Professional Documents
Culture Documents
Neither the United States Government nor any agency Thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.
BNL--36933
DE86 001183
Lawrence E. Kukacka
August 1985
Prepared f o r presentation a t the Fourth Annual DOE Geothermal Program Review W s hiag ton , D .C a September fl-12, 1985
DISCLAIMER
This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or respnsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process. or seMce by trade name, trademark, manufacturer, or otherwise does not necessarily .constitute or imply its endorsement, mommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
Meyer S teinberg PROCESS SCIENCES DIVISION D P R M N O APPLIED SCIENCE EA T E T F BROOKHAVEN NATIONAL LABORATORY ASSOCIATED UNIVERSITIES, INC.
This work was performed under the auspices of the o f f i c e of Biomass Energy U.S. Department of Energy Washing ton, DC, under c o n t r a c t No. DE-AC02-76CH00016
The primary goal of the geothermal m a t e r i a l s program is to ensure that the p r i v a t e s e c t o r development of geothermal energy resources is uot cons t r a i n e d by the a v a i l a b i l i t y of technologically and economically viable materials of cons t r n c tion. This requires the performance of long- term high Ongoing programs t o be described in-
clude high temperature elastomers f o r dynamic s e a l h g a p p l i c a t i o n s , advanced materials f o r l o s t c i r c u l a t i o n control, waste u t i l i z a t i o n and disposal, corrosion r e s i s t a n t elastomeric l i n e r s f o r . w e l l casing, and non-metallic h e a t exchangers
-1
Lawrence E Kukacka . Department of Applied Science Brookhaven National Laboratory Uptoa, NY 11973
SUMMARY
The Geothermal Technology Division i n i t i a t e d the Geothermal Materials Program i n 1976 t o ensure t h a t the p r i v a t e s e c t o r development of geothermal energy resources is not constrained by the a v a i l a b i l i t y of technologic a l l y and economically viable materials of construction, Since 1978 Major Brookhaven National Laboratory (BNL) has provf ded technical and managerial a s s i s t a n c e i n the implementation of the long-term high-risk e f f o r t . temperature successes have been a t t a i n e d i n the development of eiastomers f o r higha p p l i c a t i o n s and i n the use of polymer concrete l i n e r s f o r Both technologies have been successfully transfercorrosion protection. red t o industry. I n the case of the high temperature Y-267 EPDM (ethylene propylene, diene, methylene) elastomer, the o p e r a t i % l i m i t s f o r elastomeric p a r t s were increased from the range 149C-2040C t o 260OC-316OC, extensive t e s t i n g by L'Garde, Inc., Based upon and over 25 other organizations dur-
ing the past 6 yr, no better elastomer for geothermal service is known.
Reductions i n c o s t up t o several hundred times compared t o those of other high temperature elastomers have been attained. f i e l d case h i s t o r i e s have been documented.
logging tools, casing packers, g a t e valves, BOP rants, shock subs, and
jars.
The materials program has a l s o produced the most comprehensive and thorough examination of the geothermal cementing problem undertaken thus
#
far,
in
test criteria.
before d e f i n i t i v e conclusions can be made regarding the hydrothermal s tab i l i t y a t economically a t t r a c t i v e well conditions,
0
. )
temprature elastomers f o r dynamic s e a l i n g applications, advanced materials f o r 10st c i r c u l a t i o n control, waste u t i l i z a t i o n and disposal, corrosion r e s i s t a n t elastomeric l i n e r s f o r well casing, high temperature lightweight cements, and non-metallic materials f o r h e a t exchanger applications. major t h r u s t s of the FY 1985 e f f o r t s a r e summarized below, The
1 .
Optimization of EPDM formulations f o r use i n c r i t i c a l high c o s t a p p l i c a t i o n s such as i n downhole d r i l l motors and openhole packers,
2.
Hydrothermally s t a b l e and pumpable chemical sys tems a r e being investigated f o r use a s l o s t c i r c u l a t i o n control materials i n geothermal well d r i l l i n g operations,
3.
P i t t i n g Resistant Steels
0
Studies of the mechanism whereby high corrosion r e s i s t a n c e i s obtained through alloying of s t a i n l e s s s t e e l s with molybdenum combined with n i trogen.
4 .
Studies of methods f o r u t i l i z i n g waste c o n s t i t u e n t s a s raw materials *for cementi t i o u s binders o r a s nonleachable f i l l e r s i n composites t h a t can be used f o r general construction purposes.
-3-
Analyses of biochemical techniques f o r concentration and subsequent removal of heavy metals from waste,
5.
Development of .corrosion r e s i s t a n t m e t a l l i c and s i l i c o n c a r b i d e - f i l l e d composites which have thermal conductivities i n the range of s t a i n l e s s steels.
6.
I n v e s t i g a t i o n of high temperature chemical coupling systems f o r bonding elastomeric l i n e r s to carbon s t e e l well casing.
Data on corrosion r e s i s t a n c e of Y-267 EPDM-lined carbon steel casing f o r comparison with those f o r high chrome and nickel alloys.
7.
Charac t e r i z a t i o n of promising high temperature well cements under placement and downhole environmental conditions duplicating most of the well comple t i o a variables. Preliminary screening tests on lightweight cement s l u r r i e s .
8.
Quantitative corrosion data from laboratory and plant t e s t s f o r metals presently used i n binary p l a n t s and o t h e r more p o t e n t i a l l y r e s i s t i v e metals and nonme tals.
9,
Testing and c h a r a c t e r i z a t i o n of high temperature elec trochemical processes designed t o cathodically protect the external surfaces of w e l l casing and heat exchangers.
Recent r e s u l t s from several of these e f f o r t s are given in the body of t h i s paper. 1986.
-4-
INTRODUCTION
Among the most pressing problems constraining the development and ex6
panded use of geothermal energy resources f o r electric power generation i s the lack of s a t i s f a c t o r y component and system r e l i a b i l i t y . This is due to the u n a v a i l a b i l i t y , on a commercial scale, of cost-effective materials
materials s e l e c t i o n experience.
t h i s requires materials t h a t can withstand high- temperature, highly-corI n addition to requiring a high degree of chemical and thermal r e s i s t a n c e , the downhole environment places demands on the physical/mechanical properties of materials f o r components u t i l i z e d i n w e l l d r i l l i n g , completion, pumping, and logging. I n 1976, the GHTD s t a r t e d the Geothermal Materials Program t o address materials-related problems, the e f f o r t . and s i n c e 1978 Brookhaven National Laboratory has provided technical and managerial assistance i n the implementation of Major successes have been a t t a i n e d i n the development of Both technologies have been elastomers f o r hightemperature applications1 and i n the use of polymer concrete l i n e r s f o r corrosion protection.* successfully transferred to industry. Other outputs from the materials
'
. thermal
environments.4,5
Achievement of the program goal requires the e f f e c t i v e management of a wide range of technological and economic problems.
n
proach is t o optimize the b e n e f i t s of materials-re1ated R and D through the resolution of selected problems. The program s t r a t e g y concentrates on developing an optimum balance between 1) problems whose s o l u t i o n s have a
s h o r t t o moderate term impact on the operation of prototype p l a n t s , and 2) long-term R and D designed to have s i g n i f i c a n t impacts on i n d u s t r i a l viab i l i ty and productivity through improvements i n materials performance and costs. The program s t r a t e g y i s to conduct projects t h a t ' l ) i d e n t i f y
-5-
materials-related needs cons t r a i n i n g commercialization, 2 ) evaluate the a p p l i c a b i l i t y of e x i s t i n g .materials and technology to geothermal problems,
major impacts oa geothermal energy c o s t s and productivity, and 4) provide appropriate and adequate incentives and mechanisms f o r the stimulation of
i a d u s try-sponsored
1.
High Temperature Elastomers For Dynamic Sealing Applications This p r o j e c t performs applied research t o optimize a Y-267 EPDM elas-
tomer formulation, developed earlier by GHTD f o r s t a t i c s e a l applications, f o r use i n dynamic seal applications a t temperatures up to 26OOC. opment could s u b s t a n t i a l l y reduce d r i l l i n g and completion costs. ElastoThe mers f o r these conditions do not c u r r e n t l y e x i s t , and a successful devele f f e c t s of compositional changes on the p r o p e r t i e s of the elastomer are being determined, and the formula t i o n optimized t o y i e l d the s p e c i f i c s e a l i n g requirements. Prototype and f u l l - s c a l e t e s t i n g w i l l be performed. 'Based upon the r e s u l t s from the generic research, a s p e c i f i c sealing app l i c a t i o n w i l l be targeted f o r coatinued R and D. The Y-267 EPDM elastomer compound was o r i g i n a l l y developed f o r geothermal casing packer applica t i o h s .The primary requirements were t o develop a thermochemically stable compound with e x c e l l e n t extrusion resistance.
Consequently, the Y-267 EPDM compound contains no s p e c i a l considera t i o n f o r dynamic s e a l applications. However, i t is highly abrasion r e s i s t a n t ,
a c h a r a c t e r i s t i c t h a t comes along with i t s e x c e l l e n t e x t r u s i o a r e s i s t a n c e
which is p a r t i a l l y provided by a small particle s i z e black. The c u r r e n t p r o j e c t i s to modify the Y-267 E W M compound f o r b e t t e r
1
dynamic s e a l c h a r a c t e r i s t i c s while maintaining its excellent thermochemic a l resistance. The e f f o r t is centered around improving the l u b r i c i t y and The e f f o r t evaluates developmental Once the i n i t i a l development is the l u b r i c a b i l i t y of the compound.
-6-
complete, the development w i l l move i n t o a phase devoted t o a s p e c i f i c application, e,g., Moineau motor s t a t o r , The precise application w i l l be selected based on the r e s u l t s of the i n i t i a l development. The i n i t i a l development is scheduled f o r completion towards the end of calendar year
1985.
2.
This p r o j e c t is i n v e s t i g a t i n g hydrothermally s t a b l e and pumpable chemical systems f o r u s e as l o s t c i r c u l a t i o n control materials (LCM) a t temperatures up to 3OO0C, Lost c i r c u l a t i o n problems d i r e c t l y and indir e c t l y represent 20 t o 307. of geothermal w e l l costs, and. high temperature materials t h a t w i l l y i e l d permanent r e p a i r s that can be made without removal of the d r i l l s t r i n g i n order t o s e t casing and cement, do not e x i s t . The inves t i g a t i o n s include laboratory s t u d i e s of i n t e r a c t i o n s between bentonite-based d r i l l i n g muds, r e a c t i v e s o l i d additives, and chemical f l u i d s , The pumpability c h a r a c t e r i s t i c s of the s l u r r i e s and the properties of the
, borax,
The
appropriate combination of these ingredients r e s u l t s i n the formation of s l u r r i e s with v i s c o s i t i e s and thickening times adequate to allow placement. After curing a t elevated hydrothermal tempera tures, the cement proThe duced was characterized by a compressive s t r e n g t h >SO0 p s i a t 2 hr age, a permeability to water C2.0 x lom4 Darcy, and a l i n e a r expansion >15X. found to be an assemblage of interlocking c r y s t a l s composed of a grown thin-plate c r y s t a l .
c
s i s tome ter t e s t s performed a t Sandia confirmed the pumpabili ty of the materials a t high temperature and pressure
Another promising high temperature LCM was recently identified.7 I n t h i s work, i t was found t h a t the addition of a cement, borax and g l a s s f i b e r mixture to bentonite s l u r r i e s produces a LGi t h a t is pumpable a t
-7
'
series of larger-scale tests i n the Sandia Natioaal Laboratory Lost Circul a t i o n T e s t F a c i l i t y are scheduled f o r FY 1986.
6
3.
a
The geothermal f l u i d s i n the Imperial Valley a r e characterized by brines with high levels of corrosive substances. ing.
tors t o using super a l l o y s f o r routine components such as tubing and pipThis can be extremely expensive, suggesting the use of the process industry p r a c t i c e of l i n i n g pipe to p r o t e c t i t from corrosion, a perfect a p p l i c a t i o n f o r Y-267 EPDM.
DOE/BNL formed a c o s t sharing p r o j e c t with a geothermal operator to
s t e e l pipe a r e the primary technologies to be developed to be i n a posit o bond the Y-267 EPDM to s t e e l e x i s t s which can withstand the 288OC postcure and the usually high temperatures associated with Y-267 EPDM applications.
casing s e c t i o n s which can be f i e l d t e s t e d with a c t u a l brine flowing through them. The development of the prototypes i s scheduled f o r complet i o n i n early 1986.
4 .
Before the large-scale development of geothermal energy can occur, e n v i r o m e a t a l l y and economically acceptable methods f o r t h e disposal of l a r g e q u a n t i t i e s of waste m u s t be developed. l a r g e , low-grade domestic mineral. resource.
r,
covery are developed, the wastes-could provide an important source of s t r a t e g i c a l l y important metals a s w e l l as revenues comparable to those
e
from e l e c t r i c power generatiqn. The i n i t i a l phase of the DOE/BNL program c o n s i s t s of an assessment i n which' data pertaining to the following questions a r e being compiled.
-8
0
c
What a r e the applicable federal environmental regulations pertaining to geotherfnal resources and t o what e x t e n t w i l l they be involved?
A r e any of the e x i s i t i n g regulations expected to change? what a r e the timeframes f o r resolving these issues?
I f so,
Evaluate the regulations f o r def i n i t i o n s of waste c l a s s i f i c a t i o n s and f o r standard/proposed t e s t s required. required tests formulated and why?
e
disposal p r a c t i c e s f o r these
wastes?
0
Can the operators of the geothermal projects meet the current regulation requirements and waste disposal standards? disposal p r a c t i c e s adequate? to develop a d d i t i o n a l or a1t e r m t i v e disposal methods? Are current
W i l l these companies need more time
Two experimental approaches which a r e compLementary a r e being used i n attempts to develop methods which w i l l economically meet the disposal regulations i d e n t i f i e d above. The f i r s t i s the use of biochemical techniques to concentrate and remove toxic metals from wastes, and the second is to develop processes f o r converting toxic cons ti tuents from the wastes i n t o nonleachableforms which can be used as a construction material o r disposed of i n conventional l a n d f i l l sites. The i n i t i a l r e s u l t s from the BNL s t u d i e s on the biochemical treatment of wastes have rqcently been published.8 These s t u d i e s have demons t r a t e d t h a t c e r t a i n microorganisms can grow i n the presence of high concentra-
-9-
heavy metals
The bioaccumulation is selective- and several microorganisms The r e s u l t s have shown t h a t under
have been t e s t e d f o r selective adsorption of uranium, thorium, cobalt, chromium, manganese, t i u , and platinum.
iE
E.
E.
fluorescens e x h i b i t a preference
the surface s e l e c t i v i t y may be r e l a t e d to r e s i s t a n c e , or may be due only to the chemical s t r u c t u r e of the c e l l wall and c e l l membrane components. The r e s u l t s support the view t h a t i n the metal-microorganism i n t e r a c t i o n s , several mechanisms may be operative , which involve special ized m e tabori t e s , such as exo-cellular chelators, s p e c i f i c c e l l surface sites, and transport agents
With regard to the conversion of toxic wastes i n t o nonleachable forms, several inorganic and organic encapsulants have been tested. phosphate cement, and portland cement. Mater i a l s used include methylmethacrylate, polyester, s u l f u r , magnesium polyOther variables included water Preliminary r e s u l t s conteat, particle s i z e , and method of encapsulation. i n the S t a t e of California regulations. and to estimate costs is in progress.
5.
indicated t h a t several systems had leach r a t e s welL below those specified Work to optimize the processes
This p r o j e c t is iuves t i g a t i n g thermally conductive polymer-based comp o s i t e s f o r use as corrosion r e s i s t a n t materials of construction f o r s h e l l and tube heat exchangers i n binary geothermal processes, Corrosion of Compared t o the brine s i d e of tubing i n s h e l l and tube heat exchangers has been a m*j o t problem i n the operation of binary geothermal processes.
1
-10-
The work
c o n s i s t s of determinations of the e f f e c t s of compositional and processing v a r i a b l e s on the thermal properties of the composite, and measurements of
c
the physical and mechanical properties a f t e r exposure t o hot brine and isobutane.
OF,
To date, the maximum thermal conductivity obtained is 3.5 BTU/hr-ftcompared to a value of 11.2 BTU/hr-ft-oF f o r the AL 29-4C f e r r i t i c
Assuming
s t a i n l e s s s t e e l used i n the tubes of the Heber heat exchangers. a l l other design f a c t o r s equal
, direct
For the Heber binary plant, i t has been reported t h a t the heat exchangers and condensers represent -30% of the t o t a l investment i n plant equipme~t.~ Therefore, since the c o s t of the polymer composite tubing
i s estimated to be i n the same range as t h a t f o r carbon s tee1 , substitut i o n f o r the AL 29-46 could s i g n i f i c a n t l y reduce the c o s t of future binary plants
6.
This program y i e l d s corrosion data from laboratory and p l a n t t e s t s f o r metals presently used i n binary plants and other rdore p o t e n t i a l l y res i s t i v e metals and nonmetals.
age i n t o the organic working f l u i d s i d e of the plants has r e s u l t e d in unanticipated corrosion problems. Data are not a v a i l a b k on the e f f e c t s of s a l t , oxygen, and water i m p u r i t i e s i n isobutane and/or isopentane on the corrosion rates of metals.
*
,
i n operating p l a n t s and i n a laboratory test loop in which the l e v e l s of water, oxygen and s a l t can be varied. When completed, t h e program w i l l y i e l d q u a n t i t a t i v e information regarding the e x t e n t of corrosion t h a t w i l l occur upon contamination of the binary side of a plant, thereby allowing designers materials options.
..
-11-
CONCLUSIONS
s o l u t i o n s have a s h o r t to moderate term impact on the operation of prototype p l a n t s as well as conducting long-term R and D designed to have sign i f i c a n t impacts on i n d u s t r i a l v i a b i l i t y and productivity i n materials performance. maintained. Active technology t r a n s f e r linkages a r e established and To date, the program has resulted i n the development of the Cura
b e s t known high temperature elastomer f o r geothermal service, and several o t h e r outputs from the program a r e being used o r tested by industry. r e n t R an D e f f o r t s on dynamic s e a l s , l o s t c i r c u l a t i o n control materials, and lightweight w e l l cements may be used by industry i n the near future.
0 t h e r e f f o r t s on e l a s tomer-lined w e l l casing, encapsulation o r biochemical
concentration and separation of wastes, and nonmetallic heat exchanger tubing w i l l require considerably longer development times.
REFERENCES
1.
Hirasuma, A.R., e t al., Geothermal Elastomeric Materials Technology Application (GEM-TA) Program, DOE/SF/11537-1 (D385003232) , August 1984
2,
Kaeding, A.O., Design and Fabrication of Polymer Concrete-Lined Pipe f o r Testing i n Geothermal Energy Processes, Final Report, BNL 33019, J u l y 1981. American Petroleum I n s ti t u t e Work Group Reports Field Tests of Geothermal Cements, Technology, O i l and Gas Journal, 93, February 11, 1985. E l l i s , P.F., e t al., Materials S e l e c t i o n Guidelines f o r Geothermal Energy U t i l i z a t i o n Sys terns, DOE/RA/27026-1, January 1981.
E l l i s , P.F., e t al., Corrosion Reference f o r Geothermal Downhole Materials Selection, DOE/SF/11503-1 (DE 83010306), March 1983.
3.
4.
5.
m
6.
L
Sugama, T., e t al., Bentonite-Based Ammonium Polyphosphate Cementitious Lost C i r c u l a t i o n Control Materials, BNL 36340, March 1985, J , Mat. sci. ( i n press).
-12-
REFERENCES (cont.)
7.
Sugama, T, e t al., C h a r a c t e r i s t i c s of High Temperature Cementitious . Lost-Circulation Control Materials For Geothermal Wells, Informal BNL Report, ( i n press).
8.
.. aud Lin, M., Chelating V e r s a t i l i t y of Toxic Metal Premuzic, ET R e s i s t a a t Microorganisms, BNL 36548, May 1985. Presented a t Workshop on Biotechnology f o r the Mining, Metal-Refining, and F o s s i l F u e l Processing Indus t r i e s , Rensselaer Polytechnic i n s ti t u t e , Troy, May 28-30, 1985.
Lacy, R.G., Heber Binary P r o j e c t , Proc. DOE Geothermal Program Rqview 111, E l Centro, California, October 16-19, 1984, 29-33.
9.
-13-