Zeolites are crystalline aluminosilicates

1.0INTRODUCTION TO ZEOLITES

Zeolites are crystalline aluminosilicates, composed of TO4 tetrahedra ( T = Si, Al ) with O atoms linking neighbouring tetrahedral, that contain pores and pits of molecular dimensions ( Breck, 1974 ) . Many occur as natural minerals, but it is the man-made assortments which are among the most widely used sorbents, accelerators and ion-exchange stuffs in the universe ( Barrer, 1982 ) .

The channels are big plenty to let the transition of invitee species. In the hydrous stages, desiccation occurs at temperatures largely below approximately 400°C and is mostly reversible. The model may be interrupted by ( OH, F ) groups: these occupy a tetrahedron vertex that is non shared with next tetrahedra. Zeolites are different from other porous hydrates, as they retain their structural unity upon loss of H2O.

The Structure Commission of the International Zeolite Association identifies each model with a three-letter mnemotechnic codification ( Baerlocher et al. , 2001 ) e.g. Amicite- GSI ; Faujasite- FAU etc.

1.1IMPORTANCE OF GREEN PROCESSES

In the chemical industry, the acceptableness of a procedure is non merely governed by cost and output but in footings of eco-friendliness and pollution suspension. Choosing a more efficient catalytic path has greatly improved the efficiency of chemical procedures.

Green chemical science has been defined as the design of chemical merchandises and procedures in order to cut down or extinguish the coevals of risky substances ( Armor, 1999 ) . The rules of green chemical science listed by Armor ( 1999 ) employs future attacks to new chemical procedures. It includes: efficient usage of natural stuffs, energy efficiency, usage of biodegradable merchandises and other elusive characteristics.

2.0 HISTORICAL DEVELOPMENT OF ZEOLITES

2.1NATURAL Zeolites

Research in the field of zeolite scientific discipline and engineering made its first stairss with natural zeolites and was largely focused on natural zeolites until the beginning of the fiftiess. The history of zeolites began in 1756 when Swedish mineralogist A.F. Cronstedt discovered the first zeolite mineral, stilbite when analyzing its apparent belongingss discovered its unusual behavior upon heating although there is no certain cogent evidence of its individuality. The term ‘zeolite ‘ was coined from two Grecian words, ‘zeo ‘ ( to boil ) and ‘lithos ‘ ( rock ) . On the contrary, the first zeolite, chabasite, described by Bosch D’Antic in 1792 has clear grounds in literature. Several other zeolites were discovered in the undermentioned old ages and around 1850, merely about 20 zeolite types were reported in mineralogy books, including analcime, brewsterite, chabasite, edingtonite, epistilbite, faujasite, gismondine, gmelinite, harmotome, heulandite, laumontite, levyne, mesolite, natrolite, phillipsite, scolecite, stilbite, and thomsonite. Get downing from the center of the nineteenth century until about 1975, there was a moderate increase in the figure of zeolites discovered ( about one new type every 6-7 old ages ) and a clear acceleration in the last 20 five-thirty old ages. About 40 natural zeolites are known ( Tschernich, 1992 ) . Most zeolites known to happen in nature are of lower Si/Al ratios, since organic structure-directing agents necessary for formation of silicious zeolites are absent. Sometimes natural zeolites are found as big individual crystals, though are really hard to do in the research lab. The catalytic activity of natural zeolites is limited by their drosss and low surface countries.

However, involvements in natural zeolites shifted towards zeolite synthesis and man-made stuffs, as they offered a series of advantages such as wider versatility, more unfastened models ( for surface assimilation and contact action ) , and quality in fundamental law and chemical science. As a consequence, research on natural zeolites, was chiefly devoted to ion exchange procedure which was discovered around 1850 ( Thompson, 1850 ; Way, 1850 ) . Few old ages subsequently, Eichhorn observed that chabasite and natrolite behaved as reversible ion money changers. In the early decennaries of the twentieth century, ion exchange selectivity of a assortment of zeolites for curious cations, e.g. , ammonium was performed ( Barrer, 1950 ) and get downing from the terminal of the 1950s, found utilizations in assorted sectors of environmental relevancy, e.g. , intervention of effluents and dirt rebuilding and redress. The most recent frontier in the application of natural zeolites is in the field of life scientific disciplines.

One of the drawbacks of natural zeolite research for application intents is due to the limited handiness of zeolite as it is a cherished mineral, compared to the man-made opposite numbers which could be mass produced at a lower cost ( Colella, 2005 ) .

2.1.1 Formation

The tract of natural zeolite formation is similar to the laboratory synthesis of zeolite. Zeolite nucleation, crystallization and crystal growing take topographic point as a consequence of slow to fast chilling of warm to hot magmas ( of volcanic beginning ) , which are basic, oversaturated in silicate and aluminate species and contain alkalic and/or alkali-earth cations.

hot fluid + volcanic ash oversaturated basic magma zeolite crystals

{ solution + gel )

The magma is obtained via hydrolysis of the original glassy stuff and is responsible for the tetrahedral coordination of aluminum and together with Si. The chief factors responsible for the structural formation are temperature, chemical science of the ash and the chemical composing of the resulting solution. Gel is formed along the procedure but is nevertheless non straight connected to nucleation and growing, as there is grounds that zeolite nuclei signifier from the oversaturated solution at the glass sherds / solution interface ( Aiello et al. , 1980 ) .

Temperature and clip are two factors which differentiate natural zeolitisation from laboratory synthesis.

2.1.2 Physico-chemical belongingss

i.Cation exchange: The ion exchange belongingss of natural zeolites depend on their chemical science which ismainly in footings of selectivity. Selectivity depends on the model topology, ion size and form, charge denseness on the anionic model, ion valency and electrolyte concentration in the aqueous stage ( Barrer et al. , 1978 ) .

ii.Reactions with bases: Oncein alkaline environments, zeolites become unstable as they tend to transform, similarlyto glassy systems, into more stable stages, normally into other model silicates ( Goto and Sand, 1988 ) . The interaction of zeolite-rich stuffs with Ca ( OH ) 2 give rise to calcium silicates and aluminates, which upon hydration are able to indurate in both aerial and aqueous environments. This behavior makes them to be known as pozzolanic stuffs

Thermal belongingss: Heating of zeolite pulverization induces physical and chemical alterations, which have been shown to include H2O loss ( which causes enlargement on warming ) , decomposition and gas development, stage passage, construction dislocation, re-crystallisation, runing etc ( Colella, 1998 ) . This belongings enables zeolite tufa rocks to expose good sound-proofing and heat insularity and service as good edifice stuffs. Depending on zeolite nature, chemical composing and stone fundamental law, the tufa expands as a consequence of speedy warming at temperatures of 1250°C or supra, unwittingly followed by a rapid extinction to room temperature.

2.2SYNTHETIC Zeolites

Early work could be traced back to the claimed synthesis of levynite by St Claire Deville in 1862 as there were no dependable methods for to the full placing and characterizing the merchandises. The beginning of zeolite synthesis nevertheless, evolved from the work of Richard Barrer and Robert Milton which commenced in the late fortiess. The first man-made zeolite unknown as a natural mineral subsequently found to hold the KFI construction ( Baerlocher et al. , 2001 ) was discovered by Barrer when look intoing the transition of known mineral stages under the action of strong salt solutions at reasonably high temperatures ( ca. 170-270 °C ) . Robert Milton was the first individual to utilize newly precipitated aluminosilicate gels to transport out reactions under milder conditions. This led to the find of zeolites A and X ( Milton et al. , 1989 ) . Initially, the synthesis of zeolites required the usage of merely inorganic reactants but was nevertheless expanded in 1961 to include quaternate ammonium cations taking to the find of silica-rich stages ( high-silica zeolites ) . Subsequently, more man-made zeolites have been discovered ( Baerlocher et al. , 2001 ) , every bit good as zeolite-like or zeolite-related stuffs ( Szostak, 1989 ) known as zeotypes- represented by microporous alumino- and gallo phosphates ( AlPO4s and GaPO4s ) and titanosilicates.

Surveies on understanding zeolite synthesis have continued to be carried out upto the present twenty-four hours ( Table 1 ) . This has been due to finds of new stuffs, progresss in man-made processs, inventions in theoretical modeling methods and, particularly, by the development of new techniques for the probe of reaction mechanisms and the word picture of merchandises.

Table 1: Development of stuffs development in the zeolite field

‘‘Low ” Si/Al zeolites ( 1-1.5 )

A, Ten

‘‘Intermediate ” Si/Al zeolites ( f2-5 ) A )

Natural zeolites: erionite, chabasite, clinoptilolite,

Mordenite

Man-made zeolites: Yttrium, L, large-pore mordenite, Z

‘‘High ” Si/Al zeolites ( ?10-100 )

By thermochemical model alteration:

extremely siliceous discrepancies of Y, mordenite, erionite

By direct synthesis: ZSM-5, Silicate

Silica molecular screens

silicalite

Beginning: Flanigen ( 1980 )

2.2.1Mechanism of Hydrothermal Synthesis

Experimental observations of a typical hydrothermal zeolite synthesis

Due to its chemical responsiveness and low cost, formless and oxide-like Si and Al which make up the microporous model are mixed with a cation beginning normally, in a basic water-based medium. The ensuing aqueous mixture is so heated in a certain sterilizer at above 100?C leting the reactants to stay formless for sometime ( induction period ) after which crystalline zeolites are detected ( Figure 2 ) . Gradually, an about equal mass of zeolite crystals which is recovered by filtration, rinsing and drying replaces all the formless stuffs ( Cundy and Cox, 2005 ) .The bond type created in the crystalline zeolite merchandise ( e.g. zeolite A or ZSM-5 ) which contains Si-O-Al linkages is similar to that present in its precursor oxides, therefore the heat content alteration is non great. This procedure reduces nucleation rates, thereby organizing larger crystals.

Responsiveness of the gel, temperature and pH affect the rate of zeolite formation as an addition in pH and temperature leads to increase in the rate of formation of zeolite crystals. In their female parent spiritss, the zeolitic stages are metastable, thereby transforming the initial zeolite into an unsought thermodynamically more stable stage ( Ullmann, 2002 ) .

2.2.3 Synthesis from Clay minerals

Kaolin and metakaolin ( calcining china clay at 500-700°C ) are two of import clays used for the production of the zeolites NaA, NaX, and NaY ( Breck, 1974 ; Barrer, 1978 ) because binder-free extrudates and granules which offer advantages in surface assimilation engineering are produced.

2Al2Si2O5 ( OH ) 4

2Al2Si2O7+4H2O

Kaolin Metakaolin

Depending on the zeolite, the clay is shaped and, SiO2and seed crystals are added and while in the preformed form, the zeolite crystallises. Alternatively, zeolite is formed when the binder constituent of metakaolin undergoes hydrothermal intervention with Na hydrated oxide solution ( Goytisolo et al. , 1973 ; Chi and Hoffman, 1977 ) . Using supersonic radiation, reaction rate is enhanced and there is energy salvaging and lower production cost due to lower temperatures. This procedure is less frequently used as it could do olfactory property of the merchandise due to drosss present in clay e.g. Fe

2.2.2Industrial Zeolite Synthesis

Zeolite synthesis is an highly wide country of research and due to differences in the readying of each zeolite type, two representative zeolite types, TPA-ZSM-5 and zeolite Na-A, are chosen for a more elaborate presentation of the synthesis { Table 2 } ( Jansen, 2001 ) .

Table 2: Synthesis mixtures, physical & A ; chemical belongingss of the representative zeolites

Molar oxide ratio

Na-A

TPA-ZSM-5

SiO2

1

1

Al2O3

0.5

& lt ; 0.14

Na2O

1

0.16

Water

17

49

TPA2O

0.3

T ( ?C )

& lt ; 100

& gt ; 150

Physical & A ; Chemical belongingss

Pore agreements

3D, coops connected via Windowss

2D, crossing channels

Bronsted activity

low

High

Affinity

hydrophilic

Hydrophobic

Pore volume ( cm3/g )

0.37

0.18

Beginning: Jansen ( 2001 )

The composing of zeolite merchandise can be expressed by the cation type and its overall Si/Al ratio. In the readying of zeolite, nucleation is the rate finding measure which is influenced by a scope of factors dependent on the temperature of the reaction mixture.

Low Temperature Reaction Mixture: Here, the reaction mixture is prepared at low temperature, & lt ; 60?C supplying equal ripening. Sol atoms which are homogenously dispersed or aggregated are present in the ( aluminum oxide ) silicate gel stage. If OH- is the mineralising agent, the pH of the liquid stage will run between 8-12 ( Jansen, 2001 ) . At comparatively high pH, the monomeric ions of Si-species are abundant which is released via hydrolysis ( Figure 4 ) .

At high pH, condensation occurs when the nucleophilic deprotonated silanol group on monomeric impersonal species is attacked ( Figure 5 ) . The sourness of the silanol group depends on the figure and type of substituents on the silicon-atom ( Jansen, 2001 ) .

Temperature rise of the reaction mixture from & lt ; 60?C to & lt ; 200?C depends on the sterilizer size, form of agitation and viscousness of the reaction mixture. Gel re-arrangement, disintegration of gel into monomeric silicates and dissociation of silicates, and debasement of quaternate ammonium ions take topographic point ( Jansen, 2001 ) .

High Temperature Reaction Mixture: At this temperature, zeolites are formed from formless stuff which involves, reorganization of the low temperature synthesis mixture, nucleation and precipitation ( crystallization ) . During the initiation period, gel and species in solution rearrange from a uninterrupted altering stage of monomers and bunchs which disappears through hydrolysis and condensation, in which nucleation occurs ( Jansen, 2001 ) . The procedure particles become stable and nuclei signifiers, followed by crystallization which could happen in metastable solid, extremely dispersed or heavy gel signifiers.

Product quality, reaction clip and output influence efficient production of zeolites by optimizing their composing.

2.2.2 Secondary Synthesis Methods

Catalytic or adsorptive belongingss that can non be achieved by direct synthesis utilise post-synthesis ( secondary ) interventions to increase catalytic activity, form selectivity or porousness and thermal/hydrothermal stableness. Dealumination and ion exchange are used to transport out these alterations.

Dealumination

The zeolite construction is selectively dealuminated by acerb solutions, rinsing out aluminum out of the crystal, as was observed for zeolite A. However, for higher silicon oxide incorporating stuffs ( clinoptilolite ) , a to the full decationated construction is produced after uninterrupted acerb intervention. The metal ion is replaced with H3O+ followed by ( Al+3 + H3O+ ) remotion, bring forthing a hydroxyl nest.

Aluminum is removed from the model but non the crystal by hydrothermal dealumination. The heterogeneousness in the concentration of the model and non-framework of aluminum depends on the type of alteration used. Hydrothermal intervention causes the formless aluminum to roll up on the crystal surface which through fluorosilicate intervention can cut down aluminum centred acerb sites. Often, a secondary pore system is generated and hydroxyl nests can be annealed. In order to heighten the catalytic belongingss every bit good as stableness, Si, aluminum and other metal ions are introduced into the model ( Szostak, 2001 ) . Other methods of bring forthing thermally and hydrothermally stable checking accelerators include: usage of EDTA, SiCl4 vapour, and ( NH4 ) 2SiF6.

Acid mediated dealumination procedure via aluminum extraction and coevals of hydroxyl nest ( Szostak, 2001 )

Ion Exchange

This is an of import technique in pore-size technology for the production of zeolitic adsorbents ( Breck, 1974 ) . Ion exchange used in the production of Bronsted acid sites has major importance in the synthesis of solid acid accelerators ( Ullmann, 2002 ) . Ion exchange can be achieved besides, for certain intermediate-silica and high-silica zeolites ( e.g. , mordenite ) by intervention with mineral acids although involves the hazard of dealuminating the zeolite model ( McDaniel and Maher, 1976 ) . An indirect path via an ion exchange with ammonium salt solutions must be followed, bring forthing the “ammonium form” calcined at ca. 400°C to emancipate ammonium hydroxide and give the H signifier ( Ullmann, 2002 ) . When cations to be exchanged are positioned unaccessible coops, a sieve consequence is produced.

pH is an of import factor in ion exchanging of extremely charged passage metal ions in order to forestall metal hydroxide precipitation particularly at low pH.

2.3 CHARACTERISATION OF ZEOLITES

In order to find the relationships between the physical and physicochemical every bit good as sorptive and catalytic belongingss of zeolites, it is of import to cognize the structural, chemical and catalytic features of zeolites. Several criterion techniques are employed in zeolite word picture. The most common of which is X-ray diffraction used in finding the construction and pureness of zeolites. Others include: x-ray fluorescence spectrometry ( XRF ) or atomic soaking up spectroscopy, used to analyse elemental composing, sorption analysis to analyze the pore system, IR-spectroscopy, typically utilizing adsorbed investigation molecules to qualify the acid sites, scanning negatron microscopy ( SEM ) , for finding the size and morphology of zeolite crystallites, high-resolution transmittal negatron microscopy ( HRTEM ) , atomic magnetic resonance ( NMR ) spectrometry, temperature programme desorption ( TPD ) and many others ( Schuth, 2005 ) .

3.0 GENERAL APPLICATIONS OF ZEOLITES

Zeolites are used chiefly in 3 major applications: ion-exchange, adsorbents, and accelerators. Natural zeolites play an of import function in bulk mineral applications.

Adsorbent applications:

Common adsorbent applications focus on remotion of little polar molecules and majority separations, by more aluminous zeolites and based on molecular sieving processes severally ( Table 3 ) .

Table 3: Zeolite commercial applications as adsorbents

Purification

Bulk separations

Drying: natural gas ( including LNG ) , checking gas ( ethylene workss ) , refrigerating

Normal/iso-paraffin separation, Xylene separation

CO2 remotion: natural gas, flue gas ( CO2 + N2 ) cryogenic air separation workss

Olefin separation, Separation of organic dissolvers

Pollution suspension: remotion of Hg, NOx, SO

Separation of amino acids, n-nitrosoamines

Sweetening of natural gas and liquefied crude oil gas

Separation of CO2, SO2, NH3

Beginning: Flanigen ( 1980 ) .

Catalyst applications:

Zeolites have the greatest usage in catalytic snap. They besides play a function in hydroisomerisation, hydrocracking and aromatics processing. The strong sourness of zeolites plays a function in hydrocarbon processing. Asides this, they are happening increasing usage in synthesis of all right chemicals and organic intermediates in isomerization reactions, nucleophilic permutation and add-on etc.

Table 4: Zeolite applications in Catalysis

Inorganic reactions: H2S oxidization, NO decrease of NH3, CO oxidization, decrease

Hydrocarbon transition: Alkylation, Cracking

Organic reactions: Aromatization ( C4 hydrocarbons ) , Aromatics ( disproportionation, hydroalkylation, hydrogenation, hydroxylation, nitration, etc. )

Dehydration

Epoxidation

Beckman rearrangement

( cyclohexanone to caprolactam )

Methanol to gasoline

Chlorofluorocarbon decomposition

Shape-selective reforming

Beginning: Flanigen ( 1980 ) ; Galarneau et Al ( 2001 ) .

Ion-exchange applications:

Zeolite belongingss are straight exploited in several applications such as in the detergent industry, where zeolites are used for H2O softening or ‘building ‘ , carnal nutrient supplementation and in the intervention of effluent ( Townsend and Coker, 2001 ) . Zeolite A has selectivity for Ca2+ , thereby supplying a alone advantage. Besides, natural zeolites can be used to take of Cs+ and Sr 2+radioisotopes through ion-exchange ( Payra and Dutta, 2003 ) .

Table 5: Applications and advantages of Ion-exchange

Applications

Advantage

Metallic elements remotion and recovery

High selectivities for assorted metals

Removal of Cs+ and Sr2+

Stable to ionising radiation

Detergent builder zeolite A, zeolite X ( ZB-100, ZB-300 )

Remove Ca2+ and Mg2+ by selective exchange, no environmental job

Ion exchange fertilisers

Exchange with works foods such as NH4+ and K+ with slow release in dirt

Beginning: Flanigen ( 1980 )

Other Applications:

Zeolites besides play of import functions in health-related applications ( such as antibacterial agents, vaccinum adjuvants, drug bringing, bone formation, biosensors and enzyme mimetics ) , oil refinement, and petrochemical procedures. Zeolite pulverizations are used for odor remotion and as fictile additives. Zeolitic membranes offer the possibility of organic transmutations and separations coupled into one unit ( Payra and Dutta, 2003 ) .

3.1 Zeolites AND THE ENVIRONMENT

About all applications of zeolites are driven by environmental concerns, from cleaning toxic ( atomic ) wastes, to intervention of effluent, thereby cut downing pollution. Zeolites have now been used to replace harmful phosphate builders in pulverization detergents due to H2O pollution hazards. Zeolite catalysts aid to salvage energy as they make chemical procedures more efficient, understating un-necessary waste and byproducts. When used as solid accelerators and oxidation-reduction catalysts/sorbents, they cut down the demand for caustic liquid acids and take atmospheric pollutants, ( such as engine fumes gases and ozone-depleting Chlorofluorocarbons ) severally ( Bell, 2001 ) . In effluent, zeolites ( clinoptilolite, mordenite ) are used to take ammonium hydroxide and ammonium ions ( Townsend and Coker, 2001 ) , every bit good as heavy metal cations and passage metals.

3.2 ZEOLITE CATALYSTS IN GREEN CHEMISTRY

Zeolite accelerators have contributed to the design and synthesis of fresh stuffs and development of new methodological analysiss in organic synthesis, displacing the conventional and waste bring forthing reagents thereby maximizing atom use and cut downing waste generated ( E-factor ) .

Zeolites play an of import function in acid-catalyzed reactions such as acylation, alkylation, isomerization and condensation, cyclisation and electrophilic aromatic permutation.

Acylation of aromatic substrates: used in all right chemicals industry although has proven unsuccessful in less reactive aromatic compounds due to adsorption instability, unless performed in vapor stage utilizing H-ZSM-5 ( Singh and Pandey, 1997 ) .

4.0 Decision

Due to the function zeolites play chiefly as accelerators in the environment every bit good as in chemical industry, the efficiency of the zeolite accelerators has been greatly improved. The output and selectivity of the zeolite procedure is quantitative and in add-on, reduces energy demands, capital costs and complexness of equipments.

Over the old ages, the synthesis procedure of zeolites have encompassed the rules of green chemical science as described in the study which has included waste bar, energy efficiency, fewer environmental impacts, safer dissolvers, renewable stuffs, procedure intensification, contact action and decrease in capital cost.

Though present techniques seem to use some of the rules of green chemical science, farther research is still being employed to better the overall procedure.

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