In order to explore the adsorptive denitrogenation of liquid hydrocarbon streams for producing ultraclean fuels, the adsorption performance of seven representative activated carbon samples and three activated alumina samples was evaluated in a batch adsorption system and a fixed-bed flow adsorption system for removing quinoline and indole from a model diesel fuel in the coexistence of sulfur compounds and aromatics. Different adsorbents show quite different selectivity toward basic and nonbasic nitrogen compounds (quinoline and indole) and sulfur compounds (dibenzothiophene and 4,6-dimethyldibenzothiophene). The activated carbons generally show higher capacity than activated alumina samples for removing the nitrogen compounds. The adsorption capacity and selectivity of the activated carbons for nitrogen compounds were further correlated with their textural properties and oxygen content. It was found that (1) the microporous surface area and micropore volume are not a key factor for removal of the nitrogen compounds in the tested activated carbons; (2) the oxygen functionality of the activated carbons may play a more important role in determining the adsorption capacity for the nitrogen compounds since the adsorption capacity for nitrogen compounds increases with increase in the oxygen concentration of the activated carbons; and (3) the type of the oxygen-functional groups may be crucial in determining their selectivity for various nitrogen or sulfur compounds. In addition, regeneration of the saturated adsorbents was conducted by the toluene washing followed by the heating to remove the remained toluene. The results show that the spent activated carbons can be regenerated to completely recover the adsorption capacity. The high capacity and selectivity of carbon-based adsorbents for the nitrogen compounds, along with their good regenerability, indicate that the activated carbons may be promising adsorbents for deep denitrogenation of liquid hydrocarbon streams.

The carbon-based adsorbents are promising for adsorptive denitrogenation (ADN) of liquid hydrocarbon streams. The objective of the present study is to develop a fundamental understanding of the role of surface oxygen-containing functional groups on carbon-based adsorbents in adsorption of nitrogen compounds that are known to be present in liquid fuels. The adsorption properties of four representative activated carbons were evaluated in a batch adsorption system for removing quinoline and indole respectively from decane. The adsorption was found to obey the Langmuir adsorption isotherm. The adsorption isotherms were obtained and the adsorption parameters (the maximum capacity and adsorption constant) were estimated. The surface chemical properties of the adsorbents were characterized by temperature-programmed desorption (TPD) technique with a mass spectrometer to identify and quantify the type and concentration of the oxygen-containing functional groups on the basis of the CO 2 -and CO-evolution profiles. It was found that both the type and the concentration of surface oxygen-containing functional groups play an important role in determining the ADN performance. Higher concentration of the oxygen-containing functional groups on the adsorbents resulted in higher adsorption capacity for the nitrogen compounds. A fundamental insight was gained on the contributions of different oxygen functional groups by analyzing the changes in the monolayer maximum adsorption capacity q m and the adsorption constant K for nitrogen compounds on different carbon adsorbents. The acidic functional groups, such as carboxyl and carboxylic anhydride groups, appear to contribute more for adsorption of quinoline, whereas the basic oxygen-containing groups such as carbonyl and quinone groups may have more contribution to adsorption of indole.

In the upgrading of heavy petroleum oils and residues by hydrotreatment, multiple-reactor fixed-bed units loaded with different types of catalysts are used extensively. Catalysts for such hydrotreatment processes are chosen on the basis of activity, selectivity, and life. The performance of the overall hydrotreatment process, with regard to various reactions, such as hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), asphaltenes cracking (HDAsph), and conversion to distillates, as well as catalyst life-on-stream, are clearly linked to the performance of the catalyst in different reactors. Information regarding the activity, selectivity, kinetic parameters, and deactivation of the individual catalysts are, therefore, highly desirable for optimizing reactor loading in the multiple-catalyst system. This paper presents the performance tests for various reactions on two types of industrial hydrotreating catalysts: those used at the midsection and the tail-end of a graded catalyst system designed to hydrotreat atmospheric residual oils. The tests were conducted using straight-run Kuwait atmospheric residue, a demetallized residue, and a demetallized/desulfurized residue. The activity and kinetic parameters for different reactions that are typically occurring during the hydroprocessing of these feedstocks were determined. The results revealed significant changes in activity, depending on the feedstock used for the tests. Furthermore, apparent rate orders and rate constants for some reactions were significantly changed. The study demonstrates the importance of proper selection of the feedstocks used in the performance evaluation and screening of candidate catalysts for graded catalyst systems for residual-oil hydrotreatment.

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