Kinetic Models for Hydrogenolysis of Thiophene on Co-Mo/γ-Alumina Catalyst

Abstract

A feasible, comprehensive, and rigorous mechanistic kinetic model was developed for hydrogenolysis of thiophene on a commercial hydrodesulphurization Co-Mo/γ-Al₂O₃ catalyst. The kinetics were modeled with 24 rate expressions based on three modes of adsorption: molecular and atomic adsorption of hydrogen, and Eley Rideal mechanism. The experimental data were obtained in a bench-scale tubular reactor with plug flow, and the conditions varied over the following range: total pressure, P _t = 2–30 bar, temperature = 533–625 K, and molar hydrogen to hydrocarbon ratios 4–9. The experimental rate data were described by a set of Lagmuir-Hinshelwood-Hougen-Watson rate equations for both the hydrogenolysis of thiophene to butene and the hydrogenation of butene to butane on two different sites, σ and τ. The kinetic rate constants and adsorption equilibrium constants were estimated for each model using the optimization routine of Nelder-Mead simplex algorithm. Discrimination among rival models was based upon physicochemical criteria, analysis of the residuals, and statistical tests. The surface reaction between adsorbed thiophene and adsorbed hydrogen on σ sites in the hydrogenolysis, and the surface reaction between adsorbed butene and adsorbed hydrogen on τ sites in the hydrogenation when hydrogen is adsorbed molecularly are found to be the rate-determining steps. The predicted activation energies, enthalpies of adsorption, Gibbs free energies, and adsorption entropies compare exceedingly well with previously reported values in the literature.     

Oil and Gas International

Oil and Gas International，中文刊名《国际石油与天然气》(网络版)，由美国Oil and Gas International公司发行，全年365期。报道内容为：石油业在线数据库，提供国际石油业新闻、信息及分析，包括相关特写、技术报告、每日石油与天然气价格及分析、地区热点、勘探与发现、钻井与完井、开发与生产、地球科学、卫生安全环保、最新行业统计数据以及大量的档案资料、照片和地图等。     

The Innovative Research Team of Oil ＆ Gas Well Engineering

Over more than ten years‘ construction and development, China University of Petroleum has gradually formed an innovative research team composed of young and middle-aged researchers led by Dr. Gao Deli (a Yangtze River Scholar). The team was selected in 2004 into the Developmental Program (Grant Number:     

Separator on the Principle of Gravitational-Dynamic Separation of Emulsions (Water–Oil Type) for Solving Various Problems of Oil and Gas Production,Petrochemistry, and Ecology

Chemical and Petroleum Engineering - The article presents a gravitational-dynamic separator with the implementation of the principles of liquid dynamic filtration, hydrostatic and hydrodynamic...     

Current Conditions and Outlook of Global Offshore Oil and Gas Exploration

The world is rich in offshore oil and gas resources. The offshore oil reserves account for about 34 percent of the world＇s total. With a 30 percent proven rate, offshore oil exploration is still in its preliminary stage. Based on the statistics by ＂Oil ＆ Gas Journal,＂ as of the January 1, 2006, the proven oil reserves worldwide are 175.7 billion tons and the proven natural gas reserves 173 trillion cubic meters. The global offshore oil reserves approach 135 billion tons, of which 38 billion tons are proven, while the offshore natural gas reserves amount to about 140 trillion cubic meters, of which 40 trillion cubic meters are proven.     

The Density Functional Study of Thiophene Adsorption on Zeolite Clusters

The density functional theory and the cluster model methods have been employed to investigate the interactions between thiophene and the HZSM-5 zeolites. The molecular complexes formed by the adsorption of thiophene on silanol H3SiOH with two coordination forms, and the model Brrnsted acid sites of zeolite cluster H3Si（OH）AI（OH）2SiH3 upon the interaction with thiophene have been comparatively studied. Full optimization and frequency analysis of all cluster models have been carried out using the B3LYP hybrid method at 6-31G basis level for hydrogen atoms and 6-31＋G（d） basis set level for silicon, aluminum, oxygen, carbon, and sulfur atoms. The calculated results showed that the nature of interactions leading to the formation of the zeolite cluster-thiophene and silanol-thiophene complexes was associated with the van der Waals force confirmed by a slight change of geometric structures and properties. Thiophene is adsorbed on bridging hydroxyl group prior to silanol OH group judging from the magnitude of adsorption heat. The cluster model calculation reproducing the experimental prediction to form the experimental adsorption spectra of thiophene in HZSM-5 zeolite has illustrated the validity of the proposed adsorption models.     

Low Oil Prices—Impact on Natural Gas and Associated Industries

The suddenness and severity of oil price drops have certainly taken their toll on the collective psyche of the oil and gas industry. The natural gas industry had been living with very modest prices most of the time since abundance really took hold in 2009 or so, but the overall economics of the exploration and production industry—and the booms being experienced in South Texas, West Texas, North Dakota, and the Pennsylvania/Ohio producing area—were more than sustained by oil and wet-gas development. Losing half the price of crude oil, with its companion impacts on the pricing of natural gas liquids, pretty much brought the boom to a screeching pause. In time-tested oil-and-gas industry fashion, this has been called a crash, a collapse, a meltdown—you name the apocalyptic thesaurus entry and it has probably been used.     

Sinopec Raises 2006 Oil and Gas Production

Sinopec Corp., the nation＇s second-biggest oil company, is expected to produce 1.9 percent more crude oil and 11 percent more gas in 2006 as the nation＇s energy demand continually rises. The company may pump 40 million tons of crude oil and 7 billion cubic meters of natural gas from domestic fields this year, said Sinopec Corp in a statement released in late December. The company produced 39.27 million tons of crude oil and 6.3 billion cubic meters of gas last year. Chinese oil companies are increasing investments in oil and gas exploration to meet demands by the world＇s fastest-growing major economy, which expanded 10.7 percent in the first three quarters of this year.     

CNPC Refreshes Oil and Gas Production Records

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PetroChina’s Oil and Gas Breakthroughs

<正>The net profits of PetroChina in the first nine months of 2010 surged 23 percent on a year-on-year basis,totaling 100.03 billion yuan (US$14.93 billion),while the earnings per share stood at 0.55 yuan,according to a statement submitted by the company to the Shanghai and Hong Kong stock exchanges in late October.For the third quarter alone,the net profit was up 12.5 percent to 34.7 million yuan from a year earlier.     

Sinopec Encouraged for Oil and Gas Exploration

Shengli hopeful to find oilfield with 100-million-ton reservesA total of 27 wells have been so far drilled in Zhuanghai area of Sinopec Shengli Oil Field with the proven oil in place accumulated to 45.46 million tons. It is hopeful to prove another 50 million tons of oil in place in this region next year so that another oil field with the reserves of 100 million tons is taking shape.     

Hart＇s Oil and Gas World

Hart‘s Oil and Gas World，中文刊名《哈氏石油天然气世界》，由美国Hart出版公司发行。创刊于1908年，国际标准刊号：ISSN 1075-5365，全年12期。报道美国各州天然气、石油的开发、钻井、生产、运输和精炼等方面的技术进展。     

Trend of Sino-Canada Oil ＆ Gas Cooperation

China＇s more dependence on oil and gas import,great fluctuation of international oil prices,and soaring prices of imported natural gas brought new pressure to the nation＇s economic development.Now,China urgently needs to diversify oil and gas supply,which objectively requires oil companies to ＂go out＂,strengthen international oil and gas cooperation,and enhance capacity in safeguarding national energy supply.     

Panorama of PetroChina Oil and Gas Development in 1996～2000

As of the end of 2000,PetroChina found 293 oil fields in total across China with the proven oil in place being 14.35 billion tons and the recoverable reserves being 4.38 billion tons. A total of 219 oil fields in its affiliated 13oil areas have been put into development.……     

Review of China’s Oil and Gas Policies in 2013

In 2013, oil and gas industry policies deepened, oil and gas pricing system improved, oil quality upgrading accelerated, the central government canceled approval examination and approval or delegated it to lower levels and a series of policies released such as supporting private capital entering the oil and gas industry and encouraging coal-bed methane （CBM） development. The Third Plenary Session of the 18th Communist Party of China （CPC） Central Committee has put forward that let the market play a decisive role in resource allocation, which will lead the development of oil and gas industry and enterprises toward a more act vigorous and competitive direction.     

What Impact Will COVID-19 Have on the Oil and Gas Market of China and the World?

正Since the Spring Festival of 2020,affected by the Coronavirus Disease 201 9 (COVID-19),the vast majority of Chinese people have had to go out less or even stay at home.What impact will this epidemic have on the energy industry?What impact will this epidemic have on the oil and gas industry?     

Current State and Prospect of China’s Oil and Gas Pipeline Development

By the end of 2010, China has completed 85,000 kilometers of oil and gas pipelines in length, of which natural gas pipelines were 45,000 kilometers, crude oil pipelines were 22,000 kilometers, and products pipelines were 18,000 kilometers. An oil and gas network that covers China