols, suggesting instead a vinyl C-H activation pathway with opposite electronic polarization. 相似文献
10.
Periana RA Taube DJ Evitt ER Löffler DG Wentrcek PR Voss G Masuda T 《Science (New York, N.Y.)》1993,259(5093):340-343
A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid. 相似文献
11.
Earlier workers have described a submarine gas seep in Norton Sound having an unusual mixture of petroleum-like, low-molecular-weight hydrocarbons. Actually, only about 0.04 percent of the seeping gas is hydrocarbons and 98 percent is carbon dioxide. The isotopic compositions of carbon dioxide (delta(13)C(PDB) = -2.7 per mil) and methane (delta(13)C(PDB) = -36 per mil, where PDB is the Peedee belemnite standard) indicate that geothermal processes are active here. 相似文献
12.
13.
Fischer-Tropsch type (FTT) synthesis has long been proposed to account for the existence of hydrocarbons in hydrothermal fluids. We show that iron- and chromium-bearing minerals catalyze the abiotic formation of hydrocarbons. In addition to production of methane (CH4aq), we report abiotic generation of ethane (C2H6aq) and propane (C3H8aq) by mineral-catalyzed hydrothermal reactions at 390 degrees C and 400 bars. Results suggest that the chromium component in ultramafic rocks could be an important factor for FTT synthesis during water-rock interaction in mid-ocean ridge hydrothermal systems. This in turn could help to support microbial communities now recognized in the subsurface at deep-sea vents. 相似文献
14.
利用热重红外联用技术(TG-FTIR)研究了竹材综纤维素在不同升温速率下(5.0, 10.0, 15.0, 20.0和30.0℃·min-1)的热解特性和热解动力学。热重分析/热重一次微分曲线(TG/DTG)表明:竹材综纤维素热解可分为干燥、快速裂解和慢速裂解等3个阶段; 随着升温速率增加, TG/DTG曲线往高温一侧移动; 竹综纤维素热解过程发生复杂的化学反应, 包括多重、平行和连续反应; 热解挥发分主要由小分子CO, H2O, CH4和CO2, 以及一些醛类、酮类、酸类、烷烃、醇类和酚类等有机物组成。利用无模式函数积分法, 即Flynn-Wall-Ozawa(FWO)和Kissinger-Akahira-Sunose(KAS)积分法, 对其热解动力学进行研究。结果表明:竹材综纤维素的活化能随着转化率的升高先增大后减小再增大, 活化能数值的变化与纤维素/半纤维素不同的热解特性有紧密联系。 相似文献
15.
江西双季晚稻不同纬度产量、生育期及温光资源利用的差异 总被引：7，自引：1，他引：6
【目的】研究明确江西不同纬度不同类型双季晚稻产量、生育期及温光资源利用差异,为江西双季晚稻适宜粳稻品种的科学选用提供依据与参考。【方法】以籼粳杂交稻、杂交粳稻、常规粳稻、杂交籼稻(CK)4种类型品种为材料,在江西乐平市(29.00°N,117.12°E)、上高县(28.27°N,115.12°E)、赣州市(25.81°N,114.96°E)3个试验点进行试验,比较研究双季晚稻不同类型品种在纬度上的产量、生育期及温光资源利用的差异特征。【结果】随着纬度升高,3种类型粳稻产量均增加,2013年(2014年)平均纬度每增加1°,籼粳杂交稻、杂交粳稻、常规粳稻分别增产0.36(0.32)、0.18(0.22)、0.25(0.20)t·hm~(-2)。同一纬度下,除赣州试验点杂交粳稻与常规粳稻的产量低于杂交籼稻外,其余各点均表现为籼粳杂交稻、杂交粳稻与常规粳稻产量显著高于杂交籼稻。各试验点3种类型粳稻均能安全成熟,随着纬度升高,各类型水稻播种至拔节期显著延长,全生育期天数增加;同一试验点3种类型粳稻全生育期均极显著长于杂交籼稻,主要表现在抽穗至成熟期天数的增加。3种类型粳稻光照与积温及其利用效率表现为籼粳杂交稻杂交粳稻常规粳稻杂交籼稻,在安全成熟条件下,双季晚稻生育期越长,温光资源利用率越高。【结论】江西不同纬度地区实行双季晚稻"籼改粳",可显著提高当地温光资源利用率与稻谷产量。与大面积种植的籼型杂交稻相比,在乐平与上高地区选种籼粳杂交稻、杂交粳稻与常规粳稻均具有显著的产量及温光资源利用优势;在赣州地区选种籼粳杂交稻的优势明显。双季晚稻"籼改粳"可能是提高双季稻区水稻产量的现实途径之一。 相似文献
16.
The carbon in ancient carbonaceous chondritic meteorites is mainly in a hydrocarbon composite similar to terrestrial kerogen, a cross-linked structure of aliphatic and aromatic hydrocarbons. Until recently, the composite has been commonly thought to have been produced in the early solar nebula by a Fischer-Tropsch-type process, involving the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen on grain surfaces. Instead, the aromatic hydrocarbons may form in gas-phase pyrolysis of simple aliphatics like acetylene and methane by a mechanism developed recently to explain formation of soot in combustion and of aromatic molecules in circumstellar envelopes. Nonequilibrium chemical kinetic calculations indicate that this mechanism can produce meteoritic aromatics if the initial concentration of simple hydrocarbons in the solar nebula was sufficiently but not unreasonably high. 相似文献
17.
Arenes of 1, 2, 3, 4 and more rings have been synthesized in a flow system by passing methane through silica gel at 1000 degrees C. Yields of 4.8 to 7.2 percent have been obtained per single pass. As determined by combined gas chromatography-mass spectrometry, the major compound synthesized that are of less than S rings are benzene, naphthalene, acenaphthylene, phenanthrene, fluoranthene, and pyrene. Under certain conditions ( presence of ammonia and water), small amounts of aliphatic hydrocarbons are also synthesized. Even-carbon-numbered hydrocarbons (aromatic as well as aliphatic) predominate, to the extent that about 97 percent of the total weight of the analyzed arenes have even numbers of carbon atoms. 相似文献
18.
稻田土壤有机碳是甲烷排放的关键底物之一,不同研究者由于采取的有机碳研究方法不同而得出稻田甲烷排放与土壤有机碳关系的结论不一。为明确影响稻田甲烷排放的土壤有机碳组分,设计了稻田施用不同外源有机碳(稻草还田、鸡粪和猪粪)的田间试验,对稻田甲烷排放和土壤有机碳组分的动态变化及其关联性进行监测和分析。结果表明,猪粪处理的甲烷排放与化肥处理无显著差异,而鸡粪和稻草2个处理的甲烷排放分别比化肥增加1.67倍(P<0.05),2.69倍(P<0.05);甲烷排放量与土壤易氧化有机碳含量显示相同顺序:稻草>鸡粪>猪粪>化肥;通径分析表明,土壤易氧化有机碳组分1(被33 mmol/L KMnO4氧化的有机碳)与甲烷排放直接相关,其他有机碳组分仅通过组分1间接作用于水稻生育后期甲烷排放,且排放量较低。由此推断,易氧化有机碳组分1是甲烷排放的主要底物,通过有效措施降低肥源中易氧化态有机碳组分1是减排甲烷的关键技术之一。 相似文献
19.
为研究猪粪（Pig manure,PM）与稻秆（Rice straw,RS）的组配比例与进料的固形物（Total solid,TS）浓度对中温条件下厌氧产甲烷特性的影响,通过批次厌氧发酵试验摸清不同挥发性固体（Volatile solids,VS）配比（PM/RS=1：0、4：1、2：1、1：1、1：2、1：4、0：1）下的原料产甲烷规律,并选择VS配比（均以PM/RS计）为1：1、4：1的混合原料开展进料浓度（TS分别为4.6%、7.1%、9.6%、12.1%）梯度提升的连续厌氧发酵试验。结果表明：批次发酵试验中VS配比为4：1时产甲烷性能表现最好,产甲烷潜力（P值）、反应动力常数（k）、最大产甲烷速率（Rm）及甲烷产率达到峰值时间（tmax）分别为380.3 mL·g-1 VS、0.098 d-1、37.2 mL·g-1 VS·d-1、4.4 d。连续发酵试验中,在水力停留时间为30 d、VS配比为4：1时连续产甲烷性能更优,甲烷产率、产甲烷潜力转化率和容积产甲烷率分别达到354.8 mL·g-1 VS、93.3%、0.88 L·L-1·d-1。但混合物料中猪粪比例越高,发酵系统的氨抑制风险也越高。在进料浓度达到12.1%条件下,VS配比为4：1时的游离氨浓度是VS配比为1：1时的1.47倍,达到223.2 mg·L-1。研究表明,猪粪与稻秆混合原料VS配比为4：1（配比后的C/N=22~23：1）时,可提高发酵原料转化效率和容积产甲烷率;同时,进料TS浓度低于12.1%（有机负荷率为2.87 g VS·L-1·d-1）可降低厌氧发酵中的氨抑制,保证沼气工程稳定运行。 相似文献
20.
MC1预处理对豆秸水解特性及产甲烷效率的影响 总被引：1，自引：1，他引：0
为提高大豆秸秆厌氧发酵产气性能,本文利用复合菌系MC1对灭菌秸秆(SS)及未灭菌秸秆(NSS)进行预处理,研究预处理时间对秸秆水解特性及产甲烷效率的影响。结果表明:MC1能有效降解大豆秸秆,SS经12 d预处理,其纤维素及木质素降解率分别为41.71%和29.92%,显著高于NSS(P0.05)。SS预处理体系中VFAs含量显著高于NSS(P0.05),且两者分别在预处理3 d及7 d浓度达到最高,分别为2.18 g·L~(-1)(SS)和1.52 g·L~(-1)(NSS),预示杂菌减缓了MC1对秸秆的降解速率。乙酸是预处理体系中最主要的VFAs产物,整个预处理期间SS和NSS水解液乙酸含量分别高于72.41%和56.23%。与未处理大豆秸秆相比,经过3 d预处理,SS和NSS预处理体系的甲烷累积产量分别提高了36.86%和34.27%,其最大产甲烷速率分别为21.69 mL·d-1·g-1VS和17.44mL·d-1·g-1VS,表明MC1预处理能有效提高大豆秸秆厌氧发酵性能。 相似文献