As with so many things, the first step in identifying emerging technologies is
to Google®. Using the topic of desulfurization as an example, here is TODAY’S TIP:
TIP: You could just enter desulfurization in the search box. A better way is to enter the following search string …
desulfurization AND (new OR novel OR innovative)
You end up with the same total number of hits. The difference is that the hits at the top of your list will be higher quality, saving you browsing time.
HINT: Because it can take years for a technology to move from 0 to 9 on the Technology Readiness scale, don’t restrict the search to just the most recent year. You may find some items dated much older that will still be in the emergent stage.
Here are some results from the above Google® search …
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Final Report: A Novel Approach to Ultra-Deep Desulfurization of Transportation Fuels by Sulfur-Selective Adsorption for Pollution Prevention at the Source
EPA Grant Number: R831471
Title: A Novel Approach to Ultra-Deep Desulfurization of Transportation Fuels by Sulfur-Selective Adsorption for Pollution Prevention at the Source
Investigators: Song, Chunshan , Clemons, Jennifer L , Kim, Jae Hyung , Ma, Xiaoliang , Subramani, Velu , Sundararaman, Ramanathan , Wang, Xiaoxing , Yoosuk, Boonyawan , Zhou, Anning
Institution: Pennsylvania State University
EPA Project Officer: Bauer, Diana
Project Period: October 15, 2003 through October 14, 2006 (Extended to August 31, 2007)
Project Amount: $325,000
RFA: Technology for a Sustainable Environment (2003) RFA Text | Recipients Lists
Research Category: Sustainability , Pollution Prevention/Sustainable Development
Objective:
The overall objectives of this project comprise of 1) designing new adsorbents with high selectivity for removing sulfur compounds from transportation fuels under ambient temperature and pressure, 2) developing new and advanced catalysts for the HDS of concentrated sulfur fractions, and 3) understanding the fundamentals of adsorption-desorption and catalytic HDS processes by a combination of experimental and computational analysis. The objectives of this project for the present period are to evaluate the adsorption performance of the typical adsorbents, including nickel-based adsorbent, activated alumina and activated carbon, and to get a better fundamental understanding of the adsorptive mechanism and selectivity of the various compounds on the different adsorbents by a combination of the experimental results and computational results.
Summary/Accomplishments (Outputs/Outcomes):
In the whole period of performance, our approaches focused on the following aspects: 1) developing the Ni-based adsorbents and understanding the adsorptive mechanism and the interaction between the surface structure of the Ni-based adsorbents and their adsorptive performance; 2) fundamental understanding of the inherent adsorptive selectivity and adsorptive mechanism of other adsorbents such as activated carbons and activated alumina with and without oxidative modification; 3) the oxidative desulfurization performance of various catalysts by molecular oxygen (with the option of subsequent adsorption) at mild conditions; and 4) preparation and characterization of nano-sized bimetallic sulfide catalysts without using any support materials for deep hydrodesulfurization of deep hydrodesulfurization of 4,6-dimethyldibenzothiophene.
More than 20 Ni-based adsorbents were prepared and tested. These Ni-based adsorbents include Ni-Al materials (A2 adsorbents), Ni-Al and Ni-Zn-Al materials from a double layered hydroxide intermediate (A4 adsorbents), Ni/SiO2-Al2O3, Ni-loaded Y zeolite adsorbents with different loading (0.5-45 wt%) and different methods (ion-exchange, incipient wetness impregnation) and commercial Ni-based adsorbents (A5 adsorbents).Adsorptive desulfurization performances of the different Ni-based adsorbents, including the adsorptive capacity and selectivity, were examined by using different fuels in a fixed bed adsorption system.
Quantum chemical calculations of the sulfur compounds and some coexisting aromatic and olefinic compounds, including electron density, electrostatic potential, bond order, charge distribution and molecular orbits analysis, and the characterizations by various technologies were conducted for selectivity analysis and mechanistic understanding over these Ni-based adsorbents.
It was found that the direct interaction between the heteroatom in the adsorbate and the surface nickel plays an important role, indicating that the nickel-based adsorbent is an excellent one for selective removal of the sulfur compounds, which have no alkyl steric hindrance, from hydrocarbon streams, such as gasoline, kerosene and jet fuel. However, the nickel-based adsorbent is still difficult to remove the alkyl DBTs with methyl groups at the 4 and/or 6 positions due to the steric hindrance of the alkyl groups, It indicates that the nickel-based adsorbent might not quite effective for deep desulfurization of commercial diesel.
The adsorptive selectivity and mechanism of the activated alumina was studied in detail in a fixed bed adsorption system. It was found that the adsorption selectivity depends dominantly on the electrostatic interaction and the acid-base interaction. The activated alumina is very effective for selective separation of the nitrogen compounds in liquid hydrocarbon fuels, especially for basic nitrogen compounds, but not very successful for separating the sulfur compounds from hydrocarbon streams.
The adsorptive selectivity and mechanism of the activated carbon was studied in detail in a fixed bed adsorption system. The results show that the activated carbon shows higher adsorptive capacity and selectivity for both sulfur and nitrogen compounds, especially for the refractory sulfur compounds in the commercial diesel. The hydrogen bonding interaction involving surface oxygen functional groups might play an important role in adsorptive desulfurization and denitrogenation over the activated carbons. The study suggests that the carbon material might be one of most promising adsorbents for removing sulfur from the commercial diesel.
The modification of activated carbons (AC) was conducted by liquid-phase HNO3-oxidation and gas-phase O2-oxidation. The oxidation modified AC samples were further characterized by N2 physisorption, SEM, FTIR, XPS and surface pH measurement technologies. The oxidative modification can significantly improve their adsorptive desulfurization performance, through an increase of the oxygen-containing functional groups, especially carboxyl groups, on the AC surface. The results strongly indicate that the adsorption of the sulfur compounds on oxidative modified ACs may be conducted through the hydrogen bonding and/or acid-base interaction mechanism.
More than 10 promising heterogeneous catalysts were synthesized by different preparation methods. Oxidative desulfurization of model diesel fuels over these catalysts by using O2 as the oxidant was conducted in a batch adsorption system. At 140 °C without catalyst, most sulfur compounds in diesel fuels can be oxidized to corresponding sulfones which are easily removed by adsorption. However other hydrocarbons in the fuels were also oxidized and the selectivity was poor. Using catalysts could significantly reduce the reaction temperature and increase the relative selectivity to the sulfur compounds.
By comparative study of different adsorbents, we found that different adsorbents may be suitable for separating different sulfur compounds from different hydrocarbon streams. Combination of two or more adsorbents in an adsorptive desulfurization process or combination of the ODS and adsorption process might be a trend for a practical ultra-deep desulfurization process of liquid hydrocarbon fuels.
For the HDS catalyst study, new bimetallic dispersed metal sulfide catalysts have been prepared using a new hydrothermal synthesis method. The results show that unsupported CoMoS2 and NiMoS2 dispersed nano-particulate catalysts have been syn thesized and they exhibit excellent catalytic activities that are superior to the commercial hydrotreating catalysts for deep hydrodesulfurization of 4,6-dimethyldibenzothiophene.
On the basis of these approaches, we understand and clarify the adsorptive desulfurization mechanism of the thiophenic sulfur compounds in liquid hydrocarbon fuels over the different typical adsorbents, and the effects of the co-existing aromatic and nitrogen compounds on the adsorptive performance. The present study provided a close insight into the fundamental adsorption mechanism of the sulfur compounds over the different typical adsorbents through both experimental and computational approaches. These approaches improve our knowledge on the adsorptive desulfurization, and provide a great amount of scientific data and information for improving our current adsorbents, and moreover, for design and preparation of the more efficient adsorbents for deep desulfurization of liquid hydrocarbon fuels.
Based on the new findings from this project, we have published/submitted nine journal articles in prestigious journals, and given nine presentations at the international and national conferences.
Journal Articles on this Report : 8 Displayed | Download in RIS Format
TIP: You could just enter desulfurization in the search box. A better way is to enter the following search string …
desulfurization AND (new OR novel OR innovative)
You end up with the same total number of hits. The difference is that the hits at the top of your list will be higher quality, saving you browsing time.
HINT: Because it can take years for a technology to move from 0 to 9 on the Technology Readiness scale, don’t restrict the search to just the most recent year. You may find some items dated much older that will still be in the emergent stage.
Here are some results from the above Google® search …
///////
Final Report: A Novel Approach to Ultra-Deep Desulfurization of Transportation Fuels by Sulfur-Selective Adsorption for Pollution Prevention at the Source
EPA Grant Number: R831471
Title: A Novel Approach to Ultra-Deep Desulfurization of Transportation Fuels by Sulfur-Selective Adsorption for Pollution Prevention at the Source
Investigators: Song, Chunshan , Clemons, Jennifer L , Kim, Jae Hyung , Ma, Xiaoliang , Subramani, Velu , Sundararaman, Ramanathan , Wang, Xiaoxing , Yoosuk, Boonyawan , Zhou, Anning
Institution: Pennsylvania State University
EPA Project Officer: Bauer, Diana
Project Period: October 15, 2003 through October 14, 2006 (Extended to August 31, 2007)
Project Amount: $325,000
RFA: Technology for a Sustainable Environment (2003) RFA Text | Recipients Lists
Research Category: Sustainability , Pollution Prevention/Sustainable Development
Objective:
The overall objectives of this project comprise of 1) designing new adsorbents with high selectivity for removing sulfur compounds from transportation fuels under ambient temperature and pressure, 2) developing new and advanced catalysts for the HDS of concentrated sulfur fractions, and 3) understanding the fundamentals of adsorption-desorption and catalytic HDS processes by a combination of experimental and computational analysis. The objectives of this project for the present period are to evaluate the adsorption performance of the typical adsorbents, including nickel-based adsorbent, activated alumina and activated carbon, and to get a better fundamental understanding of the adsorptive mechanism and selectivity of the various compounds on the different adsorbents by a combination of the experimental results and computational results.
Summary/Accomplishments (Outputs/Outcomes):
In the whole period of performance, our approaches focused on the following aspects: 1) developing the Ni-based adsorbents and understanding the adsorptive mechanism and the interaction between the surface structure of the Ni-based adsorbents and their adsorptive performance; 2) fundamental understanding of the inherent adsorptive selectivity and adsorptive mechanism of other adsorbents such as activated carbons and activated alumina with and without oxidative modification; 3) the oxidative desulfurization performance of various catalysts by molecular oxygen (with the option of subsequent adsorption) at mild conditions; and 4) preparation and characterization of nano-sized bimetallic sulfide catalysts without using any support materials for deep hydrodesulfurization of deep hydrodesulfurization of 4,6-dimethyldibenzothiophene.
More than 20 Ni-based adsorbents were prepared and tested. These Ni-based adsorbents include Ni-Al materials (A2 adsorbents), Ni-Al and Ni-Zn-Al materials from a double layered hydroxide intermediate (A4 adsorbents), Ni/SiO2-Al2O3, Ni-loaded Y zeolite adsorbents with different loading (0.5-45 wt%) and different methods (ion-exchange, incipient wetness impregnation) and commercial Ni-based adsorbents (A5 adsorbents).Adsorptive desulfurization performances of the different Ni-based adsorbents, including the adsorptive capacity and selectivity, were examined by using different fuels in a fixed bed adsorption system.
Quantum chemical calculations of the sulfur compounds and some coexisting aromatic and olefinic compounds, including electron density, electrostatic potential, bond order, charge distribution and molecular orbits analysis, and the characterizations by various technologies were conducted for selectivity analysis and mechanistic understanding over these Ni-based adsorbents.
It was found that the direct interaction between the heteroatom in the adsorbate and the surface nickel plays an important role, indicating that the nickel-based adsorbent is an excellent one for selective removal of the sulfur compounds, which have no alkyl steric hindrance, from hydrocarbon streams, such as gasoline, kerosene and jet fuel. However, the nickel-based adsorbent is still difficult to remove the alkyl DBTs with methyl groups at the 4 and/or 6 positions due to the steric hindrance of the alkyl groups, It indicates that the nickel-based adsorbent might not quite effective for deep desulfurization of commercial diesel.
The adsorptive selectivity and mechanism of the activated alumina was studied in detail in a fixed bed adsorption system. It was found that the adsorption selectivity depends dominantly on the electrostatic interaction and the acid-base interaction. The activated alumina is very effective for selective separation of the nitrogen compounds in liquid hydrocarbon fuels, especially for basic nitrogen compounds, but not very successful for separating the sulfur compounds from hydrocarbon streams.
The adsorptive selectivity and mechanism of the activated carbon was studied in detail in a fixed bed adsorption system. The results show that the activated carbon shows higher adsorptive capacity and selectivity for both sulfur and nitrogen compounds, especially for the refractory sulfur compounds in the commercial diesel. The hydrogen bonding interaction involving surface oxygen functional groups might play an important role in adsorptive desulfurization and denitrogenation over the activated carbons. The study suggests that the carbon material might be one of most promising adsorbents for removing sulfur from the commercial diesel.
The modification of activated carbons (AC) was conducted by liquid-phase HNO3-oxidation and gas-phase O2-oxidation. The oxidation modified AC samples were further characterized by N2 physisorption, SEM, FTIR, XPS and surface pH measurement technologies. The oxidative modification can significantly improve their adsorptive desulfurization performance, through an increase of the oxygen-containing functional groups, especially carboxyl groups, on the AC surface. The results strongly indicate that the adsorption of the sulfur compounds on oxidative modified ACs may be conducted through the hydrogen bonding and/or acid-base interaction mechanism.
More than 10 promising heterogeneous catalysts were synthesized by different preparation methods. Oxidative desulfurization of model diesel fuels over these catalysts by using O2 as the oxidant was conducted in a batch adsorption system. At 140 °C without catalyst, most sulfur compounds in diesel fuels can be oxidized to corresponding sulfones which are easily removed by adsorption. However other hydrocarbons in the fuels were also oxidized and the selectivity was poor. Using catalysts could significantly reduce the reaction temperature and increase the relative selectivity to the sulfur compounds.
By comparative study of different adsorbents, we found that different adsorbents may be suitable for separating different sulfur compounds from different hydrocarbon streams. Combination of two or more adsorbents in an adsorptive desulfurization process or combination of the ODS and adsorption process might be a trend for a practical ultra-deep desulfurization process of liquid hydrocarbon fuels.
For the HDS catalyst study, new bimetallic dispersed metal sulfide catalysts have been prepared using a new hydrothermal synthesis method. The results show that unsupported CoMoS2 and NiMoS2 dispersed nano-particulate catalysts have been syn thesized and they exhibit excellent catalytic activities that are superior to the commercial hydrotreating catalysts for deep hydrodesulfurization of 4,6-dimethyldibenzothiophene.
On the basis of these approaches, we understand and clarify the adsorptive desulfurization mechanism of the thiophenic sulfur compounds in liquid hydrocarbon fuels over the different typical adsorbents, and the effects of the co-existing aromatic and nitrogen compounds on the adsorptive performance. The present study provided a close insight into the fundamental adsorption mechanism of the sulfur compounds over the different typical adsorbents through both experimental and computational approaches. These approaches improve our knowledge on the adsorptive desulfurization, and provide a great amount of scientific data and information for improving our current adsorbents, and moreover, for design and preparation of the more efficient adsorbents for deep desulfurization of liquid hydrocarbon fuels.
Based on the new findings from this project, we have published/submitted nine journal articles in prestigious journals, and given nine presentations at the international and national conferences.
Journal Articles on this Report : 8 Displayed | Download in RIS Format
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Journal Article
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Kim JH, Ma X, Song C. Kinetics of two pathways for
4,6-dimethyldibenzothiophene hydrodesulfurization over NiMo, CoMo sulfide,
and nickel phosphide catalysts. Energy
& Fuels 2005;19(2):353-364.
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Full-text: Research Gate-Abstract and Full Text HTML
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Journal Article
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Kim JH, Ma X, Zhou A, Song C. Ultra-deep desulfurization and
denitrogenation of diesel fuel by selective adsorption over three different
adsorbents: a study on adsorptive selectivity and mechanism. Catalysis Today
2006;111(1-2):74-83.
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Journal Article
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Ma X, Sprague M, Song C. Deep desulfurization of gasoline by
selective adsorption over nickel-based adsorbent for fuel cell applications. Industrial & Engineering Chemistry
Research 2005;44(15):5768-5775.
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Full-text: Certh Centre for Research & Technology-Full Text
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Journal Article
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Ma X, Velu S, Kim JH, Song C. Deep desulfurization of gasoline
by selective adsorption over solid adsorbents and impact of analytical
methods on ppm-level sulfur quantification for fuel cell applications. Applied Catalysis B: Environmental
2005;56(1-2):137-147.
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Journal Article
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Ma X, Zhou A, Song C. A novel method for oxidative desulfurization
of liquid hydrocarbon fuels based on catalytic oxidation using molecular
oxygen coupled with selective adsorption. Catalysis Today 2007;123(1-4):276-284.
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Abstract: ScienceDirect-Abstract
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Journal Article
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Velu S, Song CS, Engelhard MH, Chin Y-H. Adsorptive removal of
organic sulfur compounds from jet fuel over K-exchanged NiY zeolites prepared
by impregnation and ion exchange. Industrial
& Engineering Chemistry Research 2005;44(15):5740-5749.
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Abstract: ACS-Abstract
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Journal Article
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Yoosuk B, Kim JH, Song C, Ngamcharussrivichai C,
Prasassarakich P. Highly active MoS2, CoMoS2 and NiMoS2
unsupported catalysts prepared by hydrothermal synthesis for
hydrodesulfurization of 4,6-dimethyldibenzothiophene. Catalysis Today 2008;130(1):14-23.
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Journal Article
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Zhou AN, Ma X, Song C. Liquid-phase adsorption of multi-ring
thiophenic sulfur compounds on carbon materials with different surface
properties. Journal of Physical
Chemistry B 2006;110(10):4699-4707.
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Abstract
from PubMed
Abstract: ACS-Abstract Exit |
Desulfurization, adsorption, oxidative desulfurization, gasoline, jet fuel, diesel, liquid hydrocarbon, adsorbent, Ni, activated carbon, catalyst, selective adsorption for removing sulfur,, RFA, Scientific Discipline, Air, Sustainable Industry/Business, Environmental Chemistry, Sustainable Environment, Technology for Sustainable Environment, mobile sources, Nox, motor vehicles, engine exhaust, desulfurization, selective adsorption for removing sulfur, hydrodesulfurization, air pollutants, automotive emissions, diesel exhaust, sulfur, fuel cell, alternative fuel, pollution prevention, diesel fuel, alternative motor fuels
Relevant Websites:
http://www.energy.psu.edu/ Exit
Progress and Final Reports:
Original Abstract
2004 Progress Report
2005 Progress Report
source: https://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.highlight/abstract/6325/report/F
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Catalysis Today
Volume 86, Issues 1–4, 1 November 2003, Pages 211–263
Cover image
An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel ☆
Chunshan Song,
Clean Fuels and Catalysis Program, Department of Energy and Geo-Environmental Engineering, The Energy Institute, Pennsylvania State University, University Park, PA 16802, USA
Show less
http://doi.org/10.1016/S0920-5861(03)00412-7Get rights and content
Abstract
This review discusses the problems of sulfur reduction in highway and non-road fuels and presents an overview of new approaches and emerging technologies for ultra-deep desulfurization of refinery streams for ultra-clean (ultra-low-sulfur) gasoline, diesel fuels and jet fuels. The issues of gasoline and diesel deep desulfurization are becoming more serious because the crude oils refined in the US are getting higher in sulfur contents and heavier in density, while the regulated sulfur limits are becoming lower and lower. Current gasoline desulfurization problem is dominated by the issues of sulfur removal from FCC naphtha, which contributes about 35% of gasoline pool but over 90% of sulfur in gasoline. Deep reduction of gasoline sulfur (from 330 to 30 ppm) must be made without decreasing octane number or losing gasoline yield. The problem is complicated by the high olefins contents of FCC naphtha which contributes to octane number enhancement but can be saturated under HDS conditions. Deep reduction of diesel sulfur (from 500 to <15 2006="" 2010="" 30="" 4-="" 4="" 6-positions.="" a="" adsorbents="" affordable="" along="" also="" and="" approaches.="" approaches="" are="" as="" at="" because="" begin="" both="" br="" by="" catalysis="" catalysts="" co-existing="" compounds="" consideration="" continuing="" dearomatization="" deep="" desulfurization="" develop="" developments="" dictated="" diesel="" dimethyldibenzothiophene="" discussed="" e.g.="" effective="" effects="" end="" engines.="" exacerbated="" feed="" for="" fuel-cell="" fuel="" fuels="" gasoline="" government="" h2s="" have="" hds="" highway="" hydrodesulfurization="" ic="" in="" include="" inhibiting="" into="" is="" jet="" large="" largely="" least="" long-term="" low-aromatics="" meeting="" methods="" milestone.="" mind="" more="" needed="" needs="" new="" nitrogen="" non-hds-type="" non-road="" of="" on="" only="" or="" overall="" polyaromatics="" ppm="" problem="" process="" processing="" producing="" product.="" reactive="" reagents="" regulations="" represents="" requirement="" research="" researchers="" road="" schemes.="" should="" so="" society="" solutions.="" some="" stepping="" streams="" stringent="" substitutions="" sulfur="" take="" than="" that="" the="" to="" transportation="" try="" ultra-clean="" ultra-low-sulfur="" well="" which="" will="" with="" zero=""> Keywords
Desulfurization;
Gasoline;
Fuels;
Diesel fuel;
Jet fuel;
Catalysis;
Adsorption
Based on a keynote lecture at the international symposium on Ultra-Clean Transportation Fuels at American Chemical Society National Meeting in Boston, MA, during 18–22 August 2002.
source: http://www.sciencedirect.com/science/article/pii/S0920586103004127
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Chemical Engineering Journal
Volume 306, 15 December 2016, Pages 131–138
Cover image
Synthesis and oxidative desulfurization of novel lactam-based Brønsted-Lewis acidic ionic liquids
Huawei Yang,
Bin Jiang,
Yongli Sun, ,
Li Hao,
Zhaohe Huang,
Luhong Zhang
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People’s Republic of China
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, People’s Republic of China
Highlights
•
A novel kind of Brønsted-Lewis acidic ILs was developed.
•
The ILs were investigated in ODS process and exhibited highly efficient catalytic performance.
•
S-content in diesel was reduced to less than 10 ppm through a one-step ODS.
•
Multi-phase systems consisted of water, oil and ILs were investigated.
Abstract
Novel Brønsted-Lewis acidic ionic liquids having a protonated N-octylcaprolactam-based cation and Cl/nZnCl2 anion (n = 1, 2 and 3) were synthesized and investigated as catalysts in the oxidative desulfurization (ODS) of both model oil and real diesel fuel, with hydrogen peroxide (H2O2, 30 wt%) as oxidant. It is observed that the ODS performance increases significantly with the increase of ZnCl2 proportion. Then detailed experiments for the ODS of model oil were carried out with [Hnoc]Cl/3ZnCl2 to investigate the influence of some important factors, including reaction temperature, molar ratio of H2O2/S, ILs dosage, initial S-content and sulfide species. It is worth noting that, with the mass ratio of ILs/oil of only 1:20, satisfactory conversion rate can also be achieved for the removal of dibenzothiophene (DBT), and the ILs were used for six cycles without a noticeable decrease in activity. What is more important, the ILs can reduce the S-content of a real diesel from 559.7 ppm to 8.2 ppm with 98.5% sulfur removal rate and 96.3% diesel recovery through a one-step ODS process. Deduced from the GC-PFPD spectra, almost all the original S-compounds and their oxidized products were completely converted and extracted, respectively. The outstanding desulfurization efficiency can be attributed to the good phase transfer property of the ILs.
Keywords
Brønsted-Lewis acidic ionic liquid;
Lactam-based ionic liquid;
ZnCl2-based ionic liquid;
Oxidative desulfurization;
Diesel fuel
source: http://www.sciencedirect.com/science/article/pii/S1385894716309901
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Applied Catalysis B: Environmental
Volume 63, Issues 1–2, 22 March 2006, Pages 85–93
Cover image
A novel oxidative desulfurization process to remove refractory sulfur compounds from diesel fuel
Jeyagowry T. Sampanthar, ,
Huang Xiao,
Jian Dou,
Teo Yin Nah,
Xu Rong,
Wong Pui Kwan
Applied Catalysis Technology Group, Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research (A*STAR), No. 1, Pesek Road, Jurong Island, Singapore 627833, Singapore
Abstract
Manganese and cobalt oxide catalysts supported on γ-Al2O3 have been found to be effective in catalyzing air oxidation of the sulfur impurities in diesel to corresponding sulfones at a temperature range of 130–200 °C and atmospheric pressure. The sulfones were removed by extraction with polar solvent to reduce the sulfur level in diesel to as low as 40–60 ppm. Oxidation of model compounds showed that the most refractory sulfur compounds in hydrodesulfurization of diesel were more reactive in oxidation. The oxidative reactivity of model impurities in diesel follows the order: trialkyl-substituted dibenzothiophene > dialkyl-substituted dibenzothiophene > monoalkyl-substituted dibenzothiophene > dibenzothiophene.
Keywords
Oxidative desulfurization;
Diesel;
Sulfur;
Catalyst;
MnO2/γ-Al2O3;
Co3O4/γ-Al2O3;
Solvent extraction
source: http://www.sciencedirect.com/science/article/pii/S0926337305003358
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Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004, 49(2), 577
Oxidative Desulfurization: A New Technology For Ulsd
Ron Gatan, Paul Barger, and Visnja Gembicki
UOP LLC, Des Plaines, Illinois, USA
Agostino Cavanna
Eni S.p.A. Refining and Marketing Division, Rome, Italy
Daniele Molinari, EniTecnologie S.p.A., Milan, Italy
Abstract
Oxidative desulfurization is an innovative technology that can be used to reduce the cost of producing ultra-low sulfur diesel (ULSD). The key to successful implementation of this technology in most refinery applications is effectively integrating the oxidative desulfurization unit with the existing diesel hydrotreating unit in a revamp situation. The economics of applying oxidative desulfurization technology are dependent on the operating pressure of the existing hydrotreating capacity. A case study has been developed to illustrate how this innovative new route can be effectively utilized as an alternative to revamping existing hydrotreaters.
Introduction
Regulations regarding the sulfur content of motor fuels continue to be enacted worldwide in response to the need for cleaner air. Today, most industrialized countries have regulations in place to reduce diesel fuel sulfur to either 15 or 10 ppm by 2009. Developing countries are progressing environmental quality improvement programs as well, with most electing to enact fuel quality regulations similar to those in place in Europe. Refiners will meet the challenge of these new regulations at a significant cost. Technology licensors and catalyst manufacturers have continued to progress conventional hydro-desulfurization technology to reduce the capital and operating expense required. Revamping existing intermediate and lower pressure units will typically require addition of significant catalyst volume and equipment modifications to increase the hydrogen purity and circulation rate. However, there is a limit to the cost reduction that can be achieved as hydro-desulfurization (HDS) chemistry requires elevated temperature and pressure for deep desulfurization and, of course, consumes hydrogen in the process. Hydro-desulfurization also cannot readily achieve the very low sulfur levels envisaged for future “zero sulfur” fuels. There are alternatives to using conventional hydrotreating technology for producing ULSD, including biodesulfurization, physical separation, and oxidative desulfurization. Both biodesulfurization and physical separation processes have not been shown to be economically viable on a commercial scale. Oxidative desulfurization technology, however, has progressed to the state where it is nearing commercialization. Oxidation chemistry represents an alternative route to diesel desulfurization that complements HDS chemistry. The integration of an oxidative desulfurization unit with a conventional hydrotreating unit can improve the economics of these regulations-driven projects relative to current HDS technology. Eni S.p.A. recognized the advantages of lower capital and operating cost that oxidative desulfurization can offer and started research efforts to develop new catalysts. UOP LLC had previously developed process technology for integrating oxidative desulfurization units with hydrotreating units that could be applied to the new catalysts.1,2 In 2002, EniTecnologie S.p.A. and UOP LLC embarked on a collaborative research effort that combined each company’s catalyst and process technology expertise to develop the UOP/Eni Oxidative Desulfurization Process, a new sustainable oxidative desulfurization technology that is targeted for commercialization in 2005. The question that needs to be addressed is how best to meet future low sulfur fuel regulations such as the upcoming off-road diesel specifications in the United States and the potential for “zero sulfur” fuels at some point in the future. The preference has been to make the most with what is available, and a revamp solution is preferable to building new units. Hydrotreating is expensive, particularly for an existing low pressure unit. These units generally have been revamped to meet ULSD specifications by adding a large quantity of catalyst and reducing the available operating cycle. Hydrogen consumption is increased at the higher severity needed for ULSD, which can result in product quality give-away in some instances. The spent catalyst from these units represents a solid waste disposal issue, which combined with the additional CO2 emissions associated with increased hydrogen demand, points to the need for a more sustainable technology. A typical feedstock will contain about 30% LCO or other cracked blendstocks, with the balance being straight run diesel. Substantially higher severity is required to produce ULSD in intermediate and low pressure units. A summary of the process conditions typically required for modern HDS catalysts is shown in Table 1. Generally, a significant increase in catalyst volume is required, combined with a shorter process cycle and higher hydrogen circulation.
source: https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/49_2_Philadelphia_10-04_1055.pdf
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New Approaches To Deep Desulfurization For Ultra-Clean Gasoline And Diesel Fuels: An Overiview
Fuel Chemistry Division Preprints 2002, 47(2), 440
Fuel Science Program, Dept. of Energy and Geo-Env. Engg., The Pennsylvania State University, University Park, PA 16802
*E-Mail: csong@psu.edu
1. Introduction
The U.S. Clean Air Act Amendments of 1990 and new regulations by the U.S. EPA [EPA Gasoline-RIA, 1999; EPA Diesel-RIA, 2000; EPA RFG, 1999] and government regulations in many countries call for the production and use of more environmentally friendly transportation fuels with lower contents of sulfur and aromatics. In the mean time, the demand for transportation fuels has been increasing in most countries for the past two decades. The total U.S. consumption of petroleum products reached 18.68 million barrels per day (MBPD) in 1998. Of the petroleum consumed, 8.20 MBPD was used as motor gasoline, 3.44 MBPD as distillate fuels (including diesel fuels and industrial fuels), 1.57 MBPD as jet fuels, 0.82 MBPD as residual fuel oil, and 1.93 MBPD as liquefied petroleum gas (LPG), and 2.72 for other uses [EIA/AER, 1999]. Clean fuels research including desulfurization and dearomatization has become an important subject of environmental catalysis studies worldwide. Figure 1 presents a qualitative relationship between the size and type of sulfur molecules in various distillate fuel fractions and their relative reactivities. The reactivity ranking in Figure 1 is based on our experimental observations and a large amount of literature information [Knudsen et al., 1999; Whitehurst et al., 1998; Song et al., 2000]. With the new EPA Tier II regulations to cut the diesel sulfur from current 500 ppmw down to 15 ppmw by June 2006 and sulfur reduction from current 350 ppm to 30 ppm by 2005-2006, refineries are facing major challenges to meet the fuel sulfur specification along with the required reduction of aromatics contents. The problem of deep removal of sulfur has become more serious due to the lower and lower limit of sulfur content in finished gasoline and diesel fuel products by regulatory specifications, and the higher and higher sulfur contents in the crude oils. A survey of the data on crude oil sulfur content and API gravity for the past two decades reveals a trend that U.S. refining crude slates continue towards higher sulfur contents and heavier feeds [Swain, 1991, 1998]. The average sulfur contents of all the crude oils refined in the five regions of the U.S. known as five Petroleum Administration for Defense Districts (PADDs) increased from 0.89 wt% in 1981 to 1.25 wt% in 1997, while the corresponding API gravity decreased from 33.74° in 1981 to 31.07° in 1997. In 2000, the average crude feeds to US refineries has 1.35 wt% sulfur and 31.0° API gravity, whereas European refinery feed by comparison was sweeter at 1 wt% sulfur and 35 ° API gravity [Lawson, 2001]
source: https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/47_2_Boston_10-02_0295.pdf
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Oil Shale, 2006, Vol. 23, No. 2, pp. 164–176
$$Advances In Desulfurization Research Of Liquid Fuel
H. Rang, J. Kann, V. Oja*
Institute of Chemical Engineering at Tallinn University of Technology, Estonia
Abstract
The new requirements for sulfur content in liquid fuels demand the use of novel deep desulfurization processes. 4-methyldibenzothiophene, 4,6- dimethyldibenzothiophene and their alkyl-substituted derivatives are the key substances that need to be separated from diesel fuel and fuel oil. These compounds require higher hydrogen consumption in the hydrodesulfurization process and the use of additional infrastructure in the treatment facility. The common hydrogenation catalysts are not very effective for the hydrogenization of these compounds, and new innovation for catalysts is required. The desulfurization of fuel oil obtained from oil shale is also becoming important and has different technological needs than other fuels. This paper critically discusses the non-hydrodesulfurization processes for liquid fuels, such as extraction, oxidation, and adsorption. These processes, their development, and recent advances in this research field are briefly evaluated as possible deep desulfurization methods.
Introduction
In Europe the sulfur level in max mass% for liquid fuels is presently limited at 0.015, 0.035, and 0.2 for petrol (gasoline), diesel fuel, and light fuel oil, respectively [1]. New sulfur limits of 0.003–0.005 mass% (30–50 ppm) for petrol and diesel fuel will be introduced in the European community and USA in coming years [2, 3]. The current technology of hydrodesulfurization is quite adequate for the present standards [3], however the hydrotreating process is limited to the production of ultra-low sulfur fuels, and the consumptions are too high to meet future requirements. It must be emphasized that desulfurization processes are also essential for the production of fuel oil from oil shale and for oil obtained by the utilization of used tires. The authors of this paper are working in the last field. Although the desulfurization of non-transportation fuels in stationary applications can be realized in emissions by binding up sulfur oxide with calcium oxide [4], problems with the utilization of the obtained toxic compounds remain. Therefore the desulfurization processes of fuel oils are of current interest. Requirements for sulfur content will approach extremely low levels, preferably even zero content, in the near future [3], forcing intensive research into alternative technologies. One confounding factor in this research is that the reactivity to hydrodesulfurization of organosulfur compounds in liquid fossil fuels varies widely. In diesel fuel and fuel oil fractions 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene and other alkyl-substituted derivatives of dibenzo-thiophene are relatively inert to hydrotreating [5]. The conventional reaction model of hydrodesulfurization of diesel fuel and fuel oil does not work effectively in the ultra-deep desulfurization range down to sulfur content 100 ppm or less. The catalyst volumes must be three times more in the case of 50 ppm, and four times more if the aim is to reach the final sulfur content of 30 ppm [6]. A thorough survey concerning the reactivity of sulfur compounds is given by Cremlyn [7]. Hydrotreating processes are not discussed in this paper as many monographs [7–10] and papers [11–14] on the subject are available. This paper discusses the non hydrodesulfurization processes, such as, extraction, oxidation, adsorption, the combination of these processes, and the combination of these processes with hydrodesulfurization to reduce the consumption of hydrogen. The development of the mentioned processes is given, along with a discussion of recent studies in this field.
source: http://www.kirj.ee/public/oilshale/oil-2006-2-9.pdf
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From the journal:
RSC Advances
Issue 36, 2016, Issue in Progress
A simple and cost-effective extractive desulfurization process with novel deep eutectic solvents
Xin Wang,a Wei Jiang,b Wenshuai Zhu,*a Hongping Li,a Sheng Yin,a Yonghui Changac and Huaming Li*b
Author affiliations
* Corresponding authors
a School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, P. R. China
E-mail: zhuws@ujs.edu.cn
Fax: +86-511-88791708
Tel: +86-511-88791800
b Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, P. R. China
E-mail: lihm@ujs.edu.cn
c School of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, P. R. China
Abstract
Deep eutectic solvents (DESs), a new class of ionic liquid (IL) analogues, are easily produced through mixing Lewis or Brønsted acid and base. In this study, a class of DESs was prepared by mixing low cost triethylamine and organic acid with different molar ratios. It was found that the base/acid molar ratio (B/A) played an outstanding role in the solubility and extractive ability of DESs. When B/A was 1:3 and 1:5, the loss of DESs in model oil was even less than 0.003%. Take the DES with B/A = 1:3 for example, the extraction ability of DESs showed the following order [TEtA][Pr] > [TEtA][Ac] > [TEtA][Fo], which could be explained by 1H NMR analysis. The extractive mechanism was also discussed by density functional theory (DFT) calculations. The sulfur partition coefficient (KN) was 2.14 using [TEtA][Pr] as the extractant, and the sulfur content could be reduced from 500 ppm to 10 ppm after four times extraction.
source: http://pubs.rsc.org/-/content/articlelanding/2016/ra/c5ra27266a#!divAbstract
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Hernández-Maldonado, A. J. and Yang, R. T. (2004), New sorbents for desulfurization of diesel fuels via π-complexation. AIChE J., 50: 791–801. doi:10.1002/aic.10074
New sorbents for desulfurization of diesel fuels via π-complexation
Volume 50, Issue 4
April 2004
Pages 791–801
Abstract
Desulfurization of a commercial diesel fuel by different adsorbents was studied in a fixed-bed adsorber operated at ambient temperature and pressure. In general, the adsorbents tested for total sulfur adsorption capacity at breakthrough followed the order: AC/Cu(I)-Y > Cu(I)-Y > Selexsorb® CDX (alumina) > CuCl/γ-Al2O3 > activated carbon > Cu(I)-ZSM-5. The best adsorbent, AC/Cu(I)-Y (layered bed of 15 wt % activated carbon followed by Cu(I)Y), is capable of producing 30 cm3 of diesel fuel per gram of adsorbent with a weighted average content of 0.15 ppmw-S, and about 20 cm3 of diesel fuel per gram of adsorbent with a weighted average content of 0.06 ppmw-S. These low-sulfur fuels are suitable for fuel cell applications. The added layer of carbon not only delayed the sulfur breakthrough significantly but also sharpened the sulfur wavefronts. GC-FPD results showed that the π-complexation sorbents selectively adsorbed highly substituted thiophenes, benzothiophenes, and dibenzothiophenes from diesel, which is not possible with conventional hydrodesulfurization (HDS) reactors. The high sulfur selectivity and high sulfur capacity of Cu(I)Y were because of π-complexation.
source: http://onlinelibrary.wiley.com/doi/10.1002/aic.10074/abstract
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