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Studies in Surface Science and Catalysis 148 Terasaki (Editor) 9 2004 Elsevier B.V. All rights reserved.

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The Discovery of ExxonMobil's M41S Family of Mesoporous Molecular Sieves

Charles T. Kresge +, James C. Vartuli*, Wieslaw J. Roth*, and

Michael E. Leonowicz ++

Keywords:

Mesoporous, MCM-41, Molecular Sieves, M41S, Mobil, ExxonMobil

The quest for new molecular sieves in the late 1980's led a team of Mobil researchers to the discovery of a family of nanostructured mesoporous materials known as M41S [1,2]. MCM-41, the hexagonal phase, is undoubtedly the best known and most widely studied of this family of materials. Other discrete members of the M41S family are the cubic (MCM- 48) and the lamellar (MCM-50) forms. Each is synthesized via a counterion initiated, self- assembled liquid crystal mechanism involving oxide precursors, which form an inorganic equivalent to a liquid crystal-micelle structure [3,4]. This manuscript describes the events that led to the discovery of M41S materials. It also summarizes the supporting characterization and mechanistic studies that led to a picture of how these of materials are actually formed. The mechanistic and characterization studies involved many researchers from ExxonMobil's Paulsboro and Princeton laboratories. Relevant publications by these ExxonMobil scientists include references [3-19]. Beyond the initial discoveries of MCM-41, -48, and-50, these scientists contributed significantly to the fundamental understanding and refinement of this new class of materials. ExxonMobil has very recently scaled-up the synthesis and commercialized MCM-41 for an undisclosed application. This decade-long journey from the discovery to commercial application is similar in duration to that of many novel materials. Yet, there were many unique challenges posed by the synthesis and development of such a novel class of materials.

Like most discoveries of novel materials, the discovery of the M41S family of mesoporous molecular sieves was an unanticipated outcome of the application of observational skills, prior knowledge, and novel synthesis approaches. Paralleling the efforts of several major petroleum companies, ExxonMobil had a materials synthesis effort attempting to identify new porous materials that could selectively convert bulky, high molecular weight petroleum molecules into more valuable fuel and lubricant products. In the mid-1980's, an ExxonMobil Research and Engineering predecessor, Mobil Research and Development Corporation, had a significant effort at its Paulsboro, NJ laboratory aimed at discovering and developing layered-type materials and converting them into stable porous catalysts by pillaring. Theoretically, pillared materials offered the ability to tune the pore size, the active site density, and the composition more widely than possible in traditional aluminosilicate zeolites. The pore systems could be tuned for the desired application by varying the pillar size and density. The pillar composition also appeared to be adjustable so that various reactivities and chemistries could be obtained [see for example ref. 20].

+Currentaddresses:The Dow Chemical Company,566 Building, MidlandMichigan48674 *Current address: Exxon Mobil Research & EngineeringCo., 1545 Route 22 East, Annandale, NJ

08801 (to whom correspondenceshould be sent)

++Currentaddress: Consultant,Charlotte, North Carolina

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In the mid- to late 1980's, the authors, working together in what was then Mobil's Paulsboro Laboratory, approached the effort of synthesizing large pore frameworks by attempting to combine both the concepts of the pillared layered materials and the formation of zeolites. We worked together experimenting with novel synthesis approaches and discovering unique materials. One of these novel approaches was to consider that some zeolites were formed via layered intermediates. If these layered intermediates, so-called "zeolite precursors," could be isolated and used to form pillared porous materials, we postulated that the resultant product should have crystalline walls that would be thermally stable, catalytically active, and contain both micro- and mesoporosity. This concept had credibility because of a new framework that was discovered during that time that was found to transpose from a layered precursor to the zeolitic structure [21]. This material was designated as Mobil Composition of Matter number 22 or MCM-22.

In the case of MCM-22, it was noted earlier in exploring its physical properties that upon thermal treatment of the as-synthesized product, some of the peaks in the X-ray diffraction pattern of the material had shifted to higher 2(~ values. We initially interpreted this as indicative of unit cell contraction, similar to that of swollen layered materials when the intercalate is removed. In layered materials the low angle lines associated with the interlayer distance shift to lower d-spacings consistent with the removal of the organic template intercalate and the collapse of the layers. However, in the as-synthesized MCM- 22 sample, this shift of the d-spacings, upon thermal treatment, was subtle, ~2-3A, while the peaks associated with the intra-layer framework remained relatively unaffected. This suggested that the MCM-22 zeolite was composed of crystalline layers that were linked together by weak chemical bonds during the synthesis. Upon thermal treatment, these chemical linkages became much stronger, as the layers condensed onto each other.

Using the as-synthesized layered zeolite material, with the template intact and prior to any thermal exposure, we attempted to delaminate or separate these crystalline layers of the MCM-22 "precursor". A pillared layered material resulting from this delamination and subsequent pillaring was obtained and identified later as MCM-36 [22,23]. The process involved intercalation of the layers using an alkyltrimethylammonium compound followed by the insertion of stable inorganic oxide pillars using a reactive silica source such as tetraethylorthosilicate. This effort was expanded to other suspected layered zeolite precursor candidates and other areas involving surfactant-oxides chemistry (or systems).

The layered zeolite precursors, exemplified by MCM-22, differed from other layered predecessors such as clays and layered silicates in possessing layers with high zeolite activity and porosity. Obviously, these were very attractive from a catalytic standpoint. A complicating factor distinguishing the layered zeolite precursors from the other layered materials, was their resistance to swelling by ion exchange with neutral or mildly basic media, such as quaternary ammonium salts or amines. These swelling agents afforded only partial exfoliation. We found that the introduction of a quaternary ammonium surfactant in a hydroxide form, was more effective in swelling of the layered zeolite precursors [24].

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This general approach of interrupting zeolite syntheses, isolating the layered zeolite precursors, and using these potential crystalline layered materials as reagents to form large pore active catalysts was investigated for other zeolite families such as ZSM-35, or synthetic ferrierite. To optimize the formation of these layered precursors, several reaction conditions were identified and imposed on the traditional zeolite synthesis. The zeolite synthesis was interrupted prior to any X-ray diffraction evidence of crystallinity. The interruption could be initiated at any point within -25 to 75% of the total expected synthesis time. High concentrations of the intercalate, an alkyltrimethylammonium salt, usually in the hydroxide form, at high pH were added to this interrupted zeolite precursor media. In other syntheses, a reactive silica source, tetramethylammonium silicate, was also added as a potential pillaring agent. These new synthesis mixtures were then subjected to additional hydrothermal treatment, usually at low temperatures --100~ in an attempt to form the zeolite-layered hybrid. Many of the products exhibited some very unusual properties that later on were recognized as those of the mesoporous materials.

The X-ray diffraction pattern of these interrupted zeolite preparations were essentially featureless except for one broad low angle peak at about 2~20. This X-ray diffraction pattern was intriguing since the original zeolite templating agent still existed in the synthesis composition. The other unusual properties of this unknown material were the extremely high BET surface areas and hydrocarbon sorption capacities. These BET surface area values, typically greater than 1000 m2/g, exceeded those normally observed for zeolite samples. The hydrocarbon (n-hexane and cyclohexane) sorption capacities were in excess of 50 weight percent, also abnormally high compared to our typical microporous samples. In fact, these sorption values were so remarkable that our analytical laboratories initially believed that their test equipment was broken or out of calibration.

In a parallel and concurrent synthesis effort within our team, the cetyltrimetylammonium hydroxide reagent, which was developed for high efficiency swelling, was also used directly as a structure-directing-agent in zeolite-like hydrothermal syntheses. The properties of the products were similar to those generated in the layered zeolite precursor systems, i.e., characterized by a low angle line in an X-ray diffraction pattern corresponding to large d-spacing and unusually high BET surface area and adsorption capacities. Thus, both interrupted zeolite precursor systems and direct introduction of cetyltrimethylammonium hydroxide as a structure-directing-agent resulted in the new mesoporous molecular sieve products. As described below, subsequent detailed characterization studies allowed elucidation of the nature of these remarkable materials.

Obviously, the aforementioned unusual physical properties are characteristic of M41S

mesoporous molecular sieves.

except for one low angle line at a d-spacing of --40~,, it was impossible to discern the nature of these materials. One early theory was that we had synthesized some kind of layered silicate precursor with crystalline domain sizes below X-ray detectability.

However, with a featureless X-ray diffraction pattern,

56

A

key to the identification of this new class of porous materials was the observation, by

transmission electron microscope (TEM) analyses, of a trace amount of MCM-41 in one

of our samples. The observation of trace quantities of MCM-41 as discerned by the

uniform hexagonal pore structure in one of the interrupted synthesis preparations,

provided us with hard evidence of this new class of materials (see Figure 1).

Figure 1: The Initial TEM observation of MCM-41 [ref. 1]

After the initial observation of MCM-41, we focused our synthesis effort on identifying the

synthesis conditions required to produce this unique molecular sieve. In a relatively short time, we were able to produce enough excellent quality samples of MCM-41 for detailed analyses. After confirming reproducibility and many of the analyses, we filed our initial patent memorandum describing our observations. We concluded that we had discovered

a new class of mesoporous molecular sieves, a class that would be useful for many petroleum processes.

One of our first hypotheses, based on both the hexagonal ordering of the pores and variation of pore sizes, as seen in TEM analyses, and the XRD pattern, was that we had discovered one of the crystalline phases predicted by Smith and Dytrych, known as the 81(n) family of frameworks [25]. The theoretical XRD pattern of this family almost matched that of some of our best samples of MCM-41. However, it was not until later when we obtained the 29Si NMR data that we determined that our material was not like a

typical crystalline framework.

the pores and not by crystalline walls, was a unique feature of this new class of

That the XRD patterns could be generated by the order of

mesoporous materials.

We presented our story to the research staffs of both the Paulsboro and Princeton Laboratories. Very rapidly, many individuals from both laboratories were involved in investigating this new family of materials. Their efforts ranged from synthesis efforts of new regions such as varying the surfactant chain length and solubilization, characterization of the products using sorption and NMR techniques, and catalytic testing. In all cases, we were analyzing a new class of materials that presented unique data. For example, the pore size distribution was remarkable; the narrow pore size appeared to be like that of microporous materials but within the mesopore range. As mentioned previously, the hydrocarbon sorption capacity was unique. Benzene sorption isotherms clearly indicated pore condensation inflections at benzene partial pressures indicative of mesopore size channels. These inflections were typically not observed with microporous materials due to the low partial pressures needed.

By June of 1990, Jeff Beck, a key collaborator and a member of the Princeton Laboratory, was able to synthesize various pore size materials using both different alkyl chain lengths of the cationic surfactant as well as taking advantage of micellular swelling [26,27]. In recognition of his contributions to further advancing MCM-41, Jeff became a co-author of the seminal Nature article [3]. Another member of the Princeton Laboratory, Kirk Schmitt was able to demonstrate by 29Si NMR that the walls of these materials were amorphous. Since surfactants were used in the syntheses, other researchers investigated the

5?

connection between our molecular sieves and micelles and liquid crystal chemistry.

knowledge base and the subsequent discoveries of the other unique structures, MCM-48 and MCM-50, helped to establish the basis for the mechanism of formation of these materials.

This

In retrospect, the synthesis conditions that we were using in our aluminosilicate systems to obtain layered zeolite hybrids and/or larger pore materials, namely the high pH, high surfactant concentration, and a reactive silica source, were the very synthesis conditions conducive to the formation of the mesoporous molecular sieves. The discovery and identification of other members of this new class of porous materials, MCM-48 and MCM- 50, came during the middle half of 1990 as a result of a detailed study relating the effect of surfactant concentration on the silica reagent (Figure 2) [28]. The discovery of these additional two members of the mesoporous molecular sieve family was another key factor in supporting the proposed mechanism of formation.

Figure 2: The M41S Family of Materials Including MCM-41, MCM-48, and MCM-50.

The discovery of this new class of materials, mesoporous molecular sieves, posed several challenges for our understanding of the formation of porous materials. Understanding the mechanism of formation of these materials was a challenging task, which led to many long debates within the Paulsboro and Princeton research community. We initially approached the concept of formation of these materials like traditional zeolite chemists. One of our first proposals was that the materials might have been formed by some sort of templating structure or pore filling agent. This meant, in the case of the mesoporous molecular sieves, that the templating agent was an aggregation of molecules and not the discrete molecules that normally template microporous structures (see Figure 3). Based on our initially limited knowledge of liquid crystal structures and micelles, we concluded that the liquid crystal structure existed prior to the formation of the molecular sieve. In the case of the MCM-41, this would be the hexagonal liquid crystal phase.

Figure 3: The role of quaternary directing agents [ref. 4]

However, this simple and appealing mechanistic pathway was not universally accepted within our research community. Alternatively, it was proposed that the silicate reagent also affected the formation of these materials. It was this second proposed route that appeared operative in most systems as more data were obtained. A significant set of data that helped establish the preferred mechanistic route was a group of experiments that investigated the effect of various levels of silica at the same surfactant (SUR) concentration. By changing the SUR/Si molar ratio we were able to synthesize MCM-41, -48 and -50 while keeping the other synthesis conditions the same [28]. These conditions would then exclude the possibility of any preformed liquid crystalline phase prior to the formation of the silicon phase, since the same surfactant concentration was used for all experiments. Only the amount of silica added to each solution was changed. These data supported the concept that the anion, in this case, the silicate species, significantly affected the formation of the resultant template of the mesoporous molecular sieves (see

58

Figure 4). These data were some of the evidence that led to the proposed mechanisms of formation published in the initial MCM-41 journal articles [3,4].

Figure 4: The proposed mechanism of formation pathways [ref. 4]

In retrospect both proposed pathways proved to be valid. The predominant pathway operating in most situations appears to be the anionic species initiated one (using cationic surfactants). This concept was explained and expanded upon by many researchers, specifically by the group at the University of Santa Barbara headed by Galen Stucky [29,30]. A Michigan State University group headed by Thomas Pinnavaia, expanded this mechanistic pathway concept further to include neutral directing agents such as polymers [31,32]. Later, researchers at the University of South Hampton demonstrated that the other proposed pathway, originally labeled the liquid crystal phase initiated pathway, can also function [33,34]. George Attard and his co-researchers used a preformed liquid crystal phase to synthesize both a silica and a metal (platinum alloy) mesoporous molecular sieve.

The M41S mesoporous molecular sieves exhibit characteristics that are different than those generally attributed to typical zeolites. They contain little or no Bronsted acidity. They also contain amorphous walls, which are generally around 10A when synthesized using the initial cationic surfactants. These thin, amorphous walls limit both the thermal and hydrothermal stability under severe conditions (relative to crystalline structures). However, it was shown that increasing synthesis temperature and/or duration led to improved hydrothermal stability and quite robust silica MCM-41 structures were demonstrated [35].

Although the wall composition contains random bond angles and atomic location, there exists a uniform density of silanol groups (other than the silanols that exist due to incomplete condensation) within the channels due to surfactant packing requirements. These silanol groups provide unique anchoring sites for the functionalization of species within a mesopore channel. These functionalized products provide opportunities for designing unusual catalytic/sorptive materials for various applications and present a class of materials significantly different than other uniform porous materials [36-38].

Although we published two initial papers, Exxon Mobil's primary goal was to obtain broad applied IP coverage for the novel class of materials we discovered. We were allowed to write additional manuscripts for journals only after most of these patents were issued, i.e., after 1994. Throughout the early 90's, many aspects of the synthesis, composition of matter, modification, and applications were covered in United States Patents (see Tables 1-3). Broad claims were allowed covering any inorganic, nonlayered material having a

single X-ray

grams per 100 grams of material at 25~ Included are claims for both the as- synthesized (organic containing) and the calcined (organic removed) forms. The functionalization claims are very broad including the functionalization of the material at various stages of the synthesis and with a wide variety of organic/inorganic compositions such as metal salts and complexes with attached or accompanying groups including

diffraction peak below 5~ 2|

and a benzene sorption uptake of at least 15

59

alkyls, alkoxides, amines, phosphines, sulfides, sulfonates, nitrates, carbonyls and cyanos compounds [36-38]. Patent coverage for method of making is also broadly includes various organics that exhibit amphiphilic character [39]. Application patents covering a wide range of typical catalytic processes were also obtained. For those applications that were outside of ExxonMobil's general interest, we collaborated with outside experts. Specifically, early in our evaluation of MCM-41, we obtained patents covering sensors and optical devices with Professor Stucky of UC of Santa Barbara and in the area of separation with Professor D. L. C. Wang of MIT [40-42].

The publication of our early results and the recognition of other related materials created an extraordinary interest in the scientific community [43, 44]. More than 6000 publications covering all aspects of these materials, including synthesis, characterization, and applications have appeared in the literature since 1992. Separate sessions at international symposia dedicated to mesoporous materials began to appear regularly. Later, entire meetings were dedicated to the subject. A separate society (International Mesoporous Material Society) was formed. The interest in these materials continues to grow as shown in the number of citations in literature surveys (see Figure 5).

Figure 5 Number of publications per year

In summary, by the combination of prior knowledge, observation skills, and novel synthetic approaches, we discovered a family of mesoporous molecular sieves including discrete structures - MCM-41 (hexagonal), MCM-48 (cubic), and MCM-50 (lamellar). These materials were formed unlike that of our classical microporous structures involving reagent induced-macromolecular templating mechanism. Working with other,Mobil scientists and engineers, we were able to establish a predictive mechanism of formation and identify a broad class of templating reagents. We obtained extensive intellectual property coverage (Table 1-3) including composition of matter, methods of synthesis, templating reagents, functionalization, and a wide range of applications. Within the past several years, ExxonMobil has commercialized MCM-41 for an undisclosed application.

Acknowledgments

-

We want to thank the technical staff of the former Mobil Paulsboro and Princeton Laboratories. In particular, we want to thank C.D.Chang, R.M. Dessau and H.M. Princen

for early discussions on surfactants and liquid crystal chemistry.

Beck for his early synthesis work on the effect of pore size using both the variation of the

surfactant chain-length and solubilization.

her early synthesis efforts, K. D. Schmitt for his 29Si NMR data and early functionization

work, and J.B. Higgins and J.L. Schlenker for their assistance in X-ray diffraction indexing.

We want to thank J.S.

We also want to recognize I. D. Johnson for

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36. Beck, J.S.; Calabro, D. C.; McCullen S. B.; Pelrine, B. P.; Schmitt, K. D.; Vartuli, J. C., Method for Functionalizing Mesoporous Crystalline Material, US Patent 5,145,816, September 8, 1992.

37. idem, Catalytic Conversion over Modified Synthetic Mesoporous Crystalline Material, US Patent 5,200,058, April 6, 1993.

38. idem, Sorption/separation over Modified Synthetic Mesoporous Crystalline Material, US Patent 5,220,101, June 15, 1993.

39. Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C., Use of Amphiphilic Compounds to Produce Novel Classes of Crystalline Materials, US. Patent 5,250,282, October 5, 1993.

40. Olson, D. H.; Stucky, G. D.; Vartuli, J. C., Sensor Device Containing Mesoporous Crystalline Material, US Patent 5,348,687, Nov. 15, 1994.

41. Beck, J. S.; Kuehl, G. H.; Olsen, D. H.; Schlenker, J. L.; G. D. Stucky, G. D.; Vartuli, J. C., US Patent 5,364,797, Sept. 20, 1994.

42. Herbst, J. A.; Kresge, C. T.; Olson, D. H.; Schmitt, K. D.; Vartuli, J. C.; Wang, D. L. C., US Patent 5,378,440, Jan. 3, 1995.

64

43.

Yanagisawa, T.; Shimizu, T.; Kazuyuki, K, Kato, K., Bull. Chem. Soc. Japan, 63, 1990,

988-992.

44.

Inagaki, S.; Fukushima, Y.: Okada, A.; Kurauchi, T.; Kuroda, K.; Kato, C., New silica- alumina with nano-scale pores prepared from Kanemite, Proceedings from the Ninth International Zeolite Conference, R. von Ballmos, J. B. Higgins, M.M.J. Treacy, (eds.), 1994, 305.

Table 1

65

Selected ExxonMobil Patents on the Synthesis of M41S Molecular Sieves

U.S. Patent Number

Description

5,057,296

Use of Organic Additives to Vary Pore Size of M41S

5,098,684

MCM-41 Composition of Matter (Hexagonal)

5,102,643

Basic M41S Composition of Matter

5,108,725

Basic Synthesis of MCM-41 (Hexagonal) with CTMA

5,110,572

M41S Synthesis Using Organometallics

5,145,816

Addition of Functional Groups to M41S Materials

5,179,054

Shell/Core Catalyst with M41S Shell

5,198,203

MCM-48 Composition (Cubic)

5,246,689

MeAISiO M41S (Me = Co, Cr

)

5,250,282

Synthesis of M41S with Amphiphilic Compounds

5,264,203

Synthesis of 2 SAPO M41S Materials

5,300,277

Improved Synthesis of MCM-48 (Cubic)

5,304,363

Lamellar M41S Materials (MCM-50)

5,308,602

Synthesis of M41s using an Amphiphilic Compound

5,366,945

Heteropoly Acid Catalyst Supported on M41S

66

Selected

ExxonMobil

U.S. Patent Number

Table 2

Patents on Catalytic Applications

Description

of M41S Molecular Sieves

5,118,894

EB SYNTHESIS WITH M41S CATALYSTS

5,134,241

CONVERSION OF PROPYLENE TO C4-C5 TERTIARY OLEFINS OVER MCM-41

5,134,242

OLIGOMERIZATION OF OLEFINS IN A MIXED C3-C5 FEED OVER MCM-41

5,134,243

OLEFIN OLIGOMERIZATION OVER MCM-41

5,174,888

ORGANIC CONVERSION OVER M41S

5,183,557

HYDROCRACKING USING M41S/ZEOLITE COMBINED CATALYST

5,183,561

DEMETALLIZlNG HYDROCARBONS OVER M41S MATERIALS

5,191,134

ALKYLATION OVER TO PRODUCE HIGH VI POLYALKYLATED NAPHTHALENES

5,191,144

OLEFIN DISPROPORTIONATION OVER MCM-41

5,191,148

LEWIS ACID PROMOTED MCM-41 IN PARAFFIN/OLEFIN ALKYLATION

5,196,633

ORGANIC CONVERSION OVER MCM-41

5,2O0,058

ORGANIC CONVERSION

5,227,353

BIFUNCTIONAL HYDROPROCESSING CATALYST CONTAINING M41S MATERIALS

5,232,580

SELECTIVE LIGHT OLEFIN PRODUCTION FROM NAPHTHA CRACKING WITH M41S

5,238,676

POST-SYNTHESIS ADDITION OF ACTIVATING METALS TO M41S

5,256,277

PARAFFIN ISOMERIZATION OVER M41S MATERIALS

5,258,114

CRACKING CATALYST INCLUDING M41S MATERIAL

5,260,501

OLEFIN OLIGOMERIZATION OVER Ni-MODIFIED MCM-41

5,264,116

HYDROCRACKING/HYDROISOMERIZATION TO PRODUCE LUBES

5,264,641

AROMATICS SATURATION OVER M41S MATERIALS

5,270,273

OLEFIN OLIGOMERIZATION CATALYST COMPRISING M41S MATERIALS

5,277,792

LUBE HYDROCRACKING OVER M41S MATERIALS

5,281,328

HYDROCRACKING OVER M41S MATERIALS

5,288,395

HYDROCRACKING/HYDROISOMERIZATION TO PRODUCE LUBES

5,290,744

HYDROCRACKING CATALYST COMPRISING M41S WITH SMALLER PORE SIEVE

5,344,553

RESID UPGRADING OVER M41S MATERIALS

5,347,060

PHASE TRANSFER CATALYSIS WITH AS-SYNTHESIZED MCM-41

5,451,31 2

USE OF M41S MATERIALS TO PRODUCE LOW AROMATIC DISTILLATES

5,468,368

HYDROPROCESSING OF HYDROCRACKER BOTTOMS TO PRODUCE LUBES

5,475,178

ORGANIC CONVERSION OVER HETEROPOLY ACID CATALYSTS SUPPORTED ON

5,573,657

M41S MATERIALS HYDROGENATION OF PAO'S OVER Pt M41S MATERIALS

5,573,657

HYDROGENATION OF LUBES OVER M41S

5,583,277

SORPTION OF POLYNUCLEAR AROMATICS WITH M41S MATERIALS

5,837,639

METAL-CONTAINING M41S COMPOSITIONS AS HYDROPROCESSING CATALYSTS

Table 3

67

Selected ExxonMobil Patents on Other Applications of M41S Molecular Sieves

U.S. Patent Number

Description

5,143,707

USE OF M41S IN NOx REDUCTION

5,220,101

SORPTION/SEPARATION

5,348,687

M41S MATERIALS HAVING NONLINEAR OPTICAL PROPERTIES

5,364,797

SENSOR DEVICE CONTAINING M41S

5,378,440

SEPARATIONOVER M41S MATERIAL

68

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