zeolites in the petrochemical industry

ZEOLITES IN THE PETROCHEMICAL

INDUSTRY

Presented by:Daniel Arnold, John Baumhardt, Michael Tran, Michael TrevathanS6

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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>.

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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

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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

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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

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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.