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CSTRs: Bound for Maximum Conversion


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CSTRs: Bound for Maximum Conversion

  1. 1. January Controlling 2009 Emissions With Ceramic Filters Page 35 1 Coal-to- Mixing and Predictive Liquids Blending and PreventiveContinuously Stirred Tank Reactors • Controlling Emissions With Ceramic Filters Maintenance Pipespool Fabricators Mechanical Carbon Page 30Vol. 116 No. 1 january 2009 Facts at Your Fingertips: Tray Column Design • 01_CHE_011509_COV.indd 1 12/23/08 10:59:31 AM
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  5. 5. January 2009 In This Issue Volume 116, no. 1 Commentary 5 ditor’s Page E Our 2009 lemon- ade recipe The chemical process industries (CPI) are in a deep re- cession, marked Cover story by plant closings and layoffs. There 30 over Story CSTRs: Bound for Maximum Con- C is a sweet side, version Here, a design approach for continuous though, for those stirred-tank reactors is developed for both revers- who take advan- ible and irreversible second-order reactions tage of smart in- NEWS vestments and for 13 Chementator Commercialization is set for a meth- projects that re- anol-to-olefins technology; More efforts to capture quire a shutdown CO2 from power plants; This mechanical cleaning process reduces fouling in MBRs without chemicals; departments Pretreatments helps recover more coal from primary Letters.................. 6, 8 flotation step; Mass-production technology for mak- Bookshelf........... 9, 28 . ing functionalized organic nanotubes; Continued commercial success for a new MEG process; A hard Who’s Who. ........... 28 . coating promises to reduce wear and power use in Reader rotating equipment; and more Service page........... 58 Economic 19 Newsfront Kirkpatrick Nominations are equipment services Indicators. ........ 59, 60 . open for this magazine’s 2009 Kirkpatrick Chemi- cal Engineering Achievement Award, which 28D-1 New Products Services (Domestic Edition) Vacuum degassing advertisers honors the most-noteworthy chemical engineer- chamber connects directly to vacuum Italian ing technology commercialized anywhere in the pump; Simplify Fieldbus testing with Section .........28I-3–16 world during 2007 or 2008 this product’s bus health test; Cut costs Product Showcase.....51 20 ewsfront PM and PDM: Crucial Gear in N when operating with this vertical pump; the CPI Toolbox Given that predictive and Achieve high flowrates with these cus- Classified preventative maintenance programs save tomizable pumps; Use this ultrasonic Advertising........53–56 money and increase uptime, new solutions level transmitter in wastewater applica- Advertiser Index...... 57 are relatively easy to justify tions; Prevent spilling at liquid transfer 23 echnology Showcase A Primer On Coal- T points; and more coming to-Liquids Converting coal to liquid fuels is in February 28I-1 New Products Services one option China and the U.S. are pursing (International Edition) This new paddle Look for: Feature design simplifies installation and re- Reports on Handling Engineering moval; This little data logger stores a lot Nanoscale Materials; of measurements; HART communica- and Heat Exchang- 29 Facts At Your Fingertips Tray Column tion is now possible with this gas moni- ers; A Solids Pro- Design This one-page guide presents crite- tor; Size-up protein molecules without cessing article on ria needed for the effective specification of sacrificing samples; Temperature moni- Selecting Conveyors; trays for a distillation or stripping column toring for trace-heating applications; An Environmental 35 eature Report Controlling Emissions With F and more Manager on Eye Ceramic Filters Ceramic filters are well suited and Face Personal for high-temperature processes that are subject to 49 ocus Mixing F Protective Equipment; strict emissions limits, including those for dioxins Blending Portable A Focus on Flow mixers for pilot Measurement Con- 40 Engineering Practice Active Management plant and small- trol; News articles of Pipespool Fabricators Contractors need to scale production on Water Supply integrate and engage to improve deliveries and processing; Rout- Reuse; and Oil Sands; shorten project schedules ing maintenance Facts at Your Fin- 46 ngineering Practice Mechanical Carbon E is simplified with this mixer drive; Blend, gertips on Piping; an In Chemical Processing Equipment This heat cool and add liquids in this rotary Interphex Show Pre- self-lubricating material offers advantages batch mixer; These new laboratory mix- view and more when used for components that are running ers go digital; Easily mount these mixers submerged in the process fluid to IBCs or totes; and more Cover: David Whitcher Chemical Engineering January 2009 302_CHE_011509_TOC.indd 3 12/23/08 10:04:58 AM
  6. 6. We’re raising expectations. The presence of polar gas or steam is no match for dynamic gas phase compensation When highly accurate liquid level measurement is required, Levelflex M goes to work. Microwave pulses are directed down the instrument’s probe and reflected from the medium’s surface. Level is determined by the time required for the pulse to travel to the surface and back. This means reliable measurement is not affected by changes in process conditions, turbulence or foam. Continuous gas phase compensation technology is one way Endress+Hauser is raising expectations. With traditional level instruments, the presence of polar gas or steam can cause an error of 28% or greater depending on the pressure in the application. Levelflex M uses dynamic gas phase compensation to virtually eliminate this error. One more reason Endress+Hauser is the preferred supplier for difficult and critical level measurement applications. Endress+Hauser, Inc 2350 Endress Place Greenwood, IN 46143 Sales: 888-ENDRESS Service: 800-642-8737 Fax: 317-535-8498 Circle 06 on p. 58 or go to 8-08.indd 1 12/17/08 3:22:29 PM
  7. 7. Winner of Eight Jesse H. Neal Awards for Editorial Excellence Editor’s Page Published since 1902 Our 2009 lemonade recipe F An Access Intelligence Publication irst, you’ll need a lot of lemons. As 2009 kicks off, sour fruit happens Editors Art Design to be in great supply. To be blunt, the chemical process industries (CPI) are in the middle of what appears to be the worst recession Rebekkah j. Marshall DAVID WHITCHER Editor in Chief Art Director/ since World War II (WWII). Editorial Production Manager There are many signs that point to such a conclusion, but a particularly Dorothy Lozowski clear picture can be drawn from the November 2008 CPI operating rate (see Managing Editor Production p. 60), which is the industry’s most recent figure available on capacity utili- MICHAEL D. KRAUS GERALD ONDREY (Frankfurt) VP of Production Manufacturing zation. At 72.7%, the operating rate hasn’t been this low since the end of the Senior Editor 2001 recession. “But that data point is of cold comfort,” says Mike Montgom- kate torzewski Steve Olson ery, analyst at Global Insight, Inc., (Lexington, Mass.), “Since the low of the Director of Production Assistant Editor Manufacturing last recession will be passed (going down) with ease [in the December num- ber].” In the release of January data, Montgomery expects the operating rate SUZANNE A. SHELLEY WILLIAM C. GRAHAM Contributing Editor Ad Production Manager to fall — again, “with ease” — below any other post-WWII recession except for that of 1981–1982. “The recession is spreading fast, and all the cutbacks CORRESPONDENTS Audience in car and truck production announced recently will make January dismal, Development Charles ButcheR (U.K.) with slim chance of improvement in February or March,” he says. Sylvia sierra Senior Vice President, What is reflected in the declining operating rate is a sharp drop in demand Paul S. Grad (Australia) Corporate Audience Development for nearly everything. In response, CPI companies have idled production and Tetsuo Satoh (Japan) are implementing other cost-cutting measures. Last month, Dow Chemical John Rockwell Vice President, Co. (Midland, Mich.), the U.S.’s largest chemical company in terms of revenue, Joy LePree (New Jersey) Audience Development Chemical eliminated 5,000 jobs (or 11% of its workforce) and closed 20 facilities while Gerald parkinson also announcing plans to temporarily idle approximately 180 plants and re- Laurie Hofmann (California) Audience Marketing Director duce its contractor workforce by approximately 6,000 worldwide. Only weeks Editorial before, BASF (Ludwigshafen, Germany), the world’s largest chemical com- Advisory Board Terry Best pany, announced plans to temporarily idle 80 plants and to reduce capacity at John Carson Audience Development Manager Jenike Johanson, Inc. 100 other facilities. (For more on both, see p. 59.) David Dickey George Severine The comprehensive list of CPI companies with similar moves is long MixTech, Inc. Fulfillment Manager and includes Arkema, DSM, Eastman, DuPont, Lanxess, Air Products and Mukesh Doble Merck KGaA. While their cost cutting measures certainly help to dilute IIT Madras, India Christie Lamont List Sales, World Data 561-393-8200 the sour effects of the current economic recession, our recipe also calls for Henry Kister Fluor Corp. Conferences something sweet: strategic capital improvements, particularly those that Trevor Kletz improve performance while also reducing costs. Loughborough University, U.K. Dana D. Carey Director, Global Event Sponsorships For instance, the newsfront on predictive and preventive maintenance, Gerhard Kreysa DECHEMA e.V. p. 20, outlines a number of ways in which substantial returns can be Ram Ramachandran Peck Sim achieved in the short-term with minimal costs. The article also touches on Senior Manager, BOC Conference Programming the virtues of industrial wireless technology, yet another powerful tool that Marketing brings otherwise-expensive process improvements within reach. Holly Rountree Beatriz Suarez Marketing Manager Director of Conference Operations Even some longer-term investments make sense now, for several rea- sons. The virtual elimination of demand pressures is one; a more oppor- Information services Corporate tune time you will not find for projects that require shutdown. Meanwhile, Robert Paciorek Steve Barber the cost of capital equipment, itself, is decreasing. Chemical Engineering’s Senior VP Chief Information Officer VP, Financial Planning Internal Audit Plant Cost Index (also see p. 60) has been on a steady decline since August. Charles Sands John Pearson The only categories showing a mild increase at all this month are pumps/ Senior Developer Divisional President/Publisher compressors and electrical equipment. Categories experiencing the most Web/business Applications Architect dramatic decline are tanks and general equipment, due to their high cop- Headquarters per and steel makeup. Excess supplies of these raw materials are likely 110 William Street, 11th Floor, New York, NY 10038, U.S. to persist in the form of price breaks for awhile, says Montgomery. As an Tel: 212-621-4900 Fax: 212-621-4694 example, copper hit its low price in 2003, even though European Editorial offices the U.S. recession ended in late 2001. Zeilweg 44, D-60439 Frankfurt am Main, Germany Tel: 49-69-2547-2073 Fax: 49-69-5700-2484 Of course, nearly everyone is pointing out that there Circulation Requests: is a practical limit on how far consumer spending will Tel: 847-564-9290 Fax: 847-564-9453 retreat. No one knows for sure, however, where the limit Fullfillment Manager; P.O. Box 3588, Northbrook, IL 60065-3588 email: is. Most agree with Montgomery that the recovery will Advertising Requests: see p. 58 be strong as the inventory cycle reverses itself, and job For photocopy or reuse requests: 800-772-3350 or cuts turn to payroll gains. In the meantime, the rest of For reprints: us will continue squeezing. ■ Rebekkah Marshall Chemical Engineering January 2009 503_CHE_011509_ED.indd 5 12/23/08 10:56:50 AM
  8. 8. Letters Discussions on pressure relief I would like to draw your attention to a few points on the November 2008 article, Pressure Relief System Design (pp. 40–45): 1. Pressure drop and pressure loss: The inlet pressure “drop” that the author refers to under Relief system pip- ing is non-recoverable pressure loss, and does not include a “drop” in pressure due to elevation increase. It should be labeled as a pressure loss rather than a pressure drop as the author has specified elsewhere. It may sound trivial, but such errors are not uncommon. The 3% rule is code- mandated and should be followed. However, any excess above this can still be defended in some circumstances in the court of law, but only by an expert analysis. 2a. Bursting of rupture disk: In the penultimate para- graph, when a rupture disk is used in series with a relief valve, the author writes: “... the disk would never burst”. The rupture disk (as well as a conventional relief valve) is a differential pressure device. So the disk will burst when the difference between the upstream pressure and the down- stream pressure of the disk equals the burst pressure of the disk (or the set pressure of a conventional relief valve).* 2b. Pressure indicator between a rupture disk and relief valve: The second point in this subject is the il- lustration of Figure 5 which is backed by the author’s rec- ommendation: “whenever a rupture disk is installed up- stream of a relief valve, it is important to have a pressure indicator in the section between the two.” If the author is following the ASME VIII, Div. 1, the paragraph UG-127 stipulates the following: “the space between a rupture disk device and a pressure relief valve shall be provided with a pressure gage, a try cock, free vent, or suitable telltale indi- cator. This arrangement permits detection of disk rupture or leakage.” Because of the presence of a serial comma in Circle 07 on p. 58 or go to the phrase in italic letters, a grammatical parsing of the phrase accepts the author’s recommendation to include just a pressure gage to be in technical compliance with the code. However, the spirit of intent of the code will not be followed by such design. In fact just the installation of a pressure gage is not enough and it is unsafe to do so.* 3. K.O. drum: By showing the K.O. drum in strategic po- sition, the author implies two-phase flow possibilities. The DIERS (Design Institute for Emergency Relief Systems) does not recommend the use of conventional relief valves for applications with potential two-phase flows. The pres- sure drop calculations for two-phase flows are more com- plex than the methods used by the author.* Dilip K. Das, P. E. Bayer CropScience, Kansas City, Mo. Author replies 1. Pressure drop and pressure loss: Having worked in various projects worldwide, I had a look at process data sheets for the terminology used for permanent pressure loss. In many cases, I found that the term “pressure drop” has been used to denote permanent pressure loss, such as in flow-orifice data sheets. The following books also use the * This letter has been abbreviated to fit here. The full letter and response can be found at by searching for the title of the article.04_CHE_011509_LET.indd 6 12/23/08 12:44:42 PM
  9. 9. Circle 08 on p. 58 or go to Box 4 U 1-09.indd 1 12/17/08 3:23:27 PM
  10. 10. Letters term “pressure drop” instead of “pressure loss”: • “Control Valve Handbook”, 4th edition, by Emerson • Applied Instrumentation in the Process Industries” Vol “ III (Andrew WG/Williams HB) and Vol IV, (Leslie M Zoss) • Perry’s Chemical Engineers’ Handbook” uses the term “ frictional losses in some cases. However, at many places, it also uses the term “pressure drop” for two-phase flow, single-phase flow, flow in spirals, annular flow, flow through beds of solids and so on • ven the API 521 (5th Ed, January 2007) uses the term E “pressure drop” at many places The term “pressure drop” may be interpreted by some as a drop in pressure due to elevation increase. However, refer- ences show that in several cases, the term “pressure drop” has been used to denote frictional losses. 2a. Bursting of rupture disk: When I mentioned “rup- ture disk would never burst”, what I meant was “rupture disk would never burst at its burst pressure”. An example is illustrated in a rupture disk with a burst pressure of 90 psig. The protected equipment design pressure is 100 psig. A pinhole develops and the space between the rupture disk and the relief valve reaches a pressure of 60 psig. Now the contingency develops. The protected equipment reaches 90 psig (the burst pressure of the disk). Downstream of the rupture disk, the pressure is 60 psig. At this stage, we would expect the rupture disk to burst, but it will not, because the differential pressure is only 30 psig (90 – 60). Now the protected equipment reaches 100 psig (its design pressure). Even now the disk will not burst. This is what I meant by my statement in the article. The pressure in the protected equipment now further develops until it reaches 160 psig. Downstream of the rupture disk, the pressure has reached 70 psig. Only at this stage will the rupture disk burst. But the damage to equipment may have been done. It may be argued that there is a margin of safety in the ves- sel. However, this is not what the design was intended for. The disk should burst at its burst pressure. 2b. Pressure indicator between a rupture disk and relief valve: The pressure indicator between the rupture disk and the relief valve, of course, needs monitoring. We have detailed designs of combinations of rupture disks and relief valves with a pressure switch on the line and an on/off valve, which depressurizes the system once the pressure reaches a certain set value. Detailed schemes such as these could be the subject of another article. 3. K.O. drum: Yes there are two-phase flow possibilities. But two-phase flow will not necessarily occur all the time. Single phase flows are also possible. Please note that Figure 1, where the K.O. Drum is shown has no direct relation with the illustrated example. The example illustrates a single- phase flow calculation to show how discharge-side piping headers and branch lines are sized. The basic theory and equations for single phase flow will not change, whether it is the more recent API 521 (January 2007) or the relatively older API standard cited in the article. For two-phase flow, there are several references in the literature. But it was not the intent here to illustrate a two-phase flow calculation. Siddhartha Mukherjee Lurgi India Co., Ltd. Circle 09 on p. 58 or go to 8 Chemical Engineering January 200904_CHE_011509_LET.indd 8 12/26/08 2:26:05 PM
  11. 11. Chemical Engineering half 3 3/8 x 10:Inter labmate half page Bookshelf Patent Savvy for Managers. By Kirk Teska. Nolo, 950 Parker St., Berkeley, CA 94710-2524. Web: THE WORLD FORUM OF THE PROCESS INDUSTRIES 2007. 278 pages, $29.99 Reviewed by Charles R. Richard, Patent Attorney, Washington, D.C. T he book I am reviewing here is one in a series of Nolo guides geared toward non-lawyers on vari- ous legal topics and their aspects. I must caution readers that although this book provides some good back- ground into the world of patenting, it is no substitute for consultation with a competent patent attorney or agent when appropriate. Although I did not notice problems with it, I cannot guarantee that this book is “complete” for any reader’s purpose and/or error free, nor do I neces- sarily agree with all the author’s opinions/advice. (Sorry for the disclaimer, but that is the world we live in.) Mr. Teska takes readers through various practical and important patenting topics using easy-to-understand lan- guage and provides as illustration interesting (sometimes even humorous) stories, many based on actual patent Be part of the cases. I am pleased to see the inclusion in Chapter 3 of one of my favorites, the Dembiczak case (also known as the “Pumpkin Case”), as an illustration of non-obvious- bigger picture... ness; after reading about it, readers should agree that patents can be fun! Unfortunately, there were few if any ... and see innovations of today chemical case examples, but this is to be expected from for the solutions of tomorrow a book that is aimed at a general technical audience; ex- amples focus on technology that is generally familiar. The book contains an introduction that is worth read- The global appeal of ACHEMA gives you a competitive edge by ing, ten chapters, an extensive glossary and an index. allowing you to see the bigger picture. Chapters 1–4 cover important background patent princi- ACHEMA attracts engineers, chemists and decision makers from around ples and myths (this book might well be worth reading to the world to a single venue to showcase solutions, share ideas and see these alone), case studies, patentable subject matter interface across technology disciplines. and patentability standards, and understanding claims Be better prepared for the challenges to come – Attend ACHEMA. and how to read a patent — all very useful to know. Chapters 5–8 take up “capturing” patentable inven- � CHEMICAL ENGINEERING � SAFETY � BIOTECHNOLOGY � ADVANCED MATERIALS tions, getting to patent pending, patent prosecution and � ANALYTICAL TECHNIQUES � ENVIRONMENTAL PROTECTION going international; some very practical information/ � FLUID HANDLING � RESEARCH � PROCESS AUTOMATION � SPECIAL SHOW: advice on costs, timing and how the patenting process � PHARMACEUTICAL TECHNOLOGY INNOVATIVE CONCEPTS FOR THE should work, as well as perspective on what many activi- � THERMAL AND MECHANICAL USE OF RESOURCES ties relating to patenting actually provide and may be PROCESSES worth are included. I recommend taking a good look at the discussion on searching in Chapter 6, even though 4,000 EXHIBITORS � 180,000 ATTENDEES � 30,000 EXECUTIVES the author may be a bit more negative than warranted. 100 COUNTRIES � 900 LECTURES The comments on patent examiners in Chapter 7 should be very revealing for those with little experience with the U.S. Patent Office. Any reader who thought that patent litigation might be desirable would be advised to take the discussion in Chapter 9 into account before making any decision in an actual case. The comments on licensing in Chapter 10 will probably be illuminating for neophytes as well as for many who have had experience here. (Continues on p. 28) Circle 10 on p. 58 or go to Chemical Engineering January 2009 905_CHE_011509_BKS_WW.indd 9 12/18/08 1:06:44 PM
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  14. 14. Circle 12 on p. 58 or go to Rosemount1-09.indd 1 12/17/08 3:26:46 PM
  15. 15. Edited by Gerald Ondrey January 2009 Reaction products CO to combustion Commercialization is set for a Olefin rich methanol-to-olefins technology product to recovery L ummus Technology, a CBI company (The Woodlands, Tex.; and SYN Energy Technology Co. (Dalian, China; www. Methanol/ water to Air reactor have signed a global, cooperative Steam market agreement to license a methanol- to-olefins (MTO) process. The technology, called DMTO, was de- Methanol Recovered Reactor water veloped by the Dalian Institute of Quench and Wastewater Chemical Physics, Chinese Acad- Catalyst regenerator stripping tower stripping tower emy of Sciences (Dalian, China), which has a controlling interest in SYN. amount of propylene desired. The ratio of The first application of the technology propylene to ethylene can range from 0.8 to Bioethanol will be in a coal-gasification-MTO complex 1.2:1, depending on the reaction conditions, Last month, an energy-saving that is being built by Shenhua Baotou Coal says Helion Sardina, vice president and gen- plant for producing bioethanol Chemicals Co. in Baotou, China. The olefins eral manager of Lummus Technology. started up in Norrköping, Swe- plant will convert 1.8-million metric tons Currently, the economics of the process den, for Lantmännen Agroetanol (m.t.) per year of methanol into 600,000 are roughly equal to those of naphtha-based AB. When operating at full m.t./yr of ethylene and propylene. Startup is plants, with naphtha priced at around capacity, the plant will produce scheduled for 2010. $375/m.t. and methanol at roughly $140/m.t., 470,000 L/d of bioethanol from In the DMTO process (flowsheet), metha- says Sardina. He expects the process will grain (mostly wheat), making nol is fed to a fluidized-bed reactor and con- find a ready market in regions where there it the largest bioethanol facility verted by a molecular sieve catalyst to ethyl- is an abundant supply of coal, such as China, in Northern Europe. The plant is based on the Multipressure ene, propylene, some butene, and 1–2% coke or where there is stranded natural gas that system of Vogelbusch GmbH and light ends, plus 55% water. Conversion can be converted to methanol. He also sees (Vienna, Austria; www.vogel- takes place at slightly above atmospheric a large market potential in the addition of The Multipressure pressure and 400–550°C, depending on the capacity at existing steam crackers. system uses several distillation columns operating at different More efforts to capture CO2 from power plants steam pressures, which results in a “significant” reduction in A iming at bringing down the barriers to for flue gases. The plant will be constructed steam consumption — over the commercial deployment of post-com- in the first half of 2009 and will be ready 50% less than conventional bustion capture (PCC) of CO2, an Australian for operation in the second half of 2009 technology, says Vogelbusch. Additional energy savings are team from CSIRO Energy Technology (New- • SIRO has also partnered with the Xi’an C achieved through optimal ther- castle, New South Wales;, Thermal Power Research Institute and mal integration of the distillation CSIRO Energy Technology (Clayton South, China HuaNeng Group for the develop- and dehydration processes. Victoria), and several other research orga- ment and operation of an amine based nizations has developed an integrated PCC pilot plant at the HuaNeng Beijing Co- Photolithography RD and pilot plant program. The program generation Power Plant. This power sta- Last month, Sumitomo Chemi- includes four pilot plants: tion has fluegas desulfurization (FGD) cal Co. Ltd. (Tokyo, Japan; • he Latrobe Valley PCC pilot plant at the T and deNOx. (The Australian power plants Loy Yang power station in Victoria started do not have FGD and deNOx.) The Chi- started up a $120-million plant operating in March 2008. It is based nese plant will help CSIRO understand for producing argon-fluoride on amines as the CO2 solvent. It will be the tradeoffs between an integrated pol- (ArF) liquid immersion (LI) tested on flue gases from Victorian brown lution control system and separate con- semiconductor resist at its coal. The capture plant capacities range trol technologies for each pollutant. It has Osaka factory. The facility has a from 100 to 500 kg/h of CO2 been operating since June production capacity of 100,000 • he second pilot plant, based at Delta T PCC science leader Paul Feron, of CSIRO En- gal/yr, which the company Electricity’s Lake Munmorah black-coal- ergy Technology, says further development of says will give it one third of the global market share — two fired power station in NSW, is undergo- the capture technology and the power plant thirds of which is in Asia — for ing commissioning. The plant is based on technology can lead to power-plant-gener- ArF LI resists, which are use in aqueous ammonia for CO2 capture ation efficiencies with 90% CO2 capture, ArF excimer-laser (l = 193 nm) • third plant, to be located at the Tarong A which are equivalent to the current efficien- photolithogtaphy. power station in Queensland will focus on cies without CO2 capture (For more on CO2 (Continues on p. 14) the determination of an optimum solvent capture, see CE, December 2008, pp. 16–20). Note: For more information, circle the 3-digit number on p. 58, or use the website designation. Chemical Engineering January 2009 1306_CHE_011509_CHM.indd 13 12/23/08 11:49:27 AM
  16. 16. C hementato R This mechanical cleaning process reduces fouling in MBRs without chemicals F or wastewater treatment, membrane bio- reactors (MBRs) provide superior effluent quality in a small footprint compared to al- brane as they rise — and then settle back down by gravity after leaving the module (diagram). In ternative activated-sludge treatment meth- the pilot plants, back-washable, ods. However, MBRs are prone to fouling, flat-sheet membranes (Bio-Cel) and thus may require frequent membrane are used. The hydraulic flow cleaning with the associated manpower conditions of this module allow and chemical costs. Microdyn-Nadir GmbH the addition of particles for foul- (Wiesbaden;, in co- ing control. Also, the mechani- operation with Darmstadt University (both cally strong and permanent hydrophilic flat Germany), has developed a unique fouling- sheet PES (polyethersulfone) membranes control process, called Bio-Cel-MCP, which (Nadir UP150) have been shown to with- does not require chemicals. Tests conducted stand the cleaning action of the granules on two pilot plants operating continuously as demonstrated by the continuous opera- for more than 400 days have demonstrated tion of the MBR module at high flux rates that the process leads to a 40% increase in (23.6 gallons per square foot of membrane flux compared to a standard MBR operating per day) without significant decrease of per- without MCP, says Stefan Krause, head of meability, says Krause. After more than one water-treatment technology applications year of operating the two pilot plants, the at Microdyn-Nadir. average COD (chemical oxygen demand) re- The MPC process is based on the prin- moval was about 95%, and online measure- (Continued from p. 13) ciples of fluidized-bed technology. Small ment of the turbidity of the effluent showed The company has begun (3-mm dia.) plastic granules are added into no disturbance, indicating a constantly high mass production of Sumiresist the filtration basin (inside the activated removal of suspended solids and hence an PAR, a specific photo acid sludge), and are forced to flow upward intact membrane, he says. Krause esti- generator (PAG) for the manu- alongside the membranes by an air-induced mates the the return-on-investment for an facture of 50-nm-node memory, crossflow — mechanically cleaning the mem- MPC system at about six months. which performs well without a top coating. Another product being produced is for 40-nm- node logic device applications. Pretreatment helps recover more coal The company is also in the final stages of developing an LI re- from primary flotation step sist for 40-nm-node DRAM (dy- namic random access mem- C oal is typically cleaned by gravity separa- tion to reduce ash and pyrite content, with flotation used to recover fines. Various meth- The team has found that the removal of fine particles leads to an increase in coal recovery from 28% (after 20 minutes flota- ory) and Flash memory, and preparing for the development of 30-nm-node processes. ods have been applied to disperse fine clay tion using 64 g of diesel per ton of coal) to particles from the surface of coal particles 79% with screening at 75 µm, and 97% with Tough ceramic and thus improve coal flotation performance. screening at 38 µm (after 12 min flotation; Scientists at the DOE’s Law- A team of researchers from the Ian Wark Re- 40 g diesel/ton coal). It says that the process’ rence Berkeley National Labo- search Institute, University of South Austra- downside is that it leads to a fine product that ratory (Calif.; lia (Adelaide;, has studied cannot be discarded since it contains signifi- have synthesized a ceramic the effect of fine clay on the flotation of sev- cant amounts of coal that would be difficult that imitates the structure of Nacre (mother of pearl). eral coal samples. It found that the removal to recover by flotation. The losses of coal in Nacre is 95% aragonite, a of fine particles either from the primary tail- the screened fines represent 26% (screening hard, brittle calcium-carbonate ings or the feed sample by sieving (38 µm) or at 75 µm) and 22% (screening at 38 µm). mineral, and 5% “soft” organic de-sliming with a Mozley hydrocyclone gave However, the team also conducted experi- molecules, and yet can be vastly improved flotation performance of the ments to compare the effects of fine-particle 3,000 times more resistant coarse coal particles. Team member Keith removal by either wet screening the feed or to fracture (toughness)than Quast says this process recovers coal that the primary flotation tailing at 38 µm and aragonite. By emulating the did not float in the primary flotation stage, de-sliming the feed or tailing using the Mo- microstructure of Nacre, the and would otherwise be lost to the process. zley cyclone. The results showed that the scientists have created large, In both cases, he said, the removal of slimes removal of fines from the primary tailing by porous ceramic scaffolds and “brick-and-mortar” structures. from the circuit stage gave a better overall sieving or de-sliming allows a high propor- The hybrid ceramics are combustible recovery than processing a feed tion of the coal to float using a smaller addi- that had received no pretreatment. tion of diesel (20 g/ton instead of 54 g/ton). (Continues on p. 16) 14 Chemical Engineering January 200906_CHE_011509_CHM.indd 14 12/22/08 9:50:49 AM
  17. 17. Circle 23 on p. 58 or go to PEP-09.indd 1 12/17/08 3:28:35 PM
  18. 18. Courtesy of AIST C hementato R Mass-production technology for making functionalized organic nanotubes R esearchers at the Nanotube Research Center of the National Institute of Ad- vanced Industrial Science and Technology example, a Cu-complexed organic nanotube has been shown to selectively adsorb gold nanoparticles that have an amino group on orange ball = metal ions light blue ball = hydrophyllic part of the peptide lipids gray stick = hydrophobic part (AIST; Tokyo; have devel- their surface. of the peptide lipids oped a process for making organic nano- The new nanomaterials are made by add- tubes of metal complexes (photo, left). The ing aqueous solutions of metal salts to a (Continued from p. 14) scientists have produced organic nanotubes suspension of peptide lipids in methanol or with metal ions (Zn+2, Cu+2, Co+2, Ni+2, ethanol. Nanotubes form after 10 minutes, made through the controlled freezing of aqueous suspen- Fe+2 and Mg+2) complexed at the inner producing about 2–20 g/mL of suspension sions of an aluminum oxide and outer surfaces of organic nanotubes — a production rate about 200 times higher (alumina) and the addition (diagram, right), and believe such materi- than alternative methods. The simple proce- of polymethylmethacrylate als will find applications as: new catalysts dure consumes little energy and is easy to (PMMA), producing materi- with transient metal coordinated spatially scale up, says AIST. als that are 300 times tougher (Continued from p. 13) on the inside; low-molecular-weight com- This is the third mass-production process than their constituents. To pounds with coordinated functional groups; for making organic nanotubes that has been make even tougher materials, DNA and protein inclusion, adsorption, and developed by AIST. The previous processes the researchers are working separation for biotechnology; and new elec- produce organic nanotubes with hydroxyl to increase the proportion of tronic, magnetic and optical materials. For and carboxyl groups on the surface. ceramic to PMMA (presently 85 wt.% alumina), and by replac- ing PMMA with a different poly- Continued commercial success for a new MEG process mer or, eventually, metal. W hen completed in early 2010, Shell Chemicals’ B.V. (The Hague, Nether- lands; 750,000-m.t./yr fa- sively by Shell in 2002 (for more process details, see CE, July 2002, p. 19). The pro- cess achieves a selectivity of EO to MEG Self-healing coatings Researchers at the University of Illinois (Champaign; www. cility at the Shell Eastern Petrochemicals of 99.3–99.5%, compared to about 90% for have developed Complex in Singapore will be the world’s conventional processes, and produces up to coatings that automatically largest plant to produce mono-ethylene gly- 1.95 ton of MEG per ton of ethylene, com- repair themselves and prevent col (MEG) using Shell’s Omega process. This pared to 1.53–1.70 ton, depending on the corrosion of the underlying plant marks the fifth license of the Omega catalyst used, says Shell. substrate. The coating is made technology since the first commercial appli- According to Shell, capital costs for a new by encapsulating in separate, cation came on stream last May — a 400,000 Omega plant are about 10% less, at equal 100-µm-dia. beads, a cata- m.t./yr facility for Lotte Daesan Petrochemi- MEG yield, compared to alternative technol- lyst and a healing agent. The cal Corp. (Daesan, Korea). ogies. Omega also generates 30% less waste- beads are then dispersed Omega (short for Only MEG Advanced) water, has 20% lower steam consumption at within the desired coating material to be applied to the integrates two complementary and highly equal EO reaction selectivity, and produces substrate. When the coating is selective processes: Shell’s Master EO (eth- negligible amounts of byproducts, such as scratched, the contents of the ylene oxide) process and a catalytic MEG diethylene glycol and tri-ethylene glycol de- damaged beads is released, conversion process originally developed by rivatives, thereby eliminating the need for causing the catalyst and heal- Mitsubishi Chemical Corp. (MCC; Tokyo; the infrastructure and resources needed to ing agent to mix. The subse-, and acquired exclu- handle and market these products. quent reaction is said to repair the damage within minutes or hours, depending on the envi- A new PFSA polymer for membrane ronmental conditions. and other applications New engineered polymers S olvay Solexis S.p.A. (Bollate, Italy; www. has commercialized a new perfluorosulfinic acid (PFSA) polymer, The membranes enable PEM cells to oper- ate over a broad temperature range with improved ion conductivity. Kraton Polymers LLC (Houston, Tex; has intro- duced two new sulfonated copo- tradenamed Aquivion, which was specifi- The membranes are also suitable for ap- lymers, MD9150 and MD9200, cally designed for polymer electrolyte mem- plications in water electrolyzers, H2 separa- for ion-exchange and high-water- transport applications. The new brane (PEM) fuel cells. Aquivion ionomer tors, and pervaporization or gas humidifica- polymers are selectively mid- membranes are melt-extruded products tion systems. The polymer is also available block sulfonated copolymers and based on the Short Side Chain (SSC) copo- as a dispersion that can be used for making are available in both membranes lymer of tetrafluoroethylene and a sulfonyl electrodes, super-acid catalysts or for surface and solution form. fluoride vinyl ether of low molecular weight. treatment of membrane-filtration devices. 16 Chemical Engineering January 200906_CHE_011509_CHM.indd 16 12/22/08 9:53:27 AM
  19. 19. C hementato R Filtering oil from water Material engineers at Perdue University (West Lafayette, Ind.; have developed a new type of membrane for separating oil from water. The mem- A hard coating promises to reduce wear brane consists of a layer of perflourinated end-capped polyethylene glycol, which is and power use in rotating equipment covalently bonded to fritted glass mem- branes. When an oil-in-water emulsion is passed through the membrane, the R esearchers at the U.S. Dept. of Ener- gy’s (DOE; Washington, D.C.) Ames Laboratory ( and die at about 1,400°C and 14,000 psi to form a solid, dense block. The researchers have been using a oil beads up on the Teflon-like surface, while the water passes through. A 98% separation efficiency has been observed Iowa State University (both of Ames, technique called pulsed laser deposi- in the labortatory, using hexadecane as a Iowa) have developed a hard, smooth tion to dislodge atoms from these blocks model oil. coating that can be applied to indus- and deposit 1-µm coatings on adjacent trial equipment, such as pumps, gears targets, such as pump vanes. However, OLEDs and cutting tools, to reduce friction and this method is not practical for commer- BASF SE (Ludwigshafen, Germany; extend the life of the equipment. Ames cial use, says Russell, so Eaton is using and Osram Opto has been working with various compa- magnetron sputtering, a commercial- Semiconductors GmbH (Regensburg, nies, including Eaton Corp. (Cleveland, scale process. This is done in a vacuum Germany; have Ohio;, whose products chamber and uses radio frequency en- developed a highly efficient white or- include hydraulic pumps. ergy to ionize argon. The ions dislodge ganic light-emitting diode (OLED) that The coating material is a ceramic atoms for deposition on the target. achieves a light yield of over 60 lumens alloy that combines boron, aluminum, In laboratory tests the coating has per Watt, while also meeting the inter- magnesium and titanium boride, says proved to have only about 5% the wear national Energy Star SSL Standard with regard to color requirements. The new Alan Russell, a professor of materials rate of tungsten carbide, says Russell. OLEDs contain phosphorescent metal science and engineering at the univer- He adds that in tests of rotating parts, complexes as emitter materials and cus- sity. These ingredients are milled to a performed by Eaton, the coatings have tomized complementary materials; this particle size of 0.5–1 µm, thoroughly reduced power requirements by up to (Continues on p. 18) mixed,CHEM Ad-CE.qxd 12/2/08 10:33 9803 then compressed in a graphite 8%, due to 1 AM Page less friction. Innovative Mixing Solutions from a Global Family of Quality Products Chemineer combines the effective, innovative mixing solutions you require, with the attention and service you deserve. For high performance, high value products, choose from our family of leading brands. Kenics Prochem Greerco For the nearest sales office, call 1-800-643-0641 Chemineer is part of the Robbins Myers Process Solutions Group. More products… more solutions, from the brands you know and trust… Pfaudler, TyconTechnoglass, Chemineer and Edlon! Circle 14 on p. 58 or go to Chemical Engineering January 2009 1706_CHE_011509_CHM.indd 17 12/26/08 2:17:37 PM
  20. 20. (Continued from p. 17) C hementato R combination enables the diodes to be “color-stable” even when there are variations in luminous intensity. EPA proposal on HCFCs This LNG vaporization process will reduce air emissions The U.S. Environmental Protec- tion Agency (EPA; Washington, A new method for vaporizing liquefied natural gas (LNG) that is more envi- ronmentally friendly than the traditional porization technology (FHVT). The pro- cess uses a conventional fired heater with a low-NOx burner and fluegas recir- D.C.; has proposed a new rule to decrease the con- sumption and production of hydro- submerged combustion vaporization (SCV) culation. The combustion gases are used chlorofluorocarbons (HCFCs) for process is being offered by Black Veatch to heat a closed-loop circulating fluid the years 2010 (by at least 75%) to (BV; Overland Park, Kan.; (usually water) to 100–200°F. This loop 2014. HCFCs are ozone-depleting In an SCV process, LNG is passed vaporizes the LNG via a shell-and-tube substances and potential green- house gases, and as a party to the through stainless steel tubes in a water heat exchanger. Montreal Protocol on Substances bath that is warmed by sparging combus- The company has obtained a configura- that Deplete the Ozone Layer, tion gases from a submerged, gas-fired tion patent on the technology, but has not the U.S. will completely phase out burner. The thermal efficiency is close to piloted it, says Price, who notes that it HCFCs in 2030. 100%, says Brian Price, vice-president of uses conventional components. He points This action will also amend LNG technology for BV. However, he out that the process avoids the disposal of provisions concerning HCFC pro- points out, the downside is that the com- large volumes of wastewater and is calcu- duction for developing countries’ bustion gases create nitrous, nitric, car- lated to reduce NOx emissions to close to basic domestic needs and would bonic and other acids in the water bath those of an SCV system that is equipped clarify a ban on the sale and and the stack gas emissions contain ox- with selective catalytic reduction. CO distribution of HCFCs through interstate commerce under the ides of nitrogen (NOx) and carbon monox- emissions are expected to be less than Clkean Air Act. EPA will accept ide. Also, the bath has to be neutralized to 20% of those from an SCV. Preliminary comments on the proposed rule maintain a pH above 6 and the bath water calculations indicate that the process has for 60 days after publication in the has to be treated for disposal. an overall efficiency comparable to that of Federal Register. ❏ BV calls its method fired heater va- SCV, says the firm. ■ Circle 15 on p. 58 or go to 18 Chemical Engineering January 200906_CHE_011509_CHM.indd 18 12/22/08 9:56:35 AM