Post on 25-Dec-2015
ZEOLITES IN THE PETROCHEMICAL
INDUSTRY
Presented by:
Daniel Arnold, John Baumhardt, Michael Tran, Michael TrevathanS6http://omusinternational.com/db3/00225/omusinternational.com/_uimages/nightrefinery.JPG
Outline
Introduction Motivation Membrane Zeolites Catalytic Zeolites Further Research Impact Questions
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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>.
"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>.
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
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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 waterInternational, 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
http://www.bza.org/images/Na_lta.jpg
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
+
"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>.
Picture: http://www.cerpa.appstate.edu/images/environment.jpg
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
"Science Netlinks: Science Updates." Science NetLinks: Resources for Teaching Science. Web. 30 Apr. 2010. <http://www.sciencenetlinks.com/sci_update.php?DocID=88>.
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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>.
Introduction
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>.
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>.
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>.
Introduction- Refinery
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>.
Introduction Membranes
Applications Desalination
~90% salt rejection Ethanol
Dehydration Replaces azeotropic
distillation Separate CO2 from
air A method of CO2
sequestration H2 Separation
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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
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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.
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)http://gozonews.com/wp-content/uploads/2008/05/biofuels.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>.
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>.
Motivation- Global Market
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Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
Zeolite Membranes
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)
http://asdn.net/asdn/chemistry/images/zeolites_clip_image002.jpgCaro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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.
http://www.scielo.cl/fbpe/img/jcchems/v53n1/fig17-02.jpgCaro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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
http://www.freepatentsonline.com/6667265-0-large.jpgCaro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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
http://www.dion.che.udel.edu/images/smallTMA.gifCaro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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.jpgCaro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
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 reductionJohn Baumhardt ETC 2009
Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
Zhang, Yahong, Nan Ren, and Yi Tang. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
Zeolite Catalysis
Synthesis of Zeolites
Raw Materials (ZSM-5) Distilled Water Sodium Hydroxide Tetrapropylammonium hydroxide Silicic Acid Sodium Aluminate
Zhang, Yahong, Nan Ren, and Yi Tang. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
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. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
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. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
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. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
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. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
Synthesis of Zeolites
Zhang, Yahong, Nan Ren, and Yi Tang. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
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. "Zeolite Nanocrystals: Hierarchical Assembly and Applications." Ordered Porous Solids (2009): 441-75. ScienceDirect. Web.
Impact & Further Research
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
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
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Further Research
https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5
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
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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
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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
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Further Research
https://mailhost-2.tamu.edu/service/home/~/Zeolite_seminar.pdf?auth=co&loc=en_US&id=46940&part=5
X-axis: Years Legend
Grey: Condensate + LPG
Green: Heavy oil Orange:
Conventional Crude
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
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
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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://www.nansulate.com/pdf/Heneteks_2008savings.pdf
Questions?
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S6 RebuttalPlease Prepare a Rebuttal
Daniel ArnoldJohn Baumhardt
Michael TranMichael Trevathan
Group S1REVIEW:
Zeolites in the Petrochemical Industry
--MISSING--
Group S2 Review of S6 2nd Presentation
Chris HeflinRachel Houk
Micheal Jones
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.
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.
Review of S6—Zeolites in the Petrochemical Industry
By S3:James KancewickMichael Koetting
Bradford Lamb
PositivesSlides were universally well-made, with interesting
and relevant images and not too much text.Speaking was very strong throughout most of the
presentation. Most speakers seemed very well-rehearsed and confident.
Introduction was very informative. Although somewhat long, it did an excellent job of leading into the research papers discussed.
Speakers did a good job of highlighting both the impact and the shortcomings of current research.
Very good presentation of statistics and other technical information in an audience-friendly way.
Areas for ImprovementAlthough speaking was generally very good,
one speaker read some scripted speech. This caused him to look down, away from the audience throughout his section, which detracted somewhat from the overall presentation.
Figures in the “Zeolite Catalysis” section did not have their own individual citations.
On the whole, however, this was a very strong presentation.
S4 Review of S6Danielle Miller
Josh MorenoScott Marwil
Things Done WellExcellent job on the oral presentation.Everyone spoke clear and didn’t mess up
once.Awesome food choice- the chocolate chip
cookies were delicious.Everyone looked very professional.Topics were well researched.
Things to Improve OnPictures are covering some words.When you have a picture that takes up the
majority of the slide, it looks tacky to just put it over a title block that is defaulted in the design. Instead change the layout to a blank slide or one that doesn’t have the partially covered colored strip.
Don’t put words on top of the citation…. Two layers of text is too much.
Things to Improve OnCitations are hanging off the edge of the
slide. Make sure everything you put on the slide actually fits.
Don’t turn your head when your talking into a microphone that doesn’t move with you. You sound like you were cutting in and out.
Use consistency in your punctuation on bullets. Style should exhibit parallelism.
S5 Review of S6
• The team overall did a great job at presenting their topic.
• One of the slides had a large spreadsheet on it that had too much material—it was almost illegible and required a lot of focus, which kept us from listening to the speaker.
• John did a great job at speaking. We noticed that he asked questions during his presentation—great. It involved the audience and made his part interesting.
• Michael read off of the slides somewhat. It seemed like he knew the material but was nervous.
S5 Review of S6
• The contrast between the titles and background could have been greater. This is a picky statement, but it would have made the titles perfectly clear.
• Daniel was a good speaker, but he did not seem very interested in the topic. More enthusiasm would have made him excel greatly.