geofluid - der geothermiekongress

Scale and corrosion inhibition in the Netherlands and France

Hans van ‘t Spijker, Pierre Ungemach

Geofluid

1. Corrosion and scaling issues

2. Scaling and Corrosion in Paris Basin

4. Scaling and corrosion issues in the NL

5. Guidelines

Corrosion and scaling issues

• General (uniform) corrosion

• Pitting corrosion

• Crevice corrosion

• Underdeposit corrosion

• Galvanic c)orrosion

• Impingement

• Stress corrosion cracking (SCC)

• Erosion

• Corrosion by microbacteria


Precipitation (deposition of solids)Earth Energy (Geothermal Heat Pumps)

Component Examples

Calcium carbonate •Various sites

Iron oxides •Various sites

Low and medium-enthalpy fluids

Component Examples

Calcium carbonate •Oradea and Ciumeghia (Romania), Balcova (Turkey), Saidene (Tunisia) N.

Kessani and Nigrita (Greece),

Iron oxides •Nigrita (Greece)

Iron sulphide salts [in association with corrosion] •Dogger Basin (France)

High- enthalpy fluids

Component Examples

Calcium carbonate •Kizildere (Turkey),Miravalles (Costarika), Latera (Italy), Cerro Prieto

(Mexico), East Mesa, Nevada (USA), Krafla (Iceland)

Silica (and metal-silicates) [usually associated with small

or medium TDS]

•Svartsengi and Nesjavellir (Iceland), Dixie Valley (USA), Matsukawa,

Otake and Onuma (Japan), Berlin (El Salvador)

•Heavy metal sulphide salts (with silica and metal-

silicates) [associated with high TDS]

•Salton Sea (USA), Milos Island (Greece), Asal Wells (Djibouti)

•Oxides (and sulphide salts) •Reykjanes (Iceland)

Salton Sea, California

Broadlands 1, Ν.

Zealand

Hot Springs,

Utah

Kilauea, Hawaii

Krafla, Iceland

Kizildere (W15), Turkey

Klamath Falls, Oregon

Dogger, Paris Basin, France

Nigrita, Greece

Pijnacker, The

Netherlands

pHTemp.,°CTDS (g/L)

5.7214182

8.32703.8

-2607.4

7.119015.8

7.22201.0

8.01382.4

8.4800.7

6.27315

6.8592.5

5.980101

NaK

CaMgFePb

4270065001820057018059

1060150500.2-

2320461821-

49307563580.300

193201.50.030.020

11921351.90.20-

2054.3260.50.3

3700606301500.5-

529891601051.1-

38150230490086039<1

ClSO4

2-

HCO3-

1120006220

170040300

386072232

89702418

26194328

46631-

5133035

7980775335

1621302200

6985013

AsB

SiO2

224801150

57600

4-563

0.14.3750

--383

-24356

--48

-514

0.54.638

3012


Scaling and corrosion in Paris basin

Urban heating since the 1980s


Conditions Corrosion issues Scaling issues

TDS ~ 15 g/l Harsh (sour) conditions

Film forming amines

injected

Mostly Pyrite (FeS2)

formation due to enhanced

[Fe] concentration by

corrosion

[Fe] =0.5 mg/l Sulphide reducing bacteria

biocide injection

CO2 and H2S Sour

T = 65-90 ⁰C

Bubble point ~3-10 bar

Corrosion causes [Fe] increase, and thus results in pyrite scale formation

Corrosion control is of utmost important


AIT line (propriety GPC)

Scaling and corrosion in Netherlands


So far, geothermal energy is mostly developed by

greenhouse owners


1. How to solve


Conditions Corrosion issues Scaling issues

TDS ~110 g/l Galvanic corrosion in early

wells

Mostly calcite and siderite

deposition

[Fe] =30 mg/l

Traces Pb

Pitting corrosion? increase pressure in

surface installation

Gas composition is mainly

CH4, N2, CO2

Erosion (cavitation) of

couplings

T = 80-100 ⁰C Pb deposition

Traces of oil, aromatics

Bubble point ~20-40 bar

How to mitigate corrosion and scaling

Corrosion mitigation

• Use suitable corrosion inhibitors (filming amines)

o Test efficiency of products

o Monitor corrosion rate

• Inject inhibitor downhole

• Option: Use GRE liners

• Option: Use high steel grades


Patent GPCInstallation in Bonneuil


Scaling mitigation

• Estimate scaling risks (e.g PHREEQC)

• Determine minimum injection temperature in injection well

• Prevent CO2 degassing

• Inject inhibitor product

o Carbonate scale deposition at depth

o Most other scales (e.g. sulfate, silicate) at surface before HX


1. How to solve

Monitoring

Corrosion

Monitoring

Accuracy

Well logging +++

Coupons analysis ++

Iron content ++

Corrator (LPR) ~

Test kits ++


1. How to solve

Monitoring

Scale monitoring Accuracy

Well logging +++

Coupons analysis ++

Deposit analysis

(XRF, XRD, SEM,….)

++

Corrator (LPR) ~

Monitor ionic

concentrations

++

Measure chemical

parameters (pH, …)

+

Monitor particle

concentration

+


1. How to solve

SCALING SOLUBILITY.

SUPERSATURATION DIAGRAM

Temperature (or pH)

Co

nce

ntr

atio

n

A

B

C

D

Stable region (no precipitation)

S=1, solubility curve

Metastable

Labile region (precipitation)

Ca2++2

3CO 2CaCO3 (solid)

Langelier-Saturation-Index (LSI)

LSI = pH-pHs pHs = (9.3 + A + B)-(C+D) where :

A = [log(TDS)-1]/10 TDS in mg/L B = -13,12 x log θ + 34,55 θ, temperature in K C = log[Ca 2+]-0,4 Ca2+ as mg/L CaCO3

D = log [alkalinity) alkalinity as mg/L CaCO3

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