Beruflich Dokumente
Kultur Dokumente
a manuscript funded by
ARC0 Exploration and Production Technology, Co.
January 1, 1998
Table of Contents
Topic
Table of Contents
.._.....................................
.......................................................................
.v
Introduction ..........................................................................................................
..ii
.._......_.._.........
...............................
5
.6
ii
..4 1
.42
.42
.44
.45
.45
..4 6
.47
..5 0
.53
..5 4
..5 5
.55
..5 8
.91
.93
.93
.94
..9 5
Appendix A. Gas Hydrate Structures, Properties, and How They Form.. ............... .I03
1. Hydrate Crystal Structures.. ................................................................
103
2. Properties Derive from Crystal Structures.. .........................................
,104
a. Mechanical Properties of Hydrates ............................................
,104
b. Guest: Cavity Size Ratio: a Basis for Property Understanding ...... 105
c. Phase Equilibrium Properties.. ..................................................
,106
d. Heat of Dissociation ................................................................
,107
3. Formation Kinetics Relate to Hydrate Crystal Structures ...................... ,107
a. Conceptual Picture of Hydrate Growth. ....................................
.I07
in Handbook .................................
References ........................................................................................................
iv
,109
.I09
,123
128
.I45
149
DISCLAIMER
The description, methods, and cases discussed in this manuscript are presented
solely for educational purposes and are not intended to constitute design or operating
guidelines or specifications. While every effort has been made to present current and
accurate information, the author (and sponsoring and contributing organizations)
assume no liability whatsoever for any loss or damage resulting from use of the
material in this manuscript; or for any infringement of patents or violation of any
federal, state, or municipal regulations. This manuscript was intended to supplement,
but not to replace engineering judgment.
Use of the information in these notes is
solely at the risk of the reader.
ACKNOWLEDGEMENTS
The
by Mr. Ben
is a paean
engineering,
Amocos Mssrs. George Shoup and J.J. Xiao provided hydrate plug transientflow simulation results and they reviewed the preliminary draft.
At ARCO. in addition to Mr. Bloys continuous contributions, Mr. Phil Lynch
(ARC0 British Ltd.) kindly provided the most detailed North Sea case study.
British Petroleum contributed heavily through Drs. Carl Argo and Chris
Osborne (Sunbury) and particularly Dr. Tony Edwards (Dimlington), who related
North Sea commercial operating experiences with new inhibitors.
Chevrons Dr. Pat Shuler generously contributed his spreadsheet program
HYDCALC to determine inhibition amounts, and he provided access to offshore
engineers. Dr. Carl Gerdes reviewed the guidelines for safety, design, and operation.
Conocos Mr. Stan Swearingen and Mobils Mr. Barry Ho&ran were helpful
in reviewing both guidelines and manuscript drafts.
vi
Introduction
Natural gas hydrates are crystals formed by water with natural gases and
associated liquids, in a ratio of 85 mole % water to 15% hydrocarbons. The
hydrocarbons are encaged in ice-like solids which do not flow, but rapidly grow and
agglomerate to sizes which can block flow lines. Hydrates can form anywhere and
anytime that hydrocarbons and water are present at the right temperature and pressure,
such as in wells, flow lines, or valves and meter discharges. Appendix A gives hydrate
crystal details at the molecular level, along with similarities and differences from ice.
The low temperatures and high pressures of the deepwater environment cause
hydrate formation, as a function of gas and water composition. In a pipeline, hydrate
masses usually form at the hydrocarbon-water interface, and accumulate as flow
pushes them downstream. The resulting porous hydrate plugs have the unusual ability
to transmit some degree of gas pressure, while they act as a flow hindrance. Both gas
and liquid can frequently be transmitted through the plug; however, lower viscosity
and surface tension favors the flow of gas. Depressurization of pipelines is the
principal offshore tool for hydrate plug removal; depressurization sometimes prevents
normal production for weeks.
This handbook was written to provide the offshore facilities/design engineer
with practical answers to the following four questions:
Field case studies, pictures, diagrams, and example calculations are the basis
for this handbook. Less pressing questions regarding hydrate structures, plug
formation mechanism, etc. are considered as background material in Appendix A. A
computer program disk and Users Guide (Appendix B) are provided to enable
prediction of hydrate conditions. Appendix C is a compilation of Case Studies not in
the handbook body. A Russian hydrate perspective is presented in Makogons (1981,
1997) books. An in-depth, theoretical hydrate treatment is given by Sloan (1998).
25-200 ft. with velocities between 60-270 ft/s. Such velocities and masses provide
enough momentum to cause two types of failure at a pipeline restriction (orifice),
obstruction (flange or valve), or sharp change in direction (bend, elbow, or tee) as
shown in Figure 1. First, hydrate impact can fracture pipe, and second, extreme
compression of gas can cause pipe rupture downstream of the hydrate path.
2. Hydrates can form either single or multiple plugs, with no method to predict which
will occur. High differential pressures can be trapped between plugs, even when
the discharge end of plugs are depressurized.
3. Hydrates contain as much as 180 volumes (STP) of gas per volume of hydrate.
When hydrate plugs are dissociated by heating, any confinement causes rapid gas
pressure increases. However, hydrate plug heating is not an offshore option due to
the difficulty of locating the plug and economics of heating a submerged pipeline.
Field engineers discuss the hail-on-a-tin-roof sounds when small hydrate
particles hit a pipe wall. Such small, mobile particles can accumulate to large masses
occupying a considerable volume, often filling the pipeline to tens or hundreds of feet
in length. Attempts to blow the plug out of the line by increasing upstream pressure
(see Rule-of-Thumb 18) will result in additional hydrate formation and perhaps
pipeline rupture.
When a plug is depressurized using a high differential pressure, the dislodged
plug can be a dangerous projectile which can cause pipeline damage, as the below
three case studies (from Mobils Kent and Coolen, 1992) indicate.
_____________________________________________________________________
Case Study 1. 1991 Chevron Incident.
A foreman and an operator were attempting to clear a hydrate plug in a sour
gas flowline. They had bled down the pressure in the distant end from the wellhead.
They were standing near the line when the line failed, probably from the impact of a
moving hydrate mass. A large piece of pipe struck the foreman and the operator
summoned help. An air ambulance was deployed; however the foreman was declared
dead on arrival at the hospital. No pre-existing pipe defects were found.
_____________________________________________________________________
_____________________________________________________________________
Case Study 2. 1991 Gulf Incident
On January 10, 1991 the Rimbey gas plant was in the start-up mode. A
hydrate or ice plug formed in the overhead line from the amine contactor. The line
had been depressured to the flare system, downstream of the plug. The ambient
temperature which had been -30oC, rose rapidly due to warming winds around
midnight. At 2:00 a.m. the overhead line came apart, killing the chief operator. In
addition, approximately $6 million damage was suffered by the plant.
1a)
1b)
A hydrate plug moves
down a flowline at very
high velocites.
Closed Valve
Closed Valve
2a)
Low Pressure
High Pressure
Hydrate
Plug
Hydrate
Plug
SATELLITE
WELLHEAD
2b)
Low Pressure
Heat Addition
Gas
Hydrate Plug
Pipeline Rupture
Gas
Hydrate Plug
to lunch, intending to complete the task on their return. Upon their return the crew
found that the section of line had exploded during their absence.
Heat had apparently been applied to the mid-point of hydrate plug and the
plug-end portions served to contain very high pressures until the line ruptured. Figure
2b is a schematic of such a situation. In Section II it is shown that pressure increases
exponentially with temperature increases when hydrates are dissociated.
_____________________________________________________________________
_____________________________________________________________________
Case Study 5. 1970s Elf Incident
In the 1970s a plug occurred on a floating platform riser in the North Sea.
Blocking valves were closed and the pipeline was disconnected downstream of the
plug. The discharge end of the pipeline was aimed overboard, with the intent of using
high upstream pressure to extrude the plug from the line. When the plug was expelled
into the ocean, the force was so great that the platform was said to rise 20 cm in the
ocean.
_____________________________________________________________________
The Canadian Association of Petroleum Producers Hydrate Guidelines (1994)
suggest three safety concerns in dealing with hydrate blockages:
Always assume multiple hydrate plugs; there may be pressure between the plugs.
Attempting to move ice (hydrate) plugs can rupture pipes and vessels.
While heating a plug is not normally an option for a subsea hydrate, any heating
should always be done from the end of a plug, rather than heating the plug middle.
The last recommendation could be expanded in consideration of a subsea line:
Heating a subsea plug is not recommended due to the inability to determine the
end of the plug as well as provide for gas expansion on plug heating, and
Depressuring a plug gradually from both ends is recommended.
The above case studies warn that hydrates can be hazardous to health and to
equipment. Yet hydrate plugs can be safely dissociated through the procedure
indicated in the Remediation Section (III) of this handbook.
The preferred procedure, from both safety and economic considerations, is to
prevent the formation of hydrate plugs, through design and operating practices. While
the usage of many gallons of inhibitors may be costly on a continuous basis, such
expenses are easily overshadowed when plugs form and production is stopped. As the
case studies in this handbook show, it is not uncommon for several hundred yards of
hydrate plugs to form, preventing offshore production for a matter of weeks or
months, during remediation.
COMP.
SEP.
Platform
Ocean
- Depth 6000 ft
Well with
X-Mas Tree
Transport Pipeline
(2-60 miles in length)
Blockage in
Riser
Blockage in Tree,
Manifold, Well
Mudline
Downhole Safety
Valve
Blockage in
Flowline
Export Flowline
Riser
cooling for the pipeline fluids to low temperatures which are well within the hydrate
stability region.
The system temperature and pressure at the point of hydrate formation must be
within the hydrate stability region, as determined by the methods of Sections II.B
through II.D. The system temperature and pressure enters into the hydrate formation
region, either through a normal cooling process (Example 2 and Figures 6 and 7) or
through a Joule-Thomson process (Section II.F).
A typical plot of the water temperature in the Gulf of Mexico is shown in
Figure 4 as a function of water depth. The plot shows a high temperature of 70oF (or
more) occurs for the first 250 ft. of depth. However, when the depth exceeds 3,000 ft.
the bottom water temperature is very uniform at about 40oF, no matter how high the
temperature is at the air-water surface. This remarkably uniform water temperature at
depths greater than 3,000 ft. occurs in almost all of the earths oceans, (caused by the
water density inversion) except in a few cases with cold subsea currents.
The ocean acts as a heat sink for any gas or oil produced so that, without
insulation or other heat control methods, any flowline fluid cools to within a few
degrees of 40oF, no further than a few miles of the wellhead. The rate of cooling with
length is a function of the initial reservoir temperature, the flow rate, the pipeline
diameter, and other fluid flow and heat transfer factors. However, as shown in Section
II.B, the ocean bottom temperature of 40oF is low enough to cause hydrates to form at
any typical pipeline pressure.
_____________________________________________________________________
Example 1. Hydrate Formation in a Well. Figure 5 shows a typical subsea well in
which fluids are produced through the wing valve and choke to the pipeline. A
pressure indication just beyond the choke is essential to determination of hydrate
formation in the connecting flowline. About 300-500 ft. below the mudline is the
Downhole Safety Valve, used as the initial emergency barrier between the reservoir
and the production system. At the top of the well are Swab Valves, which provide an
entry way for lubricating hydrate dissociation tools (inhibitor injection, heaters, coiled
tubing, etc.) into the well to reach any hydrate blockage.
Hydrate formation in wells is an abnormal occurrence, arising during drilling of
the well or shut-in/start-up of the well. Normal well-testing procedures will not
promote hydrate formation. Hydrates form only in unusual circumstances, such as
pressurizing the well with water or with an aqueous acid solution. Addressing these
blockages should be done using the techniques in the Remediation Section (III). Case
Studies 11 (Section III.B.2.a) and 16 (Section III.C.3) provide two experiences with
hydrate formation in a well.
Davalath and Barker (1993) provide a comprehensive set of conditions for
dealing with hydrates in deepwater production and testing, including two case studies
100
1000
10000
20
30
40
50
60
Temperature (oF)
70
80
30 inch
Downhole
Completion
Downhole
Safety Valve
20 inch
13 3/8 inch
9 5/8 inch
of problems (summarized in Appendix C Case Studies C.23 and C.24) and four case
studies of successful hydrate management. Typically methanol injection capability is
provided in the well at two places: (1) at the subsea tree, and (2) downhole several
thousand feet below the seafloor. The injection location and amount of methanol
injection are specified using the procedure indicated in Section II.G.1.a on methanol
injection.
In offshore well drilling, frequently a water-based drilling fluid is used that can
form hydrates and plug blow-out preventors, kill lines, etc. when a gas bubble (or
kick) comes into the drilling apparatus. This represents a potentially dangerous
situation for well control. Hydrate formation on drilling is an area of active research
with several joint industrial projects underway. While a brief overview is given here,
the reader is referred to Sloan (1998, Section 8.3.2) for a detailed discussion.
Barker indicated the following rules-of-thumb used by Exxon in considering
hydrate formation with drilling fluids.
Drilling hydrate problems frequently occur, but have only been recognized in
recent years.
When hydrates form solids, they remove water from the mud, leaving a solid
barite plug.
One should not design a well to operate outside the hydrate region only if flow
conditions are maintained. If the well will be in the hydrate formation region at
static conditions, flow will stop at some period and the well operation will be
jeopardized.
Several hours may be required for hydrate formation and blockage to occur.
As of October 1988 Exxon used salt at the saturation limit range of 150 to 170
g/l to prevent hydrate formation.
As general guidelines concerning hydrate formation at various water depths,
the summary given below by Barker may be used:
By 1988 Shell had drilled 16 wells in the Gulf of Mexico at water depths
between 2,000 and 7,500 feet, using muds with 20 wt% sodium chloride (NaCl) and
partially hydrolyzed polyacrylamide (PHPA). In each well Shell experienced an
average of more than one gas kick per well, which signaled the possibility of hydrate
formation. Only one instance in 2900 ft. of water involved the possibility of hydrate
formation, when Shell experienced difficulty disconnecting the drill stack.
Barker and Gomez (1989) documented two occurrences (see Case Studies
C.21 and C.22 of Appendix C) of hydrate formation in relatively shallow waters off
California and the Gulf of Mexico, where losses in drill times were 70 days and 50
days, respectively. Recently the number of hydrate problems have increased
dramatically as drilling has moved to deeper water. In several cases where safety was
an issue (plugged blow out preventers, stack connectors, etc.) the well was
abandoned. Much remains to be done in this area.
_____________________________________________________________________
Downstream of the well and choke, the fluid flows through a pipeline of
considerable length before reaching the platform. Example 2 represents flow
conditions in the pipeline.
_____________________________________________________________________
Example 2: Hydrate formation in a Flowline. Texacos Notz, (1994) provided a
hydrate pipeline case in Figure 6 for a Gulf of Mexico gas. To the right of the diagram
hydrates will not form and the system will exist in the fluid (hydrocarbon and water)
region. However, hydrates will form in the shaded region to the left of the diagram,
and hydrate prevention measures should be taken.
Pipeline pressure and temperature conditions were predicted using a pipe
prediction program such as OLGA or PIPEPHASE and those conditions are shown
superimposed on the hydrate conditions in Figure 6. At low pipeline distances (e.g. 7
miles) the flowing stream retains a high temperature from the hot reservoir gas at the
pipeline entrance. The ocean cools the system, and at about 9 miles a unit mass of
flowing gas and associated water enters the hydrate region (shaded region to the left
of the line marked 0% MeOH), remaining in the uninhibited hydrate area until mile 45.
Such a distance may represent several days of residence time for the water phase, so
that hydrates would undoubtedly form, were not inhibition steps taken.
In Figure 6, by mile 25 the temperature of the pipeline system is within a few
degrees of the ocean floor temperature, so that approximately 23 wt% methanol is
required in the free water phase to prevent hydrate formation and subsequent pipeline
blockage. Methanol injection facilities are not available at the needed point along the
pipeline. Instead methanol is injected into the pipeline at the subsea well-head. In the
case of the pipeline shown in Figure 6 methanol is injected at the wellhead so that in
excess of 23 wt% methanol will be present in the free water phase over the entire
pipeline length.
As vaporized methanol flows along the pipeline in Figure 6, it dissolves into
any produced brine or water condensed from the gas. Hydrate inhibition occurs in the
free water, usually at accumulations with some change in geometry (e.g., a bend or
2500
30%
MeOH
Pressure(psia)
2000
Hydrate
Forming
Region
1500
20%
MeOH
10%
MeOH
7 Miles
10
15
25
Hydrate
Formation
Curve
20
30
1000
35
500
50
Hydrate
Free
Region
40
45
0
30
40
50
Temperature(oF)
60
70
80
pipeline dip along an ocean floor depression) or some nucleation site (e.g., sand, weld
slag, etc.).
Hydrate inhibition occurs in the aqueous liquid, rather than in the vapor or
condensate. While most of the methanol dissolves in the water phase, a significant
amount of methanol either remains with the vapor or dissolves into any liquid
hydrocarbon phase present as calculated using the methods shown later in this section.
In Figure 6 Notz showed that the gas temperature increases from mile 30 to
mile 45 with warmer (shallower) water conditions. From mile 45 to mile 50 however,
a second cooling trend is observed due to a Joule-Thomson gas expansion effect.
Methanol exiting the pipeline in the vapor, aqueous, and condensate phases is usually
not recovered, due to the expense of regeneration.
_____________________________________________________________________
Todd (1997) provided simulations with a different behavior from the pipeline
in Figure 6. In Todds simulations, typical gas pipeline pressure drops are small
relative to the overall pressure, resulting in an almost constant pressure cooling,
providing a straight, horizontal line between the pipeline end points on a plot like
Figure 7. Pipeline pressure drops are functions of several variables, and individual
systems should be simulated for best results.
_____________________________________________________________________
Example 3: Typical Offshore Platform Process. Manning and Thompson (1991, pp.
80-82, 344-355) detail a typical offshore platform process for a sweet crude oil with
dissolved gas delivered to the platform at 1000 psig and 120oF. The process is shown
in Figure 8 with process conditions given in Table 1 and selected stream compositions
provided in Table 2.
The process was sized for a product of 100,000 barrels per day (bpd) of oil to
the pipeline at the LACT (lease automatic custody transfer) unit, with 49 MMscf/d gas
produced at 1000 psig and an overall gas to oil ratio (GOR) of 491 scf/Bsto. The
heavy ends of the crude are divided into five boiling-point cuts while mole fractions of
individual gas components are given.
There are three objectives of the platform process:
1. to separate the gas, water, and oil, providing an oil phase which has a very low
vapor pressure, and providing water discharge to the ocean.
2. to dehydrate the gas to a water content below 7 lbm/MMscf before injection into
the pipeline to shore, and
3. to compress the gas for transport to land.
10
3000
Hydrate
Formation
Curve
10% MeOH
Pressure(psia)
2500
2000
1500
Pipeline
Separator
Wellhead
1000
500
0
30
35
40
45
50
55
Temperature(oF)
60
65
70
75
Figure
Typical
(From
Offshore
Manning
and
Pbtform
Thompson,
1991)
-u
Main oil punp
Schematic
Location
Pressure(PSIA)
Temperature( F)
Mol/Hr
Mol Wt
1019.7
120
12297.76
105.9
0.1821
1019.7
120
2238.98
18.79
1019.7
120
10058.78
125.29
111807.9
314.7
115.86
10058.78
125.29
0.2026
314.7
115.86
2038.13
20.39
314.7
115.86
8020.65
151.94
104667.3
69.7
111.45
8020.65
151.94
0.1084
69.7
111.45
869.66
27.44
69.7
111.45
7150.99
167.09
101141.7
10
16.7
106.22
7150.99
167.09
0.0664
11
16.7
106.22
474.67
43.13
12
16.7
106.22
6676.32
175.9
98533.16
13
74.7
236.54
474.67
74.7
14
69.7
100
474.67
69.7
0.9464
15
69.7
100
449.21
69.7
16
69.7
100
25.47
69.7
199.99
17
69.7
106.27
1318.87
32.2
18
319.7
280.91
1318.87
32.2
19
314.7
100
1318.87
32.2
0.8655
20
314.7
100
1141.54
28.83
21
314.7
100
177.32
53.89
1172.6
22
314.7
107.94
3179.67
23.42
23
1024.7
285.05
3179.66
23.42
24
1019.7
100
3179.66
23.42
0.9926
25
1019.7
100
3156.23
23.27
26
1019.7
100
23.43
43.18
144.6
27
1019.7
104.9
5395.21
21.41
28
314.7
95.43
200.75
52.64
0.0504
29
314.7
97.93
226.22
54.96
0.0275
30
314.7
104.75
6902.53
171.93
100000.1
Inlet Fluid
#2
#3
#5
#6
#8
#9
#11
#12
#14
#15
Gas Out
Liq. Out
Gas Out
Liq. Out
Gas Out
Liq. Out
Gas Out
Liq. Out
5th Sep.
Gas Out
1st Sep.
1st Sep.
2nd Sep.
2nd Sep.
3rd Sep.
3rd Sep.
3rd Sep.
4th Sep.
Inlet
6th Sep.
Comp.(Mol Frac.)
Nitrogen
0.0078
0.0287
0.0031
0.0137
0.0005
0.0040
0.0000
0.0004
0.0000
0.0004
0.0005
CO2
0.0005
0.0009
0.0004
0.0012
0.0002
0.0015
0.0001
0.0009
0.0000
0.0009
0.0009
Methane
0.3386
0.8705
0.2202
0.8074
0.0710
0.5605
0.0115
0.1615
0.0008
0.1615
0.1704
Ethane
0.0563
0.0607
0.0553
0.1060
0.0424
0.2118
0.0219
0.2399
0.0063
0.2399
0.2517
Propane
0.0440
0.0213
0.0491
0.0416
0.0510
0.1232
0.0422
0.2789
0.0253
0.2789
0.2880
i-butane
0.0121
0.0033
0.0140
0.0062
0.0160
0.0203
0.0155
0.0597
0.0124
0.0597
0.0598
n-butane
0.0342
0.0073
0.0402
0.0133
0.0470
0.0444
0.0474
0.1393
0.0408
0.1393
0.1371
i-pentane
0.0185
0.0022
0.0221
0.0036
0.0269
0.0118
0.0287
0.0407
0.0278
0.0407
0.0368
n-pentane
0.0244
0.0023
0.0293
0.0036
0.0359
0.0120
0.0388
0.0418
0.0385
0.0418
0.0360
Hexane
0.0429
0.0018
0.0520
0.0024
0.0647
0.0075
0.0716
0.0267
0.0748
0.0267
0.0169
248 F
0.0996
0.0009
0.1216
0.0010
0.1522
0.0027
0.1704
0.0092
0.1819
0.0092
0.0018
340oF
0.0714
0.0001
0.0873
0.0001
0.1094
0.0003
0.1227
0.0008
0.1313
0.0008
0.0000
413oF
0.0611
0.0000
0.0747
0.0000
0.0937
0.0000
0.1051
0.0001
0.1125
0.0001
0.0000
0.0544
0.0000
0.0665
0.0000
0.0834
0.0000
0.0935
0.0000
0.1002
0.0000
0.0000
472 F
657oF
Total Mol/Hr
Comp.(Mol Frac.)
0.1342
0.0000
0.1641
0.0000
0.2058
0.0000
0.2308
0.0000
0.2472
0.0000
0.0000
12297.75
2238.98
10058.78
2038.13
8020.67
869.66
7150.98
474.66
6676.31
474.66
449.2
#16
#17
#20
#21
#23
#25
#26
#27
#28
#29
#30
Liq. Out
6th Sep.
Gas Out
Liq. Out
7th Sep.
Gas Out
Liq. Out
Sales
Liquid
Liquid
Sales
6th Sep.
Inlet
6th Sep.
6th Sep.
Inlet
7th Sep.
7th Sep.
Gas
Line
Line
Oil
Nitrogen
0.0000
CO2
0.0000
Methane
0.0043
Ethane
0.0318
0.225381 0.251714 0.125021 0.154435 0.154317 0.170367 0.115474 0.130298 0.119176 0.010048
Propane
0.1190
1.3E-05
0.22876 0.032016
i-butane
0.0562
0.033794
n-butane
0.1783
i-pentane
0.1108
n-pentane
0.1438
0.020161
Hexane
0.1995
0.1398
0.002404 0.001848 0.017143 0.000654 0.000456 0.027327 0.000649 0.018329 0.032004 0.176941
248 F
o
340 F
0.0145
413oF
0.0020
2.27E-05
0.001281
472oF
0.0000
657oF
0.0000
0.239094
Total Mol/Hr
25.46
1318.88
449.2
177.33
3179.65
3156.23
23.42
5395.22
200.77
226.22
6902.57
0.000169 9.44E-06
1.3E-05
0.12715
Note that water separation and gas dehydration are vital for hydrate
prevention, so that even if the system cools into the hydrate pressure-temperature
region shown in Figure 7, hydrate formation is prevented due to insufficient water.
The export pipeline gas water content is below its water dew point (9 lbm/MMscf) at
the lowest temperature (39oF) so free water will not condense from the gas phase.
The oil is stabilized by flow through a series of four separators, operating at
1000psig, 300 psig, 55 psig, and 2 psig before the export oil pipeline, so an oil pipeline
pressure greater than 15 psia will prevent a gas phase. Hydrate formation is not a
significant problem in the oil export pipeline because relatively few hydrate formers
(nitrogen, methane, ethane, propane, butanes and CO2) are present and the water
content is low.
The gas from each separator is compressed, cooled, and separated from liquid
again before re-combining the gas with the previous separators gas for injection into
the export gas line. The additional oil obtained after cooling the compressed gas
amounts to about 1.5% of the total oil production.
In the process shown, 4310 bhp compressors represent the largest cost on the
platform, with capital cost on the order of $800-$1500 (1990 dollars) per installed
horsepower. These compressors are powered by fuel gas which operates at a low
pressure (about 200 psig), usually fed from the inlet gas passing through a control
valve with a substantial pressure reduction.
Pressure reductions after the fuel gas takeoff cause cooling, so that point is
very susceptible to hydrate formation, particularly in winter months. Also instrument
gas lines require similar pressure reductions from a header. Texacos Todd et al.
(1996. pp. 35-42) observe that when fuel and/or instrument gas lines are blocked due
to hydrates, the process frequently shuts down, resulting in pipeline cooling and
significant hydrate blockages in the production line at restart.
Hydrate limits to pressure reductions through restrictions such as valves and
orifices is shown in Section II.F.
_____________________________________________________________________
II.B. A One Minute Estimate of Hydrate Formation Conditions (Accurate to 50%)
Assuming the pipeline pressure drop to be relatively small, the engineer may do
a rough estimation to determine whether the pipeline will operate in the hydrate
region. As a first approximation, the engineer should first calculate the pressure at
which hydrates form at the lowest deep ocean temperature (38-40oF), so that if the
pipeline pressure is greater, then inhibition might be considered in the pipeline design
11
and operation. Such an approximation may indicate the need for more accurate
calculations to determine the amount of inhibition required.
Rules-of-Thumb. In this handbook, Rules-of-Thumb will frequently be stated
in bold type. These Rules-of-Thumb are based upon experience, and they are intended
as guides for the engineer for further action. For example, using a Rule-of-Thumb the
engineer might determine that a more accurate calculation was needed for inhibitor
injection amounts, or that further consideration of hydrates was unnecessary. Rulesof-Thumb are not intended to be Absolute Truths, and exceptions can always be
found. Where possible the accuracy of each Rule-of-Thumb is provided. The first
Rule-of-Thumb is given below for hydrate formation at ocean bottom temperatures.
Rule of Thumb 1: At 39oF, hydrates will form in a natural gas system if free
water is available and the pressure is greater than 166 psig.
Hydrate formation data were averaged for 20 natural gases (from Sloan, 1998,
Chapter 6) with an average formation pressure of 181 psia. Of the 20 gases, the
lowest formation pressure was 100 psig for a gas with 7 mole % C3H8, while the
highest value was 300 psig for a gas with 1.8 mole % C3H8.
Rule-of-Thumb 1 indicates that most offshore pipeline pressures greatly exceed
the hydrate formation condition, indicating:
gas drying and/or inhibition is needed for ocean pipelines with temperatures
approaching 39oF,
a more accurate estimation procedure should normally be considered, and
hydrate formation pressures are dependent upon the gas composition, and are
particularly sensitive to the amount of propane present.
12
13
a
Fi ur
- H
rat
Formati
43-
2-
3-
4 J,
30.00
45.00
35.00
40.00
50.00
55.00
I
6o)oo
Temperature (F)
65.00
70.00
75.00
80.00
Solution:
The gas gravity is calculated as 0.603 by the procedure below:
Component
Mol Fraction
Mol Wt
Avg Mol Wt in Mix
yi
MW
yiMW
Methane
Ethane
Propane
i-Butane
n-Butane
Pentane
0.9267
0.0529
0.0138
0.00182
0.00338
0.0014
1.000
Gas Gravity =
16.043
30.070
44.097
58.124
58.124
72.151
14.867
1.591
0.609
0.106
0.196
0.101
17.470
The user is cautioned that this method is only approximate for several reasons.
Figure 9 was generated for gases containing only hydrocarbons, and so should be used
with caution for those gases with substantial amounts of CO2, H2S, or N2. In addition,
the estimated inaccuracies (Sloan, 1985) for the hydrate equilibrium temperature (Teq)
and pressure (Peq) are maximized for 0.6 gravity gas as 7oF or 500 psig. In the fifty
years since the generation of this chart, more hydrate data and prediction methods have
caused the gravity method to be used as a first estimate, whose principle asset is ease
of calculation. Section II.D provides one of the most accurate methods for calculation
of hydrate conditions, but it requires some additional time as well as a computer.
II.C.2. Estimating the Hydrate Inhibitor Needed in the Free Water Phase The
above gas gravity chart may be combined with the Hammerschmidt equation to
estimate the hydrate depression temperature for several inhibitors in the aqueous
liquid:
T =
CW
M(100 - W)
where:
T =
C =
W =
M =
14
(1)
The Hammerschmidt equation was generated in 1934 and has been used to
determine the amount of inhibitor needed to prevent hydrate formation, as indicated in
Example 5. The equation was based upon more than 100 natural gas hydrate
measurements with inhibitor concentrations of 5 - 25 wt% in water. The accuracy of
the Hammerschmidt equation is surprisingly good; tested against 75 data points, the
average error in T was 5%.
For higher methanol concentrations ( up to 87 wt%) the temperature depression
due to methanol can be calculated by a modification of Equation (1) by Nielsen and
Bucklin (1983), where xMeOH is mole fraction methanol in aqueous phase
T = 129.6 ln(1 x MeOH )
(1a)
_____________________________________________________________________
Example 5: Methanol Concentration Using the Hammerschmidt Equation.
Estimate the methanol concentration needed to provide hydrate inhibition at
450 psia and an ocean floor temperature of 39oF for a gas composed of 92.67 mol%
methane, 5.29% ethane, 1.38% propane, 0.182% i-butane, 0.338% n-butane, and
0.14% pentane.
Solution:
The gas is the same composition and pressure as that in Example 4, with the
gas gravity previously determined to be 0.603 and uninhibited hydrate formation
conditions of 50oF and 450 psia. Inhibition is required since the pipeline operates at
39oF and 450 psia, well within the hydrate formation region. The weight percent of
inhibitor needed in water phase is determined via the Hammerschmidt Equation (1),
with the values:
T = Temperature Depression (50oF - 39oF= 11oF),
M = Molecular Weight for Methanol (= 32)
C = Constant for Methanol (= 2335)
W = Weight Percent Inhibitor
Rearranging in Equation (1)
W =
100 M T 100 32 11
=
= 131
.
M T + C 32 11 + 2335
15
An inlet gas water content analysis is used, if available. Then the water content
of the outlet gas (Rule-of-Thumb 2) may be subtracted from the inlet gas to determine
the water condensed per MMscf of gas. When an inlet gas water content is not
available a water content chart such as Figure 10 may be used to obtain the water
content of both the inlet and outlet gas from the pipeline.
In Figure 10 the temperature of the pipeline inlet or outlet is found on the xaxis and water content is read on the y-axis at the pipeline pressure, marked on each
line in Figure 10. The engineer is cautioned not to use the water content chart at
temperatures significantly below 38oF. At lower temperatures the actual water
content deviates from the line due to hydrate formation. An illustration of condensed
water calculation using Figure 8 is given in Example 6 (Section II.C.4).
16
17
Temperature,OF
20
30
I t I I I III
40
I,
I I,
50
60
I I I I I I,
70
1 III
I,,
80
1 I,
90
I,,
5 Ls
,z
InK,, = a + b[l/T(R)]
-3,
,I,6s
III
Z.lOE-3
0
0
1000psia 8.41233
-7250.20
2000 psia
6.82227
-6432.23
-5738.48
1111,,,,,,,,,,,,,,,,,,,,,,,,,,r
ZOOE-3
1.9oE3
lfw)
l.mE-3
100
III,
xx)100
60 =
4020IO =
6=
42I
0.6
a4
=
r
QOI
-40
/I
I
0
-20
20
40
EOlJlLlBRlUM TEMPERATURE,
60
Bo
OF
through the pipeline is cooled by the surrounding water to a temperature of 38oF. The
gas also experiences a pressure drop to 950 psia. Gas exits the pipeline at a rate of 3.2
MMscf/d. The pipeline produces condensate at a rate of 25 bbl/day, with an average
density of 300 lbm/bbl and an average molecular weight of 90 lbm/lbmole. Produced
free water enters the pipeline at a rate of 0.25 bbl/day.
Natural gas composition (mole %): methane = 71.60%, ethane = 4.73%, propane
=1.94%, n-butane = 0.79%, n-pentane = 0.79%, carbon dioxide = 14.19%, nitrogen =
5.96%.
Find the rate of methanol injection needed to prevent hydrates in the pipeline.
Solution:
Basis: The basis for these calculations was chosen as 1 MMscf/d.
Step 1) Calculate Hydrate Formation Conditions using the Gas Gravity Chart
Component
Mol Fraction
yi
Mol Wt
MW
Methane
Ethane
Propane
n-Butane
n-Pentane
Nitrogen
Carbon Dioxide
0.7160
0.0473
0.0194
0.0079
0.0079
0.0596
0.1419
1.000
16.04
30.07
44.09
58.12
72.15
28.01
44.01
Gas Gravity =
Reading the gas gravity chart (Figure 9), the hydrate temperature is 65oF at 1000 psia.
Step 2) Calculate the Wt% MeOH Needed in the Free Water Phase
The Hammerschmidt Equation is:
T =
CW
100M - MW
18
100 M T 100 32 27
=
= 27
M T + C 32 27 + 2335
day
bbl gal
1day
3.2 MMscf
lb H O
= 27.4 m 2
MMscf
- Total Mass of Water/MMscf Gas: Sum the condensed and produced water
591 lbm + 27.4 lbm = 618.4 lbm
MMscf
MMscf
MMscf
Step 4) Calculate the Rate of Methanol Injection
Methanol will exist in three phases: water, gas, and condensate. The total mass of
methanol injected into the gas is calculated as follows:
-Calculate Mass of MeOH in the Water Phase
27.0 wt% methanol is required to inhibit the free water phase, and the mass of
water/MMscf was calculated at 618.4 lbm. The mass of MeOH in the free
water phase per MMscf is:
27wt% =
M lbm MeOH
100%
M lb m MeOH + 618.4lbm H 2 O
19
= 267.4 lbm/MMscf
(or 40.33 gal/MMscf at a MeOH density of 6.63 lbm/gal)
_____________________________________________________________________
In the above example, the amount of methanol lost to the gas and condensate is
approximately 11% of the total amount injected. However, with large amounts of
condensate it is not uncommon to have as much as 90% of the injected methanol
dissolved in the condensate (primarily) and gas phases. In such cases, the Rules-ofThumb should be replaced by a more accurate calculation, as shown in section II.D.
The hand calculation example is provided for understanding of the second
approximation. The method is made much more convenient for the engineer via the
use of the below spreadsheet program.
20
Once the above values are input, HYDCALC displays calculations for both
Intermediate Results (in black) and the amount of methanol or glycol to be injected (in
blue on a color screen). In the below example, the User Input and Calculations are
both listed in black, due to printing restrictions. A prescription for the use of this
method is shown in Example 7.
_____________________________________________________________________
Example 7. Use of HYDCALC to Find Amount of Methanol and Glycol Injection
This spreadsheet problem is the identical problem worked in Example 6 by
hand. A sub-sea pipeline with the a gas gravity of 0.784 has inlet pipeline conditions
of 195oF and 1050 psia. The gas flowing through the pipeline is cooled by the
surrounding water to a temperature of 38oF. The gas also experiences a pressure drop
to 950 psia. Gas exits the pipeline at a rate of 3.2 MMscf/d. The pipeline produces
condensate at a rate of 25 bbl/d, with an average density of 300 lbm/bbl and an average
molecular weight of 90 lbm/lbmole. Produced free water enters the pipeline at a rate of
0.25 bbl/d.
Determine the rate of methanol and glycol injection needed to prevent hydrate
formation in the pipeline.
Solution:
Figure 13 on the next page is a copy of HYDCALC, highlighting the data input
that is needed to run the program. All required data are provided in the example, with
21
disk 2
P.J. Shuler
CTN 694-7572, PJSH
HYDCALC Version 2
CPTC
5/27/97
Inputs
1050
950
195
38
0.784
3.2
25
psia
psia
F
F
0.25
5.7
5.9
bbl/ H2O/day
bbl/ H2O/day
bbl/ H2O/day
MMSCFD
bbl/day
CALCULATION WORKSHEET
Water in hot gas
Water in cold gas
WATER CONDENSED
626.2
6.5
619.8
lb/MMSCF
lb/MMSCF
lb/MMSCF
1983
5.7
5.9
lb/day
bbl H2O/day
bbl H2O/day
65.0
27.0
27.0
45.6
Vapor to liquid
composition ratio
0.9162 lb/MMSCFper
% in water
Methanol in gas
MEG in gas
24.77
0
lb/MMSCF
lb/MMSCF
37.5
22.5
lb/day
lb/day
Methanol to protect
water phase
MEG to protect
water phase
767
lb/day
1735
lb/day
767
lb/day
79
37.5
884
lb/day
lb/day
lb/day
134.9
gal/day
42.2
gal/MMSCF
TOTALS
Methanol to protect
water phase
Methanol going to gas
Methanol into condensate
TOTAL Methanol Rate
Methanol Injection Rate
(pure MeOH @ 77F)
Methanol Rate/MMSCF
SUMMARY OF RESULTS
Methanol Injection Rate
(pure MeOH @ 77F)
Methanol Rate/MMSCF
134.9
gal/day
42.2
gal/MMSCF
190.0
gal/day
59.4
gal/MMSCF
Summary of Results
MEG to protect
water phase
MEG in gas
MEG into condensate
TOTAL MEG Rate
1735
lb/day
0
22.5
1758
lb/MMSCF
lb/day
lb/day
190.0
gal/day
59.4
gal/MMSCF
the exception of gas gravity. Gas gravity was calculated using the method described in
Example 4 to be 0.784. Figure 13 on the next page displays all input data and results.
The amount of methanol injected is 42.2 gal/MMscf and the amount of glycol
injected is 59.4 gal/MMscf.
_____________________________________________________________________
For ease of use, the engineer will turn to HYDCALC to perform the second
approximation calculation. The following section provides accuracy and limitations of
both HYDCALC and the hand calculation methods, which are vital to their use.
591
228.7
27
11.7
267.4
40.3
HYDCALC
Result
619.8
239.7
24.7
11.7
276.25
42.2
While the hand calculation and the computer program provide only slightly
different results, both include inaccuracies. For example, while it is possible to obtain
more significant figures with HYDCALC than with the charts in the hand method,
HYDCALC inaccuracies are those of the charts upon which HYDCALC is based.
Using HYDCALC it was estimated that 27 wt% methanol was required in the
water phase to inhibit the pipeline, while measurements by Robinson and Ng (1986)
show that only 20 wt% methanol was required for inhibition at the same gas
composition, temperature, and pressure of Examples 6 and 7.
The major inaccuracies in the second estimation method are in the gas gravity
hydrate formation conditions, which are only accurate to 7oF or to 500 psia. The
Hammerschmidt equation, the inhibitor temperature depression T is accurate to
5%. With such inaccuracies, the amount of methanol or glycol injection could be in
error by 100% or more. The principal virtue of the second estimation method is ease
of calculation rather than accuracy.
22
A second limitation is that the method was generated for gases without H2S,
which represents the case for many gases in the Gulf of Mexico. A modification of the
gas gravity method was proposed for sour gases by Baillie and Wichert (1987).
_____________________________________________________________________
Example 8: Use of HYDOFF to Obtain Hydrate Formation and Prevention Conditions.
Find (a) the hydrate formation pressure of the below natural gas at 38oF and (b) the
amount of methanol in the water phase to inhibit hydrates at 38oF and 1000 psia. The
23
gas composition (mole %) is: methane = 71.60%, ethane = 4.73%, propane = 1.94%,
n-butane = 0.79%, n-pentane = 0.79%, carbon dioxide = 14.19%, nitrogen = 5.96%
Solution: The gas in this example has the same composition as the gas in Examples 6
and 7, so the results provide a comparison with hand and computer calculations of the
gas gravity method (Section II.C.1) and the Hammerschmidt equation (Section
II.C.2).
For convenience with multiple calculations, the reader may wish to edit the
program FEED.DAT to reflect the gas composition of the problem. Modification of
the FEED.DAT program is done at the MSDOS prompt, by changing the composition
of each component to that of the example gas, and saving the result using the standard
MSDOS editing technique. However it is not necessary to use FEED.DAT; the gas
composition may be input as part of the program HYDOFF.
In the following solution, each input from the user is underlined:
1. From Windows or in the proper directory, click on, or type HYDOFF; press Enter.
2. After reading the title screen, press Enter
3. At the Units screen, press 1 (to choose oF and psia) then Enter
4. At the FEED.DAT question screen, press 2 and Enter if you wish to use the data in
FEED.DAT, or 1 and Enter if you wish to enter the gas composition in HYDOFF by
hand. The remainder of this example is written assuming that the user will enter the
gas composition in HYDOFF rather than use FEED.DAT. The use of FEED.DAT is
simpler and should be considered for multiple calculations with the same gas.
5. The next screen asks for the number of components present (excluding water).
Input 7 and Enter.
6. The next screen requests a list of the gas components present, coded by numbers
shown on the screen. Input 1, 2, 3, 5, 7, 8, and 9 (in that order, separating the entries
by commas) and then Enter.
7. The next series of screens request the input of the mole fractions of each component
Methane
0.7160 Enter.
Ethane
0.0473 Enter.
Propane
0.0194 Enter.
n-Butane
0.0079 Enter.
Nitrogen
0.0596 Enter.
Carbon Dioxide
0.1419 Enter.
n-Pentane
0.0079 Enter.
8. At the Options screen, input 1 then Enter.
9. At the screen asking for the required Temperature, input 38, and Enter.
10. Read the hydrate formation pressure of 229.7 psia, (meaning hydrates will form at
any pressure above 230 psia at 38oF for this gas.)
11. When asked for another calculation input 1 for No then Enter.
12. At the Options screen input 2, then Enter.
24
13. At the screen asking for the required temperature, input 38, and Enter.
14. At the screen to enter the WEIGHT PERCENT of Methanol, input 22.
15. Read the resulting hydrate condition of 22 wt% MeOH, 38oF, and 1036 psia.
It may require some trial and error with the use of the program before the
correct amount of MeOH is input to inhibit the system at the temperature and pressure
of the example. One starting place for the trial and error process would be the amount
of MeOH predicted by the Hammerschmidt equation (27 wt%) in Example 6. Ng and
Robinson (1983) measured 20 wt% of methanol in the water required to inhibit
hydrates at 38oF and 1000 psia. A comparison of the measured value with the
calculated value (22 wt%) in this example and through the Hammerschmidt equation
provides an indication of both the absolute and relative calculation accuracy.
HYDOFF can also be used to predict the uninhibited hydrate formation
temperature at 1000 psia at 58.5oF, through a similar trial and error process, as
compared with 65oF determined by the gas gravity method. No measurements are
available for the uninhibited formation conditions of the gas in this example.
In using HYDOFF, if components heavier than n-decane (C10H22) are present,
they should be lumped with n-decane, since they are all non-hydrate formers.
_____________________________________________________________________
(2)
In order to use Equation (2), first determine the amount of methanol required
using HYDOFF, as in Example 8. Insert the amount of methanol in Equation (2) to
determine the amount of mono-ethylene glycol needed in water to inhibit hydrates.
Equation (2) should be used for the free water phase only. Example 9 (Section II.D.5)
provides a summary calculation of all the procedures in Section II.D.
II.D.3. Solubility of MeOH and MEG in the Gas. Figure 11 is a fit of recent
measurements by Ng and Chen (1995) for KvMeOH defined as the methanol mole
fraction in gas relative to water ( yMeOH/xMeOH in H2O). Once the mole fraction of
methanol in water is determined, it may be multiplied by KvMeOH to obtain the mole
fraction of methanol in the gas. As can be determined by Figure 11, the solubility in
the water is only slightly affected by pressure over the range from 1000-3000 psia at
offshore temperatures.
For a conservative estimate the 3000 psia line is
recommended:
25
(3)
(4)
(5)
_____________________________________________________________________
Example 9: Most Accurate Inhibitor Injection Calculation. A sub-sea pipeline with
the below gas composition has inlet pipeline conditions of 195oF and 1050 psia. The
26
Temperature (OF)
20
30
40
50
60
70
80
90
100
1o-~_I1~~~~
115
s-l
7-
zi
634-
3 102u
,-
5 :_
ti
I-
.-
3-
a
3-
2.1E-3
- b
5.90062 -5404.45
[7
5.91795 -5389.73
3.55142 -3242.43
2.OE-3
1.9E-3
l/T(R)
1.8E-3
130
Temperature, OF
40
50
60
70
80
90
112
100
J!,~
a + b[l/T(Fi)]
InK,=
I
z.ooE-3
Mdlmw+Pmpm+ll-~
f3
Ibtbw+~+~~e
4A9818
-726638
-+Rupm+Tol\rar
2.65872
-5211.86
I
1.9SE-3
I I
MOE-3
l/T(R)
Las-3
I
1.SOE-3
1.7s3
gas flowing through the pipeline is cooled by the surrounding water to a temperature
of 38oF. The gas also experiences a pressure drop to 950 psia. Gas exits the pipeline
at a rate of 3.2 MMscf/d. The pipeline produces condensate at a rate of 25 bbl/d, with
an average density of 300 lbm/bbl and an average molecular weight of 90 lbm/lbmole.
Produced salt-free water enters the pipeline at a rate of 0.25 bbl/d.
Natural gas composition (mole%): methane = 71.60%, ethane = 4.73%, propane =
1.94%, n-butane = 0.79%, n-pentane = 0.79%, carbon dioxide = 14.19%, nitrogen =
5.96%
Find the rate of both methanol and monoethylene glycol injection needed to prevent
hydrate formation in the pipeline.
Solution:
Basis: the basis for solution is 1 MMscf/d.
Step 1) Calculate the Concentration of MeOH and MEG in the Water Phase.
In Example 8 the methanol concentration was calculated to be 22 wt% of the
free water phase at 38oF and 1000 psia. Using Equation (2) the MEG concentration
was calculated at 33.6 wt% in the water phase.
Step 2) Calculate the Mass of Liquid H2O/MMscf of Natural Gas
- Calculate Mass of Condensed H2O
Use the water content chart (Figure 10), to calculate the water in the
vapor/MMscf. The inlet gas (at 1050 psia and 195oF) water content is read as
600 lbm/MMscf. The outlet gas (at 950 psia and 38oF) water content is read as
9 lbm/MMscf. The mass of liquid water due to condensation is:
600 lbm _ 9 lbm = 591 lbm
MMscf MMscf
MMscf
- Calculate Mass of Produced H2O Flowing into the Line
Convert the produced water of 0.25 bbl/d to the basis of lbm/MMscf:
0.25bblH 2 O 42 gal 8.34lbm
day
bbl gal
1day
3.2MMscf
lb H O
= 27.4 m 2
MMscf
- Total Mass of Water/MMscf Gas: Sum the condensed and produced water
591 lbm + 27.4 lbm = 618.4 lbm
MMscf
MMscf
MMscf
27
M lb m MeOH
100%
M lb m MeOH + 618.4lb m H 2 O
N lb m MEG
100%
N lb m MEG + 618.4lb m H 2 O
The mole fraction MeOH in the water phase is xMeOH in H2O = 0.137. The
distribution constant of MeOH in the gas is calculated at 38oF (497.7oR) by
Equation (3), relative to the methanol in the water
KvMeOH = exp (5.706 - 5738(1/497.7oR) = 0.00296
(3)
o
o
where R = F + 459.69
The mole fraction of MeOH in the vapor is yMeOH = KvMeOHxMeOH in H2O or
yMeOH = 0.00296 0.137 = 0.0004055
The daily gas rate is 8432 lbmol (= 3.2 106 scf / (379.5 scf/lbmol), where an
scf is at 14.7 psia and 60oF), so that the MeOH lost to the gas is 3.42 lbmol (=
28
-Calculate Amount of (a) MeOH and (b) MEG Lost to the Condensate
(a) MeOH lost to the condensate. The distribution of MeOH in the condensate
is calculated via equation (4)
KLMeOH = exp (5.90 - 5404.5(1/497.7oR)) = 0.00702
(4)
where oR = oF + 459.69.
The mole fraction MeOH in condensate is xMeOH in HC = KLMeOHxMeOH in H2O or
xMeOH in HC = 0.00702 0.137 = 0.0009617
The condensate rate is 26.0 lbmoles/MMscf (= 25bbl/d300 lbm/bbl1
lbmol/90 lbm1d/3.2 MMscf) so that the amount of MeOH in condensate is
0.025 lbmol/MMscf (= 0.0009617 26 / ( 1 - 0.009617)) or 0.8 lbm/MMscf)
(b) MEG Lost to Condensate. The mole fraction MEG in the water phase is
calculated as
mole fraction MEG =
The mole fraction MEG in the water phase is xMEG in H2O = 0.128.
The distribution of MEG between the aqueous liquid and condensate is given
by
KLMEG = exp (4.20 - 7266.4(1/497.7 oR)) = 3.04 10-5
(5)
29
In Water, lbm/MMscf
In Gas, lbm/MMscf
In Condensate, lbm/MMscf
Total, lbm/MMscf
Total, gal/MMscf
MeOH
MEG
174.4
34.2
0.8
209.4
31.5
313.1
0.006
0.0061
313.11
33.3
The example illustrates that for this gas condition, the injection amounts of
MeOH and MEG are comparable. The more precise calculation shown here however,
represents a considerable savings in the amount of MeOH injected (31.5 gal/MMscf
versus 42.2 gal/MMscf in the second estimation method.)
_____________________________________________________________________
30
10 wt% MeOH
20 wt% MeOH
3500
Pressure(psia)
3000
2500
2000
1500
1000
500
0
30
35
40
45
50
Temperature(oF)
55
60
65
70
2000
25 wt%
MeOH
1800
10 wt%
MeOH
20 wt%
MeOH
0 wt%
MeOH
1600
Pressure(psia)
1400
1200
1000
Wellhead
Pipeline
Separator
800
600
400
200
0
30
40
50
60
Temperature(oF)
70
80
90
1. Burying the Pipeline. Some of the Dog Lake pipeline was built over a
stretch of marsh. The exposure to winter ambient temperatures caused rapid
reductions in the gas temperature. Burying the pipeline would protect it from low
environmental temperatures due to the higher earth temperatures. Figure 18 displays
the temperature increase in the pipeline after exposed areas were buried relative to the
exposed pipeline in Figure 17. With pipeline burial, the need for methanol in the water
phase was reduced from 26 wt% to less than 19 wt%.
2. Wellhead Heat Addition. Catalytic in-line heaters could be installed at the
wellhead to increase the gas temperature to 125oF. Figure 19 shows the pipeline
temperature increase caused by the combined prevention methods of burial and
wellhead heating. Use of these two methods permitted the methanol concentration to
be reduced to approximately 14 wt% to prevent hydrate formation in the line. It
should be noted that heating may increase the amount of corrosion in the line.
3. Insulation. Insulation of exposed areas near the wellhead and battery would
maintain higher pipeline temperatures, thereby reducing the amount of methanol
needed for hydrate inhibition. Figure 20 displays the temperature increase in the
buried and heated pipeline when exposed pipes were insulated. The pipeline is now
outside the hydrate formation region, and methanol addition is no longer needed.
4. Methanol Addition. Continued methanol injection could be done at an cost
of approximately $1.50 -$2.00 per gallon. The cost of methanol to an offshore
platform cost $2.00 per gallon during the 1996-7 winter. Since methanol recovery
may not be economical, methanol is normally considered an operating cost.
This case study illustrates how combinations of pipeline burial, insulation,
heating, and methanol injection can be used to prevent hydrates. The selection of the
hydrate prevention scheme(s) is then a matter of economics, as considered in Section
IV of this handbook.
_____________________________________________________________________
31
2000
20 wt%
MeOH
1800
0 wt%
MeOH
10 wt%
MeOH
1600
Pressure(psia)
1400
1200
Separator
Wellhead
Pipeline
1000
800
600
400
200
0
30
40
50
60
Temperature(oF)
70
80
90
2000
20 wt%
MeOH
1800
10 wt%
MeOH
0 wt%
MeOH
1600
Pressure(psia)
1400
1200
Pipeline
Sep.
Wellhead
1000
800
600
400
200
0
30
40
50
60
70
80
90
Temperature(oF)
100
110
120
130
2000
20 wt%
MeOH
1800
10 wt% 0 wt%
MeOH MeOH
1600
Pressure(psia)
1400
1200
Separator
1000
Wellhead
Pipeline
800
600
400
200
0
30
40
50
60
70
80
90
Temperature(oF)
100
110
120
130
but resource intensive method (Section II.F.2), concluding with prevention techniques
in Section II.F.3.
Figure 7 is a schematic of the pressure and temperature of a pipeline
production stream during normal flow with entry into the hydrate formation region. If
the gas expands rapidly, the normal pipeline cooling curve of Figure 7 will take on a
much steeper slope, but the hydrate formation line remains the same. Two rapid
expansion curves for a 0.6 gravity gas are shown in Figure 21. Intersections of the gas
expansion curves with the hydrate formation line gives the limiting expansion
discharge pressures from two different high initial pressure/temperature conditions.
In Figure 21, the curves specify the pressure at which hydrate blockages will
form at the restriction discharge for an upstream pressure and temperature. Gas A
expands from 2000 psia and 110oF until it strikes the hydrate formation curve at 780
psia (and 57oF) so that 780 psia represents the limit to hydrate-free expansion. Gas B
expands from 1800 psia (120oF) to intersect the hydrate formation curve at a limiting
pressure of 290 psia (42oF). In expansion processes while the upstream temperature
and pressure are known, the discharge temperature is almost never known, but the
discharge pressure is normally set by a downstream vessel or pressure drop.
Cooling curves such as the two in Figure 21 were determined for constant
enthalpy (or Joule-Thomson) expansions, obtained from the First Law of
Thermodynamics for a system flowing at steady-state, neglecting kinetic and potential
energy changes:
H = Q - Ws
(6)
32
Figure
21
Hydrate
Gas
Expmsion
into
Forrmtioo
Region
(From
Katz,
1944)
2000
1500
1000
d
.::
;I
L
Z
E
k
800
600
500
400
300
30
40
50
60
70
80
90
Temperature(F)
100
Example 10b. Unlimited Gas Expansion. How far may a 0.6 gravity gas at 2000 psig
and 140oF be expanded without hydrate formation?
Solution: In Figure 22 it is seen that there is no intersection with the 140oF isotherm.
Hydrates will not form upon expansion to atmospheric pressure..
Example 10c. Minimum Initial Temperature Before Expansion. A 0.6 gravity gas is to
be expanded from 1500 psia to 500 psia. What is the minimum initial temperature that
will permit the expansion without danger of hydrates?
Solution: From Figure 22 the answer is read as 99oF or above.
_____________________________________________________________________
Figures 22, 23, and 24 for gas expansion incorporate the inaccuracies of gas
gravity charts from which they were derived. As indicated in Section II.C the 0.6
gravity chart (used for both hydrate formation and gas expansion) may have
inaccuracies of 500 psia. Accuracy limits to these expansion curves have been tested
33
-I
_
1000
!
_
6
6
_
_
4 i
Initial
100
100
6
6
1000
Pressure (psia)
Fimure
23 - Gas
Exsansion
NG
(FromKatz,1959)
10000
_
_l
I~
I
6
-I-
I
~
_I_
r - - -/-
-I-
- -
_I_
-I-
100
-I-
I
II/I
I
4
-I-
1000
6
610000
10()OOT
- - -~
---
--
I
_
_,_
_,_
I
2
-+--
l
I
100
I
6
I
I
a 1000
by Loh et al. (1983) who found for example, that the allowable 0.6 gravity gas
expansion from 150oF and 3500 psia should be 410 psia rather than the value of
700psia, given by Figure 22.
_____________________________________________________________________
Example 11: Hydrate Formation on Expansion of a Natural Gas
A simple natural gas consists of 90 mol% CH4 , 7% C2H6 , and 3% C3H8 with
free water in a pipeline. Two initial inlet process conditions are considered for
expansion across a valve: (a) 68oF and 2180 psia, or (b) 77oF and 2180 psia. For
either condition, is hydrate formation a possibility? Are there process limitations on
the expansion from either initial condition to 1450 psia?
34
Solution: Before doing any hydrate calculations, one should confirm that this gas is
not close to the hydrocarbon dew point, to eliminate the possibility of encountering
both vapor and liquid hydrocarbon phases. The expansion program was written for a
gas phase. A vapor-liquid equilibria flash calculation indicates that the highest
temperature at which a hydrocarbon liquid can occur (the cricondentherm) for this
mixture is -44oF, so the process will not form hydrocarbon liquid.
Figure 25 shows the expansion conditions of both inlet conditions for the gas.
The remainder of this example concerns the generation of Figure 25 and the
processing implications. First, the pressures and temperatures of hydrate formation
are calculated using the program HYDOFF as in Section II.D as:
T(oF)
P(psia)
32
119
35
149
40
213
45
303
50
368
55
551
60
718
65
1117
68
1624
71
2509
77
4046
2100
68.0
As shown in Figure 25, the isenthalpic expansion system extends further into
the hydrate region. Only with subsequent heating at a constant pressure of 1450 psia,
will the system become hydrate-free at 66.6oF.
A similar calculation for the system initially in the fluid region at 77oF and 2180
psia shows the problem with isenthalpic expansion. The result, plotted as line ABC in
Figure 25 shows an isenthalpic intersection with the hydrate formation boundary at
approximately 70.5oF, 1990 psia. To prevent expansion into the hydrate region four
options may be considered, as illustrated in Example 12:
1. limit the final expansion pressure to a higher value than 1990 psia,
2. add inhibitor at the restriction inlet,
3. dehydrate the gas before expansion, or
35
3000
Isenthalpic Expansion
From 77oF, 2180 psia
Isenthalpic Expansion
From 68oF, 2180 psia
2500
Pressure(psia)
H = 0
2000
1500
Isothermic Expansion
From 68oF, 2180 psia
H = 0
T = 0
1000
500
0
30
35
40
45
50
55
60
Temperature(oF)
65
70
75
80
Pipeline hydrate plugs are frequently porous, so that depressurization from one
(downstream) side can result in Joule-Thomson cooling as gas flows through the plug.
Expansion across a hydrate plug yields identical results to expansion across a valve. In
the initial part of the above example, it was seen that expansion from a condition
which has a hydrate plug (e.g. 68oF and 2180 psia) will only cause the downstream
portion of the plug to progress further into the hydrate region. Heat must be put into
the system from the surroundings to dissociate hydrates. The field tests which confirm
the above discussion are given in Case Studies C.15 and C.17 in Appendix C.
There are several limitations to XPAND. First, it is limited to the vapor phase
and will not account for expansion of a fluid containing any liquid amount. If there is
a question whether the system might contain a liquid either at the inlet or discharge,
the engineer should calculate the hydrocarbon dew point, and an isenthalpic flash
should be performed to obtain the cooling curve, using a process simulator package
like HYSIM , ASPEN , or PROCESS . Secondly, XPAND was generated only for the
first five common paraffins (methane, ethane, propane, normal butane, iso-butane, and
normal pentane) so XPAND cannot be used with nitrogen, acid gases (H2S or CO2),
or with significant amount of heavy components. With the above restrictions, the
engineer may group components larger than pentanes into the pentane plus fraction
of the gas.
36
composition of the components were: 0.927 methane, 0.053 ethane, 0.014 propane,
0.0018 i-butane, 0.0034 n-butane, and 0.0014 i-pentane.
Is there a chance that hydrate formation might occur in the fuel gas line? If so,
which of the following ways could be used to prevent hydrates?
1.
2.
3.
4.
37
Hydrate
Formation
Curves
1400
20 Wt% MeOH
10 Wt% MeOH
0 Wt% MeOH
Inlet
Pressure(psia)
1200
1000
Hydrates
800
600
Gas Expansion Curve
400
Outlet
No Hydrates
200
0
30
40
50
60
70
80
o
Temperature( F)
90
100
110
Joule-Thomson charts, the inlet temperature using XPAND should be 108oF for
hydrate-free expansion from 1500 psia to 300 psia.
Ex12.B.2. Methanol Addition. Methanol can be injected into the fuel supply
line upstream of the control valve to prevent hydrate formation downstream of the
valve. Figure 26 shows that more than 10 wt% methanol is needed in the free water
phase to prevent hydrate formation. A better estimate of 12 wt% methanol in the
38
In-Line Heater
P1 = 1500 psia
P4= 300
psia
T1= 100oF
T2= 58oF
T3= 68oF
T4= 44oF
Estimated Using
HYDXPAND
1600
Inlet
1st Valve(T1)
10 Wt% MeOH
0 Wt% MeOH
1400
Hydrates
Heating Line #2
Pressure(psia)
1200
Line #1
1000
Outlet
1st Valve
(T2)
800
Inlet
2nd Valve(T3)
600
Gas Expansion
Curve
Line #3
400
No Hydrates
Outlet
2nd Valve(T4)
200
0
30
40
50
60
70
Temperature(oF)
80
90
100
110
water phase was obtained through interpolation using XPAND and HYDOFF. The
total amount of methanol required for upstream gas injection is calculated through
methods of Section II.D.
Ex12.B.2.a.Water condensation with expansion. Gas flows into the fuel line at
a rate of 0.02 MMscf/d. Since the gas is saturated with water, one can
calculate the mass of free water in the pipeline due to dewpoint condensation
from Figure 10 (45 lbm H2O/MMscf in the vapor at 1500 psia and 100oF and 16
lbm H2O/MMscf in the vapor at 350 psia and 33oF). The amount of free water
that forms from the vapor is
45 lbm/MMscf- 16 lbm/MMscf = 29 lbm/MMscf.
Consequently, the total amount of water (W) condensed per day is:
29lbm H2 O 0.02 MMscf 0.58lbm H2 O
=
MMscf
day
day
M (lbm MeOH )
X 100%
M ( lbm MeOH ) + W ( lbm H2 O)
The mole fraction MeOH in the water phase is xMeOH in H2O = 0.071. The
distribution coefficient of MeOH in the gas is calculated at 33.03 oF (492.7oR)
by Equation (3), relative to the methanol in the water
KvMeOH = exp (5.706 - 5738(1/492.7oR) = 0.00263
(3)
39
The daily gas rate is 52.7 lbmol (= 2.0 104 scf / (379.5 scf/lbmol)), so that
the MeOH lost to the gas is 0.0098 lbmol (= 0.000187 52.7) or 0.314
lbm/day.
No condensate is formed in the pipeline, consequently there is no MeOH lost
to the liquid hydrocarbon phase.
Ex12.B.2.d. Total Mass of MeOH Needed. The total amount of MeOH
injected is the sum that in the vapor (0.314 lbm) condensate (0), and water
(0.079 lbm) = 0.393 lbm MeOH/day (0.06 gal/day) injection required to inhibit
the fuel gas line, with injection before the control valve as shown in Figure 29.
Ex12.B.3. Parallel Gas Expansion. Operating personnel sometimes suggest
that fuel gas lines be placed in parallel to provide more than one gas expansion as
shown in Figure 30. If one control valve becomes plugged with hydrates and shut
down, the second gas line is then opened while the first line is depressurized for
hydrate dissociation. In this manner, it is hoped that flow can be maintained in one
fuel gas line without the need for hydrate inhibition.
Conditions of hydrate formation on parallel gas expansion are exactly the same
as shown in Figure 26. The capital cost is doubled however, and there is the risk that
the parallel valve may become hydrated before the plug is removed from the initial line.
This solution technique addresses the effect of hydrate formation rather than its cause,
and should be considered less than optimal operating practice.
Ex12.B.4. Drying the Inlet Gas. If the gas inlet is dry, hydrate formation
cannot form due to insufficient water. It is good design practice to place both fuel gas
and instrument gas lines downstream of a TEG drying unit or a molecular sieve
adsorption tower. The design of a drying unit is outside of the scope of this
handbook, but it is readily available in standard texts on gas processing (e.g. Manning
and Thompson, 1991).
_____________________________________________________________________
Of the above four design methods to prevent hydrates in fuel gas lines, the
most satisfactory from the standpoint of expense and operating practice is to provide
dry inlet gas with a fuel gas line downstream of the TEG dryer. As Deaton and Frost
(1946, p. 41) stated in their classic study of hydrate formation and prevention:
The only method found to be completely satisfactory in
preventing the formation of hydrates in gas transmission lines is to
dehydrate the gas entering the line to a dew point low enough to
preclude formation of hydrates at any point in the system.
40
P1=1500 psia
P2=300 psia
T1=100oF
T2=33oF
P1=1500 psia
P2=300 psia
T1=100oF
Flowline #1
T2=33oF
Flowline #2
T2=33oF
41
period without growing to larger masses. While thermodynamic inhibitors are the
standard practice offshore, there are successful commercial instances of kinetic
control. The incentive for newer kinetic control methods is a substantial capital cost
reduction by the elimination of the need for offshore platform equipment, a small
operating cost reduction, and elimination of some environmental concerns. In the
future innovative methods of heat management through heating and insulation may
provide thermodynamic protection against hydrates.
Section II.G.1 discusses design and operation with thermodynamic inhibition
chemicals (methanol and monoethylene glycol). Section II.G.2 discusses design and
operation with kinetic inhibitors. Section II.G.3 summarizes the chemical inhibitor use
guidelines. Section II.G.4 shows the methods of heat management to retain a high
inlet temperature in the fluid region.
42
methods of Sections II.C and II.D, and are usually taken as operating expense losses.
Methanol loss costs can be substantial when the total fraction of either the vapor or
the oil/condensate phase is very large relative to the water phase. Sample economics
for methanol are provided in Section IV and in the following Case Study 7.
Makogon (1981, p. 133) noted that in 1972 the Soviet gas industry used 0.3
kg of methanol for every 1000 cubic meters of gas extracted. Norsk Hydro workers
(Stange et al. 1989) indicated that North Sea methanol usage may surpass the ratio
given by Makogon by an order of magnitude. The use of methanol in the North Sea
has become so expensive that alternatives to methanol injection are considered.
_____________________________________________________________________
Case Study 7. Methanol Recovery from the Water Phase
Paragon Engineering (1994) performed a study for DeepStar (DSII CTR 2211) of the impact of methanol recovery on offshore systems. As an evaluation scenario,
a conventional, shallow water platform was designed solely for methanol recovery in
100-150 feet of water, with methanol return lines 40-60 miles to deepwater subsea
wells. Figure 31 shows a block flow diagram for methanol recovery and injection.
Costs were determined for methanol recovery on the platform for eight cases
of methanol in the produced water. Table 3 shows results for four cases: 20wt% and
30wt% methanol in the free water phase, for (a) high water production in late field life,
and (b) low water production in early field life.
13,191
14,498
15
4,537
4,430
0.35
1,456
0.11
48,802
3,188
57
960
15,977
5.53
5,224
1.81
43
Gas Treating
Dehydration
Compression
& Metering
Oil/Gas/Water
Separation
Water
Oil/Gas to Sales
Pipeline
Oil
Oil Treating
Pumping
Metering
Water Treating
50 miles to Platform
12 Production Pipeline
4 Methanol Re-injection
Methanol
Storage
Methanol
Recovery
Facilities
Water Overboard
In all cases methanol was recovered as the overhead product from a 40 tray
distillation column. The bottoms methanol concentration was less than 1000 ppm so
that water could be dumped overboard.
Paragon Engineering also reported methanol losses which were greater than
anticipated in North Sea recovery systems from three Conoco facilities (4-5 gal MeOH
lost/MMscf), a Norsk Hydro recovery unit (29% MeOH losses), and an Amoco
Netherlands recovery unit (12% MeOH losses).
_____________________________________________________________________
Methanol recovery is possible from the vapor phase, using a cryogenic
recovery process, but this is seldom done due to the expense involved. Methanol can
be recovered from the condensate via a water-wash and subsequent distillation, but
this is also seldom done. Environmental concerns have a major impact on recovery.
44
Wellstream
Free Water
Knockout
Gas
Glycol Inj.
Nozzle
Bypass Valve
HXER
Water
Low Temp
Separator
Choke
Residue Gas
Water
Vapor
Lean Glycol
Filter
Glycol
Pump
Glycol-Oil
Separator
Oil to Stabilizer
Fuel
Gas
Glycol
Regenerator
Glycol-Glycol
HXER
Rich
Glycol
Methanol (MeOH)
Advantages
-easy to recover
-for plugs in wells and risers
-low gas &condensate solubility
Disadvantages
-costly to recover
-high gas & condensate losses
-too little is worse than none
-costly in condensate product
(See Table 13 Section IV.B.1.a)
46
Without Anti-Agglomerantes
Condensate
Hydrate Plug
Condensate
With Anti-Agglomerantes
Condensate
Hydrates in
Suspension
100
Not Tested
90
No Hydrate
Hydrate, No Plugs
80
Plugs
70
T = 0-4 oC
60
Watercut %
P = 70 bar
50
40
30
20
10
0
0
10
Wt% MeOH
15
47
70
WOR = 0.1 Ft3/Ft3
3.5
60
50
Temperature
2.5
Pressure Drop
40
2
30
1.5
20
Plugging
10
0.5
0
0
10
20
30
40
Time (min)
50
60
70
80
Temperature (oF);
Gas Consumption (mMol)
Gas Consumption
70
4
Gas Consumption
60
3.5
Pressure Drop
50
3
2.5
40
WOR = 0.1 Ft3/Ft3
30
1.5
20
No Plugging
10
0.5
0
0
50
100
Time (min)
150
0
200
Temperature (oF);
Gas Consumption (mMol)
Temperature
Pressure (psia)
10000
1000
(Tsubcooling)
100
il
qu
ib
m
riu
(l we
in
V
H-
Cooling
Teq
Hydrate
Onset
(Tonset)
Start Experiment
10
20
40
60
Temperature (oF)
80
100
gravity curve (Section II.C) or by HYDOFF (Section II.D), with hydrate formation to
the left and non-hydrate conditions to the right of the line. The horizontal line in
Figure 37 represents a cooling curve for hydrate forming mixtures, such as may occur
in a pipeline (Figure 7). The object of kinetic inhibition is to maintain the operating
condition of a pipeline as far as possible to the left of the Lw-H-V line without
formation of hydrate plugs during the residence time of the fluids in the flow line.
In Figure 37, subcooling (T) is the measure of the lowest temperature that
the system can be operated relative to the hydrate formation temperature at a given
pressure. The maximum value of T is determined by a laboratory and/or pilot plant
experiment, and the pipeline is operated at a smaller value of T. The value of T
appears to be pressure independent; however T does depend upon the polymer,
molecular weight, and the amount of salt, glycol, and alcohol present. Recent results
suggest that water residence time can be as long as 30 days without hydrate formation,
when the lowest temperature of the pipeline is at least 3oF less than the maximum
subcooling (Tmax) with a good kinetic inhibitor.
Kinetic inhibitors are commonly polymers with several chemical formulas
shown in Figure 38. Each of the chemicals has a polyethylene backbone, connected to
pendant groups typically containing an amide (-N-C=O) linkage, frequently within a
five- or seven-member ring. As the inhibitor adsorbs on the hydrate crystal, the
pendant group penetrates specific sites (cages) of a hydrate crystal surface while the
polymer backbone extends along the surface. In order to continue growing, the crystal
must grow around the polymer; otherwise crystal growth is blocked.
Figure 39 is a schematic of one type of kinetic inhibition. Adsorption of three
kinetic inhibitor polymer strands are shown on a hydrate crystal surface. The filled
stars on each polymer strand represent the pendant groups which dock at the empty
star sites on the hydrate crystal surface. As indicated on the figure, the subcooling
T is directly proportional to the liquid-crystal surface tension (), but inversely
proportional to the length (L) between polymer strands.
If the amount of polymer adsorption increases, the distance L between the
strands decreases, resulting in an increased subcooling T performance. Conversely,
if the amount of inhibitor adsorption decreases (due to depletion by multiple small
hydrate crystals) the distance L between polymer strands increases, resulting in a
smaller subcooling T.
One of the first kinetic inhibitors developed was polyvinylpyrrolidone (PVP), a
polymer whose structure is shown in Figure 38. Several companies have adopted the
use of PVP in onshore fields with a small subcooling (T) and short residence time.
Initial field tests of kinetic inhibitors were reported by ARCO (Bloys et al.,
1995) and Texaco (Notz et al., 1995). Bloys reported the effectiveness of 0.3-0.4
wt% VC-713 in a 17 day test in a North Sea pipeline. The pipeline (8 in. diameter, 9.4
48
PVCap
H3C
vc-713
NCH3
tal
ys
Cr
Po
lym
er
Su
rfa
Ch
ce
ain
4
T
CL
km long) had a flow rate of 20 MMscf/d, 0.5 bbl/MMscf condensate and 0.2
bbl/MMscf condensed water at a subcooling between 1oC and 9oC. Bloys suggested
that economics were very favorable for new developments, but marginal for retrofits
of systems with traditional inhibitors such as monoethylene glycol.
Texacos Notz et al. (1995) indicated successful use of polyvinylpyrrolidone
(PVP) in several wells and flow lines in Texas and in Wyoming, concluding that PVP
was in routine use in some Texaco fields. Notz further reported that PVP (at less than
1 wt%) was effective in replacing methanol (at concentrations from 10 to 60 wt% in
free water) resulting in savings of as much as 50%. See Texaco Case Studies C.13
and C.14 in Appendix C.
Rule-of-Thumb 12. PVP may be used to inhibit pipelines with subcooling less
than 10oF for flow lines with short gas residence times (less than 20 minutes).
Rule-of-Thumb 12 comes from Texacos Reliability Engineering: Gas Freezing
& Hydrate Study, a handbook for field personnel by Todd et al. (1996) which reflects
Texaco operating kinetic inhibitor practice with approximately 30 flow lines from their
Brookeland field.
Kinetic inhibitors more effective (but more expensive per pound) than PVP
(illustrated by the other chemical formulas in Figure 38) have a seven-member ring
pendant group in place of the five-member PVP pendant ring. The better kinetic
inhibitors provide additional subcooling with long water residence times.
Rule-of-Thumb 13: VC-713, PVCap, and co-polymers of PVCap can be used to
inhibit flow lines at subcooling less than 18oF, with water phase residence times
up to 30 days.
Rule-of-Thumb 13 comes from commercial use of kinetic inhibitors, as
indicated in the below case study.
_____________________________________________________________________
Case Study 7: North Sea Use of New Inhibitors
On July 22, 1996 British Petroleum (BP) initiated continuous commercial use
of kinetic inhibitors (called threshold hydrate inhibitors, THI) in flowlines in the West
Sole gas export lines (Argo et al, 1997). This followed from an extensive set of field
trials carried out in the Ravenspurn to Cleeton wet gas line (Corrigan et al., 1996).
BP began THI use in a 16 inch I.D., 13 mile long pipeline from three
Ravenspurn platforms to Cleeton. At the time of the trial the maximum flow rate was
195MMscf/d. For the purpose of the trial the flow rate was cut back to 90mmscf/d to
put the line as far into the hydrate region as possible (16oF of subcooling). Three trials
were carried out, all of which were successful. The trials included extensive periods of
49
shut-in, up to 7 days with successful restart. A typical water production rate was 1.6
bbl/MMscf with a line pressure of 1088 psia and a low temperature of 48oF. The THI
dose rate was 3000-5000 ppm based on the free water phase. See Corrigan et al.
(1996) for further details.
Currently two lines (24 inch and 16 inch I.D., 35 miles long) from West Sole
A,B, and C and Hyde are being inhibited with THI. Water residence times can be as
long as 2-3 weeks, and the lines are 11oF inside the hydrate region at operational
conditions. The gas is very lean producing very little condensate. Water content is
low and free water comes mainly from condensation. Due to the low amounts of
water and condensate, this is an atypical case, but nonetheless represents a severe test
for kinetic inhibitors.
Water production from all four West Sole platforms is 150-200 bbl/d, or about
0.3 bbl/MMscf with 250 MM scf/d total produced from the 3 West Sole platforms and
the remainder from the Hyde platform. The condensate rate is also 0.3 bbl/MMscf.
The THI pumping rate per platform is 2-3 liters/hr of solution which contains about
15wt% active ingredient. The target injection rate is 3000 ppm based on the free
water phase.
_____________________________________________________________________
_____________________________________________________________________
50
4. Determine the water production profile over field life (see Table 6 example).
5. Consider the pipeline topography along the ocean floor to determine where water
accumulations will occur at dips, resulting in points of hydrate formation.
6. Simulate the pipeline pressure-temperature profile using a simulator such as
OLGA or Pipesim to perform hydraulic and heat transfer calculations in the well,
flow lines, and separator over the life of the field.
7. Determine the water residence times in all parts of the system, especially in low
points of the pipeline.
8. Estimate the subcooling T (at the lowest temperature and highest pressure)
relative to the equilibrium line over all parts of the system, including fluid
separators and water handling facilities. List the parts of the system which require
protection.
9. If T < 14oF, consider the use of kinetic inhibitors. If T > 14oF, consider the use
of standard thermodynamic inhibitors or anti-agglomerants (no one has used antiagglomerants commercially as of January 1, 1998).
10. Perform economic calculations (capital and operating expenses) for four options
(a) drying, (b) methanol, (c) monoethylene glycol, and (d) kinetic inhibitors.
11. Determine if inhibitor recovery is economical.
12. Design the system hardware to measure: (a) temperature and pressure at pipe inlet
and outlet (b) water monitor for rates at receiving facility, and (c) the below
chemical check list
a) Has the inhibitor been tested with systems at the pipeline temperature and
pressure?
b) Consider the environmental, safety, and health impact of the chemical.
c) Determine physical properties such as flash point (should be < 135oF),
viscosity ( should be <200 cp at lowest T), density, and pour point ( should
be >15oF).
d) Determine the minimum, maximum, and average dosage of inhibitor.
e) Determine the storage and injection deployment methods.
f) Determine the material compatibility with gaskets, seals, etc.
g) Determine compatibility with other production chemicals.
h) Determine the compatibility with the process downstream including cloud
point, foaming, and emulsification tendencies.
51
_____________________________________________________________________
52
_____________________________________________________________________
Case Study 8. Pipeline Temperature with Heat Loss
Figure 40 (from DeepStar Report CTR 223) shows an offshore pipeline
temperature as a function of length, at various values of U, between the pipeline inlet
temperature (140oF) and a separator 50 miles away. The pipeline in the figure was
assumed to be 50% buried and had a water flow of 1,527 bbl/d, a gas flow of 30.76
MMscf/d, and an oil flow of 22,723 bbl/d.
In Figure 40 the lowest, dashed line shows the temperature of the ocean with
length. The upper lines represent the pipeline temperature with no heat loss through
the pipe wall, with the temperature drop being due to expansion. However, with heat
loss through the pipewall, the temperature drops dramatically. With overall heat
transfer coefficients of U = 0.17 and U = 3.3 BTU/hr-ft2-oF, the separator temperature
is 70oF or 50 oF, respectively. Hydrates can easily form at these temperatures,
particularly at the higher pressures (densities) necessary to make pipeline transport
economical. It is concluded that a lower heat transfer coefficient is needed to prevent
hydrate formation.
_____________________________________________________________________
The temperature profiles in the above case study are for a flowing pipeline. If
the pipeline were shut-in, the system would rapidly cool to the ambient conditions
represented by the dashed line at the bottom of Figure 40. At the low ambient
temperatures, hydrate problems are particularly severe and blockages may occur,
particularly when the system is re-started.
If hydrates form in an insulated pipeline, the pipeline may be depressurized to
achieve a hydrate equilibrium temperature just above 32oF, so that heat will flow into
the hydrates from the ocean, which has a temperature around 40oF. In such cases, the
insulation is a hindrance or barrier which prevents heat flow from the ocean, making
53
160
Little Heat Loss
Through Pipewall
140
120
100
Heat Loss
Through Pipewall
80
60
Ambient Conditions
40
20
0
0
50000
100000
150000
Pipeline Length (ft)
200000
250000
300000
54
Insulation
Insulation
(Max. 3 in.)
Steel Flowline
110
Flow to Each Pipeline
22,723 Bbl/day oil & condensate,
30.76 MMSCF/D gas, and
1,527 Bbl/D water
105
Temperature (oF)
100
95
Two Pipeline Flows
90
85
80
75
70
0.4
0.6
0.8
1.2
1.4
1.6
1.8
obtain a given riser temperature, or the second flowline will provide a higher riser
temperature for a given insulation.
Figures 43 and 44 (from DeepStar Report CTR A601-a) compare the cost of
the three above types of insulation for water depths of 6000 ft. over 60 miles at oil
production rates of 25,000 and 50,000 bbl/d, respectively. If an average U = 0.3
BTU/hr-ft2-oF is required with a flowline pressure of 4000 psia, bundled flow lines are
more cost effective.
II.G.3.b Pipeline Heating Methods. DeepStar Report CTR A601-b concludes
that, where pipeline depth precludes depressurization below the hydrate formation
pressure, heating may be the only option to clear a hydrate plug. Yet as noted in
Section I, heating a hydrate plug can be very dangerous. DeepStar Report CTR
A601-c concludes that pipeline heating will be very expensive, at least 1MW of
power is required for a 20oC (36oF) increase of a 10 inch pipeline 15 miles long.
In the future Statoil will use heating more extensively in order to reduce the
amount of methanol or other chemicals used. Bundles will be used in 1998, and direct
heat thereafter. The Chevron/Conoco Britannia project will start in the North Sea in
1998 using a bundled line to heat fluids. The three common means of heat
management are (a) bundling hot water lines (for 10 km and return) in production lines
to prevent hydrate formation (b) Combipipe (shown in Figure 45) for induction
heating, with current flowing through 3 cables outside of pipe but within insulation,
with corrosion protection,), (c) direct electrical heating for 50-60 km long lines
(shown in Figure 46) in which the pipeline is the primary conductor with a current
return line at 1m in parallel to the pipeline. It should be noted however, that such
heating tools are in the planning stage and commercial use has yet to be documented.
55
900
14" Non-Jacketed
2x10" Non-Jacketed
14" PIP
3x8" PIP
3x8" Bundled
3x8" Vacuum Tube
3x8" Non-Jacketed
2x10" PIP
2x10" Bundled
800
700
Cost($/ft)
600
500
400
300
200
100
0
0
0.1
0.2
0.3
U-Value (Btu/hr-sqft-oF)
0.4
0.5
0.6
1200
18" Non-Jacketed
2x12" Non-Jacketed
18" PIP
3x10" PIP
3x10" Bundled
3x10" Non-Jacketed
2x12" PIP
2x12" Bundled
1000
Cost($/ft)
800
600
400
200
0
0
0.1
0.2
0.3
U-Value (Btu/hr-sqft-oF)
0.4
0.5
0.6
Hot Water
Input Line
B) Combi- Pipe
Thermal
Insulation
Insulation
Pipeline Pipeline
Flowline
Insulation
Cold Water
Return
Heating
Cables
Pipewall with
Corrosion Protection
Electric Current
Pipeline
1 meter
Current Return Wire
Electric Current
COMP.
SEP.
Platform
Ocean
- Depth 6000 ft
Well with
X-Mas Tree
Transport Pipeline
(2-60 miles in length)
Mudline
Downhole Safety
Valve
Export Flowline
Riser
water residence times at all points in the system. Account for both normal cooling
(e.g. in pipelines as in Example 2 of Section II.A) and Joule-Thomson expansions
across restrictions (e.g. in wells, chokes, and control valves as in Section II.F).
3. Estimate the subcooling T (at the lowest temperature and highest pressure) at
each point in the process relative to the hydrate equilibrium curve. Hydrates may
form in systems with subcooling Ts less than 2-4oF.
4. Where subcooling is unavoidable, determine the type of hydrate inhibition, such as
chemical inhibitor injection (Sections II.G.1, II.G.2, II.G.3, particularly Table 5),
or heat management (Section II.G.4). Choose the inhibition method with regard to
both prediction ability and operating experiences. Consider providing a heater
prior to the platform choke and separator.
5. Eliminate subcooling points of likely hydrate formation. Design pipelines to
minimize buckling and protrusions from mudlines which might promote cooling.
6. Design large pressure drops with either dry gas or expansions at high temperature
points in the process. Where large expansions of wet gas are unavoidable, (e.g. at
choke valves) provide methanol injection capability upstream of the restriction.
7. Eliminate points of water accumulation, such as upslopes in pipelines or S
configurations in risers. Where pipeline topography ensures water accumulations
(e.g. upslopes in lines, etc.) provide for frequent pigging and consider placing
methanol injection prior to the accumulation points.
8. Eliminate points of hydrate accumulation from a mechanical perspective. Hydrate
crystals in a line may be considered to accumulate (and plug) wherever light sand
particles might accumulate, such as at blind flanges at turns, elbows, screens and
filters, upstream of restrictions etc. Avoid unnecessary bends. Bend radii less than
5 times the pipe diameter should be avoided to facilitate coiled tubing entry. A
riser tube radius should be from 20-80 ft.
9. With a high probability hydrates will form over the system lifetime. Provide
hydrate remediation methods (see Section III for justification) in the design.
a) For pipelines, safe remediation often implies depressurization from both
ends of a hydrate plug. Optimally, multiple access points in a pipeline (see
b) are invaluable in locating and remediating hydrate and paraffin plugs.
Alternatively dual production lines should be used to provide for
depressurization of wellheads from the upstream side of a pipeline plug.
As a second best method, provide for depressurization through a wellhead
service line (for corrosion, paraffin, or hydrate inhibitor injection) with
bypass capability for checkvalve(s) at the point of injection. As a minimum
56
57
Fiqure
48
Yorkover
Pre-Installed
(From
Deepstar
Access
A-208-1,
Ports
on
1995)
PipeLine
Vessels
\
access Port
Coiled
Functions
Tubing
Entry
-Surface
-suLxeo.
Inject
Vent
Fluid
Fluids
Into
From
Pipeline
- Hydrate Renoval
Pipeline
An exception was the LASMO Staffa subsea field in the North Sea, which was abandoned in 1995
due to low production problems with combined waxes and hydrates. See Case Study C.6. for further
history on this field, which included a 1 mile flowline replacement.
58
Case/Operator
Field/
Region
Line
Size
Line
Type
WD
(ft)
1. Placid
GC 29
16"
Gas Cond.
200 ft
Time
1989 Complete
None
Flowing
Removed?
Current
Prev. Method
Depressurize
Gas Dehydration
MeOH Inj.
2. Chevron
Wyoming
4"
Gas Cond.
Flowing
Insulation
3. Chevron
GOM
Gas Lift
Winter Complete
None
Depressurize
Heat MeOH
Flowing
Inj. MeOH
Inj. Lines
4. Chevron
Oklahoma
4"
Gas Sales
MeOH Inj.
Inj. MeOH
Vary Flow Rate
1995
Partial
None
Depressurize
Remove Restriction
Inj. MeOH
@ Flow Meter
Heat Gas
MeOH during
Winter
5. Chevron
Canada
6"
Gas cond.
Winter Complete
None
Export
Shut in for
Depressurize
Depressurize after
Several Days
Heat w/
24 Hours S/I
Welding Rig
6. Lasmos
North Sea
8"
Multiphase
1994 Complete
MeOH
Flowing
Replaced 2km
Same as before
8. Texaco
9. Texaco
GB 189
GC 6
2-3/4"
3/4"
Gas
Gas
Instrament
Valve
725 ft
600 ft
1995 Complete
1992
Partial
Complete
None
None
None
Flowing
Flowing
Flowing
Depressurize
Inj. MeOH
Inj. MeOH
Gas Dehydration
Depressurize
Inj. MeOH
Inj. MeOH
Gas Dehydration
Inj. MeOH
Case/Operator
Field/
Region
Line
Size
Line
Type
WD
(ft)
Time
16"
Gas Cond.
1990
MeOH
Flowing
Removed?
Current
Prev. Method
Depressurize
MeOH Injection
Inject MeOH
11. Marathon
EB 873
1995
partial
Inadequate
Flowing
MeOH
12. Philips
Maintain
MeOH
MeOH Inj.
Depressurize
MeOH Inj.
MeOH Inj.
Dehydrate Cond.
Depressurize
Comb. of KI
1978 Complete
MeOH
Pig Stuck
Pigging
13. Texaco
Inject more
Wyoming
Gas
1995 Complete
MeOH
Field Test
and MeOH
14. Texaco
Gas
1995 Complete
MeOH
Field Test
Depressurize
Comb. of KI
and MeOH
15. Statoil
Tommeliten
6"
Gas Cond.
1994 Complete
MeOH Inj.
Flowing/
Depressurize
Continue
Shut-in/
Inj. MeOH
MeOH Inj.
Re-start
16. Statoil
Tommeliten
6"
Gas
MeOH
Field Study
Condensate
17. Statoil
Tommeliten
6"
Gas
Depressurize
Inj. MeOH
None
Field Study
Depressurize
MeOH
Flowing
Depressurize
Ensure Proper
MeOH Inj.
MeOH Inj.
Condensate
18. Oxy
North Sea
Gas
Condensate
Complete
Field/
Region
Line
Size
Line
Type
WD
(ft)
Time
Case/Operator
19. Amoco
North Sea
Gas Export
NA
20. Petrobras
Brazil
Manifold
NA
Complete
None(Dry)
Ethanol
Flowing
Start-up
Removed?
Current
Prev. Method
Depressurize
Ensure
MeOH Inj.
Dehydration
Depressurize
Drain Manifold of
Ethanol Inj.
21. Exxon
California
Well
NA
1989 Complete
None
Drilling
22. Exxon
Gulf of Mex
Well
NA
1989 Complete
None
Drilling
23. Exxon
S. America
Well
NA
1993 Complete
None
Testing
Coiled Tubing
Hot Glycol
24.Exxon
Gulf of Mex
Well
NA
1993 Complete
Methanol
Shut-in
Abandoned
4"
Gas/Condns Land
1997 Complete
Methanol
Shut-in
Depressurize
4"
Gas/Condns Land
1997 Complete
Methanol
Shut-in
Depressurize
4"
Gas/Condns Land
1997 Complete
Methanol
Shut-in
Depressurize
59
60
Gas Pipeline
Flow
Hydrate
Water
Initial
1 Hour
3 Hours
5 Hours
Partial Plug
Complete Plug
Condensate
Pipeline
Hydrate Plug
61
50b)
Typical
50a)
Time
Time
62
63
64
300
Water arriving as slugs - water
simultaneously being processed
from slug catcher
250
Sphere Arrived
200
High DP
MeOH Injected
150
100
Water arrival
@ 0.6bbls/mmscf
50
Water processed
Start of Trial
0
0
4
Time (days)
70
60
Differential Pressure (psi)
High DP maintained
while hydrate melts,
slug flow.
High DP due
to hydrates.
MeOH Injected.
50
40
Normal line DP
at a flow rate of
9 mmscf/d
30
20
10
0
4
Time (days)
the near-optimal fit of H2S in the small hydrate cavities (see Sloan, 1998, Chapter 5).
The same statement is not true about the other acid gas, carbon dioxide.
(3) Pressure Drop Increases. Pressure drop (P) will increase and flow rate
will decrease if the pipe diameter is decreased by hydrate formation at the wall in a gas
line. Since P in pipes is proportion to the square of turbulent flow rates, the change
in P is more sensitive than the change in flow. With hydrates however, a large
restriction may be necessary over a long length before a substantial pressure drop
occurs. For example, if a hydrate decreased the effective pipe diameter from 12 to 10
inches over a 1000 foot section, the P would only increase 0.05 psi with 10 MM
scf/d of gas operating at 1000 psia and 39oF. In addition, the P trace usually contains
substantial noise, making it difficult to observe trends.
Statoils Austvik (1997) suggested that, while a gradual pressure increase in
hydrate formation will occur for gas systems, a gradual pressure increase is not typical
for a gas and oil/condensate system. In gas and oil/condensate systems, Statoils
experience is that, without advance warning the line pressure drop will show sharp
spikes just before blockages occur. Figure 52 shows the BP field experiment
(Corrigan et al., 1996) with methanol stoppage in a North Sea gas pipeline with little
condensate or free water; in that figure step changes and spikes in P are more
prevalent than a gradual increase.
In contrast, recent DeepStar Wyoming trials (Hatton et al., 1997) show both
gradual and spiked pressure drops, in a gas-condensate field. In Case Studies C.25,
26, and 27 the pressure built gradually upstream of a plug, while pressure spikes
downstream indicated hydrate sloughing from the wall, with agglomeration and
bridging downstream.
However, the DeepStar tests had five pressure sensors spaced at intervals of a
few thousand feet. As indicated in the calculation two paragraphs earlier, with only
two pressure sensors at either end of a line, severe hydrate wall buildup must occur in
order to sense a significant pressure drop, due to the dampening effect of the gas.
Most pipelines are likely to experience hydrates as sudden, extreme pressure drops.
(4) Acoustic Sensing Along Subsea Pipeline. DeepStar IIA Report A212-1,
Paraffin and Hydrate Detection Systems, by Paragon Engineering and SwRI indicates:
The only hydrate crystal detection instrumentation suitable for subsea use
identified by this survey is sand monitoring instrumentation...In a limited number
of laboratory tests, the Fluenta acoustic sand monitor has detected hydrates.
However, a detailed study using the Fluenta monitor has not been conducted.
A typical acoustic sensor from Fluenta is shown in Figure 53. Over 280 units
have been installed to detect sand impingement on pipe by clamping the unit onto the
flow line downstream of a 90o elbow or 45o bend. At flow rates as low as 3 ft/sec the
65
Figure 53 - SAM
400s Pwtide
Detector
Underwater
Electronic
Mateable
Stainless
Connection
Cable
Length
TBO
Steel
Pad
unit can detect 50 micron sand particles. Such units are rated for water depths of
4000 ft. and may be diver-assisted or ROV installed with an underwater cable.
Acoustic sensors quantify the hail on a tin roof sound typical of hydrate
particles impinging on a wall at a pipeline bend. However, this unit has yet to be field
tested in a subsea application. The initial background note of the Paragon Engineering
and SwRI (April 1996) study presets a caution which still exists:
This survey did not identify any proven hydrate or paraffin deposition
measurement instrumentation for subsea multiphase flow lines or any other
type of fluid transmission lines. For gas transmission lines, ultrasonic
instrumentation has worked in specific applications and for single-phase liquid
or gas lines, an acoustical/pigging system has been proposed.
66
contents. This technology is over 50 years old, and is commonly used in the chemical
industry for level control in high pressure, non-visual systems.
Because densities of hydrates and water are very similar gamma-ray
densitometry alone cannot discriminate between the two; at best gamma-ray
measurements indicate changes in conditions which could be hydrates. In combination
with the temperature downstream of the densitometer (such as at the platform start-up
heater as shown in Figure 55) hydrate formation can be discriminated.
Hydrates are indicated by a low temperature in addition to an increase in
density, whereas the water temperature is similar to that of gas. A high density and
low temperature mass in the pipeline is likely to be hydrates, whereas a slug of high
density but without a temperature drop is probably water. As shown in the blockage
removal Section III.C, even small pressure reductions cause hydrate dissociation,
which results in heat being removed from the condensed phases and lower
temperatures. The temperature sensing requirement makes it difficult to use the
densitometer subsea, due to high hydrate plug velocities damaging thermowells.
67
Thermocouple
Start-up
Heater
Platform
Choke
Gas
From
Pipe
line
Gamma
Densitometer
1st Stage
Separator
Platform
To Comp./Dehydration
68
A coiled tubing (see Section III.C.4) was run down the tubing string and
ethylene glycol was jetted to remove the blockage. Jetting operations took two days,
and the entire remedial operation took one week to complete.
____________________________________________________________________
For hydrates in a well, Statoil has used a broach similar to that shown in Figure
56, lowered on a wireline to determine the blockage depth. A similar wireline heating
tool has been used by Statoil for hydrate dissociation in wells; in this case, the hydrate
blockage can be located and dissociated with the same tool. Heating a hydrate
blockage is not recommended, unless the end is determined, for safety reasons shown
in Figure 2b and accompanying discussion. However, when the hydrate end is
discernable, heating from one side of the blockage may be a viable option.
In a flowline a wireline, reach rod, coiled tubing, or fiber optics may be used to
locate a plug. However, this detection method is currently limited to the first 10,000
ft. from the platform and requires mechanical intervention in the flowline.
69
Distance L
Plug
Upstream
Downstream
2/3 L
1/3 L
2420
1760
1750
1740
1730
2380
1720
2360
1710
1700
2340
1690
2320
1680
Subsea Pressure
1670
Topside Pressure
2300
1660
0
10
15
Time (hours)
20
25
2400
Two points should be emphasized about this case study: (1) safety and (2) rate.
First, the small diagnostic pressure reduction was made from one side of the plug, well
above the hydrate dissociation pressure, to prevent safety problems associated with a
plug projectile (Section I) propelled by a high differential pressure.
Second, pressure recovery was very slow, averaging about 3psig/hr. This slow
rate may not be noticed if pressure is not carefully monitored by platform personnel,
who may be inclined to discount a slow changes. The slow rate of pressure change
was thought to be due to the fact that most of the line contained liquid, causing the
apparent plug porosity to be about 1000 times smaller than that for gas flow.
____________________________________________________________________
Statoil, the company with the most methodical, documented experience in
hydrate remediation, prefers the above method of plug location. The method locates
the blockage center and the relative volumes upstream and downstream of the
blockage(s). The disadvantage of the method is that it does not give any idea of the
length of the blockage, how close the blockage is to the platform (due to the unknown
plug porosity), or how multiple plugs may affect this location determination. Statoil
locates the plug-platform proximity by inhibitor back-injection (see Rule-of-Thumb
18) or by back-pressurization, as shown in the following method.
Pressure Increase. To locate a complete pipeline blockage one method is to
measure the pressure increase as metered amounts of gas are injected at the platform.
The rate of pressure increase is correlated to the rate of gas input to determine the
length for a given diameter line between the platform injection point and the blockage.
____________________________________________________________________
Example 13. Back-Pressurization to Determine Plug Location. An offshore 16 inch
ID gas pipeline is in full production when a hydrate plug occurs, blocking flow for a
0.6 gravity gas. The line is shut-in and the pipeline cools to the ambient temperature
of 39.2oF. Before hydrate dissociation can begin to take place, the approximate
location of the plug end should be obtained to determine the best remediation method
and evaluate safety concerns.
One standard location procedure is back-pressurization. This method consists
of pumping a known amount of gas into the pipeline and measuring the change in
pressure over time. From these pressure values, an estimate of volume can be
obtained through PV=ZnRT.
The following assumptions are made for the problem:
1. no porosity of the plug,
2. no liquid in the pipeline,
3. none of the injected gas condenses,
4. constant temperature throughout the pipeline,
70
ZnRT
P
where
Z = gas compressibility as a function of P,T, and gas composition. Values
obtained through an equation-of-state or from gas gravity compressibility
charts (Figures 23-7,8,9 of the GPSA Engineering Handbook (1994))
n = value obtained from data (data table below)
P = corresponding pressure for n (data table below)
R = 10.73 (Universal Gas Constant in units of psia, oR, lbmol, ft3)
T = 498.87oR (seafloor temperature)
Five data points are averaged to estimate the volume of the pipeline between
the hydrate plug and the platform. The first data point calculation is as follows:
A line pressure of 400 psia is attained after 60.76 minutes when 297 lbmoles of
gas have been pumped into the line. The gas compressibility is estimated at 0.915
from Figures 23-7,8,9 of the GPSA Engineering Handbook (1994). The pipeline
volume is estimated as:
ZnRT
(.915)(297)(10.73)(498.9)=3637 ft 3
V=
P
(400)
The first estimate of the pipe volume down stream of the plug is 3637ft3.
Estimated Pipeline Volumes Between Platform and Plug
Data Point #
Time (Minutes)
Pressure
Est Volume
(psia)
(ft3)
60.76
400
3637
1
96.58
600
3664
2
144.39
850
3667
3
198.61
1100
3662
4
300.01
1500
3663
5
Avg Volume (Platform to Plug
71
3658
This same calculation is summarized for four other data points, in the above
table. The average approximation for the volume after the hydrate plug was 3658ft3.
The cross-sectional area of the pipeline is calculated, in order to estimate the pipeline
length between the plug and the platform. The pipeline cross-sectional area is
A=
1 ft 2
D 2 16 2
=1.396 ft 2
=
=201.06in 2
2
4
4
144in
59a)
59b)
Strain/Pressure(bar)
7
6
5
4
3
2
1
0
1
1.5
2.5
3.5
Clear
ViscoHard
Elastic
Visco - Elastic
Clear
4.5
platform end of the flowline is pressurized inducing a hoop strain, sensed by the
pipeline caliper. The internal pressure causes a hoop strain that results in an outward
movement of the caliper which varies with the wall deposits of the pipe. Lack of hoop
strain across a section of pipe would indicate a blockage. The signal is transmitted to
a work boat at the surface.
This method was successfully used in the North Sea on an 8-inch, 15 km long
flow line. Results of the strain gage are shown in Figure 59b for 20 points at various
lengths along a line blocked with paraffin. Points 13, 14, and 15 are shown to be
blocked with hard plugs, between visco-elastic plugs (points 15-18 and 3-13) at either
end. The map in Figure 59b was in agreement with the contents of the flow line when
it was replaced. Recovery and deployment of each measurement required 1-2 hours.
Due to necessity for ROV deployment, this method yet to be used to locate a hydrate.
73
Applications of the above methods can be further divided into three cases: (a)
partial blockage, (b) total blockage without substantial liquid head, and (c) total
blockage with a liquid head. The following discussions concern only the final two
cases. It is assumed that any indication of a partial blockage will be promptly treated
with massive doses of methanol, the most effective inhibitor. Combinations of the
above methods are simultaneously tried.
Rule of Thumb 19. Regardless of the method(s) used to dissociate the hydrates,
the time required for hydrate dissociation is usually days, weeks, or months.
After a deliberate dissociation action is taken, both confidence and patience are
required to observe the result over a long period of time.
Often it is suggested that corrective actions be changed almost hourly when
immediate results are not observed. Rapidly changing corrective actions, results in
thrashing without significant effects on plug removal. The waiting aspect of plug
removal is frequently the most difficult for platform operating and engineering
personnel, who are accustomed to producing results on a continuous basis. Typical
times of days or weeks are required for plug removal as indicated by Appendix C case
studies. Measurements such as pressure drop across the plug are continuously
monitored and changed deliberately, only after some time has passed to gain assurance
of initial method failure.
Rule of Thumb 20. When dissociating a hydrate plug, it should always be
assumed that multiple plugs exist both from a safety and a technical standpoint.
While one plug may cause the initial flow blockage, a shut-in will cause the
entire line to rapidly cool into the hydrate region, and low lying points of water
accumulation will rapidly convert to hydrate at the water-gas interfaces.
74
plug is greater than the dissociation pressure. Before that point is addressed, a
conceptual picture of hydrate provides some key points in the dissociation process.
III.C.1.a Conceptual Picture of Hydrate Depressurization. When a
hydrate plug occurs in an ocean pipeline, the pressure-temperature conditions are
illustrated in Figure 60. To the left of the three phase (LW-H-V or I-LW-V) lines
hydrates or ice can form, while to the right only fluids can exist. Because the lowest
ocean temperature (39oF) is well above the ice point of 32oF, ice formation (which
could block flows) is not a normal operating concern. When hydrates form, flow is
blocked so that the plug temperature rapidly decreases to the ocean floor temperature
of 39oF at the pipeline pressure. Figure 60 shows the pressure-temperature conditions
of a pipeline hydrate plug at point A in the two-phase (H-V) region, in which liquid
water has converted to hydrate.
Pressure reduction is accompanied by a temperature decrease at the hydrate
interface. If the pipeline is rapidly depressured without heat transfer, Joule-Thomson
(isenthalpic) cooling (line AB) at the hydrate may worsen the problem. If the pressure
is reduced extremely slowly, isothermal depressurization (line AC) results. Usually an
intermediate pressure reduction rate causes the hydrate interface temperature to be
significantly less than 39oF, causing heat influx from the ocean to melt the hydrate at
the pipe boundary.
With rapid or extreme pressure reduction, the hydrate equilibrium temperature
will decrease far below 32oF, for example to -110oF for a methane hydrate depressured
to atmospheric pressure. In this case water from dissociated hydrate will rapidly
convert to ice below the solid-liquid line (I-LW-H shown in Figure 60). If ice
formation occurs with hydrate dissociation, then the question arises, How will the ice
plug dissociation rate compare to the hydrate dissociation rate in an ocean pipeline?
In 1994-1997 field studies, over 20 hydrate plugs were intentionally formed
and removed from a 6 inch North Sea line in the Tommeliten Gamma field. In both
laboratory and field studies these plugs were found to be very porous (>50%) and
permeable. Porous, permeable hydrates easily transmit gas pressure while still acting
to prevent free flow in the pipeline. When the pressure was decreased at both ends of
a highly porous hydrate plug, the pressure decreased throughout the entire plug to an
almost constant value. The dissociation temperature at the hydrate front is determined
by the pipeline pressure. The depressurization results in a uniform hydrate dissociation
temperature which is in equilibrium with the LW-H-V line pressure in Figure 60,
predicted by the methods of Section II.C and II.D.
Pipeline depressurization reduces the hydrate temperature below the
temperature of the ocean floor (39oF for depths greater than 3000 ft.). Heat flows
radially into the pipe, causing dissociation first at the pipe wall as shown in Figure 61.
Radial hydrate dissociation controls plug removal, because the pipe diameter (less than
75
B
HYDRATES
V
I-H-
HLw
T = 0
C
I-Lw-V
Pressure
H = 0
I-Lw-H
ICE
Temperature
NO HYDRATES
Heat
B) Pipeline
Longitudinal
View
Water
Heat
Heat
2 ft.) is typically at least an order of magnitude less than the length of a hydrate plug
(frequently more than 50 ft.) in a pipeline.
The radial dissociation concept presents a contrast to previous longitudinal
dissociation concepts of non-porous hydrates, in which depressurization from both
ends was supposed to result in dissociation progressing from the plug ends toward the
middle (Yousif, et al., 1990; DeepStar Report CTR IIA A208-1, 1995). As
diagrammed in Figure 62 when the temperature of the hydrate is lower than that of the
ocean floor, heat flows radially into the system, causing dissociation along the entire
length. Of course some plug dissociation occurs at the ends, but due to much smaller
dimensions the radial dissociation (which occurs simultaneously along the plug length)
controls blockage removal.
Figure 62 shows a cross section of a pipeline hydrate plug that has been
depressured to provide an equilibrium temperature just above 32oF. Such a pressure
corresponds to about 450 psia for a pure methane gas, but much lower for a natural
gas, as predicted by the methods of Sections II.C. and II.D. Figure 62a shows an
inner hydrate core enclosed in a water layer, which results from hydrate melting. The
water layer is adjacent to the pipe wall. Figure 62b shows the temperature profile
from the ocean temperature of 39oF at the pipe wall, to the hydrate dissociation
temperature (set by the line pressure to a point just above the ice point) where it
remains uniform throughout the hydrate layer. As a result, the radial disappearance of
the two-phase water+hydrate boundary (X1) determines the disappearance of the final
solid and eliminate the flow obstruction.
Because hydrate plug detachment occurs first at the pipe wall, a partiallydissociated plug will move down the pipeline when the line is re-started, only to result
in a later plug at a pipeline bend, depression, or other obstruction. The second
blockage by the plug can be more compact than the first, for example if there is
substantial momentum on impact at the bend. This phenomena relates to Rule-ofThumb 19, indicating that one of the most important aspects of plug removal is
patience to allow time for total dissociation.
In the above conceptual picture, it is assumed that the pipeline is exposed to
turbulent, deep ocean water so that the pipe wall temperature is constant at 39oF. If a
line is insulated, hydrate dissociation becomes much more difficult because the
insulation which prevented heat loss from the pipe in normal operation will prevent
heat influx to the pipe for hydrate dissociation. Alternatively, if the pipe is buried in
the ocean floor, the pipe wall temperature will be greater than 39oF, but only by an
average of about 1oF per 100 ft. of buried depth.
The cross section in Figure 63a shows a hydrate plug dissociation when the
pressure is too low. An inner hydrate core is surrounded by an ice layer, that is
enclosed in a water layer adjacent to the pipe wall. Figure 63b shows the temperature
profile from 39oF at the pipe wall, to 32oF at the water-ice interface, to a lower hydrate
76
Water
To= 40F -
Wall
Hydrate
Water
T, = 33F
5
x?
4
Moving Boundary
To= 40F
Wall
T,= 40F
v-v~*FiMoving Boundaries
dissociation temperature (set by the line pressure) at the ice-hydrate interface, where it
remains uniform throughout the hydrate layer. As a result, there are two two-phase
boundaries: a slowly dissociating water-ice boundary (X 1), and a second, rapidly
dissociating ice-hydrate boundary (X2). We are particularly interested in the rate of
progress of X1, which determines the disappearance of the final solid (ice), since any
solid phase constitutes a flow obstruction in a pipeline.
Hydrate dissociation to a low pressure almost always results in an ice problem
which may be more difficult to remove than the initial hydrate. Hydrate removal is
accomplished by both depressurization and heat influx from the surroundings, while an
ice plug removal must rely on heat influx alone. As a result an ice plug may dissociate
more slowly than a hydrate plug.
For example, if a 16 inch line containing only methane is depressured to
atmospheric pressure, 85 days are required for radial dissociation of an ice plug, while
only 17 days would be required for dissociation of a hydrate plug to water if the
pressure was maintained at 450 psig. These calculated results are based upon the
radial dissociation model of Kelkar, et al. (1997) in which radial dissociation prevails.
Austvik (1997) noted some exceptions to radial dissociation, particularly for
plugs of low porosity/permeability or for very long plugs. Plug permeability may
decrease considerably during the first hours after plug formation; this suggests that
plugs should be dissociated as soon as possible to take advantage of higher porosity.
77
Subsea, 1995, page 52). The 12 inch, 39,000 ft. line was un-insulated line. Seawater
temperature was 50oF at the base of the platform in 1400 ft. of water. Gas gravity was
0.7, without condensate. Flow rate was 140 MMscf/d at an inlet pressure of 800 psi.
Gas hydrates formed during a re-start after the platform was shut down due to
a hurricane. During the shut-in period the gas dehydrator was partially filled with
water. After production was restarted, since the dehydrator was not cleaned out
properly, it was not dehydrating gas as designed, and wet gas entered the export riser,
causing water condensation and hydrate formation. A complete hydrate blockage
formed in less than one hour, just past the base of the export riser at a low spot.
To remove the blockage, the line was depressured on both sides of the plug.
Then methanol was circulated into the line to accelerate the hydrate dissociation rate.
After complete removal of the hydrates, the dehydrator was cleaned, inspected and restarted properly. The entire remedial operation required 36 hours to complete. The
major cost was the lost production time.
_____________________________________________________________________
When depressurization cannot be easily achieved from both sides of a plug,
then more costly steps may be required to balance the depressurization to ensure
platform safety, as indicated in the following case study.
_____________________________________________________________________
Case Study 14: Removal of North Sea Hydrate Plug by Depressuring Both Sides.
This case study is a remediation summary of hydrate blockage in an ARCO 16
inch, 22 mile long pipeline between a North Sea gas field well and platform.
Plug Formation
Setting
The gas field is located in the southern North Sea and consists of three subsea
wells, flowing into a subsea manifold with a capacity of four well inputs. A graphical
representation of the field is shown in Figure 64. The wells gas compositions,
temperature, and pressure promote hydrate formation, consequently mono-ethylene
glycol (MEG) is injected into the manifold and wellheads to thermodynamically inhibit
hydrates. The inhibited water, gas, and condensate is then pumped through a 22 mile,
trenched, insulated export pipeline to a processing platform where water is removed
from the condensate. The MEG in the pipeline is recycled and piped back to the
manifold via a 3 inch pipeline piggybacked to the export line.
Blockage
On April 14th, 1996 an unusually large liquid slug over-ran the platform
primary separator causing a temporary shut down. The liquid slug was remediated,
but complete blockage of the pipeline had occurred during shut-down. It was
hypothesized that the blockage was a result of a hydrate plug. The reasons were:
78
Host Platform
Well
Well
36 km - 16 Export Pipeline
Manifold
Well
Fourth Intake
The pipeline free water, recovered during depressurization at the platform, did not
contain MEG inhibitor. The 3 inch MEG inhibitor line had ruptured.
Through back-pressurization, the blockage was found to be 150 meters away from
the platform. At this location, the pipeline was exited the mudline allowing
contents to be rapidly cooled by ocean currents, causing hydrate formation.
Slight decreases in pressure determined that the blockage had some porosity. This
had also been observed for several Statoil hydrate plugs (see Tommeliten Field
Case Studies C.15, C.16, and C.17 in Appendix C. In contrast however, two
DeepStar field trials C.26, and C.27 formed low-porosity, low-permeability plugs
which would transmit pressure very slowly and withstand high pressure drops.)
The liquid slug which shut down the compressors probably was caused by a partial
hydrate plug pushing a fluid front down the pipeline as it moved.
Depressurization Method
Initial Ideas
Three questions were raised to determine a proper depressurization method.
1. Will the remediation process effectively depressurize the pipeline?
2. What is the cost of equipment and modifications?
3. How much time is needed to complete the remediation?
Based on these questions, process engineers, consultants, safety management,
and diving specialists proposed three potential depressurization methods. They were:
1) Jack-up Rig.
Method: Tow a jack-up rig to the site. From the rig, attach a high pressure
riser to the manifolds subsea tree and flare exiting gas via the rigs flare stack.
Modification: A spool piece would have to replace a non-return valve on the
manifolds fourth well intake.
Time Required: A drilling rig was not currently available, consequently a delay
of approximately eight weeks was needed to locate a suitable rig. The time
required for hydrate removal could be twelve weeks.
Estimated Cost: $1,980,000
79
Feasibility: The large amount of time required to locate a jack up rig made this
an ineffective remediation method, useful in the absence of other methods.
2) MEG Injection Line
Method: Connect the subsea manifolds spare fourth flange to the 3inch MEG
pipeline and flare gas at the platform.
Modification: Subsea work would require a spool piece installed between the
two pipelines. Secondly, a method of injecting methanol was needed to
prevent future hydrate growth. The platform (while in operation) required
significant modification to connect the MEG pipeline to its flare stack. To
further complicate the matter, all of the MEG currently in the pipeline would
need to be stored on the platform, which had limited storage space.
Time Required: Six to eight weeks.
Estimated Cost: Unknown, expected to be higher than the other methods
based on the large amount of modifications that were required.
Feasibility: Substantial modifications to the platform made this remediation
method costly and impractical. It was deemed unusable in any circumstance.
3) Floating Production and Storage Vessel (FPSO)
Method: Connect a FPSO with a processing plant and flare to the subsea
manifolds fourth flow loop and process the exiting gas. The connection
between the manifold and FPSO would be made through a high-pressure,
flexible riser.
Modification: The platform required no modifications. A diving rig was
required to do the subsea work. A valve skid containing both emergency shutdown valves (ESDVs) and a MEG injection valve was also needed. The
flexible riser and the manifold would be connected with a spool piece. Figure
65 is a schematic of the design.
Time Frame: A FPSO was available for immediate use, consequently the
required time was expected to be 6-8 weeks.
Estimated Cost: $1,906,000.
Feasibility: This method proved to be the most feasible. The immediate
availability of a FPSO and diving rig allowed modifications to begin. It was
estimated that the FPSO could be at the site and begin within two weeks.
Establishing Procedures/Permits
It took approximately two weeks to develop potential remediation processes.
Procedures were then written to firmly establish the processes required for the pipeline
depressurization. Procedures considered the safety, process, and coordination
requirements between the diving rig and the FPSO. All parties were educated about
the tasks involved.
Government permits were applied for at the Health and Safety Executive
Pipeline Inspectorate (HSE) and the Department of Trade and Industry Oil and Gas
Office (DTI) for additional gas flaring and well modification. The permits were
80
280 meter
High Pressure
Riser
5 Ton
Clump
Weight
Valve Sled
16 Export
Pipe
Manifold
expedited by local agencies to prevent delay in hydrate removal. Two weeks were
required to prepare procedures and permits for depressurization. In the meantime, the
FPSO and diving rig were being equipped for the operation and moving to the field.
81
6 Manuli Riser
ESD Valves
ME
Manifold
GI
nje
ctio
nL
Valve Sled
ine
Initial Design
Final Design
Low Pressure
Quick-Release
Valve
FPSO
High Pressure
Quick-Release
Valve
FPSO
Choke Valves
Choke Valves
82
Sea Surface
FPSO
Chute/Disconnec
t
Umbilical
Manuli Hose
Collar Buoy
Hose
Clamp
Strops
34 km
16
Export
Pipeline
Manuel
Ball
Valve
Manifold
Clump
Weight
Safety
Valves
1400
1200
Pressure (psig)
1000
Hydrates
800
600
400
No Hydrates
200
0
30
35
40
45
50
Temperature (oF)
55
60
65
450
Platform
400
Manifold
Pressure (psig)
350
300
250
200
150
100
50
0
0
10
Time (days)
12
14
16
18
20
from a 1.25 mile long (non-porous) hydrate plug. The high flow rate of gas was
maintained until the water contained 40% MEG, ensuring that the line was fully
inhibited. The pressures and intakes were then returned to normal operating levels.
Conclusions
The remediation team removed the hydrate plug efficiently. They achieved a
monumental task in a very short period of time, preventing more severe economic
losses. Figure 71 provides a timetable of the remediation process. The procedure and
methodology followed could be applied to many different situations. Communication,
clear objectives, and excellent resources helped in removing the hydrate plug.
Despite the efficient remediation effort, the economic impact of the hydrate
plug was substantial. The cost of depressurizing the pipeline was almost 3 million
dollars, without counting lost production. On top of this, relations between the buyers
and producers were tested, due to lack of production. Fortunately, good initial
relations between the two reduced the impact of the disruption. This case study shows
the potential financial loss that can result from hydrate plugs. Hydrate prevention is
key in preventing significant economic and production losses.
_____________________________________________________________________
83
01
APRIL
08 15 22
4/14/96
29 06
MAY
13
20
27
JUNE
03 10 17
6/2/96
6/6/96
Jolliet
Cool Down
Conditions Before
Venting Gas
at Platform
Pressure (psia)
2500
2000
HYDRATES
1500
Shut-In Conditions
After Venting Gas
1000
NO HYDRATES
500
Required Pressure to Dissociate Hydrate Plug
0
20
30
40
50
Temperature (oF)
60
70
80
equilibrium pressure (200 psia) at the ocean floor temperature (40oF) with a
subcooling of 22oF.
To initiate hydrate dissociation, the hydrostatic head must be removed below
200 psia, to about 150 psia where the equilibrium temperature is 25oF, slightly inside
the ice formation region, so that a 15oF temperature gradient will cause heat to flow
from the ocean to the hydrate.
In a worst-case scenario, the entire volume from the platform to the manifold
must be removed. Assuming only 70% of the pipeline volume is filled with liquid, the
volume to be removed would be 12,000 bbls in an 8 inch line and 26,000 bbls in a 12
inch line 50 miles long. The techniques listed in Table 8 were considered for liquid
head removal.
All of the options in Table 8 require that the plug location be determined and
that the pipeline have access points in order to remove the pressurizing liquid and
plug. If there are no access points, the line will have to be hot-tapped. The figures in
the example indicate that workover vessels need to be positioned above the plug.
Of the seven options summarized in Table 8, those with gas lift were eliminated
due to low liquid removal rates. None of the depressurization options were
recommended; however, multiple access ports at 4 mile intervals were recommended
with use of coiled tubing as described in Section III.C.4 on mechanical removal.
Issues/Limitations
84
Fiaure
73
Pipeline Depressurization
-Multiphase
Pump Option
(From
Ft.
Deepstar
Hydrate
PLug
1
RCiV
A-208-1,
1995)
Methods
r ure 74 F
(From Deepstar A208-1,'
1995)
4000 Ft.
85
r-l
Pump
Hydrate Equilibrium
_______________________
_______
______________________
Pressure
_ _ _ _ _ _ _,
____--;_---;_--__-___--__
Mamtam Pressure
Slightly Below Hydrate
Equilibrium Pressure
2. Before the hydrate dissociation pressure is reached, the pressure should be reduced
slightly (e.g. 100 psia), via the access port valves. After each of several pressure
reductions wait for the pressure to be equalized across the plug. Plug permeability
and porosity permits pressure communication to determine gas volumes on each
side. While the hydrate plugs are porous, as indicated in the Statoil Gullfaks case,
pressure equalization may be as slow as 3 psi/hour if substantial liquid flows
through the plug.
3. Maintaining a low P across hydrate plugs will reduce the threat of a projectile by
providing both a low driving force and a downstream gas cushion (See Example
15) for any dislodged plug. In addition a low P across the plug minimizes JouleThomson cooling at the plug discharge end.
4. Reduce the pressure in stages to a level slightly below the equilibrium pressure,
pausing for equilibration at each stage. Do not reduce the pressure below that
required to reduce the hydrate equilibrium temperature below the ice point. If the
pressure is reduced too substantially, an ice plug will result which may be difficult
to dissociate.
5. If hydrates are dissociating (but remain in the line) the pressure will slowly rise to a
level equal to the hydrate equilibrium pressure at the ocean bottom temperature. If
hydrates have dissociated, the line pressure will remain below the hydrate
equilibrium pressure.
6. When the plug completely dissociates there will be no P across the section which
had contained the plug and Section III.D. should be consulted for system start-up.
While the above method represents an ideal depressurization from only one
side, frequently a non-ideal depressurization must be achieved, as in the following case
study for a plug which had low liquid permeability, with a very low gas to oil ratio. It
should be noted that liquid permeability through a hydrate plug is about a factor of
1000 lower than that of gas.
____________________________________________________________________
Case Study 15. Line Depressured from One Side for Hydrate Plug Removal. In
January 1996 Statoil (Gjertsen et al., 1997) depressured a hydrate plug in a North Sea
line which was alternatively used as a black oil producer and a gas injector to maintain
reservoir pressure. The oil and water production rates were 18,000 ft3/day and 16,242
ft3/day respectively, and the gas to oil ratio was usually 100-360 scf/ft 3, a fairly low
value. The line and plug location method is in Case Study 12 in Section III.B.2.b.
Since the plug was about mid-way along the 1.6 mile pipeline, there was not an
option of using an inhibitor because pipeline topology prevented inhibitor contact with
the plug. Since there were no connections at the well the plug had to be depressurized
86
from the platform side only. By considering the hydrate formation curve it was
determined that the plug equilibrium pressure was 261 psia but that ice would form
when the pressure was below 115 psia.
Figure 76 shows the depressurization of the line, with the upstream pressure,
the platform pressure, and the pressure drop. During dissociation the pressure was
decreased in steps, and a slow bleed through was observed from 0-73 hours, from 7390, 95-105 hours, and from 105 through 120 hours.
During the time prior to 120 hours, the pressure was above the hydrate
equilibrium pressure, and while the upstream pressure decreased steadily, it never
decreased to the downstream pressure, indicating that the plug was not very permeable
to black oil. A second mechanism was that the light oil ends may have been flashing to
maintain a constant pressure upstream. However the increase in downstream pressure
occurred much more rapidly as the downstream pressure was lowered, indicating that
the plug was porous, even to the black oil.
After about 120 hours the line pressure was maintained between 145 -261 psia
downstream of the plug. The plug dissociated about 50-60 hours after the
downstream pressure had been reduced sufficiently for melting by heat influx from the
ocean. This was indicated by a sudden upstream pressure decrease from 1890 psig to
1160 psig, while the downstream pressure increased from 218 psig to 1015 psig during
the same period. The pressure was decreased to 145 psig and kept there for over 30
hours to melt the remainder of the hydrates.
Restart of the well (see Case Study 18 Section III.D) was accomplished two
weeks after the original plug developed. This case is another indication of the long
times required to remediate a hydrate plug.
____________________________________________________________________
Case Studies C.25, C.26, and C.27 in Appendix C are an overview of DeepStar
Wyoming field studies of hydrate formation and dissociation from one side of the plug.
These studies have the best instrumentation of any hydrate studies to date, and provide
several exceptions to the concepts in this portion of the handbook. For example, in
two of three cases, relatively impermeable plugs were formed, one of which withstood
a P of 475 psi and was propelled down the pipeline at a velocity of 270 ft/s.
In each DeepStar field trial, depressurization was done gradually in stages from
one side of a hydrate plug with prior testing to ensure that an absorbing gas cushion
existed downstream. Where the hydrate plug existed upstream of an above-ground
bend, angle, or valve, the test was aborted and the plug was depressured from both
sides due to safety reasons.
In depressuring one side of a hydrate plug, it is instructive to simulate the
worst-case as a dislodged, frictionless, piston projectile in a pipeline, as in Example 15.
87
3000
Subsea Pressure
Pressure (psig)
2500
2000
Topside Pressure
1500
1000
500
Pressure Difference
0
0
50
100
150
Time (hours)
200
250
____________________________________________________________________
Example 15. Simulation of Hydrate Projectile Upon Depressuring One Side of Plug.
Xiao and Shoup of Amoco (1996 a,b,c, 1997) performed a series of simulations of a
hydrate projectile in preparation for depressurization from one side of a hydrate plug
in a Kerr-McGee, Wyoming 4 inch line. The plug was conservatively modeled as a
frictionless piston.
Using OLGA the steady state flow in the line was modeled prior to blockage
formation. The model included pipeline topography to obtain steady state liquid
volumes trapped at low points in the pipeline. The total mass flow was 92 BOPD and
4.166 MMscf/d. Figure 77 shows pipeline topography and the liquid holdup. At a
ground temperature of 34oF, the pipeline was simulated as shut-in for 8 hours,
resulting in a simulated plug formation.
Hydrate plugs were initially situated at 7,550 ft. from the inlet of a 17,000 ft.
pipeline, with upstream pressures of 1150 psig and 575 psig and a constant initial
downstream pressure of 50 psig. Transient velocities of two plugs were simulated
after formation: (a) a 20 lbm plug which was 5 ft. long, and (b) a 137 lbm plug which
was 30 ft. long. Velocity profiles were obtained for each plug, propelled by the initial
pressure differentials of 1100 psi and 525 psi., against an initial pressure of 50 psig
with a closed valve at the line end..
For an upstream pressures of 1150 psig, the plugs reached a peak velocity 740
ft/s (smaller plug) and 450 ft/s (larger plug). For an upstream pressure of 575 psig,
the plugs reached a peak velocity of 550 ft/s (smaller plug) and 340 ft/s (larger plug).
The inertial effects of the gas caused rapid acceleration and the final position of the
larger plug (700 ft. and 1,700 ft. from the pipe discharge at initial upstream pressures
of 1150 psig and 575 psig respectively) was governed by a pressure balance, caused by
expansion of the upstream gas and compression of the downstream gas.
The simulation indicated that liquid condensate present in the line had very
little effect on the plug maximum velocity when condensate was injected far away
from the plug initial position. Figure 78 shows the plug velocity as a function of pipe
position for the case of 1150 psig upstream pressure with a 137 lbm plug. Plug
simulation results were used to plan and execute field plug dissociation tests. The
calculated plug velocity was an acceptable match with measured plug velocities in the
field with a gamma-ray detector.
It should be noted that modeling the plug as a frictionless piston provides
conservative results. The modeled plug will be slowed by any friction between plug
and the pipe, as well as by blow-by of gas at the wall and through the porous plug.
____________________________________________________________________
88
5360
0.14
Pipeline
5340
Holdup
0.12
0.1
5300
0.08
5280
5260
0.06
5240
0.04
5220
0.02
5200
5180
2000
4000
6000
8000
10000
12000
14000
16000
18000
Holdup
5320
4%
4Oc
350
30a
.s
H
250
3
3
0
200
150
loo
50
0
10500
11500
12500
Pipeline Distance, ft
13500
14500
15500
16500
89
below the downhole safety valve in the well. This is a particularly precarious
condition which can result in a well blow out, if it is not handled properly.
Field personnel first attempted to decrease the pressure in steps to just above
the hydrate equilibrium pressure and unsuccessful attempts were made to push MEG
through the hydrate plug. The next action was to inject MEG into the well leaving
only a small gas volume at the top of the well. With a higher pressure atop the plug,
the only way to get gas into the well was by hydrate dissociation via MEG.
When the pressure dropped to 4280 psia, MEG was re-injected into the well
until the pressure rose to 4930 psia. A total of 0.14 gallons of MEG were re-injected,
indicating that a very small amount of hydrates had dissociated. It was concluded the
plug had very low permeability and dissociated very slowly. This concluded the period
of getting to know the plug.
At that point the pressure was reduced atop the well to 15 psia and shut-in so
that only the additional static head (394 ft. above the plug) maintained pressure above
the plug. The pressure recovered to 100 psia as an indication that hydrates were
dissociating upon pressure reduction. There were at least six similar pressure
reduction and recovery confirmations that hydrates were dissociating in the well; each
time pressure increases exponentially approached an asymptote of 100 psia.
It was determined the keep the pressure at 15 psia on top of the well to
provide constant hydrate melting. The plug temperature was approximately 48oF.
Five hours after maintaining the pressure at 15 psia, the hydrate dissociation was
complete and the pressure atop the well rose to 160 psia. The entire hydrate plug
melted 12 days after the initial formation. Questions remained concerning why the
plug did not respond to MEG injection, so that depressurization had to be used.
_____________________________________________________________________
90
4 or 6
4 or 6
3,000 - 5,000
6,000 - 8,000
See Case Study 11 (Section III.B.2.a) for a successful example of hydrate plug
removal with coiled tubing and glycol jetting. In other case histories coiled tubing has
been used successfully. For example coiled tubing was recently used to dissociate a
plug at Statoils Statfjord field (Urdahl, 1997). Coiled tubing is expensive, requiring
special rigs. The daily cost of coiled tubing in 1997 is $1 million/d to rent the rig.
Coiled tubing technology is being developed. For hydrate applications, three
new types of coiled tubing are listed from the DeepStar A208-1 report by Mentor
Subsea (Davalath, 1995):
1. Coiled tubing can get hydraulic drilling equipment to the plug (Figure 79).
2. A tractor can be used to pull the coiled tubing through the flowline from the
platform side (Figure 80) in lines larger than 4 inch ID at a speed of 5400 ft/hr with
penetration distances to 15,000 ft. Testing is underway in Deepstar Project 3202.
3. A promising coiled tubing being developed is composite coiled tubing. The tubing
walls are porous to allow air/gas to lubricate the tubing travel for further
penetration. Demonstration has yet to be done.
With the use of coiled tubing it is important to remember that as much as 170 scf
of gas evolves from each ft3 of dissociated hydrate. Coiled tubing must have gas
flowby capability in the drive mechanism at the tubing front. This will prevent either
pushing the tubing from the plug face or line over-pressure. For example with the pigdriven coiled tubing shown in Figure 79, gas must be produced from the tubing.
FiQure
79
Drillin
Head
for
Solids
Removal
Tubing
Insulation
SLip Actuating
sups,
w/
Flow
II
-Drlll
Integrutirlg
Reversing
/Wiper
\\
Nut
Seals
Sub
Disks
Motet-
Stationary
Rotating
Flow
Nozzles
Cutter
Grater
Blades
Type
Cutting
Plate
Figure
80
Coiled
(From
Tubing
Deepstar
Tractor
A208-1,
(Fluid
Driven
Version)
1995)
API
Tractor
Section
NorndForce
Tractor
FOrce
Flow
TrKtion
for
Force
Connection
was depressured immediately after shut-in, but the plug formation was removed via
coiled tubing with glycol jetting. Case Study 17 also illustrates the value of line
depressuring on shut-in.
_____________________________________________________________________
Case Study 17. Multiple Plug Formation after Pressurized Shut-in. The following
study is from DeepStar Report A208-1 (Mentor Subsea, 1995, page 31). Due to a
problem at a gas plant a 6 inch 600 ANSI flowline was shut-in at 1000 psi, but it was
not depressured for six days. The normal flow in the pipeline was gas with 2% H2S
and condensate in the amount of 50 bbl/MMscf.
To remove the blockage the wellhead side of the line was depressured by
venting over a 15-20 minute period. Then the valve at the header side was vented.
During this operation, one of the hydrate plugs partially melted, dislodged from the
line and was propelled by the high-pressure gas trapped inside the line. In this case
there were at least two low spots in the line, where sufficient water accumulated to
form multiple hydrate plugs. The plug length was estimated to be 33 ft. and the gas
trap between the plugs was estimated to be 160 ft. long.
The fast-moving hydrate plug blew a hole through a tee near the header within
half a second after the valve was opened at the header. The impact of the plug and
associated debris caused one fatality and one injury to personnel operating the valve.
Follow-up investigations and math modeling showed that 230 - 820 ft. of high
pressure gas in a 6 inch line would be sufficient to cause the damage that occurred. In
subsequent operations, hydrate plugging was prevented by: (1) injecting methanol or
glycol during each start-up, (2) for planned shutdowns, a hydrate inhibitor was
injected prior to stopping flow followed by depressurization, and (3) for unplanned
shutdowns, the pipeline was depressured within the first 24 hours following shut in.
_____________________________________________________________________
On start-up before reaching steady state, all parts of the system are particularly
susceptible to hydrates, while the system is heating with warm fluids from the
reservoir. During this time small hydrate particles which have formed may be
compacted by flow (or by pigs) to form a plug. A typical start-up procedure involves
injecting large amounts of inhibitor and using diesel fuel.
_____________________________________________________________________
Case Study 18. Pipeline Start-up after Hydrate Formation. In 1996 a Statoil black oil
pipeline plug occurred in the Norwegian sector of the North Sea, as described in Case
Study 15 (Section III.C.1.d). After several precautions, the pipeline was depressured
from one side of the plug, and when the plug had melted the line was maintained at
atmospheric pressure for over one day to eliminate the light components which might
form hydrates.
92
Before start-up, methanol was injected in the amount of 530 gallons in the 6
inch ID, 1.6 mile line from the platform. The pipeline was then pressurized with diesel
from the platform to the sub-sea valve, in an amount which indicated that the pipeline
was nearly empty of liquid after the previous depressurization to atmospheric
conditions. A further injection of diesel corresponding to two pipeline volumes was
pumped into the pipeline and well. Subsequently the well and the pipeline were put
into production without any hydrate problems.
_____________________________________________________________________
93
94
IV. Economics
Economics provide the motivation for all engineering action. When we ask,
Why should hydrates be of concern? the ultimate answer relates to economics. Even
concerns of higher value (e.g. safety or the environment) relate directly to economics
because such concerns can prevent process operations.
The present section is aimed at providing economics in terms of hydrate safety,
prevention, and remediation - the previous three major sections of the handbook. In
every example provided, a time stamp enables the reader to update the economics,
using such tools as the Consumer Price Index.
95
Details of annual hydrate chemical costs for 1-well and 20-well cases, 60 mile
lines, are provided in Table 11. Table 12 gives capital costs for methanol injection
systems in 1 well and 20 wells for the Jolliet and Hercules reservoirs. It should be
noted however, that both tables are based solely upon methanol only in the free water
phase. As noted in Sections II.D.2 and II.D.3. frequently methanol losses to the vapor
and condensate phases are quite important.
The amounts of chemical injection should be based upon the methods of
Section II.D, recalling the relative advantages and disadvantages of each inhibitor. For
example, methanol is significantly dissolved in the vapor and liquid hydrocarbon
phases, not just the free water phase (considered in Table 11).
Methanol had a delivered cost to an offshore Gulf of Mexico platform of $2.00
per gallon during the 1996-7 winter. Such costs fluctuate significantly and are
somewhat seasonal; typical dockside North Sea methanol costs were $0.11/lbm
($0.72/gallon) and ethylene glycol cost were $0.27/lbm during the 1997 summer.
Since methanol recovery is not economical, methanol injection is normally
considered as an operating cost. The Deepstar Study CTR 221-1 (Paragon
Engineering, 1994) shows methanol recovery to be very expensive in Table 3 of Case
Study 7 in Section II.G.1.a. For methanol recovery late in the life of a field, the total
installed cost on an existing platform was estimated at $16.7 million ($20 million total
installed cost with a new platform) while the annual operating cost is $6 million. For
ethylene glycol (MEG) a low vapor pressure results in a smaller recovery column,
making the economics much more favorable.
96
Table 11. Cost of Methanol Usage for Jolliet and Hercules Reservoirs
in Gulf of Mexico (from DeepStar I CTR 240)
H2O
Subcool
No. life
Well yr
WHP
psia
Oil
Gas
bbl/D
Mscf/d
bbl/D
T( F)
wt%
MeOH Cost
MeOH gpm
k$/yr
Jolliet
1
5
8
3,317
1,970
911
2,500
600
43
1,670
3,268
850
2
17
4
46.3
38.8
27.8
35.3
33.1
27.3
0.026
0.206
0.040
7.65
60.6
11.8
Jolliet
20
1
5
10
2,821
1,449
1,123
4,400
16,400
5,100
2,948
33,948
36,210
4
124
172
43.9
34.4
30.8
34.8
31.1
29.2
0.051
1.412
1.832
15.0
415.6
539.2
Hercules
1
5
8
2,325
1,737
1,824
1,367
465
23
869
376
30
0
666
22
41.2
37.0
37.7
33.9
32.3
32.6
0
7.889
0.263
0
2,322
77.4
Hercules
20
1
5
10
2,325
1,064
1,064
2,700
22,700
19,100
3,000
12,500
11,700
0
4,540
5,157
41.2
30.0
30.0
33.9
28.7
28.7
0
47.75
54.24
0
14,054
15,964
Rsrvr
Table 12. Transmission Lines (60 miles) Sizing, Costs and Pumping
Skid Costs (From DeepStar I. CTR 240)
Reservoir
No.
Wells
Min. Line
ID (in)
Line Cost
MM$
Skid Cost
k$
Jolliet
Jolliet
1
20
0.306
0.780
1.03
1.11
5.20
30.00
Hercules
1
1.629
1.79
34.00
Hercules
20
2.815
1.79
89.50
Additional cost of valve, actuator, manifolding,
and packaging = $6,700/well.
Rule-of-Thumb 22. Methanol loss costs can be substantial when the total
fraction of either the vapor or the oil/condensate phase is very large relative to
the water phase.
Sections II.C. and II.D. provide a quantitative means of validation of the above
Rule-of-Thumb. Example 7 provides a conservative sample calculation in which 15%
of the methanol is lost to the vapor and liquid hydrocarbon. Statoil provided the
below table showing a reduction in condensate price for different methanol
concentrations (>30 ppm by wt) in a condensate.
97
0
0-$2/metric ton (MT = 2205 lbm)
$2-4/MT (or $0.25 - $0.50/ Bbl)
$4-6/MT (excludes some crackers)
$6-9/MT (excludes most crackers)
$9-40/MT (reduced confidence in product)
phase
Life
yrs of
Use
H2O
avg,
bbl/d
Time in
hydrate
zone, hr
Max
T,
o
F
wt%
MeOH
in H2O
MeOH
1000
lbm
KI
1000
lbm
active
16
multi
0
7
15
304
287
150
0
2.3
40.9
no hyd
11.7
31.4
0
16
33
0
20.9
19.3
0
0.409
NA*
liquid
0
7
15
346
295
118
0
7.9
43.2
no hyd
17.5
19.4
0
20
21
0
21.5
8.8
0.
0.441
0.170
12
gas
0
17
8.4
25.5
28
9.7
7
10
24.6
30.8
33
5.9
15
4
72.9
32.0
33
2.4
NA* = conditions too severe for kinetic inhibitor (KI)
0.128
NA*
NA*
98
Table 15. Comparison of Methanol and Kinetic Inhibitor Cost in North Sea
(P. Notz, July 26, 1994)
Line
(in)
16
8
12
phase
multi
liquid
gas
MM
lbm
$MM
7-9
6-15
1-4
72.9
52.5
33.0
22.1
15.9
10.0
0.36
1.05
0.03
25.9
52.5
15.6
7.8
15.9
4.7
0.36
1.05
0.03
3.2
9.3
0.26
50.0
0
17.4
This includes the cost of methanol solvent for the kinetic inhibitor
This is the methanol cost in those years when a KI cannot be used because T > 27oF
Table 16. Comparison of Three Types of Inhibitor Costs in the North Sea
(M. Grainger, August 21, 1997)
Chemical
MEG
MeOH
THI
Conc/bbl H2O,wt%
Quantity, lbm
Cost/bbl H2O
15
61.7
$16-$17
15
61.7
$6.5 - $7.5
0.25
0.882
$8-$10
From the above table, operating cost benefits appear marginal (better than
MEG, worse than MeOH). Bloys et al. (1995) suggested that economics were
favorable for new developments (due for example, to capital savings of avoiding
regeneration systems) but marginal for retrofits of systems with traditional inhibitors
such as monoethylene glycol.
The incentive for newer kinetic control methods is a substantial capital cost
reduction by the elimination of the need for offshore platform equipment, and a small
operating cost reduction. In one high water production North Sea field, BP reckoned
the capital costs savings at $50 million for platform costs including methanol injection
costs, glycol drying, and regeneration (Argo and Osborne, 1997).
99
18.4
9.3
5.5
For example, BP currently operates some Southern North Sea pipeline wet,
thereby saving the capital cost of drying the gas on the platform. In addition to capital
cost, a savings may be realized on the platform itself.
Rule-of-Thumb 23. The cost of a fixed leg North Sea platform is $77,000/ton.
The above Rule-of-Thumb was given by Edwards (1997). BP would like to
use unmanned platforms, but the inhibitor recovery units on some platforms prevents
doing so. As additional costs, Edwards also estimated the operation of an inhibitor
recovery unit at 2 hrs/day operator time and maintenance requires 600-700 hr/year at
$85/hr.
The economics of anti-agglomerants are much less certain than those stated
above for kinetic inhibitors. No documented costs of anti-agglomerants were found.
However, anti-agglomerant economics should include such factors as emulsion
breaking, recovery, and disposal.
100
101
without production losses. Even with such high costs, the loss of production usually
causes time to be the deciding resource during remediation.
During remediation periods, gas supply is usually met via substitution.
However, the borrowing capacity is typically limited to 5 times the daily capacity, so
that gas supplies are purchased from the spot market. Typical non-delivery penalty
costs are $50,000/day after tax on a gas production unit of 125MM scf/d. Nondelivery contract pressures may be eased by considering hydrates as a Force Majeure
as done in ARCO Case Study 14, implying that no penalties should be incurred
because there was no human error.
102
Appendix A.
Gas Hydrate Structures, Properties, and How They Form
The following discussion is excerpted from the monograph by Sloan (1998,
Chapters 2 and 3), to which the reader may wish to turn for a more complete
explanation. Two recent hydrate conference summaries (Sloan et al., 1994; Monfort
1996) also provide research and applied perspectives of the hydrate community.
Gas clathrates are crystalline compounds which occur when water forms a
cage-like structure around smaller guest molecules. While they are more commonly
called hydrates, a careful distinction should be made between these non-stoichiometric
clathrate hydrates of gas and other stoichiometric hydrate compounds which occur for
example, when water combines with various salts.
Gas hydrates of current interest are composed of water and the following eight
molecules: methane, ethane, propane, isobutane, normal butane, nitrogen, carbon
dioxide, and hydrogen sulfide. Yet other apolar components between the sizes of
argon (3.5 ) and ethylcyclohexane (9) can form hydrates. Hydrate formation is a
possibility where water exists in the vicinity of such molecules at temperatures above
and below 32oF. Hydrate discovery is credited in 1810 to Sir Humphrey Davy. Due
to their crystalline, non-flowing nature, hydrates first became of interest to the
hydrocarbon industry in 1934, the time they first were observed blocking pipelines.
Hydrates concentrate hydrocarbons: 1 ft3 of hydrates may contain 180 scf of gas.
Hydrates normally form in one of three repeating crystal structures shown in
Figure A.1. Structure I (sI), a body-centered cubic structure forms with small natural
gas molecules found in situ in deep oceans. Structure II (sII), a diamond lattice within
a cubic framework, forms when natural gases or oils contain molecules larger than
ethane but smaller than pentane. sII represents hydrates which commonly occur in
hydrocarbon production and processing conditions, as well as in many cases of gas
seeps from faults in ocean environments.
The newest hydrate structure H (sH) named for its hexagonal framework, has
cavities large enough to contain molecules the size of common components of naphtha
and gasoline. Some initial physical properties, phase equilibrium data, and models
have been determined for sH and one instance of in situ sH in the Gulf of Mexico has
been found. Since information on structure H is in the fledgling stages, and since it
may not occur commonly in natural systems, most of this appendix concerns sI and sII.
Structure
Structure IJ
I
Structure H
34 Water Molecules
Spaces between the 512 cavities are larger cavities which contain twelve
pentagonal faces and either two, four, or eight hexagonal faces: (denoted as 51262 in sI,
51264 in sII, or 51268 in sH). In addition sH has a cavity with square, pentagonal, and
hexagonal faces (435663). Figure A.1 depicts the five cavities of sI, sII, and sH. In
Figure A.1 a oxygen atom is located at the vertex of each angle in the cavities; the
lines represent hydrogen bonds with which one chemically-bonded hydrogen connects
to an oxygen on a neighbor water molecule.
Table A.1 Geometry of Cages in Three Hydrate Crystal Structures in Figure A.1
Hydrate Crystal Structure
Cavity
Description
Number of Cavities/Unit Cell
Average Cavity Radius,
Variation in Radius1, %
Coordination Number2
Number of Waters/Unit Cell
I
Small Large
512
51262
2
6
3.95 4.33
3.4 14.4
20
24
46
II
Small Large
512
51264
16
8
3.91 4.73
5.5
1.73
20
28
136
H
Small Medium Large
512
435663 51268
3
2
1
3
3
3.91
4.06
5.713
Not Available
20
20
36
34
Inside each cavity resides a maximum of one of the small guest molecules,
typified by the eight guests associated with 46 water molecules in sI
(2[512]6[51262]46H2O), indicating two guests in the 512 and 6 guests in the 51262
cavities of sI. Similar formulas for sII and sH are (16[512]8[51264]136H2O) and
(3[512]2[435663]1[51268]34H2O) respectively.
Structure I, a body-centered cubic structure, forms with natural gases
containing molecules smaller than propane; consequently sI hydrates are found in situ
in deep oceans with biogenic gases containing mostly methane, carbon dioxide, and
hydrogen sulfide. Structure II, a diamond lattice within a cubic framework, forms
when natural gases or oils contain molecules larger than ethane; sII represents hydrates
from most natural gas systems gases. Finally structure H hydrates must have a small
occupant (like methane, nitrogen, or carbon dioxide) for the 512 and 435663 cages but
the molecules in the 51268 cage can be as large as 0.9 (e.g. ethylcyclohexane).
Structure H has not been commonly determined in natural gas systems to date.
Ice
Structure I
Structure II
P63/mmc
4
a =4.52 c =7.36
94
Peak at 229 cm-1.
220
58.1
Pm3n
Fd3m
46
136
12.0
17.3
~58
58
Peak at 229 cm-1 with others
240
25
50
50
9.5
8.4est
8.2est
0.33
8.8
3.9
1.88
~0.33
5.6
2.4
1.95
~0.33
NA
NA
NA
56x10-6
12
3.8
77x10-6
14est
3.3
52x10-6
14est
3.6
2.23
0.49.02
0.51.02
A.2.b. Guest: Cavity Size Ratio: a Basis for Property Understanding. The
hydrate cavity occupied is a function of the size ratio of the guest molecule within the
cavity. To a first approximation, the concept of "a ball fitting within a ball" is a key to
understanding many hydrate properties. Figure A.2 may be used to illustrate five
points regarding the guest:cavity size ratio for hydrates formed of a single guest
component in sI or sII.
1. The sizes of stabilizing guest molecules range between 3.5 and 7.5 . Below 3.5
molecules will not stabilize sI and above 7.5 molecules will not stabilize sII.
2. Some molecules are too large to fit the smaller cavities of each structure (e.g. C2H6
fits in the 51262 of sI; or i-C4H10 fits the 51264 of sII).
3. Other molecules such as CH4 and N2 are small enough to enter both cavities
(512+51262 in sI or 512+51264 in sII) when hydrate is formed of single components.
4. The largest molecules of a gas mixture usually determines the structure formed.
For example, because propane and i-butane are present in many natural gases, they
will cause sII to form. In such cases, methane will distribute in both cavities of sII
and ethane will enter only the 51264 cavity of sII.
5. Molecule sizes which are close to the hatched lines separating cavity sizes exhibit
the most non-stoichiometry, due to their inability to fit securely within the cavity.
Table A.3 shows the size ratio of several common gas molecules within each of
the four cavities of sI and sII. Note that a size ratio (guest molecule: cavity) of
approximately 0.9 is necessary for stability of a simple hydrate, given by the
105
superscript F. When the size ratio exceeds unity, the molecule will not fit within the
cavity and the structure will not form. When the ratio is significantly less than 0.9 the
molecule cannot lend significant stability to the cavity.
Table A.3 Ratios of Guest: Cavity Diameters for Natural Gas Hydrate Formers
Molecule
N2
CH4
H2S
CO2
C2H6
C3H8
i-C4H10
n-C4H10
Cavity Type=>
Guest Dmtr ()
4.1
4.36
4.58
5.12
5.5
6.28
6.5
7.1
0.700
0.744F
0.782F
0.834F
0.939F
1.07
1.11
1.21
0.817F
0.868
0.912
1.02
1.10
1.25
1.29
1.41
0.616F
0.655
0.687
0.769
0.826
0.943F
0.976 F
1.07
As seen in Table A.3, ethane as a single gas forms in the 51262 cavity in sI,
because ethane is too large for the small 512 cavities in either structure and too small to
give much stability to the large 51264 cavity in sII. Similarly propane is too large to fit
any cavity except the 51264 cavity in sII, so that gases of pure propane form sII
hydrates from free water. On the other hand, methane's size is sufficient to lend
stability to the 512 cavity in either sI or sII, with a preference for sI, because CH4 lends
slightly higher stability to the 51262 cavity in sI than the 51264 cavity in sII.
A.2.c. Phase Equilibrium Properties. In Figure A.3 pressure is plotted against
temperature with gas composition as a parameter, for methane+propane mixtures.
Consider a gas of any given composition (marked 0 through 100% propane) on a line
in Figure A.3. At conditions to the right of the line, a gas of that composition will
exist in equilibrium with liquid water. As the temperature is reduced (or as the
pressure is increased) hydrates form from gas and liquid water at the line, so three
phases (liquid water + hydrates + gas) will be in equilibrium. With further reduction of
temperature (or increase in pressure) the fluid phase which is not in excess (water in
pipeline environments) will be exhausted, so that to the left of the line the hydrate will
exist with the excess phase (gas).
All of the conditions given in Figure A.3 are for temperatures above 32oF and
pressures along the lines vary exponentially with temperature. Put explicitly, hydrate
stability at the three-phase (LW-H-V) condition is always much more sensitive to
temperature than to pressure. Figure A.3 also illustrates the dramatic effect of gas
composition on hydrate stability; as any amount of propane is added to methane the
structure changes (sI
sII) to a hydrate with much wider stability conditions. Note
that a 50% decrease in pressure is needed to form sII hydrates, when as little as 1%
propane is in the gas phase.
106
of
.-
l-
, ,3$,
TEMPERATURE
, , 4p
,
47
TEMPERATURE
(OF)
55
(1000/K)
67
A. Initial Condlflon
Pressure and
temperature in hydrate
forming region, but no
gas molecules dissolved
in wafer
Gas
6. Labile Clusters
Upon dissolu&n of
gas in water. labile
ctusters form
immediately.
,C. Agglomeration
Labile clusters
agglomerate by sharing.
faces, thus increasing
disorder.
2.
3.
4.
5.
Figure A.1. These fluid clusters are envisioned to join other clusters as the
beginning of the hydrate crystallization process.
Figure A.5 indicates an autocatalytic reaction mechanism hypothesized for hydrate
formation based upon limited experimental evidence. The figure depicts the
progress of molecular species from water [A], through metastable species [B] and
[C], to stable nuclei [D] which can grow to large species.
At the beginning of the process (point A), hydrogen-bonded liquid water and gas
are present in the system. Water clusters around gas molecules to form both large
and small clusters [B] similar to the hydrate cages of sI and sII. At point [B], the
cages are termed labile - they are relatively long-lived but unstable.
The cages may either dissipate or grow to hydrate unit cells or agglomerations of
unit cells [C], thus forming metastable nuclei. Since these metastable unit cells at
[C] are of subcritical size, they may either grow or shrink in a stochastic process.
The metastable nuclei are in quasi-equilibrium with the liquid-like cages until the
nuclei reach a critical radius. After attaining the critical radius [D], the crystals
grow rapidly in a period sometimes called catastrophic growth.
In our conceptual picture, when the system is heated, it is driven to the left in
Figure A.5, and stable hydrate crystals are dissociated. Once the hydrate
dissociation point is reached and passed, there are still labile microscopic species
in the water that range in size from multiple hydrate unit cells [C] to metastable
nuclei [B]. These residual structures are present up to a certain level of thermal
energy above dissociation. At temperatures below that upper boundary, these
species causes a decrease in induction or metastability time of a successive run,
because the building blocks of crystals remain in the liquid. However, once
about 100F is passed, no residual structure remains to promote hydrate formation.
The above cluster model conceptual picture is most likely to occur at the
interface, either in the liquid or the vapor side. The reader should note that the above
is a largely unproven hypothesis, whose only justification is to serve as a mental
picture for qualitative predictions and future corrections.
In contrast to well-determined thermodynamic properties, kinetic
characterization of hydrates is very ill-determined. One has only to turn to the recent
review of hydrate kinetics by Englezos (1995) or to the authors monograph (1998) to
determine the following unsettling facts which act as a state-of-the-art summary:
Appendix B.
Users Guide for HYDOFF and XPAND Programs
A Word of Caution
While it is hoped that the programs accompanying this book will be of use in
estimating the limiting conditions of hydrate formation, the author should not and
cannot be held totally accountable for the use of the predictions which the program
provide. If there is a safety consideration or an important process decision to be made
based upon the programs predictions, the user is cautioned to obtain a second opinion
from someone knowledgeable in hydrate phase equilibria, before proceeding.
Executive Summary
Program Specifications
This program has been developed to run in IBM-PC compatible computers
having DOS as operating system. The program is executable without any additional
hardware or software requirements.
Contents of the Disk
The 3.5 in. disk provided with this handbook contains four files:
1. HYDOFF.EXE, an executable file to prediction hydrate formation conditions,
2. FEED.DAT, a file to be used as external input of the feed components and
composition for HYDOFF. FEED.DAT is an optional file; it should be noted that
HYDOFF will run regardless whether the file FEED.DAT is present.
3. XPAND.EXE an executable file to determine the isenthalpic (H=0) and
isentropic (S=0) gas expansion conditions, and
4. HYDCALC.XLS, a shortcut estimation spreadsheet to calculate methanol or
monoethylene glycol amounts. Use of this program is specified in Section II.B.
Appendix B provides common examples using HYDOFF and XPAND which
may then be modified by the engineer for his/her own purposes. Section B.1 considers
the use of HYDOFF (and FEED.DAT), while Section B.2 details the use of
XPAND.EXE.
B.1. HYDOFF
B.1.a. Running the Program
The program can be executed directly from the 3.5 in disk or copied to the
hard-drive and then executed. It is recommended to make a backup copy of the
109
program in case problems occur (e.g. virus). At the DOS prompt, simply type
HYDOFF and follow the instructions given by the program.
110
internal initial guess. Also, the user does not have to specify the equilibrium phases for
any calculation. The equilibrium phases are given as output of the predictions.
1.
2.
3.
4.
5.
The standard output for hydrate phase equilibria calculations will display:
Equilibrium phases (I-H-V, LW-H-V or LW-H-V-LHC).
Equilibrium pressure.
Hydrate equilibrium crystal structure (sI or sII).
Phase components and compositions (i.e. feed, fluid hydrocarbon, and hydrate).
Fractional occupancy of cages by hydrate formers in each type of hydrate cavity.
Different outputs will be shown for each calculation type. Examples to follow
will better illustrate how the program is structured and the format of the output.
Component
Mole %
Methane
Ethane
Propane
i-Butane
n-Butane
Nitrogen
n-Pentane
n-Hexane
73.29
6.70
3.90
0.36
0.55
15.00
0.20
0.00
111
HYDOFF
FAX:(303) 273-3730
TEMPERATURE
Fahrenheit
Kelvin
PRESSURE
psia
kPa
Is the FEED COMPONENTS and COMPOSITION saved under FEED.DAT (No=1 Yes=2)?
1
2. Ethane
5. n-Butane
8. Carbon Dioxide
3. Propane
6. Hydrogen Sulfide
NON-HYDRATE FORMERS
9. n-Pentane
13. Octane
10. i-Pentane
14. Nonane
11. Hexane
15. Decane
112
12. Heptane
16. Toluene
Methane
: 0.7329
Mole Fraction of
Ethane
: 0.0670
Mole Fraction of
Propane
: 0.0390
Mole Fraction of
i-Butane
: 0.0036
Mole Fraction of
n-Butane
: 0.0055
Mole Fraction of
Nitrogen
: 0.1500
Mole Fraction of
Pentane
: 0.0020
Mole Fraction of
Hexane
: 0.0000
1
PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS
(1)
(2)
(3)
(4)
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
1
Enter the required Temperature (in
51.35
F)
399.92
psia
113
Experimental pressure
365.1 psia
FEED
.7329
.0670
.0390
.0036
.0055
.1500
.0020
.0000
Methane
Ethane
Propane
i-Butane
n-Butane
Nitrogen
n-Pentane
n-Hexane
VAPOR
.7329
.0670
.0390
.0036
.0055
.1500
.0020
.0000
HYDRATE
.5777
.0299
.3076
.0408
.0063
.0377
.0000
.0000
Methane
Ethane
Propane
i-Butane
n-Butane
Nitrogen
n-Pentane
n-Hexane
LARGE
.0444
.0739
.7602
.1008
.0155
.0011
.0000
.0000
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
7
THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE
(1)
(2)
(3)
(4)
(5)
(6)
6
End of run : HYDOFF
Stop - Program terminated.
114
Example 2 - Pressure prediction with methanol (experimental data by Ng, H.-J., and
Robinson, D.B. (1983))
HYDRATE PREDICTION PROGRAM: HYDOFF
(ACCOMPANYING THE OFFSHORE HYDRATE HANDBOOK)
Release Date : July 3rd, 1997
COPYRIGHT :
Professor E. Dendy Sloan
Center for Hydrate Research
Department of Chemical and Petroleum-Refining Engineering
Colorado School of Mines, Golden, CO 80401
PHONE:(303) 273-3723
FAX:(303) 273-3730
TEMPERATURE
Fahrenheit
Kelvin
PRESSURE
psia
kPa
Is the FEED COMPONENTS and COMPOSITION saved under FEED.DAT (No=1 Yes=2)?
1
How many COMPONENTS (excluding Water) are present?
7
sII HYDRATE FORMERS
1. Methane
4. i-Butane
7. Nitrogen
2. Ethane
5. n-Butane
8. Carbon Dioxide
NON-HYDRATE FORMERS
115
3. Propane
6. Hydrogen Sulfide
9. n-Pentane
13. Octane
10. i-Pentane
14. Nonane
11. Hexane
15. Decane
12. Heptane
16. Toluene
Methane
: 0.7160
Mole Fraction of
Ethane
: 0.0473
Mole Fraction of
Propane
: 0.0194
Mole Fraction of
n-Butane
: 0.0079
Mole Fraction of
Nitrogen
: 0.0596
Mole Fraction of
Carbon Dioxide
: 0.1419
Mole Fraction of
Pentane
: 0.0079
1
PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS
(1)
(2)
(3)
(4)
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
2
Enter the required Temperature (in
47.03
F)
773.01
psia
116
Experimental pressure
800.6 psia
Methane
Ethane
Propane
n-Butane
Nitrogen
Carbon Dioxide
n-Pentane
VAPOR
.7160
.0473
.0194
.0079
.0596
.1419
.0079
LIQUID
.7159
.0473
.0194
.0079
.0596
.1419
.0079
HYDRATE
.6033
.0405
.2615
.0132
.0167
.0647
.0000
Methane
Ethane
Propane
n-Butane
Nitrogen
Carbon Dioxide
n-Pentane
LARGE
.1036
.1094
.7064
.0358
.0011
.0390
.0000
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
2
Enter the required Temperature (in
33.71
F)
566.2
psia
117
Experimental pressure
691.8 psia
Methane
Ethane
Propane
n-Butane
Nitrogen
Carbon Dioxide
n-Pentane
VAPOR
.7159
.0473
.0194
.0079
.0596
.1419
.0079
LIQUID
.7159
.0473
.0194
.0079
.0596
.1419
.0079
HYDRATE
.5931
.0367
.2772
.0139
.0150
.0642
.0000
Methane
Ethane
Propane
n-Butane
Nitrogen
Carbon Dioxide
n-Pentane
LARGE
.0786
.0991
.7487
.0375
.0007
.0317
.0000
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
7
THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE
(1)
(2)
(3)
(4)
(5)
(6)
6
End of run : HYDOFF
Stop - Program terminated.
118
HYDOFF
FAX:(303) 273-3730
TEMPERATURE
Fahrenheit
Kelvin
PRESSURE
psia
kPa
Is the FEED COMPONENTS and COMPOSITION saved under FEED.DAT (No=1 Yes=2)?
1
How many COMPONENTS (excluding Water) are present?
2
sII HYDRATE FORMERS
1. Methane
4. i-Butane
7. Nitrogen
2. Ethane
5. n-Butane
8. Carbon Dioxide
NON-HYDRATE FORMERS
119
3. Propane
6. Hydrogen Sulfide
9. n-Pentane
13. Octane
10. i-Pentane
14. Nonane
11. Hexane
15. Decane
12. Heptane
16. Toluene
Methane
: 0.8470
Mole Fraction of
Carbon Dioxide
: 0.1530
1
PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS
(1)
(2)
(3)
(4)
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
1
Enter the required Temperature (in
40.01
F)
496.75
psia
Experimental pressure
494.6 psia
FEED
.8470
.1530
VAPOR
.8470
.1530
120
HYDRATE
.7222
.2778
Methane
Carbon Dioxide
LARGE
.6610
.3191
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
a given
given T
given T
given T
(5)
(6)
(7)
(8)
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
5
Enter the MOLE FRACTIONS of each Component :
Mole Fraction of
Methane
: 0.823
Mole Fraction of
Carbon Dioxide
: 0.177
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
a given
given T
given T
given T
(5)
(6)
(7)
(8)
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
3
Enter the required Temperature (in
47.93
F)
980.03
psia
121
Experimental pressure
1012.4 psia
Methane
Carbon Dioxide
VAPOR
.8230
.1770
HYDRATE
.7150
.2850
Methane
Carbon Dioxide
LARGE
.6566
.3305
PRESSURE
Pressure
Pressure
Pressure
PREDICTION
prediction
prediction
prediction
at
at
at
at
(5)
(6)
(7)
(8)
a given
given T
given T
given T
TEMPERATURE
with Methanol
with Salt (NaCl)
with Salt+MeOH
7
THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE
(1)
(2)
(3)
(4)
(5)
(6)
6
End of run : HYDOFF
Stop - Program terminated.
122
B.2. XPAND
123
Gas Composition:
Component
Mole %
Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
92.70
5.30
1.40
1.40
0.34
0.14
124
Component
3
Component
4
Component
5
Component
6
3:
4:
5:
6:
1st
Guess
T1 = 559.700 R
T2 = 520.000 R
1st delta H =
891.234 BTU/lbmol
Ideal gas delta H =
-376.414 BTU/lbmol
2nd delta H =
201.219 BTU/lbmol
Total delta H =
313.602 BTU/lbmol
1st delta S =
Ideal gas delta S =
2nd delta S =
Total delta S =
.179 BTU/lbmol-R
2.501 BTU/lbmol-R
.059 BTU/lbmol-R
2.620 BTU/lbmol-R
2nd Guess
125
P1 = 1500.000 psia
P2 = 300.000 psia
T1 = 559.700 R
T2 = 500.000 R
1st delta H =
891.234 BTU/lbmol
Ideal gas delta H =
-562.102 BTU/lbmol
2nd delta H =
216.348 BTU/lbmol
Total delta H =
112.784 BTU/lbmol
1st delta S =
Ideal gas delta S =
2nd delta S =
Total delta S =
.179 BTU/lbmol-R
2.136 BTU/lbmol-R
.070 BTU/lbmol-R
2.245 BTU/lbmol-R
3rd
Guess
T1 = 559.700 R
T2 = 488.700 R
1st delta H =
891.234 BTU/lbmol
Ideal gas delta H =
-665.909 BTU/lbmol
2nd delta H =
225.689 BTU/lbmol
Total delta H =
-.364 BTU/lbmol
1st delta S =
Ideal gas delta S =
2nd delta S =
Total delta S =
.179 BTU/lbmol-R
1.926 BTU/lbmol-R
.078 BTU/lbmol-R
2.027 BTU/lbmol-R
126
the two end points for the P-T expansion (1500 psia, 100 oF, and 300 psia, 29 oF) and
the hydrate formation line
127
Studies from DeepStar II.A. CTR 208A-1 by Mentor Subsea (1996) denoted by *
128
129
130
shut-in period over a 300-ft section underneath a road crossing. Previously, hot taps
had located a blockage in the same location. While hot tapping was an option, in this
case, it was considered too risky. Furthermore, hydrates do not typically form in
these 6 inch lines if depressurized within the first 24 hours.
To remove the blockage, two methods were used simultaneously. First, the
line was depressurized on both sides of the plug. Then, a welding rig applied
electrical current directly to the 300-ft section of the steel pipe. The line was heated
to 20 to 25 C (68 to 77F) using the welding rig. This approach was effective in
melting the hydrate plug. The remedial operation took two days to complete.
131
132
the gas dehydrator was turned on to remove water vapor from the gas stream and (2)
methanol was injected into the gas export line.
133
Analysis of the liquid samples showed that the methanol content was 11-wt%,
which was well below the 26-wt% required to avoid hydrate formation. However, Elf
reported that the flowline did not plug with hydrates although it experienced
subcooling up to 6C. Hydrates were found just downstream of the choke on the
platform. Due to Joule-Thomson cooling (see Section II.E) the gas/water mixture
experienced the lowest temperature downstream of the choke.
Before re-starting production, the separator was depressurized and circulated
with steam to remove the hydrates. About 9000 gal of methanol were injected into
the pipeline inlet, the outlet and upstream of the pipeline outlet choke. An additional
21,000 gal of methanol was injected during the first two days of restart, when the gas
flow rate was gradually re-established.
The liquid outlet valve of the inlet separator was severely eroded during the
hydrate formation period. This might have been due to a combination of metallic
particles, scale, or hydrate crystals flowing at high velocities through the valve. The
valve had to be replaced. Another reason for forming hydrates downstream of the
choke was the lack of an upstream heater. In many subsea completions, a heater is
installed upstream of the separator and choke to prevent hydrates or wax formation
and to improve the separation efficiency.
134
135
136
137
Case Study C.17. The uninhibited line was shut-in at full well pressure and
cooled to ambient sea temperature. The line was then started and began producing at
a rate of 12MM scf/d without any methanol present. The production line was
maintained for 40 hours without any hydrate blockage of the line. Several blocking
events occurred topside before a blockage occurred somewhere between the template
and riser. After observing pressure changes on both sides of the plug, it was
determined that the plug was approximately 2.5 miles away from the platform. The
hydrate plug was removed through one-sided depressurization. The hydrate plug
dissociated slowly, taking nine days before it was removed.
Figure C.1 shows the measured pressure difference across the two plugs in
Case Studies C.16 and C.17 as a function of time. These curves have been generated
removing large pressure fluctuations that occurred while reducing the pressure. The
figure highlights the change of permeability of the plug as a function of time.
Figure C.2 shows the pressure in the riser during the hydrate removal process.
The equilibrium pressure for the hydrate plugs was approximately 200 psi at the
ambient temperature. Plug 1 was kept under the equilibrium temperature until it was
dissociated. Plug 2 was temporarily kept above the equilibrium point to limit the
cooling effects caused by Joule-Thomson cooling. It was thought that this practice
had little effect on increasing the rate of dissociation.
138
1600
1400
1200
1000
800
600
Plug 2 (Case Study 17)
400
200
0
0
50
100
150
Time (hours)
200
250
300
400
350
Pressure (psi)
300
250
Plug 1 (Case Study 16)
200
150
100
Plug 2 (Case Study 17)
50
0
0
50
100
150
Time (hours)
200
250
300
139
carried out over a two week period, and was done in slow steps to prevent any high
pressure buildups due to multiple plugs. After eight weeks, the plug was completely
dissociated and full production could resume. The line was restarted by slowly
sweeping the pipeline with dry gas, building up to high gas rates. The line was
consistently pigged, first with undersized pigs and then full-sized. No problems were
witnessed during start-up.
The hydrate remediation process lasted eight weeks and cost $500,000 to
carry out. Overall, the plug shut-down production for three months and cost $5.5
million due to remediation expenses and loss of sales.
140
A through drillstring perforating gun was then run to shoot the 7 in. casing
just above the gas snad. The gas influx was killed by pumping a 14.2 lbm/gal mud
down the drillstring and into the formation at surface pressures up to 3,100 psi. At
the conclusions of the kill operation, both the chokeline and the kill ine were found
plugged. Subsequent operations were hampered by the inability to use either line.
After cementing operations which secured the well bore, the BOPs were recovered.
Hydrates and trapped gas were found in the chokeline and the kill line of the bottom
eight riser joints.
Case Study 23
Davalath and Barker (1993) described a hydrate problem in 595 ft. of water
located offshore South America. The well was completed with a 7 inch casing and
3.5 inch tubing. Production was gas and condensate at several hundred barrels per
day with a water cut of about six percent. A 15 hour production test was followed by
a 25 hour shut-in period to collect reservoir pressure buildup data.
The well was shut-in at the surface, which exposed the tubing to high pressure
gas and cold 45oF water, which led to the formation of hydrates. Under these
conditions the tubing fluid was about 29oF below the hydrate formation temperature.
Wireline tools were blocked by a bridge inside the tubing string and further pulling
caused separation. Subsequently the lubricator was found to be full of hydrates.
141
Attempts were made to melt hydrates by (1) pouring glycol into the top of the
tubing, (2) using heated mud and seawater, (3) increasing the pressure up to 7,000 psi
at the surface to break the hydrate plug. The above attempts were unsuccessful and
the authors noted that the pressure increase caused a more stable hydrate, rather than
blowing it from the tubing.
A coiled tubing string was stripped inside the tubing and 175oF glycol was
circulated to the hydrate plug at 311 ft. Direct contact with the hot glycol removed
the hydrate plug but more than 13 days were lost because of this incident.
Case Study 24
Davalath and Barker (1993) also reported hydrate formation during well
abandonment in the Gulf of Mexico. During normal production methanol was
injected at the subsea tree. After stopping production the flow lines and tree piping
were filled with seawater and corrosion inhibitor from the surface to the seafloor.
During plug and abandonment operations, the operator found ice-like solids inside the
tubing bore of the tree at the seafloor and in the annulus bore. The solid hydrate
plugs were dissolved by circulating heated CaBr2 brine through a coiled tubing string
run inside the tubing.
142
line was a Separator-Receiver Unit (SRU-10) which contained a pig receiver and
blowdown.
Temperatures were not analyzed because the RTD was an external measurement.
However, the pressures at the four sites, the orifice measurement, and the gamma ray
measurements proved invaluable in analyzing hydrate formation and dissociation.
The following steps were used to conduct a test:
143
Test
Dates
Block Time, hrs
Plug Length, ft
Max P, psi
Max Gas Sprfcl
Velocity cm/s
Max Load, n
Leakage, Mass/
Load (g/s/n)
Max plug
Velocity, ft/s
Shr Strss N/cm2
1
1/27-31/97
85
NA
174
12.07
2
2/1-5/97
62
NA
Aborted
NA
3
2/6-8/97
37
25
390
NA
4
2/19-20/97
143
90, 300, 30, 70
475
1.15
9857
0.00150.0067
NA
NA
NA
2960
0.00029
26908
0.00038
NA
270
65
0.13
NA
2.14
2.29
144
145
few reservoirs and no current pipelines or process conditions are above 6000
psia.
Rule-of-Thumb 12. (Section II.F.2.b) PVP may be used to inhibit pipelines with
subcooling less than 10oF for flow lines with short gas residence times (less than
20 minutes).
146
Rule of Thumb 19. Regardless of the method(s) used to dissociate the hydrates,
the time required for hydrate dissociation is usually days, weeks, or months.
After a deliberate dissociation action is taken, both confidence and patience are
required to observe the result over a long period of time.
Rule of Thumb 20. (Section III.C) When dissociating a hydrate plug, it should
always be assumed that multiple plugs exist both from a safety and a technical
standpoint. While one plug may cause the initial flow blockage, a shut-in will
cause the entire line to rapidly cool into the hydrate region, and low lying points
of water accumulation will rapidly convert to hydrate at water-gas interfaces.
Rule of Thumb 21. (Section III.C.3) Because the limits of a hydrate plug cannot
be easily located in a subsea environment, heating is not recommended for
subsea dissociation.
Rule-of-Thumb 23. (Section IV.B.1.b) The cost of a fixed leg North Sea platforms
is $77,000/ton.
147
148
References
Aarseth, F., Use of Electrical Power in Control of Wax and Hydrates, Proc 1997
Offshore Technology Conference, paper OTC 8541, Houston, TX, May 5-8, 1997.
Argo, C.B., Blain, R.A., Osborne, C.G., Priestley, I.D., Commercial Deployment of
Low Dosage Hydrate Inhibitors in a Southern North Sea 69 Kilometer Wet-Gas
Subsea Pipeline, SPE 37255, Proc. SPE Int. Symp. on Oilfield Chemistry,
Houston, Texas (18-21 February 1997)
Argo, C.B., Osborne, C.G., Personal Communication Estimation of Capital and
Operating Cost Associated with Threshold Hydrate Inhibitors, BP Sunbury
Research Centre, U.K. July 18, 1997.
Austvik, T., Personal Communication Regarding Safety, Prevention, Remediation and
Economics at Statoil Reseach Center, Trondheim, Norway, July 13 - 15, 1997.
Austvik, T., Hustvedt, E., Meland, B., Berge, L., Lysne, D., Tommeliten Gamma
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