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
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Introduction
Motivation
Membrane Zeolites
Catalytic Zeolites
Further Research
Impact
Questions
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Introduction
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“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>.
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>.
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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 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
Introduction- Environment
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
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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


Zeolites can also be used to separate
harmful organics from water

Picture:
Remove atmospheric pollutants, such as
engine exhaust gases and ozonedepleting CFCs.
Heavy metals and NH4+
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>.
Introduction - Environment

Zeolites can be regenerated by
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

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
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
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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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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>.
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>.
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>.
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%
 Ethanol
salt rejection
Dehydration
 Replaces
azeotropic
distillation
 Separate
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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
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.
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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
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>.
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Zeolite Membranes
Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent
developments and progress.“ Microporous and Mesoporous
Materilas (2008): 215-33. ScienceDirect. Web.
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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://asdn.net/asdn/chemistry/images/zeolites_clip_image002.jpg
Zeolites in Separation
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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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://www.scielo.cl/fbpe/img/jcchems/v53n1/fig17-02.jpg
Zeolites in Separation
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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
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
Carbon Dioxide Separation
Cont.
MFI type zeolite membranes
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DDR membranes as an
alternative
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Preferential adsorption of
Carbon Dioxide
Ability to modify zeolite
structure to alter selectivity
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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://www.freepatentsonline.com/6667265-0-large.jpg
Zeolites in Separation
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
p-Xylene Separation (Polymer Production)
Traditionally separated through adsorption, fractional crystallization, or
distillation
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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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://www.dion.che.udel.edu/images/smallTMA.gif
Zeolites in Separation
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
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Alcohol Separation
FAU used to separate
alcohols from organic
materials.
Using the polarity
differences between the
molecules.
Successful in a laboratory
setting.
Caro Juergan, and Noack Manfred. "Zeolite membranes- Recent developments and
progress.“ Microporous and Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
http://www.personal.utulsa.edu/~geoffrey-price/zeolite/fau.jpg
Outlook of Zeolite Membrane

25 years of intense R&D
on these membranes
Minimal industrial
applications
 Pilot plants in dewatering


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 Mesoporous Materilas (2008): 215-33. ScienceDirect. Web.
Zeolite Catalysis
Zhang, Yahong, Nan Ren, and Yi Tang. "Zeolite Nanocrystals:
Hierarchical Assembly and Applications." Ordered Porous Solids
(2009): 441-75. ScienceDirect. Web.
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
http://www3.interscience.wiley.com/homepages/26293/frontisp/2008/36_801293.jpg
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
http://wikis.lib.ncsu.edu/images/2/28/Z-a-1.png
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 longchain olefins
http://www.nsfc.gov.cn/nsfc/cen/ndbg/2000ndbg/pic/03_02.jpg
Further Research

Using New Feedstock for Existing endProducts


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
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
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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trochemical.jpg
References
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


"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 Rebuttal
Please Prepare a Rebuttal
Daniel Arnold
John Baumhardt
Michael Tran
Michael Trevathan
Group S1
REVIEW:
Zeolites in the Petrochemical Industry
--MISSING--
Group S2 Review of S6 2nd
Presentation
Chris Heflin
Rachel 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.
By S3:
James Kancewick
Michael Koetting
Bradford Lamb
Positives
 Slides 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 Improvement
 Although 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.
Danielle Miller
Josh Moreno
Scott Marwil
Things Done Well
 Excellent 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 On
 Pictures 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 On
 Citations 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.