ON THE HORIZON

Going Green with Zeolites

These inorganic materials are playing an increasing role in tackling environmental challenges.

Bonnie K. Marcus and William E. Cormier, Zeolyst International

arely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientic interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves, declared Donald W. Breck in 1974 (1). That was twenty years after the commercial introduction of synthetic zeolites. During that time, the number of areas utilizing zeolites had grown phenomenally. Since then, the variety of applications and zeolite types available has continued to increase. Indeed, growth seems to be limited only by the imagination of the people looking for solutions. Zeolites, already well established in such environmentally driven applications as the production of lead-free octane enhancers for gasoline and as phosphatefree ion exchangers for detergent water softening, now are being used or considered for a variety of other important environmental services. To put the potential of zeolites into perspective, this article looks at the properties of zeolites, and how the materials can be used.

Zeolite properties
Zeolites are members of a family of minerals called tectosilicates, which includes dense-phase materials such as the feldspars and the various forms of silica. Zeolites are microporous, high-internalsurface-area crystalline materials with an open, three-dimensional framework consisting of tetrahedral AlO4-5 and SiO4-4 units linked through shared oxygens.

available www.aiche.org

on-line

There are 40 known naturally occurring zeolites and more than 150 synthetic ones. Zeolite structures can be visualized by taking a neutral SiO2 framework and isomorphously substituting AlO2- for SiO2. The resulting structure (Figure 1) then exhibits a net negative charge on the framework aluminum. This negative charge is balanced by cations (for instance, Na+, K+, or NH4+) that reside in the interstices of the framework. Many of these cations are mobile and free for exchange. This ion-exchange property accounts for the greatest volume use of zeolites today. For instance, Zeolite A, synthesized with sodium as the cation, has widely replaced environmentally harsh phosphates as detergent water softeners; it functions by exchanging its sodium for the calcium and magnesium ions that cause hard water and poor laundry performance. The type of cation present not only inuences the ion-exchange properties of a zeolite, but also is a factor in its adsorptive and catalytic properties. High-purity synthetic zeolites exhibit uniform pore sizes that can be further tailored to specific molecular dimensions by changing the nature of the cation after synthesis. Some zeolite properties that are determined during synthesis include: structure; silica-to-alumina ratio; pore size; and framework density (that is, atoms per unit cell). The pore size is the two-dimensional opening of the zeolite and is determined

CHEMICAL ENGINEERING PROGRESS JUNE 1999 Copyright 1999 American Institute of Chemical Engineers. All rights reserved. Copying and downloading permitted with restrictions.

ON THE HORIZON

Si O O _ _ _ Al - O - Si - O - Al - O - Si - O - Al O O Si Property Channels Cavities Thermal stability Ion-exchange capability Surface area Water capacity Water affinity

Table 1. Zeolite properties.

Range 2.28 6.611.8 5001,000C Up to 700 milliequivalents/100 g Up to 900 m2/g 1 to 25 wt.% Hydrophilic to hydrophobic

I Figure 1. Zeolite structure. by the number of tetrahedral atoms joined together. The structure is built up further by connecting the tetrahedral atoms in a three-dimensional array. This array can lead to larger inner cavities connected by pore openings. In some zeolites, there are no cavities, but a series of one-, two, or three-dimensional channels through the structure. In addition, various post-synthesis modications, such as hydrothermal treatment, coating, and impregnation, may further alter catalytic and adsorptive properties. Because of this ability to customize properties, zeolites are commercially valuable as adsorbents and molecular sieves selectively admitting some molecules while excluding others whose size, shape, or polarity preclude adsorption. The rst generation of zeolites (such as A, X, Y, and mordenite) generally have a low silica-to-alumina ratio and a high ion-exchange capacity. Most boast a high affinity for water and, so, are widely used as desiccants. They also are employed to adsorb other polar molecules in separation and purication applications. Second generation zeolites (e.g., ZSM-5 and silicalite) take advantage of quaternary ammonium ions and alkali cations during synthesis to create new structures and different chemical compositions that are higher in silicato-alumina ratio. The highly siliceous materials are effective for adsorbing organic molecules, even in low-concentration, high-humidity, and hightemperature applications. A third generation of alumino-silico-metal phosphates (AlPO4, SAPO, MeAlPO, etc.) is synthesized without alkali cations present, using organic amines and
CHEMICAL ENGINEERING PROGRESS JUNE 1999

quaternary ammonium compounds as structure-directing agents. This results in materials with dramatically different properties and many new structure types. Environmentally benign zeolite catalysts have wide potential as solid acids in many commercial processes, due in part to the ability to tune their acidity. In addition, zeolites can be formulated to carry active materials such as catalytic metals. These properties, coupled with the size and shape features of the zeolites, allow the materials to be used as catalysts in extremely selective reactions, such as in the manufacture of para-xylene. High silica zeolites ability to remove hydrophobic organic compounds from many environments is expanding their use as specialty adsorbents in numerous elds. The ability to tune a number of other properties of zeolites (see Table 1) is adding to the interest in the materials. Another attraction is that zeolite powder can be formed into extrudates, beads, monoliths, and other shapes.

The subtleties of synthesis The greatest challenge in the development and commercialization of new and modied zeolites is their synthesis. Natural zeolites are found worldwide and were formed by igneous or sedimentary solution processes. Some of the parameters that controlled the type of zeolite formed are the composition and pH of the solution, as well as the temperature, pressure, and time of formation. It is possible to replicate all of the condi-

tions except the time of formation, which is thousands of years in nature. Commercially, zeolites must be produced in hours or days; this, thus, requires optimizing the other variables to change the window of formation. Progress in zeolite synthesis has been ongoing since commercial zeolites were rst introduced 50 years ago. Most zeolites are made from the same reagents: alumina, alkali cations, and silica. Small variations in conditions can cause major differences in the structures that form. Indeed, in a number of cases, new zeolites have been discovered while attempting to make known zeolites. A classic zeolite example is Zeolite X, which was rst made inadvertently in an attempt to repeat the synthesis of Zeolite A. Some of the factors that determine the type of synthetic zeolite produced are (2): composition of the gel; silica and alumina source; other materials present (such as OH- and other anions, cations (inorganic or organic), and organic reagents); time of reaction; temperature and heat-up rate; pressure; and synthesis conditions (like the order of mixing, gel aging, and stirring). The optimization of the synthesis process for a known zeolite is not a trivial task and can involve many iterations. To commercially synthesize a new zeolite type, substantial expertise in both chemistry and chemical engineering is required. Scale-up from the

Table 2. Environmental applications of zeolites.

Application Selective catalytic reduction of NOx Zeolites Used Copper ZSM-5; mordenite Advantages Good for high dust applications Extended temperature range Cheaper Higher selectivity Mordenite is particularly stable in acid streams Uses fuel hydrocarbons as reductants No ammonia No special handling Cheaper More effective than three-way catalytic converter for NOx N2O decomposes over zeolites at higher temperatures (400C) Effective where carbon is not Systems available from several vendors Achieved 3570% reduction

Lean NOx

Copper, cobalt ZSM-5; beta

Lean-burn (oxygen rich) diesel-engine NOx removal Removal of N2O

Copper, cobalt ZSM-5; beta

Cobalt, copper ZSM-5; mordenite; ferrierite; beta; ZSM-11 High silica, hydrophobic zeolites

VOC removal in dilute, high-volume, humid streams VOC removal during automotive cold starts

High silica, hydrophobic medium- and large-pore zeolites

laboratory can be tricky, and commercial production usually demands precise control of temperature, pressure, and other variables.

Improving zeolite performance New types of zeolite structures are continuing to be discovered; they undoubtedly will lead to additional applications and may offer advantages in existing services. But, signicant scope exists for enhancing current zeolites performance for specic duties. Most often, this involves postsynthesis modications including pore-size tailoring, surface treatments, acidity tuning, and changes in silica-to-alumina ratios. These types of modications have led to many materials with improved performance as adsorbents, molecular sieves, and catalysts. Today, software modeling packages that contain the known zeolite structure types are available. They allow a user to create defects in or incorporate a variety of heteroatoms, such as iron, boron, and gallium, into a framework and simuCHEMICAL ENGINEERING PROGRESS JUNE 1999

late the altered structure. Separately, reaction intermediate and product molecules can be introduced into the structure model to assess the possibility of a reaction occurring. These three-dimensional pictures simulating molecules diffusing into the pore can be extremely powerful; the models are as topically accurate as possible, all the way down to the intrinsic physics involved. Modeling capabilities are growing better every year and, while models are not yet predictive, they provide useful insights for tailoring materials for specific applications. Some research groups have succeeded in creating new zeolite structures using designer organic molecules as structure-directing agents to yield a desired pore size or shape. Many of these agents, however, pose economic hurdles being either very expensive, not available on a commercial scale, or very difficult to synthesize. In some cases, though, materials that were rst discovered using designer organic molecules have been commercialized using other organics that are more

readily available, easier to handle, and less expensive.

Environmental applications
Four interrelated forces are driving clean technologies in industrialized countries: 1. regulatory pressures to decrease the output of waste streams and byproducts or face nes and possible shutdowns; 2. the need to remain cost competitive with third-world manufacturers unencumbered by stringent environmental regulations; 3. social demands for a clean environment and sustainable production methods; and 4. increased knowledge of the causes, effects, and dispersion of pollution. It is widely recognized that the gains made by the current generation of environmental technologies are being offset by population growth. Consequently, many new and creative pollution-prevention and -abatement methods are required. The unique properties and selectiv-

ON THE HORIZON

Table 3. Waste reduction through process improvements using zeolites.

Application Production of alpha-terpinyl alkyl ethers Zeolites Used Beta Advantages Excellent yields in continuous reactor Eliminates use of HCl, H2SO4, AlCl3, toluene, sulfonic acid, boron triuoride etherate, and acidic cation resins as catalysts Lower impurities Transalkylation function Lower benzene-to-propylene ratio allows higher capacity, greater unit efficiency High selectivity Regenerable, nonhazardous, noncorrosive Eliminates cumene as an intermediate Enables possible use of N2O as oxidant Dramatic reduction in number of processing steps and waste streams Possible further reduction by using another zeolite in the last step of the process Produces methanol from coal, natural gas, or biomass and then converts it into liquid fuel Conservation of crude oil, elimination of many waste streams

Cumene synthesis

Dealuminated mordenite; MCM-22; beta; Y; omega

Direct oxidation of benzene to phenol Caprolactam (via oxidation)

ZSM-5

Titanium-framework-substituted ZSM-5 (TS-1)

Gasoline from methanol

ZSM-5

ities of zeolites can provide effective environmental solutions by minimizing the output of pollutants and by secondary treatment of effluents produced. Areas in which zeolites show strong environmental potential are: reduction of atmospheric oxides of nitrogen (NOx); cutting emissions of volatile organic compounds (VOCs), including from cold starting of automobiles; and process improvements in the chemical process industries (CPI). Tables 2 and 3 list some of these opportunities. Now, lets look at them in more detail.

Reduction of atmospheric NOx Oxides of nitrogen are a major target of clean air policies: NOx is a major contributor to acid rain (ranking second only to sulfur compounds); NOx compounds foster the creation of photochemical oxidants
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such as ozone and peroxyacetyl nitrate; and nitrous oxide, N2O, is of concern as a greenhouse gas, because it absorbs in the infrared region. NOx, naturally produced by lightning, bacterial action in the soil, and volcanic eruptions, also is generated by human activity primarily the combustion of fossil fuels at temperatures higher than about 1,000C (3). Selective Catalytic Reduction (SCR), in which ammonia is added to stack gases as a reductant, is the traditional method of NOx removal at stationary sources such as power plants. SCR is effective at lower temperatures, but NOx conversions are better at higher temperatures (4). Catalysts can extend the temperature range for NOx reduction (see Figure 2). Platinum and vanadium catalysts are effective up to 450C; ion-exchanged zeolites are applicable to 600C. Another emerging zeolite technol-

ogy is lean NOx, a catalytic process that uses methane and higher hydrocarbons as reductants, making it ideal for automotive and other mobile sources (5,6). Just as vehicle engines and fuels are being redesigned to reduce the creation of pollutants, so, too, zeolites are being developed and deployed to handle the new concentrations, combinations, and conditions of combustion products. For example, efficient, oxygen-rich, lean-burn diesel engines give off less CO2 (a greenhouse gas). Metal-exchanged zeolite catalysts have proven to be a less costly and more effective option for NOx removal from these engines exhausts than three-way catalytic converters (7,8). N2O is produced in large quantities by nitric acid and adipic acid plants. Although many zeolites have been used to decompose N2O at higher temperatures, cobalt or copper ZSM-5, mordenite, and beta zeolites

Table 4. Cumene synthesis catalysts.

Solid Phosphoric Acid Licensed by UOP Predominant process High formation of polyalkylates, high impurities, lower yield No transalkylation function High benzene-to-propylene (B/P) ratio required to maximize yield Some polypropylene oligomerization, olen impurities, lower yield, may require treatment Nonregenerable, catalyst disposal issues Small ow of aqueous phosphoric acid effluent, corrosion and environmental issues Aluminum Trichloride Licensed by Monsanto At least ve licensees Lower impurities Zeolite Catalysts Available from several vendors A number of recently announced projects Lower impurities

Transalkylation function Lower B/P ratio allows higher capacity, greater unit efficiency Greater tendency to form n-propylbenzene impurity

Transalkylation function Lower B/P ratio allows higher capacity, greater unit efficiency Excellent selectivities claimed

Hazardous waste disposal issues with spent AlCl3 Corrosive catalyst requires special, higher-cost capital equipment

Regenerable, nonhazardous catalyst

Noncorrosive

are emerging as the preferred choices due to their selectivity, availability, and relative cost (9).

Cutting emissions of VOCs VOCs are organic compounds that, together with NOx, are precursors to the formation of photochemical oxidants such as ozone. VOCs include naturally produced hydrocarbons, such as methane from biological decay, but most VOCs of environmental concern are released from motor vehicles and from chemical sources such as paints, inks, solvents, and degreasers (3). Further reduction of automotive emissions is focusing on engine cold starts. The problem is that when an engine is rst started, the three-way catalysts in the exhaust line have not heated up sufficiently to destroy the emissions produced. So, cold engine operation (particularly during the rst two minutes) increasingly is being regulated, as cars are required to approach ZLEV (zero level emission
CHEMICAL ENGINEERING PROGRESS JUNE 1999

vehicles). Hydrophobic medium- and large-pore zeolites are being investigated as adsorbers placed upstream of the catalytic converter to trap coldstart VOCs. When the catalytic converter heats up to operating temperature, the heat releases the VOCs from I Figure 2.
Performance of NOx catalysts.
100 80 NOx Conversion, % 60

the zeolite into the converter, where they are destroyed (10). A greaterthan-70% reduction has been reported with these materials (11). Several companies have announced prototype hydrocarbon traps that use zeolites (12,13).

Zeolite Catalyst V Catalyst Modified Pt Catalyst Pt Catalyst

40 20
Source: Ref. 3

0 100 200 300 400 500 600 Temperature, C

ON THE HORIZON

A variety of materials such as carbons and silicas effectively adsorb VOCs in high concentration streams. As low concentration streams become more regulated, however, more-selective materials are needed. Combinations of materials like carbon and zeolites, or mixtures of zeolites, increasingly are being investigated for concentration of VOCs. Once concentrated, the VOCs can be recovered for reuse or thermally destroyed. New, more hydrophobic zeolites such as ZSM-5 types, dealuminated faujasites, and betas are especially effective in removing VOCs from dilute or humid streams.

Process improvements in the CPI The applications of zeolites for selective chemical synthesis are growing rapidly. Using the materials as catalysts contributes to the greening of process technology in two ways: rst, by replacing many hazardous acidic catalysts such as HF, HCl, and H2SO4; second, by eliminating some intermediate steps in certain processes to reduce overall waste output and energy use. Fine chemicals. The production of avors, fragrances, and other ne chemicals often involves homogeneous catalysts that generate large quantities of wastes such as washwaHydrocarbons and Other Exhaust Components on Silicalite, I. & E. C. Res., 30, pp. 2,3332,340 (1991). 11.Hertl, W., M. D. Pahl, and J. L. Williams, Hydrocarbon Adsorber system for Cold Start Emissions, Papers 960343, 960347, Soc. of Auto. Eng., Dearborn, MI (1996). 12.Ballinger, T. H., W. A. Manning, and D. S. Lafyahs, Hydrocarbon Trap Technology for the Reduction of Cold-Start Hydrocarbon Emissions, Paper 970741, Soc. of Auto. Eng., Dearborn, MI (1997). 13.Hertl, W., M. D. Pahl, and J. L. Williams, Hydrocarbon Adsorber System, Paper 960347, Soc. of Auto. Eng., Dearborn, MI (1996). 14.Holderich, W., How Can Heterogeneous Catalysts Contribute to Environmentally Benign Production of Fine Chemicals, Keynote Speech at the 15th Meeting, N. Amer. Cat. Soc., Chicago (May 1997). 15.Holderich, W. F., K. Hansen, and C. Mahain, Heterogeneously-Catalyzed Hydroalkoxylation of Limonene and Alpha-Pinene in the Presence of Beta Zeolite, Studies in Surf. Sci. & Cat., 105B, p. 1,133 (1997). 16. Monsanto Unveils Benzene Route to Phenol, Chem. Wk., p. 11 (Jan. 1/8, 1997). 17.Clerici, M. G., Heterogeneous Catalysis and Fine Chemicals III, Elsevier, Amsterdam, pp. 2133 (1993). 18.Chang, C., C. Chu, and R. Socha, Methanol Conversion to Olens Over ZSM-5, J. of Cat., 86, pp. 289296 (1984).

Literature Cited
1. Breck, D. W., Zeolite Molecular Sieves: Structure, Chemistry, and Use, Wiley, New York, p. 1 (1974). 2. Nagy, J. B., P. Bodart, I. Hannus, and I. Kiricsi, Synthesis, Characterization and Use of Zeolitic Microporous Materials, DecaGen, Szeged, Hungary (1998). 3. Elsom, D. M., Atmospheric Pollution, A Global Problem, 2nd ed., Blackwell, Oxford, U.K. (1992). 4. Heck, R. M., and R. J. Farruato, Catalytic Air Pollution Control: Commercial Technology, Van Nostrand Reinhold, New York (1995). 5. Iwamoto, M., and H. Hamada, Removal of Nitrogen Monoxide from Exhaust Gases through Novel Catalytic Processes, Catalysis Today, 10, pp. 5771 (1991). 6. Iwamoto, M., and H. Hamada, Catalytic Reduction of NOx Using Methane in the Presence of Oxygen, U.S. Patent No. 5,149,512 (Sept. 22, 1992). 7. Engler, B. H., J. Leyrer, E. S. Lox, and K. Ostgathe, DeNOx with Metal Zeolites, Paper 930735, Soc. of Auto. Eng., Dearborn, MI (1993). 8. Bellussi, G.,and V. Maratano, Process and Catalyst Reducing NOx Combustion and Exhaust Gases, Eur. Patent No. 652,040 A 950619 (May 10, 1995). 9. Li, Y., and J. Armor, Catalytic Decomposition of N20, U.S. Patent No. 5,171,553, (Dec. 15, 1992). 10.Otto, K., C. Montreuil, O. Todor, R. McCabe, and H. Gandi, Adsorption of

ter streams, salts, and heavy metals. Frequently, the catalyst is not reusable. Zeolites are being extensively studied as heterogeneous catalysts that can be recovered and recycled with greater ease and less expense, leading to less waste and fewer byproducts (14). Their use also provides process advantages such as improved selectivity, higher activity, and reduced corrosion. In addition, many processes can gain efficiency and economy by using zeolites to combine several catalytic steps. Even greater returns can be achieved by the use of zeolites in continuous reactors. For example, the traditional synthesis routes for many fragrances and avors include strong acids, many steps, low yields, and much waste. Acidic zeolites have the potential to improve such processes, but they now are limited to batch reactors. The ability to form zeolites into different shapes has improved their compatibility with many reactor designs, such as the one for alpha-terpinyl alkyl ether (15). This continuous reactor uses beta zeolites, and has yielded excellent results with much less waste. Petrochemicals. The synthesis of cumene is one example in which several different zeolite catalysts have found application, replacing environmentally unfriendly catalysts such as solid phosphoric acid. Zeolite catalysts have been found to yield fewer impurities, to have higher capacity, to give greater unit efficiency, and to provide higher selectivity in cumene production. And, zeolites are nonhazardous, regenerable, and noncorrosive. Table 4 compares current commercially available cumene synthesis catalysts. Cumene is an intermediate for making phenol and acetone. Avoiding its use promises further environmental benets. The direct oxidation of benzene to phenol reduces waste output and the use of hazardous materials. A number of companies have developed processes with oxygen or nitric acid as the oxidant. A recent de-

CHEMICAL ENGINEERING PROGRESS JUNE 1999

NH3

O2

Ammonia Oxidation

NaOH

Nitrite Preparation

SO2 NH3

Hydroxylamine Sulfate Preparation Cyclohexanone Oxime Synthesis

SO2 NOx NH3 H2O2 TS-1 Ammoximation Reaction

Cyclohexanone

Ammonium Sulfate Sodium Sulfate

Cyclohexanone

NH3 Oleum

Oxime Rearrangement

Ammonium Sulfate

NH3 Oleum

Oxime Rearrangement

Ammonium Sulfate

Raw Caprolactum (~83%) a. Raschig Process

Raw Caprolactum (~90%) b. Enichem Process

I Figure 3. How Raschig and ammoximation routes to caprolactam compare. velopment employs N2O as the oxidant in a direct oxidation process with a zeolite as catalyst (16). Commercialization of this process could cut waste and energy consumption, and would improve the economics of phenol production, as well. Zeolites also can reduce wastes in the production of caprolactam, an intermediate for nylon-6 and other synthetic bers. The traditional Raschig process generates multiple waste streams. In contrast, the Enichem ammoximation process, which uses a titanium-framework-substituted ZSM-5 zeolite (TS-1), hydrogen peroxide, and ammonia, dramatically reduces the number of process steps and the volume of waste (17) (see Figure 3). Employing another zeolite in the last step of the Enichem process may lead to further cuts in waste production. The use of cheaper and more readily available feedstocks is still anothCHEMICAL ENGINEERING PROGRESS JUNE 1999

er way in which waste may be reduced and natural resources conserved. The Mobil methanol-to-gasoline process, now commercialized in New Zealand, is one such process. Methanol may be produced from coal, natural gas, or biomass, and then converted to liquid fuels or chemical feedstocks using a zeolite catalyst (18). Future possible uses of zeolites might include conversion of are gases at remote wells into a more easily transportable, waxy syncrude that could be reprocessed into fuels where needed.

B. K. MARCUS is Technical Market Development Manager for Zeolyst International, Conshohocken, PA ((610) 6514679; Fax: (610) 9414588; E-mail: bmarcus@pqcorp.com). She is responsible for custom zeolite development, testing, and marketing in the U.S. She previously worked for UOP and Sun Oil. She has specialized in inorganic synthesis of zeolites and development of new catalytic materials, holds over 30 patents in the U.S. and Europe, and has authored ten publications on zeolites. She has a MS in chemistry from Fordham Univ. W. F. CORMIER is Technical Director of Zeolyst Internationals R&D Center, Conshohocken, PA ((610) 6514623; Fax: (610) 9414588; E-mail: bcormie@pqcorp.com). His responsibilities include new product development, zeolite characterization and testing, and scale-up from bench to pilot scale to commercial production. Previously, he worked for PQ Corp., Katalistiks Intl., and Mobil R&D. He holds 14 patents and is the author of 11 articles. He received BS and MS degrees in chemical engineering from Worcester Polytechnic Inst., and is a member of AIChE.

A green light Additional methods for manipulating zeolite crystalline structure continue to be developed, and zeolite applications are expanding exponentially. Zeolites chemical inertness and unique, modiable properties make them ideal for green chemistry CEP applications.