EPA-600/2-77-023Z
February 1977
Environmental Protection Technology Series
INDUSTRIAL PROCESS PROFILES FOR
ENVIRONMENTAL USE: Chapter 26.
Titanium Industry
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-600/2-77-023Z
February 1977
INDUSTRIAL PROCESS PROFILES
FOR ENVIRONMENTAL USE
CHAPTER 26
TITANIUM INDUSTRY
by
Vishnu S. Katari and Timothy W. Devitt
PEDCo-Environmental Specialists, Inc.
Cincinnati, Ohio 45226
Contract No. 68-02-1321
Project Officer
I. A. Jefcoat
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
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 Research
Laboratory - Cincinnati, 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 endorsement
or recommendation for use.
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TABLE OF CONTENTS
CHAPTER 26
Page
INDUSTRY DESCRIPTION 1
Raw Materials 4
Products 5
Companies 6
Envi ronmental Impact 7
INDUSTRY ANALYSIS 9
Titanium Metal Production 10
Process No. 1. Mining 12
Process No. 2. Ore Upgrading 16
Process No. 3. Smelting 23
Process No. 4. Chlorination and Purification 24
Process No. 5. Reduction 26
Process No. 6. Melting and Ingot Conditioning 29
Process No. 7. Fabrication 31
Titanium Dioxide Production 33
Process No. 8. Oxidation 35
Process No. 9. Digestion, Crystallization,
Hydrolysis, and Bleaching 36
Process No. 10. Calcination 38
Process No. 11. Finishing Operations 40
APPENDIX A - Composition and Properties of Titanium Products 41
APPENDIX B - Titanium and Titanium Oxide Producers 51
APPENDIX C - References for Appendices , 55
m
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LIST OF FIGURES
CHAPTER 26
Figure Page
1 Titanium Metal Production 11
Titanium Dioxide Production 34
iv
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LIST OF TABLES
CHAPTER 26
Table Page
1 Salient Titanium Statistics, 1973 2
2 U.S. Production and Consumption of Titanium, 1974. ... 3
3 Distribution of Titanium Mill Products in 1974 6
4 Chemical Composition of Raw Waste Water from
Titanium Open-Pit Mine 14
5 Reagent Use in Flotation Circuit of Mill
at Open-Pit Mine 17
6 Chemical Composition of Raw Waste Water
at Two Dredge Mills 18
7 Chemical Compositions of Raw Waste Water and
Treated Recycle Water from the Mill at Open-
Pit Mine 20
8 Material Balance for Melting Operations at
Titanium Plants 29
9 Materials Balance for Fabrication of Mill Products ... 31
10 Materials Required for Producing One Ton of
Titanium Dioxide 37
11 Analysis of Effluent Gases of a Ti02 Calciner 39
A-l Analysis of Ilmenite Ore 42
(Percent)
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Table Page
A-2 Range of Composition of Titanium Concentrates 43
A-3 Chemical Analysis of Titanium Metal 44
A-4 Physical Properties of Commercially Pure
Titanium 45
A-5 Physical Properties of Titanium Dioxide 46
A-6 Typical Titanium Sponge Analysis 47
A-7 Chemical Analyses of Commercial Grade and
Purified TiCl^ from Sources A and B 43
A-8 Physical Properties of Titanium Tetrachloride 49
A-9 Typical Properties of Commercial Titanium
Alloys 50
B-l Titanium Industry Companies, 1972 52
vi
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ACKNOWLEDGEMENTS
This chapter of the Environmental Catalog of Industrial processes was prepared
by PEDCo-Environmental Specialists, Inc. The contributions of Vishnu S. Katari
and Timothy W. Devitt are gratefully acknowledged.
vii
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TITANIUM INDUSTRY
INDUSTRY DESCRIPTION
The titanium industry produces two principal products, titanium
metal and titanium dioxide. For purposes of analysis, therefore, the
industry is considered in two segments: titanium metal production and
titanium dioxide production.
In 1968, approximately 700 workers were employed in the United
States in mining and concentrating titanium minerals, including by-
product and coproduct materials such as zircon and monazite; about
10,000 workers were employed in titanium pigment production and an
estimated 2,500 workers were employed in producing titanium sponge
metal, ingot and mill products. In 1974, an estimated 800 people were
employed in ilmenite mining and milling, and 10 people were employed in
rutile mining and milling. Titanium metal reduction plants employed
2
about 950 people.
Table 1 presents ore production and consumption data for the United
States in 1973. In 1974, the domestic ingot production capacity was
approximately 36 million kilograms and the actual production reached
slightly more than 33 million kilograms. Aerospace applications,
including both military and commercial aircraft, accounted for the bulk
of U.S. demand for titanium metal. Consumption in other applications,
particularly chemical processing equipment, power generation, and petro-
chemicals continued to grow at an accelerated rate. In 1974, the
titanium pigment production was 715,000 tons. Table 2 presents the U.S.
4
production and consumption data for titanium in 1974-
Domestic demand for titanium for the year 2000 is expected to be
between 100 to 350 million kilograms. This demand is mainly attributed
to the use of titanium for applications in the aerospace and chemical
-------
Table 1. SALIENT TITANIUM STATISTICS, 1973
Material
Quantity, tons'
Ilmenite Concentrate:
Mine shipments
Imports
Titanium Slag:
Imports
Consumption
Rutile Concentrate:
Imports
Consumption
737,900
63,222
215,227
255,635
189,427
251,205
Metric ton (1000 kg).
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Table 2. U.S. PRODUCTION AND CONSUMPTION OF TITANIUM, 1974
Material
Quantity, tons'
Sponge:
Imports
Consumption
Scrap: Consumption
Ingot:
Production
Consumption
Mill product shipments
Titanium Pigment:
Production
6,305
24,948
9,707
33,249
28,486
15,649
715,000
Metric ton (1000 kg).
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industries and the manufacture of paints, varnishes and lacquers,
papers, plastics and floor coverings.
Raw Materials
The most common titaniferous materials are anatase, llmenite,
leucoxene, and rutile. In addition, a few deposits contain large
amounts of less common materials, such as Perovskite, Brookite, sphene,
and magnetite, which also contain titanium.
Anatase is brown, crystallizes in the tetragonal system, and in the
natural state contains 98.4 to 99.8 percent Ti02. Ilmenite is iron
black and crystallizes in the hexagonal system. It contains approxi-
mately 50 percent titanium dioxide, 30 to 50 percent iron oxides, and
trace amounts of silica, alumina, and other metals.
Leucoxene is a fine-grained type of rutile or anatase, or mixtures
of these with amorphous material. This material usually contains more
than 68 percent Ti02 and occurs with other titanium-bearing materials.
Rutile occurs as reddish-brown to red crystals of tetragonal
structure or in granular masses. It is essentially pure Ti02> but some
deposits contain large amounts of ferric iron, tantalum, or columbium.
Virtually all of the rutile used in the United States is imported.
Titanium slag may also be considered an ore. It is produced by
smelting a mixture of carbon and titanium-bearing material to yield
molten iron and slag containing about 70 to 90 percent TiOp. Analysis
of domestic ilmenite ore, upgraded ore concentrate and Canadian slag
are given in the Tables A-l and A-2 in appendix A.
Additional raw materials generally are not required for beneficia-
tion of titanium ores, although some coke is added to hematite, ilme-
nite and magnetic ilmenite ores in upgrading processes. Considerable
quantities of chlorine are required to produce titanium tetrachloride,
T1C1,, an intermediate raw material for titanium metal and pigment
production. This chlorine is later liberated when the TiCl^ is con-
verted to TiO- When titanium metal is produced, the chlorine is
-------
converted to magnesium chloride or sodium chloride. Some plants recover
the reductant metal and chlorine by electrolysis.
Products
Titanium is a low-density, silvery-white metal important for its
high strength-to-weight ratio and its resistance to corrosion. It is 61
percent heavier than aluminum but only 56 percent as heavy as alloy
steel. The strength-to-weight ratio below 540°C exceeds that of aluminum
and of stainless steel. Table A-3 in appendix A gives a chemical
analysis of titanium metal of commercial grades and Table A-4 gives the
physical properties of pure titanium metal.
Titanium dioxide pigment is sold domestically in three grades.
Rutile and anatase grades are fairly pure titanium dioxide, but because
of differences in crystal structure they differ in their covering and
chalking characteristics. Each is 95 to 99 percent pure Ti02. Extended
titanium pigment as sold commercially contains only 30 to 50 percent
TiOp. Table A-5 in appendix A lists the physical properties of
titanium dioxide. Titanium sponge is an elemental metal product with a
sponge-like appearance, obtained by reducing TiCl, with magnesium or
sodium. Table A-6 presents a typical analysis of titanium sponge.
The chemical analysis of commercial-grade and purified titanium
tetrachloride and physical properties of titanium tetrachloride are
given in Tables A-7 and A-8 in appendix A. As mentioned earlier,
titanium tetrachloride, TiCl., is an intermediate product used in
the manufacture of both titanium metals and pigments. It is a
volatile, colorless liquid.
Titanium ingots include three types, classified according to their
predominant crystal structure: alpha, alpha-beta, and beta. Aluminum
is the most prominent alpha-stabilizing addition. Alpha-beta alloys
contain some aluminum, but also contain other metals to stabilize the
beta phase. The beta alloys also have a mixed alpha-beta structure, but
are predominantly beta. About 20 commercial and semi commercial titanium
-------
alloys are available to the titanium user. Table A-9 in appendix A
gives typical properties of commercial titanium alloys.
Historically, the major fabricated product of the titanium metal
industry has been billets, which formerly accounted for some 60 percent
of all product shipments from titanium mills. The forging billet share
of shipments decreased to 42 percent in 1974. Meanwhile the share of
tubing and flat-rolled products (sheet, strip, and plate) increased.
Table 3 presents data on the distribution of titanium mill products in
1974.4
Table 3. DISTRIBUTION OF TITANIUM MILL PRODUCTS IN 1974
Product
Sheet, strip, plate
Forging and extrusion billet
Rod and bar
Wire
Pipe, tubing extrusions
Quantity, kilograms
4,977
64,729
2,167
790
1,251
Companies
In 1971, 10 companies produced titanium dioxide (TiOJ and five
companies were involved in producing titanium concentrates in five
different states. Titanium metal was produced by three corporations
owned by six companies. Nine companies produced titanium ingots from
sponge metal and scrap.
In 1973, rutile-type pigment accounted for 72 percent of total
pigment production and was produced by seven manufacturers. Anatase-
type pigment was produced by five companies.3 Appendix Table B-l lists
the companies involved in the titanium industry, their locations and
operations. During 1974, four mines located in New Jersey, Virginia,
and Florida produced titanium ore in the United States.5
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Environmental Impact
Large quantities of wastes are generated from the mining and concen-
trating of titanium and production of titanium dioxide. Disposal of
these wastes, particularly those resulting from titanium dioxide produc-
tion, represents a major environmental problem to the industry. Much of
this waste consists of weak sulfuric acid which is disposed of by either
deep sea dumping or neutralization. In 1972 domestic titanium dioxide
plants produced about 1.7 million tons9 of iron-acid sludge and 146 thou-
sand tons of iron-chloride sludge.
Air pollutants are also generated by the various processes. Major
emission sources within the titanium industry are in the mining and ben-
eficiation of ilmenite and production of TiOp pigment. Sulfur dioxide
mist and particulate emissions occur from the calcination step in the
sulfate process, and chloride emissions occur if calcination is performed
in the chloride process.
a Metric tons (1000 kg) are used throughout this report.
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BIBLIOGRAPHY
1. Stamper, J. W. Titanium. In: Mineral Facts and Problems, United
States Department of Interior. Washington, D. C., U.S. Government
Printing Office, 1970.
2. Personal communication with Mr. J. W. Stamper, Division of Minerals
Studies. United States Department of Interior.
3. Wessel, F. W. Titanium. In: Bureau of Mines Minerals Yearbook,
1973 reprint. United States Department of Interior. Washington, D.C.,
U.S. Government Printing Office, 1975.
4. Mirikler, W. W. Titanium - '74, A Boom Year; Demand Looks Good for
'75. Engineering and Mining Journal. March 1975.
5. A Study of Waste Generation Treatment and Disposal in the
Metals Mining Industry. Vol. I. MRI Report (Review Draft).
EPA Contract No. 68-01-2665. May 1975.
6. Saxton, J. C., and M. Narkus-Kramer. EPA Findings on Solid Wastes
From Industrial Chemicals. Chemical Engineering. April 28, 1975.
107 p.
8
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INDUSTRY ANALYSIS
Information for this study was largely obtained from the litera-
ture. Emission data are very sparse and existing data are variable due
to the variations in processing and raw materials. Also, most of the
information regarding specific process operating conditions and utility
requirements is not available.
The titanium industry is analyzed in two segments: production of
titanium metal and production of titanium dioxide. Flow sheets are
presented for each segment, and process descriptions are presented in
the text.
Each process description outlines the function of the process, the
input materials, energy requirements, and composition and rates of the
waste streams.
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TITANIUM METAL PRODUCTION
This Industry segment includes those processes required to obtain
and upgrade the ore and produce finished titanium metal as shown in
Figure 1.
In the production of titanium metal, the ores are mined and up-
graded by removal of impurities. The purified ilmenite ore (or imported
rutile ore) is then chlorinated to form titanium tetrachloride. This
chlorinated product is refined to high purity and reduced with magnesium
or sodium at about 870° C to a spongy mass. Excess magnesium chloride
or sodium chloride is removed by dilute acid leaching or vacuum distil-
lation. The spongy mass of titanium is then broken into about 1
centimeter pieces for melting into ingots. The ingots are fabricated
into various grades and shapes, and are subsequently used to produce
alloys.
10
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GASEOUS EMISSIONS
f
<.
1
MTMTWr
1*11 IN A Mb
v
inruniLU VIM. \f\ui ILL/ •— — •
r-- FLOTATION REAGENTS
r— UPGRAD]
1
"-FUEL
JCOAL
p FLUXES
L
«*• SMELTI
A ^^X
2 / \
i /
/ T 1 U^kl TTP \
(ILMENITE)
3 / \
-A LIQUID WAS'
<> SOLID WASTE
COKE
i CHLORINE
WATER O
» 4 J
NG — *H SLAG J »
PURIFIED
TITANIUM
FTRACHLORIDE
TITANIUM
TETRACHLORIDE
ARGON
Mg OR Na /•
FUEL
5
REDUCTION
fo
•••••M
{TITANIUM /s y>
TITANIUM V
SPONGE y
I
»•
SCRAP
MELTING AND 6
INGOT CONDITIONING
•»•
7
FABRICATION
Figure 1. Titanium metal production.
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TITANIUM METAL PRODUCTION PROCESS NO. 1
Mining
1. Function - The principal titanium-bearing minerals are rutile and
ilmenite. Rutile, which is titanium dioxide, is the most desirable
form, containing about 50 percent titanium after beneficiation, but it is
less abundant and is generally not mined in the United States. Ilmenite,
the iron titanium oxide, is more abundant but requires more processing
before extraction of the titanium oxide. Ilmenite deposits occur in
sand and rock. The Ilmenite sands in Florida are mined by underwater
suction dredges. Surface preparation includes removal of standing
timber, stumps, and roots. Holes are then drilled at 6 meter intervals,
and loaded and blasted. The sands are removed with a suction cutterhead
capable of digging 1000 tons of solids per hour at depths 14 meters
below the water surface. The slurry, consisting of 10 to 15 percent
solids, is pumped to barges where the ore is beneficiated. Ilmenite
rock deposits such as those in New York are mined by open-pit mining.
The ore is drilled and blasted in 10 meter bench heights. Electric
shovels are used for loading the ore on diesel trucks for hauling to
concentration and smelting processes.
2. Input Materials - The minable rock deposits of ilmenite at Tawahus,
N.Y., are composed of masses of closely associated magnetite and ilmenite,
separated by gabbroie and anorthositlc waste zones. As mined the ore
o
contains 32 percent ilmenite. The ore bodies mined at Piney River,
Va., contain ilmenite with apatite (calcium fluophosphate) and other
gangue materials. The titanium deposits of the Roseland district of Va.
consist of rutile and Hmenite disseminated in a feldspar rock. Sands
being worked in Florida contain about 4 percent heavy minerals. Forty-
five percent of these are titaniferous materials containing about 63
percent Ti09. The sand as a whole contains about 1.8 percent of titanium
3
mineral.
3. Operating Parameters - The operating conditions depend upon the ore
(sand or rock) deposit mined. Mining is carried out at ambient con-
ditions.
12
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4. Utilities - Energy in the form of electricity and diesel fuel is
required for operation of the power mining equipment such as tractor and
cutterhead.
5. Haste Streams - In the wet-mining of sand deposits, atmospheric
emissions are minimal. The large-scale dredging operations must be kept
isolated from other water bodies, however, to minimize potential water
pollution.
Atmospheric emissions from rock mining operations are probably
similar to those from other strip-mining activities. Approximately 1.2
tons of waste must be removed to obtain 1 ton of ore. Both the blast-
ing and the handling operations at the mine may release significant
quantities of fugitive dust. One source reports the emission factor for
titanium open-pit mining as 0.1 kg/ton, but indicates that the reliability
4
of this factor is poor. Hard rock mining of ilmenite is estimated to
produce particles of 5 micrometers average diameter, ranging from 0.5 to
10 micrometers. Provisions should also be made for backfill and land-
scaping of the mine site after the ore is extracted. Without such
treatment, erosion may lead to surface runoff, with associated water
pollution problems. Only one open-pit mine is now operating. Table 4 gives
the chemical composition of waste discharge from the mine.
6. EPA Source Classification Code - None exists
13
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Table 4. CHEMICAL COMPOSITION OF RAW WASTE WATER FROM
TITANIUM OPEN-PIT MINE
Parameter
Conductivity
Color
Turbidity (JTU)
TDS
TSS
Acidity
Alkalinity
Hardness
COD
TOC
Oil and grease
MBAS surfactants
Total Kj el da hi N
Al
As
Be
Ba
B
Cd
Ca
Cr
Cu
Total Fe
Concentration,
mg/£
1 ,000a
11. 3b
0.37
1,240
14
6.4
138.2
546.4
6.4
10.3
3.0
0.32
2.24
0.1
0.1
0.003
<1
0.01
<0.002
94.5
<0.01
<0.03
0.33
Parameter
Pb
Mg
Total Mn
Ni
Tl
V
K
Sr
Ag
Ns
Se
Te
Ti
Zn
Mo
Co
Phenol
Chloride
Fluoride
Sulfate
Nitrate
Phosphate
Concentration,
mg/H
<0.05
26.0
<0.01
<0.01
<0.1
<0.5
13.0
0.129
<0.01
140.0
0.75
<0.06
<0.2
0.007
<0.1
<0.1
<0.01
183.5
3.20
270
15.52
<0.05
Value in micromhos/cm.
Value in cobalt units.
14
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7. References;
1. Miller, A. Titanium, A Materials Survey. Bureau of Mines.
Information Circular 7791. United States Department of
Interior; Washington, D.C., U.S. Government Printing Office,
September 1957.
2. Barksdale, Jelks. Titanium, Its Occurrence, Chemistry and
Technology. New York, The Ronald Press Company, 1966.
3. Carpenter, J.H., et al. Mining and Concentration of Ilmenite
and Associated Minerals at Trail Ridge, Fla. Mining Engineering.
August 1953.
4. 6CA Corporation. National Emissions Inventory of Sources and
Emissions of Titanium. EPA Publication No. 450/3-74-008.
Distributed by National Technical Information Service. May 1973.
5. Calspan Corporation. Draft Copy. Developement Document for
Effluent Limitations Guidelines and Standards of Performance
for the Ore Mining and Dressing Industry Point Source Category.
EPA Contract No. 68-01-2682. April 1975.
15
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TITANIUM METAL PRODUCTION PROCESS NO. 2
Ore Upgrading
1. Function - The dredged ilmem'te sands are screened to remove
material larger than 1/4-inch mesh and the slurry is dewatered to about
30 percent solids. The slurry is then passed through a concentration
plant, usually mounted on a barge. Concentrates are pumped ashore at a
concentration of 25 percent solids at a rate of 30 to 45 tons per hour.
The material is dewatered and stockpiled for dry mill operations, where
the concentrates are dried at 110°C and cleaned by a series of electro-
static and magnetic separators. Ilmenite remains in the magnetic
fraction.
Ores from rock deposits are crushed and ground in several stages by
jaw crushers, cone crushers, and rod mills to produce a minus-28-mesh
material. Wet magnetic separators remove the magnetic fraction of the
material. The nonmagnetic fraction containing gangue and ilmem'te is
then concentrated on reciprocating tables or in flotation circuits,
2
filtered, and dried.
2. Input material - Commercially workable rock deposits contain
approximately 17 to 35 percent TiOp, principally as ilmenite. Ilmenite
taken from these rock deposits and also some sand deposits frequently
2
contains 35 to 55 percent Ti02. In upgrading ilmenite ores from sands,
approximately 2 percent of the feed from the dredge is titaniferous
material, of which approximately 70 percent is recovered in the final
product. Table 5 gives the quantities of reagents used in the flota-
4
tion process.
16
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Table 5. REAGENT USE IN FLOTATION CIRCUIT OF MILL AT OPEN-PIT MINE
Reagent
Tall oil
Fuel oil
Methyl amyl alcohol
Sodium bifluoride
Sulfuric acid
Purpose
Frother
Frother
Frother
Depressant
pH Modifier
Consumption,
kg/metric ton
of ore milled
1.33
0.90
0.008
0.76
1.775
3. Operating Parameters - Except in the drying step, where the temper-
ature is maintained at 110°C, the process is carried out at ambient
conditions.
4. Utilities - Electric power is required for operation of screen
mills, dry mills, pumps, and other equipment. Oil or gas fuel is
required for the drying step.
5. Waste streams - The large quantities of ilmenite sands handled in
the upgrading operations present significant waste disposal problems.
Essentially all of the waste material is returned to the vicinity of its
original location. These tailings constitute a considerable solids
burden on the body of water in which the material is being mined.
Environmental restrictions may also preclude expansion of mine pro-
p
duction. Table 6 gives chemical composition of raw waste water from
two dredge mills. Atmospheric particulate emissions from separation of
4
dredged materials are 5.0 kg/ton of product.
Wet processing of the rock deposits results in a large quantity of
sludge in which ilmenite is recovered by flotation. Table 7 gives the
chemical composition of waste water discharges and recycled water at the
only operating open-pit mine. The waste water from this mine is discharged
17
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Table 6. CHEMICAL COMPOSITION OF RAW WASTE WATER AT
TWO DREDGE MILLS
Parameter
Conductivity
Color
Turbidity (JTU)
TDS
TSS
Acidity
Alkalinity
COD
TOC
Total Kjeldahl N
Oil and grease
MBAS surfactants
Al
As
Be
Ba
B
Cd
Ca -
Cr
Cu
Total Fe
Pb
Mg
Total Mn
Ni
Tl
Raw waste water
concentration, mg/1
Mill A
200a
51,400b
<0.1
1,644
11,000
47.2
47.6
1,338
972
0.65
400
<0.01
69.0
0.05
<0.002
<0.5
0.10
<0.002
0.10
0.03
<0.03
4.9
<0.05
1.63
0.036
<0.01
<0.1
Mill B
40a
16,240b
0.54
370
209
31-4
3.4
362
321
0.65
40.0
<0.01
15.0
0.03
<0.002
<0.5
0.04
<0.002
<0.05
<0.01
<0.03
0.93
<0.05
0.66
0.01
<0.01
<0.1
Treated effluent
concentration, mg/1
Mill A
280a
75b
96
11
14.4
6.8
1.0
0.01
<0.01
<0.03
0.25
<0.01
Mill B
255a
13b
172
4
12.8
3.8
1.0
1.0
0.01
<0.01
<0.03
0.12
0.04
18
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Table 6 (continued). CHEMICAL COMPOSITION OF RAW
WASTE WATER AT TWO DREDGE MILLS
Parameter
V
K
Se
Ag
Na
Sr
Te
Ti
Zn
Mo
Co
Chloride
Fluoride
Phosphate
Phenol
Raw waste water
concentration, mg/1
Mill A
<0.5
3.5
<0.05
<0.01
27.0
<0.05
<0.06
<0.2
0.014
<0.1
<0.1
30.0
0.03
0.35
<0.01
Mill B
<0.5
1.3
<0.05
<0.01
5.0
<0.05
<0.15
0.40
0.002
<0.1
<0.1
15.0
<0.01
0.40
<0.01
Treated effluent
concentration, mg/1
Mill A
<0.2
Mill B
<0.2
<0.002
a Value in micromhos/cm.
b Value in color units.
19
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Table 7. CHEMICAL COMPOSITIONS OF RAW WASTE WATER AND TREATED
RECYCLE WATER FROM THE MILL AT OPEN-PIT MINE
Parameter
Conductivity
Color
Turbidity (JTU)
TDS
TSS
Acidity
Alkalinity
Hardness
COD
TOC
Oil and Grease
MB AS Surfac-
tants
Total Kjeldahl N
Al
As
Be
B
Cd
Ca
Cr
Cu
Total Fe
Pb
Mg
Total Mn
Ni
Tl
V
K
Se
Ag
Na
Raw waste water
concentration, rag/1
650a
18.0b
2.2
518
26,300
6.0
81.4
344.8
<1.6
9.0
2.0
0.04
0.65
210
<0.01
<0.002
<0.01
<0.002
350
0.58
0.43
500
0.05
187.5
5.9
1.19
<0.1
2.0
23.7
0.132
0.015
41
Treated recycle water
concentrati&n, mg/1
490a
0.56
526
2
12.5
2.0
0.01
<0.002
0.02
<0.03
<0.02
<0.05
0.3
<0.01
<0.5
20
-------
Table 7.(continued). CHEMICAL COMPOSITIONS OF RAW WASTE WATER
AND TREATED RECYCLE WATER FROM THE MILL AT OPEN-PIT MINE
Parameter
Sr
Te
Ti
Zn
Mo
Co
Phenol
Chloride
Fluoride
Sulfate
Nitrate
Phosphate
Hg
Raw waste water
concentration, mg/1
0.29
<0.06'
2.08
7.6
<0.1
<0.1
<0.01
19.1
32.5
213
0.68
<0.05
0.004
Treated recycle water
concentration, mg/1
<0.2
<0.002
0.50
<0.0002
Value in micromhos/cm
Value in color units
21
-------
to an inoperative open-pit quarry, from which the clarified water is
recycled into the mill circuit.
Atmospheric particulate emissions from separation operations with
4
ilmenite from rock deposits are 19 kg/ton of product.
6. EPA Source Classification Code - None exists.
7. References:
1. Miller, A. Titanium, A Materials Survey. Bureau of Mines
Information Circular 7791. United States Department of
Interior, Washington, D. C.» U.S. Govenment Printing Office,
September 1957.
2. Stamper, J. W. Titanium. In: Mineral Facts and Problems,
U.S. Department of Interior. Washington, D. C., U.S. Govern-
ment Printing Office, 1970.
3. Calspan Corporation. Development Document for Effluent
Limitations Guidelines and Standards of Performance for the
Ore Mining and Dressing Industry Point Source Category (Draft)
EPA Contract No. 68-01-2682. April 1975.
4. GCA Corporation. National Emissions Inventory of Sources and
Emissions of Titanium. EPA Publication No. 450/3-74-008.
Distributed by National Technical Information Service.
May 1973.
22
-------
TITANIUM METAL PRODUCTION PROCESS NO. 3
Smelting
1. Function - Smelting is done to upgrade certain ores containing
large quantities of iron. The ore is crushed with coal and smelted with
suitable fluxes in an electric furnace to produce iron and a slag. The
titanium-rich slag is recovered from the process. This process is used
only in Canada; there are no reports of commercial production of slag in
the United States.1
2. Input Materials - The main raw material for smelting is low-grade
ferruginous ilmenite (35 percent TiO,). The process yields pig iron and
2
a rich titanium slag of 70 percent Ti02.
3. Operating Parameters - Not available.
4. Utilities - Heat for melting is provided by electric energy to the
furnace.
5. Waste Streams - Environmental problems resulting from this process
probably are typical of those involved in the smelting aspects of the
iron-making industry. Technology is available for the control of fumes
from such processes. Slag quenching may result in emissions of hydrogen
sulfide and other undesirable volatiles. Water pollution from quenching
may also be significant. Ultimate disposal of the processed slag
constitutes a solid wastes problem.
6. EPA Source Classification Code - None exists.
7. References:
1. Stamper, J. W. Titanium. In: Minerals Yearbook.
U.S. Department of Interior. Washington, D. C., U.S.
Government Printing Office, 1970.
2. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology. New York, John Wiley and Sons, Inc.,
1968.
23
-------
TITANIUM METAL PRODUCTION PROCESS NO. 4
Chlorination and Purification
1. Function - Titanium tetrachloride is produced by the direct chlori-
nation of a titanium dioxide concentrate consisting of rutile, ilmenite,
or slag. Ilmenite ores cannot be chlorinated economically because large
quantities of chlorine are consumed by its iron content. Ilmenite
therefore is chlorinated only after removing its iron content by smelting.
The ores (rutile is preferred) are chlorinated in batch furnaces, in
fluidized beds, or in molten salt. The charge consists of the Ti02
concentrate, about 20 to 25 percent petroleum coke, and chlorine gas.
The fluidized-bed method lends itself to continuous operation. The
TiCK is purified to a clear, colorless liquid by filtration followed by
fractional distillation or rectification. Stoichiometric amounts of
water are added to precipitate the aluminum as aluminum oxychloride.
The filtration removes solid impurities present such as sodium, ealcium
and magnesium compounds. Vanadium can be removed by distillation or
alternatively as a sulfide by addition of H2S.
2. Input Materials - The process requires about 1.1 to 1.2 kilograms
of rutile, 0.15 kilogram of chlorine and 0.15 kilogram of petroleum coke
to produce enough titanium chloride to make 1 kilogram of titanium
2
sponge. Table A-2 in appendix A gives the range of composition of
titanium concentrates.
3. Operating Parameters - Chlorination takes place in the temperature
range of 800 to 1000°C and at atmospheric pressure.
4. Utilities - The furnace is heated by electricity or by burning
fuel. Since the reaction is slightly exothermic, little or no addi-
tional energy is required once the operating temperature is achieved.
5. Waste Streams - Effluent gases resulting from the manufacture of
TiCl4 have been reported to include 38 kilograms of G12, 13 kilograms of
HC1, and 12 kilograms of TiCl4 per ton of TiCK produced. Carbon
dioxide and monoxide are also present in the exit gases. These emis-
24
-------
sions are controlled by water scrubbers and occassionally caustic scrub-
bers. If the scrubber effluent becomes acidified, chlorine may be re-
leased into the atmosphere. Waste metal chlorides can release HC1 if
they are exposed to moisture in the atmosphere. These wastes are usual-
ly quenched and hydrolyzed, and injected into deep wells or disposed of
in impounding ponds. Any leakage or spill of TiCl. from product hand-
ling causes TiCl^ to react strongly with water including the water vapor
in the air to produce titanic and hydrochloric acids.
Increasing regulation of ocean dumping and land disposal operations
is of concern to processers. The chloride disposal problem is generally
considered much less severe than the problem of disposal of sulfates and
acids from other processes. Technologies that will eliminate
formation of chloride wastes are being sought.
6. EPA Source Classification Codes - Chlorination - 3-03-012-01.
7. References:
1. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology. New York, John Wiley and Sons, Inc.,
1968.
2. Stamper, J. W. Titanium. In: Mineral Facts and Problems.
U.S. Department of Interior, Washington, D.C., U.S. Government
Printing Office, 1970.
3. Control Techniques for Chlorine and Hydrogen Chloride Emis-
sions. (Unpublished draft copy). Environmental Protection
Agency. March 1971.
4. Baroch, C.T. et al. Titanium Plant at Boulder City, Nev.:
Its Design and Operation. Bureau of Mines Report of Inves-
tigation 5141. United States Department of Interior, Wash-
ington, D.C., U.S. Government Printings Office, September
1955.
25
-------
TITANIUM METAL PRODUCTION PROCESS NO. 5
Reduction
1. Function - Nearly all the current production of titanium metal
involves reduction of titanium tetrachloride with magnesium in a closed
system by the Kroll process. Sometimes sodium is the reductant instead
of magnesium. In the magnesium process, cleaned magnesium ingots are
first placed in the bottom of the reactor (a steel pot). The reactor is
then sealed, evacuated, back-filled with argon, and preheated to about
700°C. Purified TiCl4 is admitted at a controlled rate to maintain the
temperature between 850 and 900°C. Spongy magnesium metal and liquid
magnesium chloride are formed. The magnesium chloride is drained and
recycled through electrolytic cells to recover the magnesium and chlorine.
After the addition of titanium tetrachloride is stopped, the reactor is
heated to about 900°C to completely reduce all the TiCl4- When the
reactor has cooled, the spongy mass is removed. After crushing the
sponge, excess magnesium chloride or sodium chloride can be removed by
vacuum distillation at temperatures up to 925°C or by leaching in dilute
hydrochloric acid and drying. Vacuum distillation has advantages over
the leaching process which introduces oxygen, nitrogen and hydrogen into
2
the sponge titanium.
2. Input materials - Production of 1 kilogram of titanium sponge metal
requires approximately 2.5 kilograms of rutile, 5 kilograms of chlorine,
1.25 kilograms of magnesium, 56 liters of inert gas, and about 0.3
3
kilogram of petroleum coke. Approximately 4 kilograms of magnesium
chloride are produced for each kilogram of titanium. If the magnesium
chloride is processed to recover its elemental constituents, producing
1 kilogram of sponge metal requires only about 0.2 kilogram of magnesium
3
and 1 kilogram of chlorine. The common dissolved impurities in titanium
tetrachloride raw material are chlorine, carbonyl chloride or phosgene,
carbonyl sulfide, and hydrochloric acid in gaseous form; various chlo-
rides such as carbon tetrachloride, carbon disulfide, and several sulfur
26
-------
chlorides in liquid form; and many metal chlorides of which those of
silicon, vanadium, and iron are almost always present.
3. Operating Parameters - Reduction takes place at temperatures from
850 to 900°C. The excess salt is removed at a temperature of 925°C by
vacuum distillation. The distillation is carried out at a final
vacuum below 100 microns absolute pressure for 31 hours to bring both
the magnesium and chloride content of the sponge below 0.1 percent.
4. Utilities - Power requirements range from 13 to 33 kilowatt-hours
per kilogram of sponge. The higher demand includes power to recover
reductant metal and chlorine. The vessel is cooled by water circu-
lation.
5. Haste stream - Vent streams from the reactor vessel contain TiCl,
and MgClg vapors, reduced titanium chlorides, and inert argon or helium.
These waste streams must be controlled by scrubbers to prevent TiCl.
from reacting with moisture in the atmosphere to produce titanium
4
hydrate fumes and HC1. Conventional waste disposal techniques are
employed to handle impurities in the sponge that are stripped out by
distillation. Although some of the material may be drummed and sold to
refiners of other materials, most of the waste, mainly in the form of
metallic chlorides, is deposited in landfills or dumped at sea. Land-
fill material is a potential groundwater pollutant.
6. EPA Source Classification Code - None exists.
7. References:
1. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology. New York, John Wiley and Sons, Inc.,
1968.
2. Baroch, C.T. et al. Titanium Plant at Boulder City, Nev.:
Its Design and Operation. Bureau of Mines Report of Investi-
gation 5141. United States Department of Interior, Washington,
D.C., U.S. Government Printing Office, September 1955.
3. Stamper, J. W. Titanium In: Mineral Facts and Problems,
Volume I, U.S. Department of Interior. Washington, D. C., U.S.
Government Printing Office, 1970.
27
-------
4. Control Techniques for Chlorine and Hydrogen Chloride Emissions
Environmental Protection Agency. March 1971. (Unpublished
Draft Copy).
5. Baroch, C.T., and T. B. Kaczmarek. Titanium Plant at Boulder
City, Nev.: Operating Costs. Bureau of Mines Report of
Investigation 5248. United States Department of Interior,
Washington, D.C..U.S. Government Printing Office, July 1956.
6. Report of Proposal for Liquid and Gaseous Waste Treatment for
Integrated Titanium Facilities. Oregon Metallurgical Corpora-
tion. Albany, Oregon. August 1969.
28
-------
TITANIUM METAL PRODUCTION
PROCESS NO. 6
Melting and Ingot Conditioning
1. Function - The main features of this process are a cylindrical
water-cooled copper crucible, a consumable electrode, and a vacuum
system. The sponge and scrap to be melted, along with desired alloying
elements, are pressed into a large electrode. A small amount of sponge
in the bottom of the crucible acts as the other electrode. The
furnace is tightly sealed to prevent contamination by air or other gases
and melting is carried out under a vacuum or in an inert atmosphere of
argon or helium. The ingots formed in the process are commonly remelted
to improve homogeneity and to reduce the gas content of the metal.
Surfaces of ingots made by melting usually contain pits, cavities, and
pieces of incompletely melted sponge. For this reason most producers
must remove the outer surface of the ingot in a lathe prior to forging
and rolling. This operation produces 5 to 10 percent scrap metal, which
is remelted in subsequent batches. The ingot is conditioned by grinding
off surface imperfections before it is sent to a fabrication mill.
2. Input Materials - Table 8 gives a material balance for the melting
and ingot conditioning process. Table A-6 in the appendices gives the
composition of a typical titanium sponge.
Table 8. MATERIAL BALANCE FOR MELTING OPERATIONS
AT TITANIUM PLANTS
Constituents
Input
Sponge
Alloys
Scrap (purchased)
Melt scrap
Fabrication scrap
Output
Conditioned ingot
Melt loss
Melt scrap for recharging
Quantity, tons
0.544
0.047
0.185
0.059
0.240
1.0
0.0154
0.059
29
-------
3. Operating conditions - The melting operation is conducted under a
vacuum ranging from 0.05 to 0.5 mm Hg for both commercially pure and
alloy grades; an exception is processing of the higher-manganese alloys,
o
in which a lower vacuum of 10 to 15 mm Hg is maintained. In the
processing, the crucible mix is heated to about 1800°C.
4- Utilities - Typical melting currents run between 1250 and 2550
5
amperes at 40 to 60 volts DC. Total electricity requirements for
melting and conditioning are estimated to be 5.0 kilowatt-hours per
2
kilogram of ingot.
5. Waste Streams - One source reports that there are no emissions from
5
this process. About 6 percent of melt scrap from the process is
recovered and recharged. About 1.5 to 2 percent of the melt is lost from
the operation.
6. EPA Source Classification Code - None exists.
7. References:
1. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology, New York, John Wiley and Sons, Inc
1968.
2. Kellogg, H. H. What the Future Holds for Titanium. Engineer-
ing and Mining Journal. April 1955.
3. Whitemer, V. W. Titanium Production and Use. (Presented at
American Iron and Steel Institute Annual Meeting. May 1957.)
4. Barksdale, Jelks. Titanium, Its Occurence, Chemistry, and
Technology. New York, The Ronald Press Company, 1966.
5. GCA Corporation. National Emissions Inventory of Sources and
Emissions of Titanium. EPA Publication No. 450/3-74-000.
Distributed by National Technical Information Service.
May 1973.
30
-------
TITANIUM METAL PRODUCTION PROCESS NO. 7
Fabrication
1. Function - Fabrication of titanium is similar to that of stainless
steel. A great variety of shapes are produced including bars, billets,
sheets, tubes and light plates. In the mill products, the pickup of
oxygen and nitrogen is generally limited to the surface. In bars,
billets, or forgings, this surface is removed by final turning, mac-
hining, or other finishing operations. In sheets or strip products, the
contaminants are eliminated by grinding a few thousandths of a centi-
meter from the surface in the finishing operation.
2. Input Materials - Table 9 shows a material balance for the fabri-
cation of mill products.
Table 9. MATERIALS BALANCE FOR FABRICATION OF MILL PRODUCTS
Material
Conditioned ingots to be fabricated
Mill products
Fabrication scrap produced (charged to
melting unit)
Fabrication loss
Quantity, tons
1.434
1.0
0.344
0.09
A commercially pure grade of titanium referred to as RS-40 is a
high-purity titanium having moderate strength, good ductility, and
excellent formability. An intermediate-strength grade, RS-55, has good
formability. One of the highest-strength grades of commercially pure
titanium is RS-70. All of these products are available in the form of
2
sheets, plates, strips, billets, bars, wire, and welded tubing.
3. Operating Parameters - Forming is done in the temperature range of
200 to 320°C.
4. Utilities - Electric furnaces are usually used for the heating.
Gas-fired furnaces are also used, but to maintain uniformity of tem-
perature, the flame must not touch the metal. Data on quantities of
electricity and fuel used are not available.
31
-------
5. Waste Streams - metal finishing operations are a source of waste streams.
6. EPA Source Classification Code - None exists.
7. References:
1. Kellogg, H. H. What the Future Holds for Titanium. Engineer-
ing and Mining Journal. April 1955.
2. Whitmer, V. W. Titanium Production and Use. (Presented at
American Iron and Steel Institute Annual Meeting. May 1957.)
3. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology, New York, Wiley and Sons, Inc., 1968.
32
-------
TITANIUM DIOXIDE PRODUCTION
The major segment of this industry is the manufacture of titanium
dioxide (TiO^). This compound is produced either by the chloride or the
sulfate process as shown in Figure 2. In the chloride process the pur-
ified titanium dioxide is calcined or more commonly wet finished to re-
move residual chlorine or any hydrochloric acid that may be formed in
the reaction. In the sulfate process the ore or slag is dissolved in
sulfuric acid. The titanium in the solution is precipitated by hydrol-
ysis and is calcined to produce titanium dioxide.
33
-------
PURIFIED
TITANIUM
TETRACHLORIDE
FROM PROCESS 4
ALUMINUM CHLORIDE
'AIR OR OXYGEN
OXIDATION
CHLORIDE PROCESS
ILMENITE ORE-*-i
SOREL
SLAGi *•
r-WATER
IRON SCRAP
H2S04
CHLORINE FOR REUSE
FUEL
CALCINATION
10
DIGESTION, 9
CRYSTALLIZATION
HYDROLYSIS & BLEACHING
WATER
• COATING AGENTS
FUEL
FINISHING AND ]1
DRYING OPERATIONS
L- STEAM
GASEOUS EMISSIONS
LIQUID WASTE
SOLID WASTE
ALTERNATE SULFATE PROCESS
TITANIUM
DIOXIDE
PIGMENT
Figure 2. Titanium dioxide production.
-------
TITANIUM DIOXIDE PRODUCTION PROCESS NO^ 8
Oxidation
1. Function - Purified titanium tetrachloride vapor is fed to a
reaction chamber with air or oxygen, where combustion occurs. The
titanium dioxide forms as a fine smoke, which is collected by fabric
filters. The liberated chlorine is also collected separately and
reused. The recovered titanium dioxide, which contains some residual
chlorine or any HC1 formed in the reaction, may be calcined.
Aluminum chloride is added to the titanium chloride to ensure complete
oxidation of the titanium.
In alternate methods, the TiCl. can be reacted with water vapor to
produce titanium dioxide and hydrochloric acid, or hydrolized to produce
titanic acid (H,Ti00) and HC1. The titanic acid must then be precipi-
1
tated and ignited to produce titanium dioxide.
2. Input Materials - To produce one ton of titanium dioxide about 0.4
to 0.5 ton of oxygen, 1.1 to 1.2 tons of rutile and 0.03 ton of aluminum
2
chloride are required.
3. Operating Barameters - The reaction is exothermic and can be
carried out continuously at about 1000°C. No reaction occurs below
GOO0*:.1
4. Utilities - Additional heat is supplied externally by burning gas
or oil because the heat evolved by the reaction is not sufficient to
maintain the reaction.
5. Waste Streams - There are no significant wastes from oxidation,
6. EPA Source Classification Code - None exists.
7. References:
1. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology, New York, Hohn Wiley and Sons, Inc.,
1968.
2. Stamper, J. W. Titanium. In: Mineral Facts and Problems,
Volume I, U. S. Department of Interior. Washington, D. C.,
U.S. Government Printing Office, 1970.
3. Private communication, J. L. Jones, Stanford Research Insti-
tute to Research Triangle Institute. July 15, 1976.
35
-------
TITANIUM DIOXIDE PRODUCTION PROCESS NO. 9
Digestion, Crystallization, Hydrolysis, and Bleaching
1. Function - In the sulfate process, ilmenite ore or Sore! slag are
digested in sulfuric acid with steam added for heating the solution.
Scrap iron is added as a reducing agent to convert all of the ferric
iron to ferrous iron (0.5 kg Fe/kg Fe^O, in ore). Sorel slag has essen-
tially no FepOg present and thus requires no scrap iron addition while
an Australian ilmenite contains in excess of 15 weight percent of Fe^Og
and may require up to 0.16 kilogram of scrap iron/kilogram of TiO^ pro-
duct. When an ilminite ore is used, up to 75 percent of the ferrous
iron is removed from the digestion liquor by crystallization, Because
of the much lower iron content of the Sorel slag and no need to add scrap
iron, the iron content does not have to be reduced before hydrolysis.
In the hydrolysis reactor, a hydrous titanium oxide is produced and
filtered with an 18 percent I^SO^ filtrate solution produced which is
only partially recycled with the majority (1.5 H2S04 kg/kg Ti02) sent to
waste disposal. This stream is typically referred to as the strong acid
waste. Washing of the hydrolysis cake plus an acid leaching operation
(called bleaching) that follows filtration, produces about 0,9 kilogram
HUSO,. This stream is called the weak acid waste. The total quantity
of waste acid produced does not vary greatly for plants using ilmenite
ores or Sorel slag.
The hydrous oxide product after bleaching (for removal of remaining
trace impurities such as iron or chrome) is sent to a calciner. The TiOp
product from calcining is usually subjected to a wet finishing (and coating)
operating and dried although some material is shipped uncoated.
2. Input Materials - The quantities of raw materials used vary con-
siderably depending on the grade and source of the titanium raw material.
Table 10 gives the estimated requirements of raw materials for producing
2
titanium dioxide.
36
-------
Table 10. MATERIALS REQUIRED FOR PRODUCING ONE TON
OF TITANIUM DIOXIDE
Material
Ilmenite
Sorel Slag
Sulfuric acid (60° Baume)
Ilmenite Ore
Sorel Slag
Iron scrap (Ilmenite ore only)
Quantity, tons
1.9-2.6
-1.6
3.75-4.5
-2.7
0.15-0.2
3. Operating Parameters - During the exothermic reaction, the reaction
temperature rises rapidly from 125 to 200°C.
4. Utilities - Steam and electric power are used.
5. Waste Streams - This process produces four times as much waste as
the chloride process. The waste stream contains 2.4 kilograms of sul-
furic acid, 1.5 kilograms of ferrous sulfate, 0.15 kilogram of other
sulfates, and 0.06 kilogram of other metal salts including variable but
small amounts of vanadium and chrominum for each kilogram of titanium
3
dioxide produced. Of the total waste sulfuric acid, approximately 90
percent consists of weak (1.35%) acid with the balance consisting of 18
percent acid. The leachates and dilute acid resulting from the hydro-
lysis are the principal waste products of this operation. Until recently
one producer discharged acid and sulfate wastes in the ocean. Acid wastes
are neutralized and diluted before being discharged.
Particulate air pollutants from titanium dioxide production are
usually controlled by wet scrubbing. A cyclone or electrostatic precip-
itator may precede the scrubber.
When •ilmeniteore is used 2 to 4 kilograms of coppers (FeS04 • 7H20)
are produced per kilogram of Ti02-
6. EPA Source Classification Code - None exists.
7. References:
1. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemcial Technology, New York, John Wiley and Sons, Inc.*
1968.
2. Stamper, J. W. Titanium. In: Minerals Facts and Problems.
United States Department of Interior. Washington, D. C., U.S.
Government Printing Office, 1970.
3. Heavy Going Ahead for Waste Discharging at Sea. Chemical
Week. June 27, 1973.
37
-------
TITANIUM DIOXIDE PRODUCTION PROCESS NO. 10
Calcination
1. Function - The titanium dioxide hydrate from the digester is cal-
cined in direct-fired, inclined rotary kilns. As the charge travels
through the kiln, it is first dried, then water and SOg are driven off.
The kiln temperature is carefully controlled according to the grade of
pigment being made.
The titanium dioxide resulting from the chloride process may
occassionally be calcined to remove residual chlorine and any hydro-
chloric acid that is formed in the reaction. This is not common practice.
2. Input Materials - Titanium dioxide.
3. Operating Parameters - The kiln temperature may reach 1000°C in the
sulfate process. In calcination of the titanium dioxide resulting
from oxidation in the chloride process, the temperature is maintained
at about 500 to 600°C.2
4. Utilities - Oil or gas is used as fuel. Data on quantities of fuel
requirements are not available. Electric power is also used.
5. Waste Streams - Emissions from the sulfate process calciner contain
sulfur dioxide, sulfur trioxide, sulfuric acid mist, and particulate
matter. Limited field test data indicate that 20 kilograms of S09 are
3
emitted per ton of calcined titanium oxide. The gases leave the cal-
ciner at temperatures of 370 to, 480°C and at a rate of 45 m per kilo-
gram of product. Sulfur emissions result from sulfuric acid carryover
in the digested product. Emissions are controlled by scrubbers and elec-
trostatic precipitators. Atmospheric emissions from one calcining opera-
tion were reported to be: 1320 kg of S02/day, 70 kg of S03/day, 172 kg
of particulate/day and 82 kg of acid mist/day. No process through-put
data were provided. Table 11 gives typical composition of calciner
4
exhaust gases before treatment.
38
-------
Table 11. ANALYSIS OF EFFLUENT GASES OF A Ti02 CALCINER3
6.
7.
Materials
N2
H20
°2
co2
so3 + so2
Ti02(gm/m3)
Percent by volume
54.0
35.0
7.0
4.0
0.3
2.3
a Calculated from material balance
EPA Source Classification Code - None
Reference:
1. Kirk-Othmer. Titanium Compounds. In: Encyclopedia of
Chemical Technology, New York, John Wiley and Sons, Inc.,
1968.
2. Report of Atmospheric Emissions Tests Conducted at Titanium
Division! National Lead Company, Sayerville, New Jersey. U.S.
Department of Health, Education and Welfare. 1967.
3. U. S. Environmental Protection Agency. Miscellaneous Sources.
In: Control Techniques for Sulfur Oxide Air Pollutants.
(Advisory Committee Draft). Nov. 20, 1972.
4. Sittig, M. Titanium. In: Pollutant Removal Handbook. New
Jersey, Noyes Data Corp., 1973.
39
-------
TITANIUM DIOXIDE PRODUCTION PROCESS NO. 11
Finishing Operations
1. Function - Some pigment is sold for general purposes in the form
in which it leaves the calciner. The remainder usually requires wet
milling to remove oversized particles and to break up aggregates. Sur-
face coating is applied to a major portion of the pigment produced in
order to increase resistance to chalking, discoloration and fading. The
final product is then dried in a dryer.
2. Input Materials - Most of the titanium dioxide from calcination
requires milling. Surface coatings include such agents as hydrous
alumina, chromic oxide, silica and zirconium compounds. Alternatively
small proportions of conditioning agents such as antimony trioxide or
zinc oxide may be added before calcination.
3. Operating Parameters - Milling is done at ambient conditions.
4. Utilities - Energy is needed by milling equipment.
5. Waste Streams - Ti02 dust emissions are generally well controlled.
Waste water from the milling operation amounts to 46 liters per kilo-
gram of Ti02. This water may contain ammonium or sodium sulfate.
6. EPA Source Classification Code - None exists.
7. Reference
1. Barksdale, Jelks. Titanium, Its Occurrence, Chemistry and
Technology. New York, The Ronald Press Company, 1966.
40
-------
APPENDIX A
COMPOSITION AND PROPERTIES OF TITANIUM PRODUCTS
41
-------
Table A-l. ANALYSIS OF ILMENITE ORE1
(percent)
Chemi cal
constituent
Ti02
FeO
Fe2°3
Si02
A1203
P2°3
Zr02
MgO
MnO
CaO
V2°5
Cr2°3
Sn02
CuO
CoO
PbO
NiO
wo3
Piney
River
44.3
35.9
13.8
2.0
1.21
1.01
0.55
0.07
0.52
0.15
0.16
0.27
0.001
0.0005
0.005
0.005
0.05
Rose! and
51.4
37.9
1.6
4.6
0.55
0,17
2.35
0.70
0.59
0.07
0.02
0.0005
New York
44.4
36.7
4.4
3.2
0.19
0.07
0.06
0.80
0.35
4.0
0.24
0.001
0.001
0.004
Florida
64.1
4.7
25.6
6.3
1.5
0.21
0.35
, 1.35
0.13
0.13
0.1
California
48.2
39.1
10.4
1.4
0.2
0.05
0.6
0.1
0.1
0.05
0.03
0.001
0.005
0.005
42
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Table A-2. RANGE OF COMPOSITION OF TITANIUM CONCENTRATES
Titania (Ti02)
Iron oxide (Fe?0n)
Silica (Si02)
Alumina (A1203)
Calcium (CaO)
Magnesium (MgO)
Chromium (C^O-)
Vanadium (V20g)
Zirconium (Zr02)
Ilmenite
37 to 65
30 to 55
0.5 to 3.0
0.2 to 1.5
0.1 to 1.0
0.05 to 4.0
0.01 to 0.5
0.05 to 0.5
0.4 to 2.0
Rutile
94 to 98
0.2 to 1.5
0.2 to 2.0
0.2 to 0.5
0.02 to 0.08
0.02 to 0.09
0.1 to 0.3
0.4 to 0.8
0.01 to 0.4
Titanium slag
from Canada
71.4
16.3
3.8
4.6
0.8
5.0
0.2
0.6
43
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Table A-3. CHEMICAL ANALYSIS OF TITANIUM METAL3
Constituent
Carbon
Nitrogen
Iron
Titanium
Hydrogen
in bar & billet
in sheet & strip
Density
Grade 40
0.05
0.01
0.15
Balance
0.0125 max
0.0150
2.61 kg /m3
Grade 55
0.05
0.012
0.20
Balance
0.0125 max
0.0150
Grade 70
0.05
0.015
0.20
Balance
0.0125 max
0.0150
44
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Table A-4. PHYSICAL PROPERTIES OF COMMERCIALLY PURE TITANIUM^
Atomic number
Atomic weight
Density, g/ml
Melting point, °C
Boiling point, °C
Allotropic transformation temperature, °C
Heat of fusion, cal/mole
Heat of sublimation at 25°C, cal/mole
Specific heat, 0-500°C, cal/(g)(°C)
Entropy, 25°C, cal/(mole)(°C)
Thermal expansion coefficient at 25°C, per °C
Thermal conductivity, 25°C, cal/(sec)(cm )(°C/cm)
Emissivity
Electrical resistivity, 25°C,yO-cm
Magnetic susceptibility, cmu/g
Modulus of elasticity, psi x 10
tension
compression
shear
Poisson's ratio
22
47.90
4.507
1668
3535
822
5000
111,720
0.1386
7.24
8.5 x 10
9.41
9.43
47.8
3.17
-14-7
15.0
6.4
-0.41
-6
45
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Table A-5 . PHYSICAL PROPERTIES OF TITANIUM DIOXIDE^
Melting point
Boil ing point
Density
Atomic weight
TiO,
1640°C
2700°C
4.2 g/cc
79.9
46
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Table A-6. TYPICAL TITANIUM SPONGE ANALYSIS4
Element, %, max.
Nitrogen
Carbon
Sodium (total)
Magnesium
Chlorine
Iron
Silicon
Hydrogen
Oxygen
Water
All other impurities
(total)
Titanium balance
(nominally)
Percent by wt, dry8
GradeblA-0
A
0.015
0.020
0.08
0.12
0.12
0.04
0.005
0.10
0.02
0.05
99.3
B
0.015
0.025
0.40
0.15
0.10
0.04
0.03
0.10
0.02
0.05
99-1
C
0.010
0.020
0.19
0.20
0.05
0.04
0.05
0.10
0.02
0.05
99.3
GradeblB-0
A
0.015
0.020
0.08
0.12
0.05
0.04
0.005
0.07
0.02
0.05
99.3
dDried 2 hours at 135°C.
^Grades consist of the following types: A, magnesium-reduced and vacuum-
distilled; B, magnesium-reduced and acid-leached; C, sodium-reduced
and acid-leached.
47
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Table A-7. CHEMICAL ANALYSES OF COMMERCIAL GRADE AND PURIFIED TiCl4 FROM SOURCES A AND B 6
(Grams/liter)
CD
Source
A
A
A
A
A
B
B
B
B
B
Range of typical)
purified TiCl4)
Fe
0.03
0.04
0.03
0.04
0.04
0.05
0.04
0.03
0.04
0.03
0.03
0.04
V
1.9
1.9
1.7
1.2
1.1
1.8
1.9
1.7
1.1
0.95
<0.10
S
0.15
0.04
0.03
0.05
0.03
0.06
0.04
0.03
0.03
0.04
0.01
0.08
Si
0.26
0.40
0.25
0.25
0.25
0.27
0.40
0.25
0.25
0.15
<0.10
Free
ci2
2.00
1.90
1.98
1.02
1.30
2.97
1.90
1.98
1.30
3.55
<0.10
0.15
Nonvolatile
residue
1.7
1.75
3.4
5.4
5.9
1.70
1.76
3.40
5.90
4.20
Spectrographic
trace elements
Cu,Al,Pb,Mg,Mn,Ca,Cr,Sn
Cu,Al,Pb,MgsMn,Ca,Cr
Cu,Al,Pb,Mg,Mn,Ca,Ni
Cu,Al ,Pb,Mg,Mn,Ca,Cr
Cu,Al,Mg,Mn,Ca
Cu.Al ,Mg,Mn,Ca,Fe,Sn,Nb
Cu,Al ,Mg,Mn,Ca,Fe,Pb,Cr
Cu,Al,Mg,Mn,Ca,Fe,Pb,Ni
Cu,Al,Mg,Mn,Ca,Fe
Cu,Fe,Sn,Mo
-------
Table A-8. PHYSICAL PROPERTIES OF TITANIUM TETRACHLORIDE'
Color
Density, 20° C, g/ml
Freezing point, °C
Heat of fusion, kcal/mole
Boiling point, °C
Vapor pressure3 in mm Hg
At 20°C
At 50°C
At 100°C
Heat of vaporization, kcal/mole
25°C
135.8°C
Specific heat, 20°C, cal/g
Critical temperature, °C
Heat of formation of liquid, 25°C, kcal/mole
Viscosity, (dyn)(sec)/cm
20
Refractive index, nD ,
Magnetic susceptibility
Dielectric constant, 20°C
None
1.70
-24
2.249
135.8
10.0
41.4
266
9.1
8.4
0.193
358
-192.3 + 0.9
0.0079
1.6085
-0.287 x 10'
2.79
-6
ilog10Pmm = 7'64433 - 1947.6/273,16
49
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Table A-9. TYPICAL PROPERTIES OF COMMERCIAL TITANIUM ALLOYS4
Property
Density, lb,in.3
Thermal conductivity,
Btu/(hr)(ft2)(°F/ft)
Tensile modulus,
psi x 106
Tensile strength,
psi x 10-3
Tensile yield ~
strength, psi' x 10
Elongation in tension,%
Charpy impact strength
ft-lb
Creep strength (600°F,o
100 hr. 0.1%)psi x TO1*
Fatigue strength,
psi x 1$ for
107 cycles
Bend radius, r/t
Weldability
Unalloyed
0.163
9.5
15.0
75
60
25
30
20
46.0
2
excellent
Composition, wt % (balance Tia)
5Al-2.5Sn
0.162
4.5
16.0
125
117
18
18
68
76.0
4
excellent
6A1 -4V
0.160
4.2
16.5
70b
55b
ob
17
00
82.0
4.5
good
6A1 -6V-2Sn
0.162
4.2
16.0
185b
175b
8b
15
70
66.0
4.5
poor
8A1-1MO-1V
0.158
3.6
17.5
145
138
15
20
95
80.0
4.5
good
3Al-13V-llCr
0.175
4.0
14.5
190b
180b
8b
8
140
33.0
3
good
6Al-2Cb-lTa-lMo
0.162
3.7
17.0
115
no
10
34
75
55.0
4
excellent
aAnnealed condition unless otherwise noted.
bSolution-treated and aged condition.
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APPENDIX B
TITANIUM AND TITANIUM OXIDE PRODUCERS
51
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Table B-l. TITANIUM INDUSTRY COMPANIES, 1972 2»8>9
Company and location
Operation
Capacity,
tons
Ameri can Cyanami d Co.
Pigment Division at
Savannah, Ga.
Combustion Engineering
Camden, N.O.
Wilmington, De.
Crucible Steel Co., of
America
Midland, Pa.
E.I. duPont de Nemours
& Co., Inc.
Starke, Fla.
Highland, Fla.
Antioch, Cal.
Edgemoor, Del.
New Johnsonville, Tenn.
Gulf and Western Ind.
(The New Jersey Zinc Co.
Subsid)
Ashtabula, Ohio3
Gloucester City, N.J.
Harvey Aluminum, Inc.
Torrance, Cal.
Howmet Corp.
Whitehall, Mich.
Humphreys Mining Co.
Folkston, Ga.
TiO? production(s)
Ti02 production (c)
Ti02 production
production
Ti ingot from sponge
and scrap
Sand mining
Sand mining
Ti02 production (c)
Ti02 production (c)
TiO,, production (c)
Ti02 production (c
Ti02 production (s
Ti ingot from sponge
and scrap
Ti ingot from sponge
and scrap
Sand mining
65,300
36,300
N.A.
N.A.
N.A.
24,500
101,400
206,800
25,000
39,000
N.A.
N.A.
52
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Table B-l (Continued). TITANIUM INDUSTRY COMPANIES, 1972 2'8'9
Company and location
Operation
Capacity,
tons
Kerr-McGee Corp.
Hamilton, Miss.
Lonza, Inc.
Mapleton, 111.
ML Industries Inc.
Tahawus, N.Y.
Titanium Pigment -
Divisions at St. Louis
Mo.
Sayreville, N.J.
Oregon Metallurgical Corp.
(Owned by Armco Steel Corp.
and Ladish Co.)
Albany, Oregon
RMI Company
(Owned by National
Distillers and Chemical
Corp. and U.S. Steel
Corp.)
Niles, Ohio
Ashtabula, Ohio
SCM Corporation
Glidden-Durkee Corp. Division
Lakehurst, N.J.
Baltimore, Md.
Ashtabula, Ohio
Ti02 production (c)
production
Rock mining
Ti02 production (s)
Ti02 production (s)
Ti sponge production
Ti ingot from sponge
production
Ti ingot from sponge
and scrap
Ti sponge production
Sand mining
production (c)
production (s)
Ti02 production
41,700
N.A.
104,000
112,500
N.A.
N.A.
N.A.
N.A.
22,700
48,100
25,000
53
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Table B-l (Continued). TITANIUM INDUSTRY COMPANIES, 1972 2'8'9
Company and location
Operation
Capacity,
tons
Teledyne Titanium Inc.
Monroe, N.C.
Titanium Enterprise
Green Cove Springs, Fla.
Titanium Metals Corp.
of America
(Owned by N.L. Indus-
tries Inc. and Allegheny
Ludlum Steel Co.)
Henderson, Nev.
Titanium Technology
Corp.
Pomona, Cal.
Titanium West, Inc.
Reno, Nev.
Transelco, Inc.
Penn Van, N.Y.
Ti ingots from sponge
and scrap
Sand mining
Ti sponge production
Ti ingots from sponge
and scrap
Ti ingots from sponge
and scrap
Ti ingots from sponge
and scrap
Ti02 production
N.A.
127,000
N.A.
N.A.
N.A.
N.A.
Leased from Cabot Corp.
A joint venture of American Cyanamid and the Union Camp Corp.
cChloride process
sSulfate process
N.A. - not available
54
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APPENDIX C
REFERENCES FOR APPENDICES
55
-------
REFERENCES FOR APPENDICES
1. Barksdale, Jelks. Titanium, Its Occurence, Chemistry and Technology.
New York, The Ronald Press Company, 1966.
2. Stamper, J.W. Titanium. In: Minerals Facts and Problems. Volume
I, United States Department of Interior. Washington, D.C., U.S.
Government Printing Office, 1970.
3. Whitmer, V.W. Titanium Production and Use. (Presented at American
Iron and Steel Institute Annual Meeting. May 1957.)
4. Kirk-Othmer. Titanium and Titanium Alloys. In: Encyclopedia
of Chemical Technology, New York, John Wiley and Sons, Inc., 1968.
5. GCA Corporation. National Emissions Inventory of Sources and
Emissions of Titanium. EPA Publication No. 450/3-74-008.
Distributed by National Technical Information Service. May 1973.
6. Baroch, C.T., et al. Titanium Plant of Boulder City, Nev.:
Its Design and Operation. United States Department of Interior.
Washington, D.C., Report of Investigation 5141. September 1955.
7. Kirk-Othmer. Titanium Compounds (Inorganic). In: Encyclopedia
of Chemical Technology, New York, John Wiley and Sons, Inc., 1968.
8. Noe, F.E. Titanium. In: Minerals Yearbook, United States
Department of Interior. Washington, D.C., U.S. Government Printing
Office, 1971.
9. Stanford Research Institute. 1974 Directory of Chemical Producers,
United States of America. Printed in USA.
56
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TECHNICAL REPORT DATA
(Please read Inslnictions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/2-77-023Z [_
4. TITLE AND SUBTITLE'
Industrial Process Profiles for Environmental Use:
Chapter 26. Titanium Industry
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
February 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR'S)
Vishnu S. Katari & Timothy W. Devitt (PEDCo)
Terry B. Parsons, Editor
8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
P.O. Box 99)48
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
1AB015: ROAP 21AFH-025
11. CONTRACT/GRANT NO.
68-02-1319, Task
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. ENVIRONMENTAL PROTECTION AGENCY
Cincinnati, Ohio U5268
13. TYPE OF REPORT AND PERIOD COVERED
Initial: .8/75-11 /76
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The catalog of Industrial Process Profiles for Environmental Use was developed as an
aid in defining the environmental impacts of industrial activity in the United States
Entries for each industry are in consistent format and form separate chapters of the
study.
The titanium industry produces two principal products, titanium metal and titanium
dioxide. For purposes of analyses, therefore, the industry is considered in two
segments: titanium metal production and titanium dioxide production. Two in-
dustrial process flow diagrams and eleven process descriptions have been prepared
to characterize the industry. Within each process description available data have
been presented on input materials, operation parameters, utility requirements, and
waste stream. Data related to the subject matter, including composition and
properties of titanium products, as well as producer listings, are included as
appendices.
KEY WOHDS.AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Titanium Industry
Titanium Metal
Titanium Dioxide
Pigment
Process Description
3. DISTRIBUTION STATEMENT
Release to Public
b.lDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Water Pollution Control
Solid Waste Control
Stationary Sources
Titanium Industry
19. SECURITY CLASS (TMsReport)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
COSATI Field/Group
07B
11C
13B
21. WO. OF PAGES
65
22. PRICE
EPA Form 2220-1 (9-73)
57
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