TITANIUM TETRACHLORIDE PRODUCTION BY THE CHLORIDE
ILMENITE PROCESS
Technical Background Document
Supporting the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to
Newly Identified Mineral Processing Wastes
Office of Solid Waste
U.S. Environmental Protection Agency
December 1995
TECHNICAL BACKGROUND DOCUMENT
TITANIUM TETRACHLORIDE PRODUCTION BY THE CHLORIDE ILMENITE PROCESS
1. Background and Purpose
This document presents EPA's factual basis for proposing to withdraw a waste
generated in the production of titanium tetrachloride by the chloride-ilmenite process from the
RCRA Mining Waste Exclusion. The waste in question, titanium tetrachloride waste acids
(which implicitly includes iron chloride), was one of numerous mineral processing wastes that
was made conditionally exempt from RCRA Subtitle C requirements under the Bevill
Amendment to RCRA, and later codified at 40 CFR Part 261.4(b)(7). In 1989, following a study
of the nature and characteristics of this waste, EPA determined that titanium tetrachloride waste
acids (and therefore iron chloride) did not qualify for the Mining Waste Exclusion.1
In contrast to wastes from beneficiation operations, mineral processing wastes were
required to meet two criteria in order to continue to qualify for the Mining Waste Exclusion: (1)
the waste had to be a low hazard waste; and (2) it had to be generated in large volumes,
defined as greater than 45,000 metric tons per year per facility for a solid waste or 1 million
metric tons per year per facility for a liquid waste (averaged across the commodity sector).
EPA's findings indicated that titanium tetrachloride waste acids exhibited the characteristic of
EP toxicity2 for chromium, making them a hazardous waste, and were generated in annual
volumes of less than 1 million metric tons per facility; therefore, the Agency concluded that
titanium tetrachloride waste acids, implicitly including iron chloride, should be withdrawn from
the Mining Waste Exclusion.
Du Pont, which is the sole generator of the iron chloride waste in question, filed a
lawsuit against EPA claiming that its process was different than the conventional chloride
process and, therefore, that its wastes (including iron chloride) should be considered separately
for Bevill status.3 Du Pont claimed that EPA had ignored the information provided in Du Pont's
written comments on several notices of proposed rulemaking addressing the Exclusion4 , and
that the Agency had not provided an adequate justification for its decision. The federal D.C.
Circuit Court of Appeals, in reviewing EPA's decision to withdraw titanium tetrachloride waste
acids from the Mining Waste Exclusion, found that the Agency had not provided an adequate,
reasonable justification in the public record to support its action.
The purpose of this technical background document is to provide a description of the Du
Pont chloride-ilmenite process and the generation of the iron chloride waste, and to provide
EPAs' evaluation of this the process. This evaluation serves as the technical basis for EPA's
response to the Court's directives regarding the regulatory status of the iron chloride waste.
1
54 FR 36592.
2
Based upon the regulatory standard in effect and available data as of September
1989. EPA believes that the waste in question would exhibit the hazardous waste
characteristic of toxicity if tested using the currently applicable testing method (the
TCLP).
3
Solite Corporation v. U.S. Environmental Protection Agency, Case No. 89-1629,
argued September 16, 1991, decided December 31, 1991, United States Court of
Appeals for the District of Columbia Circuit (952 F.2d 473).
4
Comments submitted to RCRA docket Nos. F-88-MWEP-FFFFF (10/29/88 NPRM),
F-89-MWRP-FFFFF (4/17/89 NPRM), and F-89-MW2P-FFFFF (9/15/89 NPRM).
3
2. Commodity Summary
Ilmenite (FeTiO 3 ) is the most abundant titanium-bearing mineral and is comprised of
about 43% to 65% titanium dioxide (TiO 2 ). A second major mineral form of titanium is rutile, a
crystalline, high-temperature polymorph of TiO 2 , containing about 95% TiO 2 . Another
crystalline form of TiO 2 , anatase, is not available commercially at present, but deposits of
anatase-bearing ore are being developed in Brazil. 5 Titanium minerals are found in hard rock
deposits and in beach and alluvial sands commonly know as “beach sands.” Other sources of
titanium include titaniferous slags (70-85% TiO 2 ) made by electric furnace smelting of ilmenite
with carbon.
Titanium (Ti) metal is valued for its high strength-to-weight ratio and corrosion
resistance. Titanium metal is alloyed with aluminum and vanadium, among other metals, for
use in aircraft and spacecraft; in 1993, about 75 percent of titanium metal produced was used
in jet engines, airframes, and space and missile applications.6 Titanium metal is also employed
in the chemical, power generation, marine, ordnance, and medical industries. Titanium is also
used in ceramics, coatings for welding rods, heavy aggregate, and steel furnace flux. The
major use of titanium, however, is in oxide form (TiO 2 ) as a white pigment for paints, rubber,
paper, and plastics.7
Titanium dioxide pigment is manufactured through either the sulfate, the chloride, or the
chloride-ilmenite process. The sulfate process, used at only two U.S. plants, involves digestion
of ilmenite ore or TiO 2 -rich slag with sulfuric acid to produce a cake, which is purified and
calcined to produce TiO 2 pigment. The sulfate process generates sulfuric acid wastes in as
much as two times the product weight, resulting in the need for expensive treatment by
neutralization before disposal of the wastes.
In the more commonly used chloride process, rutile, synthetic rutile, or high-purity
ilmenite is chlorinated to form titanium tetrachloride, which is purified and oxidized to form TiO2
pigment. Titanium tetrachloride is currently manufactured at nine plants in the United States for
conversion to titanium dioxide pigment.8 (Titanium tetrachloride is also manufactured as an
intermediate product in the production of titanium sponge (metal), which is cast into ingots for
further processing and alloying.) Of these nine plants, six utilize the traditional chloride
process.
In contrast to production operations at these plants, Du Pont employs a proprietary
chloride-ilmenite process at three of its plants in which ilmenite ore is directly used to produce
high-purity titanium tetrachloride. Du Pont describes the process as a “simultaneous
beneficiation/processing operation.” Because ilmenite contains significant quantities of iron,
use of this process requires removal of the iron from the titanium value, in the form of iron
(ferric) chloride. Du Pont has claimed that the iron chloride waste is generated through the
removal of iron from the ilmenite ore before the physical structure of the ore is destroyed in the
subsequent chlorination step of the chloride-ilmenite process. This process, conducted
exclusively by Du Pont at its Edgemoor, DE and New Johnsonville, TN plants and at its DeLisle
plant in Pass Christian, MS, is described in more detail below after a description of the
conventional chloride process.
5
J. Gambogi, Annual Report: Titanium-1992, U.S. Bureau of Mines, December
1993, p. 1.
6
J. Gambogi, “Titanium and Titanium Dioxide,” from Mineral Commodity
Summaries, U.S. Bureau of Mines, January 1994, p. 184.
7
J. Gambogi, 1993, Op. Cit., p. 1.
8
J. Gambogi, 1993, Op. Cit., p. 13.
4
3. Production Processes
In this section, EPA provides brief descriptions of the two major process routes for
producing titanium tetrachloride. These descriptions provide the basis for the application of the
Agency's definitions of mineral beneficiation and processing, which is presented below in
Section 4.
3.1 Chloride Process
In the chloride process, rutile or high-grade ilmenite is converted to titanium tetrachloride
(TiCl4 ) gas. The conversion takes place in a chlorinator (i.e., fluidized bed reactor) in the
presence of chlorine gas at 850° C to 950° C, with petroleum coke added as a reductant. All
U.S. producers of TiCl 4 use fluid-bed chlorinators, though static-bed systems also can be used.9
The chief reaction products are volatile metal chlorides, including TiCl 4 , which are collected.
The non-volatile chlorides and the unreacted solids that remain in the chlorinator are wasted,
forming the special waste stream “chloride process waste solids.”10 The gaseous raw product
stream is purified to separate the titanium tetrachloride from other chlorides. Separation is by
fractional condensation, double distillation, and chemical treatment. Ferric chloride (FeCl3 ) is
removed as a major acidic liquid waste stream through fractional condensation.11 Additional
trace metal chlorides are removed through double distillation. Finally, vanadium oxychloride
(VOCl3 ), which has a boiling point close to that of TiCl4 (136° C), is removed as a low-volume
non-special waste by complexing with mineral oil and reducing with hydrogen sulfide to VOCl2 ,
or by complexing with copper. The purified TiCl4 is then oxidized to TiO2 at 985° C, driving off
chlorine gas, which is recycled to the chlorinator. Aluminum chloride is added in the oxidation
step to promote formation of the rutile crystal, which is the TiO2 product.12
3.2 Chloride-Ilmenite Process
In the chloride-ilmenite process, ilmenite, which, even at high grade, has a substantially
lower TiO2 content (approximately 65%) than rutile, is converted to TiCl 4 . The ilmenite ore used
in the process contains a much larger amount of iron than the other ores (i.e., rutile or high-
grade ilmenite) used to produce TiCl 4 . As in the chloride process, the chloride-ilmenite process
takes place in a fluid bed reactor in which the ore is chlorinated, in the presence of coke as a
reducing agent. According to Du Pont, however, the process differs from the chloride process
in that within a four step production process, there is a two-step reaction sequence referred to
as “selective chlorination,” consisting of a beneficiation step and a processing step. Both of
these first two steps occur in the chlorinator. In the first step, ilmenite ore is reacted with the
chlorine gas and coke. Within seconds, the chlorine reportedly reacts with the iron oxide in the
ilmenite ore, producing gaseous iron chlorides that are subsequently condensed (in step 3) in a
spray condenser to form iron chloride waste acids, which are either sold as product or disposed
as the waste stream “titanium tetrachloride waste acids.” The initial step is the beneficiation
portion of the process, according to Du Pont. This step also reportedly yields enriched ilmenite
9
J. Gambogi, 1993, Op. Cit., p. 3.
10
U.S. Environmental Protection Agency, “Titanium Tetrachloride Production,” from
Report to Congress on Special Wastes from Mineral Processing, Vol. II, Office of Solid
Waste, July 1990, p. 13-3.
11
U.S. Environmental Protection Agency, 1988. “Titanium,” from Summary Report
of Mineral Industry Processing Wastes (Final Draft). p. 3-222.
12
Ibid.
5
ore consisting of more than 95% TiO 2 and having the same basic particle structure as the
original ilmenite ore feed.13 Du Pont contends that
[T]he first phase of the chlorination step produces sand grains that are virtually
unchanged from the original mineral, except for a change in color as a result of
the removal of iron. Thus, this phase, which generates most of the waste from
the Du Pont process, produces nothing more than a high grade beneficiate.14
In the second step of the “simultaneous beneficiation-chlorination” process, the “beneficiated”
ore, which remains in the chlorinator, is converted to gaseous TiCl 4 over a period of several
hours. Du Pont contends that this step is the mineral processing portion of the operation. The
TiCl4 is condensed and further refined to remove contaminants in step 4 of the process. These
contaminants are then combined with the iron chloride waste stream generated at step 3.15
4. Application of Definitions of Mineral Beneficiation and Processing
By classifying the first phase of its chloride-ilmenite process as benef iciation, Du Pont is
seeking to include the iron chloride waste generated through steps 1 and 3 of the process
within the Mining Waste Exclusion. Du Pont bases its classification on its belief that the
“beneficiation” step renders the structure of the ilmenite ore intact and essentially unchanged
after the initial reaction with chlorine gas and coke.16 Based on this criterion alone, Du Pont
concludes that because the ore structure remains essentially unchanged, the initial step
constitutes beneficiation. According to the preamble of EPA's final rule on the Mining Waste
Exclusion, however,
Most beneficiation processes, at least those immediately upstream from the
initial processing operation in a production sequence, generate high volume solid
waste streams that are essentially earthen in character. Despite the fact that
valuable constituents have been removed, the remaining material is often
physically and chemically similar to the material (ore or mineral) that entered the
operation, except that particle size reduction has often occurred. Processing
operations, in contrast, generate waste streams that generally bear little or no
resemblance to the materials that entered the operation. These operations most
often destroy the physical structure of the mineral, producing products and waste
streams that are not earthen in character.17
Based upon detailed evaluation of the information submitted by Du Pont, EPA has found
that in the initial step, chlorine gas is reacted with the solid ore, inducing significant chemical
changes in the ore and forming a new chemical compound, ferric chloride. The reaction
forming this new compound is the first of two that fundamentally alter the physical and chemical
nature of the mineral feedstock. Indeed, the reaction of chlorine with iron and the changes in
13
Memorandum from D. Derkics, U.S. Environmental Protection Agency, Office of
Solid Waste and Emergency Response, “Notes of the October 24, 1989 Meeting with
Representatives of E.I. DuPont de Nemours & Company,” submitted to Mining Waste
Docket No. F-89-MW2P-FFFFF, 1989, p. 2.
14
Letter from C. Goldstein, Covington & Burling, Washington, D.C., to Randolph L.
Hill, U.S. Environmental Protection Agency, Office of General Counsel, November 16,
1990, p. 2.
15
Ibid.
16
Letter from Aldo Morell, Du Pont, to Van E. Housman and George B. Wyeth, U.S.
Environmental Protection Agency, May 12, 1995, p. 1.
17
54 FR 36619.
6
the ore that it induces are very similar to the subsequent reaction between chlorine and titanium
and its impacts upon the mineral feedstock. Both of these reactions occur in the same vessel
using the same reagent and reaction conditions, and both contribute to the physical and
chemical destruction of the ore.
In terms of the nature of the waste in question, the ferric chloride waste acids do not
resemble the ore feedstock entering the operation, and instead are much more similar to typical
mineral processing wastes such as metallurgical acid plant blowdown than to beneficiation
wastes such as mill (flotation) tailings. In this example, the removal of iron as an impurity from
the titanium ore is directly analogous to the removal of sulfur and heavy metal impurities during
the primary smelting of base metals such as lead and copper. Furthermore, ferric chloride is a
highly corrosive material. While EPA has not collected analytical testing data for this waste in
order to apply the hazardous waste test for corrosivity, it is known generally that FeCl 3 in
solution has corrosive properties18 . Data submitted by Du Pont to the Agency in 199019 show,
in fact, that the liquid iron chloride waste has a pH below zero and exhibits the hazardous waste
characteristic of toxicity for cadmium, lead, and silver. Published information20 also shows that
Du Pont markets the ferric chloride solution that it produces from titanium tetrachloride
production as a wastewater and drinking water treatment reagent. Clearly, this material more
closely resembles a concentrated chemical product or waste than a typical earthen
beneficiation waste such as flotation tailings.
Finally, it is worthy of note that, according to EPA's codified definitions, chlorination
constitutes beneficiation only when it is used in preparation for a leaching operation that does
not produce a final or intermediate product that does not undergo further beneficiation or
processing.21 In the case of Du Pont's process, the first step of the "simultaneous
beneficiation/processing" operation is followed not by a leaching step but by further chlorination
(destructive chlorination, in this case). In other words, notwithstanding Du Pont's technical
arguments, no part of the production sequence involving the reaction of ilmenite ore with
chlorine in the fluid bed reactor falls within EPA's established and codified definition of
beneficiation. Accordingly, all wastes associated with this production sequence are mineral
processing wastes. Furthermore, because the liquid wastes from this operation are not high
volume (whether considered separately or as part of the larger TiCl 4 industry), they are not
eligible for retention within the Mining Waste Exclusion.
In response to Du Pont's most recent submission concerning the chloride-ilmenite
process and the wastes that it generates22 , EPA believes that the central point is that within one
reaction vessel and set of reaction conditions, a beneficiated ore is treated so aggressively that
solid metals are vaporized. The fact that more than one gaseous (metal chloride) stream
emerges from this operation is irrelevant, as is the fact that one stream is a product and the
other (primarily) is a waste. While the Agency recognizes that it has previously suggested that
the Kerr-McGee synthetic rutile plant is a beneficiation operation, EPA wishes to clarify that
18
A five percent solution of FeCl 3 has a pH of 1.7 at equilibrium (Kirk-Othmer
Encyclopedia of Chemical Technology, Third Ed., vol. 13. John Wiley and Sons, New
York, 1981. p. 773.).
19
Letter from C. Goldstein, Covington & Burling, Washington, D.C., to Randolph L.
Hill, U.S. Environmental Protection Agency, Office of General Counsel, December 13,
1990, Table IVB.
20
American Chemical Society, 1991. Chemcyclopedia 1992. p. 171, and ERT
Hazardous Substances Database. 1995.
21
40 CFR 261.4(b)(7).
22
Morell, Op Cit., p. 1.
7
volatilization of metals in a primary mineral production sequence constitutes mineral
processing.
5. Conclusions
In this technical background document, EPA has provided the relevant facts for
determining whether iron chloride waste generated by Du Pont's chloride-ilmenite process
constitutes an exempt beneficiation waste or a non-exempt mineral processing waste. Du Pont
asserts that the initial step of its process involves beneficiation rather than processing on the
basis that the ore structure remains physically intact following chlorination of the iron in the ore.
EPA concludes, however, that due to the significant physical and chemical changes that are
induced in the feedstock (and the generation of a new chemical compound) in the first step, and
the similarity of these changes to those induced by the second step, it is most appropriate to
consider the entire sequence a mineral processing operation. Furthermore, EPA disagrees with
Du Pont's recent assertion that the Agency and Du Pont are in agreement that the chloride-
ilmenite operation involves beneficiation.23 As a final and definitive point on this question, the
form of chlorination employed by Du Pont in this process is not included within EPA's definition
of beneficiation. Accordingly, the chloride-ilmenite process is defined as mineral processing.
Hence, because the iron chloride wastes are not high volume, they are non-exempt mineral
processing wastes.
23
Morell, Op Cit., p. 2.
8
BIBLIOGRAPHY
Derkics, D. “Notes of the October 24, 1989 Meeting with Representatives of E.I. Du Pont de
Nemours & Company.” U.S. Environmental Protection Agency, Office of Solid Waste
and Emergency Response. Memorandum submitted to Mining Waste Docket No. F-89-
MW2P-FFFFF. 1989. 5 pp.
Gambogi, J. Annual Report: Titanium-1992. U.S. Bureau of Mines. December 1993.
Gambogi, J. “Titanium and Titanium Dioxide.” From Mineral Commodity Summaries. U.S.
Bureau of Mines. January 1994. pp. 184-185.
Goldstein, C. Letter to Randolph L. Hill, U.S. Environmental Protection Agency, Office of
General Counsel, from C. Goldstein, Covington & Burling, Washington, D.C. November
16, 1990. 7 pp.
Goldstein, C. Letter to Randolph L. Hill, U.S. Environmental Protection Agency, Office of
General Counsel, from C. Goldstein, Covington & Burling, Washington, D.C. December
13, 1990. 15 pp.
Morell, Aldo. Letter to Van E. Housman and George B. Wyeth, U.S. Environmental Protection
Agency, from A. Morell, Du Pont, Wilmington, DE. May 12, 1995. 3 pp.
U.S. Environmental Protection Agency. “Titanium.” From 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. 1988. pp. 3-217 - 3-227.
U.S. Environmental Protection Agency. “Titanium Tetrachloride Production.” From Report to
Congress on Special Wastes from Mineral Processing. Vol. II. Office of Solid Waste.
July 1990. pp. 13-1 - 13-31.
