Reports in Materials 

Science and Engineering 

(NBS A-CR-I 8 28 82) PRELIMINARY MARKET 

ANALYSIS FOR LARGE ZEOLITE CRYSTALS B. S, 

Thesis (Worcester Polytechnic Inst. ) 109 p 

N 88- 2 2211 7 

CSCL 12a Unclas 

G3/29 0142314 

Mechanical Engineering Department 

Worcester Polytechnic Institute Worcester, Massachusetts 01 609 
An Interactive Qualifying Project Report 

submitted to the Faculty of the 

WORCESTER POLYTECHNIC INSTITUTE 

in partial fulfillment of the requirements for the 

Degree of Bachelor of Science 

PRELIMINARY MARKET ANALYSIS FOR 

LARGE ZEOLITE CRYSTALS 

19 October 1987 

fhomas Doblmaier Paul Grasing 

This project waa aupportcd by NASA, 

MarshaLl Space Flight Center under NASA Grant Number: NAG8-619 

WPI Pro~ect Number: FRT-8671 
FIBSTRGCT 

Zeolite crystals are used in the manufacture of countle5s 

products today, which utilize their properties of absorption, ion 

exchange and catalysis. It has been determined that zeolites 

grown in space could be much larger in size than any of those 

currently available on Earth. The objective of this IQP was to 

identify and examine some of the potential uses for these new, 

larger crystals. Of the several industries examined, the medical 

and nuclear industries offer the greatest potential. 
RCKNOWLEDGEMENTS 

We would like to gratefully acknowledge the help of 

Professor Floyd Tuler (Mechanical Engineering Department, WPI) 

for all his help and time throughout this project, from its 

proposal, throughout its completion. 

We would also like tu thank Professor Rlbert Sacco (Chemical 

Engineering Department, WPI) for his time and information, which 

was necessary for this project. 

Lastly, we would like to thank Mr. Harry Rtkins, Mr. Frank 

Penaranda and NRSFI for having an interest in the students of WPI 

and for sponsoring this IQP. 
TGBLE OF CONTENTS 

Rbstract ...................................... i 

acknowledgements .............................. ii 

1.Introduction .................................. 1 

I I . Background 

E . 1 Technical Qspects of Zeolites ........ 4 

2.2 Current Uses of Zeolites .............. 14 

2.3 Customer and Manufacturer 

Generated Innovations ................ 23 

2.4 Industrial Marketing ................. 27 

2.5 Product Life Cycle ................... 32 

I11 . Methodology ................................ 35 

IV . Results and Flnalysis 

4.1 The Cost of Large Zeolite Crystals ... 37 

4.2 Nuclear Waste ........................ 41 

4.2.1 Radioactive Waste ................ 42 

4.2.2 Uses of Zeolites 

in Nuclear Waste ................. 57 

4.2.3 Institutional .................... 59 

4.2.4 Industry ......................... 70 

4.2.5 Commercial Power Plants .......... 72 

4.2.6 Government Facilities ............ 80 

4.2.7 Low Level Waste Conclusions ...... 81 

4.2.8 High Level Waste ................. 83 

4.3 Waste Water Cleanup 

4.3.1 Leather Tanning Industries ....... 85 

4.3.2 Battery Manufacturers ............ 86 

4.4 Medical/Pharmaceutical Uses 

of Zeolites .......................... 87 

4.5 The Space Program and Zeolites ....... 30 

4.6 Large Zeolites as Competition 

for Small Zeolites ................... 34 

V . Summary and Conclusions .................... '36 

References .................................. 39 

Companies contacted ........................ 1.01 
I. INTRODUCTION 

The promise of space has opened up a countless number of new 

frontiers. Microgravity, low vibration platforms, and an almost 

perfect vacuum have caused scientists for decades to wonder haw 

these unique properties of space can be applied to making 

products which would improve the quality of life on Earth. 

Experimentation in space has been steadily increasing since 

the beginning of the United States’ space program in the 1950s. 

With the advent of the Space Transport System, or Space Shuttle, 

more experiments are being carried out at greatly reduced cclst. 

Rnd with the coming of a permanent space station in the 1’390s’ 

space based manufacturing will also become a reality. 

Today, zeolite crystals are used in the manufacture of a 

variety of numbers of products used in the United States, such as 

gasoline, and plastics. Their importance is undisputed. 

Recently, research conducted in the Chemical Engineering 

Department at Worcester Polytechnic Inst it ute in Massachusetts 

has indicated that it would be possible to grow significant1.y 

larger zeolite crystals in the microgravity of space. WPI is 

also a member of the Clarkson Consortium, an association of 

colleges performing research for the purpose of growing various 

kinds of crystals in space. The National Rir and Space 

Rdministrat ion (NRSF)) has agreed to have art experimental crystal 

growth chamber, also designed at WPI, fly on the next Shuttle 

mission, currently scheduled for February of 1988. 

The prospect of having zeolites which are much larger than 

1 
any of those which could be grown on Earth opens the door to many 

potential new applications which were not previously possible 

with smaller crystals. 

The objective of this IQP was to identify possible areas of 

use for large zeolites. We identified those industries which we 

felt had applications to which large zeolites may be suited. We 

then tried to determine if zeolites could be introduced to the 

application and what, if any, advantages would they offer as 

compared to the existing way of doing things. The objective was 

not to examine all of the potential new uses of large zeolites - 

this would have been an impossible task, since many new uses 

might not be apparent until the large crystals are actually 

developed. Nor was the objective to justify the attempt to gr-ow 

large zeolites in space - that has already been accomplished. 

The Interactive Qualifying Project (IQP) is an essential 

part of the WPI Plan. It is required that all students complete 

an IQP, which relates science and technology to social needs and 

issues, to broaden their awareness of the importance of social/ 

technological interactions. We felt materials processing in 

space was a topic which fully met this requirement. Upon 

narrowing this topic down, we felt a preliminary market study for 

space grown zeolites would also benefit the students and faculty 

working on large zeolites, in addition to meeting our own degree 

requirements. 

This report will reveal our efforts and frustrations in 

identifying and investigating potential markets for large 

zeolites crystals. In the Background Section, some of the 

2 
technical highlights of zeolites are discussed, as well as why 

space based manufacture is thought to provide a solution tu the 

problem of growing large crystals. The Background Section also 

discusses the current markets for small synthetic and natural 

zeolites. In the Methodology Section, there is a discussion of 

market studies and more specifically, how we did one for this 

IQP. The Results and Rnalysis Section includes the markets we 

examined, and the conclusions we came to concerning them. 

Finally, our Conclusions Section contains a summary of our 

thoughts on the large zeolites and this IQP. 

3 
I I. BRCKGROUND 

2.1 Technical aspects of Zeolites 

Zeolite minerals are a type of porous or "hollow" crystal. 

Porous crystals (porous on a molecular scale), like all crystals 

are orderly, three dimensional arrays of atoms, ions or 

molecules. The porous nature of the crystals results in one, two 

and three dimensional channels, cavities and windows formed by 

the specific arrangement of atoms into a framework Ell. c7s an 

analogy, a building can be thought of as a framework (walls, 

ceilings, . . . 1 surrounding the channels, cavities, and windaws 

(halls, rooms, doors). 

although there are spaces between the atoms of the zeolite 

crystal, they are too small to readily allow the entrance of evert 

the smallest molecules or atoms, such as water, oxygen, or carbon 

dioxide (these elements can diffuse slowly into the crystal). The 

class of crystal zeolites is unique in admitting and retaining 

both small and somewhat larger molecules C23. 

Some other types of porous crystals include crystalline 

porosiles, porous aluminum phosphates, expanded clay mineral.^, 

and clathrates. These all exhibit molecular shape and size 

selectivity and (to different degrees) crystalline stability fr-t>ni 

the presence of guest molecules Cll. Zeolites can trap certain 

molecules as a sieve does. They can also bind up and selectively 

release specific molecules by adsorption or ion exchange C33. 

In 1756 the Swedish mineralogist a. F. Cronstedt not iced 

that certain minerals appeared to swell and boi1,upon heating. 

He appropriately named these minerals zeolites meaning 'boiling 

4 
stones' (from the Greek; zein 'to boil' and lithos, 'stone') C43. 

The bubbling he observed was from the release of water from the 

crystal. 

There are 37 natural zeolite minerals known to exist today. 

The natural zeolites, including faujasite, chabazite, mordenite, 

and clinoptilolite, occur in various geological environments in 

the Earth's crust C21. 

The framework of a zeolite crystal is composed of silicon, 

aluminum ,and oxygen atoms. These three elements are combined into 

Si0 and FllO tetrahedra, each tetrahedron consisting of four 

oxygen atoms surrounding a central silicon or aluminum aturn (see 

4 4 

Figure 2. 1). Each oxygen atom is shared by two adjacent 

tetrahedra. Flluminum tetrahedra do not connect in series with 

themselves. These primary units join into secondary building 

units (SBU)(see Figure 2.2). It is a characteristic ctf zeolites 

to be composed of polyhedral, cage like structures (also formed 

of SBUs). The secondary units and polyhedra combine to form the 

zeolite frameworks. The ring like structures of the secondary 

units form the cavities and 'windows' of the porous crystals. 

Four typical zeolite structures are shown in Figure 2.3 

[E', 3'41. 

The framework cavities contain alkali and alkaline metals 

such as lithium, sodium, potassium, calcium, and water molecules. 

+4 +3 

The replacement of the silicon ions (Si ) by aluminum ions (R1 1 

gives rise to a net negative charge on the zeolite framework. The 

residual charge due to the R10 tetrahedra is compensated by the 

4 

presence of the metal cations. Each sodium or lithium ion can 
n 

Silicon or Aluminum 

Oxygen 

FIGURE2.1: Representations of the Si0 or AlO tetrahedron. Each tetrahedron 4 4 

consists of four oxygen atoms'surrounding a central silicon or 

aluminum atom, 

4-1 

S8R 

cd. 

3-1 

B 

Da D6R 

4-4-1 

Y 

FIGURE 2.2: (a) Secondary building units of the zeolite frameworks: S,@ or 

single four-ring; S6R or single six-ring; S8R or single eightring; D4R or double fourwing; D6R or double six-ring; complex 

4-1 or T 0 unit; complex 5-1 or T 0 unit; complex 4-40? or 

T10020 unit. (b) Geometrical representations of some polyhedra 

5 10 8 16 

zeolite frameworks; u or truncated cubo-octahedron; B or 

truncated ocahedron; and 7 or 18-hedron; Each circle in (a) or 

corner in (b) represents the center of a tetrahedron. 
IW 

IN 

4 

Q 

T 

0 

- 

a 

. 

.. 

4 

W 

IJ 

'0 

W 

N 

- 

0 

a 

rn 

k 

a 

4 

d 

*rl 

d 

4 

d 

v1 

0 

3 

4 

rn 

h 

5 

2 

Q) 

4 

d 

a 

N 
balance one aluminum atom (R10 tetrahedron); each calcium ion can 

balance two aluminums. These cations are only loosely bonded to 

4 

the zeolite structure and there is considerable free space tct 

move in the large cavities. The water molecules are adsorbed on 

the inner surfaces of the channels of the framework. Rn important 

property of most zeolites is their ability to maintain crystal 

structure upon losing intracrystalline water E!, 4, SI. 

These unique structural properties give the zeolites their 

desirable qual it ies, namely crystal 1 ine ion exchange, reversible 

dehydration, absorption molecular sieving, and uses as catalysts. 

The porous structure allctws them to selectively separate, 

according to the size and shape of molecules, desired ctr 

undesired substances from each other. There is considerable 

variation in the size of these cavities, both within a given 

species and from one type of crystal species tcl the next. The 

molecular size pores range in size from about 2.5 to 10 angstrcas 

in diameter (1 angstrom = 10 meters). Some of the zeolites 

-10 

have a porosity of nearly fifty percent of the total crystal 

volume C53. 

Zeolites are among the most abundant of mineral species, 

being found in major deposits on every continent C63. They occur 

in igneous, metamorphic and sedimentary rocks. Most of the large 

natural zeolite crystals come from filled cavities and fractures 

of igneous rocks, especially basalt, a common volcanic rock E41. 

Volcanic ash serves as a source of silica and alumina which along 

with alkaline surface waters causes alterations in the basalt. 

Sedimentary zeolites occur as very small crystals, from 5 to 10 

6 
microns in size. These deposits are often huge and workable 

(suitable for mining). Zeolites are particularly abundant in 

saline alkaline lakes. Most sedimentary deposits consist af 

several types of zeolites, but virtually pure beds of single 

zeolite species have been found in the western United States 

desert areas. Other deposits are found in Japan, Italy, Cuba 

Bulgaria, New Zealand, Nova Scot id, Korea, Mexico, and Germany. 

Rnalcime and clinoptilolite are among the most commcwl type of 

sedimentary zeolite. Table 2.1 lists some representative natur-a1 

zeolites and their properties. Table 2.2 lists natural zeolite 

mineral occurrences. Table 2.3 lists some synthetic zeolites and 

their properties C6,71. 

Naturally occurring zeolites tend to be less than perfect. 

They tend to have structural errors and impurities. This has led 

scientists to develop synthetic versions of zeolites. In this way 

they can better control the conditions under which the zeolites 

form, a1 lowing more specific and consistant chemical properties 

for use. The increasing present uses for zeolites and the future 

potential uses have prompted the demand for large amounts of 

pure, perfect crystals. Excellent results have been obtained in 

producing synthetic zeolites. Many of the natural zeolites can be 

produced synthetically, but new and unique crystal structures can 

also be produced. Synthetic zeolites (also called permutites) 

such as Zeolites FI, X, Y, and ZSM-9 are extremely valuable since 

they can serve in specific applications not suited to other 

zeolites. The synthetic zeolites allowing the engineering of a 

crystal with the desired specific properties. There are, however, 

9 
: .q ,# **. I - r 1- i 

TABLE 1.1 -ci- , bhjr- . l,.+zy*>-.~ .*-..hl - . I- 

.I.. .>A 

---.. 2lolit.S *’ 1 

name colour lustre Mohs specific habit or cleavage refractive crystal remarks 

hardness gravity form Indices system 

space 

group ,3h I 

analcime colourless, vitreous 5-5H 2S2.3 transparent to nearly very poor n = 1.479-1.493 isometric classified as a 

Ia3d zeolite because 

of its exchange * 

and dehydration 

properties and 

a = 1.497-1.508 orthorhombic y = 1.499-1.508 

a = 1.503-t.508 monoclinic 

7 = 1.514-1.525 Cm 

= 1.491-1.500 heKagonal 

u = 1.496-1.505 R3m 

needlelike crystal one perfect a = 1.505-1.507 monoclinic chemically inter- I . masses; almost in- cleavage j3 - 1.505-1.507 C2 mediate between . y = 1.508-1.508 

colourless. vitreous 3-4 

brittle. coffin-shaped one good j3 = 1.475-1.485 Cmcm or S~~OOZ,.~H~O brown, yellow crystals; rosettes cleavage y = 1.477-1.487 CmcP 

I two distinct a = 1.483-1.504 monoclinic I 

CazA14SisOro* white; gray, silky crystals, frequently perfect 8 = 1.518-1.520 Cc 

6Hz0 pink. red, twinned; radiating cleavage y = 1.517-1.521 

* yellow crystal masses; 1 fibrous massive .i 

sblbite white; yellow, vitreous 3H-4 2.1-2.2 sheaflike crystal one very a = 1.484-1.500 monoclinic 

Ihomsonite colourless. vitreous to 5-5’h 2.1-2 4 radiating spherical one perfect, a = 1.497-1.530 orthorhombic pyroelectric 

(Ca. Na2. Kz),AIa red, brown aggregates: cross- good j3 1.492-1 SO7 2 

SizaOn.28HzO like penetration twins cleavage 7 - 1.494-1.513 Cm 

NaCazAI& white: pink. pearly concretions; one good @ - 1.513-1.533 Pnma i 

OZO*BHZO brown compact massive; cleavage - 1.518-1.544 I ‘. . columnar 3 

colourless to vitreous 5H-6 2.3 usually twinned a = 1.498 monoclinic 

y = 1.502 

mira kite 

mawaralite , ’ n = 1.495-1.504 mono 

CaAbSi,OlZ- white 

6) * 

I. 

v.: 
Occurrences of natural zeolite minerals 

Name Typical Occurrence 

in Igneous Rocks 

Occurrence in 

Sedimentary Rocks 

Analcime 

Brewsterite 

C habazi te 

Clinoptilolite 

Dachiardite 

Edingtonite 

Epistilbite 

Erionite 

Fau j asite 

Ferrierite 

Cismondite 

Gmelinite 

Gonnardite 

Harmotome 

Heulandite 

Laumontite 

Levynite 

Mesolite 

Mordeni3e 

Natrolite 

Phillipsite 

Scolecite 

Stillbite 

Thom soni te 

Yugawaralite 

Ireland, New Jersey, etc, Western U.S., deep sea floor 

Scotland 

Nova Scotia, Ireland, etc. Arizona, Nevada, Italy 

Wyoming 

Elba 

Scotland 

Iceland 

Rare; Oregon 

Rare; Germany 

Rare; British 

Rare; Italy 

Nova Scotia 

France, Italy 

Scotland 

Iceland 

Western U.S., deep sea floor 

Columbia 

Nevada, Oregon 

Utah 

\ 

Nova Scotia, Faroe Islands 

Iceland 

Nova Scotia 

Nova Scotia 

Ireland, New Jersey 

Ireland, Sicily 

Iceland, Colorado 

Iceland, Ireland, Scotland 

Scotland, Colorado 

Japan 

New Zealand 

New Zealand, U.S.S.R., Calf. 

U,S,S,R., Japan, Western U.S. 

Western U.S., Africa, Sea floor 

(D.lsl. Breck. Re-cent Ad-vanc-e-s in Zeolite Science, 7970) 
h 

'. 

. '. 

a3 

.L1 

4 

x 

- .-. 

l -___.. 

. .. 

m 
a number of quantitative and theoretical aspects of zeolites not 

yet fully understood. 

Zeolites are produced under condit ions of low temperature 

and pressure. The typical approach used in making synthetic 

zeolites starts with very reactive compounds including freshly 

prepared aluminosilicate gels, sodium aluminate, and sodium 

silicate. The starting materials are placed in a high pH 

solution, obtained by using alkali metal hydroxides and or 

organic bases. The solution is then appropriately enclosed, 

heated and pressurized. The crystals form and settle from the 

solution. Many of the synthetic zeolites are formed at 

temperatures rang i ng from room temperature to the boi 1 i ng poi nt 

of water, and with no more pressure than that generated by the 

react ion itself (autogenous). The format ion of the zeal ites is 

influenced by such factors as: the nature of the starting 

materials, homogeneity or heterogeneity of the mixture, pH of the 

mixture, seeding, temperature and pressure of the mixture, and 

reaction time (typically hours to days). Fls a result of the high 

degree of variability in forming zeolites, both natural arid 

synthetic zeolites have a wide range of chemical compositian, 

including variation in water, cation, and fll/Si ratios. The ease 

with which zeolites can be made makes them an ideal product forlarge scale manufacturing C8,93. 

13 . 
2.2 Current Uses of Zeolites 

Since Cronstedt’s discovery mare than two centuries ago of 

the zeolite mineral stilbite, these crystals have only recently 

been commercially used to large extent t63. Originally, the early 

investigations of zeolite properties were performed on rare 

mineral specimens collected from cavities of basaltic rocks (a 

common volcanic rock). In the 18OO’s, the ion exchange abilities 

of the minerals were discovered. These cations could be exchanged 

with other cations, with preferential exchange depending on the 

zeolite specie and the intrastructural variations. (such as the 

Si/Rl ratio). This led to the use of zeolites in softening hard 

water; that is exchanging calcium and magnesium of hard water with 

sodium ions from the zeolite. Heating zeolites to drive out 

intracrystalline water made ’dry’ or active zeolites which then 

had enormous adsorption properties. These active zeolites can be 

used as drying agents (water adsorbers) C23. 

Researchers of the early 19OO’s, recognizing the value of 

zeolites as ion exchangers, sought to prepare synthetic zeolites, 

since the natural minerals were not found in significant amounts. 

Reports in the late nineteenth century recorded occurrence of 

zeolites in sedimentary tuffs (compacted volcanic ash) and marine 

deposits. Discovery of deposits have increased since then, 

especially since World War I1 C2,Sl. These deposits consist of 

very small crystals (compared with the basaltic zeolite samples) 

homogeneously distributed throughout the rock. Rlthough the 

variety of sedimentary zeolites is limited (about five major 

types), a typical deposit can yield millions of tons annually. 

14 
With the advent of synthesizing zeolites in large quantities and 

discovery of workable natural zeolite deposits, significant 

progress was made in zeolite research. Various uses continue to 

be developed for the crystals today in the areas of synthesis, 

structure, ion exchange, catalysis, diffusion and adsorption. 

There are specific fields of application in which synthetic 

zeolites have no alternative (interchangeable) natural zeolite, 

owing to their strict uniformity of ccmposition, efficiency, 

performance quality, characteristics, size and operat ion of 

plants, and economic costs. In general, large scale, less 

sophisticated utilizations are reserved for natural zeolites. 

Rpplication of natural zeolites (as with synthetic) requires 

careful examination of original rock deposit in terms of zeolite 

type and constancy of cumposition. Regenerability of a zeolite 

product is also important in considering which specie (natural or 

synthetic, type 1 can be most economically utilized C’31. 

It is difficult to accurately Judge the present commercial 

usage of zeolites (natural or synthetic). Rccording to a 1’380 

investigation carried out in Italy, the production of nati-iral 

zeolites reached 300,000 tons per year, most of this production 

belonging to Europe and Japan. The greatest usages were in the 

building and paper industries C91. Clarke (also 1980) noted use 

of some 150,000 tons annually in the building industry (mostly as 

components of blended cements) and 480,000 t/a in paper making 

industries (as a substitute for kaolin clay which is used a$% a 

paper filler or coating) C61. The United States produces less 

natural zeolites due to extensive synthetic product research. 

15 
Table 2.4 gives some utilizations of natural zeolites (1984) E91. 

Most of the uses of zeolites come under one of three 

categories (there are no exact categories), namely; ion exchange, 

sccrption, and catalysis. Some uses of zeolites in these 

categories are given below. 

Sorption: Simple heating of zeolites will cause loss of 

water, in this dry or activated state the crystals will readily 

readsorb water. These activated zeolites are used as ant i-fog 

agents for double and triple glazed windows (dries the air space 

inside glazed or insulated glass units), as air driers in truck 

air-activated braking systems, and in natural gas pipelines or 

industrial gas processes, including removing water from ethylene, 

hydrogen, ethanol, alcohol, and CO streams C21. ktivated zeolites 

will also adsorb other molecules sufficiently small to enter the 

2 

pores. Materials having this size selective adsorption are 

called molecular sieves. Molecules larger than the nominal pore 

diameter are excluded from adsorption. 

With appropriate modifications, the natural zeolite 

clinoptilolite proves especially useful as a desiccant (since 

clinoptilolite is one of the more common types), removing water 

from air, refrigerants, organic 1 iquids (xylene, transformer oi 11, 

and in adsorbing SO and CO from gas streams C61. In the case of 

refrigeration, clinoptilolite proves to have comparable chemical 

2 2 

stabi 1 ity (after mechanical and chemical treatment 1, adsorpt icm, 

mechanical properties, and is less expensive then any synthetic 

adsorbent C101. 

Some sorption properties of nat ural and synthetic zeol ites 

16 
are given in Table 2.5. 

Ion Exchange: In this area, zeolites compete with resin ion 

exchangers. Only where resins are unsuitable have zeolites found 

application. Zeolites are used in four main areas as ion 

exchangers. 

Rs mentioned earlier, zeolites are used to soften water, 

making them particularly useful in detergents where they partially 

replace environmentally undesirable tri polyphosphate. Synthetic 

zeolites fare better in water softening than natural zeolites, 

since the synthetic crystals have higher ion exchange capacities. 

In the treatment of waste, zeolites are used in removal of 

ammonia and ammonium from municipal, industrial, and aquacultural 

(fish ponds) waste waters. Natural zeolites, clinoptilolite and 

phillipsite, have high selectivity for the NH ion. Rgain the 

synthetic zeolites (Linde F and W) may replace the natural 

+ 

4 

materials, though good results (especially in large scale u5e) 

have been obtained with the natural zeolites. Zeolites also find 

agricultural use in retaining fertilizer, pesticide, and soil 

nutrients for extended periods of time. Finally, there is widespread application of zeolites to the removal of radioactive 

isotopes from radioactive waste. In 1980-82 Union Carbide used a 

mixture of natural (chabazite) and synthetic (Zeolite fl) to treat 

the contaminated waters at Three Mile Island t5,6,11,3. 

Catalysis: R catalyst is a substance that modifies and or 

increases the rate of a chemical reaction without being consunied 

or changed in the process. With zeolites, reactants enter into 

the porous structure and react with the internal surface of the 

17 
TABLE 2.4. 

Picture of the present world utilization of natural zeolites 

(Approximate consumption values in ton/year) 

Buildinp industm 

(zeolitic tuffs) 

Industm/Amiculture 

Insitation/protec tion 

Paper filler 

Soil conditioner 

Additions to diets 

Chelating agent (NH ) 4 

fish cultural systems 

Deodorizing animal excr. 

Japan 

8,000 

1-2,000 

57,000 

?O,OOO 

5-6,OOO 

2.5-5,OOO 

200 

Chelating agent (NH ) * 4 

Chelating agent (metal ions, * 

municipal waste waters 

radionuclides, etc.) 

O2 air enrichment * 

Natural gas cleaning * 

Exhausted gas (SO2) treatment 

Energy storage * 

Gas and water adsorption, (world) 15,000 

USA 

* 

* 

* 

+f 

* 

* 

2-3, ooo 

* 

* 

* 

* 

Europe 

? 40,000 

* 

* 

* 

it 

* 

_- 

(*) utilization verified but data unavailable. 

(R. Sersale, Natural Zeolites: Processing, Present and Possible Applications) 
Molecular diameter (I) 

Zeolite type 

10 

9 

8 

7 

6 

5 

4 

3 

2 

Neopentane 

Cyclohexane 

Benzene 

Isobutane 

CF4 

CF2C12 

Propane 

Cyclopropane 

Xe 

GO/CH4 

N2/S02 

O2 

c12 

H2 

*2O 

Kr 

A 

"3 

TABIZ 2.5: Sorption in zeolites, Molecular sieving. 

(J. Dwyer,ItZeolite structure, ComDosition and Catalysistf, CJheg-, sd Is&-, 2 Ami1 84) 
crystal (although some reactions can occur on the external 

surface). For zeolite catalysts to be practical, reactants must 

be able to invade the crystals and products of the reactions must 

be able to leave. Typical one micron size zeolite crystals have a 

ratio of external surface to internal surface area of approximately 

0.5 percent Cl23. 

cls the reactants must enter the zeolite crystal interior, 

the adsorption and diffusion properties of the crystal are 

extremely important in relation to catalysis. Both the size and 

shape of the oxygen windows can influence the entrance of 

reactants. The arrangement and types of cations in the crystal 

also have significant effects with respect to interior access. 

The ion exchange abilities of zeolites often allow a 'fine 

tuning' of the window size (in zeolite FI a Na ion can be sited 

+ 

in the center of the 8-ring window while higher valence cations 

are not) [e, 123. 

Perhaps the most important uses of zeolites as catalysts is 

in the field of petroleum processing, in particular, the cracking 

of gas oil to gasoline. The term cracking refers to breaking down 

of the large, bulky molecules into smaller molecules. Essentially 

all of the gasoline made worldwide by catalytic cracking depends 

on some form of zeolite Y. In these Y zeolites, rare earth ions 

(RE 1 are exchanged for the normal cations (sodium). These rare 

3+ 

earth ions react with the water to form hydroxides and protons 

3+ e+ + 

RE + H 0 --) RE(OH) + H 

e 

+ 

During the process the protons (H 1 react with the hydrocarbon 

eo 
molecules of the gas oil to form carbonium ions. These ions then 

split further but return the protons to the zeolite in the 

process. So, the rare earth hydroxides and the protons are 

regenerated, producing no effective change to the zeolite C21. 

Other catalytic processes include converting toluene to 

benzene and para-xylene (both somewhat more useful than toluene 

itself), and converting methanol to gasoline. Both the above 

processes use a form of ZSM-5 synthetic zeolite. In New Zealartd, 

natural gas is converted to synthesis gas (mixture of hydrogen 

and carbon monoxide) and then to methanol. Coal can also be 

treated similarly C23. The conversion of ethanol to 

hydrocarbons, the alkylation of benzene, and the synthesis of 

amines from alcohols, ethers or olefins represent other areas of 

interest. Table 2.6 lists some of the most commonly used natural 

and synthetic zeolites in catalysis 1121. 

21 
Table 2.6 

Properties of Common Zeolites Used as Catalysts 

Zeolite Window. Free Dimenrion- Types of 

name Peripheral dimensions, ality of pore cavity 

0 - atoms with out system and size 

cations (R) (FI) 

Linde R 8 4.1 3 Sodalite (6.61, 

26 hedrcln (1 1.4) 

Er ioni t e 8 3.6 x 5.2 3 23 hedron (6.3 x 13) 

ZSM- I 1 10 5.4 x 5.6 3 

ZSM-5 10 5.4 x 5.6 

5.1 x 5.5 

Mordenite 12 6.7 x 7.0 

2.9 x 5.7 

Linde X,Y 12 7.4 

E: 

3 Soda1 ite (6.61, 

26 hedrun (11. 8) 
2.3 Customer and Manufacturer Generated Innovations 

In both consumer and industrial markets tctday, there are two 

basic methods by which manufacturers get ideas which they turn 

into new products. The first is a manufacturer-act ive process, 

where the onus is on the manufacturer to find the ideas. The 

other is a customer-active process where the manufacturer gets 

new products ideas from customers. 

The manufacturer-active process has been very successful in 

the consumer product marketplace. In this process (see Figure 

rZ.4a), the manufacturer surveys potential customers to determine 

their needs. Based on this data, ideas for new products are 

generated. The customers are later surveyed again to determine 

if these new products would meet their needs. Manufacturers ~tse 

a variety of techniques to determine customers’ needs, from phone 

surveys to free trial usage of a new product. These feedback 

techniques are very important because quite often the 

manufacturer who can better and more quickly determine the needs 

and wants of his customers, can gain control of a large portion 

of the market. 

The other way new products and innovations can come into 

being is as a result of customer generated ideas and requests 

(see Figure 2.4b). With this customer-active process, the 

manufacturer does not go out and look for new ideas, but merely 

accepts customers’ ideas and problems and decides which ones have 

the potential to become successful new products. In addition to 

supplying ideas, sometimes customers also supply part of the data 

as to how ideas can be implemented. This approach has also 

e3 

enjoyed success in the consumer marketplace. On example of this 

is the Pillsbury Bake-Off. Pillsbury uses this annual contest for 

publicity as well as for new product ideas, having derived one of 

its current cake lines directly from a Bake-Off winner C133. 

But the industrial marketplace is different from the 

consumer marketplace. Eric Von Hippel has compiled data fr-on1 

several other studies concerning the origins of companies, 

successful products C133. In one study, 62 percent of the 

successfully implemented projects of a RRD group concerned with 

plant processes were "initiated in response to direct customer 

request."Cl43 In another example, 80 percent of the new 

instruments manufactured by scient if ic instrument companies were 

a result of users developing ideas for manufacturers C12'3. 

However, Von Hippel's study also revealed that certain products 

such as plastic additives and engineering polymers were nclt 

developed as a result of user requests or user supplied ideas. 

His hypothesis is that in these and similar industries, the 

manufacturer is very well acquainted with the needs and desir-es 

of the customer arid therefore does not need to wait for a 

specific customer request before beginning development. He 

argues that in the computer business, the manufacturers know that 

users want more speed and computations per dollar, so they do not 

have to wait for a user to ask for a faster computer before 

developing one. Similarly, in the plastic additives business, 

manufacturers know customers want plastics which will degrade 

more slowly in sunlight, so they develop these additives without 

waiting for (a specific request. Common sense seems to support 

25 
this hypothesis. 

In industries where "he who comes out with the better product 

first, wins" is a fact of life, it would be suicide to wait for a 

customer request to start development on a new product if it is 

known what customers will want it. 

Von Hippel's data indicates that a product has a greater 

chance for success if it was generated in response to a 

customer's idea or request for a solution to a problem, or at 

least if it is known that the product will fill a well 

established and defined need of a customer. 

26 
2.4 Industrial Marketing 

Industrial or business markets exist in all the steps in the 

production chain from the extraction of raw materials up to, but 

not including wholesale and retail transactions, which are 

consumer activities (see Table 2.7) C151. The primary 

distinction between consumer and industry is in their motives for 

buying. For example, pub1 ic consumers purchase products to 

satisfy a personal or household need, while industrial consumers 

buy products to make other products, operate a business, or 

provide some form of public service C161. The nature of a market 

induces the use of value analysis, which thereby increases the 

use of standarditat ion and buying by technical specificat ions. 

The setting of standards is the process of obtaining an agreement 

on quality, design and composition for a material, component or 

machine and is therefore used in most all purchases C151. 

The demand for industrial goods is derived from the demand 

for (1) consumer goods, (2) products needed by governmental 

agencies, and (3) goods used by nonbusiness, nongovernmental 

organizations 1163. Of these three the first is the most 

important as can be proven by past influences on the industrial 

market by consumer markets and shifts in social trends. Since 

the demand for industrial products fluctuates so widely, it is 

desirable to establish a broader base of customers, or more uses 

per product, in order to reduce the vulnerability to business 

swings when the customer base is too narrow. 

Industrial purchasing is influenced by many factors such as 

27 
. 

-- . 

. .. , ,. 

. -i 

STRGE 1 

Raw Materials 

Extract i un 

STRGE 2 

Materi a1 

ProcessinR 

STRGE 3 

lrlanuf act ur i riq 

of Parts and 

Su basserrrb 1 y 

STRGE 4 

F i na 1 Rssiernbl y 

STRGE 5 

Distribution 

and Rftermarket 

CONSUMPT I13N 

Wholesale 

and Retai 1 Saie 

CCI~IS LI rfl e r s 

to HCiLtEjehcild 

Table 2.7 

E 
product quality, cost, post-sale service, efficiency, seller. 

reliability, terms of sale, ease and speed of delivery, and 

variety. "Industrial products are bought only to help the user 

manufacture, distribute, or sell more effectively so that it can 

improve its economical and competitive position. "C153 Thus, 

industrial buyers require much more specific cost and performance 

information about the products they purchase. Technology is 

therefore important since purchasing costs include (1) initial 

purchase cost - amount customer pays up front, list or quotad 

price of product, charges for financing, freight, insurance, 

installat ion, technical assistance at startup, warranty and/or 

service, (2) installation and startup costs - including space 

alterat ions, connect ions to power sources, facilities for 

ensuring proper temperature and ventilating cundit ions, and 

arrangements fur handling noise, waste materials, scrap and so 

on, and (3) operating costs - which include costs of utilizing a 

particular product or system, most standard accounting chargers 

such as labor, material, power, maintenance and repair, 

depreciation and interest charges on the purchased item or 

inventory C 151. 

In a market study it is necessary to examine the competiturs 

that provide a product which performs a similar function or 

functions. Such a competitor may not supply an exact product or 

one made of the same material, but if in the customer's eyes the 

competitive product fulfills the same function, it is very much a 

competitive product and therefore one to analyze. Fln analysis of 

competitors is an analysis of businesses that compete far the 

29 
same customer's sales dollars C151. "This compet it ive assessment 

entails a knowledge of who present and potential competitors are; 

an analysis of how well each competitor meets the requirements of 

a segment; and an analysis of competitors plans and likely 

react ions. I' C 151 

This previously mentioned competitive assessment may not be 

as direct as it appears, for companies within the same industry 

may have very different cost structures, which can be due to a 

number of factors. These include (1)'the age and condition OF 

the physical plant; (2) the effectiveness and efficiency of theirmachines; (3) the productivity of their labor forces; (4) the 

degree of forward of backward integration (which implies the use 

of technology or a move back to basics); and (5) size and market 

share C153. Thus the study of cornpetitor economics employs many 

research tools. 

It is often thought that how competitive a firm is in the 

marketplace depends on the cost and productivity of its work 

force and manufacturing process. Thus the need for efficient 

technologies arises. This trend of thinking is especially true 

in mature industries where one must be a lower-cost producer ta 

be an effective competitor C151. 

Even though the preceding comments may hold true, before a 

supplier can compete in any industrial product or market 

situation, it must possess at least certain capabilities. These 

factors vary by market, but often include having a minimum level. 

of quality, proven manufacturing capability, technical ability, 

service capability, and possibly an extensive distributor network C151. 

30 
The final stages of the production cycle include pricing. 

Once the product is designed to meet or excel the operating 

specifications and therefore enhance the economics of a 

particular set of customers, pricing strategies can be developed. 

For example, cost analysis tends to cause the producer to price 

to what the market will bear, rather than using a cost-plus 

approach that might be below the customer's value-in-use and 

willingness to pay. However, if the competitive products are not 

as cost effective, competitive prices will not be as relevant 

C151. 

I 

31 
2.5 Product Life Cycle 

"Every product goes through a cycle from birth, into an 

initial growth stage, into a relatively stable period, and 

finally into a declining stage that eventually ends in the death 

of the product." C173 (see Figure 2.5~). In the early stages OF 

such a cycle, consumer acceptance is low, and therefore sales are 

low. It is during this initial stage that management makes the 

most decisions concerning product ion. 

The next stage is the growth stage, in which the product has 

reached a growing number of customers. During this stage, design 

tailoring usually occurs. The following stage consists of the 

maturity of the product. During this stage sales are stable and 

grow at the rate of the economy. Competition plays a major role 

in this stage, as pressure exists to decrease prices. During the 

mature stage, new innovations or markets should be developed in 

order to achieve the maximum life of the product before it 

reaches the decline stage. During the decline stage, sales 

because of new technologies are introduced which can better 

accomplish the same job C173. Figure 2.5a shows an expanded 

product life cycle which includes both the market and prernarket 

phases, while figure 2.5~ shows the simple view of the product 

life cycle. 

Figure Z5b shows the technology development cycle. In its 

early stages progress is limited by lack of ideas. Fls the ideas 

progress the curve becomes exponential until growth becomes 

linear. Rt this point progress is concerned with meeting the 

needs of the ideas with greatest potential. This is the period 

32 
.. . 

+ 

t Ii 

1 

- 

Lmrt s ---------- r 

f 
of commercial exploration as market analysis and manufacturing 

develop in an unsettled field. 

F)s progress continues, technologies eventually expire and 

improvements become difficult. "Now the market tends to beccme 

mare stabilized, manufacturing methods become fixed in place, and 

more capital is expended to reduce the cost of manufacturing. 

The business becomes capital-intensive; the emphasis is on 

product ion know-how and financial expertise rather than 

scientific and technological expertise. 'I 1173 The graph thus 

approaches its natural or social limit asymptotically. Finally, 

it can be seen that the success of a technalogy-based company 

depends on realizing when the technology which governs the 

campany begins to mature, and using research and development to 

emphasize other uprising technologies. Figure 2.5d shows tho 

nature of this technology transfer. 

34 
I I I. METHODOLOGY 

To understand the steps taken to secure a market study of 

large space-grown zeolites, the methodology we employed should be 

discussed . It was first necessary in our research to assume that 

these large zeolites could indeed be produced readily. The 

products were treated as industrial goods rather than consunier 

goods, based on the proposed uses. Lastly, it was necessary to 

gather information on both present and proposed future technolmgy 

in the areas of the potential available markets, in order that a 

comparison could be achieved. These individual steps shall know 

be explained. 

The informat ion concerning the properties, costs and 

expectations of the space-grown zeolites were supplied by WPI: 

faculty, and existing literature. Fls previously stated, it was 

necessary to assume that (1) the large crystals could be grown 

and that (2) these large crystals would maintain the existing 

properties of zeolites today. The proposed costs of the crystals 

include growth on space shuttle flights as well as growth ort a 

space stat ion laboratory. 

The compet it ive product informat ion which was needed was 

gathered through a person-to-person contact system. Telephone 

calls were made and letters sent out tcc various officials, 

representatives, and scientific personnel in order to obtain the 

various technologies, costs and requirements of the procedures in 

question. Much information was also acquired through catalogues, 

pamphlets, and brochures which were obtained through such 

35 
contacts. Finally, it was necessary to acquire as much 

information as possible in any one particular area, in order that 

a true cost comparison could be achieved. 

Based on the available information, proposed markets were 

discovered in which the new crystals could possibly prove 

beneficial. Decisions were made concerning the possibility of a 

market impact based on economic and cost factors. These 

decisions were influenced by such factors as the present economy 

and industrial trends which were assumed to remain relatively 

constant. Finally, it can be inferred that this report cannot be 

a true market study as it is often defined, due to the lack of 

information regarding the nature and cost of the zeolite pvocess 

including its material, space, ventilation, and power 

requirements. Therefore, our analysis should be considered a 

suggested incentive for further in-depth research into the 

markets for space-grown zeolites which this paper finds suitable. 

36 
1V.RESULTS FIND RNFILYSIS 

4.1 The Cost of Large Zeolite Crystals 

Rs the zeolite growth process is simple, requiring no 

exotic chemicals or procedures, the major cost of producing lar-ge 

zeolite crystals in space, as with other materials, is the cost 

of launching the,materials and equipment into orbit. Initially, 

large zeolites could be manufactured in small scale on the Space 

Shuttle. but, in the long run, large scale production of the 

crystals would be carried out most economically in an orbiting 

space station. FI space station can offer both more time and ar-ea 

for a manufacturing operation than the shuttle. In either case, 

if the raw materials are to come from Earth, the cost of lifting 

the materials to orbit via the shuttle still exists. 

From information given by Dr. B. Stone, an estimate of the 

cost of large zeolites can be given. In 1982 dollars a fully 

dedicated shuttle launch (the entire cargo bay) costs 74 million 

dollars or approximately 07 million dollars in 1903 dollars. 

Since the shuttle accident no exact figures can be given. The 

maximum load of the shuttle is some 65,000 lbm (29,484 kg). The 

ratio of maximum load to maximum cost gives a rough estimate of 

the cost per pound of zeolite; 

$87,000,000/65,000 lbm = $1,340/lbm = $2, 951/kg. 

It is unlikely that a fully dedicated launch would be available 

at convenience or necessary. In the case of a shared use of the 

shuttle there are two cases to consider in pricing. With respect 

37 
to a given payload a weight load factor and a length load factor 

can be calculated. The weight load factor is the ratio of the 

weight of the payload in qLtestion to the maximum load of the 

shuttle (65,000 lbm) ; 

Weight Load Factor = W (lbm)/65,000 lbm. 

The length load factor is the ratio of the length of the payload 

to the total length of the cargo bay (60 ft); 

Length Load Factor = L (ft 1 /60 ft. 

The width of the load is taken into account by the weight and 

length (W/L = Flrea). The larger of these two factors (WLF. or 

LLF.) determines the price charge factor. Since the average 

shuttle launch has only a 314 full payload, this is included in 

the general pricing; 

Price Charge Factor =E Load Factor (WLF. or LLF. )/. 75 

Finally the charge factor is multiplied by the total shuttle 

flight cost; 

Cost of Load = Price Charge Factor x $87,000,000. 

Since no specific process for groiwing zeolites (as they have not 

yet been grown) can be pinpointed, no exact prices can be given 

for the crystals. 

In general, it will cost approximately $3,300 per kilogram 

of material produced (information given by Prof. FI. Sacco). This 

figure is what NFISFl expects any type of commercial materials 

38 
processing in the shuttle to cost. 

Beyond the costs of transporting the materials, the 

materials must also be processed. This additional cost consists 

of power consumpt ion, cost of container, equipment, and control 

systems for the device. Rn average figure for the processing is 

$1,300 per kilogram. So this gives a total cost of $4,600 

per kilogram. 

Processing 

Load Cost Cost Total Cost 

#3,300/kg + $l,300/kg = $4,60O/kg. 

If large zeolites can be made, it is believed they will be 

useful in the form of thin membranes. These membranes would be 

cleaved from a large crystal. There is a pcesibility these 

membranes would be structurally weak, however, composite 

membranes offer a solution to this. R sample calculation can be 

made to estimate the cost of one of these membranes. First, the 

cost will vary depending on the type of zeolite produced, since 

this will change the amounts of raw materials used (silicon, 

alwninum, oxygen, and cations). It can be assumed that the cost 

of the raw materials is negligible compared tcl the total cost. 

Rssume a 25 centimeter cube of a zeolite will be cleaved 

into 10,000 layers (10,000 membranes). The average density of 

zeolites is on the order of 2,200 kg/m . Therefore the mass of 

3 

the cube is given by; 

3 

25 cm x (1 m/100 cm) x 2,200 kg/m = 34.4 kg. 

39 
Multiply this by the average cost per kilogram (above); 

34.4 kg x 64,600/kg = $158,125. 

Divide by the number ctf layers (10,000) ; 

$158, 1PS/10, 000 membranes = $15. Bl/membrane. 

Since no competitive product exists (membrane wise) it is 

difficult to say whether this is a high or low price. Certainly 

in a very specific application where only a zeolite membrane 

cctuld be used this is not an unattractive price. 

In the long run, larger scale production of the crystals 

would reduce the price. Fln especially attractive idea is that of 

using raw materials mined from the Moon. 

The large zeolites could also be used in the pellet (bead) 

form now used for small zeolites. Essentially a large zeolite 

would be crushed to appropriate sized particles. These particles 

would offer substantially higher efficiency and lower pressures 

(as in a columnar separation process). It is not likely that large 

zeolites would be competitive in this area (especially large 

scale industrial uses) but perhaps in rmre specific, scientific 

applications (calibration of equipment, small scale specific uses 

with chemicals). 

40 
4.2 Nuclear Waste 

Low level radioactive waste material has become a major 

source of controversy. This waste is produced by various sources 

such as t he med i ea 1 f i e 1 d, industry, government, and commerc i a 1 

nuclear power plants. These institutions differ not only in the 

types of wastes produced, but also in the amounts produced and 

the types of processing methods employed. In this section, the 

different fcwrns of wastes will be explored as well as their 

associated treatment methods in order that a comparison an be 

made with processes utilizing zeolites. This section will be 

broken tup by waste classification and its various producers. 

41 
4.2. 1 Radioactive Waste 

One of the proposed uses for space-grown zeolites is for the 

handling and storage of low level radioactive waste. Flt this 

time, the different forms of waste should be characterized. 

"Spent fuel consists of irradiated fuel discharged from a 

commercial reactor or spent fuels from test or research 

reactors. 'I ti201 These fuels are either government or commercially 

owned and are wsually stored in pools at reactor sites and other 

locations. High level wastes are highly radioactive material 

resulting from the reprocessing of spent nuclear fuel and 

contains fission products which result in the release of lar-ge 

amounts of decay ener-gy. The waste consists mainly of the liquid 

wastes remaining from the recovery of uranium and plutonium in a 

fuel reprocessing system and may also be in the form of sludge, 

calcine, or other such products into which these liquid wastes 

are converted to facilitate their handling and storage C203. 

Transuranic (TRU) wastes are "radioactive wastes which 

-9 

contairr more than 100 nCi/g (CuriesxlO per gram) of alphaemitting isotopes with atomic numbers greater than 9s and halflives greater than 20 years."C201 These wastes result mainly froni 

fuel reprocessing and from the fabrication of plutonium weapons 

and plutonium-bearing reactor fuel. 

Low level waste is radioactive waste not classified as mill 

tailing (earthen residues), high level waste, transuranic waste, 

spent fuel, or by-product material. It is material contaminated 

with small, but potentially hazardous, levels of radioactivity. 

42 
They usually appear in the form of dry trash, paper, plastics, 

glass, clothing, and discarded equipment to wet sludges and 

aqueous, organic liquids C211. The radiation level from this waste 

may be high enough to require scme shielding for handling and 

transport. 

There are basically three forms of low level waste: liquid, 

wet solids, and dry solids. Liquid low level wastes are fluids 

ccmtaminated with radioactive particles in relatively low 

concentrations, such as less than one percent by volume. For-ras 

of 1 iquid include chemical regenerative solut ions, 

decontamination solutions, contaminated oils, and liquidscintillation. Wet solids are ccmsidered to be moderately thick 

slurries containing at least 10 percent solids by volume. It 

irteludes evaporator bottoms, spent ion-exchange media, filter 

precoat material, and expanded filter cartridges. Finally, dry 

sc~lids consist of three main types of waste forms including 

trash, contaminated material, plant equipment and irradiated 

hardware 1211. See Tables 4.1 a-e for associated low level waste 

volumes. Based on these definitions the processing applications 

far zeolites would fall under the liquid and wet solid waste 

categories, since dry solids are usually just compacted. 

The waste management procedure depends on the physical and 

chemical characteristics of the waste, its radionuclide content, 

half-life of the radioactive atoms, specific activity, as well as 

or1 regulat icwts governing packaging, transportat ion, and disposal 

of the waste (see Figure 4.1). Tables 4.E and 4.3 show the 

relative importance of waste characteristics as a function of 

43 
waste farm, and the various technologies associated with waste 

forms. 

i 

44 
kh RA New England Hospitals, Universities, Research, Manufacturers, Utilities 

LOW LEVEL RADIOACTIVE WASTE 

-FACT S 

LLN VOLUMES, 1986 - BY INTERSTATE COMPACTS 

NUMBER'S IN THOUSANDS OF CUBIC FEET 

NORTHEAST CENTRAL STATES ROCKY MOUNTAIN 

Connecticut 56.7 Arkansas 6.0 col orado 1.4 

New Jersey 

APPALAC IAN 

Pennsy 1 van i a 

West Virginia 

Ma ryl and 

Del aware 

SOUTHEAST 

Georsia 

Florida 

Tennessee 

A1 abam 

North Carolina 

South Carolina 

Mississippi 

Vi rg i ni a 

37.9 - 

94.9 

191.2 

0.0 

12.9 

- 1.1 

m52 

50.5 

31.5 

63.7 

51.3 

79.7 

113.6 

14.1 

M 

Louisiana 20.1 

Nebraska -21.8 

0 kl ahom 50.6 

lDi3 

CENTRAL MIDWEST 

.I 1 1 i no i s 211.9 

Kentucky 

MIDWEST 

Wisconsin 

2.9 

214.8 

5.4 

Indiana 0.0 

Iowa 9.5 

Ohio 17.8 

Michigan 41.5 

Minnesota 26.7 

Missouri 12.2 

1TZZ 

Nevada 

New Mexico 

Wyomi rig 

WESTERN I1 

South Dakota 

Arizona 

NORTHWEST 

Idaho 

Wash i ngton 

Oregon 

Utah 

Alaska 

Hawa i i 

Montana 

0.0 

0.0 

0.0 

1.4 

0.0 

3.0 

3.0 

- 

0.0 

53.3 

98.5 

3.7 

0.0 

2.7 

158.9 

.a 

UNA11 GNED 

Rhode Island .2 

Vermont 13.7 

New Hampshire 1.0 

Massachusetts 66.7 

New York 119.3 

Maine 6.6 

Texas .6 

North Dakota 0.0 

California 92.5 

District of 

Col umbi a .2 

300.8 

TOTAL 

1,671,100 cubic feet 

*NOTE: These figures were projected using the first nine months figures of 1986 

for the three facilities. 

STATE COMPARISONS FOR 1979, 1983 & 1986 

1979 - 

1. New York 

2. South Carolina 

3. Pennsylvania 

4. Illinois 

5. North Carolina 

*6. Massachusetts 

7. California 

8. Virginia 

9. Connecticut 

10. Alabama 

1983 

1. Pennsylvania 

2. Illinois 

- 

3. New York 

4. South Carolina 

6. Virginia 

7. North Carolina 

8. Tennessee 

9. Alabama 

10. California 

*5. Massachusetts 

1986 

1. Illinois 7 

2. Pennsylvania 

3. New York 

4. South Carolina 

5. Oregon 

6. California 

7. North Carolina 

8. Virginia 

*9. Massachusetts 

10. Tennessee 
LOW-LEVEL WASTE VOLUMES 

Institutional and industrial low-level wastes are generated in all 

50 states, the District of Columbia, Puerto Rico, and the Virgin Islands. 

In 25 states, low-level wastes are produced at commercial power reactors. 

The volume of wastes from the various sources transported to commercial 

burial sites in 1981 is illustrated in Figure 1. Table 4 shows the volumes 

of low-level waste disposed of in 1980 and 1981 at commercial burial sites. 

-_ 

.. . 

Industrial and 

Institutional Waste 

38,328 m3 

Commercial Power 

Reactor Waste 

47,382 m3 

Government and Military Wastes 

1,611 m3 

INEL 3 0466 

- . Sources of low-level waste, by generator category for 1981. 

Table 4.lb 

. . 
f 

ln 

0 + 

W 

ul - 

-1 

a 5 

Iv, 

QT 

e 

0 

a 

w 

Ly: 

0 

e 

L 

n 

w 

s - 

I 

w 

n 

a 

0 

a 

LJ 

v, 

Z 

w 

G 

w 

P 

0 

n 

I 

=R 

gr 

Wc 

n 

w 

0 

I 

n 

z 

0 - 

Z 

c 

> 

0 

0 

U 

r 

0 

E 

s 

- a 

4. 
Sector 

Low Level Waste in the United States 

Volume Z Radioactivity % 

Cubic ft Cur i es 

Nuclear Power P1 ant s 1 , 527,700 57 ,582,500 78 

Rcaderni c/Medi cal 78,600 3 900 0. Y 

I nd ust r i a 1 986,600 37 158, 300 21 

Government a 1 87,960 3 7,400 - - 

Tot a 1 e, 680, BO0 I, 468, 000 

Government a 1 

Table 4.1d 
_- 

I 

8 

I 

I 

I 

I 

8 

I 

m 

n 

w 

IY 

Es 

CK 

n 

00 

no 
- 

OD N OD n 

. .. 

U 
TABLE 4.2 RELATIVE IMPORTANCE OF WASTE CHARACTERISTICS AS A FUNCTION 

OF WASTE FORM 

- Parameter 

Generation rate 

* Specific activity. 

Radionuclide content 

Sol ids content 

Oxidizability 

Fr ee-water content 

Mu1 tiple 1 iquid phases 

Major ihemical content 

Organic species 

Ionic species 

Viscosity 

PH 

Bulk density 

Shredabi 1 i ty 

Combustibi 1 ity 

Waste Form 

Liquids Wet Solids Dry Sol ids 

Major Major . Major 

Major Major Major 

Major Major Major 

Major Major 

Mi nor 

-Major 

Major 

Major 

Major 

Minor 

Minor 

Mi nor 

00 

0- 

Major 

Major 

0- 

-- 

Mi nor 

00 

Minor 

0- 

Mi nor 

-0 

Minor . 

Major 

0- 

-- 

Mi nor 

-- 

-- 

-- 

-- 

Minor 

Major 

Major 
TABLE 4.3 MATRIX OF TREATMENT/CONDITIONING TECHNOLOGIES AND WASTE FORMS 

Type of Technology 

Transfer Technologies 

- Decontamination 

Filtration 

Ion exchange 

Chemical regeneration 

Ultrafiltration 

Reverse osmosis 

Concentration Technologies 

E v aporat i on 

Distillation 

Crys ta 1 1 i zat ion 

F1 occu 1 at i on 

P rec i pi tat i on 

Sedimentation 

Centrifugation 

Orying 

Dewatering 

Dehydration 

Compaction 

Baling 

Shredding 

Integrated systems 

Transformation Techno1 og 

Incineration 

Calcination 

Con d i t i on i n g Techno 1 o g i es 

es 

High-integrity containers 

Solidification 

Absorption 

Waste Form 

- t iaui ds 

00 

X 

X 

X 

X 

0- 

X 

X 

X 

X 

X 

X 

X' 

-- 

IO 

.I 

-- 

-- 

IO 

X 

X 

x 

00 

X 

X 

Wet Solids 

x 

X 

X 

X 

x 

Dry Solids 

X 

0. 

00 

00 

00 

00 

00 

IO 

IO 

0. 

00 

-0 

I. 

II 

I0- 

X 

X 

.x 

X 8 

0- 

X 

-x 00 

.. I- . .. ._ . 
Conditioning and treatment of the waste refers to the processes 

which transform these radioactive products into suitable fclrms 

for transportat ion and burial. The waste processing techniques 

used today are usually chosen because they are cost effective or 

satisfy regulatory requirements. Some examples of treatment/ 

conditioning processes for liquid waste are defined for 

reference. 

Transfer technology refers to the removal of radioactivity 

from waste streams and its transfer to another medium. These 

processes include f i ltrat ion, ion-exchange, and membrane 

processes such as osmosis and ultrafiltration. Filtration is the 

process of separating undissolved or suspended particulate sol ids 

in a liquid stream from the liquid media by forcing it through a 

porous body. "Factors which should be considered in the 

selection of a filter include: (a) degree of filtration 

required; (b) the chemical compatibility of the filter medium 

with the liquid being processed; (c) the concentration and 

particle-size distribution of the salids to be removed; and (d) 

the volume, flow rate, temperature, and pressure of the liquid 

waste."C213 In general, filtration should be used when the volume 

of the liquid is above 38 m/year and suspended solids content is 

3 

above 2 to 3 percent. 

Ion-exchange processes consist of select ive removal of 

particles from liquids onto an exchange medium (resin). "The 

mechanism of ion-exchange consists of a reversible interchange of 

ions of the same sign between an electrolyte solution and a solid 

phase. "t2ll Types of ion-exchange methods include cation and anion 

53 
exchangers as well as mixed or separate-bed ion exchangers 

(demineral izers) combining the use of both cat ion and anion 

media. Filtration is often a pretreatment with this process 

which works best with low suspended solid content and 

teniperat ures below 60 C. 

Membrane separation treatments include reverse osmosis and 

ultrafiltration. These processes have been used highly with 

nonradioactive products and have provided favorable results on 

tests with low level wastes. They provide the advantage of (1) 

no need for mechanical filter aids; (2) minimization of the 

requirements for chemical regeneration or disposal of expensive 

resins; and (3) preconcentration of the wastes without the need 

of major process equipment with large auxiliary heat supplies C2l.I. 

Concentration technologies are used to reduce waste volume 

by concentrating the radioactive species without removing them 

from the original waste form. The types of concentration 

technologies often used for liquids include evaporation, 

di st i 1 lat ion, crystal 1 izat ion, f locculat ion, preci pit at ion, 

sedirnentat ion, centrifugation, and integrated systems. 

Evaporation can be applied to a variety of liquid wastes to 

concentrate relatively nonvolatile radioactive atoms from 

solutions with high solid content. However, due to high energy 

costs, evaporation is considered economically unfavorable forlarge volumes of liquid, over 3800 m/y 1213. 

3 

Dist i 1 lat ion and crystal 1 i zat ion are test -proven techniques 

which have not been used extensively. These processes involve 

removal of dissolved material from- liquid waste, usually by 

54 
evaporation near atmospheric pressures. "Crystal 1 izat ion induces 

nucleation of particles of dissolved materials either by thermal 

activation or by seeding with ultrafine nuclei. "Cell Flocculatiun, 

sedinientat ion, and centrifugation are processes which can be used 

to remove suspended scalids from liquid waste with the help of 

such things as interaction agents and gravity. These processes 

are mcwe commonly found at large Department of Energy (DOE) 

facilities where they experience specific limited use. 

The final concentrat ion procedure involves integrated 

systems which combine volume reduction through evaporation with 

volume increase through absorption. Based on such things as the 

binding material of the absorbent, this system would have to be 

evaluated on plant and waste basis C211. 

Transformat ion technologies are similar to concentrat ion 

technologies in principal, however, concentrat ion is achieved by 

changing the physical form of the waste. The major method of 

this area is incineration which involves thermal decomposition of 

organic liquids at moderate temperatures. The resultant waste is 

usually of a solid form with decreased volume, but it may require 

some conditioning C213. 

FI final category of technology is that of conditioning, 

which involves solidification of the liquid or the use of 

absorbents to transform the waste into a suitable form for 

transport at ion and d i sposa 1. 

55 
Solidification systems are those that achieve 

the immobilization of liquid waste within an 

inert matrix. These systems usually chemical ly 

encapsulate the liquid within an inert matrix. 

Rbsorbents are used to store the liquid within 

a porous material, from which the liquid could 

be extracted. E213 

Ccmdit ioning wi 11 never result in reduced total management cost 

because it adds steps and operations, yet does nothing to 

decrease waste volume. For this reason condit ioning is not as 

extensively used at nuclear fuel-cycle and government facilities 

as in industrial and institutional facilities due to the smaller 

amount of liquid waste produced annually by the later (1 m 1. 

3 

Before looking at the various possible uses for zeolites in 

waste treatment, it is necessary to understand some of the 

regulations which govern the transportat ion and disposal of low 

level waste. These regulations are determined by the various 

organizations including The Department of Transportat ion, The 

Nuclear Regulatory Commission, the particular states in which 

transportat ion routes occur, The Department of Energy, and the 

particular disposal site operators. For example, the main 

regulations concerning the conditioning of waste which relate tct 

zeolites include that liquids must either be solidified or 

packaged with materials capable of absorbing twice the liquid 

volume, and that wastes must cctntain less than one percent of the 

vctlcirne as free liquid. The next sections will discuss the major 

sources which produce such waste, namely inst itut ional, 

industrial, commercial (nuclear), and governmental sources. 

56 
4.2.2 Use of Zeolites in Nuclear Waste Treatment 

It is nc~w necessary to describe the way in which these large 

zeolites would be used. First, the zeolitic material would cost 

approximately 9;4600 per kilogram. This cost would cover both 

space-shot and processing costs. These products would follow a 

filtration/ion-exchange method of operation similar to the ionexchange process now used (see Figure 4.3). The "channels" of 

the zeolite crystals would be highly selective and able to be 

controlled in order to remove the radioactive atoms existent in 

the contaminated solution. These crystal beds would most likely 

be highly efficient, due to the lack of binding material existent 

in the present pelletized zeolitic material. The resulting 

crystals would be processed by either some type of small scale 

solidification or absorption, or- if the crystals were extremely 

dry as somewhat suspected, they could be directly packed for 

burial. This small quantity of zeolitic material would contain a 

great concentration of radioactivity and would thus have to be 

disposed of accordingly. 

57 
FlllRATlON AN0 ION EXCHANGE 

Wastewater . 

Reqenerition 

Pump 

. . Flow chart of wastewater treatment process using 

clinop tiloli te io n-ex change processes. 

-. 

Figure 4.2 

.. +.'.., . .. 

...... .:-.. .... . .-. .... .--. .. .. . .- - _. -. 

....... - .... 
4.2.3 Institutional 

Hospitals, universities, and research centers are three major 

contributers to institutional waste. This waste is produced 

through such sources as nuclear medicine, bioresearch, and other 

research in physics, inorganic chemistry, materials analysis, and 

geology. The liquid waste pbduced from such activity ccmmonly 

occur in the forms of liquid-scintillation waste - organic 

fluids, usually toluene, contained in a plastic of glass vial; 

organic liquids - organic laboratory solvents including alcohols, 

aldehydes, and or-ganic acids; aqueous liquids - radionuclides 

suspended in a water solution; and biological wastes. Hardly any 

wet solids are produced C223. 

Most institutional facilities handle the problems of 

radioactive waste in two ways. First, many of the smaller. 

research facilities produce wastes with radionuclides that have 

relatively small half-lives. For these institutions the process 

of holding fur decay is prevalent. This process involves 

storage of the particular waste in drums for a period of time 

equal to ten half-lives of the material. Fur example, 

Technetium-9% which has a half-life of 6.05 hours, can be held 

far 60.5 hours and then considered to be legally ncmradioact ive 

for disposal purposes. Other such radionuclides include Iodine- 

-125, Iodine-123, Gallium-67, as well as many others (see Table 

4.4). 

The second method for the processing of liquid waste 

for long half-life or for facilities without the room or ability 

for decay is through the use of commercial waste-handling firms 
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(brokers). Waste brokers collect the waste from variuiis 

institutions, store it for a period of time, and then make bulk 

shipments to disposal facilities. These brokers may either pick. 

up the bulk waste and use their own equipment to process the 

waste at their facility, or provide the institutions with the 

necessary material to process the waste themselves, and then pick 

up the resulting compound. Table 4.J displays some of the major 

brokers along with their processing methods and handling char-yes. 

The processing of the various waste is different depending 

on its particular type. For scint i 1 lat ion and certain other 

organic liquids, incineration is the primary method of treatrtierrt. 

Of the remaining liquid wastes which are handled, of which 

Tritium (Hydrogen-31, Carbon-14, Phosphorus-32, and Iodine-125 

are the principal radionuclides present, absorption or 

solidification are used. The differences in prices and procedure 

of the particular brokers interviewed, can be explained scmewhat 

by location of particular organization, including particular 

state and distance to burial site, and personal preference of the 

brokers choice of material and processing technique. Table 4.6 

gives a list fo cost variables associated with a typical 

industry. Components FI-R sunimerise basic operat ions. Scme 

typical costs for materials are listed as well as some additional 

cost considerat ions. 

In the processing of the liquid waste , only about ten to 

fifteen gallons of radioactive liquid exists in the 55 gallon 

drum, due to the regulations regarding the liquid waste. This is 

in comparison to the amount of absorption or solidification 

62 
material in the 55 gallon drum which usually ranges in the amount 

of three or four to one with respect to conditioning material tu 

liquid waste. Thus the prices in Table 4.5 increase 

dramatically when the criterion of money tu actual radioactive 

mat er i a 1 i s cons i dered. 

63 
Table 4.5 

Processing brokers and their prices 

QDCO.. . ... ..Chicago * scint i 1 lat ion (organic) - incinerated * use of both absorbent and solidification 

mater i a1 amount needed 2: 1 requirement 

speedy dry (clay) 100 lb. 150 lb. water- / 

200 lb. material 

diatomaceous earth 80 lb. in bet ween 

perlite 40 lb. 150 lb. water / 

* 15 gallons of radioactive liquid per 55 gallon druni 

u approx. cost $25-26 per gallon of waste 

100 lb. material 

NDL Organization.... .... New York * use absorbent (speedy dry) * process 

(1) 10 gallon liquid in 30 gallon drum (4 cu.ft.1 

(2) Insert (1) into 55 gallon drum (7.5 ci~ft.) and 

and rest absorbent 

fill void with absorbent 

u total amount of absorbent approx. 6-7 cubic feet * use 1.5-2 4cu. ft. bags approx. $9.64 each 

Teladine Isotopes........New Jersey * use of stabilization media and absorption (pearlite) * approx. cost - $500 per 55 gallon drum * price dependent on content and mass quantity 

Radiation Service Organization (RSO) . . . . . . . . Marylarad * use of *portland cement 

u costs - $522 for 55 gallon drum 

$400 for 30 gallon drum 

Examples of in-house using 

Harvard University * use of speedy dry as absorbent and then shipped out 

Y absorbent to liquid approx. 3 or 4 : 1 

* radionuclides- 1-125 

commercially 

P-32 

Cromi um-5 1 

Su 1 f er-35 

u cost approx. $350 per 30 gallon barrel (cost covers speedy 

dry, transportat ion, and disposal) 

64 
Table 4.5 cont. 

MIT * solidify by concrete and plaster of *paris * material cost approx. $5.00 per 5 gallon dr-uni * radionuel ides- Carbon-14 

Su 1 f er-35 

Hydrogen-3 * processing3 or 4 5 gallon pails in a 55 gallon drum 

15-20 1 gallon jugs in 55 gallon drum 

or 

* liquid to conditioning material in druni is 1:E: * cost- 6400-450 per 55 gallon drum (price includes total 

processing) 

65 
Table 4.6 

Components of cost 

Col lect ion at lab 

R. Plastic container 

B. 55 gallon bag 

C. Computer card 

D. Rrray sample 

E. 7 liters of absorbent/ 3 liters waste 

F. Plastic bag drum liner 

G. 30 gallon drum 

H. More absorbent to fill SO/ 50 void 

I. Plastic bag for 55 gallon drum 

J. 55 gallon drum 

K. Nut- bolt- wire 

L. Man power * load * array * supply area 

Y data * identification of drum * wipe test survey * transport out * total time 

M. Load on truck 

N. Prepare truck papers 

13. Survey truck 

P. Transport cost 

a. Burial cost 

R. Surcharge 

Record i nt o inventory for f ut ure 

Basic Costs 

Transportat ion varies/ area 

Drums approx. $60-80 total (includes bags, bolts, paint etc.) 

Fi 1 ler approx. B2-4.50/ bag 

Manpower- 1 man 2OK/yr. 

Rdditional Considerations 

Surcharges on burial: $10 per cubic foot till 1/88 than more 

Rre there burial charges for Isotope quantity? $/ci. 

66 
Fls mentioned previously, liquid waste contains less than one 

percent dissolved particles in the solution. However, it appears 

that not all this material is radioactive. Since the actual 

volume concentration of the radionuclides in the liquid are not 

specified by law, this figure is virtually unknown or cared 

about. This concentration is instead measured in curies which is 

a measure of radioactivity. Yet, it is this volume or mass 

concentration of the radioactive atoms which is needed in order 

tcl calculate the feasibility of implementing a zeolitic process 

in order to handle the waste problem. It would indicate that if 

the radionuclide concentrations existed near one percent, no type 

of ion-exchange process would be economically feasible due tct 

operat ion cctsts, labor costs, and material costs. However, if 

this figure was condiderably less, as suggested by the nuclear 

power liquid waste, any type of ion-exchange process cctuld be 

feasible, with zeolites as a possible prime candidate (see Figure 

4.3). 

The handling of institutional liquid waste as it is done 

today is geared on the process of conditioning technology. 

Evaporation, ion-exchange, and f i ltrat ion processes are general ly 

not used due to reasons such as lack of room, increased initial 

cclsts, inability to procure a license, and inability to provide 

proper ventilation. The zeolite based process would have to be 

able to meet the capabilities of these technologies, while not 

requiring special regulations and operating conditions which 

could hinder its use. However, as previously indicated, zeolites 

would be used as an ion-exchange medium, and thus it most 

67 
. a L 
probably would not find its use in such a situation without the 

means of effective technology, and change in certain regulations. 

Thus, the theory that for radioactive liquid the technology that 

yields the highest packaging efficiency is usually the most cc& 

effective and therefore employed, would nut truly apply to 

inst it ut i anal wastes. 

69 
4.2.4 Industry 

The chief contributers of low level waste from the 

industrial sector are manufactures of radiopharmaceut icals for 

hospitals and universities, as we1 1 as manufactures of consumer 

products, gauges, or other special instruments that use 

radioactive materials. "The industry of radiopharmaceut icals 

includes companies that produce nuclides as raw materials For 

other pharmaceutical companies, as we1 1 as secondary companies 

that produce radiopharmaceuticals through radioactive tagging and 

labeling processes. 'I C223 

The waste produced in the industrial field is similar to 

that in the institutional phase in that it is comprised mostly of 

liquid and dry solid components, with H-3 and C-14 the chief 

components in the radioactive liquid. Both components are termed 

"soft energies", with the tritium resulting mainly from the 

purification of exhaust air. The waste processing methods are 

also very similar to institutional methods with most organic 

wastes incinerated, wastes with short half-lives allowed to 

decay, and the remaining liquid usually absorbed or solidified 

and packaged for transportation and disposal. For example, one 

such major industry used a cat litter material for absorption and 

concrete for sol idif icat ion. 

Fls far as available prices for processing, this information 

was not procured due to the competitive nature of the business. 

However, by consulting marketing personnel at WPI, it was 

estimated to expect a 100 percent overhead fee applied ta the 

prices which were available through the institutional handling. 

70 
In this way one can expect the price of handling tu decrease by 

half, still rendering a chance for zeolites to drastically cut 

the existing cclsts. Here again, however, lies the problems of 

undocumented concentrations of radionuclides and existing regulations 

regarding the use of ion-exchange processes. It would be 

possible to assume that industry would be capable of handling the 

need for the requirements of space, proper ventilating 

conditions, and costs. For these reasons, the future of large 

zeolites is unpredictable in industry. 

71 
4.2.5 Commercial Nuclear Power Plants 

Most low level waste from fuel-fabrication plants is trash 

material, including clothing, filters, wastepaper, and discarded 

equipment. The radioactive liquid produced is either the direct 

result of fabrication or from use as a cleaner. It is usually 

processed by a combination of filters and ion-exchange methods. 

The wet solids produced are either direct results of the fuel 

fabricat ion or secondary products produced by the treatments of 

the liquid waste and appearing in the form of ion-exchange resins 

and filter sludges (see Tables 4.7 and 4.8). 

The liquids produced are generally treated by filter, ionexchange processes as discussed above and in the beginning pages 

of the section. Typical filters used are cartridge filters, edge 

filters, and precoat filters. Cartridge and edge filters are 

similar in construction with the cartridge filters being 

disposable, while the edge filters being reusable. The precoat 

filters consist of porous vertical tubes called septa on which 

filter medium is deposited. Flfter the filter is used, it is 

cleaned and then precoated again. Most treatment techniques 

previously discussed for liquids are applicable for wet solids. 

Generally, when high water content exists, physicall mechanical 

concentrat ion techniques are used, whereas when free-water 

content is low, conditioning is frequently more cost effective 

c203. 

Nuclear power plants porovide perhaps the largest area for 

the growth of large zeolite crystals. Fls previously mentioned, 

zeolites have already 
Low Level Waste From a Power Reactor 

Type Vu1 ume Radioactivity Treatmem 

{Cubic Ft) (Curi es3 

................................................................. 

SDent Res i rts 11,000 1,900 Dewatered by 

Concentrated Liquid5 2,000 1 Solidified irr 

cent r i f uge 

cant ai ner 

Filter Sludge 0 0 - 

Cartridge Filters 0 0 

Nom-Fuel Core Camp. 0 0 

Tot a 1 3’3,000 1,911 

- 

Trash 26,000 10 Cornoacted by 

hydraulic Dress 

- 

................................................................. 

Cant ai ners Number Descr i pt i on 

St rorq, Ti ght 3 

Packages 240 1OO-ft metal boxes 

55 Gallan Drums 275 Specially made steei barrels 

Liners 0 

High Integrity Containers 1500 55 gallon high impact glactic 

- 

cant ai ners 

Total 2015 

Sh i prnent 5 Number Descri pt i on 

Flat bed Truck 

Type F) Package 

Type E Package 

Total 

20 Exclusive cargo of strong. tit$= 

pac ka ges 

traffic conditions 

acci dertt s 

100 Protect i on aga i nst normal 

5 Safegaurds against severe 

125 

Classificatiort Per Cent Descri pt i OIJ 

90 Processed to essentially dry 

10 Stabilized to retain size ar?d 

solid 

shape 

0 - 

Table 4.7 
TULE 4-8 TYPICAL L'rlR WET SOLID WASTES AND CHMACTE2ISTICS 

Annual 

Volume 

Reactor 

BWK Ad ..Dewatered powdered resin and .- 255 

Type Waste Description (m3) 

ion-exchange resin 

bWK Bb .Spent resins, concentrates 2 69 

- and filter sluages 

6WR CC I Spent resins and concentrates 368 

PWR Od Resins', sludges, ana 65 

evaporator bottoms 

?%H €e Sol iaified concentrates 2 83 

Dewatered resins 142 

Solidified resins 340 

.. Filter cartridges _- 17 

DbiR Ff Spent resins 9 

Sol i di f ied concentrates 283 

Filter cartridges 71 

Gross 

Speci fi c 

Act i v i t y 

j~i/a3) 

7.1 

7.1 

2.5 

2.1 

3.5 

0- 

0- 

0- 

0.10 

0.18 

1.06 

Major lvucl ide 

Cr-51, CO-60, 

and Zn-65 

co-60 and 

CS-137 

Mn-54 and 

CO - 60 

Co-57 and 

CO-60 

CO-58, CO-60 

End Cs-134 

CS-137 

Mn-54, Co-58, 

Co-60 and 

CS-137 

CS-137, CS-134 

CO-60 

Co-58 and 

4. Typical 1000-MWe unit (6 years ola) 

0. Typical 800-MWe unit (10 years old) 

to Typical 800-MWe unit (5 years old) 

Q. Westinghouse 800-MWe unit (2 years old) 

J. trabcock 8, Wilcox 800-MWe unit (6 years Old) 

f* dabcock & Wiicox 900-fiiWe unit (6 years old) 
been used in the cleanup of radioactive liquid. It is estimated 

that the larger crystals would not create intercrystal diffusion 

limitations due to the lack of pelletizers. This poses the 

possibility of cleaving semi-permeable membranes which would be 

highly selective. The large zeolites would possess the 

capability of greater absorption due to the lack of binding 

material, as well as the possibility of establishing a large 

scale ion-bed process. 

Zeolites would be in direct competition with the exchange 

resins used today. These resins range in price from about $100 

per cu.ft. for average resins to greater than $200 per cu.ft. for 

very good resins. These resins are carefully monitored. One 

such method for monitoring includes recording conductivity before 

and after processing. When a resin bed reaches a certain level 

on the measuring device, it is either packed with absorbents a5 

with cheaper resins, or cleaned and/or regenerated for further 

use. Methods for this required measurement include recording 

conductivity before and after processing. One popular method for8 

washing the resins involves ultrasonic cleaners, in which an 

ultrasonic field is created, which separates the waste and resin 

beads due to differences in densities. These beds may be cleaned 

once per week on the average. Regeneration involves a chemical 

process which returns the capacity of the beads. For example, 

after washing resins which have been depleted to 50 percent of 

their original capacity, they return to use with the same 50 

percent capacity, whereas regenerat ion could increase the 

capacity to possibly 80 percent. Thus the resins would lose 20 

75 
percent capacity after each regenerat ion from its original state. 

FIn example of regeneration frequency could be about every five ta 

six months. 

Zeolites offer many benefits when compared to resins. Since 

they can be as much as 50 percent hollow, zeolites can hold much 

more waste per volume of exchange bed material than resins. This 

is also enhanced by the fact that zeolites are more selective 

than resins. Thus in processing a waste stream which cclntains 

radionuclides with typical concentrations in the parts per 

billion range, and various added chemicals which comprise most of 

the volume in a bed, zeolites would be more efficient at 

separating the various materials and holding them. 

FI second benefit of zeolites is that resins degenerate under 

the presence of radioactivity. Thus their efficiency decreases 

with time as well a5 only being able to regenerate them to a 

percentage of their original capacity. However, zeolites are not 

effected by the radioactivity, and will thus keep their high 

efficiency even under high radioactive concentrations and long 

periods of exposure. Because of this property, they are 100 

percent regenerative. There are st ill other examples of zecllit ic 

benefits such as being able to run at higher temperatures as 

ccmpared to resins, thus allowing for higher processing rates 

(see Table 4.9). 

FIs mentioned in the other sections there is a need for the 

concentrations of the nuclei present in the waste, such as Sr-90, 

Cs-137, Co-60, Mn-54, (see Table 4.101, as well as the 

concentrations present in the various added chemicals. FI typical 

76 
TFlBLE 4.9 

Comparison of resins and zeolites 

Chemical nature 

Structure 

Poros i t y 

Particle size 

Ion sitings 

Thermal stabi 1 i ty 

Solution stabi 1 ity 

Radiation stability 

Mechanical st rengt h 

Flttrition resistance 

Cost 

Organic co-polymer 

Flmorphous 

Disperse, about 

1 Onm 

Va-riable, up to 

several mm 

Non-specific 

Low 

High 

Usually low 

Variable 

High 

High 

Flluminosilicate 

cryst a1 s 

Crystalline 

Specific, less 

than lnm 

0. 1-5C)um* 

Clearly defined 

sets of sites 

Usually high 

Usually low 

High 

Usually high 

Var i ab1 e 

Usually low 

77 

I 
TABLE4.10 PRINCIPAL RADIONUCLIDES FOUND IN REACTOR LOW-LEVEL WASTES 

Radionuclide 

Barium-1 40 

Ceri um-1 41 

Cesium-134 

Cesi um-1 37 

Cesium-1 36 

Chromi um-51 

Cobalt-58 *- 

Cobalt -60 

Iron-59 

Manganese -54 

Zinc-65 

Zi rconi um-95 

Half -Life 

12.8 days 

32.5 days 

2.05 years 

30.0 years 

13.7 days 

27.8 days 

71.3 days 

5.26 years 

45.6 days 

303.0 days 

245.0 days 

65.5 days 

Type of Radiation 

Emitted 

Beta, gamma 

Beta, gamma 

Beta, gamma 

Beta, gamma 

Beta, gamma 

Gamma 

Beta, gamma 

Beta, gamma 

Beta, gama 

Gamma 

Beta, gamma 

Beta, gamma 

-- 

Source: 

Radioactive Wastes Shipped to Commercial Burial Grounas, NUS-3440, 

Revision 1, November 1980. 

Taken from The 1979 State-by-State Assessment of Low-Level 
cost for processing and burial of reactor waste would be about 

$30,000 based on the use of a 6 ft. high by 6 ft. diameter 

fiberglass high integrity container (160 cu. ft.) with a 200 

cubic foot outside liner (cost based on liner’s dimensions). 

However this cost does not convey the information needed to 

compare the efficiencies of the two systems. FI typical 

filter/ion-exchange process may involve efficiencies of 80-70 

percent for the filter and about 90-95 percent for ion-exchange. 

Zeolite processes are expected to at least meet, but most likely 

surpass these va 1 ues wh i 1 e possessi ng many benefit s, some of 

which discussed. Thus the zeolitic benefits would have to 

cumpensate for the higher cost for materials and further research 

would have to go into creating an effective zeolitic process. 

79 
4.2.6 Government Faci 1 it ies 

Low level waste is generated through government research and 

defense programs. The Department of Energy, which conducts 

research in nuclear energy, reactor safety, and waste treatment 

techniques, produces vast types of low level waste. Waste is 

also produced through the fabrication of nuclear weapons and fuel 

for nuclear ships and'submarines C223. 

The methods far processing this waste consists of virtually 

all of the methods described in the first section along with 

others not listed. Fl11 government waste is buried at government 

waste sites and handled by government facilities. In this way a 

true cost of procedure can never be attained due to the 

noncompet it i ve nat ure of the system. 

Fls in the reactor waste, the future use of large zeolites is 

highly possible. This is due to the many similarities existing 

between the reactor and governmental waste. It therefore can be 

assumed that if large zeolites tend to be effective in 

either government or reactor technology, it will also be 

effective in the other. 

80 
4.2.7 Low level Waste-Conclusion 

Fls seen in each of the previous subsections, the question of 

possible use of large space grown zeolites in the various areas 

of radioactive waste is not a clear answer. More information is 

required before these decisions can be made. For example, as 

stated, the volume or mass concentrations of the nuclides and 

chemicals are neededin each case. It seems that in order to find 

this information, independent tests will have to be run since the 

information is not required by law and therefore not readily 

available. also, the effectiveness of the large zeolites will 

have to be proven, as well as research provided for the 

production of such processes. Large zeolites offer the 

possibility of volume reduction through a highly selective, mare? 

packing efficient material. However, this information will never 

be known until an actual large crystal is tested. 

Rnother problem to consider is that of volume. While such 

places as industry may produce enough waste as a whole to favorthe use of zeolites, when this volume is broken down by the 

number of industries actually contributing to this amount, the 

same opinions may or may not hold true. 

a final piece of information which should be considered, is 

that due to new regulations, each state is now required to bury 

its own nuclear waste, or set up a regional pact with a few of 

its surrounding states to designate a burial site. Violations to 

this law induces surcharges placed on waste still shipped to out 

of state grounds. Far example, in January 1987 the surcharge 

placed on the burial of the waste was $10 per cubic foot. This 

01 
number is designated to rise in the following years and reach 640 

per cubic foot by the year 1’390 C231. These charges will not be 

directly paid by the states rather they will be passed on to the 

research facilities which produce these wastes. Thus as a recent 

comment by an official from NELRRD ( a consortium of New England 

low level waste producers) suggests, facilities will now have to 

set aside enough extra money to cover these costs, thereby 

hurting such inst itut ions as medical and industrial. 

The estimated cost of setting up a waste site was twenty 

million dollars in 1985 C231. Since more of these sites will nuw 

be demanded by regulations, it will also be possible for the 

states to provide efficient means for waste processing. In this 

way, zeolites and its associated processes would be in direct 

competition with resins and their associated processes. Thus 

zeolites would not have to compete a5 a new process which has to 

be far superior and cost efficient to replace an already existent 

process, yet as a new process which would be in direct 

competition with other processing for the ability to be employed. 

82 
4.2.8 High Level Waste 

There is an ongoing effort to select a suitable treatment 

for the high level waste produced in the United States and most 

other countries which have nuclear power capability. The most 

promising option is that of solidification of the liquid, package 

into carbon or stainless steel containers, and then burial in 

deep, stable ecological strata, on land or under the deep ocean. 

The major consideration is that the wastes should be prevented 

from returning to man's environment at least until their activity 

has decayed to safe levels C243. In rno'rt countries, including 

the United States, these wastes are being stored in containers 

until these decisions are made. However, in France, processes 

involving solidification of the wastes in glass form and burial 

have been implemented. 

The proposed use of glass for solidification tends to be the 

mo5t accepted option. Solidification immobilizes nuclear waste 

by embedding nearly all by-products into a single, inert form. 

There exists a few processes by which glass conversion is used. 

They can be broken up into broad groups depending on the number 

of stages in the cycle. One group exists of one-stage processes 

in which the liquid waste together with glass forming materials 

are continuously fed into a heated stainless steel vessel in 

which the mixture fuses to a homogeneous glass. Rnother group 

consists of two stage processes, in which the liquid is first 

dried and then mixed with glass powder into a glass-making 

furnace C251. 

Glass has been chosen due to the ability of the high level 

a3 
nuclear wastes to combine well with the standard ingredients used 

in glass making. Vitrified waste glasses, such as Pyrex, are 

very stable and have good resistance to heat, chemical action, 

radiation, and mechanical stress 1261. These glasses have been 

shown tu be highly resistant to leaching of their radioactive 

content by ground-water. However, there has been a considerable 

amount of work done on the development of other solids, such as 

artificial rocks, in which to incorporate the high level waste. 

These products have also been shown to possess high leaching 

resistance. 

Zeolites exist as one of the possible choices fcw material 

in disposal of high level waste. It has already been used today 

to help store high level waste due to its ability to hold its 

reactants for long periods of time C63. Zeolites, could be used 

in two distinct ways. The first could be the direct conversion 

of liquid to solid waste through the use of the crystals, and 

then encapsulated in tanks for disposal. The second is as a 

pretreatment to the glass process. Since zeolites possess the 

ability to mix well with glass, they could be used to convert the 

liquid waste to solid zeolitic form, and then processed into 

glass. However, due to the depth of research needed, the future 

of large zeolites in disposal of high level waste is uncertain. 

84 
4.3.1 Leather Tanning Industries 

In the leather tanning industry, filtration and separation 

processes are required to clean up waste waters produced. We 

contacted several leather tanneries in New England tu determine 

the current costs and procedures involved with current waste 

water treatment procedures. Fls we expected, several tanneries 

refused to discuss this information. Fl few, however, did supply 

us with helpful information. 

The cost of waste water treatment depends on many variables 

including plant size and geographic locat ion, but an average 

estimate on the day to day operation seems tu be about $40 far a 

plant with a daily output of 14,000 square feet of leather. This 

indicates that the primary costs of the water treatment is not in 

operations, but rather in the initial plant setup. To setup a 

typical waste water treatment plant today costs in the area of 

$750,000. Therefore, in order for a large zeolite process to be 

cost effective, it would have to significantly reduce the cost of 

a processing plant. While this might be possible, it would 

require an in depth study of the clean up processes and current 

plant setups to determine this for sure. We suspect, however-, 

that given the low costs of current daily operation, as well as 

the relatively low cost of plant setup, a large zeolite setup 

would probably not be cost effective. 

, 

85 
4.3.2 Battery Manuf act ur-ers 

as with leather tanneries, battery manufacturers must also 

clean up waste waters. Duracell supplied us with some very 

helpful information. Plant size, what kinds of batteries are 

made, and the changing EPR requirements are only a few of the 

variables which would determine the cost of waste water clean-up. 

an average battery plant might produce 10 to 20,000 gallons of 

waste water per day, and it typically costs around $100,000 per 

year to operate the plant. Fs wide variety of chemicals must be 

removed from the water including zinc, mercury, manganese and 

lubricants. Current processes for water purification include 

fairly simple and inexpensive ones such as gravity separation, 

but as the EPQ standards become more rigid, Duracell will need to 

look into more complicated and expensive procedures, such as 

ul traf i 1 trat ion. Current ly, an ul traf i ltrat ion set up costs in 

the neighborhood of $200,000. Here a zeolite process might be 

introduced in an attempt to achieve a high order of filtration at 

a lower cost. However, Duracell did mention that a fairly large 

portion of clean up costs were devoted to sludge removal and 

disposal, which would also be required in a zeolite process. 
4.4 Medical/Pharmaceutical Uses of Zeolites 

Zeolites could prove useful in the medical field in both 

separation and catalysis processes. For separation, major 

considerations are the size of the particles (molecules) in 

question and any specific constraints (such as a high pH 

environment) of the process incorporat ing the zeolites. 

Most of the general separations in gas and fluid preparation 

involve comparat ively large sized particles. Particulate matter 

is often present in industrial grade chemicals purchased by 

medical centers. In addition, particles may be incidentally 

introduced into a preparation (such as bits of rubber from a 

stopper) . In preparation of an intravenous nutrition solution, 

consisting of amino acid, dextrous, fat emulsion, electrolytes 

and additives, particulate matter is easily removed by a 0.5 

micron filter (about J to 1,000 times too big for zeolites 1. 

Sterility is ensured by a second filtering with a 0.2 micron 

filter. Sterilization is also performed with infrared, 

ultraviolet, or gamma ray radiation, and autoclaving. Filtration 

is the preferred method when there is question of destroying or 

deactivating medicines such as antibiotics and biological 

solutions. Bacteria and mycoplasmas are typically 1 to 5 microns 

in size while rickettsias vary from 0.3 to 0.5 microns in size. 

Viruses, the smallest agents of infestation, are from 0.02 to 0.4- 

microns. Since zeolites average pore size ranges from 2 to 10 

angstroms (0.002 to 0.01 microns), they cannot be used to 

efficiently separate these microbes. Clearly, other methids 

would do as well as zeolites and likely at lower cost. Rlthough 

87 
the microbes cannot be trapped by the zeolites, a zeolite 

membrane could be used separate and purify a fluid (blood, for 

example). Unfortunately, many of the components of the fluid 

itself may also be excluded by the membrane. 

Dialysis is a process where purification of a blood is done 

by a simple filter when kidney function is impared. Blood is 

taken from the patient and passed through a filter (the 

dialyzer), then returned to the patient. The filter consists of a 

coil of fibers (typically made of cupra-ammonium) inside a 

container. Blood is passed under pressure through one side of 

the dialyzer and an equalizing fluid (the dialysate) is passed 

through the other. Fls the blood passes through the dialyzer, 

impurities are adsorbed by the fibers. Unfortunately, many of 

the necessary blood chemicals are also filtered. These blood 

chemicals are maintained at correct levels by the dialysate. 

Large zeolite membranes may offer a simplification of this 

process. The zeolite membranes could be engineered to filter 

blood impurities with significantly less loss of necessary blood 

chemicals. Currently, large volumes of blood are removed from 

the patient and sent through the dialyzer under high pressure. 

This allows for faster purification (four to eight hours at a 

time, rather than continuous dialysis). The greater pressure 

across the fibers increases the rate of adsorption. The greater 

efficiency of zeolite membranes would allow filtration with 

significantly less pressure. This would reduce the volume of 

blood necessary to remove from the patient per period of time, 

and corrections of chemical blood levels could be done on a much 

88 
smaller scale. In addition, the patient’s own cardiovascular 

system would supply sufficient pressure to run the process. With 

the use of large zeolite membranes, significant reductions in 

size and cost of dialysis equipment could be realized. 

Zeolites have already proved effective in separating blood 

impurities. Zeolites also offer the considerable advantage of 

constant regenerabil ity compared with current dialyzers (a 

dialyzer is typically used 6 to 7 times and then discarded). The 

possibility of a portable, zeolite-based, dialysis machine 

exists. However, there remains the question of the precise 

monitoring of the blood (monitoring the air in the blood ancl 

electrolyte levels). These monitoring devices represent an 

appreciable portion of the cost and size of the present dialysis 

machinery. Overall, large zeolites represent an excellent 

commercial option in the area of dialysis and filtraticln C27,281. 
4.5 The Space Program and Zeolites 

Students and faculty at WPI have already developed an 

experimental zeolite growth chamber to fly on the Space Shuttle 

flight planned for February 1’388. The chamber consists of an 

insulated, closed container of water with reactive chemicals in 

it, which is heated by battery supplied power. 

The simplicity of growing zeolite crystals have made them a 

.perfect candidate for space based manufacturing. The plans for a 

permanent space station will provide facilities where long term 

microgravity research and large scale manufacturing of large 

zeolite crystals can be conducted. To mass produce large 

zeol ites, however, a much larger scale process would be required. 

Before such a process can be implemented, Flrnerica’s space 

program wi 11 have to mature further. 

Flt the very least, a permanent space station would have to 

house the reaction vessels, so they would not have tu be 

repeatedly flown into and out of orbit. Fllso, it isn’t certain 

that costly shuttle flights could continue without a space 

station in orbit. So, if the US Space Program is to continue, a 

space station must be in its near future. 

It has been suggested that all the raw materials needed to 

manufacture the large zeolites could be mined from the Mcan C2’33. 

These materials could then be used to manufacture zeolites on the 

Moon or transported to’an orbiting or stationary materials 

processing station. This would greatly reduce the cost of 

transporting the materials to the reactor. Since the surface 

gravity of the Moon is approximately 1/6 that of the Earth, much 

90 
less energy would be needed to lift materials from the surface. 

It is also a good question whether large zeolite crystals can be 

produced on the lunar surface; a combination of lower gravity and . 

increased viscosity of the reactant mixture may be sufficient tu 

allow larger crystal growth. 

Transportation of materials to and from space represents the 

greatest percentage cost of producing zeolites in space. Materials 

sent from the Mclon would not require cargo hauling space crafts. 

Prepared packages of materials could be launched from the lunar 

surface off magnetic rails and ‘caught’ in space by large conical 

Kevlar bags C303. 

Under mild hydrothermal conditions, zecllites can be easily 

synthesized from a variety of starting materials, especially 

volcanic glass. Glass is a major constituent of the lunar 

surface, and is similar in chemical composition to the volcanic 

glasses found on Earth. Since true lunar sail samples are 

limited in quantity and availability, ‘analog’ lunar glasses have 

been used to test this possibility on Earth. Hydrothermal 

alterat ion of these glasses has successfully produced a number of 

zeolites. Few problems are anticipated in developing procedures 

to produce and engineer any of the major zeolite types. Several 

zeolite types have been made on Earth by using similar glasses to 

those found on the Moon’s surface, including clinoptilolite, 

phillipsite, and mordenite. The alteration of the glasses depends 

on: 1) temperature, 2)chemical composition and pH of the solution, 

3)chemical composition of the starting material, and 4) the 

existence of an open or closed system during the alteration 

91 
process. R variety of solutions would be used to act as solvents 

of the glass during the synthesis procedure. Flssurted carbonates 

and hydroxides (K CO , Na CO , NaOH, Ca(OH) ) would be included 

in the solutions. The majority of the additional substances are 

23 23 e 

also present in the lunar soil or will be byproducts of Mcton 

based metal product ion C293. 

There are several strong potential uses far for zeolites in 

space and on the Moon. Rny type of isolated base requires 

recycling of both air and waste. Zeolites are already used on 

Earth for large scale sewage treatment, and would prove 

especially useful in a closed environment. The ease of making, 

wide range of properties, and regenerability of zeolites makes 

them ideal for any closed environment. Zeol ites can be engineered 

to selectively filter harmful, toxic or unwanted gases from both 

sewage and air, including SO , CO , and N . Rn atmosphere 

regeneration device can be made by choosing the appropriate 

2 2 2 

combination of zeolites. Large zeolites membranes offer a higher 

efficiency of separation with less overall space being used, an 

important consideration in limited area space or lunar bases. R 

separate system could be used tca provide a different atmosphere 

mare appropriate for plant growth. Fert i 1 izers could be provided 

by released ammonium from sewage treatment. 

Rside from space uses of zeolites there remains the problem 

of returning them to Earth. Presumably this cclst would be mirtor 

compared to the cost of getting materials. The estimated cost of 

transport and processing costs is $4600 per kilogram. 

These suggestions are very long term at best. If the 
Rmerican people do not show an interest in continuing the space 

program, at least to the point of establishing a permanent space 

station, the future of any space based manufacturing ventures is 

in doubt. Internat ional cooperat ion with European nations wi 11 

reduce the United States’ economic burden of developing materials 

processing in space. The Space Shuttle would be used tu transpcwt 

the European Space Station to orbit. This will allow an earlier 

start and an incentive to process zeolites in space. 

93 
4.6 Large Zeolites as Competition for Small Zeolites 

Small zeolites are quite popular as cracking catalysts as 

well as in othe; roles. We wondered if, perhaps, large zeolites 

might be more effective in this important aspect of the chemical 

industry. 

Large zeolites would have greater selectivity due to longer 

diffusion paths and could also have increase efficiency over 

small pelletized zeolites due to the absence of binder material. 

The way small zeolites work as cracking catalysts are as 

follows. Microspheres of amorphous silica-alumina have sniall 

channels (around 10 microns) leading into them. Qlong these 

channels are zeolite crystallites with pore sizes on the order- of 

a few angstroms. Material diffuses into these channels and the 

molecules enter the zeolite cavities where a reaction takes 

place. The new material then diffuses back out. 

It appears that if the crystal size is significantly 

increased, it would take much longer for the material to diffuse 

into the center of the crystal. In fact, it is possible that the 

inside may not be used at all as reactions would occur on the 

outside surface of the crystal and activated diffusion in the 

microspheres of the zeolite would effectively prevent access tcl 

the center of the zeolite crystal. 

Q similar problem exists with adsorption - with a much 

larger zeolite, it might take a very long time for the material 

to be absorbed to diffuse into the center of the crystal. If time 

is not important, than large zeolites could be used. But if time 

is important, it might be more effective, in some cases, to use . 

94 
many small zeolites, which would have more easily accessible 

surf ace area. 

95 
V.SUMMRRY RND CONCLUSIONS 

Based on the markets we investigated, it is our conclusion 

that the areas with the greatest potential for large zeolite 

crystals is that of the nuclear and medical industries (see 

Summary Table). Nuclear waste cleanup is a problem that cannot 

be ignored. With growing pressures on states to dispose of their 

own waste, rather than ship it out, we feel that the use of lar-ge 

zeolites will be a competitive technology. Large zeolites also 

offer the medical industry several advantages, especially in the 

areas of chemical preparation and dialysis. 

Some of the other industries we examined, such as leathertanning and battery manufacturing could probably employ zeal ite 

processes, but initial indications suggest that it probably wauld 

not be cost effective. 

We do feel that the research being conducted on the present 

scale into the manufacture of large zeolites is useful. It is 

probable that in the process of attempting to develop large 

crystals in space, much will be learned about zeolites and how 

they form. This knowledge may be put to use on Earth to develop 

larger, or better zeolites without the expense of a space based 

process. Rlso, it is possible that, upon attempting to grow 

zeolites in space, other unforeseen properties of space grown 

zeolites may become apparent, as well as new stuctures and 

chemical compositions. These findings may lead to new 

applications for space grown zeolites. 

Large zeolite crystals are not being developed in response to 
a customer initiated request or idea. Large zeolites are being 

developed along the line of reasoning that "there must be some 

problem this product will solve," rather than "there must be 50me 

product which will solve this problem." This does nclt mean that 

it will not be successful, but it does mean that extensive market 

studies and projections must be done on an ongoing basis to 

ensure success, because it is well known that having a goad, 

innovative product does not guarantee having a successful one. 

97 
------ Summary Table of 

-------- Passible qpplicationg 

RPPLICRTIONS f RDVRNTRGES I DISRDVRNTRGES I RECOMMENDRTRTIONS 

Low Level Volume Reduction Cost and Deserves lcloking 

Nuclear Waste Increased Eff ic. Operating into, especial. ly 

Cleanup Regenerab i 1 i ty Limit at ions in light of new 

leg is1 at ion. 

Battery/ Better Filter Cost of New Cost overrides 

Leather Tanning Resolution Plant/Process advantages at 

Water Cleanup this time. 

98 
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C11 R.M. Barrer, "Porous Crystals: R Perspective, 'I New 

Dsveloeaents in, Zeo_lit,e_ sc_ieylce_ a_yld_ Iechselss~, 

C2l G.T. Kerr, "Zeolites: Solid service from Hollow Crystals," 

---- 1987 -------- Yearbook gf Science 2~d th_e Futurg, Encyclopaedia Britannica 

Inc., Chicago, 1986. 

C31 Rrlon., "How Zeolites are Zeroing in on New Markets," 

Business Week, December 14, 1981. 

C41 Encyclopedia Britannica, Encyclopaedia Britannica Inc., 

Chicago, 1974. Volume 19, pages 1139-43 and Volume X, page 874-5. 

C51 J. Dwyer and R. Dyer, "Zeolites - an Introduction," 

Chemistry a_n,d_ Industry, Rpril 2, 1984. 

C61 R. Dyer, "Uses of Natural Zeolites, 'I Chemistry _and Irrdust_ry,. 

Rpril 2, 1984. 

C71 E. M. Flanigen, H. Khatami, H. R. Snymanski, "Infrared 

Structural Studies of Zeolite Frameworks, I' gn,d_ Internat iorral, 

Conference pn_ Molecular Sieve Zeolites, Worceste_r_ hlytechnic 

Institute, 1970. Rmerican Chemical Society, Washington, DC. , 

1970. 

C81 D.W. Breck, Zeolite Molecular Sieves, John Wiley & Sons, 

Inc., New York, 1974. 

C91 R. Sersale, "Natural Zeolites: Processing, Present and 

Possible Rpplications, 'I Zeolites. synthesis, Structure, 

Technoloqy a_& @eplication. Elsevier Science Publishing Company, 

Inc., New York, N.Y., 1985 

C101 S.L. Zhukoborsky, "Rpplication of Natural Zeolites in 

Refrigeration, 'I Zeolites, Synthesis. Structur_e_, Lgc_h_nctlcaqy 

a_r~d_ eeplication. Elsevier Science Publishing Company, Inc., New 

York, N.Y., 1985. 

Clll R. P. Townsend, "Ion Exchange in Zeolites - Basic 

Principles, 'I Chemistry a_n,d_ Industry, Rpril 2, 1984. 

C121 J. Dwyer, "Zeolite Structure, Composition and Catalysis," 

-------- Chemistry --- and ------- Industry, Rpril 2, 1984. 

E131 E. Von Hippel, "Get New Products from Customers," HarvarcJ 

Business Review, Mar/Rpr. 1982, vol 60, pp. 117-122. 

E141 E. Van Hippel, "Successful Industrial Products from Customer 

Ideas," Journal o,f Marketing, Jan. 1978, vol 42, pp. 163-174 

99 
C151 B. C. Flmes, J. D. Hlavacek, Manaoerhial Marketing fgr Indqtrial 

Firms, New York: Random House, 1984. 

C163 D. J. Schwartz, Marketinq Today; fl Basic fl~~y_oa_ct,, New York: 

Harcourt Brace Jovanovich, 1981. 

(173 G. Dieter, Ensineeyrinq Gesion, McGraw-Hill, New York, NY., 

1983. 

(183 Fltomic Energy Commission Nuclear Waste, Washington DC, July, 

1984. 

(193 L. B. Sand, F. Fl. Mumpton, Natural Zeolites: Occurrence, 

Propert ies, Use, Pergamon Press, Oxford, 1970. 

C201 Oak Ridge National Laboratory, Inteurated _Dg&g Base fgy 

Characteristics, Oak Ridge National Laboratory, Sept. 1986. 

See_n_t EMEL an_@ Radinacth~e W_a_s_t_e Ls~estnriez~ Prn~ecthnns, SK! 

C211 Oak Ridge National Laboratory, Low-Leygl Egdioact ive Waste 

PJanaqgment Handbook Series: Low-Level Radioactive W_a_s_t_e_ Lr_ea_t_m_efit_ 

Technoloqy, Oak Ridge National Laboratory, July, 1984. 

C223 EG&G Idaho, Inc., Low-Leygl Radioactive Waste ManaqemeEt 

-------- Handbook ------- Series: -- Flrl ------------ Introduct ion, Rugust, 1983. 

C233 NELRRD, 549 Fllbany Street, Boston, MB. ~ 

C243 International Fltomic Energy Flgency, Radioactive W_a_st_gsL 

September, 1983. 

C253 N. J. Keen, "The Management of Radioactive Waste from Civil 

Nuclear Power Generation." 

E61 International Rtomic Energy Fluency, Lh,e Manaqement of 

Radioactive Wastes. 

C273 Private Communications, University of Massachusetts Medical 

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C283 G. L. Bailey, Hemodialysis, eri_nciglg_s _amJ Practices, Flcadeniic 

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New York, NY. 1977. 
RPPENDIX f7 - Companies Contacted 

Mr. G. Rndrews 

Yale University 

New Haven, Conn. 

203-432-3040 

Mr. Kerri Bennett 

New England Nuclear CDuPontI 

Bi 1 lerica, Mass. 

617-667-9531 

Ms. Paula Bigwcmd 

Un i v. Mass. Med i ca 1 Center 

Worcester, Mass. 

617-856-3814 

Campella Tanning 

Brocktan, Mass. 

617-586-5662 

Ms. Kitty Dragonett 

Nuclear Reg. CrJmrnission 

Mary 1 and 

SO1 -427-4300 

Mr. B. Freshia 

Mary 1 and 

301-453-2482 

R. S. 0. 

Mr. Ed. Greenwich 

EGLG 

Idaho 

208-526-9490 

Harvard University 

Radiation Protection Office 

Cambridge, Mass. 

617-495-2060 

Mr. C. Killian 

NELRRD 

Bast on, Mass. 

617-350-9108 

Mr. J.R. Klein 

Dept. of Energy 

Oak Ridge, Tenn. 

615-574-6823 

101 
Dr. E. J. Luberuff, Ph. D. 

Editor, CHEMTECH Magazine 

Summit, NJ. 

201-277-4923 

Lawrence RC. Leather Co. 

Danvers, Mass. 

617-774-2400 

Professor Y. Ma 

Chemical Engineering Dept. 

WPI, Worcester, Mass. 

617-793-5000 

Mr. F. Massey 

MIT 

Cambridge, Mass. 

617-245-6600 

Mr. J. McCormick 

RDCO 

Chicago, Ill. 

312-429-1660 

Mr. Bob Menke 

Duracell 

Needham, Mass. 

6 17-449-76300 

Millipore Carp. 

Rshby, Mass. 

617-Z75-%!00 

Mi llstone Nuclear Power Plant 

Connect icut . 203-447-1791 

Mr. Doug Ming 

Johnson Space Center 

Rpol lo, Texas. 

713-483-0123 

North Shore University Hospital 

Great Neck, NY 

516-562-4400 

Mr. P. Pasterel 

NDL 

New Ycwk. 

914-737-7330 

1 02 
Mr. Pierce 

Sloan Kettering Inst. 

New Ysrk, NY. 

212-794-8081 

Professor R. Saccci 

Chemical Engineering Dept. 

WPI, Worcester, Mass. 

617-793-5000 

Mr. J. Smallwood 

Pilgrim Power Plant 

Plymouth, Mass. 

617-747-0912 

Mr. Stagliola 

Pilgrim Power Plant 

Plymouth, Mass. 

617-747-8108 

Dr. B. Stone 

NFlSFI Headquarters 

Washington, DC. 

202-453-1896 

St. Vincent’s Hospital 

Worcest er, Mass. 

617-798-1234 

Teledyne Isotopes 

New Jersey 

201-664-7070 

University of Massachusetts 

Medical Center 

Worcester, Mass. 

617-656-3208 

Professor FI. Weiss 

Chemical Eng i neer i ng Dept . WPI, Worcester, Mass. 

617-793-5000 

Worcester Hanneman Hospital 

Worcester, Mass. 

61 7-792-8000 

Worcester City Hospital 

Worcester, Mass. 

617-799-8227 

103 
Mr. S. Zdanuk 

Chem-Nucl ear 

220 Staneridge Drive, CR. 

803-256-4355 

104