EPA-670/2-75-043
May 1975
Environmental Protection Technology Series
                    DISPOSAL AND UTILIZATION  OF
   WASTE  KILN  DUST  FROM  CEMENT INDUSTRY
                                  National Environmental Research Center
                                    Office of Research and Development
                                   U.S. Environmental Protection Agency
                                            Cincinnati, Ohio 45268

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                                 EPA-670/2-75-043
                                 May 1975
DISPOSAL AND UTILIZATION OF WASTE KILN

       DUST FROM CEMENT INDUSTRY
                  BY

            Thomas A. Davis
             Don B. Hooks
      Southern Research Institute
      Birmingham, Alabama  35205
         Project No. R-801872
      Program Element No. 1BB036
            Project Officer

            Edmond Lomasney
  U.S. Environmental Protection Agency
               Region IV
        Atlanta, Georgia  30309
NATIONAL ENVIRONMENTAL RESEARCH CENTER
  OFFICE OF RESEARCH AND DEVELOPMENT
 U.S. ENVIRONMENTAL PROTECTION AGENCY
        CINCINNATI, OHIO  45268

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                        REVIEW NOTICE
      The National Environmental Research Center—
Cincinnati has reviewed this report and approved its
publication.  Approval does not signify that the
contents necessarily reflect the views and policies
of the U. S. Environmental Protection Agency, nor
does mention of trade names or commercial products
constitute endorsement or recommendation for use.
                         11

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                          FOREWORD
      Man and his environment must be protected from the
adverse effects of pesticides, radiation, noise and other
forms of pollution, and the unwise management of solid
waste.  Efforts to protect the environment require a
focus that recognizes the interplay between the components
of our physical environment—air, water, and land.  The
National Environmental Research Centers provide this
multidisciplinary focus through programs engaged in

            studies on the effects of environmental
            contaminants on man and the biosphere, and

            a search for ways to prevent contamination
            and to recycle valuable sources.

      The studies for this report were undertaken to
determine the nature, quantity and fate of dust collected
from the effluent gases of cement kilns, to identify and
describe potential uses for the dust, and to identify
specific areas where the Agency's participation in the
development of new technology could have maximum effect
on the cement industry's efforts to protect our Nation's
environment.
                              A. W. Breidenbach, Ph.D.
                              Director
                              National Environmental
                                Research Center, Cincinnati
                            111

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                            ABSTRACT

A survey that included 60% of the cement manufacturing plants
in the United States was made to determine the fate of dust
collected from the gases emanating from cement kilns.  Because
of high alkali content, large quantities of the dust cannot be
returned to the cement-making process.  A survey was made of the
literature in the United States and Europe pertaining to handling,
reclaiming, and utilizing the collected dust.  Abstracts of 71
references are included in the Appendix.  Acid neutralization
capacity and potash content make the dust valuable for appli-
cation to farmland, and the potential market for agricultural
use alone could consume all of the waste dust that is now being
discarded.

This report was submitted by Southern Research Institute in
fulfillment of Project No. R-801872 under the sponsorship of
the Environmental Protection Agency.
                               IV

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                         CONTENTS
                                                         Page
Abstract                                                  iv
List of Figures                                           vi
List of Tables                                           vii
Acknowledgments                                         viii
Sections
I      Conclusions                                         1
II     Recommendations                                     2
III    Introduction                                        3
IV     The Industry                                        6
V      Dust Collection                                    10
VI     Characteristics of Kiln Dust                       14
VII    The Alkali Problem                                 17
VIII   Dust Disposal                                      19
IX     Dust Reclamation                                   21
X      Dust Utilization                                   29
XI     List of Publications                               36
XII    Appendix                                           37

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                         FIGURES

No.                                                      Pages

1      Sample Form Used to Record Survey Data              5

2      System for Containment and Treatment of
       Runoff from Kiln Dust Disposal Pile                20

3      Flow Diagram Showing Steps in Electrodialytic
       Concentration of Leachate                          23

4      Diagram of Electrodialytic Concentration Stack     25

5      Fuller-Pyzel Fluidized Bed Process for Produc-
       tion of Clinker and By-Product Alkalies            27

6      Rotary Unloader for Nodulizing Waste Kiln Dust     30

7      Agricultural Lime and Limestone Usage in the
       Contiguous United States,  and Locations of
       Plants Known to be Discarding Kiln Dust            33
                             vi

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                          TABLES

No.                                                      Page

1      Plant Production Costs                              9

2      Distribution of Kiln Dust Collection Systems
       in Wet and Dry Process Cement Plants               11

3      Particle Size Analysis and Distribution of
       Alkalies in a Specimen Kiln Dust from an
       Electrostatic Precipitator                         14

4      Composition of Dried Kiln Dust                     16

5      Withdrawal of Potassium by Agricultural Crops      34
                            vii

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                         ACKNOWLEDGMENTS

The authors gratefully acknowledge the assistance of the Portland
Cement Association in our literature survey and in establishing
contact with appropriate individuals in the cement industry.  We
express appreciation to the managers of the individual plants who
generously provided data and insights concerning problems of dust
handling.  We especially appreciate the assistance of Mr. Bruce E.
Kester, Vice President, Environmental Systems, Missouri Portland
Cement Company, who contributed greatly to our understanding of
the industry and who verified the technical descriptions presented
in this report.

We acknowledge the aid of Mr. George A. Wieczorek of the Division
of Chemical Development, Tennessee Valley Authority, in providing
considerable information concerning the use of cement dust for
fertilizer, and of Dr. Robert C. Rund, Secretary of the Association
of American Plant Food Control Officers, for providing information
on specifications for fertilizer materials.

Dr. Charles E. Feazel, Senior Research Advisor, Southern Research
Institute, assisted in our literature survey by translating a
number of patents and journal articles that were available only
in German or Russian.  He also assisted in editing this report.
                               Vlll

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                           SECTION I.

                          CONCLUSIONS

The exhaust gases from portland cement kilns carry away an aver-
age of 12.2% of the kiln feed.   To reduce particulate emissions,
an average of 96% of this material is removed from the exhaust
gases by dust collectors.  Since the dust has an estimated value
of $2 per ton, it is returned to the kiln whenever possible.  Of
the 16.4 million tons of dust collected annually from cement kiln
exhausts, 11.9 million tons are returned to the cement-making
process, and 4.5 million tons are discarded.

The major factor preventing return of more dust to the kilns is
that the high concentration of alkalies in the dust would cause
the alkali content of the clinker to exceed the limit of 0.6%.
Seven plants employ a leaching process to remove the alkalies so
that the dust can be returned, but the alkalies in the leachate
pose a serious water pollution problem.  Several other techniques
for removing alkalies are described in the literature, but none
is presently used in the United States.

Most waste kiln dust is stored in open piles on the ground or in
abandoned cjuarries.  The highly alkaline runoff of rainwater from
disposal sites can cause pollution of streams or ground water
unless it is contained and treated.  The combined costs of hauling
the dust and controlling runoff appear to make dust disposal
economically and ecologically unattractive.  In most cases cement
manufacturers would give away their waste dust if someone would
take it.

The markets for agricultural lime and potash fertilizer materials
are large enough to consume all of the waste kiln dust that is
currently being discarded.  Moreover, on the basis of numerous
studies cited in this report, the chemical  composition of kiln
dust appears suitable for the dust to be applied to acidic  soils
and to soils that require additional potassium.  However, only
small amounts of the dust are being used for this purpose in the
United States.

Other uses for waste dust from cement kilns include landfill,
soil stabilization, neutralization of acidic wastes  (e_.g_. mine
drainage and pickle liquor), absorption of  S02 from stack gases,
water treatment, glass making, and production of light-weight
aggregate.

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                        SECTION  II

                    RECOMMENDATIONS

This  state-of-the-art  study was  limited  to  a  survey of  the
industry to determine  present practice of dust disposal and
utilization and a  survey of the  literature  to identify
potential  alternatives to wasting high-alkali kiln dust.
It was not within  the  scope of 'the program  to perform demon-
stration experiments or to establish the economic feasibility
of various alternatives for dust utilization.

Since agricultural uses appear to be the most promising appli-
cations of dust that cannot be returned  to  the cement-making
process, we recommend  that action be initiated with the
Association of American Plant Food Control  Officials  (AAPFCO)
to have cement dust specified as an agricultural liming mate-
rial and as a potassium fertilizer material.  The data
obtained in our survey concerning the quality and quantity
of dust available  from cement plants could  be used by the
AAPFCO to  establish specifications that  might allow the dust
to be applied to farmlands without any modifications of its
properties.  Specifications that require little or no monitor-
ing and control of the  composition of the material would
facilitate distribution and marketing of the  dust by the
cement manufacturers.   On the other hand, AAPFCO may deter-
mine that  modifications of the chemical  composition and
physical form of the dust would make it more  suitable as a
fertilizer material.   This may require a research program to
develop methods of treating the dust from various cement
plants to  meet the specifications.

The dust leaching systems presently in operation at seven
plants appear to be economically attractive;  however, sub-
stantial modifications  to the leaching process will be  re-
quired to meet water pollution control regulations.  We
recommend  that studies be undertaken to determine the
economic feasibility of recovering alkalies from the leach-
ate so that they are not discharged to the environment.  If
alkali recovery appears justified, we recommend that pilot
plant facilities be set up and operated with  an existing
leaching operation to demonstrate technical feasibility.

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                          SECTION III

                          INTRODUCTION

The manufacture of portland cement is accompanied by the genera-
tion of large quantities of dust.  Grinding and conveying raw
materials, heating them in a rotary kiln, and grinding the result-
ing clinker are all dust-producing operations, and the dust
escaping from these operations must be collected to prevent air
pollution.1  Dust collected in raw material processing operations
can be returned to the process, and dust from clinker grinding
can be sold as cement.  Since the manufacturer has economic in-
centive to collect and reuse these dusts,2 their disposal is
seldom a problem, and they will not be discussed further in this
report.

The dust generated in the rotary kiln is difficult to collect
because it is entrained in large volumes of hot exhaust gases.
Moreover, it often contains unacceptably high concentrations of
alkalies  (sodium and potassium) which make it unsuitable for re-
turn to the cement-making process.  Disposal of the dust is com-
plicated by the presence of soluble alkalies in the dust; when
these are leached out by rainwater, they can cause pollution of
surface or ground waters.  This study was undertaken to assess
the problems associated with kiln-dust disposal and to find and
evaluate possible solutions to these problems with an emphasis
on utilization of waste dust rather than development and
maintenance of expensive and wasteful disposal systems.

A successful assessment of the state of the art of collection,
disposal and utilization of waste kiln dust required a review of
pertinent technical literature.  Chemical Abstracts, the reference
files of the Portland Cement Association and a bibliography from
the Tennessee Valley Authority were used to gain initial access
to the literature.  The literature search yielded numerous refer-
ences, both foreign and domestic, which were screened for their
applicability to the purpose of the study.  Polish, Russian, and
German articles made up the bulk of the pertinent foreign liter-
ature.  Whenever the title or published abstract of an article
appeared relevant, the original article was copied and read.  In
several cases we corresponded with the author to update or
elaborate on the information published in his article or patent.
Many articles in foreign languages were translated by members
of the staff of Southern Research Institute.  Abstracts for
references cited in this report are given in the Appendix.

Concurrent with this study, we were also engaged in a survey to
obtain the background data necessary to establish the Effluent
Limitation Guidelines for the Cement Industry.  The data forms

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used to record information from phone calls and plant visits for
that study also had space for data on collection, disposal, and
utilization of kiln dust.  Later another data form shown in
Figure 1 was used for further contacts with cement manufacturers.
Date from about 60% of the active cement plants in the United
States were processed by computer to provide a basis for estimating
the amounts of kiln dust collected, discarded, and utilized by the
entire industry.

In addition to contacts with plant personnel for acquisition of
operating data, we contacted corporate environmental and managerial
personnel of several cement companies, consultants, equipment
manufacturers, EPA personnel, potential consumers of waste dust,
and suppliers of materials for which kiln dust may be a substitute.
These contacts were made to solicit opinions and facts on problems
attendant to utilization of dust in particular applications and to
seek additional potential applications.

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                   CEMENT KILN-DUST  WORKSHEET          SRI ID
Company name	
Plant name and location
Contact	Ph:	
1.   Kiln-dust collection

     a.  Collection equipment (check one or more)
                Cyclones or multiclones	Q
                Baghouse	Q
                Electrostatic precipitator...... p
                Wet scrubber	Q
                Other (specify)	p
                None	O

     b.  Estimated collection efficiency  (%)   	

2.   Kiln-dust disposition

     a.  Total collected (tons/day)             	
            Alkali content - K20(%)             	
                           - Na20(%)           	
                           - Na2O equivalent(%)	

     b.  Total returned to kiln (tons/day)      	
            Alkali content - K->O(%)             	
                           - Na20(%)
                           - Na~O equivalent(%)	
         Method of return
                insufflation	Q
                mixed with feed	Q
                leached	Q

     c.  Total discarded (tons/day)             	
            Alkali content - K-0(%)             	
                           - N32O(%)           	
                           - Na20 equivalent(%)	
         Method of disposal
                Surface piling	O
                Quarry piling	O
                Slurry to quarry	a
                Slurry to pond	a
                Other (describe)	a
                Utilization (describe)	a
     c.  Does this company have plans for future utilization
         of cement dust?  If yes, how?	
3.  Additional remarks (novel practices, special problems/ etc)
 Figure 1.   Sample form used to record  survey data.

                                   5

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                           SECTION IV

                          THE INDUSTRY

Portland cement is composed of the oxides of calcium, silicon,
aluminum, and iron, bound in a complex mineralogical matrix, with
the ability to hydrate and harden into a stone-like material.
The raw materials generally include a calcium carbonate source
such as limestone, cement rock, marl, chalk or oyster shell, a
silica source such as sand, quartzite or Fuller's earth, an
alumina source such as clay, shale, slag, aluminum ore tailings
or fly ash, and an iron source such as iron ore, iron oxide,
blast furnace flue dust or iron pyrites.3  Some raw materials
contain several of the necessary constituents and thereby reduce
the number of materials that must be handled by a manufacturer.
The most common combinations of materials are:  cement rock;
limestone and clay; limestone and shale; and limestone, clay,
and iron ore.  Naturally occurring raw materials contain un-
necessary or undesirable elements such as magnesium, potassium,
sodium, sulfur, chloride, fluoride, phosphate, and heavy metals;
however, when these are present in only trace amounts, they are
not deleterious to the manufacturing process or to the product.

The principal steps in the manufacture of portland cement are
quarrying (or dredging of shells), crushing, grinding, blending,
firing, and finish grinding.  The quarrying and crushing opera-
tions are not unique to the cement industry, in fact, almost all
mineral quarrying and crushing operations use the same techniques
and equipment.  Raw grinding of the sized materials reduces them
to a fineness of about 200 mesh.  Most plants employ ball mills
for raw grinding and some add water to the material being ground.
Those plants grinding raw material as a water slurry usually keep
the material wet until it is dried in the kiln, thus the term
"wet process".  In those plants grinding raw material dry the
term "dry process" has been adopted.  Wet process plants pump
the ground material to large stirred tanks, called slurry tanks,
where the composition is adjusted as necessary and the batch is
stirred to assure uniformity.  The analogous dry process equip-
ment is a homogenizing or blending silo stirred by introduction
of compressed air at the base.  Factors that determine whether
wet or dry grinding will be used include:  moisture content of
the raw materials, availability of water, and the price of fuel.
(Wet-process plants require additional fuel to evaporate the
moisture in the kiln feed.)

Quarrying, crushing, grinding, and blending prepare raw material
for the most important step in processing, burning in the kiln.
The kiln feed (also called raw meal or raw mix) is continuously
metered into the upper end of the kiln to begin its transit of one
                                 6

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to four hours through the kiln.   A burner maintains the tempera-
ture at the lower end of the kiln at about 1500°C and the feed
temperature approaches this value as it traverses the kiln.   Dur-
ing the movement of feed through the kiln, three thermally induced
events occur:  moisture is driven off, the calcium carbonate
calcines to calcium oxide, and then the entire mass fuses into
semi-liquid, marble-size balls called clinker.  The fusion step
involves several complex chemical reactions resulting in a new
mineralogical material, portland cement clinker.

Clinker discharged from the kiln, usually onto a moving grate
clinker cooler, is cooled by a stream of air passing up through
the grate.  Usually a portion of the hot air from the clinker
cooler is used as combustion air for the burner.  Water spray
cooling is the only other significant clinker cooling method in
the industry.  After cooling, gypsum  (usually about 5% by weight)
is added to the clinker to retard hydration.  Then the mixture is
finely ground  (325 mesh) prior to bagging or bulk shipment.

The various standard grades of cement available are all produced
with the same equipment and essentially the same raw materials.
The differences between cement grades are achieved by variations
in kiln operating conditions and ratios of raw materials.

The cement industry is now in a period of growth in production
capacity.  During the period 1965-70 the cement industry suffered
from excess capacity.  There were 177 active plants in 1964,l and
several of these were shut down due to reduced profits and air
pollution regulations that required expensive additions of
emission control devices.  During the 1970's the number of plants
has remained in the range of 165 to 170 as new plants come on
stream and older plants are closed.  However, the larger capacity
of newer plants and the expansion of  some existing plants resulted
in a steady increase of cement shipments in the United States
from 75.3 million tons* in 1970 to 87 million tons in 1973.*  The
value of the 1972 cement shipments was about  $1654 million, pro-
ducing a profit of about 9% return on net worth.5

Locations of portland cement plants are dictated normally by
distance to market, availability of transportation and availability
of raw materials.  Typically, the market area is considered to be
within 100-200 miles from the plant along transportation routes.
Low cost transportation such as rail  or water is usually required
to profitably  ship cement further than the 10-50 mile radius of
the local market.  Similarly, proximity of raw materials is im-
perative if a  plant is  to compete economically.  Most plants utilize
*The cement industry has adopted the short ton, 907 kg, as its
 standard unit of weight.  Therefore, all production  figures  in
 this report will be expressed in short tons.

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stone quarries adjacent to the plant so that raw material trans-
portation costs are kept low.  Some plants, however, are located
so as to minimize distribution problems and must transport raw
materials several miles from quarry to plant site.  Still other
plants purchase shell or stone from other suppliers.

The costs of cement production do not depend as much on materials
as on labor, which accounts for roughly one-third of the total
inplant cost for producing cement.  Examples of major costs for
14 plants are given in Table 1.

The future of portland cement is good despite the more stringent
pollution control laws.  Demand is increasing due to increased
construction and increased use of prestressed concrete products.
The average annual increase in shipments of portland cement is
predicted to be about 3.4%.**  Factors which could adversely affect
the cement industry are as yet speculative.  The greatest threat
to the industry is the fuel shortage, which is likely to result in
significant process modifications to improve thermal efficiency.

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                                                 Table 1.  PLANT PRODUCTION COSTS
                                                    (1973 dollars per short ton)


   Plant	      ABCDEFGHIJKLMN    Avg.
Purchased
Raw Material
Freight on
Limestone
Haste Dust
Disposal
Labor
Fuel
Power
Operating
and Repair
Supplies
Taxes and
Insurance
Miscell-
aneous
Depreciation
& Depletion
Total Plant
Cost
0.69 1.82

0.16
5.85 5.00
2.18 2.39
1.17 1.92
1.92 2.07
0.37 0.32

0.05 0.05

1.49 2.55
13.72 16.28

1.13
1.06

6.40
2.83
1.17
2.12
0.53

0.05

1.59
16.86

0.76 4.22 5.25 0.76 0.59
1.01

7.23 5.75 4.52 8.40 6.80
2.39 2.39 1.76 3.46 3.40
1.55 1.86 1.70 1.17 0.75
2.44 1.92 1.23 1.27 1.75
0.21 1.59 0.59 0.11 0.80

0.05 0.50 0.50 0.05 0.05

1.81 1.59 2.39 0.59 1.27
16.33 19.25 17.45 15.80 16.44

0.76 0.85 0.91 4.17 0.65 0.59
1.38

7.08 5.48 4.00 3.84 5.59 5.96
2.29 1.80 3.09 2.13 2.08 2.66
1.27 1.54 1.59 1.27 1.13 0.75
1.38 1.97 2.44 1.81 2.24 2.92
0.48 0.64 0.37 0.53 0.32 0.69

0.05 0.16 0.05 0.05 0.05 0.05

1.59 1.70 1.92 1.59 3.03 1.86
14.89 14.15 14.36 15.37 15.05 16.86

1.65
0.25
0.01
5.35
2.49
1.34
1.96
0.54

0.06

1.78
15.91

Source:  J.D. Wilson/ Bendy Engineering Company, St. Louis, Missouri.

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                           SECTION V

                        DUST COLLECTION

The Environmental Protection Agency and most state air pollution
control agencies have set standards for particulate emissions
from cement manufacturing processes.  United States Environmental
Protection Agency guidelines call for a maximum dust emission from
the stack of 0.3 Ib of particulates per ton of dry raw feed, and
a maximum dust emission from the clinker cooler of 0.1 Ib per ton
of dry raw feed to the kiln.2'6  Because it is almost always
relatively coarse and low in alkalies, clinker cooler dust can be
collected and returned to the process without any problems.  Since
clinker cooler dust is seldom discarded it was not covered in this
study.

An example of the level of control represented by the EPA guide-
lines can be demonstrated by the following calculations:

    • The average production of a portland cement plant in
      the United States is about 1670 tons per day.

    • Approximately 1.6 tons of raw material are required to
      produce one ton of clinker resulting in an average feed
      of about 2672 tons per day.

    • The average amount of dust collected (not emitted) is
      312 tons per day.

    • The average collection efficiency of 101 plants studied
      is about 96%, so total dust generated is about 325 tons/day.

    • The average amount of dust generated per ton of feed is
      325/2672 or 0.122 tons (244 Ib) of dust per ton of feed.

    • To reduce emission to 0.3 Ib of dust per ton of feed,
      243.7 Ib of dust must be collected which is  (243.7/244)
      x 100% or 99.88% removal.

This example is consistent with actual requirements faced by the
industry.  Most modern dust collection equipment is certified above
98% for normal operating conditions and some collectors have tested
as high as 99.98%.  The amount of dust that must be removed from
exhaust gases depends, naturally, on the total amount of dust in
the gases and this can vary tremendously.  Dust generation depends
on almost every factor that affects cement making.  Some of the
more noticeable causes of high dust generation are non-uniformity
of feed particle size and operation of kilns above the design
production rate.
                                 10

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The most important step in preventing air pollution is preventing
escape of kiln dust to the atmosphere.  To prevent kiln dust escape,
many types of collectors have been utilized by cement manufacturers.
The types of dust collectors used in the 101 plants surveyed are
shown in Table 2.
     Table 2.  DISTRIBUTION OF KILN DUST COLLECTION SYSTEMS
              IN WET AND DRY PROCESS CEMENT PLANTS
Kiln-dust collection system

   Single dust collector

   Cyclones
   Precipitators
   Baghouses
   Wet scrubbers
   Settling chamber

   Combinations of dust collectors

   Precipitators and wet scrubbers
   Cyclones and wet scrubbers
   Cyclones and precipitators
   Cyclones and baghouses
   Cyclones, baghouses, and precipitators
   Baghouses and precipitators
   Baghouses and wet scrubbers
Type of Process
     and
Number of Plants
Wet

 2
31
 3
 1
 1
 1
 1
14
 4
 2
 1
 0
Dry

 2
 3
 3
 0
 0
 0
 0
12
16
 2
 1
 1
The earliest and least expensive dust collector is the settling
chamber.  A settling chamber is typically a large box in the duct
between a kiln and the exhaust stack or chimney.  Exhaust gases
passing through the chamber experience a reduction in velocity
due to the larger cross sectional area of the chamber compared to
that of the kiln.  Reduced velocity allows large dust particles
to settle to the bottom of the chamber.  Such "dense" particles
are usually  20 to 30% of the dust emanating from a cement kiln.
The settled dust is removed from the chamber and usually added
to the kiln feed.  Only one plant contacted in our survey used
a settling chamber as its only dust collector, and this plant is
in the process of upgrading its collection system.  Although not
reported, it is likely that many plants still use settling chambers
ahead of more efficient dust collectors.
                                 11

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 Cyclones  produce better  separation  results  than  settling chambers
 and  are utilized extensively  in  the cement  industry.  Over half
 of the plants  surveyed use  cyclones for kiln dust collection, but
 only four plants still use  them  as  the only dust collectors.  The
 operating principle of the  cyclone  is the application of centri-
 petal force  to a moving  gas stream  by introducing the gas tangen-
 tially to the  inner surface of a cylinder thus forcing the gas in
 a circular path.  The radial  acceleration experienced by the dust
 particles concentrates them against the wall of  the cylinder while
 gases depleted of dust are  removed  from along the axis of the
 cylinder.  Both cyclones and  settling chambers use a force directed
 at right  angles to the stream flow  to remove dust particles but in
 a cyclone the  percentage of dust removed is greater because the
 radial acceleration is much greater than the acceleration of gravity
 employed  in  a  settling chamber.

 Electrostatic  precipitators have been in use in  the cement in-
 dustry for many years.  Early installations were generally only
 slightly  better than cyclones but continuing research in construc-
 tion and  materials have made precipitators  extremely efficient
 and  have  improved economy.  The  principle of electrostatic pre-
 cipitation involves the attraction  of electrically charged par-
 ticles to an electrode of opposite  charge.  As dust laden gas passes
 through a precipitator, the dust particles  are exposed to a corona
 discharge in an electric field and  acquire  static electrical
 charges.   Under the influence of the electric field, the charged
 particles  are  attracted to  electrodes bearing a charge opposite
 to that imparted to the particles,  and are  deposited on these elec-
 trodes, from which they fall to  hoppers below.  Usually, electro-
 static precipitators comprise two,  three, or four stages
 pneumatically  in series.

 Electrostatic  precipitators are  used in 67  of the 101 plants
 surveyed.  As  shown in Table 2,  they are the preferred dust col-
 lector for wet process plants (49 of the 61 plants).  The moisture
 content of the exhaust gases helps  in the conditioning of the dust
particles  that results in electrical conductivity properties of
collected dust that are desirable for electrostatic precipitation.

The  fabric filters most commonly used to collect cement kiln dust
are baghouses.  They consist of hundreds of siliconized-glass fab-
ric  tubes through which the dust laden gases flow, leaving the
dust particles on the inside walls  of the vertically hanging bags.
The bags are shaken to dislodge the dust which falls into a hopper.
The maximum temperature tolerated by the glass bags is somewhat
less than 300°C.7
                                 12

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Wet scrubbers are employed by only two of the plants in our survey.
Only one scrubber is actually used as the primary dust collector,
and it has a history of mechanical problems.  The dust laden exhaust
gases are brought into contact with a high-velocity water spray
that entraps the dust particles.  The droplets are collected in
cyclones and sent to a settling pond.  The sludge from the settling
pond is usable as kiln feed, but the overflow is a potential water
pollution problem.8

Combination systems utilizing the best features of two or more
collectors are quite common in the cement industry.  The most
common multiple systems are cyclones with precipitators and
cyclones with baghouses.  Cyclones are used ahead of the other
collectors to remove coarser particles inexpensively and the second
system then collects the finer particles.  Usually, when alkali
problems are encountered with the dust collected in a combination
system, only the fine fraction from the final dust collector needs
to be discarded.
                                 13

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                           SECTION VI

                  CHARACTERISTICS OF KILN DUST

 In the process of grinding the raw materials to a fineness of
 minus 200 mesh, a significant amount of extremely fine particulate
 matter is produced.  When the raw materials are subjected to the
 tumbling action of the kiln, these fine particles become airborne
 and are swept away by the hot combustion gases.

 Dust collected in an efficient U.e_ 98-99.9%) collector shows a
 wide range of particle sizes depending upon the type and extent of
 grinding, the type of kiln, and the type of dust collection system
 employed.  The dust sample in Table 3 was extremely fine; most of
 the particles were less than 6 microns in diameter.9  Other studies
 of particle size analysis reported substantial fractions of the dust
 with particle sizes as large as 100 microns.10
 Table 3.  PARTICLE SIZE ANALYSIS AND DISTRIBUTION OF ALKALIES IN
          A SPECIMEN KILN DUST FROM AN ELECTROSTATIC PRECIPITATOR9
Particle Size
Range  (Microns)
          Total Alkalies Water Soluble
Weight   	%	  Alkalies, %
Percent  Na20      K20   Na2O     K20
                                 Water
                               Insoluble
                                 K20, %
+68
-68+48
-48+34
-34+24
-24+17
-17+12
-12+6
-6
  0
 0.3
 0.4
 0.7
 1.8
 5.1
27.3
64.4
0.30
0.31
0.35
0.38
0.40
0.33
0.42
3.62
3.46
4.51
5.08
5.15
5.35
10.72
*
*
0.094
0.117
0.134
0.134
0.242
it
*
1.927
2.560
3.072
3.252
8.191
2.58
2.52
2.08
2.10
2.53
*Insufficient sample for analysis,
An important factor associated with dust particle size is the dis-
tribution of alkalies in the dust.  Sodium and potassium sulfates,
chlorides, and carbonates exhibit a strong tendency to concentrate
in the finer fractions of collected dust because the specific surface
area of the particles increases dramatically as effective diameter
decreases.  This relationship is best shown by the data in Table 3.
The relationship of alkali content to surface area is explained by
the following sequence of events.  First, as the raw materials
proceed down the kiln and increase in temperature, sodium and potas-
sium compounds reach their boiling or subliming temperature and
vaporize; then, as the gases containing airborne raw material and
vaporized alkalies leave the hot part of the kiln, the alkalies
                                  14

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cool and begin to condense both as a fume and onto particles in the
gas stream.  The fume produced is composed of extremely fine par-
ticles and apparently accounts for only a small part of the volatil-
ized alkali.  Most of the alkali present in the gases condenses on
entrained dust particles, and since the finer particles have more
surface per unit of weight to be coated, they contain more alkali
per unit of weight, i.-e_. , higher concentration of alkalies than
the larger particles. ~"

The chemical composition of kiln dust is determined by the composi-
tion of the raw materials and the conditions the dust particles
have encountered in the kiln.  Published data on the proportions
of major constituents, Ca, Mg, Si, K, Na, S, C, etc. vary so widely
that no really typical dust composition can be assumed.    Careful
analysis of a dust sample would reveal a variety of elements, some
present in only trace concentrations as shown in Table 4.  This
particular sample had a high concentration of the usual alkali
metals Na and K and smaller concentrations of the others in that
group*Li, Rb, and Cs.11  Most of the cations are associated with
C0a~  and SO4—, but halide anions are also present.  Volatile
heavy metals such as Zn and Pb are likely to be present in con-
centrations significantly higher than those found in the raw
materials.

The collected kiln dust has experienced some degree of calcination
and thus has a lower content of CO3than the raw materials.  The
"loss on ignition" value of the dust may range from 10 to 35% com-
pared to a typical value of about 36% for raw materials.  The
degree of CO3depletion is an indication of how hot the dust be-
came and, therefore, how far down the kiln it traveled before
becoming airborne and escaping with the gases.  Since the dust is
partially calcined it has the ability to harden somewhat upon
exposure to moisture.
                                 15

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            Table 4.   COMPOSITION OF DRIED KILN DUST11
 Clay (HC1  insoluble,  fired at 800°)
 Organic  substance
Cations

Lithium
Sodium
Potassium
Rubidum
Cesium
Magnesium
Calcium
Strontium
            Li*
            Na+
            K  +
           Cs'
           Mg"
           Ca'
            Sr
Sum of Cations
             "1"1"
                                     Weight,  %

                                       4.61
                                       2.06
                                       0.0064
                                      12.25
                                      24.50
                                       0.475
                                       0.0074
                                       Trace
                                       9.26
                                       0.015
 Meg/10Q q

    0.92
  523
  627
    5.56
    0.06

  462
    0.34

1,618.88
Anions

Fluoride   F ~
Chloride   Cl~
Bromide    Br~
Iodide     I ~
Carbonate  CO3
Sulfate    SO i,
Sulfide
Borate
Phosphate
Sum of Anions
           S —
           B03-
          Heavy Metals
Chromium
Manganese
Iron
Zinc
Lead
Cr
Mn
Fe
Zn
Pb
0.011
0.013
0.84
1.62
0.562
Sum of all determinations
Oxygen (from CaO not bound in carbonate)
Sum of all constituents
0.46
1.43
0.040
0.0552
29.59
9.06
Trace
0.152
Not detectable

Heavy Metal
Cr203
Mn02
Fe2O3
ZnO
PbO

bonate )

24.2
40.3
0.5
0.44
987
189

2.58

1,244.02
Oxides
0.016
0.021
1.19
2.02
0.607
97.825
2.98
100.805
                             16

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                         SECTION VII

                      THE ALKALI PROBLEM

The major sources of alkalies in the raw materials for cement
manufacture are the argillaceous and siliceous components rather
than the limestone or the fuel.  Fixed alkali cations in the raw
materials are not susceptible to removal by direct water leaching
or ion-exchange methods.  The only practical way of removing them
is through decomposition of the clay structure by heating a lime-
clay mix at ratios approaching the formulation of portland cement.12
Under these conditions changes in mineralogical structure of the
clay allow the alkalies to escape as vapors that subsequently
condense on the surfaces of cool dust particles in the kiln.
When necessary, CaCl2 can be added to the kiln feed to further
volatilize the alkalies.

The alkali content of collected kiln dust is the most important
characteristic determining whether the dust can be reused in
the manufacture of cement.  If the total alkali content of the dust
(expressed as NaaO equivalent) is below about 1%, usually most or
all of the dust can be returned to the kiln.  Alkalies in the dust
upset kiln operation by lowering the fusion temperature of the other
materials and thereby increasing the fluidity of the kiln load.
This causes a* reduction in the thickness of the layer of material
coating and protecting the refractory lining of the kiln.  Also,
the presence of substantial quantities of free alkalies in the kiln
material during the burning process results in the formation of
free lime, as an equilibrium product.13  Moreover, since most of
the alkali returned to the kiln eventually finds its way into the
clinker, return of high-alkali dust can result in the production
of clinker with an alkali content above the limit of 0.6% specified
for low-alkali cement.  This specification is an effort to avoid
problems with the well known "alkali-aggregate reaction".

When the aggregate in concrete contains amorphous silica, alkalies
in the cement can react with the silica to cause swelling of the
concrete.11*'15  This slow, insidious deterioration of concrete can
be a serious problem in construction of a dam or the foundation
of a building, but it would be of no consequence in a sidewalk or
driveway.  High alkali content of the cement also has an adverse
effect on the rate at which concrete gains strength.16

Many construction contracts and codes routinely specify low-alkali
cement, even when non-reactive aggregate is to be used.  This trend
has forced many cement manufacturers to supply low-alkali cement
                                 17

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when normal cement would be quite adequate.  If the manufacturer
is fortunate enough to have raw materials with low alkali content
he can make low-alkali clinker with no problem.  However, if the
raw materials contain more alkali than can be tolerated in the
clinker, some of the alkali must be removed and discarded.  Since
alkalies tend to accumulate in the fine dust entrained in the
exhaust gases of the kiln, discarding dust is the easiest way to
reduce the alkali content of clinker.  As dust collection
efficiencies for cement kiln effluent gases are improved from
the average of 96% presently achieved to the 99.88% required by the
New Source Performance Standards, the amount of high-alkali dust
collected will increase substantially.
                                18

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                         SECTION VIII

                        DUST DISPOSAL

Kiln dust with a high alkali content or other property making it
unsuitable for return to the process is usually discarded.  Of
the 101 plants surveyed, 16 discard all of the dust they collect,
and 57 discard a portion of their dust.  The most common method
of disposal is piling on plant property.  Most often these piles
are begun on an unused, fairly level location, convenient to the
collection equipment and downwind of the plant proper.  Another
common practice is to dump the waste dust into an abandoned quarry
near the plant.  In either case, water pollution problems are
encountered due to the solubility of the alkalies in kiln dust.
Typically, 30 to 60% of the alkalies present in kiln dust are
water soluble and can be leached out as water percolates through
the dust piles.  The runoff from a dust pile usually has a pH of
12 to 13 and will kill most vegetation.  One dust pile containing
discarded cyclone dust at least 5 years old produced a leachate
solution with a pH of 12.5 while a nearby pile of freshly deposited
dust collected in an electrostatic precipitator produced a leachate
solution with a pH of 12.9.  Thus, the alkalies leached from a dust
pile in this instance decreased very little over a period of 5 years
A considerable retention time must be assured before runoff from a
dust pile can be released untreated to the environment.

Effluent guidelines for the cement industry require containment
of a rainwater runoff from materials storage piles including waste
kiln dust piles.17  In many cases this will require construction of
a dike around the dust piles as illustrated in Figure 2.  Facilities
will be needed for adding acid to obtain a pH in the range of 6 to
9 for the runoff water that percolates through the pile into the
containment pond before it is released to the receiving stream.
Water slurries of dust occur when wet scrubbers are used for dust
collection as in two plants of the 101 surveyed.  Another situation
resulting in water slurries of dust arises when plants mix dust
with water and pump the slurry to a disposal pond or lagoon.18
Some plants use abandoned quarries as the disposal site for dust-
water slurries.  Others construct ponds or lagoons where the water
slurry can settle, concentrating the suspending solids as a sludge
in the lagoon.  Most plants that dispose of dust as a slurry use
waste water from the plant and discharge the supernatant liquid
from the settling pond to surface waters.  Naturally, the waste
water must be retained or treated before discharge just as rainfall
runoff from a dry disposal pile.  One alternative to treating water
before discharge is to maintain a closed water system by recycling
the supernatant liquid back to slurry more dust.  In areas where
the mean annual evaporation exceeds the rainfall, large evapora-
tion ponds could be used to dispose of alkaline wastewater.
                                 19

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Figure 2.  System for containment and treatment of
           runoff from kiln dust disposal pile.
                      20

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                          SECTION IX

                       DUST RECLAMATION

Presently, 28 out of the 101 plants surveyed return all of the
dust they collect to the process, while 16 discard all of the
dust they collect.  The remainder of the plants, well over half
of those surveyed, recycle as much dust as they can without
exceeding the limits for alkali content in their clinker, and
they waste the remaining dust.  On an industry-wide basis, our
survey of the amounts of dust collected and discarded indicated
that about 73% of the collected dust is reprocessed to make
cement.  A variety of methods are employed for recycling dust
to the kiln.  Dust can be introduced to the kiln by insufflation
through the burner pipe or a pipe parallel to the burner pipe so
that the dust reaches reaction temperature very rapidly.  '
One disadvantage of insufflation is the tendency of the dust to
remain airborne due to its fineness, thus establishing a recircu-
lating dust load and wasting energy for collection and reheating.
Also, in insufflation the dust cloud in and around the burner
causes difficulty in measuring flame temperatures by optical
methods.

A second method of dust return employs scoops located about mid-
length of the kiln which feed dust from a collar around the kiln
to the interior.  Scoops appear to be decreasing in popularity
as a means of dust return.

Probably the most popular method of dust return to dry process
kilns is by blending with the raw feed to obtain a uniform mix so
that a more consistent product is obtained.  In wet process plants
blending of dust with kiln feed is difficult because the partially
calcined dust tends to harden when exposed to moisture.  Some wet
process plants have solved their dust return problems by carefully
adding dry dust to the feed slurry just before it enters the kiln.
A Russian plant made a slurry of the dust and mixed it with the
feed slurry.21  Other plants use additives such as molasses or
lignosulfonates from pulpwood mills to retard the setting of the
dust when it is hydrated.22

As mentioned previously, most manufacturers discard dust that has
too much alkali to allow it to be returned directly to the kiln.
The dust has an estimated value of $2 per ton as a cement raw mate-
rial because it has already been mined, crushed, and ground.  The
4.5 million tons of dust discarded in the United States  in 1972
would have been worth $9 million if it had been used to  make
cement.  Although a variety of methods for reclaiming high alkali
dust have been investigated, only one process,  leaching,  is  in use
in the United States, and this process is now practiced  in only
seven plants, six of which are wet-process plants.  All  of the
leaching plants use electrostatic precipitators to collect the
dust.


                                21

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 In the leaching process, collected dust is thoroughly mixed with
 water in a pugmill or mixing tank.  This slurry which contains
 about 10% solids is pumped to a clarifier or thickener where the
 solids settle to the bottom and excess water overflows.23  The
 underflow from the clarifier, a slurry containing about 50% solids
 is returned to the kiln and burned to clinker.   In the single dry-
 process leaching plant this slurry is injected  through a pipe
 extending down from the feed end of the kiln into a region where
 the temperature is high enough to flash off the water.  In wet
 process leaching plants the underflow is either mixed with the
 feed slurry or pumped into the kiln through a pipe parallel to the
 kiln      ^1*
 Disposal of the  alkaline  wastewater from the  leaching process  is
 a serious problem faced by  cement  manufacturers .   Two leaching
 plants  discharge their wastes  to municipal  sewage  treatment systems
 where they claim it  is beneficial  in neutralizing  the acidic wastes
 in the  sewage.   Presumably  they will be  allowed to continue this
 practice in the  foreseeable future.   One plant adds acid  to the
 leachate to lower the pH  to acceptable levels and  one plant
 carbonates the leachate with stack gas.   The other plants dis-
 charge  the alkaline  wastewater directly  to  rivers,  a practice  that
 will  be prohibited by the Effluent Limitation Guidelines  recently
 promulgated by the Environmental Protection Agency.17  By 1977 the
 levels  of pH and suspended  solids  of the discharge must be con-
 trolled,  and by  1983 discharge of  dissolved solids must be curtailed
 This  gives manufacturers  almost ten  years to find  a way to recycle
 leachate or face shutdown of their leaching operations.

 The diagram in Figure 3 shows  a scheme for  eliminating discharge
 of pollutants from a dust leaching operation.  The  overflow from
 the primary clarifier, the  water that is now being  discharged  by
 most  leaching plants, is  saturated in lime, has a  pH of 13,  and
 contains  10,000  ppm  of dissolved solids.  In the first carbonator
 C02 from_the stack gas reacts  with OH~ ions in the  leachate  to
 form C03    ions.   If the  alkalinity  of the  leachate exceeds  the
 hardness,  almost  all of the  calcium  is precipitated as CaCOs
which has  its minimum solubility,  16 ppm, at pH 9.5.25  This pre-
 cipitate settles  to  the bottom of  the secondary clarifier  and  is
 ultimately returned  to the kiln.   Residual  suspended CaC03  in  the
overflow from the secondary  clarifier redissolves  as the pH
decreases  in the  secondary carbonator.26  This overflow would
be within  the limits of pH and suspended  solids required by  1977.

Electrodialysis appears to be  the  process of choice to remove
alkali salts from the leachate and concentrate them in a solution
for recovery of valuable by-products by  evaporation and fractional
crystallization.   The operation of an electrodialysis  stack  is
                                 22

-------
to
CJ
                                      Stack
                                        gas
           Primary
           clarifier
                         pH=13.0
         Underflow returned
           to kiln feed
                                       I
                                                         Stack
                                                           gas
             First
          carbonator
PH=9.5>
Secondary
clarifier
                                              pH=9.5.
       Underflow returned
                               to primary clarifier
         Kiln dust
           Mixerl
                     T
 Partially  desalted
  water  returned
	  for  reuse  in .«
   slurrying  dust
    Electrodialysis
        units
  (detailed in Fig.4)
                  Make-up
                   water
                                  1
                                                 Concentrated brine
                                                 (ca. 20% solids) to
                                                     evaporation
                                                            1
  Second
carbonator
                                                              pH=8.0
                      Sand filter
                    Figure 3.  Flow diagram showing steps in electrodialytic
                               concentration of leachate.

-------
 shown in Figure 4.   An electric potential forces  ions  through
 semipermeable  membranes into a concentrated  brine.   Water enters
 the  brine by osmosis and carries away the concentrated salts.   The
 partially desalted  water is  reused  to leach  alkalies from collected
 dust, and no water  is discharged.

 In electrodialysis  of water  containing appreciable  concentrations
 of calcium, problems are encountered  with precipitations  of  CaSOi,
 and  CaCOa from the  concentrated brine.   These  precipitates damage
 membranes and  block the flow of solutions in the  electrodialysis
 stack.   Therefore,  it is important  that the  calcium content  of  the
 water be reduced to a very low level  by the  carbonation procedure
 described above.  Univalent  cation-selective membranes that  prevent
 the  passage of calcium ions  can be  used if the alkalinity (OH"  ion
 content)  of a  particular leachate is  insufficient to allow nearly
 complete removal of calcium  upon carbonation.27   However,  this
 problem  would  be expected to occur  only in plants that use fuel
 with very high sulfur content.

 The  concentrated brine from  the electrodialysis stack  would  contain
 about 20% dissolved solids,  mainly  K+,  Na+,  C03   ,  and SOi,  .   Since
 the  ratio of K to Na in the  solution  is likely to be greater than
 10:1,  the concentrated leachate may be  suitable as  a liquid
 fertilizer.  Further purification and concentration of the K, which
 is the more valuable of the  two alkalies,  could be  achieved  by
 fractional crystallization and  evaporation.

 Other processes for leaching alkalies from dust have been  reported
 but  none  is presently being  used commercially.  During World War I
 potassium was  produced by the Riverside Cement Company.28  CaF2 was
 added to  the kiln feed to volatilize  the K which  was subsequently
 converted to K2SOi»  in the combustion  gases.  Collected dust  was
 leached,  the leachate was filtered  and  evaporated,  and a  precipitate
 of KaSOit  was collected.
A process described in a British patent by Singleton and Bruce
utilizes a strong solution of potassium chloride to selectively
remove Na from the dust.29  Then l^SOi*  is removed from the dust by
a second extraction.  The leached dust is suitable for return to
the kiln and the separated K2SOi* is a valuable by-product.

Leaching with hot water is reported to be more effective than leach
ing at ambient conditions.  Patzias found that a larger portion of
the total alkali in the dust was soluble when the dust-water slurry
was heated.90'31  Palonen and Kaiser found that high concentrations
of alkalies in the leachate could be achieved by countercurrent
extraction with hot water.15
                                 24

-------
   Partially
   desalted
   water
Cathode
i
               ^-^
                                                     -*• Concentrated
                                                          brine
                     rs///s,
                    A    C     A
                            K+
                          Y///S*
                              C     A     C
C  - represents cation-exchange
    membranes

A  - represents onion-exchange
    membranes
                           T
                            Solution to be

                               treated
x\ Anode


1
   Figure 4.   Diagram of  electrodialytic concentration stack,
                                  25

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 One reason that electrostatic precipitators have found wide
 acceptance as kiln dust collectors is their ability to separate
 coarse and fine dust particles.  Coarse particles are more easily
 collected and they tend to predominate in the fraction of dust
 collected in the first section of the precipitator.  The finest
 particles/ which because of their large surface-to-mass ratio have
 high alkali content, predominate in the fraction of dust collected
 in the last section of the precipitator.   Discarding this fine,
 high-alkali fraction allows the manufacturer to discard the minimum
 amount of dust while maintaining acceptably low alkali content in
 the clinker.   Heilmann patented a process in which dust collected
 in intermediate sections of the precipitator is subjected to further
 size classification to achieve greater fractionation of alkalies.32

 In a process  developed by Bade, hot gases from the kiln with
 alkalies  still in vapor form are cleared  of coarse dust particles
 by a cyclone.33  Then cool fine dust particles are mixed with the
 hot gases to  condense the alkalies which  are subsequently removed
 with the  dust in a second cyclone.   Then  the hot gases are used to
 preheat raw materials in a turbulence stack.   Cool exhaust gases
 from the  turbulence stack are cleaned by  an electrostatic pre-
 cipitator and the collected dust is recycled to condense alkalies.

 A  process developed and tested in Russia  used cyclone  heat exchangers
 to recover heat and large particles of dust from hot exhaust gases.
 Then the  gases  were cooled with finely dispersed water spray to
 condense  the  alkalies so they could be subsequently removed in a
 second  dust collector as a powder with 70  to 80% alkali carbonates
 and sulfates. 31f

 When cement is  made in  a fluidized  bed, the hot exit gases  carry
 away the  volatile  alkalies.   When these gases  are cooled either by
 heat exchangers  or  by water  sprays,  the alkalies condense  in a form
 that can  be used as  a high-grade  by-product.35'36'37   Fluidized-
 bed  reactors  emit very  low levels of  particulates and  they  can use
 low-grade  fuels  such  as  kerogen-rich  shale.   However,  since they,
 unlike rotary kilns,  do  not  employ  countercurrent flow of gases  and
 raw materials, expensive heat exchangers are  required  to achieve
 reasonable utilization of  heat  in the  system.   Figure  5  shows
 schematically how such a system operates.   A  fluidized bed  pilot
 plant was operated by the  Fuller Company several  years  ago,  but
 no commercial operation  is in existence.

Flame volatilization  for alkali recovery utilizes  the  high  tempera-
 ture of a flame to volatilize the alkalies  from  the  surface  of dust
particles.  The alkali vapors are removed from the hot  gases by
condensation on a cool surface.9  Although  flame  volatilization
actually occurs during insufflation, the alkalies recondense on
the dust particles in the kiln, and useful  separation  of alkalies
is not achieved.
                                 26

-------
to
                     RECYCLE CLINKER
                           COOLER
            SCREEN
                CLINKER
                PRODUCT
                                           REACTOR
                     RAW MATERIAL
                                                                 FAN
PREHEATED AIR
                                                                             STACK
                                                                               t
                                                                           ALKALI
                                                                          COLLECTOR
                       HEAT
                       EXCHANGER
                                                                            -*• AIR
FUEL
                                                                      BLOWER
                 Figure 5.  Fuller-Pyzel  fluidized bed process for production
                            of clinker  and  by-product alkalies.

-------
Preheater kilns are commonly used in Europe for fuel economy, and
their use is likely to increase in the United States as the fuel
shortage worsens.  Hot gases from the kiln are brought into direct
contact with raw materials in cyclonic-, grate-, or hearth-type
preheater.  Since alkali vapors in these hot gases will condense
on the cool feed materials, preheaters cannot be used with high-
alkali raw materials unless the alkalies can be removed from the
kiln gases.

Several processes for removing alkalies from preheater kilns are
described in the European literature.  Polysius developed a
process for removing alkali-laden gases from the Lepol preheater
collecting the dust, leaching the alkalies, and evaporating the
leachate to dryness in a thin film evaporator.38  In a process
developed in France, alkalies are condensed from hot kiln gases
onto a curtain of moving endless chains.39  The chains are then
drawn through a water bath where the alkalies on their surfaces are
dissolved and the chains are cooled.  In a similar process for re-
moving alkalies from a preheater kiln, the hot, alkali-laden gases
pass over cool tubes. "°  The alkalies that condense on the tube
surfaces are scraped off and recovered.

Alkalies can also be removed from preheater kilns via bypass of a
portion of the kiln gas that would ordinarily enter the preheater.
Nordquist and Heian reported substantial alkali reduction in the
clinker produced in a traveling grate preheater (Lepol) kiln when
30% of the 870°C gas was bypassed, cooled to 315°C by mixing with
ambient air. cleaned by a cyclone and returned to dry the raw
materials."   Weber found that considerable alkali reduction could
be achieved in a Lepol preheater, but very little alkali was lost
from a suspension preheater."2  However, his study showed that the
alkali content of the clinker could be reduced by adding CaCl2 to
the kiln feed to increase the alkali volatility.  Brachthauser
patented a process for converting alkalies to the more volatile
hydroxide form by vaporizing water in the clinker cooler and
blowing this hot moist air into the burner section of the kiln.1*3

A process for making low alkali clinker from feed materials which
may have high alkali content has been patented by Union Carbide.""
In this process, the kiln is replaced by a much smaller, stationary,
vortex reactor in which clinkering occurs.  Alkalies are removed
in the gas stream from the clinker reactor.  A separate burner and
off-gas system are used for suspension preheating the feed prior
to clinkering.   The process seems particularly useful for convert-
ing high alkali dust into clinker and fertilizer.
                                28

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                          SECTION X

                       DUST UTILIZATION

In our survey we found that of the 73 plants that discard some
or all of their collected kiln dust/  only 13 reported any utiliza-
tion of the discarded dust.  From the figures they reported we
estimated that about 1.5% of the 4.5  million tons of waste kiln
dust discarded annually is actually being used constructively, and
over half of that usage is for landfills.  In our review of the
literature we found many documented uses of cement dust and in
our discussions with industry personnel we received many sugges-
tions for potential uses.

The largest single use of waste dust  in the United States is for
landfill.  In many cases it is difficult to ascertain whether
the purpose of the landfill is to dispose of dust or to increase
the value of the land.  In the former case the cement manufacturer
may pay to have his dust hauled to the landfill; whereas, in the
latter case-he may be able to sell the dust.  Both cases were
found in our survey.  The high temperature when collected and the
extreme fineness of the waste dust make it difficult to handle. **s
Windblown fugitive dust from waste piles or landfills is a signi-
ficant source of air pollution.  Spraying the dust with water is
helpful in alleviating this problem.

Some manufacturers employ a rotary unloader like the one shown
in Figure 6 to agglomerate the dust before loading it into trucks.
The device consists of a rotating inclined drum with water sprays
inside.  As the hot, dry dust tumbles through the drum it becomes
moist and forms nodules that are easy to handle and can be hauled
in open trucks to disposal sites.  The moisture in the nodules
hydrates the cement to some extent so that the nodules do not
disintegrate as they dry.  Thus, compared to loose dust, the
nodulized dust is not as subject to wind erosion or flowing down
the pile when it is dumped.

The ability of waste kiln dust to harden after exposure to mois-
ture makes it useful for soil stabilization.  One plant in our
survey reported that their waste dust was mixed with shells and
used as a sub-base for roads.  Another reported that they dump
their dust in strip mines where it neutralizes acid mine drainage
and precipitates iron from the runoff water.  Such an application
could potentially use large quantities of waste dust.

Kiln dust has also been used as a mineral filler for bituminous
paving materials and asphaltic roofing materials.  It has also
been suggested as a filler for plastics  and for asphaltic products
                                29

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Figure 6.
Rotary unloader for nodulizing waste kiln dust
(photograph courtesy of United Conveyor Corp.)

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such as insulating board, concrete expansion strips and sound
deadening material.  There is at least one process under develop-
ment to use waste kiln dust in the manufacture of lightweight
aggregate.

The lime content of the dust makes it useful as a neutralizing
agent for acidic bogs, lakes and streams.   In a study carried out
in 1957, waste kiln dust was used to kill  vegetation in an acidic
bog."16  Considerable interest has been expressed in the possible
use of waste kiln dust to treat acid mine  drainage.  Since fresh
dry dust flows so easily, it might be pumped into abandoned mines
to neutralize acid, precipitate dissolved  iron, and possibly re-
duce seepage of water from the mine.  Industrial acidic wastes
that might be neutralized by kiln dust include spent pickle liquor
and wastes from leather tanning and cotton seed delinting processes

Kiln dust has been successfully substituted for lime in coagula-
tion processes.  In Oregon, kiln dust was  used as a partial and
total replacement for lime in the preparation of alum flock for
removal of turbidity from water.1*7  The dust successfully neu-
tralized the water and in addition improved flocculation,
apparently because the small residual insoluble dust particles
provided dense nucleation sites for the alum floe.

In the adsorption of SOa from stack gases  by wet scrubber slurry,
cement kiln dust was found to be better than limestone and almost
as good as lime.1*8  Surprisingly, problems of scaling in the
scrubber system were less severe with kiln dust than with lime
in the slurry.

In the manufacture of glass large amounts  of soda are used.  Emer
found that kiln dust could be used beneficially as a partial
replacement for soda in making green glass, because it increased
the rate of decomposition of sulfates which is the main cause of
foaming in glass baths.1*9  Gregor and Hives reported similar
success in the use of kiln dust to make glass where color and
high chemical stability are not essential considerations.10

Agricultural use of kiln dust promises to be a way of converting
a waste material into a valuable by-product.  Two properties
of the dust that make it useful for agricultural purposes are
its acid neutralizing capacity and its potassium content.  Re-
searchers at the United States Department of Agriculture station
at Beltsville, Md., found that cement dust had about 80% of  the
soil neutralizing capacity of lime and about the same  liming
qualities as pulverized limestone.50'51  Studies carried out  in
Latvia showed that cement dust could fully replace  lime  for  treat-
                                 31

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 ment of  acidic soils to grow sugar beets or corn, and the dust
 could partially replace lime for growing potatoes and rye.52  A
 study in Hungary indicated that in addition to its stimulation of
 plant growth, it also had insecticidal properties.53

 In Russia and Poland several studies have demonstrated the utility
 of cement dust application on potato crops.  One group found that,
 whereas  most inexpensive potassium fertilizers contain appreciable
 amounts  of chloride which is bad for potatoes, the high alkali
 fraction of kiln dust had essentially no chloride and was an
 acceptable, inexpensive substitute fertilizer for potatoes. 5I*
 Rogalov  found that application of cement dust increased the starch
 content  of potato tubers but had no greater affect on the yield of
 potatoes than other fertilizers.55  Litynski explained that the
 sulfate  in kiln dust was responsible for the increased starch con-
 tent of  potatoes fertilized with the dust.56  He also suggested
 that the presence of calcium in fertilizer favorably influenced
 the uptake of potassium in acidic soils.57

 A Dutch  study indicated that comparable yields of oats were achieved
 when cement dust or limestone and KaSOi, were used for fertilizer.58
 Litynski found that mixed peas-and-oats crops fertilized with kiln
 dust contained about 2% more protein than crops grown with KC1
 fertilizer.59  He also found that the dust produced more starch
 in fodder and more sugar in sugar beets.6 °

 The size of the market for agricultural lime and limestone makes
 it potentially a very good route for disposal of waste kiln dust.
 More than 20 million tons of lime and limestone are sold each year
 for agricultural purposes.61  This single market if properly
 developed could use most of the 4.5 million tons of kiln dust being
 discarded in the United States each year.  Figure 7 shows the
 usage of agricultural lime in the United States on a statewide
 average basis.  Also shown are the locations of plants that our
 survey revealed to be discarding major amounts of dust.  Most of
 these plants appear to be located in or near states where sub-
 stantial amounts of agricultural lime are used.

Approximately 94% of the potash consumed in the United States is
used in  fertilizer.62  Of the 14 chemical elements essential to
plant growth,  nitrogen, phosphorus, and potassium are the most
rapidly exhausted from the soil and must be replaced by the addi-
tion of fertilizers to assure optimum plant growth.6 3 »***  Examples
of amounts of potassium withdrawn by various crops are presented
 in Table 5.
                                32

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uo
U)
        2-20lb/acre


        20-501 b/acre


        50 -100 I b/acre


        >IOOIb/acre
                    Figure  7.   Agricultural lime  and limestone usage  in  the
                                contiguous United  States,6  and locations of
                                plants known to be discarding kiln dust.

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             TABLE 5.  WITHDRAWAL OF POTASSIUM BY
                     AGRICULTURAL CROPS65

                                  Good Acre     K2O Removed,
   	Crop	                 Yield         Ib/acre

   Soybean                            50 bu         120
   Clover grass                     9000 Ib         175
   Peanuts                          3000 Ib         120
   Alfalfa                             6 tons       270
   Coastal Bermuda
     grass                            10 tons       400
   Cabbage                            25 tons       210
   Irish potatoes                     20 tons       310
   Tomatoes                           30 tons       480
   Sugar beets                        30 tons       550
   Sugar cane                        100 tons       590
   Rice                             4500 Ib         110
   Corn, ears                        150 bu         195
   Corn, silage                       30 tons       245
   Wheat                              60 bu         110
   Cotton                           1250 Ib          90
   Tobacco                          2800 Ib         190
   Apples                            600 bu         135
   Peaches                           600 bu         120
   Grapes                             10 tons        80
   Oranges                           800 boxes      175


Many of the cement manufacturers contacted in our survey reported
that local farmers occasionally visit their plants and haul away
truck loads of waste kiln dust to spread on their fields.  Although
the farmers and cement manufacturers alike recognize the value of
the dust as a fertilizer material, apparently no great effort has
been made to exploit this resource.  One hindrance to its exploita-
tion appears to be fertilizer specifications.

Fertilizer is sold on the basis of its nutrient content.  The
three nutrients mentioned earlier  (nitrogen, phosphorus, and
potassium) are measured in "units", each unit representing one
percent of an available nutrient.  A 6-8-4 fertilizer, for example,
is guaranteed to contain at least 6 percent of available nitrogen,
8 percent of available phosphoric acid, and 4 percent of available
potash  (K2O).  There are at least 33 cement plants discarding dust
with an average potash content greater than 7 percent.  With addi-
tions of phosphorus and nitrogen compounds a commercially acceptable
fertilizer could be produced using kiln dust without further con-
centration of the potassium present.  Under regulations set by the
Alabama Department of Agriculture and Industry, fertilizers offered
for sale must meet certain minimum standards for available nutrient
                                 34

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content.  There is a regulation which,  while not written to cover
the sale of cement dust,  allows the sale of cement dust without
major modifications.  Under section 3(b)(1), Act 434,  a material
which "... contains important quantities of no more  than one of
the primary plant nutrients (nitrogen,  phosphorus, and potassium)"
is defined as a "fertilizer material."6*  Cement dust  satisfies
this definition if the potassium content is considered.  Other
regulations which might be met by cement dust are in the areas of
a soil-conditioning material and a fortified liming material.

Most of the states adhere to the Uniform State Fertilizer Bill
suggested by the Association of American Plant Food Control
Officers.  This bill cites definitions  in the AAPFCO annual
publication.  Cement dust easily meets  fertilizer material defini-
tion C-13.67  Thus cement dust can meet commercial content re-
quirements.

Once the question of the legality of sale and use of kiln dust for
fertilizer is settled, the next question is how can it be applied.
One serious problem is the handling of  the fine dust.   When dry,
it flows readily and is easily carried  away by the wind.  A
Russian patent suggests the preparation of granules by rolling the
dust in water.68  A device like the rotary unloader shown in
Figure 6 can be used for this purpose.   Then the granules are
treated with C02 to make them non-hygroscopic and mechanically
strong.

If fertilizer markets for kiln dust are developed, it is likely
that the manufacturer will want to modify the composition of the
fertilizer to meet specific soil and crop needs.  Chlorination
roasting was used by a Russian group to raise the KaO content
of kiln dust to over 20%.69  A Russian patent describes a process
in which kiln dust is mixed with a nitric acid-phosphate extract
to yield a ternary N-P-K fertilizer.70

Fortunately there are abundant supplies of potash in North America
so that there is no danger of long-term shortage.  However, the
potash fertilizer consumption in the United  States is over 5 million
tons per year,62 and there is a general shortage of other fertil-
izer materials.71  Cement manufacturers with waste dust problems
would be well advised to contact their  State Fertilizer Control
Officers for a first-hand opinion of the possibilities of using
the dust as a fertilizer material.
                                 35

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                         SECTION XI

                    LIST OF PUBLICATIONS

1.  Davis, T. A., and D. B. Hooks.  Utilization of waste kiln
    Dust from the Cement Industry.  In:  Proceedings of the
    Fourth Mineral Waste Utilization Symposium, Aleshin, E.
    (ed.).  Chicago, IIT Research Institute, 1974. p. 354-363.

2.  Davis, T. A.  Disposal of Waste Dust From Cement Kilns.
    Record of the 1974 IEEE Cement Industry Technical Conference,
    Library of Congress Catalog Number 75-28930.  IEEE Catalog
    Number 74CH0785-6 IA.
                               36

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                         SECTION  XII

                           APPENDIX
1.   Kreichelt T.  E.,  D.  A.  Kemnitz,  and S.  T.  Cuffe.   Atmospheric
     Emissions From the Manufacture of Portland Cement.  Bureau
     of Disease Prevention and Environmental Control,  Cincinnati,
     Ohio.  PHS No. 999-AP-17.  1967.
     Abstract:  Air pollution control in cement manufacturing was
     studied in detail.  This report gives descriptions of raw
     materials, processes, equipment, volumes of dust, and methods
     of dust control employed.

2.   Anonymous.  Background Information for Proposed New-Source
     Performance Standards:   Portland Cement Plants.  NTIS
     Publication PB-202 459, Technical Report 3, August 1971.
     Abstract:  Proposed standards for particulate emission of
     0.3 Ib from the kiln and 0.1 Ib from the clinker cooler
     per ton of kiln feed (dry basis) are justified.  The economic
     impact of the proposed standards is also presented.

3.   Anonymous.  Concrete Information.  Portland Cements (IS 004.
     04T), Portland Cement Association, Skokie, Illinois, 1971.
     Abstract:  Raw materials, processes, types, chemical compo-
     sitions, physical properties and handling requirements of
     Portland Cement are discussed.

4.   Levine, S. and E. W. Stearn.  The Year Ahead—1974.  Rock
     Products, 39-43, December 1973.
     Abstract:  Construction minerals shipments and values for past
     years and estimates for 1974 are tabulated.  Included is a list
     of cement plants, capacities, and process types.

5.   Grancher, R.  A. Cement's Second Look at Capacity.  Rock
     Products.  50-53, 74, December 1973.
     Abstract:  Cement plant capacity increases, especially in
     the Southeastern U.S., are forecast through 1978.

6.   Anonymous.  Standards of Performance for New Stationary
     Sources.  Federal Register 36(159): 15707, August 17, 1971.
     Abstract:  Standards of performance for portland cement
     plants are specified for new sources, including plant
     expansions.  Particulate emissions are set at 0.3 Ib per ton
     of feed and 10% opacity  (1/2 on Ringleman scale)  for the kiln
     gas effluent.  For the clinker cooler these values are  0.1 Ib
     per ton of feed and 1/4 on the Ringleman scale.
                                  37

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  7.    McCubbin,  T.  L.   Dust  Control  Techniques  for  a  Portland
       Cement Plant.  Minerals  Processing.   24-25, 35, May  1969.
       Abstract:  Generation, composition,  and return  of kiln
       dust  are discussed.  Design  and operation of  glass-fabric
       bag collectors are described.

  8.    Goldberger, R. H.  Rx  for Cement Dust.  Rock  Products.  55
       76, 78, August 1973.
       Abstract:  The wet scrubber  used for  kiln dust  collection
       at National Portland Cement  Company's plant in  Bethlehem,
       Pennsylvania, is  described in  detail.  Water  that accumulates
       in the quarry is  pumped  through venturi scrubbers where it
       washes out particles of  dust from the exit gases of  the kilns
       with  97.7% efficiency.   The  C02 and SO2 in the  gases neutral-
       ize the alkalies  leached from  the dust.   The  water is then
       treated in an 80-ft-diameter clarifier where  the suspended
       dust  particles are removed for return to  the  kiln feed.
       After treatment to oxidize dissolved H2S, the scrubber
       water is diluted with quarry water and discharged to a nearby
       C1T66JC •

 9.    Greening, N.  R.,  R. j. Hinchey, and H. Nagao.   Elimination of
       Water Pollution by Recycling Cement Plant Dust.  Progress
       Report No.  2, Contract No. 802196, Project CR-7050, Basic
       Research Department,  Portland Cement Association, Skokie, 111
       for Office of Research and Monitoring, U. S. Environmental   *'
       Protection Agency.  October  1973.
      Abstract:  A system for flame volatilization of
      alkalies is described.   Particle size analysis, chemical
      analysis, alkali  distribution,  and results of  experiments
      are presented.

10.   Gregor, M., and L. Hives.  Potash  Balance of Cement
      Shaft Kilns with  Special  Regard to Possibilities of
      Potash Recovery.   Proc. 6th Conf.  Silicate Ind.,
      Budapest 1961.  177-89, Pub.  (in English)  1963.
      Abstract:   Flue dust  samples  from  shaft kilns  at a
      cement plant  were analyzed over a  period of  12 weeks.
      The  raw material  was  lime marl  which had a K20 content
      of 1.2%.  The K20 content of  the flue dust averaged
      34%.   The quantity of dust collected was 1.7%  of the
      weight of clinker produced.   The clinker contained
      0.86%  K20.  In addition to its  value as an agriculture
      material, tests showed  the flue dust to be a satis-
      factory substitute for  potash in making glass  where
      color  and high chemical stability  are not  essential
      considerations.
                                38

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11.   Kasz, W. Chemical Investigation of the Dust Collected in an
      Electrostatic Precipitator at a Portland Cement Plant in
      Blaubeuren.   Jahresber.  Mitt. Oberrhein.  Geol. Ver.   (Stuttgart).
      46:1-8, January 12,  1964.
      Abstract:  The dust was  analyzed by chemical methods  and x-ray
      fluorescence spectroscopy, and the composition of the dust
      was compared with that of  the Upper Weissjura marl and chalk,
      which is the raw material.  The dust was enriched in  the
      elements from the raw material that were volatilized  in the
      kiln, specifically,  rubidium (0.475% of dust by weight),
      cesium  (0.0074%), iodine (0.0552%), zinc (1.62%), and
      lead (0.562%).

12.   Kester, B. E. Development  of Low Alkali Processes in  Port-
      land Cement.  Preprint No. 63H43, a paper presented at the
      Annual Meeting of the American Institute of Mining, Metallur-
      gical, and Petroleum Engineers Inc., Dallas, Texas,
      February 24-28, 1963.
      Abstract:  The source and  nature of alkalies in cement and
      their effects on certain aggregates are discussed.  Leaching
      systems for wet and dry  process plants are described.  Steam
      treatment was studied as a method for destroying hydraulic
      set properties of dust.  The use of CaCl2 to volatilize
      alkalies was found to be effective but was more expensive
      than leaching.

13.   Palonen, C.  V. and E. W. Kaiser.  Inorganic Dust Treatment
      Process.  U. S. Patent No. 2,871,133, January 27, 1959.
      Abstract:  Kiln dust is  pelletized and heated to about 950°C
      and then leached.  The normal 10 to 60% water-soluble content
      is raised to 94 to 96%.

14.   Kryzhanovskaya, I. A., et  al.  The Effect of Alkalies
      on the Behavior of Cement.  Tsement  (Moscow), April 1969.
      Translation by R. Keen.  Cement and Lime Manufacture (London).
      97-100, September 1969.
      Abstract:  Data are presented on cure rates and strengths
      of cements containing varying amounts of added alkali.
      The investigations established that, in the presence of
      0.6% alkali, the activity  of portland cement is reduced
      irrespective of the kind of alkali compounds present.
      An increase in the alkali  content reduces the activity
      both at early and late ages due to suppression of the
      hydration of the clinker materials by the alkalies in
      the liquid phase.
                                  39

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15.   DePuy, G. W.  Experiments with Alkali-silica Re-
      active Constituents of Sand-gravel Aggregate.  National
      Academy of Science - National Research Council, Publ. No.
      1367.  41-9, 1966.
      Abstract:  A pilot study investigated the effect of
      alkali-silica reactive constituents in a sand-gravel
      aggregate in the sealed moist-storage and the Con-
      row cycle mortar bar expansion tests.  A highly
      .alkali-silica reactive sand-gravel from the Republican
      River was tested against South Platte River aggregate
      as control.  It produced deleterious expansion in
      both the sealed moist-storage test and the Conrow
      cycle mortar tests.  The removal of the alkali-
      silica reactive particles reduced expansion in the
      sealed moist-storage test to within safe limits, but
      in the Conrow cycle test, expansion was reduced but
      a significant amount of expansion remained.  The re-
      maining expansion appeared to be due to the character-
      istic cement-aggregate reaction of sand-gravel aggregates.
      The tests indicate that the alkali-silica reaction is
      a major factor in the cement-aggregate reaction with
      alkali-silica reactive sand-gravel aggregates.  The
      tests also indicate that the Conrow cycle mortar bar
      expansion test is sensitive to alkali-silica reaction.

16.   McCoy, W. J.  and O. L. Eshenour.  Significance of Total and
      Water Soluble Alkali Contents of Portland Cement.  Journal of
      Materials, JMLSA.  3(3):684-45, September 1968.
      Abstract:  The amount of alkali in cement clinker depends on
      the raw materials, the burning temperature, and the presence
      of SO3.  The ratio of water-soluble to non-soluble alkali
      can vary from 1:9 to 6:4 (10% to 60%).  Relation of Na2O
      volatilization to K20 volatilization:  Na20 volatilizes
      until about 30% of the K20 present has volatilized and
      after that point K20 volatilizes about 50% faster than
      Na20.   Tests reveal that early strengths of cements are
      higher with some alkali than with none.   The amount of
      soluble alkali has little effect on the pH of aqueous
      extracts of cement.
                                 40

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17.   Anonymous.   Effluent Guidelines and Standards - Cement Manu-
      facturing Point Source Category.   Federal Register 39(35):
      6590, February 20,  1974.
      Abstract:  Plants in which kiln dust is not contacted with
      water as an integral part of the process are in the nonleaching
      subcategory.  Effluent limitations (maximum for any one day)
      for these plants are 0.005 kg of suspended solids per kkg
      of product, temperature not to exceed 3°C rise above inlet
      temperature, and pH within the range 6.0 to 9.0.  These
      standards apply to both existing sources and new sources.
      Plants in which kiln dust is contacted with water (leaching
      for dust reuse, slurrying for dust disposal, and wet
      scrubbing for dust collection or gas conditioning) are in
      the leaching subcategory.  By 1977 new or existing leaching
      plants must meet effluent limitations of 0.4 kg suspended
      solids per kkg of dust leached, temperature not to exceed
      3°C rise above inlet temperature, and pH within the range
      of 6.0 to 9.0.  By 1983 leaching plants must meet the same
      standards as nonleaching plants.   For all existing cement
      manufacturing plants, the runoff of rainfall which derives
      from the storage of materials, including raw materials,
      intermediate products, finished products, and waste materials,
      must meet effluent limitations of 50 mg/1 and pH within the
      range at 6.0 to 9.0 except when the flow exceeds the 10
      year, 24 hour rainfall event.

18.   Cohrs, F.W.  How the Newer Plants Handle Kiln Dust Dis-
      posal.  Rock Products.  58-59, 80-82, November 1971.
      Abstract:  An overview is given of dust collection, return
      and wasting, with results of a questionnaire sent to 30
      plants built after 1960 detailing the trend of -thinking
      about dust and the dust handling methods employed.  A
      description is given of the wet dust disposal system at
      Charlevoix, Michigan, giving the particulars of the system:
      alkali reduction in the dust, neutralization of the
      disposal (leachate) water, and suspended solids content
      of the water  (15 ppm).  Reuse of the leached and dried dust
      as a raw material for dry plants is suggested.

19.   Rygaard, O. F.  Utilization of Cement-kiln Dust.  U.S.
      Patent No. 3,206,526, September 14, 1965.
      Abstract:  Insufflation of dust as a cloud above the burner
      pipe avoids obscuring optical pyrometry measurements of flame
      and clinker.  The cloud also helps insulate the upper side
      of the kiln from radiated heat.  Further, a uniform clinker
      is produced because the dust is mixed with the clinkering
      mass before its temperature reaches the reaction point.
                                  41

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20.   Siegert, L. D. Kilns Reuse Dust the Insufflation Way.
      Rock Products.  52-54, 81, 84, February 1974.
      Abstract:  This is a discussion of methods of insufflation
      of dust and parameters affecting or affected by insuffla-
      tion, including fuel, flame emissivity, flame propagation,
      exhaust gas velocity, dust loading, particle size, position
      of insufflation pipe, and coating of refractories.

21.   Dyatlov, I. P.  Utilization of Dust Collected in
      Electrostatic Precipitators.  Tsement  (Moscow).
      28(3):18-19, 1962.
      Abstract:  The Kuvasaisk cement combine in Russia experi-
      mented with techniques for returning collected dust to
      their wet-process kiln.  With 97% collection efficiency
      in an electrostatic precipitator, the dust represented
      10 to 20% of the dry mass of kiln feed.  Adding dry dust
      to the feed slurry containing 31-35% moisture resulted in
      the formation of hard rings that interfered with the move-
      ment of the charge through the kiln.  The problem was
      solved by making a slurry of the dust with 45 to 48% water.
      The dust slurry and the normal slurry were mixed in a
      scoop slurry feeder and introduced to the kiln via a batch
      feeder.

22.   Dersnah, W. R. and C. F. Clausen.  Can That Dust be Used
      Again?  Pit and Quarry.  84-85, 88-91, September 1958.
      Abstract:  Problems associated with return of dust to
      wet-process kilns are discussed.  Methods of return
      include hydration and regrinding, leaching, insuffla-
      tion, and addition via scoops, feed pipes, vortex
      feeders, and pug mills.  Addition of molasses to inhibit
      hardening is also discussed.

23.   Goller, C.  H., Jr.  Is Dust Leaching Worthwhile?  Pit
      and Quarry, 122-123,  August 1966.
      Abstract:  The four most popular ways to produce low-
      alkali cement are:  use low-alkali raw materials, waste
      the dust, increase the amount of alkali in the dust and
      gas,  and leach alkalies from the dust to be returned to
      the kiln.  In comparison with the first three ways, the
      disadvantages of leaching are:  higher capital investment,
      lower reliability, large water consumption, and water
      pollution.
                                42

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24.    Lindsay/  G.  C.   Don't Throw Away Dust.   Rock Products.
      65:87-89, 125,  July 1962.
      Abstract:  Missouri Portland's  reprocessing  of  kiln-dust
      is described.   Plant operating  advantages  are cited:   less
      mud-ring  buildup,  more uniform  product  allowing uniform
      gypsum addition, reduction of alkali sulfate buildup  on
      electrostatic  precipitator electrodes,  and better control
      of dust addition to kiln.

25.    Quinn, E. L. and C. L. Jones.  Carbon Dioxide.   American
      Chemical  Society Monograph Series No. 72,  1936. p. 121-125.
      Abstract:  The action of carbonic acid  on  calcium compounds,
      solubility of  CaCO3 in water solutions  of  CO2,  and relation-
      ship of CO2 and pH in natural waters are explained.

26.    Wilson, J. B.  Controls Spark Waste Water Dilemma.  Rock
      Products.  75-76,  92, March 1973.
      Abstract:  The major water discharges from cement plants  are
      cooling water  and water that has been in contact with kiln
      dust containing soluble alkalies.  Leaching of  alkalies
      may occur from runoff of rainwater from waste dust piles,
      from dust-slurry disposal ponds, or from dust leaching
      facilities.  Leachate may be used to adjust the pH of sewage
      plants or acid mine drainage.  Carbonation of leachate reduces
      its pH to levels acceptable for discharge.

27.    Nishiwaki, T.   Concentration of Electrolytes Prior to
      Evaporation with an Electromembrane Process.  In:
      Industrial Processing with Membranes, Lacey, R. E., and
      S. Loeb  (ed.).  New York, Wiley-Interscience, 1972.
      p. 83-106.
      Abstract:  This book was written for engineers  who wish
      to determine whether membrane processes should be consider-
      ed for a given situation and, if so, which process should be
      used.  It also offers theoretical and practical information
      for the design and operation of membrane processing plants.
      The use of electrodialysis to recover NaCl from sea water
      is described in detail.  From an initial concentration of
      3%, the concentration of salt in the brine is raised to
      about 20% with an expenditure of about 250 KW-hr per ton of
      salt concentrated.
                                 43

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28.   Anonymous.  Potash from Cement at the Riverside Portland Cement
      Company.  Metallurgical and Chemical Engineering.  16(12):701-
      703, June 15, 1917.
      Abstract:  A process to recover 6 Ib of K2SOi* per bbl of clinker
      manufactured for each 1% K20 in the raw mixture  (theoretical
      yield) gave, in fact, 2/3 of this amount.  KF is formed when
      CaF2 is added to the raw material and the temperature reaches
      1100°C; this is above the KF boiling point and about 90%
      volatilizes.  The combustion gases convert this to K2SOi» and
      the fluoride recombines with calcium in the dust.  The dust is
      leached and the leachate is filtered and evaporated to satur-
      ation to precipitate KaSOi*.  The CaF2 in the filter cake is
      returned to the kiln feed.

29.   Singleton, F. H. and J. W. Bruce.  Improvements re-
      lating to the Treatment of Inorganic Dust.  British
      Patent No. 1,131,354, October 23, 1968.
      Abstract:  A solvent extraction method for removing alkali
      metals from cement-kiln dust as sulfates and chlorides is
      described.  The process relies on the solubilities of the
      alkali sulfates and chlorides in various chloride and
      sulfate solutions.  Batch and continuous schemes use
      compounds recovered in one step to prepare the solvent in
      the next.

30.   Patzias, T.  Extraction of Potassium Oxide From Cement Kiln
      Flue Dust.  M.S.C.E. Thesis, Wayne State University, Detroit,
      Michigan.  1959.
      Abstract:  Kiln dust is leached with hot water to increase
      solubility of alkalies.  Leached dust is suitable for return
      to the kiln.  K2SO«, is recovered from the leachate by cry-
      stallization, and the supernatant is recycled to the leach-
      ing system.

31.   Patzias, T.  Recovery of Potassium Sulfate from
      Cement-kiln  Flue Dust.  U.S. Patent 2,991,154,
      July 4, 1961.
      Abstract: Cement rotary-kiln flue dusts are leached for
      extraction and recovery of K2SOi».  For example, cement
      dust is drawn from bins under an electrostatic precipitator
      and mixed with H2O in closed tanks.   The steam pressure
      is kept at 150 Ib/sq in.  absolute, and the extraction is
      completed in 30 min.   The mixture is then filtered, and
      the solution containing 4.5% K2SOi» is evaporated to 19.4%.
      This solution is neutralized with H2SOi» and crystallized.
      The K salt is centrifuged, and the mother liquor is
      recycled to  the evaporator.  When 200 tons of flue dust
      is extracted with a water-dust ratio of 3:1, 85% of the
      K2SOU is recovered.  The K salts can be worked up for use
      in fertilizers.
                                  44

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32.    Heilmann,  T.  Treatment of  Dust from Cement Kilns.   British
      Patent No. 1,145,827,  March 19,  1969.
      Abstract:   Fractionation of dust in multistage electrostatic
      precipitators is a method  of removing  the high-alkali dust
      for use as a potash fertilizer and returning the coarse,
      low-alkali dust to the kiln.  Data on  percentages of
      potassium, sodium, sulfate and chloride vs_ particle size
      are given.

33.    Bade,  E. Method of and Apparatus for Recovering Substances
      with a High Alkali Percentage from the Flue Gases of Cement
      Kilns.  U. S. Patent No. 3,288,450, assigned to Polysius  G.
      M. B.  H.,  November 29, 1966.
      Abstract:   Large particles of dust are recovered from flue
      gases by cyclones and small particles  by an electrostatic pre-
      cipitator.  The large, low-alkali particles collected in  the
      first cyclone are returned directly to the kiln with the  feed,
      The fine precipitator dust is then added to the still hot
      flue gases where the volatile alkalies condense on the cooler
      dust particles, increasing their size  and weight.  The alkali-
      coated particles are collected in a second cyclone, and the
      cooler gas with its uncoated dust passes through the preci-
      pitator where the dust is  collected for recycle to the hot
      flue gases.

34.    Kravchenko, I. V. and I. A. Fridman.  Process of Removing
      Volatile Compounds.  Russian Patent 258,906, June 29, 1970.
      Abstract:   Volatile compounds, e.g., alkalies, are removed
      from the gaseous effluent of cement kilns by preliminary
      dedusting followed by cooling with finely dispersed water.
      The gas stream is cooled to the temperature of condensation
      of the volatile compounds — alkali sulfates 900-950°C,
      carbonates 800-850°C, etc.  The consumption of water for re-
      moving the volatile alkalies is 0.08-0.09 kg water per kg
      calcined charge.  Full-scale experiments carried out in a
      dry-process kiln produced a powder containing 70-80% alkali
      carbonates and sulfates suitable for use in fertilizer.

35.    Van Dornick, E. New Cement Process Offers many  "Pluses".
      Rock Products. 57, 89, August 1972.
      Abstract:  A heat exchanger is proposed  to preheat  incoming
      gases above  (1100°C), thus preventing condensation  of vola-
      tilized alkali within the kiln but allowing condensation and
      recovery  from the self-scouring heat exchanger  outside the
      kiln.
                                 45

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36.   Van Dornick, E. Will Kilns Give Way to Fluo-Solid Reactors?
      Rock Products.  116, 138, September 1969.
      Abstract:  The Fluo-solid reactor is compared with rotary
      kiln.  No specific data are given because of the status of
      a patent application.

37.   Pyzel, R.  Hydraulic Cement Process. U.S. Patent No. 3,013,786,
      December 19, 1961.
      Abstract:  A process is claimed for production of portland
      cement by maintaining reaction temperature in a fluidized
      bed of raw materials in contact with the burning fuel.  The
      fuel can be pulverized coal suspended in the bed, carbonaceous
      raw materials, or gas mixed with the fluidizing air stream.
      Advantages claimed include lower capital cost due to smaller
      equipment necessary, elution of volatilized alkalies away
      from reacting mass, and small clinker size.

38.   Polysius, G. M. B. H. Method of Recovering the Content of
      Alkali Metal Compounds from Alkali-Rich Dust Obtained when
      Producing Cement Clinker and Apparatus for Performing the
      Same.  British Patent No. 1,000,984, August 11, 1965.
      Abstract:  Dust collected from preheater gases at 100 to 300°C
      is leached with water.  The leachate is evaporated in a heat
      exchanger and dried in a thin film evaporator.  Heat for
      evaporation comes from steam generated by exhaust gases from
      the clinker cooler.  Evaporation is carried out under partial
      vacuum.

39.   Deynat, G. Device for Continuous Extraction of Alkalies from
      the Escape Gases of a Cement Kiln.  U.S. Patent 3,503,187,
      March 31, 1970.
      Abstract:  An array of endless chains is exposed to the
      exhaust gases of a cement kiln, and alkali metal compounds
      condense on the cool chains.  The chains coated with alka-
      lies are revolved out of the gas stream, and the alkalies
      collected thereon are removed by immersion in a tank of water
      which dissolves the compounds and cools the chain.

40.   Schlauch, R. G. Method for the Production of Hydraulic Cement.
      U.S. Patent No. 3,043,703, July 10, 1962.
      Abstract:  A means of condensing alkali vapors on cooled
      tubes and recovering the alkalies is described.  Alkalies
      in the gases emanating from the reaction zone of a cement
      kiln condense as a solid on tubes cooled with air or water.
      The condensed alkalies are scraped from the surfaces of the
      tubes and collected in a bin.
                                 46

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41.   Nordquist, E.  A.  and G.  A.  Heian.   Alkali Removal via the
      Grate-kiln System.   Rock Products  7th International Cement
      Industry Seminar.  17-27, 1971.
      Abstract:  Portions of kiln exhaust gases are cooled to 230°C
      to solidify gaseous alkalies.   Then the warm gases are used to
      dry the pelletized  feed.  Alkalies in the clinker and recir-
      culating in the kiln are reduced.   Various configurations of
      the traveling-grate preheater  kiln with and without by-
      pass and cooling of portions of gas stream are described.

42.   Weber, P.  Alkali Problems and Alkali Elimination
      in Heat-Economizing Dry-Process Kilns.  Zement-
      Kalk-Gips (Wiesbaden, Germany).   17:335-44, August
      1964.
      Abstract:  Investigation of alkali conditions in
      11 Lepol kilns and  7 suspension-preheater kilns
      showed that suspension preheaters  allow very little
      alkali (3 to 19%) to escape from the kiln system
      into the dust collectors or the atmosphere.  Lepol
      kilns allow more alkali  (34 to 100%) to escape so
      that alkali content of the clinker is lower.  Mater-
      ial balance is used to develop an  alkali cycle
      factor that is a function of the volatility and
      content of raw material alkalies and the amount
      of residual alkali  in the clinker.

43.   Brachthauser,  K.  Process for Producing Substantially Alkali-
      free Kiln Output when Burning  Minerals Containing Difficult-
      to-volatilize Alkali.  U.S. Patent 3,365,521, January 23, 1968,
      Abstract:  A process is described for converting alkalies
      to the more volatile hydroxide form by reaction with vaporized
      water in the kiln.

44.   Kiyonaga, K. and P. Wrampe.  Method and Apparatus for Pro-
      ducing Cement Clinker.  U. S.  Patent No. 3,584,848,
      June 15, 1971.
      Abstract:  Cement-forming raw materials are introduced into
      a swirling stream of hot gas in a cylindrical reaction
      zone where the raw materials react to form clinkers and
      where the gas stream holds the clinker particles in sus-
      pension until the particles grow heavy enough to drop to
      the lower portion of the reaction zone.  Apparatus suitable
      for carrying out the process is also described.

45.   Wolfe, J. M. Kiln Dust - Properties and Handling.  Pit
      and Quarry.  136-7, 140-2, 145, March 1964.
      Abstract:  Kiln dust is difficult to handle because of its
      fineness, excessive heat, aeration, stickiness, lumpiness,
      and alkali content.  Flow sheets are presented for a variety
      of methods for discarding dust or returning it to the kiln.
                                 47

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46.   Trembly, F. J.,  J. A. Mihursky, and E. W. Hertz.  Use of
      Cement Plant Stack Dust as a Neutralizing Agent in Acid
      Water Lakes.  Trans. Northeast Wildlife Conf.  1:55-60,
      1958.
      Abstract:  Cement dust, applied at 40 tons per acre, suc-
      cessfully killed off the acidophilic vegetation in a bog
      that was to become the bottom of a new lake.  A study was
      begun in 1958 on long term cement kiln dust neutralization
      of some acidic lakes and ponds in Pennsylvania.

47.   Farnham, W. Process of Clarifying Turbid Water Using
      Cottrell Flour and Acidifying Coagulant.  U.S. Patent 2,964,466,
      December 13, 1960.
      Abstract:  Kiln-dust from the Oswego plant of Oregon Port-
      land Cement, used as a partial of total replacement for lime as
      a co-coagulant with alum, improved floe formation so that
      three test waters were substantially clearer than when
      treated with alum and lime.  The dust successfully neu-
      tralized the water to the required range of pH 6.1 to 6.9
      and apparantly provided floe nucleation sites by virtue of
      the very small insoluble particles in the dust.

48.   Gorman, P. G.  Cement Dust as an Absorbent for S02 Removal
      from Stack Gases.  Master of Science in Engineering Thesis-
      Graduate School of University of Missouri.  1972.
      Abstract:  Cement dust was compared with lime and crushed lime-
      stone as a sorbent for S02 from stack gases in a wet scrubber
      slurry.  The dust was found to be better than limestone and
      almost as good as lime for sorption of S02 and even better
      than lime when scaling problems are considered.

49.   Emer, P.  Formation of Foam on the Surface of Molten Glass
      Baths.  Glastech. Ber. (Frankfurt, Germany).  42:30, June 1969.
      Abstract:  Kiln dust can serve as a partial replacement for
      the soda used in glass making.  Decomposition of sulfate in
      the melt is responsible for foaming problems, and the potassium
      in cement kiln dust accelerates the decomposition, allowing
      more rapid degassing.

50.   C. W. Whittaker, C. J. Erickson, K. S. Love, and D. M. Carroll.
      Liming Qualities of Three Cement Kiln Flue Dusts and a Lime-
      stone in a Greenhouse Comparison.  Agronomy Journal.
      51:280-2, 1959.
      Abstract:  Three cement kiln flue dusts had about the same
      soil liming qualities as pulverized limestone.  In cultures
      all receiving the same total amount of soluble potash, the
      dusts produced alfalfa yields on initially acid soils equal
      to or exceeding those produced by the limestone and had
      similar effects on soil pH, potassium and calcium contents
      of the crop, and on crop reduction through overliming.
                                  48

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51.   Carroll, D.  M.,  C.  J.  Erickson,  and C.  W.  Whittaker.   Agronony
      Journal.  56:373-76,  1964.
      Abstract:  Researchers in Beltsville, Md.  evaluated kiln
      dust from 21 cement plants  as a  substitute for agricultural
      lime and found that it had  about 80% of the soil neutrali-
      zation power of lime.   Kiln dust was found to be superior
      to crushed limestone for some applications.

52.   Bambergs, K. and R. Apenite.   Cement Dust  as a Lime
      Fertilizer.   Tr. Latv. Sel'skokhoz. Akad.  (Latvia).
      18:151-63, 1967.
      Abstract:  Cement dust containing 42-47% CaO (of which
      44-59% was CaCO3, the  rest  Ca silicates),  2.57-2.64%
      MgO and 1.3% available K20  was rotary-hoed into acidic
      soils in the month of  May.   It was applied at 2-10
      tons/ha, and supplemented with lime.  If soil with
      pH above 4.5 was used  for neutral-soil  plants,  e.g_.,  sugar-
      beets or corn,  cement  dust  could fully  replace lime,
      but for plants growing in slightly more acidic soils,
      e.g., potatoes or rye, cement dust addition could
      be  50-60% of total lime.

53.   Simakin, A.  I.  Agrochemical Properties  of  Slime Dust
      of Cement Plants.  Vestn. Sel'skokhoz.  Nauk. Ves.
      Akad. Sel'skokhoz.  Nauk (Budapest). 8 (5):62-4,  1963.
      Abstract:  Slime dust  of cement  plants  proved useful
      as a fertilizer on acidic soils.  A typical composition
      on air-dry basis is N  0.2,  P205  0.1, and K20 15.4%.
      Trace elements include Mg 1,  Mn  0.03,  Pb 0.03-0.1,
      Ag 0.001, Ba 0.01-0.03, Be  0.001, Cr 0.003, Ti 0.1-0.3,
      V 0.003, Zr 0.001 and  Sr 0.1%.  It also had insecticidal
      properties.

54.   Kobeleva, E. N., N. N. Popova, and L. G. Shvetsova, Cement
      Dust - A Valuable Potassium Fertilizer for Potatoes.  Trudy
      Sverdlovsk. Sel'skokhoz. Inst.  (Sverdlovsk, USSR).
      15:59-68, 1969.
      Abstract:  Cheap potassium fertilizer usually contains an
      appreciable amount of chloride which can markedly  interfere
      with the development  and yield of potatoes, and better grades
      are too expensive  for use on potatoes.  The high-alkali  fraction
      of cement dust, which has essentially no chloride, was found
      to be an inexpensive  and acceptable substitute fertilizer.
                                   49

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55.   Rogalev, I. E.  Improved Forms of Potassium-Ceinent Dust
      and its Effect on Potato, Peas, Flax, and some other
      Crop Yields.  Agrokhimiya (Moscow).  56-9, January, 1966
      Abstract:  Three forms of K-cement dust
      were used to fertilize a heavy loam podzol
      soil growing potatoes, peas, and flax and a light
      sandy soil growing corn.  The content of K2O in
      the three K-cement dusts were 34.9%  (in the sulfate
      form), 40.3%  (in the carbonate and sulfate forms),
      and 41.0%  (in a reduced-carbonate and sulfate forms),
      respectively.  It was established that these forms
      of dusts had no greater effect on yield than ordin-
      ary mineral fertilizers.  In their effect on the
      quality of the crops, these K-cement dusts have
      proven to be superior to KC1.  As a result of dust
      applications, the content of starch in the potato
      tubers increased 1.3-1.6% compared to results ob-
      tained from an application of KC1.  The same differ-
      ences were found for peas (an increase in weight of
      grains) and flax (an increase in fiber and straw).
      The intensity of absorption of K in the growth phase
      from the K-cement dust does not substantially differ
      from that obtained by the application of ordinary
      mineral K fertilizers.

56.   Litynski, T., K. Mazur, and A. Siekanski.  Fer-
      tilization of Potato Fields with Cement-kiln Dust.
      Zesz. Nauk. Wyzszej Szkoly Rolniczej, Krakow,
      Rolnictwo  (Warsaw,  Poland) 5:85-95, 1958.
      Abstract:  Crops of potatoes exactly similar in
      quantitative respects were obtained by using cement-
      kiln dust or 40% K salts as a K fertilizer.  Starch
      content in potato tubers was higher in the case of
      cement-kiln dust.  The favorable effect on starch
      content is probably due to K being present in the
      sulfate form.  Sulfate ions, unlike chloride ions,
      have a contracting effect on the colloids of the plasma;
      this causes a rise in starch content of potatoes.

57.   Litynski, T., and K. Gorlach.  Fertilizing Value of
      Cement Plant Flue Dust Dependent on Soil Reaction.
      Roczniki Nauk Ronlniczych, Ser. A. (Warsaw, Poland).
      90 (1):113-30, 1965.
      Abstract:  Two problems were investigated:   (1) whether
      and to what extent the presence of Ca in cement plant
      flue dust influences its K fertilizing properties, and
      (2) to what extent the fertilizing value of the flue
                               50

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      dust changes in relation to the pH value of the soil.
      The experiments were carried out under strictly con-
      tolled conditions by a pot culture of sunflower/  oats,
      white mustard,  and buckwheat.   It has been ascertained
      that Ca present in cement plant flue dust favorably
      influences the  uptake of K from it, and at the same time
      it creates more favorable conditions for plant develop-
      ment by reducing the soil acidity.  On acidic soils the
      fertilizing value of flue dust vastly exceeds that of the
      40% K salt fertilizer.  If however, the pH of the soil
      is raised by liming, the uptake of K from the flue dust
      remains practically unchanged while the uptake of K from
      the K salt fertilizer increases.  The reason for this
      phenomenon may  be attributed to different solubility of K
      in both types of fertilizer and (or) to the antagonism
      between Ca and  K.  In general, the raising of the soil
      pH by liming increases the availability of K in it.

58.   Hudig, J., and  J. P. Planje.  The Cement Dust of the Cement
      Industry as Fertilizer.  Landbouwkund. Tijdschr.    (Wageningen,
      Netherlands).  48:593-624, 1936.
      Abstract:  Comparative yields of oats fertilized with  cement
      dust, CaCOa, R^SOi, and K2CO3 separately and in various  com-
      binations are given.  The cement dust contained about  4% K
      in one case and 10% in another.  The content of Ca in  the
      form of silicate and carbonate was about 40%.  Both Products
      had about the same effect as combinations of limestone  and
      K2SOi».  The cement dust does not add superfluos mate-
      rial to the soil, as most artificial fertilizers do.  The
      authors consider the application of this material as an
      advantage in cases where K- and Ca- poor soils are to  be
      brought back to profitable production.

59.   Litynski, T. Cement-kiln Dusts and their Value for Agri-
      culture.  Zesz. Nuak. Wyzszej Szkoly Rolniczej. Krakow,
      Rolnictwo  (Wroclaw, Poland). 4:3-27, 1958.
      Abstract:  Cement-kiln dusts from rotary kilns in the
      production of portland cement may be an important source
      of K for plants.  The dusts contain approximately 9% K2O
      (70% soluble in HjO, the rest soluble in 2% citric acid)
      and can be enriched by adding aluminosilicates to the crude
      mixture.  K in  these dusts occurs as K2SCK, which by some
      plants is preferred to KC1.  The important other compo-
      nents of the dust are sulfates, CaCOj, and colloidal silica.
      Thus, the dust  is a low-percentage K-Ca fertilizer good
      for acid soils  with weak structure.  Pot and field experi-
      ments showed it equal to, or better than, KC1  and  40% K
      salts as a source of K.  Mixed peas-and-oats crops con-
                                 51

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      tained more proteins  (about 2% more than crops grown on the
      latter mixture).  The cement dust increased especially the
      content of starch in potato tubers.  It was a good K fer-
      tilizer for meadows, where in two experiments protein
      synthesis was enhanced.

60.   Litynski, T. Flue Dusts from Cement Rotary Kilns as
      Chemical Fertilizers.  Przemysl Chem.  (Warsaw, Poland).
      40:260-2, 1961.
      Abstract:  The potential use of flue dust from cement
      rotary kilns containing SiO2, A1203, CaO, and KjO was
      investigated in Poland.  Potassium compounds in dusts
      are partly soluble in H2O and about 80% soluble in 2%
      citric acid.  Field and pot tests showed good fertilizing
      properties for clinker dusts which contained SiO2 24.16,
      CaO 19.94, and K20 13.36%.  Fertilizing action of this dust
      compared favorably with that of equivalent quantities of
      40% H2O-soluble standard K fertilizer.  It produced more
      proteins in fodder, starch in potatoes, and sugar in sugar
      beet roots.  Cement dust can be used as chemical ferti-
      lizer, preferably in a granulated form as a low grade K
      fertilizer.

61.   Hargett, N. L. 1972 Fertilizer Summary Data.  National Fer-
      tilizer Development Center, Tennessee Valley Authority,
      Muscle Shoals, Alabama.  1972.
      Abstract:  Agricultural materials (limestone, potash, etc) are
      listed by region and State with consumption from 1950
      through 1971.

62.   Anonymous.  Commodity Data Summaries.  Bureau of Mines,
      Department of Interior.  January 1974.
      Abstract:  Data on production, consumption, and value and
      forecasts for 95 minerals, metals, and fuels, including
      cement, lime, potash, phosphate rock and nitrogen compounds.

63.   Lodge, F. S.  Potash in the Fertilizer Industry.  Ind Eng
      Chem,  30:878-882, August 1938.
      Abstract:  Sources of potash that have been used in the manu-
      facture of fertilizer are described.

64.   Rouse, R. D. Potassium Requirements of Crops on Alabama Soils.
      Bulletin 324, Agricultural Research Station, Auburn Univer-
      sity,  March 1960.
      Abstract:  An analysis of 50,000 Alabama soil samples shows
      that 75% need a fertilizer with equal amounts of P and K and
      18% need more K than P.  Sources of K are listed and crop
      requirments of and response to K are discussed.
                                 52

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65.    Anonymous.   Potassium for Agriculture.   American Potash Institute,
      Revised January 1965.
      Abstract:   History of potassium in agriculture,  function in
      plants and animals, and relationship to other nutrients are
      given as introduction.   Description of  various potassium
      fertilizer materials,  production methods,  application methods,
      and crop responses to potassium are given.

66.    Alabama Legislature (Young and Smith),  Alabama Fertilizer Law
      of 1969.  Act 434, Regular Session, 1969.
      Abstract:   This act of the Alabama Legislature sets forth the
      regulations applicable to the manufacture  and sale of ferti-
      lizer, fertilizer materials,  and other  plant food and soil
      conditioning materials.  The  regulations follow the recommen-
      dations of the Association of American  Plant Food Control
      Officials.

67.    Association of American Plant Food Control Officials.
      Official Publication No.27  Lafayette,  Indiana, 1974.
      p. 37.
      Abstract:   Officially adopted documents of the Association
      included in the Uniform State Fertilizer Bill are; Rules
      and Regulations, Statement of Uniform Interpretation and
      Policy, Official Fertilizer Terms, and Definitions of
      Fertilizer Materials.  Definition C-13 reads in part,
      "Waste lime, by-product lime is any industrial waste or
      by-product containing calcium or calcium and magnesium
      in forms that will neutralize acids."

68.    Dymshits, R. A., N. N. Tikhomirova, E.  Ya. Gryazina,
      E. N. Ostapenko, and L. V. Nelidova.  Granular Fertilizers
      from Cement Dust.  Russian Patent 220,  277, June 28, 1968.
      Abstract:  Granular fertilizers are prepared from cement
      dust with a high K2CO3 content by rolling the dust with
      an additive of water or a solution of this dust.  To pre-
      pare non-hygroscopic, mechanically strong granules, the
      granules are treated with C02 or gases containing C02.

69.    Nudel'man, B. I.,  S. Tokhtakhodzhaev, and M. N.
      Nabiev.  Preparation of Quality Standardized
      Potassium Fertilizers During the Production of
      a Portland Cement  Clinker by Means of Chlorina-
      tion Roasting.  Dokl. Akad. Nauk. Uzb. SSR  (Tash-
      kent, 24(10):30-1, 1967.
      Abstract:  K from  the cement kiln charge can be
      almost  fully recovered in the dust collected by
      electrostatic precipitators when 0.61-1% of
      NaCl or CaCl2 is added to the charge.  K, present
      in various compounds and minerals, is converted
                                   53

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      into KC1 by their interaction with the added Cl
      and sublimed off.  The K20 content of the flue
      dust of the Kuvasai and Dushanbe plants is thus
      increased from 6.0 and 7.1 to 13.81 and 20.72%,
      respectively.  The dust can be used efficiently
      as K20- and CaO-bearing raw material by the local
      fertilizer industry.

70.    Tokhtakhodzhaev, S. T., M. N. Nabiev, and B. I. Nudel'man,
      Process For Munufacturing Fertilizer.  Russian Patent No.
      176,595, November 17, 1965.
      Abstract:  The familiar process for manufacturing fertilizer
      from cement dust consists of recovering the dust obtained
      from calcining the cement slurry, mixing it with water and
      neutralizing the alkaline content with phosphoric acid in
      a mixture of mineral acids.  With the goal of manufacturing
      a fertilizer with a high content of soluble potassium salts,
      NaCl is added to the cement slurry before it is calcined.
      The cement dust is recovered in an electrostatic precipitator
      and mixed with water.  The solution obtained is freed from
      insoluble particles and is mixed with a nitric acid-
      phosphate extract.  The solution may be applied as a liquid
      ternary N-P-K fertilizer or converted to a solid fertilizer.

71.    Anonymous, Potassium Phosphate Fertilizer Use Expands.  Chem.
      Eng. News.  17-18, September 10, 1973.
      Abstract:  Pennzoil's plant in Hanford, Calif, is doubling
      its production of ?20s to 60 tons/day with plans to produce
      a 0-50-40 fertilizer by next year.  Rising production costs
      have stimulated the replacement or augmentation of organic
      and nitrogen fertilizers with potassium-phosphorus fertilizers,
      Some production costs and material values are given.
                                 54

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                              TECHNICAL REPORT DATA
                        (Please read Instructions on the reverse before completing)
 REPORT NO.
    EPA-670/2-75-043
                                                   3. RECIPIENT'S ACCESSIOf*INO.
4. TITLE AND SUBTITLE

DISPOSAL AND UTILIZATION OF WASTE KILN DUST
FROM CEMENT INDUSTRY
                                                   5. REPORT DATE
            May 1975;  Issuing Date
           6. PERFORMING ORGANIZATION CODE
 . AUTHOR(S)

 Thomas A. Davis  and Don B. Hooks
                                                   8. PERFORMING ORGANIZATION REPORT NO.
                                                    SORI-EAS-74-237
I. PERFORMING ORGANIZATION NAME AND ADDRESS

Southern Research Institute
2000 9th Avenue,  South
Birmingham, Alabama  35205
           10. PROGRAM ELEMENT NO.

            1BB036; ROAP 21BET; Task 11
           11. CONTRACT/GRANT NO.
            R-801872
12. SPONSORING AGENCY NAME AND ADDRESS
National Environmental Research Center
Office of Research and Development
U.S.  Environmental Protection  Agency
Cincinnati, Ohio  45268
           13. TYPE OF REPORT AND PERIOD COVERED
            Final
           14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
 A survey that  included 60%  of the cement-manufacturing plants in  the
 United States  was made to determine the  fate of dust  collected from the
 gases emanating from cement kilns.  Because of high alkali content,
 large quantities of the dust cannot be returned to the cement-making
 process.  A  survey was made of the literature in the  United States  and
 Europe pertaining to handling, reclaiming,  and utilizing the collected
 dust.  Abstracts of 71 references are included in the Appendix.   Acid
 neutralization capacity and potash content  make the dust valuable for
 application  to farmland, and the potential  market for agricultural  use
 alone could  consume all of  the waste dust that is now being discarded.
 7.
                           KEY WORDS AND DOCUMENT ANALYSIS
               DESCRIPTORS
                                        b.lDENTIFIERS/OPEN ENDED TERMS
                       c. COSATI Field/Group
 *Portland  cements
 *Dust control
  Alkali aggregate reactions
  Fertilizers
  Potassium inorganic compounds
                             13B
18. DISTRIBUTION STATEMENT
  RELEASE  TO PUBLIC
19. SECURITY CLASS (This Report)
    UNCLASSIFIED
                                                               21. NO. OF PAGES
                                                                     63
20. SECURITY CLASS (This page)
    UNCLASSIFIED
                                                               22. PRICE
EPA Form 2220-1 (9-73)
                                      55
                                            U.S. GOVERNMENT PRINTING OfFICE: 1975-657-593/5375 Region No. 5-11

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