Shape-Selective Catalysis - American Chemical Society

Chapter 3

Recent Advances in Shape-Selective Catalysis and Its Industrial Applications Nai Y. Chen

Downloaded by UNIV QUEENSLAND on June 4, 2013 | http://pubs.acs.org Publication Date: November 2, 1999 | doi: 10.1021/bk-2000-0738.ch003

Technical Consultant, 4 Forrest Central Drive, Titusville, NJ 08560-1310

Presented herein is a general review of the advancement of a selected list of industrial applications and selected potential opportunities in shape selective catalysis. Also included is a review of the advances in the understanding of the catalytic properties of other useful molecular sieves than the traditional medium pore zeolites and the advanced practical catalyst modification methods. Molecular sieves covered in this paper include four major classes: (1) Intersecting channels of different size openings (2) Non-intersecting channels (3) Two, non-intersecting pore systems, such as MCM-22 and (4) Mesoporous molecular sieves, or the MCM-41S family.

Since writing the 2nd Edition of the book, Shape Selective Catalysis in Industrial Applications, first published in 1989 by Marcel Dekker, co-authored by me and my co-workers, Bill Garwood and Frank Dwyer at Mobil, was completed in 1995 after we retired from Mobil (published in 1996 by Marcel Dekker), three years have passed and a surprisingly large group of molecular sieves, mostly zeolites, established their commercial importance. Chemical modification of the molecular sieve catalysts also led to second and third generation catalysts for quite a few petrochemical processes. This paper is written to briefly review the advances in the following four areas: 1. The chemical and physical characteristics of useful molecular sieves with respect to their catalytic properties. 2. Practical methods in the modification of molecular sieves to improve activity, stability and selectivity in shape selective catalysis. © 2000 American Chemical Society

In Shape-Selective Catalysis; Song, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1999.

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40 3. Advances in industrial applications 4. New opportunities in shape selective catalysis


New Useful Molecular Sieves The crystal structure of a molecular sieve is defined by the specific order in which a network of tetrahedral units are linked together to form a set of open pores and channels. The closeness of the pore size of these materials to the size of many organic molecules of practical interest, gave birth to a new type of catalysis known as "shape selective catalysis". Beginning in the late fifties with the original discovery of the selective conversion of straight chain hydrocarbons using small pore (8-membered oxygen ring systems) zeolites, led to the first commercialized process known as the "Selectoforming" process in the mid-60's (1). This was followed by the discovery in 1967 of the unusual catalytic properties of ZSM-5 (2,3), the first medium pore (MFI, 10-membered oxygen ring systems) zeolite, and extended the application of shape selective catalysis to organic reactions involving not only linear and branched paraffins and olefins, but also aromatics, naphthenes and non-hydrocarbons. By now, not only we have quite a number of medium pore molecular sieves but also have learned many sophisticated physical and chemical techniques of selecting and/or modifying the catalyst to achieve the desired activity and selectivity in practical applications. In addition to classical medium pore molecular sieves (MFI, MFL), industrial application of shape selective catalysis has extended to four new classes of molecular sieves: 1) Molecular sieves possessing intersecting channels of different size openings with examples shown in Table 1 (4). '

Table 1. Intersecting Channels Of Different Size Openings IZA Code EMT ΒΕΑ DFO CON GME MOR OFF BPH MEI MFI FER HEU MFS

Name EMC-1, CSZ-l, ECR-30, ZSM-20

Zeolite Beta DAF-1 CIT-l,SSZ-33, SSZ-36

Gmelinite Mordenite Offretite, Linde T,LZ-217

Linde 0 ZSM-18 ZSM-5, Silicalite Ferrierite, FU-9, ISI-6, NU-23, ZSM-35

Heulandite, Clinoptilolite ZSM-57

Intersecting Channels 12, 12 12, 12 12, 10, 8 12, 12, 12, 12, 12, 12, 10, 10, 10, 10,

10 8 8 8 8 7 10 8 8 8

Pore size, Â 7.4 χ 7.6 7.6 χ 6.4 5.5 7.3 3.4 χ 5.6 6.0 5.4 χ 6.4 6.4 χ 7.0 1000 24 10 1

Oxime Conv. Wt% 66 46* 76* 34*

Caprolactam Selectivity, wt% 93 40* 61* 89*

Source:Yashima, et al. (1997); *values different from their 1994 data (78,79).


56 Table 9. Benzene vs. Ethanol as the Solvent


Feed: 15% Cyclohexanone oxime in Solvent and He, 4/35/61 mol ratio Feed Rate: 0.098 Mois feed per hr per gm cat. Temperature: 320°C; Pressure: 1 atm; Time on Stream: 1.75 Hr. Zeolite Silicalite-1 (MFI) Silicalite-1 (MFI) HZSM-5 (MFI) HZSM-5 (MFI) H-Ferrierite (FER) H-Ferrierite (FER) CaA (LTA) CaA (LTA)

Solvent Benzene Ethanol Benzene Ethanol Benzene Ethanol Benzene Ethanol

Oxime Conv. Wt% 66 80 46 82 76 54 34 34

Caprolactam Selectivity, wt% 93 98 40 88 61 84 89 91

Source: Yashima, et a l (1997) (79).

New Opportunities in Shape Selective Catalysis 1. Linear Alkylbenzenes Long chain linear alkylbenzenes are currently produced by the HF technology. The discovery of new molecular sieves offers an opportunity to selectively produce the desired 2-phenyl linear Qo to C alkylbenzenes for the detergent industry. ! 4

2. Alkylation of Naphthalene and Biphenyl Advanced polymers such as polyethylene naphthalate (PEN) and polybutylene naphthalate (PBN) requires 2,6-dialkyl naphthalenes (2,6-DAN) for making the monomers. Shape selective alkylation of naphthalene and biphenyl over molecular sieves catalysts to produce the desired isomer has attracted some attention as recently reviewed by Song (80). Compared to monocyclic hydrocarbons, it is more difficult to achieve high selectivity because of the larger number of possible isomers. With the availability of a large number of new molecular sieves, it is quite possible that the shape selective alkylation and/or transalkylation to obtain the desired isomer can be achieved. 3. Update of In Vivo "Shape Selective Catalysis" at Body Temperatures Since 1994, Visek and Mangian at the College of Medicine, University of Illinois (81,82) first reported the beneficial effects of adding less than 0.5 wt % (equivalent to about 10 lbs/ton of feed) of NaZSM-5 to the diet of Sprague Dauley rats such as binding ammonia ( N H + NH4 ") and adsorbing dimethylamine which could lead to the formation of N-nitroso-dimethylamine, a known carcinogen, formed in the gastrointestinal tract. Their study has extended to the diet of chickens. There is suggestive evidence that NaZSM-5 has similar benefits. 4

3


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The estimated annual quantity of NaZSM-5 required based on the production of animals in the U.S. alone could be as high as 5.5 million tons, much higher than its current use as industrial catalysts, if the cost of NaZSM-5 could be reduced to less than $1.50 per lb. This cost estimate is derived from the relative dosage and the cost of other feed additives such as antibiotics. Many years ago, with the objective of reducing the cost of zeolite synthesis. Chen et al. (83) studied the continuous crystallization of ZSM-5 by maintaining a steady state rate of rapid synthesis of the zeolite at below 100°C. Rollmann and Valyocsik (84) followed with the design of a continuous up-flow ZSM-5 crystallizer. Recently, Slangen et al. of the Netherlands (85) reported the continuous synthesis of zeolites, including ZSM-5 using a tubular reactor. Additional effort in this area would certainly reduce the cost of the synthesis of NaZSM-5 and make it possible to use it as a feed additive. 4. Aromatization Of Natural Gas Under Non-Oxidative Condition +

The aromatization of light paraffins (C ) over the ZSM-5 was discovered by me in the late 60's, now known as the M-2 Forming to produce B T X aromatics (86,87). It was extended to the upgrading of ethane in the 70's during the Middle East Oil Crisis (88,89) using metal loaded ZSM-5, but the aromatization of methane was not achieved until researchers at the Dalian Institute of Chemical Physics reported in 1993 (90) the production of 100% benzene and hydrogen using a Mo/ZSM-5 at 700°C in the laboratory. Methane conversion increased at higher pressures. At 2 atm. and employing a 50/1 S1O2/AI2O3 ratio Mo/ZSM-5, methane conversion of 7.2% was observed. 3

In a more recent paper, Lunsford's group attempted to characterize the active sites of a Mo/ZSM-5 catalyst for the conversion of methane to benzene (91). They found that the exposure of a 2 wt% Mo/ZSM-5 ( S i 0 / A l 0 = 50) catalyst to C H or CH4/H2 at 700°C causes reduction of Mo ions to M o C , rather than to metallic Mo. Benzene selectivity has an induction period. It increases with on stream time and after the reaction reaches steady state, about 60-80% of Mo species are present in the form of M 0 2 C while the rest remain present as M o / and M o and are not reduced even when the catalyst is treated in C H / H at 700°C for many hours. It is believed that the clean surface of M02C may be too reactive to form higher hydrocarbons and a "coked modified Mo C" may be the actual active species in the formation of ethylene as the reaction intermediate. 2

2

3

4

2

+

5

4

2

2

5. Hydrogen Fuel Cells For Transportation The U.S. Department of Energy (DOE) manages a National Hydrogen Program. In this role, DOE acts as a catalyst through partnerships with industry. This program has set a goal for 25% of all new vehicles sold in the United States in 2010 to be hydrogen powered, either as hybrids or as fuel cell vehicles. This will result in an important reduction in NO , CO, and C 0 emissions. x

2


58 A consortium that includes the City of Palm Desert, California, the Schatz Energy Research Center, and E.I. DuPont de Nemours & Co. among other activities, is currently working on a hydrogen-fueled, Proton Exchange Membrane (PEM) fuel cell for the future hydrogen-based transportation vehicles, including the test of more conductive membrane, such as the Nation® 1135 experimental membrane.


Daimler-Benz A G , Ford Motor Company, and Ballard Power Systems jointly own D B B Fuel Cell Engines GmbH, which is responsible for fuel-cell systems. They announced in August 1998 (92) a joint enterprise - Ecostar Electric Drive Systems Company to put high-volume fuel-cell production vehicles on the road by 2004. These fuel-cell vehicles could either powered directly by stored high-pressure hydrogen or methanol using an onboard steam reformer (93). On board production of hydrogen by steam reforming of gasoline fuel was first patented by Newkirk and Abel (94) in 1972. A pre-engine converter concept (95) presented the data of attaching a ZSM-5 catalytic reactor to an internal combustion engine to convert a low octane liquid fuel to a high octane gas/liquid fuel in 1974. Since then, the chemistry of converting light paraffins to hydrogen and aromatics over metal loaded medium pore zeolites has advanced to the stage that at least in the laboratory, it is already possible to convert methane directly to benzene and hydrogen (90,91). M y opinion is that instead of converting a hydrocarbon fuel to hydrogen and C O by steam reforming, additional research and development effort in paraffin aromatization could lead to a pre-engine converter designed to convert a hydrogen rich fossil fuel to co-produce hydrogen for the fuel cells and aromatic petrochemicals which could be recovered during refueling the vehicle. For example, 2 mois of propane could yield 3 mois of hydrogen and 1 mol of benzene. x

Conclusions The commercial application of shape selective catalysis continues to blossom with advanced technologies in petroleum refining and petrochemical industries since its inception in the late 1950s. Its extension to other industries may include the fine chemicals and pharmaceuticals (80,96), the automobile engines, the upgrading of natural gas and the production of animal feed additives. We welcome innovations and scientific understandings in selective hydroisomerization reactions, alkylation of polycyclic aromatics and the selective oxidation chemistry; similar activities in the synthesis of new molecular sieves and in the modification and formulation of industrial catalysts. However, the general de-emphasis of fundamental research by the energy industries in recent years is worrisome to me. By leaving all the fundamental research to the academic researchers will open wider the gap between knowing the basic principles governing shape selective catalysis and understanding the practical but often proprietary applications. The establishment of the rationality of the practical innovations is not only important to the advancement of the science of


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catalysis but also crucial to future discoveries. This review paper will provide (I) a reasonable interpretation of some of the new shape selective catalytic processes and (II) our understanding and our confusion in terms of theories and basic principles. I hope it will alert the academic and industrial researchers to work toward closing the gap for the sake of science and technology.

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Shape-Selective Catalysis - American Chemical Society

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