Ten for 10 … The 10 most popular posts since the Desulf Blog began 10 years ago

Unbelievable … in March, 2019, the Desulfurization Blog will be 10 years old. In celebration of that fact, here is a list of the top 10 posts since March, 2009.

Caveat … the Web is an ever changing organism. While I have done my best to review the links in the following posts, some of them may be obsolete.

Post Title	Post Date
Murray Gray, Specializing in Canada Oil Sands Research	May 1, 2009
UPDATE: Since the publication of this post, Dr. Gray, who was the scientific director for the Institute for Oil Sands Innovation until summer of 2014, retired from the University of Alberta and became Professor Emeritus. He is not accepting any new graduate students or post-doctoral fellows. Source https://www.ualberta.ca/chemical-materials-engineering/faculty-and-staff-new/professors-emeriti/murray-gray
Google Scholar: Desulfurization at Saudi Aramco	January 1, 2011
Here is something you can do to improve your online research results … Let’s say you’re interested in recent published results of Saudi Aramco’s desulfurization activities. But you’re interested in substance, not news. Try the TIPS offered in this post.
Revisiting a LinkedIn Discussion	October 27, 2010
Not all LinkedIn groups are created equal. Some are little more than infomercials. Others are a mix. The Oil Refining Global Technology Forum is a mix. UPDATE: A recent search on the Oil Refining Global Technology Forum resulted in the following message: ***THIS PAGE IS NO LONGER UP TO DATE: Please join our other group 'Oil Refining: World Refining Association'​ ***
ChevronTexaco, Vacuum Resid Slurry Hydrocracking (VRSH)	November 13, 2009
A few posts ago I highlighted Sulphco’s efforts to commercialize its Sonocracking™ desulfurization technology. As noted in the Wikinvest article on Sulphco, “Major companies like Merichem, ChevronTexaco (CVX) , CONOCOPHILLIPS (COP) and other large oil producers have been actively pursuing their own versions of sonocracking.” However, even companies with such vast resources at their disposal can have setbacks. TIP: For current information on similar processes, Google® the phrase vacuum residue slurry hydrocracking
Why search more than one journal database: ACS v. ScienceDirect	March 29, 2010
Why search more than one journal database? Simple answer … because they cover different journals.
You’re an expert in something … let the rest of us know	June 8, 2010
Consider showing your expertise by following and participating in a LinkedIn® group. I do. I am not an expert in the technologies used in refining heavy oil. But I am an expert in searching for information on these technologies. So when I found the following post to the Heavy Oil group, I responded with a helpful comment
Case Study: Stay Alert … With Alerts	April 22, 2011
Online database vendors like EbscoHost, LexisNexis, and ScienceDirect work hard to make it easy for you to access their data.  Librarians and other information professionals work hard to make your people aware of the resources and how to use them.
iGoogle Tool: Arabic Keyboard	March 1, 2010
Foreign languages have fascinated me since I was a kid. So every once in a while, I use the Arabic Keyboard, an iGoogle tool, to type in words I have found as I search the Internet for useful desulfurization items. Of course, I can’t read the resulting pages, and the Google® translation is sometimes bizarre. But if you are fluent in the language, you might try it out. UPDATE: iGoogle was discontinued November 2013. TIP: To find an Arabic keyboard, visit: http://www.arabic-keyboard.org/
More Free Stuff ... 16 Desulfurization Articles	June 26, 2011
It is nearly impossible to find quality technical articles for free these days … nearly, but not entirely.  Here are 16 items I found recently.  Browse through and pick out the ones you like. NOTE: The Web changes over time. Some of the links in this post may no longer work. TIP: Try Googling an article title. It may lead you to the current location of the free full text.
Ionic Liquids Update	September 14, 2011
Today’s tip … if you don’t have time to browse the Web, consider hiring someone else to do so.  Jean Steinhardt Consulting specializes in blogs customized for your particular organization.  Pick a topic, and we will design a blog to follow that topic … and to provide tips and tricks to your colleagues on how to improve their research results, no matter what the technology

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Jean Steinhardt served as Librarian, Aramco Services, Engineering Division, for 13 years. He now heads Jean Steinhardt Consulting LLC, producing the same high quality research that he performed for Aramco.

Follow Jean’s blog at: http://desulf.blogspot.com/  for continuing tips on effective online research
Email Jean at research@jeansteinhardtconsulting.com  with questions on research, training, or anything else
Visit Jean’s Web site at http://www.jeansteinhardtconsulting.com/  to see examples of the services we can provide

What Do Patents & Hindawi Have in Common? They’re Both Free!

“Why can we remember the tiniest detail that has happened to us, and not remember how many times we have told it to the same person.” -- François de la Rochefoucauld (French classical author, leading exponent of the Maxime, 1613-1680)

Two free full text desulfurization items of interest … a patent, and an article from the amazing Hindawi (http://www.hindawi.com/) open access journals database.

Details below …
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PATENT
Desulfurization of hydrocarbons by Ionic liquids and preparation of ionic liquids (Instituto Mexicano Del Petroleo)
Publication number
US20130118955 A1
Publication type
Application
Application number
US 13/733,173
Publication date
May 16, 2013
DE102009022284A1, US20090288992
Inventors
Natalya Victorovna Likhanova, Rafael Martinez Palou, Jorge Froylan Palomeque Santiago
Original Assignee
Instituto Mexicano Del Petroleo
Abstract
The present invention relates to an improved desulfurization process using an ionic liquid compound of general formula C+A−, where C+ represents an organic cation such as alkyl-pyridinium, di-alkyl imidazolium and tri-alkyl imidazolium; and A− is an anion of halides of iron (III), such as, for example, FeCl4 −. The desulfurization process is also improved when producing the ionic liquid compound by heating the reactants using microwave energy. The ionic liquids can be used to desulfurize hydrocarbon mixtures by a liquid-liquid extraction.
FIELD OF THE INVENTION
This invention provides a process for the synthesis of ionic liquids which can be used for the efficient removal of sulfur compounds from hydrocarbon mixtures. The ionic liquids related are insoluble in hydrocarbons but are able to dissolve aliphatic and aromatic sulfur compounds. Thus, the ionic liquids can be used for removal of sulfur compounds by a liquid-liquid extraction process at room temperature and pressure. The invention is also directed to a process for extracting sulfur from a hydrocarbon liquid by contacting the hydrocarbon with the ionic liquid.
More preferably, this invention is related to the synthesis of ionic liquids with general formula C+A−, where C+ is an organic cation preferably but not exclusively alkyl pyridinium, dialkylimidazolium, and trialkylimidazolium, the anion A− is preferably halogen ferrate (III), particularly Cl*FeCl3 − and Br*FeCl3. The invention is also directed to the process for the extraction of sulfur-containing compounds, such as sulfur compound that are present in gasoline and Diesel as contaminant obtained in petroleum refining processes by contacting with the ionic liquids.
BACKGROUND OF THE INVENTION
The production of gasoline according with the new European Environmental Standards requires that the refiners to lower the sulfur content in gasoline to values that are lower than 50 ppm since 2005. For example in Germany he content of sulfur in gasoline should be lower than 10 ppm. For the case of USA the content of sulfur is limited to lowest than 80 ppm and with average of 30 ppm. In attention to this claims, PEMEX Refining should be produce gasoline with sulfur content between 15 and 30 ppm for the years 2008-2010.
The classic method used for sulfur removal in Refining Processes is the catalytic Hydrodesulfurization (HDS technology) at high temperature and pressure. This method is very costly process that required drastic operation conditions and it is inefficient to reduce aromatic sulfur compounds especially for Mexican heavy crude oil, so is more reasonable the use of alternative desulfurization process. For increasing the efficiency of HDS process some technology modification are required such as the addition of other catalytic bed, more efficient catalyst, higher temperature and pressures and to reduce LHSV to expense of few processing capacity.
New technologic lines have been develop on in several countries in order to resolve this problem (Zaczepinski, S. Exxon, Diesel Oil Deep Desulfurization (DODD) in Handbook of Petroleum Refining Processes, ed. R. A. Meyer, Mc Graw-Hill, NY, 1996, Ch. 8.7), i.e.: the absorption of sulfur compounds over solid absorbents, like IRVAD® process (U.S. Pat. No. 5,730,860, dated Mar. 24, 1998) from Black & Veatch Pritchard Inc.; the process S-Zorb® from Phillips Petroleum (http://www.eia.doe.gov/oiaf/servicerpt/ulsd/uls.html), the process Haldor Topsoe (EP 1057879, dated Dec. 6, 2000); and the liquid-liquid extraction with volatile organic solvents (Petrostar Refining, 217 National Meeting, American Chemical Society, Anaheim, Calif., Marzo, 1999). An original process is the oxidative desulfurization with different oxidant agents (Unipure Corp., NPRA Meeting No AM-01-10, Marzo 2001; Sulphco Corp, NPRA Meeting No AM-01-55, March 2001; BP Chemicals UK, Journal of Molecular Catalysis A: Chemical (1997) 397-403; UOP LLC, U.S. Pat. No. 6,171,478, dated Jan. 9, 2001; EXXON Research and Engineering Co., U.S. Pat. No. 5,910,440, dated Jun. 8, 1999; U.S. Patent Publication No. 2002/0035306 A1 with publication date of Mar. 21, 2002; U.S. Pat. No. 6,596,914 B2, dated Jul. 22, 2003; U.S. Pat. No. 6,406,616, dated Jun. 18, 2002 and U.S. Pat. No. 6,402,940 B1 dated Jun. 11, 2002; Fuel 82 (2003) 4015; Green Chemistry 5 (2003) 639). Recently the extraction of sulfur-containing compounds using liquid-liquid extraction employing ionic liquids have been welcome by scientific community.
Ionic liquids are known for more than 30 years, but their industrial applications began in the last 10 years (Rogers, R. D.; Seddon, K. R (Eds.), Ionic Liquids: Industrial Applications of Green Chemistry, ACS, Boston, 2002). They are applied as solvents and catalyst in alkylation reactions, polymerization and Diels-Alder cycloaddition. In addition they are employed in electrochemical processes, in supercritical CO2 extraction of aromatic compounds and sulfur compounds in hydrocarbon mixtures. One of the first publications mention the use of ionic liquids for the removal of mercaptans (WO 0234863, dated May 2, 2002). The patented method is based on the use of sodium hydroxide in combination with ionic liquids for the conversion of mercaptans to mercaptures, which were removed using ionic liquids. Peter Wassercheid and coworkers published several papers and patents between 2001 and 2005 about the use of ionic liquids for desulfurization of gasolines (Chem. Comun. (2001) 2494; WO 03037835, with publication date of 2003 May 8; U.S. Publication No. 2005/0010076 A1, published Jan. 13, 2005). In these works the authors employed ionic liquids with C+ being 1,3-dialkylimidazolium or tetralkylammonium, and A− being tetrachloroaluminates or methanesulfonates. By means of a process with several extractions (up to 8 extractions), high extraction of sulfur compounds were achieved using model gasolines. However these kinds of compounds are air and moisture sensitive and a polymerization reaction was observed during the extraction process. U.S. Patent Publication No. 2003/0085156 A1 published May 8, 2003 and U.S. Pat. No. 7,001,504, dated Feb. 21, 2006, also mention the use of ionic liquids, where C+ is an ammonium o fosfonium and quaternary, A− being tetrachloroaluminates for the extraction of sulfur from model gasoline. In the paper published in Energy & Fuels 18 (2004) 1862, the use of ionic liquids containing Copper chloride (I) anion with the same application, and in the papers Ind Eng. Chem. Res. 43 (2004) 614 and Ind. Eng. Chem. Res. 46 (2007) 5108-5112) several ionic liquids were evaluated for the extraction of sulfur and nitrogen-containing compounds. More recently, some papers (Energy & Fuels 20 (2006) 2083-2087; Green Chemistry 8 (2006) 70-77; Progress in chemistry 19 (2007) 1331-1344; Green Chemistry 10 (2008) 87-92) also report the use of IL for desulfurization processes. U.S. Patent Publication No. 2004/00445874 A1, published Mar. 11, 2004, discloses a procedure for desulfurization and denitrogenation of hydrocarbons fractions using a wide family of ionic liquids and alkylations agents with high efficiency in some cases.
SUMMARY OF THE INVENTION
The present invention is directed to the use of ionic liquids containing halogens of Fe (III) as an anion for these purposes, where these compounds presented very high efficiency for extracting sulfur-containing compounds from gasoline, turbosin, diesel and other petroleum fractions. Another important and novel aspect of the invention is the use of microwave irradiation for synthesizing the ionic liquids suitable for use as extracting agents (symmetric and non-symmetric compounds) with a corresponding shorter time and higher yields in the synthesis of these ionic liquids compared to the conventional methods of synthesis.
The invention is also directed to a process for extracting sulfur and sulfur compounds from a sulfur-containing hydrocarbon liquid by contacting the hydrocarbon liquid with an ionic liquid of the invention for sufficient time to extract the sulfur and sulfur-containing compounds, and thereafter recovering the hydrocarbon liquid.
The ionic liquids of the invention comprise a heterocyclic cation and an iron (III) halide. The heterocyclic cation is an imidazolium compound having at least one C1-C10 alkyl group or alkoxy group where the alkyl group and alkoxy group can be linear, branched, substituted or unsubstituted. The heterocyclic cation can be symmetrical or asymmetrical.
Free Full Text Source: http://www.google.com/patents/US20130118955

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International Journal of Chemical Engineering, Volume 2013, Article ID 951045, 10 pages, http://dx.doi.org/10.1155/2013/951045
Investigation of Influential Parameters in Deep Oxidative Desulfurization of Dibenzothiophene with Hydrogen Peroxide and Formic Acid
Alireza Haghighat Mamaghani, Shohreh Fatemi, andMehrdad Asgari
shfatemi@ut.ac.ir
School of Chemical Engineering, College of Engineering, University of Tehran, Enghelab Avenue, P.O. Box 11155-4563, Tehran 11155-4563, Iran
Abstract
An effective oxidative system consisting of hydrogen peroxide, formic acid, and sulfuric acid followed by an extractive stage were implemented to remove dibenzothiophene in the simulated fuel oil. The results revealed such a great performance in the case of H2O2 in the presence of formic and sulfuric acids that led to the removal of sulfur compounds. Sulfuric acid was employed to increase the acidity of media as well as catalytic activity together with formic acid. The oxidation reaction was followed by a liquid-liquid extraction stage using acetonitrile as a polar solvent to remove produced sulfones from the model fuel. The impact of operating parameters including the molar ratio of formic acid to sulfur (nF/nS), hydrogen peroxide to sulfur (nO/nS), and the time of reaction was investigated using Box-Behnken experimental design for oxidation of the model fuel. A significant quadratic model was introduced for the sulfur removal as a function of effective parameters by the statistic analysis.
Using hydrogen peroxide with an acid has been widely investigated by several researchers. However, to the best knowledge of the authors, there are few studies which are concerned with optimizing the process parameters. The objective of the present work is to develop an efficient system for oxidative desulfurization of model fuel. ODS of dibenzothiophene (DBT) in n-octane as simulated fuel was performed in the presence of H2O2, formic acid, and H2SO4 as the oxidation system. After the oxidation step, a twostep liquid-liquid extraction with acetonitrile was applied to remove the oxidated sulfur compounds from the model fuel. Influences of operating conditions including H2O2/S molar ratio, acid formic/S molar ratio, oxidation duration time, and mediumaciditywere examined.Theextraction step was carried out at the same conditions in all experiments. Box-Behnken experimental design was implemented as a kind of response surface methodology (RSM) to arrange the experiments and develop amodel to explain the relationships of sulfur removal and the studied parameters and finally optimize the operating conditions.
Free Full Text Source: http://www.hindawi.com/journals/ijce/2013/951045/abs/

Why use DOIs?

“There are evils that have the ability to survive identification and go on forever... money, for instance, or war.” -- Saul Bellow (Canadian born American Novelist, 1915-2005)

A DOI, or Digital Object Identifier, is to a Web document what ISBN, International Standard Book Number, is to printed books.  It is a registered, unique identifier of a work.

This means that when you find an article of interest and include the DOI in your cite, readers will be able to locate the article no matter how the URL changes in the meantime.

For example, let’s say you find the following article …

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Petroleum Science and Technology, Volume 30, Issue 15, 2012, pages 1619-1628, DOI:10.1080/10916466.2010.509071
Desulfurization From Model of Gasoline by Extraction With Synthesized [BF4]−- and [PF6]−-based Ionic Liquids
N. Farzin Nejad a,b, E. Shams b, M. Adibi c, A. A. Miran Beigi a & S. K. Torkestani a
a Analytical Department, Research Institute of Petroleum Industry, Tehran, Iran
b Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan, Iran
c Chemistry and Petrochemicals Division, Research Institute of Petroleum Industry, Tehran, Iran
Abstract
Reports the synthesis and testinf of 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF₄], and 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], ionic liquids for their capability to desulfurize model gasoline.
Results demonstrate that the aromatic sulfur compounds with higher π-electron density were favorably adsorbed. They also show that [BF₄]⁻-based ionic liquid displays higher extraction efficiencies than [PF₆]⁻-based ionic liquid. The extractive ability of the imidazolium ionic liquids was dominated by the structure of cation and anion.
Full Text Source (Subscription or Fee): http://www.tandfonline.com/doi/abs/10.1080/10916466.2010.509071
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In this example, the URL for the article is: http://www.tandfonline.com/doi/abs/10.1080/10916466.2010.509071

But what if Taylor & Francis does a radical reorg of its Web, and the URL changes?  Or, what if Taylor & Francis ceases to exist, and some other publisher inherits the article?

If you have the DOI, you will be able to find the article with minimal effort.  So, in this example, if you paste DOI:10.1080/10916466.2010.509071 into the Google search box, it will lead you directly to the article.

More information on the DOI concept is available at the Bowker DOI Web: http://www.usdoi.org/index.php?page=why_use_DOI

A Few More Ionic Liquids

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“I think it's liquid aggravation that circulates through his veins, and not regular blood” -- Charles Dickens (English novelist, 1812-1870)

Here are four more articles on ionic liquids, all available on the Web at no charge …

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Separation and Purification Technology (2012)
Preparation and characterization of ionic liquid polymer microspheres [PEEKWC/DMF/CYPHOS IL 101] using the phase-inversion technique
D. Shanthana Lakshmi a, A. Figoli a,⇑, G. Fiorani b, M. Carraro b, L. Giorno a, E. Drioli a
a Institute on Membrane Technology (ITM-CNR), c/o University of Calabria, Via P. Bucci, 17/c, I-87030 Rende, CS, Italy
b ITM CNR, Section of Padova and Department of Chemical Sciences, University of Padova, via Marzolo, 1, 35131 Padova, Italy
Abstract
The membrane process concept coupled with phase inversion technique has been successfully applied for the first time for the preparation of ionic liquid (IL) encapsulated microspheres using polyetheretherketone with card group (PEEKWC), trihexyl(tetradecyl)phosphonium chloride[CYPHOS IL 101] in N,Ndimethylformamide (DMF) as dispersing phase and dodecane, ethanol and water as continuous phases. The technique yields porous, spongy, spheres with smooth surface and diameter around 1000 lm, with morphology and chemical composition strongly affected by preparative conditions. IL loading capacity and subsequent surface topography has been investigated using optical microscopy, FT-IR, SEM, EDX, TGA and SDT.
Free Full Text Source: http://www.researchgate.net/publication/221966813_Preparation_and_characterization_of_ionic_liquid_polymer_microspheres_PEEKWCDMFCYPHOS_IL_101_using_the_phase-inversion_techniqueD._Shanthana_Lakshmi_a_A._Figoli_a_G._Fiorani_b_M._Carraro_b_L._Giorno_a_E._Drioli_a/file/f2faf4f75700495fb6.pdf

International Workshop on Ionic Liquids– Seeds for New Engineering Applications, 2-3 February 2012, Lisbon, Portugal
Ionic Liquids As Thermal Fluids: Feasibility Study Of Itsapplication On A Heat Exchanger Of A Plastic Production Machine
T.I.L. Antunes 1, L.M.L. Mendes 1, C. A. Nieto de Castro 2,3 and V. M. B. Nunes 1,3*
valentim@ipt.pt
1 Escola Superior de Tecnologia, Instituto Politécnico de Tomar, Campus da Quinta doContador, 2300-313 Tomar, Portugal
2 Departamento de Química e Bioquímica Faculdade de Ciências da Universidade deLisboa, Campo Grande, 1749-016 Lisboa, Portugal
3 Centro de Ciências Moleculares e Materiais, Faculdade de Ciências - Universidade deLisboa, Campo Grande, 1749-016 Lisboa, Portugal*
Introduction:
Authors evaluate the viability of replacing the conventional thermal oil used in a heat exchanger of a plastic production machine, by an ionic liquid of known properties. Thermal fluids have many industrial applications covering all aspects from unit operations to chemical processes.
Free Full Text Source: http://scholar.googleusercontent.com/scholar?q=cache:cHJLqtoMwzYJ:scholar.google.com/+%22ionic+liquids%22++AND+(refinery+OR+refining+OR+hydrocarbon+OR+petroleum+OR+oil)&hl=en&as_sdt=0,14&as_ylo=2012&as_yhi=2012

PATENT
Process For Removing Metals From Hydrocarbons
Pub. No.:    WO/2012/046057   
International Application No.:    PCT/GB2011/051906
Publication Date:  12.04.2012
Applicants: 
The Queen's University Of Belfast [GB/GB]; University Road Belfast Antrim BT7 1NN (GB)
Inventors: 
ABAI, Mahpuzah; (GB).
ATKINS, Martin Philip; (GB).
CHEUN, Kuah Yong; (GB).
HOLBREY, John; (GB).
NOCKEMANN, Peter; (GB).
SEDDON, Ken; (GB).
SRINIVASAN, Geetha; (GB).
ZOU, Yiran; (GB) 
Abstract:  
The present invention relates to a process for the removal of mercury from a mercury- containing hydrocarbon fluid feed using specifically selected ionic liquids comprising, contacting the mercury-containing hydrocarbon fluid feed with an ionic liquid having the formula[Cat+][M+][X-] and separating from the ionic liquid a hydrocarbon fluid product having a reduced mercury content compared to the mercury-containing fluid feed.
Free Full Text Source: http://patentscope.wipo.int/search/en/WO2012046057

Bull. Korean Chem. Soc. 2012, Vol. 33, No. 7 2325
Equimolar Carbon Dioxide Absorption by Ether Functionalized Imidazolium Ionic Liquids
Pankaj Sharma, Sang Do Park,† Ki Tae Park, Soon Kwan Jeong, Sung Chan Nam, and Il Hyun Baek*
ihbaek@kier.re.kr
Greenhouse Gas Research Center, Korea Institute of Energy Research.
†Korea Carbon Dioxide Capture & Sequestration R&D Center, Daejeon 305-343, Korea
Abstract
A series [C3Omim][X] of imidazolium cation-based ILs, with ether functional group on the alkyl side-chain were synthesized and structure of the materials were confirmed by various techniques like 1H, 13C NMR spectroscopy, MS-ESI, FTIR spectroscopy and EA. More specifically, the influence of changing the anion with same cation is carried out. The absorption capacity of CO2 for ILs were evaluated at 30 and 50 ºC at ambient pressure (0-1.6 bar). Ether functionalized ILs shows significantly high absorption capacity for CO2. In general, the CO2 absorption capacity of ILs increased with a rise in pressure and decreased when temperature was raised. The obtained results showed that absorption capacity reached about 0.9 mol CO2 per mol of IL at 30 ºC. The most probable mechanism of interaction of CO2 with ILs were investigated using FTIR spectroscopy, 13C NMR spectroscopy and result shows that the absorption of CO2 in ether functionalized ILs is a chemical process. The CO2 absorption results and detailed study indicates the predominance of 1:1 mechanism, where the CO2 reacts with one IL to form a carbamic acid. The CO2 absorption capacity of ILs for different anions follows the trend: BF4 < DCA < PF6 < TfO < Tf2N. Moreover, the as-synthesized ILs is selective, thermally stable, long life operational and can be recycled at a temperature of 70 ºC or under vacuum and can be used repeatedly.
Free Full Text Source: http://newjournal.kcsnet.or.kr/main/j_search/j_download.htm?code=B120737

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