Oakwood Consulting, Inc.

Consultants for Polyolefin Catalysts, Processes, and Marketing

Oakwood Consulting, Inc. (OCI) incorporated in April 1995 and teamed with several colleagues to offer  services to the petrochemical industry.   Our colleagues constitute a unique team that has the appropriate skills and experience to perform technical consulting services and market analyses in polyolefins, in process, product, and catalyst related areas.  As a team, we have accumulated 138 man-years of experience in the petrochemical industry, most of it in PP with one of the largest PP producers.  As a team project, one of the leading PP high-activity supported Ziegler-Natta catalysts was developed and patented during this period and continues in use.  Those available, either as individuals or in combination, are described in the following biographical sketches.

Services            Biographies            Assignments            Contact Us

Our Services

With this team, we are able to provide advice, critique, process design, process simulation, polymerization reactor modeling, licensing evaluation, market analysis, and cost estimation in the petrochemical field, especially polyolefins and their catalysts.

    Bench-scale continuous polyolefin pilot plant design (collaboration with Xytel Corporation for marketing and construction worldwide)

    New catalyst development, pilot plant design, and scale-up to production

    Process design and modernization, process simulation, and polymerization reactor modeling

    Market analysis and cost estimation

    Client-commissioned customized studies

 

Services            Biographies            Assignments            Contact Us

 

Our Biographies of Experts

   Dr. Gregory Arzoumanidis (BS/MS U. Thessaloniki, Greece 1959; PhD Inorg. Chem., U. Stuttgart, Germany 1964; MIT postdoc 1964-66; MBA UConn 1980) has been a polyolefin catalyst chemist since 1973. After spending seven years developing new processes for metal catalyzed synthesis of aromatic compounds (aniline, anthraquinone, etc), and a process to convert phosphine to hypophosphorous acid, he turned his focus on Ziegler-Natta catalysts. He has considerable experience with a major catalyst manufacturing company, and has been doing PP catalyst research for a leading PP producer, Amoco Chemical, now part of Ineos. He has been the leader for the development and commercialization of the Amoco CD catalyst for PP, receiving a company award for his invention. He has 26 US patents, numerous publications, presented many seminars in polyolefin catalysis and taught a short course on metallocene technology in several countries. Since 1996 as partner of Oakwoodconsulting.com or as a private consultant, he has written dozens of research reports and proposals to international companies in the USA, Europe, and Asia, and collaborated with several of their research departments in the development and commercialization of polyolefin catalysts. He is now proposing some new types of orthometallated heteroaromatic complexes discovered by him, as catalysts for commercial olefin polymerizations.

    Mr. Norman Stein, a chemical engineer (M.S., U. of Wisconsin, 1950), has over 40 years of R&D experience, serving Oakwood Consulting, Inc., since 1995 – consulting for polyolefin catalysts, processes and marketing. He has been a Senior Consulting Engineer in R&D with a major petrochemical firm, Amoco Chemical Company. Mr. Stein’s industrial experience comprises 42 years in applied research and development with E.I. DuPont Corporation and Amoco, where he had served during the last 23 years as Director of Polyolefins and Catalyst Research. He has almost thirty years of progressively responsible supervisory assignments with Amoco. His management responsibilities include director level positions, supervising work on products, processes, and catalysts for a $500 million polypropylene and polyethylene business. He also directed research and development work in processes and products for a $150 million polystyrene and hydrocarbon resins business. His functional responsibilities have included commercial development, economic analysis, strategic planning, competitive intelligence, market research, as well as research and development including budgeting and planning. Mr. Stein’s specific areas of expertise include polypropylene, polystyrene, polyethylene, aromatic hydrocarbons, aromatic acids and esters, blends and alloys, engineering polymers and thermoplastic olefins. Mr. Stein has had responsibility for research budgets for up to $10 million, supporting annual sales of up to $500 million. He has special skills in licensing processes and negotiating technical exchange agreements with international companies including extensive experience with Japanese, German, British and Italian firms.

   Dr. Norman F. Brockmeier (PhD, MIT, 1966), is a chemical engineer and president of Oakwood Consulting, Inc., serving many petrochemical companies since its formation in 1995. His special focus is polyolefin process design and economics, recently in the field of metallocene catalysis, with many publications in both areas. A registered professional engineer, he was codesigner of the first Amoco gas-phase manufacturing process for homopolymer PP resin, and part of the design team for a new gas-phase ethylene-propylene copolymer plant in Texas. He has served as a member of the team assembled to promote and license this new PP technology. He has taught the capstone senior design course at The Ohio State University, and much earlier, taught in the Chemical Engineering Department for five years at the University of Texas--Austin. Norm has over 43 years of industrial experience—this includes acting as an expert witness in federal court. He also worked for seven years in process evaluation at Argonne National Lab, where he had a major responsibility in process simulation. In 1999 he was elected a Fellow of the Amer. Inst. of Chemical Engineers.

    With this team, we are able to provide advice, critique, process design, process simulation, polymerization reactor modeling, licensing evaluation, market analysis, and cost estimation in the petrochemical field, especially polyolefins and their catalysts.

Services            Biographies            Assignments            Contact Us

Our Recent Assignments:

    1. "Commissioned Catalyst Study for Polyolefin Manufacture Offshore. " 5/25/13

    2. "Stabilizer Recipe for Specialized Fiber Grade Polypropylene (PP). " 2010

    3. "Commissioned Economic Study of Medical PP Random Copolymer. " 2009

    4. "Commissioned Economic Study of Medical PP Random Copolymer. " 2009

    5. "Air Force Research on Polyolefin Core for RADAR Application. " 2007

    6. "Polyolefins from Single Site Metallocene Catalyst ", Processes, Catalyst, Polymer Products, Patents and Licensing, Super Memorandum for Teltech and a major oil company.

    7. "Ziegler-Natta Catalysts for Polypropylene ", Catalysts, Products, and Process Economics and Future Volumes, Memorandum for a major oil company.

    8. "EPDM Rubber from Metallocene Catalyst", Memorandum for a major rubber company.

    9. "Impact Polypropylene Copolymer", Catalysts, Processes and Polymer Properties, Memorandum for a Marketing Consulting Group ".

    10. "Polystyrene, Bulk Continuous Process for Impact and Crystal Grades", Consulting for a major petrochemical company.

    11. "High Activity Supported Catalyst Manufacturing Process (for Polyethylene)", Design and Economics Scoping Study for a major company.

    12. "Polyolefin Ziegler-Natta Catalysts -- Components, Prices, Recipes, and Productivities", Memorandum for a Marketing Consulting Group.

    13. "Care and Feeding of Polyolefin Catalysts", Article published in Chemical Engineering, Sept., 1996.

    14. Evaluated the leading eight Polypropylene Licensor’s brochures; submitted evaluation to a foreign polymer processing company contemplating construction of a PP plant. A memorandum evaluating licensor’s process, product, economics, and licensing fees. Rated licensors ordinally, recommended two best choices.

    15. "Polyolefin Comonomers--World Markets 1995 - 2005", a detailed report projecting the effects of factors such as business alliances, patents, catalysts, processes, and products on the polyolefins market opportunities for alpha-olefins.

    16. "Facilities Design for the Manufacture of Supported High Activity Ziegler-Natta Catalysts for Polyolefins", assistance in the design of facilities for a major chemical company.

    17. "Polyolefin Resins as a Key Component of Industrial Roofing", commissioned study for a vendor client.

    18. "Polypropylene Homopolymer and Random Copolymer Reactor Simulation Models", Computer models for either Aspen PlusR or stand-alone PC platforms.

    19. "NOVEL Ti-Aryl COMPLEXES AS INTERNAL OR EXTERNAL MODIFIERS, IMPROVING PERFORMANCE OF MgCl2 SUPPORTED POLYPROPYLENE CATALYSTS" by Gregory G. Arzoumanidis - Oakwood Consulting, Inc.   

ASTRACT: NOVEL Ti-Aryl COMPLEXES AS INTERNAL OR EXTERNAL MODIFIERS, IMPROVING PERFORMANCE OF MgCl2 SUPPORTED POLYPROPYLENE CATALYSTS

The recently announced multi-site behavior of some Hf organometallic complexes in olefin polymerizations (1) may be attributed in part to olefin insertion into the Hf-aryl bond. We have now applied for the first time a number of novel hindered aromatic complexes, featuring a Ti-aryl bond and one or more heteroatoms, to demonstrate substantial improvements in catalytic performance of MgCl2 supported Polypropylene (PP) catalysts. Complexes with other metals, such as Zr, showing identical structures, have also been prepared.

These complexes may be used either as internal or external modifiers of MgCl2 supported PP catalysts. As internal modifiers, may not replace entirely the existing, e.g., phthalates or other well known internal modifiers. Instead, by an optimum partial replacement of the existing modifiers, they may impart mainly activity enhancements up to 80%.

As external modifiers that could be delivered mixed with the aluminum alkyl, they may replace 70-100% of the silane commonly used. Besides the activity enhancement, they are expected to impart substantial improvements to PP product properties, due to their multi-site behavior. To take advantage of this technology in a PP process, there is no need for changes in the use and operation of an existing MgCl2 supported catalyst, except for the addition of the complexes as external modifiers.

The complexes were prepared in an one-pot, single step reaction in toluene of TiCl4 or ZrCl4 with compounds of the general formula Arx-L-E, where Ar=Aryl attached to L, x=1-4, L= a polycyclic or monocyclic heteroaromatic ligand, containing one or more heteroatoms, E=heteroatom available for coordination/bond formation with the metal. The reaction involves an orthometalation and formation of a 5- or 6-member metalocyclic ring. These complexes further undergo chemical transformation and metal reduction with aluminum alkyls, such as triethylaluminum (TEA). The resulting products may accept a great variety of aprotic electron donors.

Although we prepared only a few orthometalated complexes, we have identified dozens of ligands that have the potential to form such compounds. If one counts one or more substituents on these ligands, it appears that this new technology offers endless possibilities.

The complexes are expected to be utilized as independent catalysts as well, in several other alpha-olefin polymerizations and copolymerizations such as ethylene, butene, etc, and particularly in high temperature solution processes. Their great advantage is their activation with aluminum alkyls such as TEA, not MAO or other non-coordinating anions.

To be presented at the SPE International Polyolefins Conference, Houston, Texas, February 24, 2014

 

 

 

          HOW MUCH DO WE KNOW ABOUT MgCl2 SUPPORTED POLYPROPYLENE          

                             CATALYSTS?   A CASE OF UNEXPECTED RESULTS.

 

                                                           Gregory G. Arzoumanidis

                                                           Oakwood Consulting, Inc.

                                                            Wheaton, Illinois 60187

                                                           arzoumandis@gmail.com

                                                            oakwoodconsulting.com

 

Abstract


The answer to the question is, probably less than what we think we know!  To borrow from Prof. Vincenzo Busico (1), high yield MgCl-supported Ti based catalysts for PP is an extreme case of fundamental ignorance.  According to QM (quanto mechanic) calculations, most proposed TiCl supported adducts do not "stick" to MgCl.

 

In my 2014 SPE paper I proposed a MgCl supported PP catalyst featuring organometallic complexes as the active sites, instead of just TiCl. Catalysts with the organometallic complexes showed 40% to 60% higher activity.

 

I now report that treatment of the latter with TiCl at a Ti level equal to the already existing on the catalyst, increases the yield by 70%  to 95%.  Perhaps more important are the observed changes in  some fundamental properties of the polymer produced.  The extractables are still 99%+, and the MFR dropped by about 50%, a profound change in H response.  

 

These results are rather unexpected, and an attempt has been made to rationalize them. I believe the TiCl treatment replaces the organometallic complex out of its position, essentially restoring the catalyst in its original form.  At the same time, the organometallic complex becomes free (but remains mixed with the MgCl catalyst), and changes its role from  internal modifier to external.  The new catalyst system comprises  two components,

 

1. DPI Annual Meeting, 2007

the "original" MgCl catalyst and the

organometallic complex.  Each component contributes roughly 50/50 to the activity, but at different ratios to polymer properties such as extractables and MFR.  Synergistic effects may not be ruled out.

 

Furthermore, it is possible to incorporate the organometallic compound in-situ on an existing catalyst (or support), by treating them consecutively with the ligand and TiCl.

 

One very important aspect of the two component system, is the activation with TEA. There is no surprise here, as far as the MgCl component is concerned.  But the organometallic component, is apparently also activated with TEA. This is a rare example of an organometallic complex activated by an aluminum trialkyl.  It represents a process and a financial advantage with significant value.

 

We have indicated that these organometallic complexes act as multi-site catalysts due to olefin insertion into the metal carbon bond, with formation of up to ten new srereo-isomers, affecting the  polymerization  in different ways.

 

However,  certain reactive monomers, other than olefins, may retain the symmetry of the complex after the insertion, and could convert the complexes into single-site catalysts. This implies that we could very likely convert the MgCl supported catalyst for PP into single-site as well.

 

 

 



Services            Biographies            Assignments            Contact Us

 


Oakwood Consulting

255 E Liberty Dr, #208

Wheaton, IL 60187 - 5414

Phone  (630) 740 - 0095   

Click the computers to send email

 

Designed by the EngineersWebSite