On the Edge: Nanostructures

Nanotech is destined to impact desulfurization in a big way. How long it will take for current research to achieve commercial success is anyone’s guess … but it behooves anyone interested in reaping the benefits to pay attention to developments in the field. The abstract of the article “Chemistry of one-dimensional metallic edge states in MoS2 nanoclusters” provides useful nuggets of insight. For example, a sentence from the abstract states …

“The new chemistry identified in this work has significant implications for an important catalytic reaction, since MoS2 nanoclusters constitute the basis of hydrotreating catalysts used to clean up sulfur-containing molecules from oil products in the hydrodesulfurization process”

The cite for the article is …
Nanotechnology 14 (2003) 385–389
Chemistry of one-dimensional metallic edge states in MoS2 nanoclusters
J V Lauritsen1, M Nyberg2, R T Vang1, M V Bollinger2,
B S Clausen3, H Topsøe3, KWJacobsen2, E Lægsgaard1,
J K Nørskov2 and F Besenbacher1
1 Department of Physics and Astronomy, Centre for Atomic-ScaleMaterials Physics (CAMP)
and the InterdisciplinaryNanoscience Centre (iNANO), University of Aarhus,
DK-8000 Aarhus C, Denmark
2 Department of Physics and Centre for Atomic-ScaleMaterials Physics (CAMP),
Technical University of Denmark, DK-2800 Lyngby, Denmark
3 Haldor Topsøe A/S, Nymøllevej 55, DK-2800 Lyngby, Denmark
E-mail: fbe@phys.au.dk

View the full article at:
http://isis.ku.dk/kurser/blob.aspx?feltid=63018

The Technomics of Desulfurization

Technology is all well and good, but if the economics aren’t there, the technology will fail. A DOE funded report titled Distributed Hydrogen Fueling Systems Analysis provides hard numbers comparing various gasoline desulfurization technologies. Couched in the context of the movement toward a hydrogen economy powered by fuel cells, it is somewhat dated … and yet, the problem of commercializing deep desulfurization of gasoline persists.

To quote from the document …

“While gasoline is widely available in the industrialized nations, we expect that a new fuel cell grade of gasoline might be required to support fuel cell vehicles should onboard gasoline processors be developed. Therefore the oil industry might have to make new investments to reduce if not eliminate sulfur or other compounds that might damage or impair the performance of fuel processor or fuel cell catalysts. Another option would be to produce a new fuel such as synthetic gasoline, naphtha, diesel fuel or dimethylether (DME) made from natural gas – the “gas-to-liquids” pathway. These synfuels would contain negligible sulfur, and might also be used as a clean diesel substitute for compression ignition engines. “

The report also is useful for succinct descriptions and comparisons of the various technologies on the market …

“Mobil Octgain 125, Exxon Scanfining, and IFP Prime-G are similar in that they are fixed bed reactor technologies. They differ in approach in that the Octgain 125 process permits saturation of olefins, but recovers octane through isomerization and alkylation reactions within the process reactor, whereas Scanfining and Prime G reduce the severity of temperature and pressure and use catalyst selectivity to minimize octane loss. Where deep desulfurization is required, octane loss would be more extensive with certain of the technologies presented in Figure 31, resulting in higher processing costs than are presented here. The improved Octgain 220 is similar in approach to Octgain 125, but reduces costs by reducing the severity of processing conditions. However, its application is not intended for very high sulfur streams where deep sulfur conversion is required. CD-Tech uses a twin catalytic distillation reactor to proportionate more extensive hydrotreating to the heavier fraction of the FCC naphtha stream. The Black and Veatch adsorption process (IRVAD) uses twin reactor columns with a regenerable alumina adsorbent that is transported circuitously though the adsorber column and the regenerator column. The sulfur heteroatom-containing molecules are scavenged in the adsorber and released in the regenerator in a hydrogen environment. Black and Veatch claim negligible hydrogen consumption with a zero to moderate increase in octane value of the product. It should be noted, however, that the Black and Veatch (IRVAD) adsorption technology produces a ~10,000 ppm S heavy product stream that would also require desulfurization or further processing prior to blending in other product streams. These additional costs were not included, but may be important. In contrast, the Phillips S-Zorb process, which is also a proprietary adsorbent technology, combines desulfurization and adsorption in a single reactor. The adsorbent is regenerated with air and reactivated with hydrogen prior to recycling back to the adsorbing reactor. There is no high sulfur product stream for S-Zorb.

“Mathpro has published two reports estimating the cost of low sulfur gasoline for U.S. refineries in PADDs 1-3. One such study was funded by the American Petroleum Institute (API) estimating the cost of 40 ppm S gasoline based on CDTech and Mobil Octgain 220 used in a notional refinery representing those in PADDs 1-3. (Mathpro-1999a). Their cost estimate for sulfur reduction was 2.25¢/gal for CDTech and 2.6¢/gal for Octgain 220. The EPA reviewed their results adding an incremental cost to achieve 30-ppm standard (2.65¢/gal average) adjusting for 7% ROI before taxes results in 2.2¢/gal. The EPA reviewed several other studies and used the same models to make incremental adjustments for the 30 ppm S standard with updated processing cost numbers and the same capital recovery factors. The studies included the National Petrochemical and Refiners Association (NPRA) funded Mathpro study (Mathpro-1998), the Association of International Automobile Manufacturers (AIAM) funded Mathpro study (Mathpro-1999b), and the Oak Ridge National Laboratories (ORNL) DOE study for mid capacity refinery (Oak Ridge-1999). Finally, Mustang Engineers and Constructors, Inc. published an estimate of ultra low sulfur gasoline (Lamb-2000). The EPAadjusted desulfurization costs are summarized in Tables 21 and 22 below. The fuel costs to the consumer are calculated based on 12,500 miles per year, with the fuel cost present value assuming 7% discount factor for consumer purchasing. “

The report was prepared for DOE in 2001 by Directed Technologies (http://www.directedtechnologies.com/)

View the entire document at: www.ecosoul.org/files/knowledge/downloads/30535bk.pdf

Why did the chicken … Proccess Dynamics’ IsoTherming

A fairly recent (Sept. 2007) article describing a partnership between Process Dynamics (http://www.processdyn.com) and DuPont (Process Dynamics Inc. Partners with DuPont Chemical Solutions to Offer Clean Fuel Technology) demonstrates the long road from innovation to commercialization. According to a 2003 article (Process Dynamics ready to refine diesel) the firm was created in 1993. The innovation actually created “began as an effort to make food-grade wax coatings like the kind Tyson Foods uses to ship its meat products. (It) turned out to be equally good for hydrotreating fuel.”

View the complete text of both articles at:
http://www.sflorg.com/ear/?p=59
http://www.thefreelibrary.com/Process+Dynamics+ready+to+refine+diesel-a0110267353

Desulfurization Vendors

Sometimes it's nice to just have a simple listing of desulfurization technologies and the vendors who provide them. The powerpoint presentation "Hydrodesulfurization Technologies and Costs" by Nancy Yamaguchi of Trans-Energy Research Associates, Inc. (http://www.trans-energy.com/) for The William and Flora Hewlett Foundation Sulfur Workshop, Mexico City, May 29-30, 2003 does just that. There are three lists in the presentation ...

Hydrotreating Technologies and Vendors, Gasoline-Oriented
Hydrotreating Technologies and Vendors, Middle Distillate-Oriented
Hydrotreating Technologies and Vendors, Resid and Cracker Feed Oriented, Other

Find a pdf of the powerpoint presentation at: www.theicct.org/documents/Yamaguchi_Mexico_2003.pdf

Sing a Song of Sulfur

My father is a civil engineer, so when I was hired to be the librarian for Turner Collie & Braden, a Houston based civil engineering firm, I asked him for a little advice. “How,” I asked him, “am I going to provide these engineers the information they need to do their work? I majored in philosophy, for heaven’s sake.”

His answer … “Engineers are good at details, but sometimes they are not so good at seeing the big picture. That’s where you can help.”

That is the single most valuable piece of advice I have ever received. Since that time my research support in civil engineering, space engineering, and petroleum engineering has been performed in the context of the “big picture.”

That’s why I value an article like Chunshan Song’s “Effects of Support in Hydrotreating Catalysis for Ultra-clean Fuels” (Catalysis Today, Volume 86, Issues 1-4, 1 November 2003, Pages 211-263).

Interesting for the overview it provides of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel, the abstract has a sentence that really piqued my interest …

“The society at large is stepping on the road to zero sulfur fuel, so researchers should begin with the end in mind and try to develop long-term solutions.”

We may think we are searching for ways to desulfurize to the levels required by current regulations, but ultimately, we will have to desulfurize to ZERO! As plants are designed, built and retrofitted, the ultimate goal should be kept in mind … it will save huge amounts of money in the long run.

Chunshan Song (csong@psu.edu) is Professor of Fuel Science and Chemical Engineering; Director, EMS Energy Institute; and Associate Director, Penn State Institutes of Energy and the Environment

View his bio at: http://www.eme.psu.edu/faculty/song.html

Chevron’s "Motor Gasolines Technical Review”

Visit the Chevron site and browse the “Motor Gasolines Technical Review” (March 2008) to glean some useful desulf nuggets. One such nugget is a listing of all the ASTM standards pertaining to testing for sulfur content …

Sulfur Content
ASTM D 1266 – Test Method for Sulfur in Petroleum Products (Lamp Method)
ASTM D 2622 – Test Method for Sulfur in Petroleum Products by X-Ray Spectrometry
ASTM D 3120 – Test Method for Trace Quantities of Sulfur in Light Liquid Hydrocarbons by
Oxidative Microcoulometry
ASTM D 4045 – Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric
Colorimetry
ASTM D 4294 – Test Method for Sulfur in Petroleum and Petroleum Products by Energy-Dispersive
X-ray Fluorescence Spectrometry
ASTM D 5453 – Test Method for Determination of Total Sulfur in Light Hydrocarbons, Motor
Fuels and Oil by Ultraviolet Fluorescence
ASTM D 6334 – Test Method for Sulfur in Gasoline by Wavelength Dispersive X-Ray Fluorescence
ASTM D 6445 – Test Method for Sulfur in Gasoline by Energy-Dispersive X-ray Fluorescence
Spectrometry

As the sulfur test method names indicate, there are several technologies used to determine the sulfur content of gasoline. Some of the methods are applicable only to high sulfur levels, others cover a broad range, and some can be used only for low sulfur levels. Specific test methods need to be reviewed for applicability before selecting one to use.

Download the full review at: www.chevron.com/search/?text=driveability&Header=FromHeader

Regulatory Impact Analysis

The U.S. Environmental Protection Agency produces a large volume of reading matter, much of which is useful to anyone interested in the technology of desulfurization. For example, if you visit the page for Clean Air Nonroad Diesel - Tier 4 Final Rule, you will find links to the Regulatory Impact Analysis, as well as to individual chapters within that document.

Chapter 5: Fuel and Standard Feasibility, for example, describes and compares a number of desulfurization technologies offered by IFP, UOP, Akzo Nobel, Haldor Topsøe, and others.

Regulatory Impact Analysis (PDF) (Full Document, 1,568 pp, 8.5MB, EPA420-R-04-007, May 2004)
Individual Chapters:
Executive Summary (PDF) (14 pp, 185K)
Chapter 1: Industry Characterization (PDF) (42 pp, 513K)
Chapter 2: Air Quality, Health, and Welfare Effects (PDF) (155 pp, 1MB)
Chapter 3: Emission Inventory (PDF) (105 pp, 450K)
Chapter 4: Technologies and Test Procedures for Low-emission Engines (PDF) (184 pp, 1.3MB)
Chapter 5: Fuel and Standard Feasibility (PDF) (112 pp, 463K)
Chapter 6: Estimated Engine and Equipment Costs (PDF) (98 pp, 421K)
Chapter 7: Estimated Cost of Low-sulfur Fuels (PDF) (220 pp, 1.3MB)
Chapter 8: Estimated Aggregate Cost and Cost Per Ton of Reduced Emissions (PDF) (155 pp, 1MB)
Chapter 9: Cost-Benefit Analysis (PDF) (274 pp, 1.4MB)
Chapter 10: Economic Impact Analysis (PDF) (206 pp, 669K)
Chapter 11: Small Business Fexibility Analysis (PDF) (28 pp, 174K)
Chapter 12: Regulatory Alternatives (PDF) (22 pp, 161K)

source: http://www.epa.gov/nonroad-diesel/2004fr.htm

Technology Alerts

Copyright compliance is always a concern in corporate or academic research. You want to be able to share articles and conference papers with your colleagues. But you don’t want to place your organization in danger of a mulit-million dollar lawsuit.

As a librarian serving the Saudi Aramco enterprise, I faced the same problem. A solution to the problem was to produce a weekly listing of several technical articles of interest to some 100 engineers and scientists throughout the enterprise. Dubbed Technology Alert, it provided a brief description of each article, and served three purposes …

• Awareness … Provided busy researchers with a quick look at articles and other documents of interest
• Copyright Compliance … The description of each item provided enough information for an individual subscriber to decide whether to request a copy of the full document. When I received such a request, I provided the document to the requestor, following copyright guidelines. This avoided the problem of “broadcasting” a document by posting it to a Web site, a clear violation of copyright
• Quality Control … The number of requests for articles described in the weekly alerts provided feedback indicating whether the alerts were providing any value to subscribers. Over time, the feedback guided me in the areas of interest to the subscribing community, improving the value of the alerts

You might suggest a similar service to your corporate librarian, if your management is farsighted enough to employ one.

Nebula

CHAPTER 5: Fuel Standard Feasibility IN: Final Regulatory Impact Analysis (2004) (www.epa.gov/nonroad-diesel/2004fr/420r04007f.pdf) is useful for its descriptions of the various desulfurization technologies available as of the time of the document. For example, here is its description of Akzo Nobel’s Nebula …

“In 2001 and 2003, Akzo Nobel announced two new catalysts. In 2001, Akzo announced the introduction of a highly active catalyst named Nebula, which offers a different way to use coatings for catalysts. A typical catalyst is composed of two parts: an active coating containing metals and a generally inactive substrate. For Nebula, Akzo Nobel concentrated the metal coatings and omitted the substrate. Because of the very high metals content, Nebula costs several times more than conventional catalysts. The higher activity of the Nebula catalyst leads to an increased tendency for coking, which must be countered by using a high hydrogen partial pressure, resulting in a higher hydrogen consumption. (The hydrogen consumption is higher because a higher percentage of the aromatics are saturated to nonaromatic compounds.) According to Akzo Nobel, a refiner may be able to meet the 15 ppm sulfur standard by simply replacing a part of or all of its existing catalyst with Nebula and providing significantly more hydrogen (which may possibly require the addition of a hydrogen plant). Nebula may significantly reduce the capital investment for meeting the 15 ppm sulfur standard. In 2003, Akzo announced that Nebula was modified somewhat to contain 15 - 20 percent less metals, but with the same activity as the original Nebula. The updated Nebula catalyst, now called Nebula 20, can better handle heavier feeds.18

“In 2003, Akzo Nobel announced a new catalyst named KF-760. The KF-760 catalyst is a CoMo catalyst designed for better denitrogenation of diesel fuel, in addition to the desulfurization being sought after. Where the nitrogen content is inhibiting the desulfurization of the diesel fuel, this catalyst can have 15 - 20 percent higher activity compared to their previous best, KF-757, with only a modest increase in hydrogen consumption. “

Core Documents

Librarians and independent bibliographic researchers such as myself provide research support for a broad range of clients, each of whom may be pursuing any number of lines of research. Since we can’t be experts in every technology we are asked to research, one of the first things we like to do is to find an article or other document that gives us an overview of a particular area of technology. Reading the document gives us clues as to possible strategies to produce the results our clients expect.

So when I ran across …
CHAPTER 5: Fuel Standard Feasibility IN: Final Regulatory Impact Analysis (2004)

I browsed through it for clues on how to research the deep desulfurization of diesel. Here is a representative paragraph that caught my eye …

“After careful review of all these approaches, we expect that the sulfur reduction required by the 500 ppm sulfur standard will occur through chemical removal via conventional hydrotreating. For complying with the 15 ppm cap for NRLM diesel fuel, we expect it will be met primarily through liquid-phase hydrotreating, which is an emerging advanced desulfurization technology. This section will begin with a relatively detailed discussion of the capabilities of these various processes. Refiners may use the other methods to obtain costeffective sulfur reductions that will complement the primary sulfur reduction achieved via hydrotreating. These other methods, such as FCC feed hydrotreating, adsorption and chemical oxidation are discussed following the primary discussion of distillate hydrotreating and liquidphase hydrotreating. Another means for aiding the desulfurization of diesel fuel, particularly to comply with the 15 ppm standard, is undercutting, which removes the most difficult-to-treat sulfur compounds. Since undercutting can help ease the task of complying with the 15 ppm standard for any of the desulfurization technologies, we provide a discussion of undercutting below.”

This may be old news to you, the primary researcher. However, it may be very helpful to your partner in research, the corporate librarian or the independent bibliographic researcher. If you know of such a document in your area of interest, share it with your research support person.

Read the complete document at:
www.epa.gov/nonroad-diesel/2004fr/420r04007f.pdf

Prep Your Partners

Searching for SCANfining® turned up this conference preprint, “Advanced Catalyst Technology and Applications for Higher Quality Fuels and Lubes.” One paragraph in particular caught my eye …

“In the development phase, the most viable catalyst is selected and a process initiated to find a cost effective preparation route for the catalyst of choice. We then set a path to scale-up the catalyst, which could include internal manufacture or joint work with a catalyst vendor. Finally, we commercialize the catalyst with the objective to apply it as broadly as possible across our refinery circuit. This feedback loop provides critical performance information about the performance of the catalyst and allows us to further identify and develop next generation catalyst systems.” (Emphasis added)

There, in a nutshell, is the full circle … development, scale-up, commercialization, and feedback. People engage in desulfurization research typically focus on one stage in the cycle. You, the researcher, know which stage you are focusing on.

But your corporate librarian (if you are lucky enough to have one) or your independent research support specialist (like me, for example) may NOT know. We typically provide research support for researchers throughout the cycle.

So, when you make your request for a literature search on a particular topic, let your research support person know which stage of the cycle you are interested in. That will make the search results more relevant to your purpose.

By the way, you can read the complete article referenced above at …
www.anl.gov/PCS/acsfuel/.../49_2_Philadelphia_10-04_1024.pdf