Flow assurance in sub-sea pipelines

www.conservaenergia.com

Aims & Objectives to review the types of materials constituting petroleum fluids to identify and describe the types and the properties of materials which compromise pipeline flow assurance to relate how phase equilibria diagrams (PTx) can be used to predict conditions of precipitation of these materials to consider means to inhibit formation of these materials

Reference Sources used: MR Riazi, Characterization and Properties of Petroleum Fractions, ASTM International, (2005). Y Bai and Q Bai, Subsea Pipelines and Risers, Elsevier Science, 2nd Ed, (2005)

n-octane

Hydrocarbon structures
n-butane methane ethane propane C4 H10 isobutane (methyl-propane) C1 CH4

C2
C2H6

C3 C3H8 C4 C4 H8
1.E+10

2-methylheptane

C8

Cycloalkanes
No of compounds
1.E+08

1.E+06

ethylcyclopentane

o-xylene

1.E+04

1.E+02

naphthalene

dibenzothiophene
heteroatom

1.E+00 0 10 20 30 40

No of carbons

Composition (mol%) and Properties of Various Reservoir Fluids and Crude Oil*
Component CO2 N2 H2S C1 C2 C3 iC4 nC4 Dry Gas 3.7 0.3 0 96 0 0 0 0 Wet gas 0 0 0 82.28 9.52 4.64 0.64 0.96 Gas condensate 0.18 0.13 0 61.92 14.08 8.35 0.97 3.41 Volatile oil 1.19 0.51 0 45.21 7.09 4.61 1.69 2.81 Black oil 0.09 2.09 1.89 29.18 13.60 9.20 0.95 4.30 Crude oil+ 0 0 0 0 0.19 1.88 0.62 3.92

iC5
nC5 C6 C7+ Total GOR M7+ SG7+@ 15.5oC API7+
+stock

0
0 0 0 100

0.35
0.29 0.29 1.01 100 69917 113 0.794 46.7

0.84
1.48 1.79 6.95 100 4428 143 0.795 46.5

1.55
2.01 4.42 28.91 100 1011 190 0.8142 42.1

1.38
2.60 4.32 30.4 100 855 209.8 0.844 36.1

2.11
4.46 8.59 78.23 100

266 0.895 26.6

tank conditions

*measured by analytical tools (gas chromatography, mass spectrometry, etc.)

From MR Riazi, Characterization and Properties of Petroleum Fractions, ASTM International, p6, (2005).

Infra-red and Near Infra-red spectroscopy

50

100

150

200

250

300

350

400

450

500

550

home.flash.net/~acqsol/BatchReport.htm

Aske, N, Kallevik, H, and Sjblom, J., Energy & Fuels, 15, 1304-12, (2001)

Petroleum fluid fractions

Hydrocarbons Asphaltene Resin Oil

M 1000-5000 800-1000 200-600

H% 9.2-10.5 10.5-12.5 12.5-13.1

H/C 1.0-1.4 1.4-1.7 1.7-1.8

V 900 700 200-500

d, 14.2 13 8-12

D 4-8 2-3 0-0.7

Insoluble in n-hexane 80:20 isobutyl alcohol:cyclohexane

Pan, H. and Firoozabadi, A., SPE Production and Facilities, 13, pp118-127, (1998)

A knowledge of the composition of a reservoir fluid can enable the phase equilibrium (vapour-liquid and solid-liquid equilibrium) modelling of the pressure temperature properties of the fluid

240 Pressure (bar) 200 critical point dew point bubble point

L L+V

160 C7+ (5 components) 120 80 40

C7+ (1 component)

200 www.jee.co.uk

300

400

600 500 Temperature (K)

700

800

PressureTemperatureComposition (PTx): Effects on Phase Equilibria

pressure reduction at valves compositional changes from injection processes temperature/pressure changes during pipeline transit (flow) phase separation (suspended solids agglomerates) adhesion to transmission control system reduction in throughput (revenue) blockage

www.ifos.com

There are three types of heavy hydrocarbons that exist in a heavy petroleum fluid which due to PTx effects can precipitate in transmission systems: waxes asphaltenes resins

Also, interactions between oil/gas constituents and injection media can lead to formation of: gas hydrates salts

Waxes (or paraffins)

typically long chain (C6- C36) normal (n-)alkane compounds that are naturally resident in crude oil average molecular weight around 350 and freezing points in the range 30 70oC crystalline waxes (iso- and cycloparaffins, C30-60, M in the range 500800 and melting pt. 70-90oC) Consistency ranges from petroleum jelly to hard wax. Density around 0.8 g.cm-3

Pigging to remove wax from a subsea transfer line (http://www.hydrafact.com)

can deposit from the oil as a result of temperature/pressure changes (particularly susceptible are sub sea production facilities and pipelines) forms as waxy elongated crystals.

Wax deposition characteristics

The temperature at which wax begins to form is called the cloud point or the wax appearance temperature (WAT). The WAT is not an equilibrium point; wax appearance is a kinetically-controlled nucleation process; influenced by temperature, (e.g. temperature gradients from wall cooling), cooling rates and availability of nucleation sites (e.g. small particles). Below the WAT, crystals may form and be transported with the remaining fluid or deposit on a cold surface, leading to fouling. The pour point is the temperature at which a fluid ceases to pour the formation of a 3D network spanning the pipe - can occur when flow is interrupted.

Measurement of wax appearance characteristics (http://www.hydrafact.com)

In subsea systems: wax deposition in pipelines is gradual but can lead to blockage

crude oil gelation can occur during shut-in (zero flow)

leads to high start-up pressures and high pumping pressures due to increased viscosity temperature gradients can be reduced by insulating pipes (increased capital expense)

Wax precipitation models

solid solution multisolid phase model calculation of cloud point temperature (CPT) equivalent to WAT Both models are based on the relationship:

f iV (T , P, yi ) f i L (T , P, xiL ) f i S (T , P, xiS ) VLE SLE

yi K i xi
and

xiS K iSL xiL

WAT values derived from solid solution models are close to the pour points of oil WAT values derived from multisolid phase models are close to the cloud point Effect of temperature and Pressure on WAT

Pan, H., Firoozabadi, A and Fotland, P., SPE Production and Facilities, 12, 250-8, (1997)

Wax Inhibition
Cloud points for crude oils are generally in the range 300-315K (80-110oF)
Protection strategies may include: temperature control at CPT + 15oF

readily achieved in the wellbore and subsea tree

subsea flowlines may require electric or hot fluid heating

thermodynamic wax inhibitors (TWI), e.g. solvents polyalkyl acrylates, low molecular weight polyethylene waxes, ethyl-vinyl acetate (EVA)
wax-saturated solvents must be removed to avoid re-precipitation elsewhere

pour point depressants/dispersants/surfactants

modify crystal structure and reduce viscosity, i.e. additives with wax-like (n-alkane) part to bind the wax but non-wax-like terminating group as in surfactants, e.g. linear sulphonates.

Remediation strategies: mechanical pigging. NGS (nitrogen generating system) combines thermal, chemical, and mechanical effects by controlling nitrogen gas generation to comprise the reversible fluidity of wax/paraffin deposits

EVA
dispersant/crystal modifier properties

Asphaltenes
a black, brittle component of the bitumen in petroleum organic materials consisting of aromatic and naphthenic ring compounds which carry the main inorganic components of crude oil, including nitrogen, sulfur, oxygen, nickel and vanadium insoluble in non polar solvents but soluble in toluene or other aromatics-based solvents. frequently occurs with wax deposition
Pipeline asphaltene fouling (http://www.hydrafact.com)

generated as a result of pressure drop, high shear (turbulent flow), acids, soluble CO2 (EOR), injected condensate, mixing of incompatible crudes, etc. deposition is non-reversible, i.e. difficult to remove by manipulation of pressure/ temperature. colloidal suspensions in resins in the oil. Dispersion stability depends on the ratio of resin to asphaltene molecules.

Asphaltenes molecular characteristics

Various shapes of asphaltene micelles formed in the presence of large amounts of polar or aromatic solvents Molecular structure of asphaltene proposed for Maya crude (Mexico) by Altamirano, et al. [IMP Bulletin, 1986]

Molecular Structure of asphaltene proposed for 510C Residue of Venezuelan Crude by Carbognani [INTEVEP S.A. Tech. Rept., 1992]
Pan, H. and Firoozabadi, A., SPE Production and Facilities, 13, pp118-127, (1998) http://tigger.uic.edu/~mansoori/Asphaltene.Molecule_html

Rapid physical methods of assessing asphaltene on-set refractive index electrical conductivity kinematic viscosity..

Relevance of Equilibrium Phase Diagrams to asphaltene management

Tank Oil specifications
Mol% C1+ C2 Mol% C3 - C5 Mol% C6 Mol% C7+ M SG 0.6 10.6 4.3 84.5 221.5 (M7+ = 250) 0.873 (SG7+ = 0.96) M (precipitated) 4500

Asphaltene specifications
Wt% resin in oil Wt% asphaltene in oil Density (g/cm3) 14.1 4.02 1.2

Px diagram for an oil-CO2 system at 24oC

1400

1300

2500 Pressure (psi) 1200

L
1100

2000 Pressure (psi)

L
1500

1000

LS

1000 900

500

LV
98

LV
98.5 99

LVS
99.5 100 Mole % CO2

25

50 Mole % CO2

75

100

- asphaltene precipitation predicted in LS and LVS fields

Kawanaka, S., Park, SJ, and Mansoori, GA, SPE Reservoir Engineering, 6, 185-192, (1991)

Relevance of Equilibrium Phase Diagrams to asphaltene management

P-T diagram for asphaltene precipitation predictions

Region of asphaltene precipitation reservoir pressure

Pressure

saturation pressure

asphaltene solubility

Temperature

Once formed difficult to remove by manipulation of PT conditions

chemical treatments
Y Bai and Q Bai, Subsea Pipelines and Risers, Elsevier Science, 2nd Ed, 2005

Micellebased model of asphaltene precipitation (and dissolution)

Tank Oil specifications Mol% C1+ C2 Mol% C3 - C5 Mol% C6 Mol% C7+ M 0.6 10.6 4.3 84.5 221.5 (M7+ = 250)

Asphaltene specifications Wt% resin in oil Wt% asphaltene in oil Density (g/cm3) 14.1 4.02 1.2

M (precipitated)

4500

SG

0.873 (SG7+ = 0.96)

Onset of asphaltene precipitation shown where curve levels off Lighter solvents cause higher precipitation Dilution ratio (RS, i.e. the volume in cm3/g of crude) at the onset is a function of solvent molecular weight, MS, i.e. increases with MS

resins

The amount of solid precipitated in the presence of propane increases with temperature but decreases for n-heptane. Effect of pressure above the bubble point of oil decreases precipitation but below, precipitation increases.
Pan, H. and Firoozabadi, A., SPE Production and Facilities, 13, pp118-127, (1998) Wu, J., Prausnitz, JM, and Firoozabadi, A., AICE Journal, 44, 1188-99, (1998)

Asphaltene precipitation from tank oil in presence of C5-C10 diluents at 295K and 1 bar.

Effects of chemical treatments on asphaltene solubility

propane

n-heptane

Strategy is to maintain asphaltenes in the fluid (dispersed or solubilised state)

Natural Gas Hydrates

formed at high pressure and low temperature from combination of water and constituents of hydrocarbon fluid stream (e.g. CH4, C2H6, C3H8, N2, CO2, H2S) increasingly important in O&G operations in deeper waters most commonly encountered during drilling and production
Gas hydrates removed from a subsea transfer line (courtesy of Petrobras, Brazil).

A gas hydrate Image courtesy U.S. Geological Survey

One volume of this saturated methane hydrate contains up to 189 volumes of methane gas at STP. This large gas-storage capacity of gas hydrates may represent an important source of natural gas.
www.csiro.au/files/files/pl1k.pdf

Hydrate Formation Requires Five Ingredients:

Water Gas - CH4, CO2, C2H6, H2S, etc.

Pressure
Temperature Nucleation Site

Hydrate Structures - variable

http://www.telusplanet.net/public/jcarroll/HYDR.HTM

http://www.telusplanet.net/public/jcarroll/HYDR.HTM

Hydrates Formation and Dissociation

Stable Hydrate Region Pressure (psi)

Metastable Region
hydrate formation curve hydrate dissociation curve

Hydrate-free Region Temperature

Hydrate Inhibition
Stable Hydrate Region

Inhibitors (10-50 wt%) can reduce hydrate formation temperature (HFT) to below the hydrate dissociation curve. Low dose hydrate inhibitors (LDHI 0.30.5 wt%) interfere with crystallisation.
Metastable Region hydrate dissociation curve Hydrate-free Region

Pressure (psi)

Cold flow technology controlled growth of hydrates to unsure stable suspensions.

hydrate formation curve

Temperature

T
Inhibitor
Methanol Ethanol Ethylene glycol Diethylene glycol Triethylene glycol

KW M (100 W )
K Value
2335 2335 2700 4000 5400

T- temperature shift (oC) W inhibitor concentration (wt%) M molecular weight of inhibitor/molecular weight of water

Low dose hydrate inhibitors

hydrate surface has open cavities penetrated by hydrocarbon component amide group hydrogen bonds to hydrate surface via carbonyl adhesion to hydrate surface prevents further hydrate growth limited growth keeps hydrates in suspension

Tutorial Questions
1. Identify factors during fluid transfer from a wellbore which can lead to precipitation and conductivity problems in flowlines. 2. Sketch the basic features of a PT diagram for the methane-water system and describe the effect of sub-cooling. Use the diagram to illustrate why this presents a threat to the integrity of a sub-sea flow line. 3. Explain why dehydration is a possible approach to the inhibition of natural gas hydrates in a pipeline and what type of chemical treatment might be suitable. 4. How do low does hydrate inhibitors (LDHIs) function in comparison to thermodynamic hydrate inhibitors (THIs). 5. Discuss the benefits of dispersion over dissolution in the remediation of flow. 6. Discuss the role of resins in maintaining flow where there is a realistic risk of asphaltene precipitation. What specific properties do these have which enable this function? 7. Distinguish between the various constituents of a petroleum fluid and explain the chemical principles involved in defining a remediation treatment for fouled valvework and pipelines. 8. Identify an equilibrium thermodynamics approach to predicting precipitation under various PTx conditions, i.e. how to construct a PTx phase diagram.