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Zeolites in the petrochemical industry

Zeolites in the petrochemical industry. http://omusinternational.com/db3/00225/omusinternational.com/_uimages/nightrefinery.JPG. S6. Presented by: Daniel Arnold, John Baumhardt , Michael Tran, Michael Trevathan. Outline. Introduction Motivation Membrane Zeolites Catalytic Zeolites

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Zeolites in the petrochemical industry

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  1. Zeolites in the petrochemical industry http://omusinternational.com/db3/00225/omusinternational.com/_uimages/nightrefinery.JPG S6 Presented by: Daniel Arnold, John Baumhardt, Michael Tran, Michael Trevathan

  2. Outline • Introduction • Motivation • Membrane Zeolites • Catalytic Zeolites • Further Research • Impact • Questions http://www.arabianoilandgas.com/pictures/gallery/Industry%20Trends/olefins_unit_web.jpg

  3. Introduction • “Zeolite” is a broad term used to describe a family of minerals called tectosilicates • Contain small pores and large surface area • Constructed of AlO4-5 and SiO4-4 molecules bound by oxygen • Zeolites are synthesized by manipulating: • Structure • Silica-Aluminum Ratio • Pore Size • Density "Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <http://www.cheresources.com/zeolitezz.shtml>.

  4. Introduction • Zeolites contain void space that can host cations, water, or other molecules • Molecular sieves • Do not allow molecules larger than 8 to 10 nm to enter lattice • Zeolites: • 40 known natural zeolites • > 140 synthetic zeolites "Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <http://www.cheresources.com/zeolitezz.shtml>. http://www.freefoto.com/images/13/53/13_53_21---Sunset--Teesside-Industry_web.jpg

  5. Introduction – Major Applications • Adsorption • Drying, purification, and separation • Powerful desiccants- able to hold 25% of their weight in water • Remove VOC from air streams & separate gases • Catalysis • Shape-selective catalyst- on the basis of molecular diameter • Acid catalysts – used in the petrochemical industry • Ion Exchange • Detergent formulas- replace phosphates as water softening agents • Exchange Na in zeolite for Ca or Mg in water http://www.bza.org/images/Na_lta.jpg International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>. http://upload.wikimedia.org/wikipedia/commons/5/58/Zeolite-ZSM-5-3D-vdW.png

  6. Introduction- Environment • Contribute to a cleaner, safer environment • In powder detergents, zeolites replaced harmful phosphate builders • Solid acids, zeolites reduce the need for corrosive liquid acids • Redox catalysts and sorbents • Remove atmospheric pollutants, such as engine exhaust gases and ozone-depleting CFCs. • Zeolites can also be used to separate harmful organics from water • Heavy metals and NH4+ Picture: http://www.cerpa.appstate.edu/images/environment.jpg "Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <http://www.cheresources.com/zeolitezz.shtml>.

  7. Introduction - Environment • Zeolites can be regenerated by • Heating to remove adsorbed materials • Ion exchanging with sodium to remove cations • Pressure swing to remove adsorbed gases. • University of New York at Stony Brook • Developed a zeolite to trap radioactive strontium • Heating the material makes the holes clamp shut, sealing the radioactive waste inside http://www.ecofriendlymag.com/wp-content/plugins/wp-o-matic/cache/3ad14_us-import-radioactive-waste.jpg "Science Netlinks: Science Updates." Science NetLinks: Resources for Teaching Science. Web. 30 Apr. 2010. <http://www.sciencenetlinks.com/sci_update.php?DocID=88>. http://jdlong.files.wordpress.com/2009/05/nuclear-plant.jpg

  8. Introduction International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>.

  9. Introduction- Applications International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>.

  10. Introduction- Registered Zeolites International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>.

  11. Introduction- Refinery International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>.

  12. Introduction – FCC International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>.

  13. Introduction Membranes • Applications • Desalination • ~90% salt rejection • Ethanol Dehydration • Replaces azeotropic distillation • Separate CO2 from air • A method of CO2 sequestration • H2 Separation http://cdn.physorg.com/newman/gfx/news/hires/energyeffici.jpg http://www.freepatentsonline.com/20040144712-0-large.jpg

  14. Introduction - Membranes • Research Efforts • Decrease membrane thickness • Increase flux • Determine sustainability/durability • Analyze replacement time and cost for industrial applications • Potential to replace current energy consuming separation devices • Distillation Column Welk, Margaret E. "Microporous Zeolite Membranes and Their Potential for H2 Production." Http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/separ_06_molecular_welk.pdf. Sandia National Laboratories. Web. http://bioage.typepad.com/photos/uncategorized/2007/07/11/mitsui_2.png

  15. Motivation • Reduce Operating Costs • Lower reaction temperature and pressure • Superior control of reaction selectivity • Reduces feed costs – less waste and treatment streams • Challenges • Energy efficiency – CO2 emissions • Product/Process specifications- heavier & dirtier crudes • Changing feedstocks (biofuel, biomass, unconventional oils) International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>. http://gozonews.com/wp-content/uploads/2008/05/biofuels.jpg

  16. Motivation- Global Market International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>. http://www.theage.com.au/ffximage/2005/03/24/oil_generic_wideweb__430x317.jpg

  17. Zeolite Membranes Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web.

  18. Zeolites in Separation • Water Separation • Hydrophilic LTA zeolite membrane • Highly selective in separation of water from organic solutions • Ethanol applications • Mitsui-BNRI successfully tested the de-watering of bio-ethanol using LTA (2003) Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web. http://asdn.net/asdn/chemistry/images/zeolites_clip_image002.jpg

  19. Zeolites in Separation • Hydrogen Separation • Offer better thermal and hydrothermal stability • MFI zeolites are the only developed membrane • Developing 6-ring zeolites for the purpose of reducing the thickness of membrane layers. Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web. http://www.scielo.cl/fbpe/img/jcchems/v53n1/fig17-02.jpg

  20. Zeolites in Separation • Carbon Dioxide Separation • Traditional glassy polymer membranes used • Natural Gas purification • Swelling-induced plasticization by carbon dioxide • Eliminated with the zeolite membrane • More selective for carbon dioxide/nitrogen separation http://s3.amazonaws.com/memebox/uploads/3562/kanatzidis-gasNorthwester.jpg Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web.

  21. Zeolites in Separation • Carbon Dioxide Separation Cont. • MFI type zeolite membranes • Preferential adsorption of Carbon Dioxide • Ability to modify zeolite structure to alter selectivity • DDR membranes as an alternative • Improved permeances with the same high carbon dioxide methane selectivity • Both membranes are being used in industry currently • Cost Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web. http://www.freepatentsonline.com/6667265-0-large.jpg

  22. Zeolites in Separation • p-Xylene Separation (Polymer Production) • Traditionally separated through adsorption, fractional crystallization, or distillation • Costly • Energy intensive • Add organic templates to polymeric silica sols • Tetraethyl or tetrapropyl ammonium bromide • Higher Stability • Significantly reduced energy costs Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web. http://www.dion.che.udel.edu/images/smallTMA.gif

  23. Zeolites in Separation • Alcohol Separation • FAU used to separate alcohols from organic materials. • Using the polarity differences between the molecules. • Successful in a laboratory setting. http://www.personal.utulsa.edu/~geoffrey-price/zeolite/fau.jpg Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web.

  24. Outlook of Zeolite Membrane • 25 years of intense R&D on these membranes • Minimal industrial applications • Pilot plants in de-watering • A lot of promising applications • Alcohol, xylene, hydrogen, and carbon dioxide separation • Energy usage reduction John Baumhardt ETC 2009 Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web.

  25. Zeolite Catalysis Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  26. Synthesis of Zeolites • Raw Materials (ZSM-5) • Distilled Water • Sodium Hydroxide • Tetrapropylammonium hydroxide • Silicic Acid • Sodium Aluminate Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  27. Synthesis of Zeolites • Concerns on Raw Materials • Water Content • Source of Sodium Aluminate • Source of Silica • Purity of Materials Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  28. Synthesis of Zeolites • Nucleation • Primary • Homogeneous or Heterogeneous – No significant Difference • Secondary • Initial breeding – Parent crystals aid nucleation • Contact - No significant difference • Shear - No significant difference • Fracture – No significant difference Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  29. Synthesis of Zeolites • Process Steps (ZSM-5) • Seeding Gel Preparations • Mix water + NaOH + TPA-OH • Add Silica in portions • Agitate for 1 hour • Hold at 100C for 16 hours • Synthesis of Gel Preparation • Add water + NaOH + Sodium Aluminate • Add Silica in portions, agitate for 1 hour • Add Seeding gel • Agitate for 1 hour Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  30. Synthesis of Zeolites • Process Steps (ZSM-5) • Crystallization • Hold at 180C for 40 hours, no agitation • Product Recovery • Recover product by filtration • Wash thoroughly with distilled water • Dry at 105C for 24 hours • Pulverize dried product for 24 hours Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  31. Synthesis of Zeolites Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  32. Synthesis of Zeolites • Safety Concerns • Silica and Alumina are inert in most forms • Alkoxides are skin irritants • Hydrolysis of Alkoxides produces heat • Crystallization is done at high temperatures and pressures Zhang, Yahong, Nan Ren, and Yi Tang. "ZeoliteNanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.

  33. Impact & Further Research

  34. Further Research • International Zeolites Association (IZA) has registered 179 different zeolites structures • 18 are reported to be used in commercial operation http://www.molecularsieve.org/image/Zeolite_Molecular_Sieve_4A.gif

  35. Further Research • SAPO-34 • Alleged that in the very near future it will be commercially used in the Methanol-to-Olefins (MTO) process • It will take more than 25 year to reach commercialization • Identified that this material exhibited the right structural and compositional features for the selective conversion of methanol into ethylene and propylene http://www3.interscience.wiley.com/homepages/26293/frontisp/2008/36_801293.jpg

  36. Further Research https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5

  37. Further Research • Separation of water from Ethanol • LTA-zeolite containing membranes • Developed by Mitsui & Co • Supported on ceramic tubes operating in Vapor Permeation mode • Save ~ 10 % of the energy requirement for the production of fuel grade bio-ethanol • Can be used in more diluted ethanol streams http://wikis.lib.ncsu.edu/images/2/28/Z-a-1.png

  38. Further Research • Zeolite-base material for removal of olefins in aromatic • Replace the used of clay materials • Reduces the solid waste by more than 85% • Higher removal efficiency • MCM-22 is one of the efficient zeolites for alkylation with long-chain olefins http://www.nsfc.gov.cn/nsfc/cen/ndbg/2000ndbg/pic/03_02.jpg

  39. Further Research • Using New Feedstock for Existing end-Products • Methane conversation into aromatics • Catalytic naphtha cracking • Adapt zeolitic catalyst to obtain high selectivity for light olefins • Conversion of methanol into light olefins • Near industrialization • Two families of technologies • SAPO-34 molecular sieve • ZSM-5 type zeolite http://www.hgs-model.com/gallery/img/pho_010.gif

  40. Further Research • X-axis: Years • Legend • Grey: Condensate + LPG • Green: Heavy oil • Orange: Conventional Crude https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5

  41. Further Research • X-axis: Country • Y-axis: Distribution (%) • Legend • Blue: Coal • Pink: Natural gas • Green: Oil https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5

  42. Further Research • Potential of natural gas and coal are still enormous to transform into transportation fuels and petrochemicals • High investments in heavy oil production • Technological progress in biomass to convert it using clean and efficient processes into valuable products http://www.eimcowatertechnologies.com/intakes/images/stories/Water_Intake/petrochemical.jpg

  43. References • "Green Chemistry with Zeolite Catalysts." Chemical Engineering, The Chemical Engineers'Resource Page, Distillation, Heat Transer, Design, Spreadsheet Solutions, Departments, Chemistry. Web. 22 Apr. 2010. <http://www.cheresources.com/zeolitezz.shtml>. • International, Zeolyst. "Zeolyst International - Zeolite FAQ's - Specialty Zeolites." Zeolite Manufacturer, Supplier of Zeolite Catalysts and Powders. Web. 22 Apr. 2010. <http://www.zeolyst.com/html/faq.asp#one>. • Zhang, Yahong, Nan Ren, and Yi Tang. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web. • Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and MesoporousMaterilas (2008): 215-33. ScienceDirect. Web. http://www.nansulate.com/pdf/Heneteks_2008savings.pdf

  44. Questions? http://www.legis.state.wi.us/senate/sen11/news/images/questions.jpg

  45. S6 RebuttalPlease Prepare a Rebuttal Daniel Arnold John Baumhardt Michael Tran Michael Trevathan

  46. Group S1REVIEW:Zeolites in the Petrochemical Industry --MISSING--

  47. Group S2 Review of S6 2nd Presentation Chris Heflin Rachel Houk Micheal Jones

  48. Done Well • Excellent description of applications in the introduction. This is by far the most informative introduction we have seen thus far. • Each speaker was well poised in front of the audience and was well prepared for their portion of the presentation. It was clear they had practiced and prepared thoroughly.

  49. Needs Improvement • The presentation never provides a real definition of what a zeolite is to start off, but rather jumps straight into the applications. • Other than this, the presentation was strong and well done.

  50. Review of S6—Zeolites in the Petrochemical Industry By S3: James Kancewick Michael Koetting Bradford Lamb

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