Titanium In The Geothermal Industry

By
Roger Thomas
TIMET
Swansea, Wales

ABSTRACT

Titanium resists seawater and brine at temperatures as high as 260ºC, and is

also resistant to corrosion by sulphur dioxide; hydrogen sulphide; and aqueous
solutions of those gases. Titanium is fully resistant to corrosion and stress
corrosion cracking in the standard NACE test solution containing 3,000ppm
dissolved H2S, 5 percent NaCl, and 0.5 percent acetic acid (pH 3.5.). To avoid
pitting at temperatures above 80ºC, titanium alloys containing nickel,
molybdenum, palladium or ruthenium are used.
Examples of equipment fabricated in titanium in order to withstand the corrosive
fluids present in some geothermal installations are plate heat exchangers and
well casing. By careful selection of the grade of titanium, material thickness (with
no corrosion allowance) and fabrication method, an economic fabrication with low
maintenance costs and high availability can be achieved.
A prime example of the application of titanium in the geothermal industry is the
use of Grade 29 well casing in the Salton Sea, USA, which enables the
exploitation of a geothermal resource containing highly corrosive brine. Advances
in production technology are being applied to reduce the cost the casing pipe.
This technology may enable the use of sea water injection to augment weak or
depleted aquifers, or to generate steam from Hot Dry Rocks.

INTRODUCTION

The realization that titanium exhibited remarkable corrosion resistance in

oxidizing chloride environments led to some of its first applications in the
chemical process industry [CPI], such as wet chlorine gas coolers for chlor-alkali
cells, chlorine and chlorine dioxide bleach equipment in pulp/paper mills, and
reactor internals for pressure acid leaching of metal ores. Now many applications
have greater than 25 years of service history, including heat exchangers, reactor
vessels, and distillation columns in areas of chemical plants, refineries, chlorine
and chlorine chemicals production, pulp and paper mills, and salt plants.

TITANIUM CHARACTERISTICS

Table 1 lists the titanium alloys well suited for use in the CPI. The materials in
this list exhibit a baseline corrosion resistance in chloride media that includes
resistance to general corrosion, pitting, and stress corrosion cracking (except
grade 5). While certainly not a complete list of titanium materials available, this
 list provides for all the basic requirements (physical, mechanical, & corrosion)
needed for the majority of CPI applications. Each material can be listed by UNS
or ASTM designation. Following the convention popular in the US, the titanium
materials will hereafter be referred to by their ASTM grade designation. A
complete listing of chemical and mechanical properties for each popular mill
product form (ie-strip, plate, bar, tubing, pipe, forgings, & castings) can be found
in Volume 2.04 of the ASTM standard specifications. Generally the lower
strength grades are the easiest to fabricate, and are economically available as
thin strip and tube, whereas the higher strength grades need to be hot formed
into seamless pipe or forgings.

Table 1. Titanium for the CPI

TIMET NOMINAL ASTM UNS ALLOY
DESIGNATION COMPOSITION GRADE DESIG. TYPE STRENGTH FEATURES

Most formable grade-for

TIMETAL@ 35A Unalloyed Titanium 1 R50250 Alpha Low cladding & PHE
Most widely used titanium grade-
TIMETAL@ 50A Unalloyed Titanium 2 R50400 Alpha Low best comb. of props
TIMETAL@ 50A Pd Ti-0.15Pd 7 R52400 Added corrosion resistance over
TIMETAL@ 50A 05Pd Ti-0.05Pd 16 R52402 Alpha Low
grade 2
TIMETAL@ 50A Ru Ti-0.10Ru 26 R52404
Lean
TIMETAL@ 65A Unalloyed Titanium 3 R50550 Alpha/Beta Medium Added strength vs grade 2
Lean Added corrosion resistance &
TIMETAL@ CODE 12 Ti-0.3Mo-0.8Ni 12 R53400 Alpha/Beta Medium strength vs grade 2
Lean Cold formable, med. strength
TIMETAL@ 3-2.5 Ti-3Al-2.5V 9 R56320 Alpha/Beta Medium titanium alloy
Ti-5Al-1Sn-1Zr-1V-0.8Mo- Lean High toughness/weldable alloy
TIMETAL@ 5111 0.1Si 32 R55111 Alpha/Beta High for plate/fasteners
Std. aero alloy-some SCC
TIMETAL@ 6-4 Ti-6Al-4V 5 R56400 Alpha/Beta High concerns in sea water
Low oxygen grade 5-no SCC but
TIMETAL@ 6-4 ELI Ti-6Al-4V-0.1O 23 R56407 Alpha/Beta High lower strength
Added corrosion resistance over
TIMETAL@ 6-4 Ru Ti-6Al-4V-0.1O-0.1Ru 29 R56404 Alpha/Beta High grade 23

CORROSION RESISTANCE

The majority of titanium applications in the CPI have resulted from the excellent
corrosion resistance it exhibits in common organic and inorganic media. In
particular, the resistance to chloride containing media is first and foremost.
Titanium resists general, crevice, and pitting corrosion and SCC in all near
neutral chloride brine up to a minimum of 85-90°C. Grades with enhanced
corrosion can extend this resistance to 300°C or more. Titanium’s corrosion
resistance relies upon the formation of a very thin oxide film, which occurs
spontaneously in air or water. As long as this oxide film remains passive,
corrosion rates for titanium will be insignificant. However, once destabilized,
corrosion damage can occur very rapidly. Thus, it is important to understand the
regions of stability for the oxide film. An important aspect of the passive nature of
the oxide film is the necessity for oxygen either in the liquid or vapor phase of a
process stream.

Titanium is immune to general corrosion attack in all natural, cooling tower, and
high purity waters to temperatures in excess of 600°F. This includes seawater
and brackish water, typically some of the most corrosive of environments for
common engineering materials. Contaminants, such as metal ions, sulfides,
sulfates, and carbonates do not affect the passivity of titanium in these
environments. Utilities have installed nearly 400 million feet of welded titanium
tubing in seawater cooled condensers without a single incidence of corrosion.
Reducing acids are most often the cause of general corrosion on titanium. These
include the mineral acids hydrochloric, hydrofluoric, sulfuric, and phosphoric, and
organic acids like oxalic and sulfamic. The resistance of titanium to these acids
will vary according to alloy, acid type, concentration, and temperature. An
example is shown for hydrochloric acid media in Figure 1. Titanium should never
be used in the presence of hydrofluoric acid. Extremely high corrosion rates are
observed even at ppm concentrations. Oxidizing acids, like nitric and chromic,
pose little threat of corrosion to titanium due to the inherent stability of the oxide
film under oxidizing conditions.

Besides precious metal alloying, another useful technique for extending the
general corrosion resistance of titanium is with the presence of oxidizing ionic
species in process media streams. Minute (ppm levels) quantities of certain
multi-valent transition metal ions and other species, such as halogens, nitrates,
oxychloro anions, and certain organic compounds can have dramatic effects on
the corrosion rate of titanium. As an example, the corrosion rate for grade 2
titanium is reduced from about 800 mpy to 1 mpy in boiling 3% HCl with the
addition of 100 ppm Fe3+. Often, necessary inhibitor levels are present as
contaminants in process streams, allowing use of titanium in environments that if
pure, would rapidly attack the metal.

Crevice attack of titanium tends to be the limiting factor with regards to material
selection for most CPI applications. Brine chemistry is a secondary issue, assuming
chloride concentration is above the threshold level for titanium, which is about 1000 ppm
As shown in Figure 4 (a general guideline only), CP titanium can exhibit crevice attack at
temperatures above about 80°C, when the pH falls below about 9. Grade 12 reduces the
threshold pH to about 3. Grades 7 and 11 (Ti-.15 Pd) exhibit remarkable crevice
corrosion resistance, and are suited for even the most aggressive of environments where
brine pH falls below 1. Lower cost options, such as grades 16 and 26 offer nearly
identical crevice corrosion performance as grade 7. These grades allow the design
engineer to select a more conservative (i.e. corrosion resistant) titanium grade if crevice
corrosion is deemed a possibility, without incurring a substantial cost penalty. Grade 12
can be used to advantage in applications requiring moderately better corrosion resistance
 50

Note: Relative Corrosion Rates Shown

40
(1mm/yr) Grade1-3 Ti
Grade 9 Ti
Rate (mpy)
Corrosion

Grade 5, 23, 32 Ti
30
Grade 12 Ti

20
(.5mm/yr)

Grade 16, 26 Ti
10 Grade 29 Ti
5mpy
(.127mm/yr) Grade 7, 11 Ti
0
0 pH 1 1 2 3 pH 0 4 5 6
Boiling HCl Concentration (wt.%)

Figure 3. Relative general corrosion resistance of several titanium grades.

than commercially pure titanium and where the added strength can be utilized. Options
other than alloy selection are also available to prevent crevice corrosion. These include
grade mixing (i.e. use of more corrosion resistant and costly grades only in susceptible
areas such as weld joints and flange faces), gasket selection and/or impregnation, and
process modifications.

Review of field and laboratory experience clearly indicates excellent corrosion resistance
of titanium alloys to all geothermal brine environments. Specifically, the titanium alloys
evaluated proved to be, for all practical purposes, immune to general corrosion and stress
corrosion cracking, regardless of fluid chloride level and /or temperature. In addition,
their erosion-corrosion résistance was found to be unexcelled in high velocity geothermal
brine / steam fluids.

Overall titanium alloys display good resistance to localized attack in geothermal

environments. However, deposit crevice corrosion limitations of C.P. titanium and Ti-
6A1-4V alloys are apparent in high temperature hypersaline brines. Crevice attack of
C.P. titanium was observed with the hypersaline Salton Sea brine exposures only. This
attack was not experienced in low to medium (< 15,000 ppm) chloride-containing KGRA
fluids. In contrast, the Grade 12 titanium and Ti-Pd alloys resisted chloride crevice
corrosion and pitting attack in all cases, including corrosion Salton Sea brine exposure.
 14 -

Resistant to crevice

Grades 1-3,5, 9, 23, 32

pH 7-
Crevice corrosion possible

Grade 12

0- Grades 7, 11, 16, 17, 26, 29

0 150 300
Temperature (ºC)
Figure 2. Crevice corrosion guidelines for titanium in

ECONOMICS

Table 1 presents a relative cost comparison between the various grades of

titanium. This can only serve as a cursory guide, as product form and fabrication
cost differences could significantly impact these figures. Only titanium grades are
shown in this table. However, as a general rule, grade 2 titanium costs are on a
par (±10%) with the 6-Mo super austenitic stainless steels.

Table 1. Relative cost of various titanium grades

Approximate
Titanium Grade
Relative Cost Ratios
1-3 1.0
12 1.25
16, 26 1.4
7, 11 2.25
9 1.3
5, 23, 32 1.5
29 1.8
 When examining overall costs (material, manufacture, and installation) for
process equipment, often the higher material acquisition costs for titanium are
diluted to a large extent by the other costs involved. The end result can often
surprise design engineers that have a mindset to use titanium only as a last
resort. Figure 3 presents data on vessel costs for the CPI, comparing titanium to
stainless steel and other high performance metals.

20
Ref: Stainless Steel World, Vol.12, April 2000, pp.39-47
18

16 316 L SS
Ti Grade2
14 6 Mo SS
C-276
Vessel Cost, $/liter

12 Zr

10

0
0 5000 10000 15000 20000 25000 30000 35000 40000
Volume, liters
Figure 3. Cost comparison of high performance metals for

Clearly, titanium can compete favorably with other metals used in the CPI.
Titanium should always be viewed as one of several candidate materials for
process equipment without any pre-existing notions of which material would be
the most cost-competitive. This allows the engineer much more flexibility in the
original design perhaps avoiding the pitfall of assuming a less corrosion resistant
material will also be less costly.

Application Considerations For Titanium Alloys In Geothermal Service

Where to Use Titanium

Based on comparative cost and the performance reviewed above, titanium alloys
are certainly viable candidates for geothermal system components when
common stainless steels have previously failed or are anticipated to exhibit
marginal performance. This would include equipment in which high reliability and
near-zero corrosion allowances are required, from a performance, maintenance,
cost and /or safety standpoint.

Consideration of titanium is promoted when chloride levels exceed 5000ppm and

with temperatures greater than 100ºC. When oxygen intrusion is possible,
titanium alloys become preferred materials in geothermal systems because hot,
oxidizing-chloride conditions are known to cause severe localized attack of
stainless steel and nickel-base alloys. Oxygen entry into these systems can
occur during brine well re-injection, brine processing, system leakage, equipment
downtime, or brine residence in holding ponds.

Equipment surfaces exposed to direct hypersaline geothermal brines are obvious

candidates for titanium. These include critical wellhead components, such as
valves, gages, piping, and blowout preventers. For total flow geothermal
systems, critical components exposed to two-phase brine additionally involve
turbine components (blades, rotor, seals, and shrouds), expansion nozzles,
valves, venturis, steam seperator components, and barometric condensers.
Direct binary cycle geothermal systems require that binary heat exchanger tubes
be immune to all forms of corrosion. These systems can also include brine
reinjection pumps, which involve critical components such as impellers, shafts,
and seals.

Flashed steam geothermal systems, which derive energy from medium to high
salinity brines, are also good candidates for application of titanium alloys. These
not only encompass equipment exposed to direct geothermal brine, including
various stage seperator (flash tank) components, but also equipment
downstream of the separated steam. The need for titanium would depend on
steam seperation efficiencies, which determine chloride carry-over; and by
system air leakage, which is more likely, to occur under that lower pressure
conditions associated with separated fluid processing.

Multiple flash steam systems often include brine processing equipment, such as
evaporator / crystallizers, to prevent scaling in downstream separators and
associated piping. These represent potential problem areas, associated with
brine concentration effects and possible entry of air, for which titanium should be
considered.

Geothermal Brine Well Tubulars

The primary incentive for selecting Ti Grade 29 alloy tublar strings in geothermal
brine well is hot chloride corrosion resistance. These alloys become especially
attractive when total dissolved solids (TDS) in the brine exceed approximately
100,000 ppm, brine pH is less than or equal to 4, and/or downhole temperatures
exceed ~230ºC. Published corrosion data confirm that these Ru-enhanced alloys
resist localized attack and stress corrosion in naturally-aerated or fully-deaerated
sweet or sour NaCl-rich brines to temperatures as high as 330ºC and pH’s as
low as 2.3, regardless of CO2 and /or H2S partial pressures.

Perhaps the most prominent example of the performance and economic merits of
Ti-6-4-Ru alloy use in the energy industry today is in Salton Sea geothermal
brine wells in Southern California. More than 1,000,000 lbs (550kg) of Ti-Grade
29 hot rolled seamless tubulars have been produced for brine production and
reinjection wells since the early 90’s to handle these semi-sweet hypersaline
(TDS ~ 260,000 ppm) NaCl-rich brines exhibiting reservoir temperatures as high
as 315ºC. These threaded and coupled 10.75 in (273 mm) and 13.375 in (340
mm) oOD tublar strings have been economic replacements for thicker steel and
extruded Ti-38644/Pd tublars previously used for the following reasons:

1) Grade 29 tublar strings offer a projected service life in excess of 15 years and
can be permanently cemented-in.
2) Elimination of the cost of steel string replacement, drill rig use, and associated
well production downtime, which was incurred every 18 months or so.
Additional cost associated with heavy metal and radioactive scale removal
and disposal from corroded steel strings were also saved.
3) Elimination of the risk of formation damage, total well loss , and/or string
parting during steel string retrieval.
4) Elimination of well bore plugging from iron-rich silicate scaling, particularly
after steam flashing and during brine reinjection, which was aggrevated by
steel corrosion products (i.e Ferrous ions). Reduced topside brine
acidification (via HCl addition to ~pH4) now effectively inhibits silicate scaling
during brine reinjection.

Grade 29 may be the only practical tubular material fully resistant enough to
provide economic justification for development of high-temperature (<330ºC),
highly acidic (pH > 2.3) and sour geothermal brine fields for power generation in
the Philippines.

It has also been suggested that Grade 29 well casing may enable a great
expansion of geothermal energy generation by allowing sea water injection to
depleted or inadequate aquifers, or to Hot Dry Rock geothermal energy facilities.

SUMMARY

Titanium has enjoyed nearly forty years of service in the CPI and can be
considered a mature engineering material. Extensive technical literature and
plant experience supports the fact that titanium offers exceptional value to the
CPI engineers have discovered that titanium equipment can and does lower
overall maintenance and downtime, and hence gives the lowest life-cycle costs
for plant handling corrosive materials. This experience is spreading through the
geothermal industry, with the use of Grade 29 well casing in the Salton Sea,
USA, geothermal facility being an important example. This development may be
very significant if it enables the use of sea water injection to augment depleted or
low fluid aquifers, or to develop Hot Rock systems.

REFERENCES

J.S. Grauman, “Titanium-Properties and Applications for the Chemical process

Industries,” Reprinted from, Encyclopedia of Chemical Processing and Design,
J.J. McKetta, ed., Marcel Dekker, New York, Vol. 58, 1998, pp.123-147.

"Corrosion Resistance of Titanium", TIMET Brochure, [www.timet.com]

"Titanium Design and Fabrication Handbook for Industrial Applications", TIMET

[www.timet.com]

R.W Schutz, “Performance and Application of Titanium Alloys in Geothermal

Brine Service”, Paper 139, Corrosion 84, New Orleans.

R.W.Schutz and H.B.Watkins, “Recent Development in Titanium Alloy

Applications in the Energy Industry”, Symposium on Titanium Alloys at
Th=HERMEC ’97, Woolongong, Australia, TMS.