EPA-600/2-76-301
December 1976
Environmental Protection Technology Series
AN ASSESSMENT OF TECHNOLOGY FOR POSSIBLE
UTILIZATION OF BAYER PROCESS MUDS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
- 2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-76-301
December 1976
AN ASSESSMENT OF TECHNOLOGY FOR POSSIBLE
UTILIZATION OF BAYER PROCESS MUDS
by
B. K. Parekh and W. M. Goldberger
Battelle
Columbus Laboratories
Columbus, Ohio 43201
Grant No. R-803760-01
Project Officer
Donald L. Wilson
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Re-
search Laboratory, U.S. Environmental Protection Agency, and approved
for 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 en-
dorsement or recommendation for use.
ll
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FOREWORD
When energy and material resources are extracted, processed, con-
verted, and used, the related pollutional impacts on our environment and
even on our health often require that new and increasingly more efficient
pollution control methods be used. The Industrial Environmental Research
Laboratory - Cincinnati (lERL-Ci) assists in developing and demonstrating
new and improved methodologies that will meet these needs both efficiently
and economically.
This report reviews the technology in use in the United States for
production of alumina from bauxite. The purpose of the study was to assess
the possibility for utilization of the rnud wastes generated by the domestic
alumina industry. Included in the study is a review of the published litera-
ture (1940-1975) on bauxite processing technology, waste mud dewatering,
and the utilization of Bayer process muds.
This report will be of interest to alumina producers and to those in-
dividuals involved in dewatering studies of slimes and tailings produced in
the minerals processing industry.
Further information on the subject could be obtained from the Indus-
trial Environmental Research Laboratory, Office of Research and Develop-
ment, U. S. Environmental Protection Agency, Cincinnati, Ohio.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
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ABSTRACT
This report concerns a study of the possible utilization of the mud
wastes generated in the domestic production of alumina from bauxite ores.
The -work was done by Battelle's Columbus Laboratories for the United
States Environmental Protection Agency under EPA Research Grant No.
R 803760-01.
The program comprised review of technical literature published from
1940 to the present on subjects related to technology of processing bauxite,
and studies on dewatering and impoundment of the mud residues and their
possible utilization. Visits were made to six alumina plants in the United
States to observe operations and to discuss mud-handling methods and the
possibilities for utilization. Mud samples were received from the alumina
plants visited for characterization experiments and dewatering studies at
Battelle and at the laboratories of the Dow Chemical Company in Midland,
Michigan. The Dow study was conducted under a subcontract from Battelle.
A workshop was held at Battelle on March 30-31, 1976, attended by repre-
sentatives from four domestic aluminum producers. Comments offered by
the workshop attendees are, in part, incorporated in this report.
It was concluded from the study that there is no possibility for utiliza-
tion of the muds that could significantly affect the need for impoundment
within the near term. However, it appears possible to develop improved mud
dewatering and methods of impoundment, and a program of joint industry-
government demonstration and pilot projects is recommended. In addition,
a basic research program to study the mineral surface chemistry controlling
the mechanism of dewatering is recommended. Investigations of the possible
beneficiation of the muds into a raw-material supplement in iron making and
the possible use of mud as an absorbent in pollution-abatement processes are
also recommended.
IV
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CONTENTS
Foreword iii
Abstract iv
Figures vii
Tables viii
Acknowledgements ix
Section I Introduction 1
Purpose 1
Authority 1
Scope 1
Section II Conclusions 3
Section III Recommendations 7
Industry Government Demonstration
and Pilot Projects 7
Basic Research on Physical-Chemical
Mechanisms of Red Mud Dewatering 8
Red-Mud Utilization 8
Section IV Technical Background 10
General 10
The Domestic Alumina Industry 11
Bauxite 13
Process Technology 13
The Bayer Process 13
The Combination Process 17
Mud Disposal 17
Plant Trips 22
Section V Literature Review 24
General 24
Bauxite Refining 27
Bayer Process Technology 27
Lime-Soda Sinter Process Technology 28
Alumina From Low-Grade Bauxite 29
Bauxite Beneficiation 30
Pedersen Process 30
Red-Mud Dewatering 30
Flocculation 31
Centrifugal Dewater 32
Filtration 32
Utilization of Red Mud 33
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CONTENTS (Continued)
Metallurgical 33
Ceramic 35
Waste Treatment 41
Section VI Experimental Program 43
Characterization of Mud Samples ;. 44
Composition . 44
Particle Size Distribution . . . . . .... . . 44
Specific Gravity 47
Dewatering Studies 47
Sedimentation Experiments 47
Effect of Synthetic (Polymer) Flocculants 58
Magnetic Flocculation 61
Flotation 61
Centrifuging 61
Reductive Roasting of Bauxite as an Alternative to
^Conventional Bayer Processing 65
Section VII Literature Cited , . . . 71
Section VEI Glossary 84
Appendixes A: Literature References by Category ... 89
Bauxite Refining 89
Red Mud Dewatering 108
Red Mud Utilization 115
Nonmetallurgical 127
Effluent Treatment 136
Appendix B: Workshop Sessions 140
VI
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FIGURES
Number
1 Generalized flow diagram of the Bayer Process. 16
2 Generalized flow diagram of the Combination Process. 18
3 Mud lake dike construction. 20
4 Construction of red-mud lake based on gravity
drainage system. 21
5 Distribution of literature in English and non-English
languages from the year 1940 to 1975. 26
6 Particle size distribution of various muds 49
7 Particle size distribution of Alcoa - Point Comfort,
Texas, red mud using Coulter-counter and Andreason
pipette methods 50
8 Generalized settling rate curve 52
9 Settling rate curves for various muds (as received) 54
10 Laboratory evaluation of efficiency of coagulation
the jar test 59
11 Effect of dilution on settling rate behavior of Jamacian
Red Mud 60
12 Effect of various synthetic flocculants on filtrability
of diluted (10 x) Jamaican Red Mud 62
13 Effect of various synthetic flocculants on filtrability of
diluted (10 x) Jamaican Rud Mud 63
14 Settling rate curves for the reductive roasting of
bauxite process mud (9. 7% solids) and the Jamaican
Red Mud (11% solids) slimes (no flocculant added) 70
Vll
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TABLES
Number Page
1 List of Domestic Bauxite Refining Plants 12
2 Characteristic Analyses of Various Bauxites 14
3 Publications Pertaining to Bauxite Processing
Technology - By Category 25
4 Classification of Literature by Subject on
Metallurgical Uses for Red Mud 33
5 Classification of Literature on Red-Mud Utilization
By Country (Mstallurgical) 34
6 Classification of Literature By Subject on Ceramic
Uses for Red Mud 37
7 Classification of Literature on Red-Mud Utilization
By Country (Ceramic) 38
8 Raw Materials in Portland Cement 38
9 Classification of Literature on Waste-Treatment
Applications of Red Mud 41
10 Classification of Literature on Waste-Treatment
Applications of Red Mud by Country 42
11 Initial Characterization of Mud Samples 44
12 Chemical Analysis of Mud Samples 45
13 Optical Emission Spectrographic Analyses of
Mud Samples 46
14 Particle-Size-Distribution Data for Various Muds 48
15 Specific Gravity of Mud Samples 52
16 Settling-Rate Data For Various Muds (As Received) 55
17 Effect of pH and Metal Ions on Settling Rate of
Jamaican Red Mud 57
18 Synthetic Flocculant Selected for Evaluation 64
19 Settling Rate Data for Undiluted Jamaican Red Mud
Using Different Polymer Flocculants 64
20 Centrifuge Test Data of Jamaican Red Mud 65
21 Chemical Analyses of Products Obtained By the
Reductive Roasting of Bauxite (Experiment 1) 68
22 Chemical Analyses of Products Obtained by the
Reductive Roasting of Bauxite (Experiment 2) 68
23 Metallurgical Weight Balance for Iron and A12O3
Obtained in Reductive Roasting of Bauxite 69
24 Settling Rate Tests Data for the Reductive Roasting
Product Mud and the Jamaican Red Mud 70
B-l Program of the Workshop 141
B-2 List of the Workshop Attendees 142
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ACKNOWLEDGMENT
The technology and processing of bauxite for alumina recovery is well
established through more than 75 years of commercial operation in the
United States and throughout the world. Within the limitations of a review
study, it is not possible to assess fully the interrelationships and constraints
relating to the mud disposal problem. The opportunity to visit plant opera-
tions and to discuss the study with representatives of Kaiser Aluminum and
Chemical, Alcoa, Reynolds, and Martin-Marietta is therefore gratefully
acknowledged. Special thanks are extended to Dr. R. M. Hansen, Kaiser,
Mr. T. Galloway, Reynolds, Messrs. R. Carwile, R. Frye, and R.
Newsome of Alcoa, and Mr. J. Bou, Martin-Marietta, for time spent at the
plant and for providing samples for study.
The collaboration of the Dow Chemical Company in the experimental
part and the work of Dr. Stacy L. Daniels of Dow are also acknowledged.
The research grant support provided by the Environmental Protection
Agency and the interest by individuals of that agency in the Battelle program
are also gratefully acknowledged.
IX
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SECTION I
INTRODUCTION
The major process waste in production of alumina is the leach residue
from the caustic digestion of bauxite. This waste mud is impounded to pre-
vent the contamination of surface waters. In the United States approximately
ten-million tons of mud waste is generated annually. This mud is impounded
in lakes built adjacent to the refineries; mud impoundments commits land
areas in the range of 2000 to 3000 acres (810 to 1215 hectares). Mud impound-
ment is not an ideal solution to the disposal problem. The dikes of mud lakes
must be maintained, and there is always risk of a break and spill of the mud
into a nearby stream or waterway. There has been little economic opportunity
to date to utilize the mud.
PURPOSE
This study was made to determine whether technology is available that
could make possible the economic utilization of alumina-process red- and
brown-mud wastes to an extent that would eliminate the need for impoundment.
AUTHORITY
This program was initiated on June 1, 1975, by Battelle's Columbus
Laboratories under U.S. Environmental Protection Agency Grant No.
R-803760-01.
SCOPE
The study comprised a review of technical literature published world-
wide on subjects related to technology of processing bauxite, and studies on
the dewatering and utilization of red and brown muds produced during the
processing. The literature review covered the period 1940 to present. Vis-
its were made by Battelle staff to six alumina production sites to observe
operations and the methods used in current disposal of the mud wastes.
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Selected experiments were done to characterize red- and brown-mud
samples received by Battelle from five of the six alumina plants visited.
Emphasis in this experimental work was on study of the red mud derived
from Jamaican bauxite because this type of mud is more difficult to dewater
and presents a greater disposal problem. Laboratory studies on the use and
effect of synthetic polymer flocculants to promote the settling and dewatering
of the mud were made by the Dow Chemical Company under a subcontract to
Battelle.
The results of the program were reviewed by Battelle with representa-
tives of EPA and the alumina-producing industry during a workshop conference
sponsored by the EPA and held at Battelle on March 30-31, 1976.
This report discusses the general background of the red-mud problem
and reviews the reported research on the subject. Experimental results ob-
tained in this program are included with Battelle's conclusions and recom-
mendations for research to alleviate and ultimately to possibly eliminate the
need for mud impoundment.
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SECTION II
CONCLUSIONS
On the basis of this review, Battelle has reached the following general
conclusions:
(1) Despite extensive studies made worldwide to develop means
to utilize Bayer Process muds, no technology has been de-
veloped that would enable economic processing of the muds
into products having sufficient existing markets to reduce
the present need for impoundment of the muds generated in
current domestic alumina-production operations.
(2) Virtually all potential commercial uses of the muds require
that the muds be dewatered to the extent that the solids can
be transported and/or stored in consolidated dry form with-
out tendency to leach or repulp. Low-cost dewatering of the
muds is therefore considered the key to their possible future
utilization.
The present cost of mud impoundment ranges from $0. 50 to
perhaps as high as $4.00 per ton of dry solids, depending on
factors such as land cost, distance of the impoundment area
from plant, availability of sand and other aggregate for dike
construction, rainfall, evaporation conditions, and the char-
acteristics of the mud. Costs for future impoundment by
present methods are projected to increase. It was therefore
concluded that methods enabling muds to be dewatered to the
conditions cited at a cost less than about $5. 00 per ton of
dried solids would be of interest to the industry. However,
no process technology is reported to be available to do this.
(3) The chemical and physical characteristics of the Bayer
Process muds, i.e., composition, particle size, and min-
eralogy, differ with the origin of the bauxite ore. Variations
in settling and dewatering characteristics of red muds relate
to these differences in the bauxite ores. Chemical factors
such as pH and presence of metal ions appear to have little
effect on the settling rate and ultimate settled density. Use
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of flocculants can increase settling rate but offer little promise
to increase ultimate settled density beyond that now achieved
in mud lakes. It was therefore concluded that from the stand-
point of mud disposal, little change in dewatering properties
and the requirement for impoundment can be effected by changes
in the conditions of operation of the Bayer Process.
(4) Chemical treatment in combination with mechanical dewatering
was not found to result in a higher degree of dewatering of red
mud. No improvement in ultimate solids content was achieved
in tests made using magnetic flocculation, or using flocculants
or coagulants in combination with centrifugation. Additional
research of this type is not warranted.
(5) The physical characteristics of Bayer Process red muds may
be substantially altered by energy-intensive processing such as
kiln treatment, as in the case of the Combination Process used
to process Arkansas bauxites. So called "brown muds" gener-
ated by the Combination Process are sintered materials of
coarser particle size which settle and dewater more readily
than the red muds of the more conventional Bayer Process.
(6) The addition of energy-intensive process steps to the present
Bayer Process, for example, an initial reductive roasting of
the bauxite, may alter its physical character and that of the
mud residues in a manner analogous to the changes brought
about by the Combination Process, and possibly lead to im-
proved dewatering and a possible basis for increased recovery
of metal values. However, in-plant modification of this type
would probably require very substantial addition of new process
equipment and major changes in present Bayer Process opera-
tions. It was concluded that relative to red-mud disposal,
process-development effort that would entail substantial change
in the Bayer Process flowsheet is not warranted.
(7) Installation of bottom drainage in newly constructed mud lakes
appears to offer improved rates of dewatering and the oppor-
tunity to achieve high-density, stable mud solids, particularly
in geographic regions with a net accumulation of rainfall. Mud
lakes constructed with a bottom drainage system may develop
greater permeability and a higher degree of leaching of solubles
from inactive or dried mud lakes. The incorporation of bottom
drainage may therefore improve the ability to grow vegetative
cover on old mud-impoundment areas. Bottom drainage may
also lead to improved ability to harvest dry mud which could be
more economically utilized. Additional study of bottom drainage
4
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systems and their construction, drainage and effluents, cost
factors, and maintenance characteristics is warranted.
Conclusions reached by Battelle related to specific areas for possible
utilization of the muds are these:
(8) Metallurgical Uses - Past interest in red mud for metallurgi-
cal purposes has been mainly as a possible source of iron for
iron and steel manufacture. The production of iron from muds
represents one possible use that could consume the total tonnage
of mud generated by the domestic alumina industry. The muds
as generated represent unacceptable material for ironmaking
by conventional blast furnace or direct reduction methods. To
be useful as a source of iron, the muds require processing to
concentrate the iron to 55-60 percent and to substantially elimi-
nate alumina, titania, phosphorus, and vanadium components
which are considered detrimental in iron and steel making.
Technology to effectively and economically do this is not pres-
ently available. Additional study to develop a nonsmelting
method for concentration of iron and elimination of undesired
elements for iron and steel making is considered to be war-
ranted. Emphasis should be on production of an iron-rich
material suitable for blending with other sources of iron units
in iron- and steel-making operations.
To be economically viable, the cost of drying, beneficiation,
and pelletizing to meet iron-making specifications, including
transportation to the steel mill, must be competitive with cost
of iron units as ore pellets. At present, this cost would be
of the order of $50 per ton of contained iron, or equivalent to
about $30 per ton of dried mud solids.
Metals other than iron and aluminum can be recovered from
the muds. For example, in some cases titanium can be re-
covered as ilmenite or rutile concentrates by conventional
gravity concentration. Removal of titanium minerals may be
economical, depending on the amount and mineralogical form,
but such processing has little influence on the need for im-
poundment of the bulk of the mud. Work on titanium-mineral
separation technology is therefore not warranted. Vanadium,
gallium, and scandium have also been recovered from muds
in laboratory studies. Because these elements are present
in very low concentration and have very limited markets,
there is little merit to further development of extraction meth-
ods for these metals from the standpoint of any impact such
work would have on the impoundment of alumina-process muds.
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(9) Ceramic Uses - The possible use of Bayer Process muds in
ceramic applications has been very extensively studied and
reported. Although muds may have been tested as an additive
agent in high-tonnage products such as cements, construction
block mix, and lightweight aggregate, the muds have not been
proven to offer any unique and beneficial properties as a raw
material for these applications. It was therefore concluded
that no additional general studies of use of muds in ceramic
mixes is warranted.
(10) Use as a Waste Treatment Agent - Bayer Process muds have
been tested and found effective as agents in treatment of both
gaseous and liquid effluents. The potential merit of the use
of mud for waste-treatment processing depends on location,
the need to predry the mud, and the subsequent disposal pro-
cedures that will be needed. Additional study of this possible
use is warranted.
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SECTION III
RECOMMENDATIONS
In view of the foregoing conclusions, the following recommendations
are offered.
Industry - Government Demonstration
and Pilot Projects
Emphasis in the near term should be directed toward study of methods
that not only will assure environmentally acceptable containment, but also
offer potential for improving reclamation of impoundment areas and the possi-
bility of harvesting the dried mud, either for commercial use or for alterna-
tive off-site disposal. Recognizing that each operating plant has different
conditions and constraints in disposal related to bauxite sources, geography
and hydrology of the site, land availability, and other factors, it is recom-
mended that a series of demonstration or pilot projects be initiated in collab-
oration with EPA and interested individual operating companies on the site of
the company. Such demonstration projects could be of sufficient general
interest to the industry and to the public benefit to warrant EPA program
funding on a cost-sharing basis. Specific topics considered pertinent by
Battelle as subjects for such EPA-industry cooperative demonstration projects
at specific operating sites are:
(1) Impoundment area drainage systems, construction, and
cost factors
(2) Development of methods to achieve vegetative cover over
inactive disposal areas to include study of flora that could
tolerate high levels of sodium ion
(3) Study of methods to prevent airborne dust from dried mud
areas
(4) Factors in the removal of dried mud solids for alternative
storage or use
(5) Ability to reclaim mud lake areas for alternative uses.
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Such demonstration projects should be conducted by the operating com-
pany and the activity reported to and monitored by the EPA. Award of fund-
ing support for such programs should be based on proposals submitted by the
operating company to the EPA. An estimated budget believed to be warranted
for demonstration projects is of the order of $500, 000 during a 3-year period
with cost sharing at a 50 percent Government-industry basis.
Research and development efforts considered by Battelle to have merit
for possible longer range improvement and which warrant Government
support are:
Basic Research on Physical-Chemical
Mechanisms of Red Mud Dewatering
The inherent difficulty in developing chemical agents or apparatus to
dewater the muds is related to the extreme hydrophilic tendency of the clay-
like minerals comprising the structure of many of the bauxites and muds.
Despite extensive research and development by the alumina industry world-
wide on various chemical and mechanical methods of dewatering muds, a
relatively simple or rapid and economic means to achieve a relatively high
degree of dewatering of Bayer Process muds has not been found. Because
of the importance of improving technology to possibly eliminate the need for
impoundment, it is recommended that a research effort be established to
study the mineral surface chemistry of various red muds and to better under-
stand the mechanisms which limit and/or control the removal of interstitial
and bound water by physical-chemical methods. This research should include
detailed study of the mineralogic structure of various muds, using a combi-
nation of optical and physical-chemical analyses to examine the microstruc-
ture and nature of the surfaces and their affinity for water. The physical
chemistry of the response of mud surfaces to various flocculants, floe
strength, use of chelating agents, and possible chemical adsorbents for water
should be part of a broad basic program on dewatering fundamentals and
mechanisms.
An estimated budget of $150, 000 covering a period of 2 years is
recommended.
Red-Mud Utilization
Pertaining to possible future utilization of mud residues, Battelle
recommends the following studies:
Metal Recovery-
Red muds contain a significant amount of iron and could be developed as
a source of iron units in the production of iron and steel. Emphasis should be
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on technology for beneficiating the mud into a usable iron-ore supplement to
blast furnace charge ore. For this purpose, the beneficiated mud would not
be required to meet the rigid specifications placed on blast-furnace feed ore.
A metallurgical process that could offer merit as a beneficiation procedure
is the segregation roast method that has been applied commercially for ex-
traction of copper and nickel from oxide ores. Segregation roasting employs
a reductive chloride roast conducted with solid carbon present in the charge.
In situ volatilization and reduction occur under proper roasting conditions to
yield a roaster calcine containing coalesced iron adhering to the surface of
the carbon particles in the charge. Iron can be removed relatively free of
contaminants by usual magnetic-separation methods.
It is recommended that initial laboratory study be made of the technical
feasibility of the application of the segregation roasting method for
beneficiation of selected red muds.
This program can be completed within 12 months at an estimated cost
of $50,000.
Adsorbent Material for Pollution Abatement--
Red and brown muds could be used as adsorbents in removing sulfur
oxides from flue gases and for other gaseous- or liquid-effluent treatments.
The ability to leach and recover other metal values from sulfated muds, and
the factors involved in the disposal of the sulfated and/or leached mud
adsorbent are of sufficient interest to warrant investigation.
To properly evaluate this potential use, it is recommended that system
studies be made, including development of data on the structural strength of
various dried muds to determine whether muds can be used as adsorbent
without need for prilling or pelletizing. The extent of sulfur oxide adsorption
of various muds and effect of different conditions of temperature should be
evaluated.
A systematic study of the possible use of mud residues as adsorbents is
estimated to require 18 months to complete at a cost of approximately
$75,000.
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SECTION IV
TECHNICAL BACKGROUND
GENERAL
Aluminum metal and aluminum oxide products are made almost en-
tirely from bauxite ore. Bauxite is a naturally occurring mineral composed
principally of a mixture of one or more of the hydrated aluminum oxide min-
erals gibbsite (A12O3« 3H2O), boehmite (AlzOs'HzO), and diaspore
(Al2O3'H2O) and impurities of silica, iron oxide, titania, and other elements
in trace amounts. It is generally believed that bauxite deposits result from
intense chemical weathering of aluminum-bearing rocks or formations under
tropical or subtropical conditions with alternating wet and dry seasons. De-
pending on the source location, the texture of the ore may be fairly granular
or it may contain or be essentially all extremely fine-grained claylike
material.
Alumina is extracted from bauxite using the Bayer Process. The initial
step is to partially digest the ore in a caustic solution. The caustic reacts
with the major part of the aluminum oxide content of the bauxite and causes it
to dissolve. This reaction is specific to the aluminum oxide and some reac-
tive silica; however, unreactive silica (i.e., quartz), iron, and titania min-
erals are not dissolved to any significant degree and remain as a solid
residue. The residue is a solid waste which is washed to recover the active
solution and then discarded. This mud material is generally extremely fine
and difficult to filter. It has been least costly to dispose of this waste by
pumping it as a relatively dilute suspension to holding ponds and lakes con-
structed for that purpose. Sufficient pond area is provided to allow the mud
to settle and for clear water to be recycled to the process. Because of the
iron oxide content of the waste, the waste has a red color and has been termed
"red mud"; the impoundment areas are called "red-mud lakes".
From the standpoint of effluent control, impoundment of the red mud is
a practical method which has been used for many years by the industry.
With proper pond construction and adequate pond holding area, the red-mud
waste can be retained and contamination of surface waters can be virtually
eliminated.
10
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Impoundment is not an ideal solution to the red-mud disposal problem,
however, for many reasons. Red-mud lakes require a significant amount of
land. The settling rate of solids is generally slow. Certain muds are almost
thixotropic in character and even the old, apparently dried lakes cannot sup-
port heavy equipment or construction. These ponds, in fact, must be main-
tained even after they are no longer in use, and always there is some risk
that a break or spill will occur and allow mud into a nearby stream or
waterway.
The problems, of course, vary with the location. Availability of land is
a most important factor. Moreover, commitment of the land for mud disposal
may impact on land-use plans in the region. Rainfall and seasonal weather
conditions play a significant role. Long periods with little rainfall cause the
mud lakes to dry on the surface and become a source of windblown dust. Long
periods of heavy rainfall increase the risk of a break in the dikes or can cause
runoff from the pond into surface waters.
The question of whether technical developments can be made to provide
practical improvements in or alternatives to present impoundment is not
simple to answer. Alumina refineries are major complexes with many inter-
related operations and, therefore, considerable constraint in operating con-
ditions. Major changes in processing would be difficult and costly to imple-
ment. Ideally, such changes would provide economic benefit to the processor
through recovery of additional values or reduced overall cost in disposal of
the muds. It is, therefore, important to consider the structure of the domes-
tic industry, the Bayer Process, present impoundment methods, and the
probable future costs for impoundment.
THE DOMESTIC ALUMINA INDUSTRY
Bauxite ore is refined into alumina in nine refineries in the United
States. * These process plants are owned by five primary aluminum producers.
The location of the refineries, countries of origin of bauxite used, annual
production, and waste (mud) produced are shown in Table 1. Most of the
bauxite^used in the United States is imported. Jamaica and Surinam are the
principal suppliers. The only commercial bauxite deposits in the United
States are located in Arkansas.
The amount of mud produced in processing differs for the types and
ranges of bauxite and ranges from 0. 3 ton (Surinam bauxite) to 2. 0 ton
(Arkansas bauxite) per ton of alumina produced. The domestic alumina plants
generate about 10 million tons of mud waste annually.
The terra domestic industry is intended to include the refinery in St. Croix, Virgin Islands,
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TABLE 1. LIST OF DOMESTIC BAUXITE REFINING PLANTS
Company
Plant location
Type of bauxite used
Approximate
plant capacity'a),
metric tons
alumina / ye a r
Approximate
waste (mud)
produced'a',
metric tons /
year
Aluminum Company of
America (Alcoa)
Mobile, Alabama
Point Comfort, Texas
Surinam-African
Caribbean-Surinam-
African-Australian
1, 500,000
1, 100,000
450,000
1, 100,000
Aluminum Company of
America (Alcoa)
Kaiser Aluminum and
Chemical Corp.
Reynolds Metals Co.
Bauxite, Arkansas
Domestic (Arkansas)
Baton Rouge, Louisiana Jamaican
Gramercy, Louisiana Jamaican
Corpus Christi, Texas
Hurricane Creek,
Arkansas
Jamaican-Haiti
Domestic (Arkansas)
225,000
1, 000,000
800,000
1,300,000
755,000
450, 000
1,000,000
800,000
1,300, 000
1,510, 000
Ormet Corporation
Martin-Marietta
Aluminum Co.
Burnside, Louisiana Surinam
St. Croix, Virgin
Islands
Weippa -Guyana -
Surinam-Kassa-
Boke (Guinea)
560,000
325,000
168,000
(a) Information provided by individual operating company.
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Bauxite
Alumina is produced domestically only by extraction from a bauxite ore
mineral. The term bauxite refers to an ore or mixture of minerals formed
by the weathering of aluminum-bearing rocks. Bauxite deposits are found
throughout the world. Bauxites are composed principally of a mixture of one
or more of the hydrated aluminum oxide minerals. Gibbsite (also called
hydrargillite) is a trihydrate form, of alumina (A^O^-3H2O). Boehmite and
diaspore are two forms of alumina monohydrate (A^Og-H^O). The relative
amount of each form present in the bauxite is very important because the
trihydrate is more readily extracted and-milder digestion conditions can be
used.
Other aluminum oxide minerals generally contained in bauxites include
the hydrated aluminum silicate minerals halloysite and kaolinite. The associ-
ated iron minerals are goethite and hematite. Titanium is often present in
the minerals rutile, anatase, and ilmenite. Silica is present in quartz and
clays. The form and extent of silica contained are very important in the
economics of alumina extraction. Silica in the form of quartz is only moder-
ately attacked during the extraction of bauxite; however, silica in kaolinite
(A12O3* 2SiO2'2H2O) dissolves in the caustic (soda) causing a loss of soda and
loss of alumina through formation of insoluble sodium aluminum silicate
(3Na2O* 3Al2C>3* 5SiC>2" nH^O). Soda represents a significant investment and
its recovery makes the process economical. Other elements are generally
present as indicated in Table 2. It might be noted that bauxites used by the
domestic industry are relatively low in the monohydrate minerals. Mono-
hydrate ores are processed more commonly in Europe.
PROCESS TECHNOLOGY
The domestic alumina industry uses two basic processes for alumina
production. Imported bauxites are treated by the Bayer process. The
Arkansas bauxites are processed by a "Combination Process" which incor-
porates a sinter step with the BayeiMnethod.
The Bayer Process
The Bayer Process for extracting alumina from bauxite was invented
by Karl Josef Bayer in Austria in 1888. This process has been used in the
U. S. since 1894.
The basic principle involved in the Bayer Process is to dissolve the
aluminum component of bauxite ore in caustic soda solution. The solution is
first treated to remove impurities such as silica and iron, and is then con-
ditioned to precipitate alumina trihydrate. This material produces aluminum
oxide (alumina).
13
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TABLE 2. CHARACTERISTIC ANALYSES OF VARIOUS BAUXITES
Weight percent
Constituents
A12O3, total
Si02
Fe203
Ti02
F
P2°5
V2°5
H->O} combined
A12O3, trihydrate
A12O3, monohydrate
Jamaican
49.2
0.7
19.3
2.5
--
0.4
0. 03
26.5
44.4
2.8
Surinam
55. 0
3.8
7.0
2.4
--
0.06
0.04
31.2
50.0
0.2
Arkansas
48.7
15.3
6.5
2.1
0.2
--
--
25.8
34.1
14.6
Guyana
58.6
4.9
4.1
2.5
0.02
--
--
29.6
52.7
5.9
(a) Analyses provided as typical by the operating company.
14
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A generalized flowsheet of the Bayer Process is shown in Figure 1.
The first" step in the process is to grind or break up the nodules of bauxite.
The bauxite is then slurried with a portion of the recycle caustic soda solution
(spent liquor) and pumped to large pressure vessels (digestors) where it is
mixed with the main stream of spent liquor and heated with live steam. The
temperature and pressure required for alumina digestion depend on the rela-
tive amount of monohydrate and trihydrate in the ore. For a predominantly
monohydrate bauxite, a temperature of 200 to 250 C (392 to 482 F) and a
pressure of about 35 atmospheres (500 psi) would be used; for trihydrate, a
temperature of 120 to 170 C (248 to 338 F) and a pressure of 3 to 5 atmo-
spheres (50 to 70 psi) are used. The operating conditions are also adjusted
depending on the ratio of monohydrate and trihydrate alumina forms. The
digestion reactions form soluble aluminate by the following reactions:
(Monohydrate) A12O3'H2O + 2NaOH^2NaAlO2 + 2H2O
(Trihydrate) A12O3' 3H2O + 2NaOH-2NaAlO2 + 4H2O.
The solution bearing the dissolved aluminum component of the bauxite
(green liquor) is sent to a "flash" heat recovery operation, where both the
elevated temperature and pressure are reduced to near atmospheric condi-
tions. The heat recovered from the green liquor as flashed steam is used in
heat exchangers to preheat the solution going into the digestor. From the
flash tanks, the slurry is sent to thickeners where the suspended undissolved
solids are flocculated (usually with a starch) and removed in the thickener
underflow. The separated mud is washed by counter cur rent decantation to
recover dissolved alumina and caustic. The mud in the thickener underflow
is pumped at 15 to 22 percent solids to the mud-lake -impoundment areas.
The separation and washing of mud from the pregnant liquor can also be
done by filtration. The use of filters depends on the characteristics and the
amount of mud produced.
The thickener and washer overflow (green liquor) is sent to the pressure
filter (Kelly filters) for removal of fine solids. The green liquor is then
supersaturated with respect to the dissolved alumina content by a further
cooling operation (vacuum flash). The liquor is then sent to precipitators,
where fine alumina (known as seed) is added to enhance trihydrate alumina
[A1(OH)3] precipitation. The settled coarse particles of alumina trihydrate
are washed, filtered, and calcined in a kiln to yield the calcined alumina
(A12C>3) product. The spent liquor from the primary classification is sent
to secondary and tertiary classification to recover fine alumina that is
used as the seed material in the classifiers. The spent liquor from the final
classification is sent to vacuum evaporators for concentration and is then
recycled to the digestion process. A certain amount of caustic is lost in
processing and this is made up either through direct addition of caustic,
15
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BAUXITE-
I GRINDING I
MIXING
RECONCENTRATED
CAUSTIC LIQUOR
f WASHING PRECIPITATES
CONDENSATE - TO < BOILER FEED WATER
MUD WASHERS
STEAM
CALCINED ALUMINA
PRODUCT
Figure 1. Generalized flow diagram of the Bayer Process,
16
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through use of soda ash, or by use of hot caustic solution for descaling of
various items of equipment such as the digesters, flash chambers, and
classifiers.
The Combination Process
The Combination Process is a modification of the Bayer Process de-
veloped for bauxite containing high amounts of silica, such as those from
Arkansas. The digestion of this type of bauxite by the conventional Bayer
method would result in excessive loss of alumina through formation of insolu-
ble sodium aluminum silicate. The Combination Process, also known as the
sinter/leach process, recovers the alumina values that become trapped in
the Bayer red mud as silicates. This additional extraction step is accom-
plished by mixing the red mud from the Bayer circuit with limestone and
sodium carbonate and then sintering the mixture in a kiln at 1100 to 1200 C
(2030 to 2192 F). The kiln product is ground and leached to produce addi-
tional sodium aluminate solution which is filtered and is either added to the
main stream for precipitation or is precipitated separately. Precipitation
of aluminum trihydrate is done as described previously for the Bayer. Process.
The washed residual solids (brown mud) consisting mainly of dicalcium
silicate are pumped to a mud lake. A generalized flow diagram of the Com-
bination Process is shown in Figure 2.
One feature of the Combination Process is that lime and soda ash sub-
stitute totally for caustic soda as the starting agent, utilizing the familiar
causticizing reaction:
Ca(OH)2 + Na2CO3^2NaOH + CaCOs.
During sintering of red mud with lime and soda ash, the important
reaction is the conversion of silica to calcium silicate and residual alumina
to sodium aluminate:
2CaO + 2H2O - ZNaAIOz + 2CaO 2SiC>2- 2H2O
"
Red Mud Brown Mud
Mud Disposal
Solid wastes are generated in virtually all mining and processing of hard
rock minerals. Mineral process wastes are generally impounded in tailings
ponds. Alumina production is no exception. The mud -lake impoundment is
the lowest cost method for containment of these muds from alumina produc-
tion. Because of the enormous tonnage of solids generated and their near-
colloidal character, these lakes present special problems in construction and
maintenance. It is pertinent to consider present mud disposal and the cost
17
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I -
BROWN MUD-*
TO LAKE
AI2O3
PRODUCT
AI2°3
PRODUCT
Figure 2, Generalized flow diagram of the Combination Process.
18
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factors involved in evaluating possible alternative uses for the mud and costs
likely to be required to convert the mud into usable forms.
Construction of mud lakes depends principally on the type of mud to be
impounded. The mud-lake dikes for the more claylike muds will differ from
those for the sandlike muds. The general approaches to the construction of
the mud lakes have been previously described. (1> 2) Typical construction
plans are illustrated in Figure 3. These differ in that one is for initial full-
height dike construction, while the other calls for first building a low dike
which is later raised as the lake fills. A final construction plan for a mud
lake will depend on the type of mud and the extent of land available.
The cost of mud-lake construction and mud disposal can vary signifi-
cantly depending on the location and the nature of the mud. Land cost is a
major factor. The distance of the lake from the plant is important as is the
net rainfall/evaporation rate. Available costs data were in the general
range of $1. 00 to $5. 00 per metric ton (dry) of mud disposed.
The Kaiser Aluminum and Chemical Corporation has reported
studies (3, 4) made to develop improved methods for impoundment of red muds
generated by processing Jamaican bauxite at Kaiser's plants in Baton Rouge
and Gramercy, Louisiana. On the basis of results from laboratory and pilot
impoundment projects, Kaiser has constructed a 200-acre red-mud lake to
serve the Gramercy plant. This lake incorporates sand-bed filtration of the
"French Drain" type with drainage pipes and covering layers of different
size sand and gravel to give permeability through the base of the lake. The
placement of a drainage pipe during construction of the lake is shown in
Figure 4.
Kaiser has termed the disposal system the Deep DREW System
(Decantation, DRainage, and Evaporation of Water). A mud lake employing
the DREW System is being constructed by Kaiser to serve its Baton Rouge
refinery.
The mud-disposal program and pilot development work by Kaiser has
provided a basis to anticipate a reduction in slurry volume contained in a
lake with bottom drainage to about one-fourth the volume in the conventional
"as-is" impoundment. Kaiser anticipates that the mud will consolidate in
these lakes to an overall average of 50 percent solids through the combination
of drainage and evaporation. It is believed, based on demonstration plots,
that the lakes will dry to sufficient stability to support men and equipment.
Thus, the dried lakes might be periodically surface mined to remove a sub-
stantially dry mud that would be a more economical source for iron values
or for other purposes than the wet muds.
19
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MUD LINE
ROADWAY 6 m WIDE
TAMPED EARTH
AND CLAY
DIKE KEY
3-4.5 m DEEP
2.5 m MIN. WIDTH
A. INITIAL FULL DIKE CONSTRUCTION
PHASE II RELOCATION
OF MUD LINE
MUD LINE - PHASE I
ROADWAY
4.5-6 m WIDE
1.5-2 m HIGH
B. BUILDUP CONSTRUCTION OF MUD LAKE DIKE
Figure 3. Mud lake dike construction.
20
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A system to permit use of red mud tailings as land fill instead of discharging
them into the Mississippi River is under construction at a Louisiana alumina
plant. Here drainage pipe is placed in a trench at bottom of storage pond;
later it will be covered with coarse permeable gravel bed.
Kaiser Aluminum & Chemical Corporation photo
Figure 4. Construction of red-mud lake based on gravity
drainage system. (Reprinted by special per-
mission from Miller Freeman Publications, Inc. )
21
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PLANT TRIPS
Visits were made by Battelle staff to review the refinery practices and
methods used in mud disposal and to arrange for acquisition of mud samples
for laboratory study. The plants visited by Battelle were:
(1) Alcoa - Point Comfort, Texas
(2) Alcoa - Mobile, Alabama
(3) Alcoa - Bauxite, Arkansas
(4) Reynolds Metals - Hurricane Creek, Arkansas
(5) Kaiser Aluminum - Gramercy, Louisiana
(6) Martin-Marietta - St. Croix, Virgin Islands.
These plants were selected because each used a different ore source and the
mud-disposal requirements for each were different. Except for the Arkansas
operations, the Bayer Process was in use. Because of the high silica content
of the Arkansas bauxite, the Combination Process is used for this ore.
During the visits to the plants, discussions were held with company per-
sonnel concerning factors related to alumina production and the mud problem.
The salient points were as follows.
(1) The key factor is the nature of the bauxite used. Both the quantity of
mud produced and the ability to wash and dewater the mud depend almost en-
tirely on the bauxite. The quantity of mud obtained from processing a sandy-
type bauxite is generally substantially less per ton of alumina made. Sandy
bauxites usually contain hematite as the predominant iron mineral and can be
filtered and more easily washed.
(2) Within practical limits of variation of the process conditions, the
chemistry of the process has little influence on the nature of the mud or its
dewatering characteristics.
(3) Transportation of the mud from the plant to the impoundment lake
is done most conveniently and economically by pumping as a slurry. The
practical limit of the solids content of such a slurry is 25 to 40 percent solids;
20 percent solids content is usual. To transport the mud by mechanical means
such as a conveyor belt would require dewatering the mud to at least 55 to 60
percent solids. It does not appear possible by conventional dewatering methods
to achieve a mud with this high a solids content except by partial drying. In-
plant drying would generally involve substantially higher disposal costs than
present mud-lake disposal. * It must be anticipated, therefore, that general
practice in the near-term will continue to be impoundment of the mud slurry.
*One operating company stated that mud-disposal methods now being implemented at that operation will allow
the mud to be transported from the plant as material dried to its maximum shrinkage.
22
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(4) The development of a more rapid settling character of a mud has
benefits of interest to the operators. Methods used to control the flocculation
in the thickener circuit are considered a highly proprietary subject. Use of
synthetic flocculants is of continuing interest because synthetics offer oppor-
tunities to achieve better quality control of the flocculant and, therefore,
better process control. Synthetics have been tested in plant runs with mixed
success. Only one processor stated that synthetic flocculants were being used
at that site as standard plant practice.
(5) All operators are aware of prior commercial use of red and brown
muds of certain size fractions, for example, the making of aggregates for
dike construction and as a soil conditioner for acidic soil. However, these
have been specialty uses that have involved only a minor amount of the total
mud discharged. No major use was reported by the operators.
23
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SECTION V
LITERATURE REVIEW
GENERAL
A detailed review was made of the published technical literature per-
taining to the processing of bauxite and the red-mud problem. The period
covered by the review was 1940-1975. The following journals were used to
make the search:
Chemical Abstracts
Engineering Index
National Technical Information Service (NTIS)
U.S. Bureau of Mines Reports of Investigations
Mining Engineering.
Chemical Abstracts was noted to cover Metallurgical Abstracts,
Ceramic Abstracts, and World Aluminum Abstracts.
The journals were searched under the following key terms:
Bauxite refining/treatment
Red-mud (or brown-mud) de water ing/bauxite refinery waste
treatment
Red-mud (or brown-mud) utilization.
The articles found in the search that were determined by review of the
abstracts to be of interest were reviewed in the original and classed in the
following categories:
(1) Bauxite Refining
(2) Red-Mud Dewatering
(3) Red-Mud Utilization.
The literature review disclosed more than 600 pertinent articles. Much
of the publically available information was found in non-English-language
publications. Table 3 shows the number of publications reviewed under each
24
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category. Figure 5 shows the overall distribution of articles published in
English and non-English languages from, the year 1940-1975. After 1950, a
majority of articles were found to be in foreign languages. The number of
foreign publications on bauxite processing increased sharply in the early
1970's. Approximately 45 percent of the abstracts reviewed were patents.
Of these, only 30 percent were in English.
TABLE 3. PUBLICATIONS PERTAINING TO BAUXITE PROCESSING
TECHNOLOGY - BY CATEGORY
Title
Bauxite refining
Red-mud dewatering
Red-mud utilization
Total
Number of
publications
250
80
286
616
Language
English
78
20
56
154
distribution
Non-English
172
60
230
462
The literature review established that new methods are being developed
to utilize alumina sources other than bauxite. However, the majority of the
publications concern modifications of the basic Bayer Process to increase
alumina recovery and to reduce alkali (soda) loss.
Developments were reported concerning red-mud dewatering technology.
Most of the publications were related to the use of synthetic polymers to
flocculate the red-mud suspensions. The use of combination flocculants for
example, starches and polymers, metal ions and polymers, and flours and
polymers, was described.
The literature search also showed that a substantial amount of research
has been conducted on the subject of utilization of red muds. Numerous publi-
cations were noted which dealt with recovery of different metals from the
muds. Of these, the recovery of iron, aluminum, and titanium shows some
potential. Publications were reviewed which concerned use of the red mud in
ceramic products. Other publications relate to the application of the red mud
in paints, as a fertilizer, and as an adsorbent for gases.
A complete listing of the literature references found in the search is
given in Appendix A. Pertinent articles in the various categories were
reviewed in detail and the information obtained in each category is described
in brief in the following sections.
25
-------
50
o
<
cc
u.
O
CO
5
40
30
20
10
O ENGLISH
NON-ENGLISH
1940
1950
1960
1970
YEAR
Figure 5. Distribution of literature in English and non-English
languages from the year 1940 to 1975.
-------
BAUXITE REFINING
Bayer Process Technology
The Bayer Process is the conventional method used worldwide for
extraction of alumina from bauxite. Of the total 250 literature references
to refining of bauxite reviewed in this study, approximately 60 percent
referred to the basic Bayer Process while the remainder referred to
methods to process alternative sources of alumina and various bauxites not
suitable for Bayer methods.
In general, hot alkali leaching of the bauxite as is used in the Bayer
Process allows recovery of 90 percent or more of the contained Al^O?.
Various techniques to improve recovery, for example, using additives to the
alkali such as Al^Oj* , changing the temperature and pressure^'', or grind-
ing the bauxite during digestion in the autoclave* ', are reported, but these
offer only a marginal advantage. Dunn'"' recommended use of vertical di-
gesters rather than the more common horizontal units where "sand" or in-
soluble coarse portions of bauxite are present which tend to be held in sus-
pension in the lower part of the vessel. This was found to avoid scaling of
interior of digesters and to decrease retention time needed in the digester.
Adjustment of the alumina-to-soda ratio was shown to provide means to im-
prove decantation and also to reduce the amount of soda solution to be
concentrated and recycled. ' '
For continuous rather than batch or semibatch digestion of bauxite, a
fill
tubular reactor in a turbulent flow condition was proposed by Plass. \li' He
recommended heating an ore suspension of 3 to 6 volume percent solids at
95 to 150 C (200 to 300 F) and at 200 atmospheres (3000 psi). Soudan, et
al, (12) proposed using a gradually increasing temperature of digestion from
88 to 234 C (190 to 450 F) in two heating tanks and eight autoclaves operated
in series. Ninety-five percent solubility of alumina was reported. Similarly,
Juhasz, et al, * ' recommended preheating a bauxite-soda mixture in several
stages in a shell-tube heat exchanger at 100 to 140 C (212 to 280 F) before
digestion in autoclaves.
The use of increased temperature during bauxite digestion was also
recommended as a means to increase A^C^ yield and also to allow reduction
in the strength of the recirculating solution. This procedure was reported to
reduce the heat requirement by 35 to 40 percent. '''*> *-o, 16) jjse o£ j^g^
Na£O concentration, however, was recommended to avoid A^Oj precipitation
in thickeners and to digest excess of bauxite without increasing the digester
capacity. (17-19)
The A12O3 recovery was found to be increased by Scholder* ', who
proposed decomposing calcined bauxite by heating for several hours at
27
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180 C (360 F) in a liquor containing an alkali metal oxide and a halide such as
NaCl, NaBr, or KC1 in a ratio of 3:1. Antipin, et al, ^L> suggested adding a
small quantity of organic matter to leached pulp, while others^ > recom-
mended using a mixture of K-Na alkali mixture to increase A12O3 yield and
to decrease alkali loss during the process.
Belyaev, et al, (23^ observed improved leaching of bauxite when MgO
was used with lime as an activator. Wolf(24) reported that on addition of
meta-, tetra-, or perborate to the bauxite at a digestion temperature of 145
to 165 C (290 to 330 F), the A12O3 extraction requires about half the usual
time and calcining of the ore may often be omitted. Similarly, addition of
lime or soda ash(25) or FeO^26) was noted to reduce the alkali and alumina
losses and to improve sedimentation rate of the red mud.
Numerous pretreatment steps and other modifications have been recom-
mended to increase A12O3 recovery in the Bayer Process. Preliminary cal-
cination of bauxite at 260 to 310 C (500 to 600 F) was proposed^ '; addition of
lime to bauxite and then calcining and grinding of the mixture before digestion
was recommended* °'; addition of some red mud in digester was reported to
be beneficial^ "', as was the addition of 0.6 to 0. 7 g (1. 3 to 1. 5 Ib) lignin/ton
of bauxite'-^ '. One of the proposed methods'-^ ' involved heating of bauxite
with NaOH at 220 C (430 F) in a rotating stainless steel autoclave for 10 to 20
minutes and then quenching the apparatus in water to lower the temperature
to 100 C (212 F). The resulting suspension when washed with dilute NaOH;
the alumina extraction was found to be essentially complete -with 0. 05 ton
NaOH/ton A12O3 consumed.
Gebefuegi' ' reported an improvement in A12O3 recovery by first mix-
ing ground bauxite with 10 percent Na2CO3 at 95 to 105 C (203 to 225 F).
Then CaO and NaOH was added to the mixture and maintained at 105 to 125 C
(225 to 260 F) for 10 minutes before subjecting it to Bayer Process. Other
publications on improved methods to increase A12O3 recovery included grind-
ing of bauxite with recycled sodium aluminate solution^33); ieaching bauxite
with alkaline aluminate solution'34'; addition of 5 to 20 g NaCl and/or
Na2SO4/liter to the digestion system^35); pulverizing and sintering a mixture
of bauxite, Na2CO3, lime, and coke to make pellets and then grinding it and
leaching at 90 C (194 F) with water (36-38). utilizing a tube reactor for
bauxite leaching(39). an(j treating bauxite with CaO and NaCl, which converted
goethite to hematite which, in turn, also improved red-mud filterability^4^.
Lime -Soda Sinter Process Technology
This process was initially developed by Alcoa during World War II to
recover A12O3 from domestic kaolinite. The technique is a modification of
the Bayer Process whereby the red mud obtained after the usual Bayer
digestion is mixed with soda ash and lime and sintered in a kiln. The sinter
28
-------
product is ground and leached with hot water to extract sodium aluminate
liquor which is recycled back in Bayer's circuit. '41' This method is par-
ticularly suitable for processing siliceous ores in which the alumina is
chemically bound to silica. '^' Flint, et al, ' ' described a cyclic process
in which high- silica bauxite is boiled with NaOH-NaCl solution, filtered, and
AloOo precipitated with carbon dioxide gas. The leach residue in this
process was also sintered with CaCOg, ground, and the A^Og extracted at
70 to 80 C (160 to 180 F) with water.
Grigoreva, et al, ''*'*' reported that when bauxite was roasted with soda
and lime in the presence of solid carbon, less soda was consumed and high
AUOo was extracted. Fusion of bauxite with Na2CC>3 and CaCC>3 gave a
porous material which could be leached at low temperature. ' '
Dobos' ' proposed an improved technique involving leaching bauxite by
the Bayer Process, then reduction of the red mud by puddling and removal of
iron by magnetic separation. The slag was sintered with Na2COj and CaO
and then leached to recover additional A^Og. An alternative to the sinter
method proposed by Calhoun, et al, ' '' involved calcining bauxite at 980 C
(1796 F) and then leaching by percolation with 15 percent NaOH solution at
94 to 96 C (201 to 205 F). This procedure was reported to remove up to 77
percent SiCX.
Alumina From Low -Grade Bauxite
Numerous methods have been proposed to recover A^Oo from low-
grade ores. One method involves reduction to yield a product" containing an
Al-Fe-Si metallic phase. This can be leached with NaOH to recover sodium
aluminate. (48) Digestion of the ore in an autoclave with both NaOH and
Ca(OH)2 solution was proposed'^'); and use of a tube autoclave with NaOH at
300 to 350 C (570 to 660 F) was recommended^50).
For bauxite which digests slowly in NaOH, the rate and yield can be
increased by grinding in a vibratory ball mill which disturbs the internal
structure of bauxite and increases the solubility by a factor of six. l^l, 5
-------
Desilication of aluminate liquor has been recommended by adding hy-
drated alkali aluminosilicate^ ^ or by adding 4 percent white mud (mineral
noselite with sulfate)^2) to the heated liquor. General methods recommended
to remove most of the impurities referred to removing 03 and 804 by
evaporation and crystallization at 40 C (104 F). On cooling the liquor, a resi-
due rich in P2°5 and V2°5 was found- ^63^ Addition of Ca(OH)2 to the liquor
was noted to precipitate all salts. (64> Zinc, if present, could be removed by
precipitation as ZnS, ("5)
Bauxite Beneficiation
Studies on the physical beneficiation of bauxite in general concern the
removal of reactive silica. Pickens'""' recommended dispersing the bauxite
in an agitated slurry and then removing silica by desliming. Prasad, et al'° ''
reported that a majority of silica from bauxite could be removed by grinding
and screening at minus 20 mesh. Other publications referred to flotation of
silica with a cationic collector (e. g. , an amine)' ' or, flotation of bauxite
with an anionic collector (e.g., oleic acid)(69)( gravitation-magnetic separa-
tion''^', ph.otoseparator(7-U, and selective dispersion'^2'.
Pedersen Process
The process was developed to process ferruginous bauxite containing
high SiO2 and TiO2 which could not be effectively treated by standard Bayer
methods. It involves smelting the bauxite with lime and coke in an electric
furnace at 1750 C (3180 F). The iron oxide can be reduced to molten iron
with the formation of a calcium aluminate slag; alumina is recovered from
the slag by grinding and leaching with Na2COo solution. The A12O3 is pre-
cipitated by neutralizing the liquor with CO2.1?3-75) Some improvement in
the leaching step was reported by using a temperature of 80 C (176 F). This
allows an increase in the A12O3 content of the solution which then permits
precipitation of the A12O3 by seeding. (76)
RED-MUD DEWATERING
The partial dewatering of red mud is an integral part of the Bayer
Process operations in the washing circuit for recovery of caustic. Practical
considerations require that the mud be thickened to about 20 percent solids.
If the degree of thickening is not achieved, plant capacity is adversely affected.
For this reason and to reduce the capital cost of thickening and washing,
considerable laboratory and in-plant studies have been made of the factors
that affect the settling and thickening of the red mud.
Seventy-one literature abstracts pertaining to red-mud dewatering were
reviewed. About 85 percent of this literature referred to the flocculation of
red mud with a wide variety of reagents. The remainder referred to
30
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filtration and centrifugation methods of dewatering. The pertinent literature
on dewatering is reviewed in the following paragraphs.
Flocculation
Flocculation is the addition of a chemical agent which causes the fine
particles in suspension to agglomerate and, therefore, settle more rapidly
by gravitational force. The common flocculating agent used in the alumina
extraction industry is cooked starch. It was reported that the method of
preparation of the colloidal starch solution was important; for example,
heating the starch solution makes it a more effective flocculation agent. ' '
Some investigators(7°, 79) reported starch phosphate as being more effective
than natural starch. The use of rye bran, rye flour, and corn flour as a
red-mud flocculant has also been tried. (8^> 81) The most effective of these
were found to be rye bran and corn flour in the range of concentration from
0. 1 to 0. 125 g/1 of slime pulp.
Numerous publications describe the use of synthetic polymers (poly-
acrylamide) as a red-mud flocculant. Wolf, et al, (82) reported different
sedimentation rates and end volume percent for red mud, depending on the
molecular weight of the polymer used. In general, the high-molecular-
weight polymers are more effective than the lower molecular weight ones.
Generally, also, a lesser amount of polymer [50 to 100 g/ton (0. 11 to 0.22
Ib/ton) of red mud] is required compared to the amount of natural starch
needed [ 1 kg/ton (2. 2 Ib/ton of red mud] . (83> 84> Sullivan^85) reported an
increase in settling rate of red-mud slime by adding 0.0125 to 0.2 weight
percent solution of an ultrahigh-molecular-weight polyvinyl aromatic sulfonate
and also by the addition of lignosulfate product (about 25 weight percent active
lignosulfonic acid). Polysodium acrylate prepared by irradiation was also
reported to be an effective coagulant for red mud. '°°> Ismatov, et al, (87)
reported an optimum settling of solids at a polymer concentration of <125
g/ton and liquidrsolid ratio of 20:1. Werner'88' reported that the polysodium
methacrylate gave the highest settling rate of all the polymers investigated.
A higher sedimentation rate was also reported when an emulsion of
polyacrylic acid ester and polymethylacrylate was used. (89)
Skobeev' ' reported a threefold increase in settling rate of red-mud
slurry using a flocculating mixture of 6. 25 g/rn^ polyacrylamide and 25 g/m.3
flour. Sibert(91, 92) observed that the separation rate of dispersed red mud
was increased when treated with cooked starch and a polymer of molecular
weight greater than 50, 000.
Addition of certain minerals was shown to accelerate or retard settling
of red mud, e. g., rutile, magnetic, melanterite, and siderite accelerated
the settling; limonite, kaolinite, quartz (opal), and pyrite retarded the settling
rate of the red-mud suspension. (93-95) chu, et al, (°°' reported that the
31
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addition of CaO to the Bayer Process increased the extraction of A12O3 and
increased the sedimentation rate of the red mud. He also reported that
addition of lime and BaO increased, while MgO retarded, the sedimentation
rate of red-mud suspension.
Makary, et al, (9?) reported using homogenizing wheat flour with caustic
for red-mud sedimentation, while Goldman, et al, (9^ obtained positive
results with a composite flocculant consisting of 1. 1 ratio of polyacrylamide
and rye flour.
A mixture of 0. 1 to 2. 0 weight percent starch (based on red mud) and
0. 3 to 12 times the weight of starch of calcium compounds, e. g. , Ca(OH)2,
CaCO3, and CaO. gave a high sedimentation rate compared to that obtained
by starch alone. (99) Similarly, a mixture of calcium compounds and a
polymer, lime Na polyacrylate, accelerates sedimentation and filtration of
redmud.
Derevyankin, et al, reported that an optimum concentration of
Na?O (15 to 20 g/dm^) is necessary for attaining maximum settling rate.
Other publications on red-mud sedimentation dealt with addition of sea
weeds' 10Z;^ clarified aluminate solution' 103)^ gelatinizing' 104)^ freezing and
thawing of red mud^OS)^ and use of higher temperature (10°).
Centrifugal Dewatering
Centrifugal methods studied for partial dewatering of red muds included
the use of the hydroclones and centrifuges. However, the number of studies
done were limited. German-Galikana, et al, (107) found that hydroclones
installed ahead of thickeners are able to eliminate 75 percent of solids
provided that the liquid -to- solid ratio in the cyclone feed is maintained at
0.8 to 1.0.
Good, et al, (1°8) showed an increase in solids content of sludge from
20 to 25 percent to 40 percent with a centrifuge. They also reported an
increase in centrifuge capacity by about 35 percent by addition of a flocculant.
Filtration
Polyakov, et al, (109) concluded that for efficient filtration of the red
mud, the liquid -to -solid ratio should be 1.8:1, and that the rate of filtration
increases proportionally to the increase in pulp temperature and inversely to
total thickness of cake layer. These workers also reported that filtration
rate depends little on the Na2O or sodium aluminate contents in the pulp
within 5 to 40 g/1 (0. Oil to 0. 088 Ib/ton) concentration.
32
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and Plaetschke' ' have reported that rotary drum filters
are more economical than the conventional Kelly press for red-mud filtration
due to reduced labor and wash water requirements. The Na£O losses were
also noted to be reduced considerably. Konig'H2) reported achieving a fil-
tration rate of 125 to 155 kg/m2 (25 to 32 lb/ft2) with a rotary drum filter.
Recently, VogtW reported a filtration rate of 190 kg/m2 (39 lb/ft2) of
Jamaican red mud using a rotary drum filter operating at 75 C (167 F). The
filter cake obtained had 40 percent solids and was thixotropic in behavior.
Martine(^ ") reported that red mud obtained from previous filtration
is more effective as a filter aid than the conventional materials such as
diatomite.
UTILIZATION OF RED MUD
The search of the literature pertaining to possible commercial use of
red mud was organized in three categories: (1) metallurgical, (2) ceramic,
and (3) waste treatment. The references totaled 267 articles, and more than
half concerned metal recovery from the mud. Ceramic-use references
totaled 96 articles, or approximately 30 percent of the citations. The pattern
that the recent research has been done largely outside the United States is
clearly established. More than 90 percent of all literature in the field of
red-mud utilization was based on the work of foreign investigators.
Metallurgical
Literature references on metal recovery totaled 140 articles classed
as shown in Table 4. It can be noted that approximately half the references
pertain to recovery of iron. Recovery of titania and additional alumina is
also proposed. The higher value metals such as niobium, gallium, and
vanadium have received attention but are present in such low concentration
that their commercial recovery has not been tried.
TABLE 4. CLASSIFICATION OF LITERATURE BY SUBJECT ON
METALLURGICAL USES FOR RED MUD
Material recovered Number of articles
Alumina 12
Titania 11
Iron 62
Iron, alumina 20
Iron, titania 2
Miscellaneous metals 33
Total 140
33
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A listing of these references by country of origin is given in Table 5.
TABLE 5. CLASSIFICATION OF LITERATURE ON RED-MUD
UTILIZATION BY COUNTRY (METALLURGICAL)
Country Number of abstracts
U.S.S. R. 37
Japan 1°
Hungary 24
U.S.A. 9
Germany 10
France 10
Czechoslovakia 6
India 4
Yugoslavia 3
England 1
Italy 1
Canada 1
Spain 1
Belgium 1
Korea 1
Unidentified 13
Total 140
IronSeveral processes have been developed to recover iron from the
red-mud residues. One method is the carbon-lime-soda sinter process which
can be applied either to ore or to the red mud. ' J-J-4> ll->; j^ this process, the
iron is reduced and recovered by magnetic separation from the waste resi-
dues after alumina leaching. A U.S. patent has been issued describing the
application of a fluidized bed to produce sponge iron by these techniques. (
Another patent was granted for a process to treat high-iron-content bauxite
ores involving reductive roasting with magnetic separation of iron from the
leach residues. ^ '
Direct electric arc smelting of the red mud has been proposed for
recovery of iron from high-iron-content bauxites. In this case, pig iron can
be produced with up to 98 percent recovery of iron value in the bauxite. The
slag from the smelting operation can also be further treated to recover up
to 84 percent of the alumina lost by the Bayer Process. This particular
process was recently advocated by the McDowell Wellman Engineering
Company as being both technically and economically feasible and they have
developed the process through a pilot-scale stage. '1J-°' The economics
34
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assume that the pig iron or steel would be produced near the bauxite refining
plant to take advantage of low-cost iron units in the red mud. The U. S. iron
and steel industry has not taken steps to commercialize the process. Eco-
nomics require a low-cost means to completely dewater the mud. Trace
elements, for example, phosphorus, can have a very significant and adverse
effect on steel quality.
Alumina and titania recovery - Alumina and titania recovery from the
red mud are only of secondary interest. However, if the mud is smelted for
iron recovery, the slag from the smelting operation can be leached with
sodium carbonate solution to recover most of the alumina values. Titania
can be recovered by leaching the residue of the carbonate leach with sulfuric
acid. ''''*' The recovery of titanium from the red mud is technically feasible
but the complicated processing is too costly to compete with the recovery
from natural titanium ores such as ilmenite or rutile.
Other metals - Various other rare metals such as gallium, vanadium,
and scandium can be recovered from the red-mud residues or at various
stages in the Bayer Process. It has been reported that gallium recovery is
economical by direct electrolysis of the caustic aluminate liquors. (H9)
Several studies have also been conducted on vanadium recovery. In one
method a vanadium slag is separated from the pig iron mud. (120)^ jn another
method, liquid-liquid extraction by amines is used on the leach liquors from
the Bayer Process to recover vanadium. (121)
Again, it appears that these recovery methods are only of secondary
interest after first extracting the iron values from the red-mud residues.
Ceramic
For most of the possible uses of the mud in ceramics, it would be
necessary to dry or at least partially dry the mud, for example, before
firing in a brick kiln. Certainly the red mud would require drying to allow
transportation for distances greater than 50 miles. Drying would likely
entail costs of the order of the present cost of most raw materials for the
large-tonnage ceramic products. Although certain specialty uses might be
made of the mud, they are of little significance, since uses relate to the
overall problem of utilization of the muds to eliminate the disposal problem.
Therefore, review of the literature was done using the general criteria that
uses offering the greatest potential would be those that are large-volume
applications, require minimum pretreatment of the red mud, and require
minimum transportation, e. g. , less than a distance of 50 miles.
Cement, building blocks, or brick and to a lesser extent lightweight
aggregate and rubber are potential large-volume applications where red mud
might be used. It is expected that a minimum pretreatment (dewatering)
35
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would be required for use of red mud in brick and lightweight aggregate. For
use in cement and as a rubber filler, acid washing would be required and
complete drying and powdering would be necessary for the filler application.
Cement and brick manufacturing plants are fairly widely distributed through-
out the United States, with lightweight aggregate plants being less numerous.
There is potential for such plants being located near the source of the red
mud which is considered necessary to minimize transportation costs.
Other applications for red mud, such as those listed in Table 6, as
well as applications in exothermic mixes, as a scouring or polishing medium,
or as a drilling mud, are considered of low potential for either technical,
economic, or low-volume reasons.
Ninety-six papers were found on uses of red mud in ceramic applica-
tions. The various uses are shown in Table 6. Table 7 indicates the degree
of activity, by country, relative to developing uses for red mud.
From these tables, it can be noted that about 65 percent of the abstracts
dealt with applications of red mud as cement, construction block material,
lightweight aggregate material, plastic and resin filler, and pigment. The
other 35 percent of the abstracts concerned 13 other applications.
Five countries, Japan, Germany, France, the U.S.S.R. , and Hungary,
were the origin of slightly more than 75 percent of the publications. Three
abstracts were of U. S. origin.
Cement Three potential applications for red mud as a cement material,
with varying degrees of promise, were indicated in the literature.
Cement raw material - Portland cement generally consists principally
of silicates and aluminates as shown in Table 8.
Thus, the oxides of calcium, aluminum, silicon, and to a minor extent
iron make up the major portion of the cement. A typical red mud contains
CaO, SiC>2, and Fe2C>3 in the range around 5 to 10 percent, 2 to 10 percent,
and 40 to 50 percent, respectively. Thus, its potential use as a raw material
for cement manufacture has been of interest. (H2, 123) However, the amount'
of red mud that might be incorporated directly as a raw material would be low
because it contains a relatively high iron oxide. (124)
Additions of ~5 percent of treated red muds to portland cement were
reported to increase strength and affect setting time. (125-128) Greater addi-
tions decreased strength. Pretreatments of the red-mud slurry included
carbonic or sulfurous acid treatments, drying or calcining, and grinding. Un-
treated red-mud additions in small amounts had some affect on setting time.
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TABLE 6. CLASSIFICATION OF LITERATURE BY SUBJECT
ON CERAMIC USES FOR RED MUDS
Field of application Number of abstracts
Cement material 22
Construction block material 16
Lightweight aggregate material \Q
Plastic and resin filler 9
Pigment 6
Miscellaneous materials recovery 5
Caustic recovery 5
Catalyst material 4
Fertilizer material 4
Coating material 3
Insecticide material 2
Refractory cement material 2
Road, pavement, soil stabilization material 2
Metal surface treatment material j
Sewage treatment material 1
Glass material 1
Insulation material 1
Coke additive 1
Total 96
37
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TABLE 7. CLASSIFICATION OF LITERATURE ON
RED-MUD UTILIZATION BY COUNTRY
(CERAMIC)
Country Number of abstracts
Japan
Germany
France
USSR
Hungary
U.S.
India
England
Taiwan
Czechoslovakia
Australia
Switzerland
Ukraine
Poland
Unidentified
32
21
8
9
6
3
2
2
2
2
1
1
1
1
5
Total 96
TABLE 8. RAW MATERIALS IN PORTLAND CEMENT
Component Amount, percent
Tricalcium silicate 45
Dicalcium silicate 27
Tricalcium aluminate 11
Tetracalcium aluminum ferrite 8
MgO 3
Other miscellaneous 6
38
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Cement for iron ore briquetting - Cements produced by sintering red
mud or red mud and limestone have been considered as possible binders in
iron ore briquetting. (129, 130) For this application, the relatively high
^e2^3 content of the red mud is an advantage.
Construction block and brick material The use of red mud for making
structural shapes was considered in 16 publications. However, it was found
that the resulting products were mechanically weak. The compressive
strength of the standard U. S. common bricks exceeds 8000 psi. In most
cases the red-mud products had strengths less than this. This was true
even in the case of brick made of mixtures of red mud and clay fired at
temperatures comparable to those used in firing all-clay brick. '"1, 132)
A 5 to 10 percent addition of red mud to clay was used to make roofing
tile. (133)
However, brickmaking could be an important possible use of the muds.
Construction, and thus the structural brick industry, is currently below its
peak of several years ago. However, in 1973, around 350 plants in the U.S.
were producing 18 million tons of brick annually. Sixty-four of these plants
were in Alabama, Arkansas, Louisiana, and Texas. At a 300 ton/day typical
capacity of a plant, these 64 plants would account for 19, 200 tons of brick/day.
It is judged from the literature that it is not likely that the red-mud
content of brick can exceed 50 percent and that 25 percent is a more likely
prospect. Brick with more than 50 percent red mud were mechanically weak
by U.S. standards.
If the 64 plants cited above made brick comprising 25 percent red mud,
the daily red-mud consumption (on a dry red-mud basis) would be 4, 800 tons.
It is questionalbe that all of the 64 plants could use red mud because of the
distance of some of them from the source of the red mud, resulting in pro-
hibitive shipping costs. If one-fourth of these 64 plants could use the red mud,
1,200 tons/day could be consumed. This is considered a likely maximum use
of red mud for brickmaking but is still a significant use.
Possible contributions of a red-mud addition to clay in brickmaking
include
Pleasing color and color shades dependent on content
Improved dry strength for handling before firing
Lower firing temperature and thus fuel or energy savings.
In the evaluation of this use of red mud, it is recommended that various
red muds be blended with a light (color) burning clay in various ratios.
Specimens formed from this mixture would be evaluated for dry strength,
39
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strength after firing at various temperatures, water absorption, and color.
The water absorption, as well as fired strength, would indicate whether the
typical 1900 F firing temperature was appropriate or whether a lower tempera-
ture might be tolerated or even preferred.
Lightweight aggregate material - Lightweight aggregate is used with
cement to make a lightweight strong concrete. Some clays or shales bloat
and expand when heated to give the lightweight aggregate. Others do not.
The literature(134-138) indicated that combinations of red mud and non-
bloating clays or shales would bloat on heating to yield lightweight aggregate.
One mechanism accounting^13^) for the bloating is the evolution of COz gas
resulting when Fe2O3 in the red mud converts to Fe3O4 on heating. The
oxygen that is evolved during heating of the mud combines with carbon from
organic matter to give the CO2. Red mud:clay ratios for making lightweight
aggregate in the range of 50:50 to 90:10 were given which could potentially
represent a significant use of red mud in this product.
It is estimated that the lightweight aggregate industry is about one-
eighth the size of the brick industry. However, it also appears from the
literature that a lightweight aggregate comprising 75 red mud (dry basis)
25 clay or shale is feasible. This would be three times the maximum con-
sumption in brick using 25 red mud - 75 clay. Thus, at a maximum daily
consumption of 1200 tons of red mud/day for brickmaking, the maximum
consumption for lightweight aggregate production would be of the order of
1200 tons x 3 , cri ,. , ,
= 450 tons/day.
o
A possible attraction to the use of red mud in lightweight aggregate lies
in location of the plant site. Since red mud can be the predominant raw mate-
rial, possibly up to 90 percent in content, location of the plant should be at or
near the source of the red mud. The clay or shale, which apparently need not
possess bloating characteristics itself and which comprises the minor raw
material, can then be shipped to the red-mud source.
There could be merit in study of the mixing of red muds with nonbloating
clay or shale in the ratios of the order of 75 red mud - 25 clay and the mixes
granulated and fired to determine bloating characteristics. Evaluation of the
fired granulated material would be by visual inspection and bulk density
measurement, the latter to determine how "lightweight" the aggregate is.
Plastic and resin filler - Though numerous materials can be used as
fillers, it was considered significant that red mud as a filler in rubber gave a
rupture strength higher than all other fillers excepting carbon black. (139-141)
It should thus be a suitable substitute for carbon black in some applications.
Thus use as a filler requires that the red-mud slurry be acid washed, dried
and powdered.
40
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Pigment - Red mud was indicated to have possible application as a
pigment for coloring concrete' ^', glass^14^), and paint(144). Consistency
of color is a requirement for any pigment application. This factor could
make it difficult to use the mud for this purpose.
Miscellaneous applications - There was no evidence that red mud has
unique yet useful characteristics not to be found in other materials. Basically,
it is a "filler" type of material which can be used in some applications. For
instance, it can be used as an insecticide carrier(145> 146)^ a sojj liming
equivalent^147', a coating filler^148? 149)? a soil stabilization material150),
or a fertilizer^151; 152) if potassium or nitrogen chemicals are added to it.
Other materials can serve these same purposes.
Some of the publications(153, 154) dealt with the recovery of caustic
associated with the red mud while others mentioned its application as a
catalyst material^155; 156)^ a refractory cement material157), a metal
surface treatment ingredient158), a sewage treatment material 159)? an
insulation material'1 ', and a coke additive'1"1).
Waste Treatment
Red mud has been tested as a possible agent in a number of waste-
treatment-abatement applications involving both gaseous and liquid effluents.
For example, it has been found effective as an adsorbent for various chemical
pollutants such as sulfur oxides'1"^, 163) an(j H^s'1" ' from gaseous effluents.
It has also been reported as a good adsorbent of arsenicC1"5) from industrial
wastewaters. In addition to these aspects, it has been investigated as a
coagulant or flocculating agent'15"? 166) for municipal wastewater treatment.
The total number of articles published on different waste-treatment
applications and by country of origin are listed in Tables 9 and 10.
TABLE 9. CLASSIFICATION OF LITERATURE ON WASTE-
TREATMENT APPLICATIONS OF RED MUD
Application Number of articles
Adsorption of sulfur oxides 14
As a coagulant 8
Adsorption of t^S 7
Others _2
Total 31
41
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TABLE 10. CLASSIFICATION OF LITERATURE ON WASTE
TREATMENT APPLICATIONS OF RED MUD
BY COUNTRY
Country Number of articles
U.S.S.R.
Japan
U.S.A.
Germany
France
England
Unidentified
4
11
7
4
1
1
3
Total 31
Adsorbent for sulfur oxides - Dried or calcined red mud has been found
effective for adsorption of sulfur dioxide from industrial waste gases. (1^4)
In this investigation, the gases were passed through an adsorption bed of red-
mud granules at modest temperatures. The adsorbent bed was found to be
over 90 percent effective in removing 803 and could be regenerated with a
reducing gas such as hydrogen. Similarly, good results were obtained when
red mud was mixed with coal for 803 control in industrial boilers.
Use as a coagulant - An interesting possible use of red mud is as a
coagulant for the treatment and sedimentation of municipal wastewaters and
for sludge flocculation. This has been done on a. commercial scale in England
before the war. ( ^' The process involves treatment of the red mud with
concentrated acids, then drying at modest temperatures, and crushing to give
a granular product. Either sulfuric or hydrochloric acids can be used to con-
vert the iron and aluminum oxides in the red mud to sulfates or chlorides.
Thus, ferric chloride or alum can be produced which are well known for their
coagulating properties. In addition to these effects, it has also been reported
that the red-mud materials are effective for removing phosphorus from the
municipal wastewaters with 70 to 80 percent effectiveness.
42
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SECTION VI
EXPERIMENTAL PROGRAM
There are substantial differences in various bauxites and the red muds
or residues from current alumina recovery operations. A part of this study
concerned acquisition of samples and a comparison of the chemical and phys-
ical characteristics of these materials.
In addition to analytical characterization, it was considered important
to examine the relative ability to dewater the muds. Particular attention was
given to factors affecting the flocculation and settling of mud suspensions
using various synthetic polymer flocculants. The influence of dissolved
metals on the coagulation of the muds was studied. Limited experiments
were made on mechanical dewatering, magnetic flocculation, and flotation as
possible methods to achieve partial dewatering. These experiments were
intended to provide a basis to judge the practical limit in partial dewatering
by methods conventionally applied in general processing of minerals.
In addition to the analyses and characterization of the bauxites and mud
samples, several experiments were done to verify results previously re-
ported in the literature concerning a kiln pretreatment of bauxite before
leaching that might allow magnetic separation of iron from the residue after
leaching for recovery of alumina. The results of these experiments are pro-
vided in this section of the report.
SAMPLE ACQUISITION
Mud samples were provided to Battelle from five alumina refineries.
These samples were obtained as slurry samples, generally from the pipeline
going to the mud lake. The slurry samples were sent to Battelle in 55-gallon
drums.
The samples were prepared for study by first mixing thoroughly, using
a motor-driven agitator to mix the entire sample. When it was determined
that all settled material was in active suspension, 5-gallon aliquot samples
were taken from the drum for the various tests and analyses. *
The brown-mud sample provided by Reynolds was not effectively jredispersed after receipt by Battelle. This
mud appeared to have partially set with cementlike character.
43
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A listing of the samples received along with the initial characterization
is provided in Table 11. The solids pulp density provided in the table was
measured by weighing 200 ml of the well-mixed pulp, and then filtering and
drying the solids at 105 C for subsequent weighing.
TABLE 11. INITIAL CHARACTERIZATION OF MUD SAMPLES
Physical properties of mud slurry
Company
Kaiser Aluminum
Alcoa
Alcoa
Reynolds Metal
Martin-Marietta
Location
Gramercy,
Louisiana
Mobile, Alabama
Point Comfort,
Texas
Hurricane Creek,
Arkansas
St. Croix,
Virgin Islands
Type Percent
bauxite Color pH solids
Jamaican Red 11.7 22.1
Surinam- Reddish- 11.9 7.8
African orange
Surinam- Red 11.8 31.0
Caribbean-
Australian-
African
Arkansas Brown 11.7 34.5
Boke' Red 12.5 35.6
(Africa)
Pulp
density
1.16
1.08
1.30
1.33
1.27
CHARACTERIZATION OF MUD SAMPLES
The mud samples as received at Battelle were analyzed for chemical
composition, particle size distribution, specific gravity, and settling rate.
It should be noted that these samples may be typical but not necessarily
representative of the average mud compositions. Details of these analyses
studies are presented below.
Composition
The wet chemical analysis of the dried muds and the supernatant liquid
associated with the as-received samples is given in Table 12.
The results of semiquantitative analyses by optical emission spec-
troscopy (OES) are given in Table 13.
P.a.rticle Size Distribution
The particle size distribution of the mud samples was determined by
wet screen analysis in the size above 44 microns and by Coulter counter
44
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TABLE 12. CHEMICAL ANALYSES OF MUD SAMPLES
(PERCENT BY WEIGHT)
Kaiser Aluminum,
Component
A1O
2 3
Fe 0
2 3
SiO
2
TiC-
2
CaO
Na O
LOI
Gramercy,
Jamaican
Louisiana,
bauxite
Dry Supernatant
mud liquid
15.00
51.50
1.70
6.70
7.0
0.97
9.30
0.58
1.11
Alcoa,
Mobile, Alabama,
Surinam- African bauxite
Dry Supernatant
mud liquid
29.10 8.79
28.20
10.80
12.70
5.72
1.34 15.96
12.90
Point
Alcoa,
Comfort, Texas,
mixture of four bauxites
Dry
mud
17.80
40.00
9.59
8.48
7.57
2.69
10.30
Supernatant
liquid(a)
3.34
14.24
Reynolds Metal,
Hurricane Creek,
Arkansas,
Dry
mud
6.31
10.70
19.90
3.32
42.50
1.34
5.04
Arkansas bauxite
Supernatant
liquid(a)
1.89
7.62
Martin-Marietta,
St. Croix,
mixture
Dry
mud
33.80
22.90
8.49
.-
12.90
3.52
6.0
12.4
Virgin Island,
of bauxites
Supernatant
liquid^3)
N.A.
N. A.
(a) The amounts are reported in grams/liter.
(b) Loss on ignition at 1000 C.
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TABLE 13. OPTICAL EMISSION SPECTROGRAPHIC
ANALYSES OF MUD SAMPLES
(Percent by Weight)
Reynolds
Alcoa, Metals
Alcoa, Point Comfort, Texas Hurricane
Kaiser Aluminum Mobile, Alabama (Surinam-Australian- Creek, Arkansas
Element (Jamaican) (Surinam-African) African) (Arkansas)
Al
B
Ba
Be
Ca
Co
Cu
Cr
Fe
K
Mg
Mn
Na
Ni
Pb
Si
Sr
Ti
V
Zr
2-4
<0.005
0. 02
<0. 0001
5-10
0. 01
0. 02
0. 1
10-20
0. 03
0. 1
1.0
0. 5
0. 1
0.02
0.8
0. 05
2-4
0. 1
0. 1
5-10
0. 005
0. 01
<0. 0001
3-6
<0. 005
<0. 005
0. 05
5-10
0.2
0.03
0.02
1-3
<0.005
0.01
2-4
0.01
3-6
0. 1
0.2
3-6
0. 005
0. 01
<0. 001
4-6
0.01
0. 01
0. 1
20-40
0. 1
0. 1
0.4
2-4
0.03
0.02
2-4
0.03
2-4
0.03
0. 1
1-3
0.005
0.01
<0. 001
20-40
<0. 002
0.002
0.005
5-10
0.3
0.3
0.2
1.0
0. 002
0. 005
5-10
0. 03
1-2
0.01
0.2
-------
technique for particles less than 44 microns in size. For Coulter counter
studies, the particles were suspended in the supernatant liquid and were
thoroughly dispersed with an ultrasonic bath. These data are given in
Table 14 and are shown as composite curves in Figure 6. Particle-size
analyses were also performed on the Gramercy and Point Comfort mud by
the Andreason pipette technique for particle sizes finer than 44 microns.
The results for the Alcoa - Point Comfort, Texas, mud are presented in
Figure 7 for both the techniques. The results are in general agreement,
with each method giving about 50 percent of the mud less than 4 microns.
Specific Gravity
Specific gravities of the dried mud samples were determined with a
pycnometer. The specific gravities were calculated as follows:
Specific Gravity = (C-A)/[ (B-A) - (D-C)] ,
where: A = weight of pycnometer (plus stopper), B = weight of pycnometer
filled with water, C = weight of pycnometer and some solids, and D = weight
of pycnomer plus solid plus water. The results obtained are given in
Table 15.
DEWATERING STUDIES
Dewatering of suspended solids as it applies to this discussion refers
to partial dewatering by removal of bulk and interstitial water from the
suspension. Such physical dewatering methods as sedimentation, filtration,
and centrifugation are of interest. Coagulation and flocculation induced by
addition of chemical agents to the suspension can agglomerate the solids
into larger and more compact aggregates which in turn are more readily
dewatered. Therefore, the influence of such agents is pertinent to this
study.
The mud samples used for the dewatering studies were obtained from
the pipeline going to the mud lake. Hence, the muds were in a partially
flocculated state. Dewatering studies presented in this report do not sim-
ulate the plant flocculation of mud, but pertain to dewatering of mud being
discharged to the lake.
Sedimentation Experiments
The partial dewatering of suspended solids by sedimentation is in-
duced by gravity and follows the generalized pattern illustrated in Fig-
ure 8. , A plot of the height or volume of the settled solids versus settling
time provides initial and final settling rates calculated from the slopes of
47
-------
TABLE 14. PARTICLE-SIZE-DISTRIBUTION DATA(3) FOR VARIOUS MUDS
Kaiser Aluminum Company,
Gramercy, Louisiana,
Jamaican Bauxite
Size
+28 mesh
28 x 48
48 x 100
100 x 200
200 x 270
270 x 325
325 x 35 microns
Average Diameter,
microns
29
13
18
15
12
9
7
6
5
4
3
2
1.5
1.2
0.9
Weight
percent
_ _
0.1
0.4
1.2
0.6
0.4
0.8
0.2
0.8
1.3
1.8
1.8
2.2
3.9
7.0
19.0
14.8
5.7
13.1
19.1
4.8
1.0
Cumulative
weight percent
..
0.1
0.5
1.7
2.3
2.7
3.5
3.7
4.5
5.8
7.6
9.4
11.6
15.5
22.5
41.5
56.3
62.0
75.1
94.2
99.0
100.0
Alcoa,
Mobile, Alabama
Surinam- African Bauxite
Weight Cumulative
percent weight percent
0.2
1.7
6.8
11.8
3.1
1.5
0.9
0.9
1.6
1.6
1.5
1.8
1.5
3.4
10.4
15.6
7.6
4.8
8.4
9.9
4.4
0.6
0.2
1.9
8.7
20.5
23.6
25.1
26.0
26.9
28.5
30.1
31.6
33.4
34.9
38.3
48.7
64.3
71.9
76.7
85.1
95.0
99.4
100.0
Reynolds Metals,
Hurricane Creek, Arkansas,
Arkansas Bauxite
Weight
percent
0.4
8.5
19.7
6.7
4.7
1.0
1.1
3.7
4.3
4.3
3.7
3.4
3.8
4.7
7.1
5.8
9.5
4.2
2.0
1.0
0.4
Cumulative
weight percent
0.4
8.9
28.6
35.3
40.0
41.0
42.1
45.8
50.1
54.4
58.1
61.5
65.3
70.0
77.1
82.9
92.4
96.6
98.6
99.6
100.0
Point Comfort, Texas
Jamaican- Australian-
African Bauxite
Weight
percent
0.1
0.4
1.0
2.9
1.3
0.7
--
0.7
0.7
0.8
1.3
1.5
3.6
5.9
8.6
13.9
16.3
9.0
8.2
9.7
8.6
4.8
Cumulative
weight percent
0.1
0.5
1.5
4.4
5.7
6.4
--
7.1
7.8
8.6
9.9
11.4
15.0
20.9
29.5
43.4
59.7
68.7
76.9
86.6
95.2
100.0
(a) Obtained with Coulter-counter method.
-------
100
2 80
z
<
ui
DC
60
u
DC
UI
a.
ui
U
40
20
-KAISER,
GRAMERCY, LA
ALCOA,
_ PT. COMFORT, TX
REYNOLDS, HURRICANE CREEK, ARK.
ALCOA, MOBILE, ALA.
I I
1.0
10
100
PARTICLE SIZE (/it)
1000
Figure 6. Particle-size distribution of various muds
-------
ioo r
Ui
o
10
PARTICLE SIZE
100
1000
Figure 7. Particle size distribution of Alcoa-Point Comfort, Texas, red mud using Coulter-
Counter and Andreason pipette methods
-------
TABLE 15. SPECIFIC GRAVITY OF MUD SAMPLES
Company
Kaiser
Alcoa
Alcoa
Reynolds
Martin-Marietta
Mud Type
Jamaican Red Mud
Surinam African Red Mud
Australian African
Jamaican Surinam Red Mud
Arkansas Brown Mud
Boke" (South Africa ) - Red Mud
Specific Gravity
3. 10
2.67
2.69
2.65
2.89
51
-------
QC
UJ
co
Q
O
LL.
O
O
Q
01
HINDERED
COMPRESSION
\
SETTLING TIME
Figure 8. Generalized settling rate curve
52
-------
the straight line representing the hindered and compression regimes, re-
spectively, as shown in the illustration.
The settling-rate studies of the red-mud-samples suspensions were
performed in graduated cylinders. The mud slurry, after gentle but
thorough mixing, was poured into the cylinder and the settling tests were
begun. The volume corresponding to the heights of the developing inter-
faces between settled solids and bulk overhead liquid were measured at in-
tervals during a total period of up to 24 hours. The final volume of the
solids layer was noted and the percent solids in the settled sludge was de-
termined by weighing the sludge before and after filtering and drying. The
sedimentation rates reported are based on measured rates in the hindered
settling regime. The initial part of the experimental study involved sedi-
mentation experiments without any addition of chemical reagents to estab-
lish the differences in the individual samples received. Subsequent work was
done to examine the influence of various flocculants and solution chemistry
on the sedimentation.
The settling-rate data for the as-received mud samples are plotted in
Figure 9. It was noted that the Kaiser-Gramercy (Jamaican) mud, the
Alcoa-Point Comfort mud, and Martin-Marietta-St. Croix mud* had a very
similar slow settling behavior. The Alcoa-Mobile (Surinam-African) mud
and the Reynolds-Hurricane Creek (Arkansas) brown-mud sample showed
substantially higher initial settling rates. With the exception of the
Arkansas brown mud, the final settled density of the red muds was 25 to 33
percent solids (Table 16).
As the initial settling tests illustrate, the more severe problem in de-
watering is with the red mud from digestion of Jamaican bauxite. The
settling characteristics of the samples of red mud received from Kaiser's
Gramercy refinery and Alcoa's Point Comfort plant appeared to be quite
similar. The sample from Alcoa, Point Comfort, was not fully representa-
tive as it contained an unexpectedly high percentage of solids (-«30. 0 per-
cent) and no coarse sand. According to information provided at the plant,
the solids content of the mud is generally between 15 and 20 percent and the
material contains a sand fraction. Because the experimental activities in
this program were of limited scope, detailed dewatering studies were con-
ducted only on the red mud derived from Jamaican bauxite. The term
Jamaican Red Mud, as used in the report, refers to the red mud supplied by
Kaiser Aluminum Company, Gramercy, Louisiana. The following conditions
and operations were studied:
(1) Effect of pH on settline rate
(2) Effect of metal ions on settling rate
*A very small sample of the mud was provided for the study; therefore, no detailed tests were made.
53
-------
en
200
180
- 160
E
cc
>
140
| 120
° 100
2
D
O
>
80
60
40
20 -
-I
D
I
-R
SOURCE OF MUD
KAISER - GRAMERCY, LA.
£ ALCOA - POINT COMFORT, TEX.
O REYNOLDS - HURRICANE CREEK
D ALCOA - MOBILE, ALA.
MARTIN-MARIETTA - ST. CROIX, VI.
-!>
I
._.O
-CW _ p _ _
1
8 10
TIME (HOURS)
i>
24 HRS
Figure 9. Settling rate curves for various muds (as received)
-------
TABLE 16. SETTLING-RATE DATA FOR VARIOUS MUDS (AS RECEIVED)
Initial Percent
percent solids in
Settling solids in the sludge
rate, the mud after 24-hr
Mud source Type of mud pH cm/hr slurry settling
Kaiser, Jamaican 11.8 0.10 22.2 25.6
Gramercy,
Louisiana
Alcoa, Surinam-African 11.7 2.96 7.8 28.2
Mobile,
Alabama
Alcoa, Mixed 11.9 0.05 31.0 33.0
Point Comfort,
Texas
Reynolds, Arkansas 11.8 2.15 35.06 55.5
Hurricane Creek,
Arkansas
Martin-Marietta, Bokex 12.3 0.12 35.85 38.04
St. Croix,
Virgin Islands
55
-------
(3) Effect of polymers on settling
(4) Effect of solids concentration on settling
(5) Effect of magnetic field, i.e., magnetic flocculation, on
settling
(6) Flotation as a means to dewater
(7) Centrifuging with and without reagents as a means to dewater.
Effect of pH-The red mud contains different solids with different sur-
face electrical charges. The chemistry of a suspension, particularly the con-
dition of pH can be used to induce a mutual coagulation of mud particles and
thereby alter the settling and dewatering character. For this reason, sedi-
mentation experiments were made at different pH.
The settling rate data for the Kaiser-Gramercy (Jamaican) mud at
pH 5. 2, 7. 0, 8. 5, and 11. 7 are given in Table 17. The pH was not found to
have a significant effect on the settling rate. It was noted that adjustment
of the pH to below 5. 0 caused considerable effervescence and swelling of the
mud. No significant change was found in the final solid density of the sludge
with pH variation within the 24-hour time period of the experiments.
Effect of metal ionsThe fact that metal salts and metal precipitates
induce coagulation and settling is well established. Precipitated metal hy-
droxides enmesh fine particles and accelerate the settling of a suspension.
Several experiments were performed by adding the red-mud slurry to
solutions of aluminum (Al""), ferric (Fe""), and magnesium (Mg"*"^) salts.
The quantity added was adjusted to give pH values of 8. 0, 7. 0, and 10. 5,
respectively, in the final slurry. These pH levels are known to be effective
for these metals in industrial wastewater-treatment systems.
An experiment was also made by first lowering the pH of the mud to
/V2. 0, assuming some of the iron present in the mud might dissolve at this
low pH, and then raising the pH to 8. 0 to precipitate any dissolved iron as
hydroxide. The results are summarized in Table 17. Despite some appar-
ent improvement in the initial rate of settling, particularly in the case of
iron, the ultimate settled density of the sludge was not increased above that
of the "as-received" sample, or, in the order of 20 to 25 percent solids.
56
-------
TABLE 17. EFFECT OF pH AND METAL IONS ON SETTLING RATE OF JAMAICAN RED MUD
Volume of
red mud,
ml
100
100
100
100
75
50
75
75
100
Reagent
H2S04
H2S04
H2S04
--
0. 1 M A12(S04)3
0. 01 M Al2(S04)g
0. 1 M FeCl2
0. 1 M MgSO4
H SO
NaOH (IN)
Volume of
reagent,
ml
1.0
0.5
0.3
--
25.0
50.0
25.0
25.0
4.0
10.0
pHof
the
mixture
5.2
7.0
8.5
11.8
8.0
8.0
7.5
10.5
8.0
Settling
rate,
cm/hr
0.188
0.072
0.085
0.100
0.080
0.148
0.789
0.12
0.075
Percent solids
in original
slurry
22.72
22.18
24.85
24.70
15.03
7.25
16.94
19.56
22.61
Percent solids
in sludge
after 24 hr
23.97
23.68
25.91
25.46
25. 28
8.14
21.79
22.60
24.07
57
-------
Effect of Synthetic (Polymer) Flocculants
This part of the experimental program was conducted by the Environ-
mental Products Research and Development Group of the Dow Chemical
Company under subcontract from Battelle. ''*
Flocculation due to polymers (or poiyelectrolytes) involves adsorp-
tion of the polymer with formation of larger aggregated floes due to a
chainlike bridging action. Polymer flocculants are linear or branched high-
molecular-weight organic polymers which are water soluble. They are
classed according to their ionic character as anionic, cationic, or nonionic,
depending on whether their electrical charge is negative, positive, or neu-
tral, respectively.
The flocculation tests made in this program comprised visual obser-
vations and optical measurements made when varied quantities of selected
flocculants were added to the red-mud sample. Measured volumes of a sam-
ple of the suspension were placed in glass containers ("jars") equipped with
paddle agitators. Flocculants were then added in measured amounts at
prescribed times and agitation conditions. The experimental apparatus com-
prised six jars arranged as illustrated in Figure 10.
Filtration tests were also made on the flocculated samples. For these
tests, the flocculated samples were transferred to a Buchner funnel sup-
ported over a graduated cylinder. A record was made of the volume of fil-
trate collected with time.
In the initial experiments with polymer flocculants, it was noted that
the red mud as received formed a gel. The relative effect of different poly-
mers, however, could be determined only by diluting the mud samples.
The initial tests were conducted to establish the proper dilution.
These were performed with samples diluted to the following percentage of
the as-received samples: 100 (undiluted), 50, 20, 10, 5, and 2 percent.
The diluted red-mud suspensions were prepared by dilution with caustic of
strength comparable to the original red-mud supernatant. The settling-
rate curves for this series of samples are given in Figure 11. It was ob-
served that the 10 percent sample ( 2.2 percent solids) exhibited a moderate
settling rate with a well-defined interface and hence this dilution was se-
lected for all subsequent comparative tests of dewatering agents. The con-
centration of suspended solids was measured by scattered light and reported
in Formazin Turbidity Units (FTU).
*Dow's report on "Dewatering of Red Mud" is available upon request from the United States Environmental
Protection Agency, Cincinnati, Ohio.
58
-------
UNTREATED SUSPENSION
0 COAGULANT OR FLOCCULANT CONCENTRATION (LOGARITHMIC)
Figure 10. Laboratory evaluation of efficiency of
coagulation - the jar test
59
-------
500
100%
400
300
ui
5
_i
5
200
100
10
20
30 40 50 60
SETTLING TIME, WIN.
80 90
Figure 11. Effect of dilution on settling rate behavior
of Jamaican Red Mud
60
-------
Various synthetic flocculants, listed in Table 18, were tried with the
diluted 10 percent red-mud sample. The settling rate and the filtration rate
with each flocculant are shown in Figure 12 and Figure 13, respectively.
All loadings of flocculants are equal to 0. 54 Ib/ton of dry solids. Figure 12
shows that anionic and nonionic flocculants are more active than cationic
flocculants in effecting settling. The hydrolyzed polyacrylamide (Series III)
was most active of all dewatering agents tested for both settling and filtra-
tion at this low loading of flocculant.
A few experiments were also conducted at Battelle with undiluted red-
mud slurry containing ~22. 0 percent solids. The settling-rate experiments
using different types of anionic polyelectrolytes indicated that the addition of
a synthetic flocculant to the undiluted mud does not significantly improve the
settling rate or percent solids of the settled sludge (Table 19).
Magnetic Flocculation
Red mud contains a small amount of free iron and a part of the iron ox-
ide is present as magnetite. A few experiments were conducted to determine
whether a magnetic field would affect flocculation. One of the experiments
was also conducted with addition of fine magnetite powder (minus 200-mesh
size) to the red mud. The results did not show any improvement in the
settling behavior or percent solids in the sludge.
Flotation
Flotation of the red mud was performed with two different collectors
(an amine and the oleic acid) and frothers (MIBC and cresylic acid). In
either case, no segregation of solids was observed in either the froth or the
tailings.
Centrifuging
The Kaiser-Gramercy (Jamaican) mud was centrifuged in a laboratory
machine at 1000 rpm. The objective was to determine the maximum solids
content of a mechanically dewatered mud. Experiments were made with and
without addition of a synthetic flocculant (Superfloc C-100).
The centrifuge tubes were 200-ml capacity. These were charged with
100 ml of the mud suspension. Any reagents were added prior to charging.
Initial experiments established that compaction was essentially complete
after 10 minutes.
The data obtained without reagents and with addition of tallow amine
and various amounts of Superfloc C-100 are given in Table 20. The results
61
-------
500
400
f 300 U'
UJ
5
3
a
IU
in
100
200 h-
234
SETTLING TIME (MINUTES)
Figure 12. Effect of various synthetic flocculants on the
settling rate of diluted (10X) Jamaican Red Mud
(Loading of flocculant 0. 54 Ib/T of solids. )
62
-------
o *-
100
HI
5
§
ui
u.
200
300
400
10 20
FILTRATION TIME (MINUTES)
0
IV
II
VII
I
Ul
£
Ul
CA
III
30
Figure 13. Effect of various synthetic flocculants on filterability
of diluted (10X) Jamaican Red Mud
(Loading of flocculant 0. 54 Ib/T of solids. )
63
-------
TABLE 18. SYNTHETIC FLOCCULANT SELECTED FOR
EVALUATION
Series
I
II
in
IV
V
VI
vn
Chemical description
Sodium Polyac rylate
Sodium Polystyrene Sulfonate
Hydrolyzed Polyacrylamide
Unhydrolyzed Polyacrylamide
Dimethylaminomethyl Poly-
acrylamide
Polyalkylene Polyamine
Starch Derivative
Specific
product
XFS-4111L
Purifloc A2 1
Purifloc A23
Purifloc N20
Purifloc C41
Purifloc C31
Flocgel
Ionic
character
Anionic
Anionic
Anionic
Nonionic
Cationic
Cationic
(a) All products of Dow Chemical U.S.A. except Flocgel which is produced by W. A. Scholtens Chemische,
The Netherlands.
TABLE 19. SETTLING RATE DATA FOR UNDILUTED JAMAICAN RED MUD
USING DIFFERENT POLYMER FLOCCULANTS
Polymer
Amount
Ppm
of polymer
Lb/ton of
dry solids
Control (No Polymer Addition)
DOW
DOW
DOW
PEI 1090
PEI 1090
PEI 1090
1
5
10
0.09
0.50
0.95
Settling
rate,
cm/hr
0.03
0.54
0.60
1.20
Percent solids
in original
slurry
22.0
17.6
15.1
12.6
Percent solids
in sludge
after 24 hr
25.0
25.8
21.2
17.8
Cyanamid' Superfloc C-100
Cyanamid Superfloc C-100
5
10
0.50
0.95
0.16
0.10
13.2
20.4
28.4
23.2
Starch (potato)
100
9.5
0.22
23.0
24.2
64
-------
show that a dewatered mud of about 40 percent solids is possible by centri-
fuging. Addition of flocculants did not appear to provide a means to achieve
a higher ultimate solids content, thus indicating that only the free water and
not the interstitial (bound) water associated with red mud is removed.
TABLE 20. CENTRIFUGE TEST DATA OF JAMAICAN RED MUD(a)
Reagent
Tallow amine
Superfloc C-100
Ditto
n
ii
Volume of
reagent,
ppm
--
50
5
10
20
40
Initial percent
solids in
the slurry
22. 80
21. 78
18. 75
17.98
16. 72
15.24
Final percent
solids in
the sludge
39. 00
32.00
37.58
38.43
38.20
37.00
(a) Conditions: Centrifuge speedlOOO rpm; time of experiment--10 minutes; volume of mud sample--
100 ml.
All of the above studies indicate that additional basic research is needed
to better understand the mechanisms which limit or control the removal of
interstitial water by physical-chemical methods. This will involve study of
surface chemistry of various components of red mud, their affinity for water,
and the possibility that the hydrophilic surface properties can be altered.
Reductive Roasting of Bauxite as an Alternative
to Conventional Bayer Processing
In the Combination Process, calcination of Bayer Process red mud with
soda ash and limestone produces the brown mud (a cement-type material),
which is much more readily dewaterable and compacts to a high percent
solids. On the basis of this, it was speculated that calcination or sintering of
Jamaican bauxite before caustic leaching might alter the clay structure of the
ore and yield a different type of red mud.
Technology described by Kamlet in his patent U. S. 2, 964, 383
assigned to Reynolds Metals Company is of interest not only because it de-
scribes a kiln pretreatment before digestion, but it discloses that if the pre-
treatment is done under a reducing atmosphere condition, it is possible to
reduce the iron in the bauxite to a magnetic form, recoverable by usual mag-
netic separation methods from the leach residue. Several preliminary experi-
ments were made by Battelle using the Kaiser-Gramercy bauxite (Jamaican)
ore as the feed to the process. The laboratory procedure comprised the
following sequence of steps:
65
-------
(1) Blending the bauxite ore with sufficient sodium carbonate,
calcium carbonate, and carbon. The quantities were based
on providing sufficient soda to combine with the alumina to
form soluble sodium aluminate, sufficient calcium to com-
bine with silica and titania, and adequate carbon to reduce
iron oxides to metallic iron.
(2) Pelletizing the mixture in a balling drum using 10 percent
by weight water addition (Experiment 2).
(3) Firing the mixed material (pellets) in a reducing atmosphere
at a temperature of 1000 C (1832 F).
(4) Comminuting the calcined product and separating the
metallic iron by magnetic separation.
(5) Leaching the residue with an aqueous solution of sodium
carbonate to recover the alumina.
The composition used in the experiments was prepared in accordance
with the following ratios:
(1) 1. 1 moles of Na2CC>3 added for each 1. 0 mole of A^Oo
(2) 1.0 mole of CaCO3 added for each 1 . 0 mole of TiO2
(3) 2. 0 moles of CaCO^ added for each 1. 0 mole of SiO?
(4) Carbon added to amount to 20 percent of the furnace charge.
This part of the experimental program comprised two experiments,
which are described below.
Experiment 1 This experiment was made with a 25 -g sample obtained
from a ground mixture of bauxite (270 g), sodium carbonate (168 g), calcium
carbonate (17 g), and charcoal (121 g). The sample mixture was placed in
hollowed-out portion of a 15. 24-cm (6 in. )-long and 3. 81-cm (I. 5 in. )-outside-
diameter graphite crucible and heated in an electrically heated tube furnace at
1000 C (1832 F) for 1 hour. The cooled mixture was first leached with 0. 1
liter (100 cc) of 10 percent Na2CO3 solution and then washed with 1 liter
(1000 cc) of hot water. The settling test was performed on the leached resi-
due suspended in water. A Davis tube was used to determine the amount of
magnetic iron in the residue. The magnetics and nonmagnetics portions were
analyzed separately for iron and A^Oo.
Experiment 2 - In the second experiment, pellets 0.64 cm to 1.27 cm
(1/4 in. to 1/2 in. ) in size were made from the ground bauxite (890 g),
sodium carbonate (550 g), calcium carbonate (54. 0 g), and coke (200 g)
mixture. The pellets were placed in a 11. 43-cm (4. 5 in. )-long and 7. 62-cm
66
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(3 in. )-diameter refractory crucible and fired in an electrically heated muffle
furnace at 1000 C (1832 F) for 1-1/2 hours. Fifty grams of the pellets was
then crushed, ground, and leached with 200 cc of 10 percent Na2COo solution.
The settling test was performed on the leached solids while suspended in
liquor and also in wash water. The Davis tube test was made as before to
separate magnetic iron. Analyses of typical products are provided in
Tables 2 1 and 22.
The material balances for the two experiments are listed in Table 23.
In the second experiment, emphasis was placed on the settling behavior of
solids in pregnant liquor and the leaching of the sample was not completed.
The chemical analyses of the head bauxite .sample and other samples
obtained at each stage of the sintering process are given in Tables 21 and 22.
The overall test data indicated approximately 85 percent recovery of the total
available alumina.
Figure 14 shows the settling-rate curves for the mud obtained in the
present sinter method test and the red mud obtained in the conventional Bayer
Process supplied by the Kaiser plant. Data for the settling rates and percent
solids obtained in the sludge for the two muds are given in Table 24.
Note that the settling rate of the mud obtained from the roasted ore
experiment is approximately four times higher than that of the conventional
red mud. However, the compaction of the mud as measured by the percent
solids in the sludge after 24 hours showed no increment in either case.
In general, the preliminary investigations indicated that the soda-lime-
sinter process may offer limited potential to reduce the severity of the red-
mud problem. The recovery of iron in a magnetic concentrate was only about
30 percent of the iron content of the bauxite. Moreover, the magnetic concen-
trate was not sufficiently high in iron to be used in ironmaking furnaces.
These aspects, however, may be improved with study.
Such a procedure, however, would entail significantly higher energy
costs and possibly a need to pelletize the feed to prevent excessive dusting.
Moreover, the amount of caustic required may be more than that required
for the conventional system. It is not likely that such front-end processing
could be implemented without a major change in existing Bayer Process
plants.
67
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TABLE 21. CHEMICAL ANALYSES OF PRODUCTS OBTAINED BY THE
REDUCTIVE ROASTING OF BAUXITE (EXPERIMENT 1)
Weight percent
Product
Head sample (bauxite)
Sintered mixture
Leached liquor
Iron concentrate
Nonmagnetic residue
A1203
54. 10
__
4.91(a)
21.40
10.60
Fe
12.20
8.20
--
41.40
18.70
Si02
0.64
0.98
--
4.40
3.96
Ti02
2.44
--
--
---
3.60
(a) Grams/liter.
TABLE 22. CHEMICAL ANALYSES OF PRODUCTS OBTAINED BY THE
REDUCTIVE ROASTING OF BAUXITE (EXPERIMENT 2)
Product
Head sample (bauxite)
Sintered pellets
Leached liquor
Iron concentrate
Nonmagnetic residue
A1203
54. 10
43.40
15.78(a)
33.90
32.30
Weight
Fe
12.20
11. 10
26.00
19.00
percent
Si02
0.64
1.36
1.70
1.76
TiO*
2.44
2. 52
5.30
4.21
(a) Grams/liter.
68
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TABLE 23. METALLURGICAL WEIGHT BALANCE FOR IRON AND
OBTAINED IN REDUCTIVE ROASTING OF BAUXITE
Experiment
I
I
I
I
I
I
n
ii
ii
ii
ii
ii
Sample
Head sample mixture
Magnetic concentrate
Nonmagnetic concentrate
Leached liquor
Accountability, %
Recovery, %
Head sample pellets
Magnetic concentrate
Nonmagnetic concentrate
Leached liquor
Accountability, %
Recovery, %
Weight of
sample, g
25
0.5
5.3
--
50
6.4
19.2
--
Assays
Fe, g
2.05
0.2
1.0
--
63.0
10.0
5.55
1.64
3.65
--
95.0
30.0
(total weight)
Al203, g
6.27
0. 10
0. 57
5.40
96.8
86.0
21.7
2. 15
6.45
8.80
80.0
40.0
(a) Sample was taken from a 576-g mixture of bauxite (270 g), solution carbonate (168 g), calcium carbonate
(17 g), and charcoal (121 g).
(b) Sample was taken from a 1690-g mixture of bauxite (890 g), sodium carbonate (550 g), calcium
carbonate (540 g), and coke (200 g) pellets.
69
-------
200
180
O BAYER PROCESS RED-MUD
Q EXPERIMENTAL MUD
3 4
SETTLING TIME (HOURS)
24
Figure 14.
Settling rate curves for the reductive roasting of
bauxite process mud (9. 7% solids) and the
Jamaican Red Mud (11.7% solids) slurries (no
flocculant added)
TABLE 24. SETTLING RATE TESTS DATA FOR THE REDUCTIVE ROASTING
PRODUCT MUD AND THE JAMAICAN RED MUD
Mud type
Settling
rate,
cm/hr
Initial
percent
solids in
slurry
Final percent
solids in
sludge after
24-hr settling
Conventional Bayer
Process red mud 3.43
Sinter method
experimental mud 14.63
11.71
9. 70
22.20
28. 50
70
-------
SECTION VII
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Coagulating Red Mud. U.S.S.R. 323,364, December 10, 1971.
(104) Cook, G. W. Rapid Settling of Mud Impurities From Sodium Aluminate
Solutions. (Reynolds Metals Co.) U.S. 3,127,239. 5pp. March 31,
1964.
(105) Murphy, J. M. and P. W. Bolmer. Freezing and Melting Treatment
of Red Mud Slurries to Aid Solid Separation. (Kaiser Aluminum and
Chemical Corp. ) U.S. 3,714,792. 5pp. February 6, 1973.
(106) Dumay, S. The Influence of the Processing Temperature on the
Settling of the Red Mud. Femipari Kutato Intezet Kozlemenyei. 29-66,
1956.
(107) German-Galkina, A. S., T. M. Zlokazova, V. P. Mel'nikova, and
V. V. Sidorenko. The Use of Hydrocyclones Together With Thickeners
for Separation of Solids in Leaching Alumina-Bearing Sinter. Tsvetnye
Metally 3jt:52-4, 1961.
(108) Good, P. C. and O. C. Fursman. Centrifugal Dewatering of Jamacan
Red Mud. U.S. Bur. of Mines, R. I. 7140, June, 1968.
(109) Polyakov, L, N. and I. K. Skobeev. Filtration of Red Muds (Bayer
Process). Obogashch. Met. Polez. Iskop. 27-9, 1970.
(110) Kaempf, F. Experience With the Use of Drum Filters for the Filtra-
tion of Red Mud. Int. Leuhtmetalltag., 5th. 356-60, 1968.
(Ill) Plaetschke, H. Separation of Red Mud With Rotary Filters. Bauxite,
Alumina, Alum., Proc. Int. Symp. ICSOBA, 2nd (1969) 3:181-5, 1971.
(112) Konig, P. Filtering Red Mud in Alumina Plants With a Vacuum Drum
Filter With a Stripping Cylinder. Banyasz. Kohasz. Lapok, Kohasz.
_K)6(6):282-5, 1973.
(113) Martine, J. L., Jr. Filtration of Alkali Metal Aluminate Solutions.
(Aluminum Co. of America) U.S. 2,822,091, February 4, 1958.
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(114) Fursman, O. C., J. E. Mauser, M. O. Butler and W. A. Stickney.
Utilization of Red Mud From Alumina Production. U. S. Bur. Mines,
Report Invest. 7454, November, 1970.
(115) Calhoun, W. A., and T. E. Hill, Jr. Metallurgical Testing of
Hawaiian Ferruginous Bauxites. Concluding Report U. S. Bur.
Mines, Report Invest. 6944, 1967.
(116) Colombo, U., and G. Sironi. Iron Sponge From Bayer Process Red
Slurry. U.S. 3,295,961. 6pp. Januarys, 1967.
(117) Kamlet, J. Processing of Ferruginous Aluminum Ores. U.S.
2,964,383, December 13, I960.
(118) Guccione, E. Red Mud, A Solid Waste Can Now Be Converted to High-
Quality Steel. Eng. Mining J. 1_72(9): 136-8, September, 1971.
(119) Papp, Elemer. Possibilities of Recovery of Rare Elements From
Bauxites During Alumina Production by the Bayer Process. Freiberger
Forschungsh. B67, 117-30, 1962.
(120) Friedrich, V. Production of Vanadium Slag From Bauxite Red Mud.
Tech. Dig. _9(7):443-4, 1967.
(121) Gerisch, S., H. Martens andS. Ziegenbalg. Winning of Vanadium
From By-Product of Bauxite Treatment. Neue Huette. 14(4):204-10,
April, 1969.
(122) Urvacya, G. D. Slurry Wastes in the Metallurgical Industry and Their
Utilization. Khim.-Met. Inst., 62-114, 1964.
(123) Beisher, R. V. Use of the Tikhvin Alumina Plant Bauxite Mud in
Highway Construction. Inzh.-Stroit. Inst., 8-17, 1968.
(124) Mitsugi, T. Fluidizing Calcination of Red Mud. Tohoku Daigaku
Senko Seiren Kenyusho Iho, 18, 61-73, 1962.
(125) Katayarna, S. and Yoshikaya Horiguchi. Utilization of Red Mud.
I-Effects of Red Mud on the Properties of Cements. Rika Gaku
Kenkyusho Hokoku, 3_7, 101-105, 1961.
(126) Katayama, S. and Yoshikoya Horiguchi. Utilization of Red Mud. II-
Effects of the Addition of Red Mud on the Properties of Cements. Rika
Gaku Kenkyusho Hokoku, _3_9, 407-410, 1963.
(127) Katayama, S. Utilization of Red Mud. V. Physical Tests of Cements
Blended With Calcined Red Mud. Rika Gaku Kepkyusho Hokoku, 40,
194-202, 1964. Qn ~~'
ou
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(128) Horiguchi, Y. and S. Katayama. High Early-Strength Blended Cement.
Japan 16, 9«4, 2pp. October 20, 1962.
(129) Szekely, Istvan. Cement Production by Using the Red Sludge of the
Bauxite Industry, Epitoanyag, 12, 28-37, I960.
(130) Szekely, I. Ore Cements From Red Mud. Proc. Conf. Silicate Inds.,
6th. Budapest, 399-408, 1961.
(131) Bayer, G., E. Cherdron, M. Haerter, and E. Hecht. Bricks From Red
Mud. Ger. 2,063,028, June 29, 1972.
(132) Tauber, E., R. K. Hill, D. N. Crook, and M. J. Murray. Red Mud
Residues From Alumina Production as a Raw Material for Heavy Clay
Products. J. Aust. Ceram. Soc., _7, 12-17, 1971.
(133) Hegenbarth, R. Experiments in the Utilization of Red Mud. Aluminum
_48, 748-750, 1972.
(134) Ishihara M., K. Takada, and Y. Yamanashi, Synthetic Lightweight
Aggregate. Japan, 74, 60,324, June 12, 197~4.
(135) Expanded Clay, Kloeckner-Humboldt: DeutzA.G. Fr. 1,503,121,
November 24, 1967.
(136) Wargalla, Gerhard. Use of Red Mud in the Production of Cement and
Expanded Clay. Erzmetall 26( 1): 18-20(1973).
(137) Tacken, J., Production of Porous Clay Ceramics. Ger. 1,224,655,
September 8, 1966.
(138) Hayashi, S. and K. Kato. Lightweight Concrete With High Mechanical
Strength. Japan, 7452,213, May 21, 1974.
(139) Funke, Armin, H. Wetzel, and G. Buhler. Rubber Fillers From Red
Mud. Ger. (East) 19, 854, September 20, I960.
(140) Filler for Rubber Compositions. Fr. 978,108, April 10, 1951.
(141) Ketomo, A. G. Treating Natural and Synthetic Rubber. Swiss 274, 574,
July 2, 1951.
(142) Foerster, Herbert. Concrete Color Composition. Ger. (East), 57,543,
August 20, 1967.
81
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(143) Hahnel, K. O. Red Mud as Raw Material for Colored Glass. Glasstech.
Ber. 76_, 174-175, 1953.
(144) Ramanujam, S. Bauxite Residues as (Corrosion) Inhibitive Primers.
Paintiudia 12, 22-34, 1962.
(145) Oda, N. Agricultural Pesticide. Japan 5650 (51), September 21, 1951.
(146) Motte and Pomot. Protecting Insecticides Against the Action of Light.
Fr. 848,974, November 9, 1939.
(147) Whittaker, C. W., W. H. Armiger, P. P. Chichilo, and W. M.
Hoffman. Brown Mud From the Aluminum Industry as a Soil Liming
Material. Soil Sci. Soc. Amer. , Proc., j_9, 288-292, 1955.
(148) Ramanujam, S. and R. V. Saluja. Primers Based on Red Mud. Indian
81,431, April 11, 1964.
(149) Worzella, Gerhard. Bituminous Mixtures Containing Treated Bauxite
Residues. Brit. V1110168, April 18, 1968.
(150) Kasai, J. and K. Fukurr. Surface Treated Quicklime. Japan 74,
49, 899, May 15, 1974.
(151) Watanabe, T. Zeolitic Potassium Fertilizer From Red Mud. Japan
12, 622, September 3, I960.
(152) Hofmann, H., K. H. Reisner, S. Meyer, E. Friedrich, and E.
Guenther. Treating Red Mud. Ger. (East) 67, 721, July 5, 1969.
(153) Retezar, A., L. Pechy, and G. Gardos. Leaching of the Red Sludge.
Veszpremi Vegyipari Egyetem Kozlemenyei, 2, 213-217, 1958.
(154) Karpenko, Z. S., Kh. N. Nurmagambetov, Yu. Khaliullin, and V. D.
Ponomarev. Regeneration of Alkali From Bayer Red Slime of Turgai
Bauxites. Met. i Obogashch., _1, 3-7, 1965.
(155) Sudzilovskaya, M. S. and E. V. Robozheva. Kinetics of Destructive
Hydrogenation of Coal. VNIGI, _6, 30-45, 1959.
(156) Tabuchi, K. Sulfide Catalyst for Obtaining Ethane and Ethylene From
Mixed Gases. Japan 72 08,012, March 8, 1972.
(157) Suzuki, N. Refractory Cement Additives. Japan 73 38, 609,
November 19, 1973.
82
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(158) Machlet, A, W. Surfacing Metallic Articles. U.S. 2,551,957, May 8
1951.
(159) Edward II, Ellis. Chlorinated Copper as Treatment of Sewage at
Kingston-on- Thames. Surveyor, 106, 195-196, 1947.
(160) Hayashi, S. and Matsui, F. Hardenable Foam-Generating Compositions.
Japan, 73 36,941, November 8, 1973.
(161) Heyd, Ferdinand. Use of Sludge From Alumina Production From Iron-
Containing Bauxite in Coke Manufacture. Czech. 93, 355, January 15,
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(162) Land, G. W. Controlling Sulfur Dioxide Emissions From Coal Burning.
Nat. Eng. _73(l):6-8, 1969.
(163) Myers, J. G. , and J. H. Field. Absorbent for Removing Sulfur Oxides
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(164) Shultz, F. G. and J. S. Berber. Hydrogen Sulfide Removal From Hot
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Removal of Arsenic From Waste Waters by Sorption. Tsvet. Metal.
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(166) Bayer, G. , and E. Cherdron. Red Mud Flocculant for Waste Water
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83
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SECTION VIII
GLOSSARY
ALUMINA
Any of several forms of aluminum oxide, A12O3, occurring naturally as cor-
undum, in a hydrated form in bauxite, and with various impurities as ruby,
sapphire, and emery.
BAYER PROCESS
Process in which impure alumina in bauxite is dissolved in a hot, strong,
alkali solution, normally NaOH, to form sodium aluminate -which upon dilu-
ting and cooling hydrolyzes, forming a precipitate of pure aluminum hydroxide.
BAUXITE
A commercial ore for alumina, which is an impure mixture of earthy hydrous
aluminum oxides and various metal oxides, e. g. , iron, titanium, rare earths,
etc.
BROWN MUD
The final solid waste remaining after the alumina is leached from the calcined
red mud in the combination process.
CALCINATION
The roasting or burning of any substance to bring about physical or chemical
changes.
CAUSTIC SODA
The sum of free NaOH and the NaOH combined as NaAlO2, expressed as
Na2CO3.
CENTIMETER (cm)
0.3937 inch.
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CLEAR WATER LAKE
Nominally the lake relatively free of alkalinity and other dissolved solids
used as a fresh-water reservoir for a bauxite refinery.
COMBINATION PROCESS
Variation of Bayer Process used for high silica ores, in which the red mud
from the first-stage Bayer Process is calcined with soda ash and lime and
leached to recover additional alumina.
CONTINUOUS COUNTERCURRENT DECANTATION (CCD)
A continuous system of washing finely divided solids, such as red muds, to
free them from liquids containing dissolved substances. In practice, the
fresh water and the solids slurry start at opposite ends and move counter-
currently to each other, so that the fresh water contacts the solid to remove
soluble substances away from it.
DEWATERING
Physical separation of water from sludge by the application of an external
force.
DIGESTER
Pressure vessel or autoclave in which the alumina is dissolved from the
bauxite.
FRENCH DRAIN
An underground passageway (through gravity) for liquid through the inter-
stices of sand and gravel layer and collected in perforated pipes.
FILTER CAKE
The solids collected on a mechanical filter surface when a solids suspension
is filtered.
FLOG
Collections of smaller particles agglomerated into larger, more easily
settleable particles through chemical or physical treatment.
FLOCCULANT
A reagent which induces flocculation of suspended solids.
85
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FLOCCULATION
The agglomeration of suspended solids by adding a flocculant, thereby
forming larger aggregate floes that are easily removed by sedimentation.
FLOTATION
A process for separating suspended particles from a solution by introducing
air bubbles which carry the particles to the surface where they are removed.
GPM
Gallons per minute.
GREEN LIQUOR
The aluminum-bearing solution from the bauxite digesters before further
processing.
HINDERED SETTLING (Sedimentation)
Sedimentation that is affected by interactions among suspended particles at
high concentrations or between particles and vessel walls.
IMPOUNDMENT
A natural or artificial, usually open, body of water from which surface
water could be reused.
JAR TEST
A laboratory procedure for evaluating flocculation and sedimentation
processes in a series of parallel comparisons.
LITER
1000 cubic centimeter.
MAGNETIC SEPARATION
A physical treatment process for removing magnetic suspended solids from
a liquid by applying a magnetic field.
MICRON
0. 0001 cm (10~6 meter).
86
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mg/1
Milligrams per liter. Nearly equivalent to parts per million concentration.
MUD LAKE
The diked reservoir (tailing pond) used to impound mud.
pH
A measure of the alkalinity or acidity of a solution, in terms of the negative
logarithm of the hydrogen-ion concentration (mol/1); neutral = pH 7 =
10-"7 mol /l; acidic pH < 7; basic pH > 7.
POLYMER
Any synthetic organic compound having a high molecular weight and composed
of repeating chemical units (monomer).
ppm
Parts per million, a unit of concentration.
PRECIPITATION
The conversion of dissolved solids into suspended solids.
PREGNANT LIQUOR
Solution containing the metal values prior to their removal and recovery.
PROCESS LAKE
Reservoir used for process water; often in closed circuit with part of process;
not used for mud disposal.
RECYCLE
To return water after some type of treatment for further use, generally
implying a closed system.
RED MUD
The final solid waste remaining after the alumina is leached from the bauxite.
87
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SAND FILTER
A bed of sand through which liquid is passed to remove fine suspended
particles from it.
SEDIMENT
Any solid phase settling out of a liquid phase.
SEDIMENTATION
Solid-liquid separation resulting from the application of an external force,
usually under the force of gravity.
SLUDGE
Any solid material containing entrained water.
SLURRY
Suspension of solids in a liquid.
SUPERNATANT
The liquid remaining above the settled sludge after sedimentation.
TURBIDITY
Any suspended solids imparting a visible haze or cloudiness to water.
88
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APPENDIX A: LITERATURE REFERENCES BY CATEGORY
BAUXITE REFINING
Bayer Process
A-l. Vol'f, F. F. and A. M. Rozenberg. Polytherms of the Lixiviation of
the "Krasnaya Shapochka" Bauxite Deposits and Investigations of the
Low Moduli of Aluminate Solutions. Trudy Vsesoyuz. Nauch. -
Issledovatel. Inst. Issledovaniyu i Proektirovaniyu Alyuminievoi i
Elektrodnoi Prom. 1940. (20): 16-21, 1940.
A-2. Scholder, R. Alumina From Bauxite, Etc. U.S. 2,181,669, '
November 28, 1940.
A-3. Bauermeister, G. Determination of the Stability Limits of NaAlC>2
Solutions Between 74° and 94°. Aluminium (23):205-8, 1941.
A-4. Bauermeister, G. and W. Fulda. The Bayer Process (for Purifica-
tion of Bauxite). Aluminium (25):97-100, 1943.
A-5. Antipin, P. F. , M. N. Smirnov, and A. I. Svistunov. Aluminum
Oxide. U.S.S.R. 67,916, February 28, 1947.
A-6. Fulda, W. Preparation of Pure Alumina From Solutions of Bauxite in
Dilute NaOH. Metall. 1948:397-9, 1948.
A-7. Mooney, C. L. Recovery of Alumina From Alumina-Containing Ores.
U.S. 2,559,653, July 10, 1951.
A-8. Takemoto, M. and S. Kishimoto. Continuous Extraction of Alumina.
Japan 3963, July 24, 1951.
A-9. Sugimoto, S., et al. Extraction of Alumina. Japan 2228, May 8, 1951,
A-10. Maricic, S. and M. Mihalic. Extractibility of Bauxite by the Bayer
Process and the Solubility of the Aluminum Components. Arhiv Kem.
(25):241-9, 1953.
A-ll. Maricic, S. and M. Mihalic. The Degree of Extraction of Bauxite in
89
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the Bayer Process and the Solubility of the Aluminum Components.
Arhiv Kern. (25):241-9, 1953.
A-12. Kosugi, C. and T. Nakamura. Alumina. Japan 2474, June 2, 1953.
A-13. Holder, G. Alumina from Bauxite. Ger. 1,022,572, January 16,
1958.
A-14. Dunn, R. C. Extraction of Alumina From Its Ores. U.S. 2,785,956,
March 19, 1957.
A-15. Alumina From Bauxite. Societe d'electrochimie, d'electrometallurgie
et des acieries electriques d'Ugine. Fr. 1,010,385, June 10, 1952.
A-16. Vol'pin, P. I. and N. S. Mal'ts. Alumina. U.S.S.R. 132,208,
October 5, I960.
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chimie, d'electrometallurgie et des acieries electriques d'Ugine. Fr.
1,010,384, June 10, 1952.
A-18. Soudan, J. and P. Soudan. Dissolving Alumina from Bauxites. Fr.
1, 280,009, April 6, 1962.
A-19. Carr, A. R. Chemical Engineering Operations in the Production of
Alumina. Proc. Symp. Chem. Eng. Met. Ind. , Edinburgh (Eng).
65-70, 1963.
A-20. Malyshev, M. F. , N. N. Tikhonov, M. N. Smirnov, G. A. Panasko,
and A. B. Bykova. Preparation of Aluminum Oxide From Bauxite.
U.S.S.R. 196,751, May 31, 1967.
A-21. Oprea, Fl. , M. lenciu, and N. Panait. Processing of Bauxites by
Alkaline Methods. Rev. Chim. (Bucharest). 22^(6): 342-6, 1971.
A-22. Mal'ts, N. S. Advantages of Increasing the Bauxite Leaching Temper-
ature in the Bayer Process. Tsvet. Metal. (USSR) 44(7):34-7, 1971.
A-23. Plass, L. Leaching of Bauxite with Aqueous Sodium Hydroxide. Ger.
Offen. 2,307,922, August 29, 1974.
A-24. Coles, H. L. Production of Alumina from Bauxite. U.S. 2,283,849,
May 19, 1942.
A-25. Yasuo, K. An Improvement on the Preparation of Alumina by the
Bayer Process. Japan 2227, May 8, 1951.
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A-26. Schonfelder, H. and H. Ginsberg. Alumina From High-Silica
Bauxite. U.S. 2,939,765, June 7, I960.
A-27. Donaldson, D. J. Alumina. U.S. 2,946,658, July 26, I960.
A-28. Belyaev, A. I. and M. A. Kolenkova. Leaching Bauxite at High Pres-
sures. Sbornik Nauch. Trudov. Moskov. Inst. Tsvetnykh Metal, i
Zolota im. M. I. Kalinina. (26):120-31, 1957.
A-29. Starostina, K. M. and V. A. Pazukhin. The Effect of Calcining
Bauxite Upon the Recovery of Alumina by the Autoclave Method.
Sbornik Nauch. Trudov Moskov. Inst. Tsvetnykh Metal, i Zolota.
(24):104-16, 1954.
A-30. Derevyankin, V. A. and S. I. Kuznetsov. Utilization of Lignin Addi-
tives in the High Temperature Leaching of Bauxite (250° and Higher).
Khim. i Tekhnol. Glinozema, Inst. Met. i Obogashch. , Akad. Nauk
Kozakh. SSR, Tr. Vses. Soveshch. , Alma-Ata. 23-4, 1959.
A-31. Wolf, N. H. Leaching Alumina From Its Ores With Alkali and a
Boron Compound. U.S. 3,094,378, June 18, 1963.
A-32. Soudan, P. and H. Mercier. Continuous Digestion of European
Bauxite in Alkaline Solutions. U.S. 3,095,280, June 25, 1963.
A-33. Bernshtein, V. A. and E. A. Matsenok. Leaching of Boehmitic
Bauxite Wij>h Lime Addition and Peculiarities of Slime Sedimentation.
Tr. Vses. Nauchn. -Issled. Alyumin. -Magnievyi Inst. (46):24-30,
I960.
A-34. Timfoldgyar, A. Continuous Digestion of Bauxite With Sodium Hydrox-
ide. Hung. 149,514, June 15, 1962.
A-35. Sato, H. , T. Mitsugu, and T. Hamada. Extraction of Alumina From
Bauxite. Japan 26, 154, December 11, 1963.
A-36. Commonwealth Aluminum Corp. Ltd. Extraction of Aluminum Oxide.
Neth. 6,408,485, February 1, 1965.
A-37. Kompaneets, M. F. , K. A. Pustovalova, R. A. Sabitov, V. N.
Dement1 ev, and M. A. Smyshlyaeva. Lowering the Loss of Alkali
With Red Mud. U.S.S.R. 161,494, March 19, 1964.
A-38. Gebefuegi, I. Aluminum Hydroxide From Bauxite. Fr. 1,475,776,
April 7, 1967.
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A-39. Dobos, D. Further Technological Development of Bayer Alumina Pro-
duction with the Simultaneous Extraction of Iron. Tsvet. Metal.
(Russ). 4_l(5):60-7, 1968.
A-40. Svejda, Z. , P. Klan, and I. Poduskova. Hydrothermal Decomposition
of Bauxites. Czech. 131,481, March 15, 1969-
A-41. Poduskova, I. and P. Klan. Alumina From Diasporic Bauxites.
Czech. 142,638, September 15, 1971.
A-42. Osvald, Z. and K. Solymar. Processing Bauxites Containing Diaspore.
Hung. Teljes 2177, July 2, 1971.
A-43. Abramov, V. Ya. , T. A. Dudko, N. A. Makarov, N. M. Kontorovich,
and G. G. Pestova. Increased Effectiveness of the Flow-Type
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A-44. Johnson, A. F. Alumina From Bauxite. U.S. 3, 632, 310, January 4,
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A-45. Yamada, Y. , Y. Takenaka, and M. Watanabe. Dissolving Bauxite.
Japan. Kokai 72 18,797, September 16, 1972
A-46. Feher, I., M. Orban, Z. Osvald, K. Solymar, I. Voros, and J.
Zambo. Reducing or Compensating for Sodium Hydroxide Loss Pro-
duced During Alumina Manufacture. Fr. Demande 2, 166, 188,
September 14, 1973.
A-47. Vislyakova, L. F. , G. G. Zav'yalova, and A. I. Savchenko. Increase
in the Extraction of Alumina From Bauxites. Tsvet. Metal. (Russ).
(2):44-5, 1974.
A-48. Schepers, B. , W. Meusel, R. Haeberlein, and H. Loos. Aluminum
Oxide From Bauxite by Modified Bayer Process. Ger. Pend.
2,329,547, January 2, 1975.
Lime-Soda Sinter Process
A-49. de Vecchis, I., and O. E. Ramuz. Treatment of Bauxites. U.S.
2, 637, 628, May 5, 1953.
A-50. Ponomarev, V. D. , L. P. Ni, and V. S. Sazhin. Combined Method of
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A-51. Mansurova, Z. R. Processing Low-Quality Bauxites Into Alumina.
Tr. Sredneaziat. Nauch. -Issled. Inst. Geol. Miner. Syr'ya
(7):208-12, 1966 (Russ).
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Bishop, and L. S. Wells. Extraction of Alumina From Clays and
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A-55. Mazel, V. A., M. P. Sokolovskii, and B. Kh. Shvartsman. Produc-
tion of Alumina From Bauxite by the Sintering Method. Legkie
Metally, Leningrad, Sbornik. (4):33-7, 1957.
A-56. Rozentreter, R. G. , N. S. Berseneva, and A. A. Goryunova.
Sintering and Leaching of Sinters Obtained by Reductive Toasting of
Bayer Slimes. Tr. 3-go (Tret'ego) Vses. Soveshch. po Khim. i
Tekhnol. Glinozema, Erevan. 111-20, 1964 (Russ).
A-57. Skobeev, I. K. Extracting Alumina From Low-Quality Bauxite.
Nauchn. Tr. Irkutskogo Politekhn. Inst. (19):218-28, 1963 (Russ).
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1964 (Russ).
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A-60. Goloduoi, O. V., N. I. Eremin, M. M. Zorikov, V. A. Mazel, P. I.
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C-121. Machlet, A. W. Treatment of Ferrous Metals With Red Mud. U.S.
2,683,675, July 13, 1954.
C-122. Terebesi, L. , and J. Kornyei. Chlorination of Red Mud (From the
Manufacture of Alumina). Kohaszati Lapok. (90):460-5, 1957.
C-123. Udy, M. J. Recovery of Iron, Titanium Oxide, and Alumina From
Ores and Wastes. U.S. 2, 830, 892, April 15, 1958.
C-124. Gregoire, F. A. A. , and R. Ricard. Extraction of Metals From
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Recovery-Complex of Red Mud. Trudy Inst. Met. , Akad. Nauk
S.S.S.R., Ural. Filial. (2):257-63, 1958.
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C-128. Mitsubishi Shipbuilding & Engineering Co. , Ltd. Metal Recovery
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C-129. Cazafura, K. , and J. Feges. Principles for the Production of
Titanium, Aluminum, and Vanadium From Red Mud Acid Leaches.
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C-130. Logomerac, V. G. Metallurgical Processing of Red Mud to Produce
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C-132. Zazubin, A. I. , A. N. Barshchevskaya, and G. M. Potapova.
Complex Reprocessing of Red Mud. Tr. Inst. Met. Obogashch. ,
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C-133. Zalesskaya, S. V. Reduction of Some Components in the Smelting
of Red Mud Sinter. Izv. Vyssh. Ucheb. Zaved. , Chern. Met.
0-3, 1968.
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Manufacturing Process. Japan. 70 25, 762. 3 pp, August 26, 1970.
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C-139. Yang, C. B. , R. R. Choe, R. M. Chang, and N. S. Choe. Sintering
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C-142. Calhoun, W. A., and T. E. Hill, Jr. Metallurgical Testing of
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NONMETALLURGICAL
Cement Material
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D-2. Uryvacva, G. D. Slurry Wastes [Slags] in the Metallurgical Industry
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D 3 Beisher R V Use of the Tikhvin Alumina Plant Bauxite [Red] Mud
in Highway Construction. Sb. Tr. Melodykh Uch. Mekh. -Avtodorozh.
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D-5. Mitsugi, T. Fluidizing Calcination of Red Mud. Tohoku Daigaku
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D-6. Tohei, H. , and M. Fujii. Preparation of Refractory Concrete or
Mortar. Japan. Kokai 73 31, 228. 3 pp, April 24, 1973.
D-7. Hoguchi, Y. , and S. Katayama. Utilization of Red Mud. I. Effects
of the Addition of Red Mud on the Properties of Cements. Rika Guku
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Construction Blocks. Fr. 1,469,953. 2 pp, February 17, 1967.
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February 28, 1974.
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K'uang Yeh. £7(2):25-7, 1973.
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Slag From Red Mud. Banyasz. Kohasz. Lapok, Kohasz. 105(10):
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D-15. "Licencia" Talalmanyokat Ertekesito Vallalat. Cement Additives.
Brit. 975,378. 2 pp, November 18, 1964.
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of the Addition of Red Mud on the Strength of Cements with Time. 1.
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D-18. Karbt, D., M. Matousek, L. Novak, and Z. Vaja. Brown Bauxite
Waste Slurry, A New Kind of Admixture for Light Concrete
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Cement. Japan. 16,984('62). 2 pp, October 20,- 1962.
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Protection Given by Paints Containing Red Mud, Red Mud-Red
Oxide, Red Mud-Zinc Chromate Pigments. Paintindia. 16(3):
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D-23. Szekely, I. Ore Cements From Red Mud: Are They Fit for Use in
the Building Industry? Proc. Conf. Silicate Ind., 6th, Budapest.
399-408, 1961.
Lightweight Aggregate Material
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Aggregate. Japan. Kokai 74 60, 324. 3 pp, June 12, 1974.
D-25. Nagasaki, M., and Y. Suzuki. Artificial Aggregate Containing
Converter Slag and Red Mud. Japan. Kokai 73 49, 819. 3 pp,
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D-29 Hayashi, S., and K. Kato. Lightweight Concrete With High Mechan-
ical Strength. Japan. Kokai 74 52, 213. 5 pp, May 21, 1974.
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D-31. Pattas, E. Bloated Granules of Red Mud From Bauxite Decomposi-
tion; Ger. Offen. 2,033,260, November 25, 1971.
D-32. Tacken, J. Expanded Granules of Clay. Fr. 1,540,632. 2 pp,
September 27, 1968.
D-33. Sann, R. Vitreous, Cellular Additives for Concrete. Fr. 1,526,207.
5 pp, May 24, 1968.
Construction Material
D-34. Sugasawa, M. Solidifying Red Mud. Japan Kokai 74 52,766. 2 pp,
May 22, 1974.
D-35. Horioka, K. Building Material From Red Mud. Japan Kokai
7499,719. 3 pp, September 20, 1974.
D-36. Hegenbarth, R. Experiments in the Utilization of Red Mud.
Aluminium (Duesseldorf). 48(11):748-50, 1972.
D-37. Bayer, G. , E. Cherdron, M. Haerter, and E. Hecht. Red Mud
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D-39. Bayer, G. , E. Cherdron, M. Haerter, and E. Hecht. Bricks From
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D-41. Nakanishi, K. Solidification of Red Mud. Japan Kokai 74 45, 892.
2 pp, May 1, 1974.
D-42. Horioka, K. Hardened Products From Red Muds. Japan Kokai
74 99,781. 3 pp, September 20, 1974.
D-43. Mori, S., and K. Kitsugi. Hydraulic Composition From Red Mud.
Japan Kokai 74 69, 759. 3 pp, July 5, 1974.
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74 99,781. 3 pp, September 20, 1974.
D-46. Nudel'man, B. I., and A. T. Tairov. Use of Siliceous Bauxite
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Kremnezemistye Shlamy Kislotnogn Razlozheniya Kaolinov Puti Ikh
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D-47. Parimbetov, B. P., I. A. Kroichuk, A. G. Neiman, and N. A.
Trebukhina. Physicochemical Principles of the Use of Bauxite
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D-48. Bayer, G. , E. Cherdron, M. Haerter, and E. Hecht. Method for
Producing Bricks From Red Mud. U.S. 3,886,244, October 10,
1972.
D-49. Bayer, G. , E. Cherdron, M. Haerter, and E. Hecht. Method for
Producing Bricks From Red Mud. U. S. 3,886,245, December 21,
1971.
D-50. Bayer, G. , E. Cherdron, M. Haerter, and E. Hecht. Method of
Producing Bricks From Red Mud. U.S. Application No. 153,651,
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D-51. Intezet, F. K. , and E. Intezet. Briquetting Red Mud or Mixtures
Containing Red Mud. Hung. 151,998. 10 pp, April 22, 1965.
D-52 Mori S. , and K. Kitsugi. Solidifying Sludge By Adding Red Mud
and Lime or Dolomite. Japan Kokai 74 66, 570. 6 pp, June 27, 1974.
Plastic Resin Filler
D-53 Nagata, T. Utilization of Waste Red Mud From Aluminum Refining.
Japan Kokai 73 50,982. 2 pp, July 18, 1973.
D-54. Machi, S. , H. Kurihara, and T. W-*0*01^*0^*
Containing Red Mud. Japan Kokai 74 66, 721. 5 pp, June 28, 1974.
D-55. Funke, A. , H. Wetzel, and G. Buhler Rubber Fillers From Red
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D-57. Ketomo A. -G. Treating Natural and Synthetic Rubber. Swiss
274, 574, July 2, 1951.
D-58. Negata, N. Poly(vinyl Chloride)-Red Mud Composites. Japan Kokai
74 73,438. 4 pp, July 16, 1974.
D-59. Riesel, W. , R. Peters, and H. Weiser. Recovery of Powdered
Fillers From the Red Mud Waste Liquors Obtained in the Production
of Alumina From Bauxite According to the Bayer Process. Ger.
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D-60. Funke, A. , H. Wetzel, and G. Buhler. Light-Colo red Rubber Fillers
by Concomitant Use of Red-Mud Extracts. Ger. (East) 19, 295,
July 22, I960.
D-61. Yuan, H. C. , W. W. Hsu, U. P. Wang, C. C. Wu, J. S. Shieh,
M. L. Chang, and T. D. Kung. Gamma-Ray Induced Polymeriza-
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Pigments
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D-63. Charrin, V. Utilization of Some Industrial By-Products. Genie
civil. 131:332-4, 1954.
D-64. Habnel, K. O. Red Mud as Raw Material for Colored Glass.
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D-65. Foerster, H. Concrete Color Composition. Ger. (East) 57, 543.
2 pp, August 20, 1967.
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Coating Material
D-68. Ramanujam, S. , and R. V. Saluja. Primers Based on Red Mud
Indian 81,431. 4 pp, April 11, 1964.
D-69. Wargella, G. , and H. Plaetschke. Bituminous Mixtures Containing
Treated Bauxite Residues. Brit. 1110168. 4 pp, April 18, 1968.
D-70. Wilkening, S. , Red Mud for Concrete Coating Materials. Ger.
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D-71. Begardi, E. Caustification of the Red Mud From the Alumina
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D-72. Retezar, A., L. Pechy, and G. Gardos. Leaching of the Lime -
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Causticization of Natrolites and Red Muds. Femip. Kat. Int.
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As Catalyst
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Fertilizer
D-81. Matsumoto, E. Indirect Fertilizer. Japan 5767('53), November 10,
1953.
D-82. Whittaker, C. W. , W. H. Armiger, P. P. Chichilo, and W. M.
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12, 622 ('60), Septembers, I960.
D-84. Hofmann, H. , K. H. Reisner, S. Meyer, E. Friedrich, and
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Various Useful Components
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Red Mud. Tech. Rev., Mitsubishi Heavy Ind. 3_(l):59-67, 1966.
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Fr. 1,522,562. 3 pp, April 26, 1968.
D-87. Reisner, K. H. , and S. Meyer. Bayer Process, Red Mud By-
Product. Ger. (East) 67, 107. 2 pp, June 5, 1969.
D-88. Tsai, J. H. Separation of Useful Compounds From Waste Red-Mud
of the Aluminum Industry. U. S. 3,574,537. 2 pp, April 13, 1971.
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Japan 74 23, 115. 3 pp, June 13, 1974.
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General Usage
D-91. Motte and Pomot. Protecting Insecticides Against the Action of
Light. Fr. 848,974, November 9, 1939.
D-92. Oda N. Agricultural Pesticide. Japan 5650('51), September 21,
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May 8, 1951. ' ' ' ' '
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[Gunite] Mortars. Sb. Tr. Leningr. Inst. Insh. Zheleznodor
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November 19, 1973.
D-96. Beeching, L. , and L. Ainsworth. Material for Road Pavement. Ger.
Offen. 2,257,535. 23 pp, May 30, 1973.
D-97. Kasai, J. , and K. Fukurr. Surface-Treated Quickline. Japan
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D-98. Hayashi, S. , and F. Matsui. Hardenable Foam-Generating Composi-
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Production of Glass-Ceramics Using a Red Mud From Alumina
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Containing Bauxite in Coke Manufacture. Czech. 93,355, January 15,
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D-101. Chowdhry, N. A. Sand and Red Mud Filters: An Alternative Media
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D-102. Horvath, Gy. Test of Red Mud Smelting by Thermal Analysis.
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pounds From the Bayer Liquor. Metal Soc. AIME Pap. A74-66:
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D-105. Thome, R. , and G. Wargalla. Strong Filler. Bitum Teere
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Expanded Clay. Erzmetall. 26_( 1): 18-r20, January, 1973.
D-107. Dobos, G. , G. Horvath, and K. Solymar. Theoretical and Practical
Problems in the Complex Process of Working the Red Mud.
Aluminum. 48( 12):808-810, December, 1972.
D-108. Bayer, G. Possibilities for Economic Disposal of Red Muds.
Erzmetall. 25_(9):454-457, September, 1972.
D-109. Guccione, E. "Red Mud", A Solid Waste, Can Now Be Converted
to High-Quality Steel. Eng. Mining J. 172(9): 136-8, September,
1971.
D-110. Fursman, O. C. , et al. Utilization of Red Mud From Alumina
Production. Bureau of Mines, U. S. Bur. Mines, Rept. Invest.
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2_13j 105-22, 1967.
D-112. Treatment of Red Mud Waste From Bayer Process by Pelletizing
and Coating, Tonan Kaihatsu Kogyo Co. Ltd. Japanese 4, 845, 496,
October 14, 1971.
EFFLUENT TREATMENT
Adsorption of Sulfur Oxide Compounds
E-l. Thibon, H. J. Activation of Red Mud From the Bayer Process.
U. S. 2,432,071, December 2, 1947.
E-2. Mitsubishi Shipbuilding & Engineering Co. , Ltd. Removal of
Effluent Sulfur Dioxide With Red Sludge. Fr. 1, 350, 23 1. 5 pp,
January 24, 1964.
136
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E-3. Field, J. H., J. G. Myers, J. W. Mulvihill, and H. W. Wainwright
Potential Absorbents for Sulfur Oxides Removal From Flue Gas
Amer. Chem. Soc. , Div. Petrol. Chem., Preprints 1967
Ki(4):A9-A-15, 1967.
E-4. Land, G. W. Controlling Sulfur Dioxide Emissions From Coal
Burning. Nat. Eng. 73_(l):6-8, 1969.
E-5. Land, G. W. Trials of Additives for Sulfur Dioxide Removal in
Industrial Plants. Combustion. 4_l(6):3Q-3, 1969.
E-6. Myers, J. G. , and J. H. Field. Absorbent for Removing Sulfur
Oxides From Gases. U.S. 3,580,702. 6 pp, May 25, 1971.
E-7. Badeeva, T. 1., L. M. Belavinskaya, B. M. Gikht, N. N.
Gryazev, K. A. Dmitrieva, L. A. Novoselova, L. E. Ozerskaya,
V. P. Perfilova, M. N. Rakhlevskaya, et al. Removal of
Organosulfur Compounds From Jet Fuels. Khim. Seraorg.
Soedin. , Soderzhashchiksya Neft. Nefteprod. (9):424-8, 1972.
E-8. Sho, K. Adsorbent for Removal and Decolorization of Liquid and
Gaseous Sulphur Compounds From Red Mud. Japan Kokai 73 55,888.
4 pp, August 6, 1973.
E-9. Sho, K. Adsorbent for Removal and Decolorization of Liquid and
Gaseous Sulphur Compounds From Red Mud. Japan Kokai 73 55, 886
and 73 55, 887. 4 and 3 pp, August 6, 1973,
E-10. Oku, Tsurumi, and T. Fukanaga. Absorbing Sulfur Dioxide From
Waste Gases by a Red Mud Slurry. Japan Kokai 74 10, 868. 6 pp,
January 30, 1974.
E-ll. Grupe, K. , E. Kriegel, and P. Schmidt-Mende. Falling-Cloud
Reactor for Removal of Sulfur Dioxide From Flue Gas Using Red
Mud as Desulfurizing Agent. Desulphurization Fuels Combust.
Gases, Proc. Semin. Work. Party Air Pollut. Probl. U. N. Econ.
Comm. Eur. Addendum 3:37-42, 1970.
E-12. Oku, T., T. Fukunaga, and M. Yoshihara. Removal of Sulfur
Dioxide in Exhaust Gas With Red Mud Slurry. Japan Kokai
73 102,094. 5 pp, December 21, 1972.
E-13 lida T Removal of Sulfur Oxides From Stock Gases by Adsorption
on Red Mud. Japan Kokai 74 84, 978. 4 pp, August 15, 1974.
137
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Adsorption of H2S
E-14. Thibon, H. , and A. Maillard. The Cold Fixation of Hydrogen
Sulfide by Ferric Oxide. II. Chimie & Industrie. 54:315-20, 1945.
E-15. Compagnie de produits chimiques et electrometallurgiques Alais,
Froges et Camargue. Red Muds. Brit. 595, 733, December 15,
1947.
E-16. Ivanovskii, F. P., V. A. Dontsova, and T. A. Semenova.
Utilization of the Alumina-Production By-Product, Red Mud, in
the Removal of Hydrogen Sulfide From Gas. Khim. Prom.
218-22, 1955.
E-17. Hsu, W., and C. Ma. Red Mud Used as Desulfurizing Agent for
Removing H2& in Gas. Union Ind. Research Inst. Rept. (Hsinchu
Twian). (13):8 pp, 1956.
E-18. Kornyei, J. Absorption of Hydrogen Sulfide From Household Gas
With Iron-Containing Mixtures. Magyar Kim. Lapia. 12:304-6
1957.
E-19. Shultz, F. G. , and J. Berber. Hydrogen Sulfide Removal From Hot
Producer Gas With Sintered Absorbents. J. Air Pollut. Contr.
Ass. 2_0(2):93-6, 1970.
E-20. Shultz, F. G. Removal of Hydrogen Sulfide from Simulated
Producer Gas at Elevated Temperatures and Pressures. Air
Pollut. Contr. Off. (U.S.)Publ. AP-109, III-5, 6 pp, 1972.
Coagulant
E-21. Cocheci, V., A. Martin, P. Samarghitan, and W. Husz. Prepara-
tion of Complex, Inorganic Coagulation Agent. I. Preparation of
Coagulation Agents From Red Mud Resulting From Aluminum Oxide
Manufacture. Bui. Stint. Teh. Inst. Politeh. Timisoara. Ser.
Chim. 16(2): 163-9, 1971.
E-22. Sawai, S. , and K. Baba. Manufacture of a Coagulant Containing
Ferric Oxide. Japan 72 25,985. 2 pp, July 14, 1972.
E-23. Fujii, T., Y. Hosoi, C. Nozaki, andS. Ohwada. Acidic Solid for
Flocculation. Japan. Kokai 73 20, 786. 4 pp, March 15, 1973.
E-24. Miko, S. , H. Takahashi, A. Kurata, and A. Kawaminami. Removal
of Phosphate and Heavy Metal Ions From Waste Waters Using Red
Mud. Mizu Shori Gijutsu. _14(8):817-22, 1973.
138
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E-25. Bayer, G. , and E. Cherdron. Red-Mud Flocculant for Waste Water
Treatment. Ger. Offen. 2,242,811. 9 pp, March 14, 1974.
E-26. Takase, H. , and Y. Hata. Production of Coagulants From Red Mud
Japan Kokai 74 55, 576. 4 pp, May 29, 1974.
E-27. Sanga, S. Removal of Phosphorus From Sewage With Red Mud Ash
Japan Kokai 74 74,951. 2 pp, July 15, 1974.
E-28. Ellis, E. H. Chlorinated Copperas Treatment of Sewage at
Kingston-on-Thames. Surveyor. 106:195-6,1947.
Acid Waste Waters
E-29. Kalinin, L. G. Dry Neutralization of Acid Waste Waters. U.S.S.R.
340, 626, June 5, 1972.
E-30. Kazantsev. E. I., E. K. Stepanenko, and A. N. Gerasimenko.
Removal of Arsenic From Waste Waters by Sorption. Tsvet.
Metal. 45(1): 18-20, 1972.
RED MUD DISPOSAL
F-l. Kayatz, K. H. Solidification of Red Mud. Ger. Offen. 2,327,789.
6 pp, December 19, 1974.
F-2. Miller, V. Ya. , A. I. Ivanov, and V. A. Utkov. Sintering of
Finely Dispersed Hydroscopic Alumina Material. Tr. Inst. Met. ,
Sverdlovsk. (22):92-5, 1970.
F-3. Dethlefsen, V., and H. Rosental. Problems With Dumping of Red
Mud in Shallow Waters. A Critical Review of Selected Literature.
Aquaculture. 2J3):267-80, 1974.
F-4. Nauke, M. Disposal Problems of Red Mud in the North Sea.
Meerestech, Mar Tech. 5^(5): 149-153, October, 1974.
F-5 Rushing, J. C. Alumina Plant Tailings Storage. AIME Annual
Meeting, 102nd Proceedings (Light Metal, 1973). February.
F-6. Bayer, G. Economic Disposal of Red Muds, Environmental
Protection in the Aluminum and Nonferrous Smelting Industry-
Symposium", Technicopy Ltd. , Stonehouse, Glos., England,
12-20, 53-56, 1973.
139
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APPENDIX B: WORKSHOP SESSIONS
Draft report copies of the project were submitted for review to the
U. S. Environmental Protection Agency and aluminum industries of the
United States in the month of January, 1976. A workshop on the project
was sponsored by the U. S. Environmental Protection Agency. The work-
shop sessions were held at Battelle on March 30 and 31, 1976, to discuss
and receive comments on the report. The workshop was attended by repre-
sentatives of the U. S. Environmental Protection Agency, four domestic
aluminum companies, and Dow Chemical Company. The program and list
of the attendees with their title and organization are listed in Table B-l and
Table B-2, respectively.
The present report incorporates many of the comments and
recommendations made by the various representatives during the workshop
sessions.
140
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TABLE B-l. PROGRAM OF THE WORKSHOP
Tuesday, March 30, 1976
9:00 a.m. Welcome to Battelle
9:10 a.m. Arrangements for Workshop
9:20 a.m. Introductory Comments (EPA, Battelle)
9:30 a.m. Review of the Project and Draft Report (Battelle, Dow)
10:30 a.m. Coffee Break
10:45 a.m. Prepared General Comments by Industry Participants
12; 15 p.m. Lunch
1:30 p.m. Workshop Discussions
Topics: Processing, Disposal, and Utilization
3:00 p.m. Coffee Break
3:15 p.m. Demonstration of Advanced Information Processing and Retrieval
Systems
3:45 p.m. Continue Workshop Discussion
4:30 p.m. Adjourn
Wednesday, March 31, 1976
9:00 a.m. Recommended Research and Demonstration Projects (Industry
Participants)
10:45 a.m. Summary of Workshop Results (Battelle)
11:15 a.m. Concluding Remarks by Participants
141
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TABLE B-2. LIST OF THE WORKSHOP ATTENDEES
Organization
Name
Title
Kaiser Aluminum
Kaiser Aluminum
Alcoa(b)
Alcoa
Reynolds Metals Company
Reynolds Metals Company
Reynolds Metals Company
Reynolds Metals Company
Martin-Marietta
U. S. EPA(C)
U. S. EPA
Dow Chemical Company
Mr. A. E. McLaughlin
Dr. R. M. Hans en
Mr. J. E. Ralphe
Mr. R. H. Carwile
Mr. M. Handelman
Mr. F. N. Newchurch
Mr. J. T. Robinson
Mr. R. N. Reid
Mr. J. A. S. Green
Mr. Donald Wilson
Mr. T. G. Newport
Dr. S. L. Daniels
Manager, Process Development
Environmental Manager
Superintendent New Project
Environmental Control Engineer
Technical Assistant to Plant Manager
Process Control Leader
Senior Process Engineer
Senior Environmental Engineer
Head3 Materials Department
Research Chemist
Research Specialist
*List does not include names of Battelle's participants.
(a) Kaiser Aluminum and Chemical Corporation
(b) Aluminum Company of America
(c) U. S. Environmental Protection Agency
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TECHNICAL REPORT DATA
(f lease read Instructions on the reverse before completing)
EPA-600/2-76-301
TITLE ANDSUBTITLE
An Assessment of Technology for Possible Utiliza-
tion of Bayer Process Muds
6, PERFORMING ORGANIZATION CODE
3. RECIPIENT'S ACCESSIOP*NO.
5. REPORT DATE ~~~
December 1976 issuing date
Parekh, B. K.
Goldberger, W. M.
8. PERFORMING ORGANIZATION REPORT NO
. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle Memorial Institute
505 King Avenue
Columbus, Ohio 43229
10. PROGRAM ELEMENT NO.
IBB610; 02-01-05A
11. CONTRACT/GRANT NO.
R803760
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab.
Office of Research and Development
U. S. Environmental Protection Agency
nhir. 4526R
- Gin., OH
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report concerns a study of the possible utilization of the mud wastes generated
in the domestic production of alumina from bauxite ores. The work was done by the
Battelle-Columbus Laboratories for the United States Environmental Agency. The
program comprised review of technical literature published from 1940 on subjects
related to technology of processing bauxite, the dewatering and impoundment of the
mud residues and their possible utilization. Mud samples were received from the
domestic alumina plants for characterization experiments and dewatering studies at
Battelle and at the laboratories of the Dow Chemical Company in Midland, Michigan.
It was concluded from the study that there is no possibility for utilization of the muds
that could significantly affect the need for impoundment within the near term. How-
ever, improved mud dewatering and methods of impoundment appear possible to de-
velop and a program of joint industry-government demonstration and pilot'projects
is recommended. In addition, a basic research program is recommended to study
the mineral surface chemistry controlling the mechanism of dewatering. Investiga-
tions of the possible beneficiation of the muds into a raw material supplement in
iron making and the possible use of mud as an absorbent in pollution abatement
processes are also recommended.,, . ........ . ,
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Bauxite*, Bayer Process,
Coagulation, Composition, Dewatering*,
Disposal, Flocculants, Refining*
Utilization*, Wastes
*Important terms
b.lDENTIFIERS/OPEN ENDED TERMS
Bauxite Refining
Bayer Process Muds
Effect of Flocculants
Method of Dewatering
Mud Utilization
Brown Mud
Red Mud
COS AT l Field/Group
13B
3, DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisRepor
Unclassified
153
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
143
^U.S. GOVERNMENT PRINTING OFFICE: 1977-757-056/5571 Region No. 5-11
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