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Flow Assurance
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Oil and Gas Chemistry Management Series
Flow Assurance
Volume II
Edited by
Qiwei Wang
Saudi Aramco, Dhahran, Saudi Arabia
Gulf Professional Publishing is an imprint of Elsevier
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Contents
List of contributors ..................................................................................................xv
CHAPTER 1 Gas hydrate management ............................................. 1
Gaurav Bhatnagar and Shawn Gao
1.1 Introduction ....................................................................................2
1.2 Fundamentals of hydrate................................................................3
1.2.1 Definition ............................................................................ 3
1.2.2 Structures............................................................................. 3
1.2.3 Phase behavior .................................................................... 6
1.2.4 Properties............................................................................. 8
1.3 Hydrate formation ........................................................................10
1.3.1 Hydrate formation scenarios............................................. 10
1.3.2 Hydrate formation mechanism ......................................... 10
1.4 Hydrate management in production systems...............................11
1.4.1 Risk assessment................................................................. 12
1.4.2 Hydrate modeling.............................................................. 12
1.5 Temperature control .....................................................................27
1.5.1 Thermal insulation ............................................................ 27
1.5.2 Active heating ................................................................... 32
1.6 Chemical inhibition ......................................................................36
1.6.1 Thermodynamic hydrate inhibitors................................... 36
1.6.2 Low-dosage hydrate inhibitors ......................................... 40
1.7 Dehydration ..................................................................................64
1.8 Hydrate remediation.....................................................................66
1.8.1 Depressurization................................................................ 66
1.8.2 Heating .............................................................................. 67
1.8.3 Chemical dissociation ....................................................... 68
1.8.4 Model predictions for remediation ................................... 69
1.9 Case studies ..................................................................................69
1.9.1 Hydrate management in dry tree facility facilities .......... 69
1.9.2 Low-dosage hydrate inhibitor field application ............... 72
1.9.3 Tommeliten-gamma field ................................................. 73
1.9.4 Remediation of hydrate plug in west Africa deepwater
floating production storage and offloading............................ 75
1.10 Summary.......................................................................................77
Nomenclature............................................................................... 77
References.................................................................................... 78
v
vi Contents
CHAPTER 2 Paraffin management.................................................. 85

Mike Newberry and David W. Jennings
2.1 History of paraffin management developments ..........................85
2.2 Crude oil and paraffin chemistry .................................................88
2.3 Paraffin analysis and crude oil characterization..........................91
2.3.1 Paraffin analysis methods ................................................. 91
2.3.2 Crude oil characterization................................................. 93
2.4 Paraffin deposition .....................................................................103
2.4.1 Paraffin deposition mechanisms ..................................... 103
2.4.2 Paraffin deposition modeling.......................................... 106
2.4.3 Paraffin deposit characteristics ....................................... 111
2.4.4 Paraffin deposition control.............................................. 114
2.5 Pour point/crude oil gelling problems .......................................153
2.5.1 Crude oil gelling mechanism.......................................... 153
2.5.2 Gelled flowline characteristics ....................................... 155
2.5.3 Pour point treatment........................................................ 156
2.6 Case histories..............................................................................165
2.6.1 Formation damage .......................................................... 165
2.6.2 Well tubing deposition.................................................... 168
2.6.3 Flowline deposition......................................................... 170
2.6.4 Tank bottoms................................................................... 175
2.7 Summary.....................................................................................175
Nomenclature............................................................................. 176
References.................................................................................. 177
CHAPTER 3 Asphaltene management........................................... 185

Priyanka Juyal and Andrew T Yen
3.1 Introduction ................................................................................186
3.2 Chemistry of asphaltenes ...........................................................186
3.2.1 Composition and structure .............................................. 186
3.2.2 Solubility and aggregation .............................................. 188
3.3 Experimental techniques for asphaltene stability prediction .........191
3.3.1 Solids detection system................................................... 191
3.3.2 DeBoer plot ..................................................................... 192
3.3.3 Dead oil tests................................................................... 192
3.4 Asphaltene stability modeling....................................................194
3.4.1 Asphaltene instability trend modeling............................ 194
3.4.2 Asphaltene deposition model.......................................... 195
3.5 Asphaltene inhibitor lab tests.....................................................198
3.5.1 Precipitation tests ............................................................ 199
Contents vii
3.5.2 Deposition tests ............................................................... 201

3.5.3 Live oil tests.................................................................... 207
3.6 Asphaltene control in oil production .........................................211
3.6.1 Prevention........................................................................ 211
3.6.2 Remediation .................................................................... 213
3.7 Case studies ................................................................................213
3.7.1 Lab screening methods for field applications ................ 213
3.7.2 Evaluating asphaltene inhibitors for an offshore
alaskan producer ............................................................. 214
3.7.3 Development of multifunctional stabilizers of
asphaltenes ...................................................................... 215
3.8 Conclusion and path forward .....................................................215
Acknowledgment ....................................................................... 217
Nomenclature............................................................................. 217
References.................................................................................. 218
CHAPTER 4 Naphthenate and carboxylate soap treatment......... 227
Jonathan J. Wylde
4.1 Introduction ................................................................................228
4.1.1 Overview and chapter orientation .................................. 228
4.1.2 Naphthenates and recent history..................................... 228
4.1.3 Definitions: acid crude oil and “naphthenates”.............. 231
4.1.4 Origin of acidic crude ..................................................... 234
4.1.5 Carboxylate and naphthenate soap operational
challenges ........................................................................ 235
4.1.6 The continuum model ..................................................... 237
4.2 Fouling mechanisms of naphthenate and carboxylate
soaps ...........................................................................................238
4.2.1 Analytical techniques for acidic species in
crude oils ......................................................................... 238
4.2.2 Soap emulsions ............................................................... 244
4.2.3 Naphthenate soap solids.................................................. 252
4.2.4 High calcium in crude caused by oil-dispersible
naphthenates .................................................................... 259
4.2.5 Refinery challenges overview......................................... 262
4.3 Chemical control methodologies and laboratory testing...........263
4.3.1 Introduction ..................................................................... 263
4.3.2 Preventive chemical strategies........................................ 264
4.3.3 Remediation and remedial chemical strategies .............. 270
4.3.4 Laboratory and field testing............................................ 271
4.4 Concluding remarks and remaining challenges.........................272
viii Contents
Nomenclature............................................................................. 273
Acknowledgments ..................................................................... 274
References.................................................................................. 274
CHAPTER 5 Inorganic mineral scale mitigation.......................... 287

Gordon Michael Graham and Dario Marcello Frigo
5.1 Introduction ................................................................................288
5.1.1 The role of water............................................................. 289
5.1.2 Inorganic mineral scaling in the oil environment .......... 291
5.2 Basic principles of inorganic scale formation ...........................293
5.2.1 Types of inorganic mineral scale ................................... 293
5.2.2 Inorganic mineral scale formation.................................. 298
5.2.3 Scale nucleation and growth........................................... 305
5.2.4 Thermodynamics and kinetics ........................................ 309
5.3 Scale prediction ..........................................................................311
5.3.1 Scale prediction as a component of scale
management .................................................................... 311
5.3.2 Scale prediction outputs.................................................. 312
5.3.3 Theory of scale prediction .............................................. 315
5.3.4 Importance of quality input data .................................... 319
5.3.5 Example of the utility of modern scale
prediction packages......................................................... 321
5.3.6 Limitations of scale prediction ....................................... 322
5.4 Scale control...............................................................................323
5.4.1 Treatment options and scale control strategies .............. 323
5.4.2 Chemical inhibition......................................................... 330
5.4.3 Types of scale inhibitors commonly used in oil
industry............................................................................ 334
5.4.4 Brief history of scale inhibitor development.................. 341
5.4.5 Chemical deployment ..................................................... 342
5.4.6 Chemical inhibition......................................................... 344
5.4.7 Factors controlling the performance of
generically different inhibitor chemistries ..................... 348
5.4.8 Laboratory assessment of scale inhibitors...................... 359
5.4.9 Chemical qualification: final considerations .................. 371
5.5 Scale inhibitor squeeze...............................................................372
5.5.1 Chemical squeeze process .............................................. 372
5.5.2 Chemical retention mechanisms ..................................... 381
5.5.3 Chemical testing of scale inhibitor squeeze
treatments: reservoir condition core flooding ................ 387
Contents ix
5.5.4 The importance of appropriate core flood testing

protocols .......................................................................... 388
5.5.5 SI Application considerations: formation damage
and inhibitor retention/release properties ....................... 392
5.5.6 Importance of accurate assay and monitoring................ 403
5.5.7 Isotherm derivation and near-wellbore simulation......... 406
5.6 Scale remediation .......................................................................412
5.6.1 Acid soluble vs acid insoluble scales ............................. 413
5.6.2 Mechanical Remediation/Physical Methods................... 414
5.6.3 Chemical dissolution....................................................... 416
5.6.4 Chemical deployment in scale dissolution ..................... 417
5.6.5 Acids for Scale Dissolution ............................................ 419
5.6.6 Chelating agents for scale dissolution ............................ 422
5.7 Summary.....................................................................................426
Nomenclature............................................................................. 426
References.................................................................................. 428
CHAPTER 6 Sand control completion using in-situ resin

consolidation............................................................. 443
Philip Nguyen and Mike Sanders
6.1 Sand control................................................................................443
6.1.1 Mechanisms and causes of sand production .................. 443
6.1.2 Problems/issues of sand production ............................... 444
6.1.3 Sand control methods...................................................... 444
6.1.4 Other wellbore stabilization methods for
sand control ..................................................................... 447
6.1.5 Perforating techniques for completions using
sand-consolidation treatments......................................... 448
6.1.6 Chemical sand consolidation .......................................... 451
6.2 Fines Migration control..............................................................472
6.2.1 Mechanisms and causes .................................................. 472
6.2.2 Previous fines migration control methods...................... 474
6.2.3 Controlling fines migration into proppant pack ............. 475
6.2.4 Fines migration field case histories ................................ 478
6.3 Proppant flowback control .........................................................479
6.3.1 Primary proppant flowback control................................ 479
6.3.2 Remedial methods for proppant flowback ..................... 490
6.3.3 Lessons learned/recommendations ................................. 493
Nomenclature............................................................................. 494
References.................................................................................. 494
x Contents
CHAPTER 7 Condensate and water blocking removal ................ 503

Mashhad Fahes
7.1 Introduction ................................................................................503
7.2 Background theory .....................................................................505
7.2.1 Fluid phase behavior....................................................... 505
7.2.2 Pressure profiles .............................................................. 506
7.2.3 Two-phase flow challenges ............................................ 509
7.3 Field examples and industry practice ........................................514
7.3.1 Ichthys gas-condensate field in Australia....................... 514
7.3.2 Cupiagua gas-condensate field in Columbia .................. 515
7.3.3 Other examples ............................................................... 516
7.4 Recent advances in research and development .........................520
7.4.1 Wettability alteration ...................................................... 520
7.4.2 CO2 huff-n-puff............................................................... 528
7.4.3 Other new technologies .................................................. 530
7.5 Final remarks..............................................................................530
Nomenclature............................................................................. 531
References.................................................................................. 532
CHAPTER 8 Foam-assisted liquid lift ........................................... 541

Fenfen Huang and Kees C.A.M. Veeken
8.1 Introduction ................................................................................542
8.2 Liquid loading and deliquification.............................................544
8.2.1 Liquid loading ................................................................. 544
8.2.2 Continuous deliquification.............................................. 549
8.2.3 Intermittent deliquification ............................................. 551
8.3 Foam-assisted lift .......................................................................552
8.3.1 Foam-assisted lift performance....................................... 552
8.3.2 Foam-assisted lift operating envelope ............................ 555
8.3.3 Foam-assisted gas lift...................................................... 556
8.3.4 Surface foam-assisted lift................................................ 556
8.4 Foam-assisted lift application ....................................................556
8.5 Well performance.......................................................................557
8.5.1 Collect well data ............................................................. 557
8.5.2 Diagnose and forecast liquid loading ............................. 557
8.5.3 Predict foam-assisted lift operating parameters ............. 559
8.6 Laboratory testing ......................................................................562
8.6.1 Foamer performance ....................................................... 564
8.6.2 Secondary performance .................................................. 566
8.7 Foam-assisted lift field testing...................................................568
Contents xi
8.7.1 Batch foam-assisted lift trial........................................... 569

8.7.2 Continuous foam-assisted lift trial.................................. 570
8.8 Foam-assisted lift application ....................................................571
8.8.1 Continuous or intermittent foam-assisted lift................. 571
8.8.2 Solid or liquid foamer..................................................... 572
8.8.3 Annulus or capillary........................................................ 572
8.8.4 Capillary specifications................................................... 576
8.8.5 Surface injection system ................................................. 578
8.9 Foam-assisted lift operation .......................................................582
8.9.1 Optimizing foam-assisted lift ......................................... 583
8.9.2 Sustaining foam-assisted lift........................................... 587
8.10 Case studies of successful foamer applications.........................590
8.10.1 Optimize horizontal wells with batch foamer
treatment........................................................................ 590
8.10.2 Continuous foam in conjunction with dry-gas-lift ....... 593
8.10.3 Innovative foamer as sustainable deliquification
solution .......................................................................... 596
8.10.4 Use foam to remove liquid in subsea flow lines
and enhance production ................................................ 598
8.10.5 Foam-assisted lift to optimize mature oil wells ........... 602
8.11 Remaining challenges ................................................................603
Nomenclature............................................................................. 604
References.................................................................................. 605
CHAPTER 9 Corrosion inhibition .................................................. 609

Jeremy Moloney, Dharmendr Kumar,
Venkata Muralidhar K and Thunyaluk Pojtanabuntoeng
9.1 Corrosion inhibitors....................................................................610
9.1.1 Environmental conditioners/scavengers ......................... 611
9.1.2 Interface inhibitors .......................................................... 611
9.2 Mechanism of corrosion inhibition............................................612
9.2.1 Environmental conditioners/scavengers ......................... 612
9.2.2 Interface inhibitors .......................................................... 613
9.3 Measurement of corrosion inhibition.........................................617
9.4 Oilfield corrosion inhibitor chemistry examples .......................619
9.5 Molecular modeling of corrosion inhibitors..............................619
9.5.1 Computation of quantum chemical descriptors.............. 625
9.5.2 Metal inhibitor interactions using density functional
theory............................................................................... 628
9.5.3 Molecular dynamics study .............................................. 630
xii Contents
9.5.4 Monte Carlo simulations................................................. 632

9.5.5 Synergistic effect study using molecular modeling ....... 633
9.5.6 Screening of corrosion inhibitors using machine
learning............................................................................ 635
9.6 Corrosion inhibitor performance evaluation..............................637
9.6.1 Metal samples ................................................................. 639
9.6.2 Solution chemistry .......................................................... 640
9.6.3 Test parameters ............................................................... 641
9.7 Corrosion rate measurement techniques ....................................654
9.7.1 Gravimetry (weight loss measurements) ........................ 654
9.7.2 Electrochemical techniques ............................................ 656
9.8 Additional performance evaluations ..........................................662
9.8.1 Partitioning ...................................................................... 662
9.8.2 Persistency....................................................................... 663
9.8.3 Pitting tendency analysis ................................................ 664
9.9 Surface characterization .............................................................666
9.9.1 Atomic force microscopy................................................ 666
9.9.2 Fourier transform infrared spectroscopy ........................ 667
9.9.3 X-ray photoelectron spectroscopy .................................. 668
9.9.4 Others .............................................................................. 668
9.10 Compatibility tests......................................................................668
9.10.1 Compatibility with metallic materials .......................... 669
9.10.2 Compatibility with nonmetallic materials .................... 671
9.10.3 Foaming and emulsion tendency .................................. 672
9.10.4 Physical properties, product stability,
and additional considerations ....................................... 674
9.11 Field performance evaluation ....................................................675
9.11.1 Corrosion monitoring.................................................... 676
9.11.2 Corrosion inhibitor residual measurements.................. 677
9.11.3 Water chemistry analysis .............................................. 679
9.12 Case studies ................................................................................680
9.12.1 Field application of corrosion inhibitors in sweet
(carbon dioxide containing) systems ............................ 680
9.12.2 Field application of corrosion inhibitors in sour
(hydrogen sulfide containing) systems ......................... 684
9.12.3 Learnings from the literature case studies.................... 688
9.13 Summary.....................................................................................689
Acknowledgments ..................................................................... 691
Nomenclature............................................................................. 691
References.................................................................................. 693
Contents xiii
CHAPTER 10 Microbial control ...................................................... 709

Xiangyang Zhu
10.1 Introduction ................................................................................709
10.2 Major microorganisms in oil and gas industry..........................711
10.2.1 Sulfate-reducing bacteria and archaea.......................... 712
10.2.2 Methanogens ................................................................. 715
10.2.3 Acid-producing bacteria................................................ 717
10.2.4 Iron- and manganese-oxidizing bacteria ...................... 718
10.3 Biocide classification .................................................................719
10.3.1 Nonoxidizing biocides .................................................. 720
10.3.2 Oxidizing biocides ........................................................ 726
10.3.3 Preservatives.................................................................. 728
10.4 Biocide selection and performance evaluation..........................729
10.4.1 Considerations for biocide selection and
performance evaluation................................................. 729
10.4.2 Methods for biocide evaluation .................................... 732
10.5 Biocide treatment practices........................................................743
10.6 Biocide residual monitoring.......................................................746
10.7 Microbial monitoring for treatment effectiveness .....................747
10.8 Alternative methods for microbial control ................................749
10.8.1 Nitrate............................................................................ 749
10.8.2 Bacteriophage................................................................ 751
10.8.3 Physical processes......................................................... 752
10.9 Final remarks..............................................................................756
Nomenclature............................................................................. 757
References.................................................................................. 758
Index ......................................................................................................................775
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List of contributors
Gaurav Bhatnagar
Shell International Exploration and Production, Houston, TX, United States
Mashhad Fahes
The University of Oklahoma, Norman, OK, United States
Dario Marcello Frigo
Scaled Solutions Ltd., Livingston, Scotland, United Kingdom
Shawn Gao
Gordon Michael Graham
Scaled Solutions Ltd., Livingston, Scotland, United Kingdom
Fenfen Huang
CandV Consulting and Services, Sugar Land, TX, United States
David W. Jennings
Baker Hughes, Sugar Land, TX, United States
Priyanka Juyal
ChampionX LLC, Sugar Land, TX, United States
Dharmendr Kumar
TCS Research, Tata Consultancy Services Ltd., Pune, Maharashtra, India
Jeremy Moloney
ChampionX, Sugar Land, TX, United States
Venkata Muralidhar K
TCS Research, Tata Consultancy Services Ltd., Pune, Maharashtra, India
Mike Newberry
Baker Hughes, Sugar Land, TX, United States
Philip Nguyen
Halliburton, Houston, TX, United States
Thunyaluk Pojtanabuntoeng
Curtin University, Perth, WA, Australia
Mike Sanders
Halliburton, Houston, TX, United States
Kees C.A.M. Veeken
Mature Gas Well Consultancy, Gieten, Drenthe, The Netherlands
xv
xvi List of contributors
Jonathan J. Wylde
Heriot-Watt University, Edinburgh, Scotland, United Kingdom; Clariant Oil
Services, Clariant Corporation, Houston, TX, United States
Andrew T Yen
ENNOVA LLC, Stafford, TX, United States
Xiangyang Zhu
Saudi Aramco, Dhahran, Saudi Arabia
CHAPTER
Gas hydrate management
Gaurav Bhatnagar and Shawn Gao

1
Chapter outline
1.1 Introduction ................................................................................................... 2
1.2 Fundamentals of hydrate ................................................................................. 3
1.2.1 Definition .....................................................................................3
1.2.2 Structures ....................................................................................3
1.2.3 Phase behavior .............................................................................6
1.2.4 Properties .....................................................................................8
1.3 Hydrate formation ......................................................................................... 10
1.3.1 Hydrate formation scenarios .........................................................10
1.3.2 Hydrate formation mechanism ......................................................10
1.4 Hydrate management in production systems ................................................... 11
1.4.1 Risk assessment .........................................................................12
1.4.2 Hydrate modeling ........................................................................12
1.5 Temperature control ..................................................................................... 27
1.5.1 Thermal insulation ......................................................................27
1.5.2 Active heating .............................................................................32
1.6 Chemical inhibition ...................................................................................... 36
1.6.1 Thermodynamic hydrate inhibitors ................................................36
1.6.2 Low-dosage hydrate inhibitors ......................................................40
1.7 Dehydration .................................................................................................. 64
1.8 Hydrate remediation ..................................................................................... 66
1.8.1 Depressurization .........................................................................66
1.8.2 Heating ......................................................................................67
1.8.3 Chemical dissociation ..................................................................68
1.8.4 Model predictions for remediation ................................................69
1.9 Case studies ................................................................................................ 69
1.9.1 Hydrate management in dry tree facility facilities ...........................69
1.9.2 Low-dosage hydrate inhibitor field application ...............................72
1.9.3 Tommeliten-gamma field .............................................................73
Flow Assurance. DOI: https://doi.org/10.1016/B978-0-12-822010-8.00009-X

© 2022 Elsevier Inc. All rights reserved.
1
2 CHAPTER 1 Gas hydrate management
1.9.4 Remediation of hydrate plug in west Africa deepwater floating

production storage and offloading .................................................75
1.10 Summary ...................................................................................................... 77
Nomenclature ........................................................................................................ 77
References ............................................................................................................ 78
1.1 Introduction
First discovered in 1810, gas hydrates are nonstoichiometric crystalline ice-
like compounds composed of cooperative hydrogen-bonded water molecules
forming nano-scale clathrate cage structures that trap smaller guest molecules.
They can form naturally under certain conditions of pressure and temperature
within a gas/water mixture. Gas hydrates attract interest from many different
fields of study since naturally occurring gas hydrates have been found in
diverse conditions and locations, such as arctic permafrost, under the ocean
floor, and even suspected on some other bodies in the solar system. Gas
hydrates can also form during extraction/transport/process of oil/gas under cer-
tain pressure/temperature conditions in presence of water, which can cause
production interruption, asset integrity, and safety issues. This type of hydrates
will be the focus of this chapter, which covers the fundamentals of gas
hydrates and hydrate management strategies in oil/gas industry. Hydrates in
nature play a big role in the global carbon and climate cycles and are also con-
sidered an alternative source of energy.
Once a hydrate plug is formed in the oil/gas production system, it can be
very challenging to remediate, especially in deepwater, and can bear signifi-
cant implications in terms of deferred production, asset integrity, and safety.
The formation of hydrate can result in significant production loss. Depending
on the options available, remediating hydrate can take a long time, during
which the production can be either compromised or completely stopped. For
example, a hydrate plug in a deepwater flowline took a year to dissociate and
the production was lost during the entire time. In case the hydrate plug is
formed in gas export line, the entire production of a platform will be shut
down in that scenario.
Formation of hydrate is also integrity and safety concern. The risks are mainly
related to the remediation process. Due to the large amount of gas release when
dissociated, adding heat to dissociate hydrate in confined volume can create
extremely high pressure that can burst the containment barrier, which have
resulted in fatalities. A recent study even indicated that gas hydrate may be one
of the root causes for the Deepwater Horizon explosion [1]. When depressuriza-
tion is applied to dissociate a hydrate plug, the hydrate plug can be suddenly dis-
lodged and pushed toward to the low-pressure end at high speed. The resulting
hydrate projectile has caused asset damage in the past.
1.2 Fundamentals of hydrate 3
1.2 Fundamentals of hydrate

1.2.1 Definition
In the oil/gas industry, gas hydrates, clathrate hydrates, and hydrates are often used
interchangeably. They are ice-like solid compounds that typically form under high
pressure and low-temperature conditions in presence of both water and light hydro-
carbon molecules [2]. Natural gas hydrates are composed of approximately 85 mol.%
water, therefore they have many physical properties similar to those of ice. For
instance, the appearance and mechanical properties of hydrates are comparable to
those of ice. The densities of hydrates vary somewhat due to the nature of the guest
molecule(s) and the formation conditions but are generally comparable to that of ice.
Although hydrates were first discovered over 200 years ago, no practical
implication was realized until 1934 when it was discovered that it was gas
hydrates, not ice, that plugged natural gas pipelines. This brought a renewed burst
of research interests on gas hydrates, especially focusing on determining thermo-
dynamic and structural properties and preventing hydrate plugs.
Naturally occurring natural gas hydrates were predicted and found by Russian
researchers in 1960s. This brought another surge of research interest that considered
gas hydrates as a potential energy resource and as an important factor affecting
global climate changes. The cumulative efforts, beginning with Humphrey Davy in
1810, provided tremendous amounts of knowledge about the thermodynamic, phys-
ical, and structure properties of gas hydrates and a rich collection of hydrate for-
mers, including nitrogen, carbon dioxide, hydrogen sulfide, methane, ethane,
propane, iso-butane, n-butane, and some branched or cyclic C5C8 hydrocarbons.
1.2.2 Structures
In hydrate structures, water molecules are hydrogen bonded, while gaseous mole-
cules are bonded to those only via van der Waals forces. Though the energy
required to dissociate one hydrogen bond is about 5 kcal/mol, only 0.3 kcal/mol is
needed to break one van der Walls bond, suggesting that gaseous molecules are
only considered physically but not chemically entrapped into crystalline water
cages [2]. Depending on the sizes of the guest molecules included in the gas
hydrates, three hydrate structures are traditionally found, which are structure I, II,
and H (Table 1.1, Figs. 1.1 and 1.2). The basic repeating unit in structure I is a
primitive cubic lattice consisting of two pentagonal dodecahedra (512) (5 is the
number of edges in a face and 12 is the total number of this type of faces in a
cage) and six tetra-decahedra (51262) clathrate cages with a total number of 48
water molecules and a dimension of 1.2 nm. The average cavity radius of each
type of cage is 3.95 and 4.33 Å, respectively. Methane, ethane, CO2 and Xenon
are typical structure I hydrate formers. While methane and Xenon occupy both
small (512) and large (51262) cages, CO2 and ethane are only small enough to
dwell in large cages.
Table 1.1 Characteristics of hydrate cages of different structures.

Structure I (sI) Structure II (sII) Structure H (sH)
Small Large Small Large Small Medium Large

Cages 512 51262 512 51264 512 435663 51268
No. of cages per unit cell 2 6 16 8 3 2 1
No. of waters per unit cell 48 136 34
Average cage radius (Å) 3.95 4.33 3.91 4.73 3.91 4.05 5.71
Coordination number 20 24 20 28 20 20 36
FIGURE 1.1
Different types of cavities found in hydrates and respective unit structures of sI, sII and sH
structures [3].
Reproduced with permission from E.D. Sloan, C.A. Koh, Clathrate Hydrates of Natural Gases, third ed., CRC
Press, New York, 2008.
The repeating unit of structure II hydrate also contains two types of cavities 16
pentagonal dodecahedra 512 (3.91 Å) and 8 hexadecahedra 51262 (4.37 Å) composed
of 136 water molecules. Its lattice type is face-centered cubic and its unit dimension
is 1.7 nm. Most hydrates in the oil/gas industry are expected to be structure II
hydrates. In structure H, a layer of 512 (3.91 Å) cavities connects a layer of 51268
(4.06 Å) and 435663 (5.71 Å) cavities. In its hexagonal unit cell (a 5 1.21 nm,
c 5 1.01 nm), 34 water molecules form three 512, two 51268, and one 435663. One
unique feature of structure H is that both small and large sizes of molecules are
required to stabilize the structure. For example, neohexene and cycloheptane, which
cannot form hydrates alone, form structure H hydrates with the help of methane.
These three hydrate structures are important for the oil/gas industry because the types
of hydrocarbons encountered in the field can form all these three types of hydrates.
FIGURE 1.2
Comparison of guest molecule sizes and cavities occupied as simple hydrates.
With the advancement of experimental technologies and continuous research

efforts on clathrate hydrates, some new types of hydrate structures at high pressures
have been identified, mostly not relevant to oil/gas industry. It was discovered that
under a pressure of 0.8 GPa, tetrahydrofuran (THF) and deuterium oxide (D2O)
FIGURE 1.3
Packing and schematic view of the space-filling polyhedron.
Reproduced with permission from A. Kurnosov, V. Komarov, V. Voronin, et al., New clathrate hydrate structure:
high-pressure tetrahydrofuran hydrate with one type of cavity, Angewandte Chemie International Edition, 43
(2004): 29222924.
form an orthorhombic structure, in which water molecules form 14-hedra cages

with four tetra-, four penta, and six hexagonal faces (445466) that are able to pack
three-dimensionally without the need for other types of polyhedrons [4]. The stoi-
chiometric composition of a unit cell can be presented as 4T324D2O, where T3 is a
445466 cage. Projection of the structure along the b axis is presented in Fig. 1.3.
While investigating dimethyl ether (DME) hydrate using X-ray diffraction,
Udachin et al. [5] identified another new hydrate structure T that is dense and
highly complex (Fig. 1.4). It does not have 512 polyhedra and can contain
51263(P), 51262(T), 4151063(T’) and 425861(U) cages. This hydrate structure is tri-
gonal, space group P321, a 5 34.995 Å, c 5 12.368 Å, and stoichiometry can be
described as 12P12T24T12U348H2O. The DME molecules are accommodated
in all three types of large cages (P, T, T’) (Fig. 1.5), giving an overall composi-
tion of DME7.25H2O.
1.2.3 Phase behavior

The conditions required for hydrate formation and the resulting hydrate phase dia-
gram vary based on the types of hydrate formers. The typical four pillars of hydrate
formation are presence of free water, hydrate former(s), high pressure, and low tem-
perature with only a few exceptions, e.g., THF and ethylene oxide can form hydrate
with water under ambient pressure at B4.5 C and B11 C, respectively.
FIGURE 1.4
General view of the structure T hydrate as determined by single crystal.
Reproduced with permission from K. Udachin, C. Ratcliffe, J. Ripmeester, A dense and efficient clathrate
hydrate, Angewandte Chemie International Edition, 40(2001): 13031305.
FIGURE 1.5
View of the cages in the str. T hydrate.
Reproduced with permission from K. Udachin, C. Ratcliffe, J. Ripmeester, A dense and efficient clathrate
hydrate, Angewandte Chemie International Edition, 40(2001): 13031305.
Most hydrocarbons found in the oil/gas industry require high pressure to form
hydrate. At the same temperature, lighter hydrocarbon hydrate formers typically
require higher pressure to form hydrate than heavier hydrocarbon hydrate formers.
For example, at 10 C (50 F) with fresh water, methane hydrate’s equilibrium pres-
sure is about 1000 psia while it would only require about 250 psia to form ethane
hydrate. In addition, the salinity of water plays a key factor in the hydrate phase
diagram. From a molecular level, the presence of ions in the water can cause dis-
ruption in the formation process of hydrogen bonding structure of clathrate cages.
The higher the salinity, the higher the pressure required to form hydrate. Since the
hydrate structure itself is salt free, the hydrate formation process in saltwater would
extract water in the solution and convert them to hydrate while causing the salinity
of the remaining water to increase. For this reason, the hydrate formation in salty
Fresh Water 10wt% NaCl 20wt% NaCl 20vol% MEOH

10000
9000
8000 Hydrate Risk

i
7000
Pressure (psia)
6000
5000
4000
3000
2000 Hydrate Free Region

1000
0
30 40 50 60 70 80
Temperature (°F)
FIGURE 1.6
Typical hydrate phase diagram of a black oil system.
water will become self-inhibiting at a certain point of the conversion process. The
addition of water-soluble compounds such as methanol (MeOH) or glycol into the
water will require higher pressure to form a hydrate, a similar effect is observed
with higher salinity. This is the foundation to manage hydrate risk with thermody-
namic inhibitors (mostly MeOH, glycol, and to a lesser extent ethanol). Fig. 1.6 is
a typical hydrate phase diagram of a black oil system with different salinities. The
hydrate phase diagrams for natural gas are similar but without the inflection points
along the curve where the black oil system typically goes through the bubble point.
Obtaining accurate hydrate phase diagrams is a key step in proper hydrate risk
assessment and risk management and will be discussed in more details later.
1.2.4 Properties
All the hydrates implications and applications are rooted in their unique properties
under various conditions of temperature and pressure. The following are a few
properties that are particularly important to energy industry.
1.2.4.1 Mechanical properties

Experimental determination of the mechanical properties of clathrate hydrates is diffi-
cult due to the challenge of making pure nonporous hydrate samples. In addition, the
presence of residual water/ice and free gas in the system due to incomplete hydrate
formation process can also contribute to the measurement reliability. Therefore there
are considerable uncertainties associated with all the hydrate mechanical property mea-
surements. The following are a few general conclusions about the mechanical proper-
ties of gas hydrates based on experimental/theoretical studies and field observations.
• Generally speaking, the hydrate mechanical properties are similar to that of ice.
Once formed, they can be hard to remove mechanically and cannot be scrapped
off by sending down a pig like removing wax deposit. Doing so will only make
matters worse. Therefore the main hydrate management strategy is focused on
hydrate prevention in the first place and hydrate dissociation once formed.
• The elastic properties of gas hydrate depend on temperature, pressure, and
hydrate composition, including structure, guest molecule, and cage occupancy.
Lower temperature and higher pressure both contribute to an increased bulk
modulus and consequently make the hydrate harder.
• When well within the stability zone, the compressive strength of hydrates is
higher than that of ice however, the strengths become closer in value when
hydrate is less supercooled. This difference is attributed to the special hydrate
lattice structure and the host, guest and hostguest interactions.
1.2.4.2 Self-preservation during dissociation

Hydrate dissociation is an endothermic process similar to ice melting, but its heat of
dissociation (B54 kJ/mol for methane hydrate) is much higher than that of ice
(6 kJ/mole). During dissociation process, hydrates separate into water and guest
molecules by breaking up hydrogen bonding networks of water molecules and the
van der Waals interaction forces between guest and host water molecules. This pro-
cess takes up a significant amount of heat from the environment and causes the tem-
perature to drop, which contributes to the stability of the remaining hydrate, that is,
a self-preserving/limiting phenomenon. Without active supply of heat from the envi-
ronment, a hydrate plug can take up to a year to dissociate by itself. Therefore con-
tinuous supply of heat is key to modulate the rate of hydrate dissociation.
1.2.4.3 Large gas-to-hydrate volume ratio

A large volume of hydrate former gas can be released upon hydrate dissociation.
For example, one cubic foot of methane hydrate releases about 160 cubic feet of
gas under ambient condition. This has two key implications for oil/gas industry
applications:
• Low gas-to-oil ratio (GOR) fluid can become gas-starved during the hydrate
formation process and become self-limiting. Consequently, the hydrate
plugging risk during shut-in in such system can be much lower than a high
GOR fluid.
• Gas release during hydrate dissociation can quickly build pressure up in
confined volume, which can either cause pressure containment rupture or
rapid acceleration of dislodged hydrate plugs. This can pose asset integrity
risks and personnel safety risks.
1.3 Hydrate formation

1.3.1 Hydrate formation scenarios
As long as the requisites for hydrate formation are present, that is, high pressure,
low temperature, presence of hydrate formers and water, there are risks of hydrate
formation. The following are a few common scenarios to consider for the poten-
tial risk of hydrate formation in upstream production. Hydrate management strate-
gies will be covered in later half of this chapter.
1.3.1.1 Shut-in
Fluid temperature typically drops after production is shut-in and the flow has
stopped in cases where the environmental temperature is lower than the produc-
tion fluid temperature, e.g., deepwater, winter time. The pressure can also start
building up after shut-in. Both these changes can eventually push the system into
the hydrate formation conditions in either wells or flowlines.
1.3.1.2 Cold restart

If the shut-in period is long enough to push the system into hydrate conditions,
restarting the production from this state can pose a high hydrate formation risk since
the flow turbulence can greatly accelerate the mass transfer and cause rapid hydrate
formation. This risk is especially significant for long single flowline tiebacks.
1.3.1.3 Steady state

Some production system can enter hydrate formation condition during steady
state. This is less common for black oil system, but more common for gas system
due to the much smaller heat capacity and lack of insulation.
1.3.1.4 Gas injection, gas lift, or gas export

These gas systems rely on dehydration to control the risk of hydrate. However, the
dehydration can sometime underperform, or the water content measurement/reading
can be faulty. Hydrate can and have formed and plugged the line in these scenarios.
1.3.2 Hydrate formation mechanism

The molecular mechanism of hydrate formation is till yet to be fully understood [6].
One theory is that hydrate formation starts with some labile clusters with hydrate for-
mer molecules at the center (Fig. 1.7). These clusters then agglomerate and start to
from initial hydrate nucleation nuclei, which grows into bulk hydrate crystalline phase.
From a macroscopic perspective, hydrate is believed to form at water/oil or
gas interface. This has been the basis for the hydrate plugging model in oil/gas
industry. Jeong et al. [8] experimentally studied and imaged the hydrate formation
process of acoustically levitated water droplets in high pressure natural gas envi-
ronment. The experimental results match the existing conceptual model (Fig. 1.8).
1.4 Hydrate management in production systems 11
FIGURE 1.7
Labile-cluster model of hydrate nucleation: (A) labile clusters, (B) agglomeration of
clusters, (C) primary nucleolus, and (D) hydrate crystal [7].
Reproduced with permission from A. Hassanpouryouzband, E. Joonaki, M. Farahani, et al., Gas hydrates in
sustainable chemistry, Chemical Society Reviews, 49(2020): 52255309.
FIGURE 1.8
A series of back-illuminated optical images showing the evolution from a levitated water
droplet to a hydrate particle. (A) Initial water droplet. (B) Hydrate formation onset detected
via change in optical transmission relative to previous panel. (C) Shell thickening [2050 s
after panel (B)]. (D) Initial outward growth (14650 seconds after panel (B)). (E) and (F)
Hydrate propagation with a major roughness increase (respectively 25320 and 49410 s
after panel B).
Reproduced with permission from K. Jeong, P. Metaxas, A. Helberg, et al., Gas hydrate nucleation in
acoustically levitated water droplets, Chemical Engineering Journal, 433 (2021) 133494.
1.4 Hydrate management in production systems

Gas hydrate management in hydrocarbon production systems has conventionally
relied on complete prevention of hydrate formation, which leads to a predominantly
thermodynamics (phase behavior)-based operating strategy. As a result, system
design guidelines and operating strategies ensured that the production system is
never exposed to hydrate forming conditions during steady-state production as well
as during transient operations, such as production shut-ins and re-starts. Over the
last decade, fundamental improvements in understanding of hydrate formation,
including nucleation, kinetics of agglomeration and deposition have led the industry
to increasingly take a more risk-based approach in managing hydrates. The general
direction has been to identify the key risk factors that control hydrate formation
and then exploit them to optimize system design and operating strategies where the
risk is demonstrated to be low and manageable. The following sections discuss
some of these key risk factors involved. The strategies for prevention, mitigation,
and remediation will be presented in Sections 1.51.8.
1.4.1 Risk assessment

In hydrocarbon production systems, the following four conditions must typically
be met for gas hydrates to start forming:
• high pressure
• low temperature
• hydrate forming guest (gas) components
• water
These conditions provide a basic framework to assess the hydrate risk envelope
for the overall production system. Eliminating any of the above listed conditions/
variables effectively means that gas hydrates cannot thermodynamically form in the
system. Conventional hydrate management strategies often remove hydrate risk
through either eliminating one of the above conditions or through injection of
chemical inhibitors.
The pressuretemperature-based hydrate phase envelope defines the thermo-
dynamic risk region for a given fluid mixture. The region to the left of the hydrate
curve represents conditions where hydrates are thermodynamically stable,
whereas conditions to the right of the curve defines the region where hydrates
cannot form. This region also defines the operating envelope where hydrocarbon
production systems are typically designed to operate during steady-state produc-
tion as well as during transient events (shut-ins and re-starts).
1.4.2 Hydrate modeling

1.4.2.1 Thermodynamic modeling
As part of overall hydrate risk assessment, thermodynamic modeling often forms
the first step in evaluating whether any part of the production system is at risk of
entering or residing within the hydrate stable region. The theoretical framework
underlying thermodynamic modeling of gas hydrates was first postulated by van
der Waals and Platteeuw [9]. Their approach modeled the interaction between the
gas molecules and the clathrate lattice structure using a Lennard-Jones type poten-
tial. This model was further refined by Parrish and Prausnitz [10] using Kihara
parameters to characterize gas-water interaction. Importantly, they also developed a
simple computational algorithm to calculate the hydrate dissociation pressure at a
given temperature that formed the basis for several subsequent modeling
approaches. Since those early days of hydrate thermodynamic modeling, huge
improvements have been made in the modeling approaches and the data regression
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poisoning developed definite eye changes and retinal hæmorrhages.
Tortuosity and increased size of the retinal vessels were observed in
several instances.
Besides controlling the experiments of feeding and inhalation, the
inoculation experiments play a still more important part, as they
furnish the correlation, necessarily, of the histological changes found
as the result of poisoning by means of lead. In all the animals which
have died of poisoning, certain definite trains of symptoms made
their appearance. These symptoms were in practically all particulars
similar to those observed in industrial lead poisoning in man, the
onset of the affection and its clinical course corresponding to the
symptom-complex in man, including those of cortical involvement,
and often similar to the classical Jacksonian variety.
Throughout these experiments the animals exhibited no signs of
irritation, and during the initial period, even, when loss of weight was
a noticeable feature, their appetites remained exceedingly good;
they were quite friendly, and purred loudly when stroked; but when
symptoms of poisoning became manifest, particularly the onset of
paralysis, a definite change in mental phenomena took place: the
animals became quarrelsome, highly apprehensive of danger without
cause, morose and lethargic by turns. At this stage, in more than one
instance, acute encephalopathy supervened. The mental change
was peculiarly striking in reference to Mott’s case, quoted on p. 71,
as in all respects it was exactly analogous with the train of symptoms
recorded in that case. To sum up, the symptoms produced in the
experimental animals by the lead compounds inoculated and
respired, no matter what the particular compound of lead
experimented was, were as follows:
1. Slight preliminary rise in weight at the commencement of the
experiment, lasting from one to two weeks.
2. Progressive loss of weight, mainly due to the disappearance of
all fat, subcutaneous, kidney, mesenteric, etc., with associated
anæmia, and the curious sunken and pinched faces commonly
associated with saturnine cachexia.
3. Paresis of various types.
In the cat the muscles first affected are those of the back and the
quadriceps extensor of the hind-limbs. The onset of the paralysis is
slow and insidious, but may be acute; as a rule weakness in the
muscles of the lumbar region and the spine are the first symptoms;
secondly, inability to jump, owing to the weakness of the quadriceps
extensor, while the animal tends to fall over when turning round
quickly. Encephalitis occurs, and is frequently fatal. As a rule the
affection is unilateral; complete loss of consciousness may occur,
followed by slow but complete recovery. The animals gave no
evidence of suffering pain, and, when recovered from an attack of
encephalopathy, would at once take milk, but seemed dazed and
uncertain in their movements. When the animals reached the stage
of paralysis, they were destroyed under anæsthetics, and subjected
to post-mortem examination. The post-mortem findings of a typical
case were as follows:
The animal was emaciated, the fur easily pulled out, and the
muscles were exceedingly flaccid.
Rigor mortis was slow in making its appearance; the blood
remained fluid for a considerable time.
Practically no fat was to be found in the whole of the mesentery,
and the omentum was devoid of fat and shrivelled. The fat around
the kidneys had entirely disappeared. There was little orbital fat.
The peritoneum was thin and glistening, and very frail.
The whole of the mesenteric vessels, particularly in the region of
the large intestine and the ileo-cæcal valve, were engorged with
blood; whilst in the lower part of the small intestine, and often in the
duodenum, occasionally in the whole of the jejunum and ileum,
traces of minute hæmorrhages were found along the intestinal wall.
The liver was engorged with blood, as was the spleen.
The kidney capsule stripped easily, but was occasionally adherent
here and there. The whole of the cortical vessels were injected with
blood, the branching showing most distinctly.
A good deal of serous fluid was at times found underneath the
kidney capsule.
On section the cortex appeared engorged with blood, and showed
here and there, even to the naked eye, small hæmorrhages.
In the region of the appendix a few large mesenteric glands were
invariably found, whilst a few glands might also be found in the
wasted mesentery of the small intestine. In the region of the
appendix the glands were frequently dark in colour. On opening the
gut, minute hæmorrhages and ulcerated patches were to be found in
the lower part of the ileum; the ileo-cæcal valve, and the whole of the
large intestine, extending right up to the end of the appendix, was
covered with a dark slate-blue slime, in which lead could be easily
recognized by chemical processes.
Ulceration of the gastric mucous is uncommon, and only on one
occasion were any hæmorrhages found. In the thoracic cavity the
lungs were generally found to be emphysematous, and particularly in
those animals subjected to inhalation of lead frit containing angular
particles of lead glaze broncho-pneumonia was found.
The heart was flabby, and occasionally distinct roughening and
thickening of the valves was seen.
Nervous System.—On opening the skull, hæmorrhages were
frequently found at the base of the brain, occasionally situated over
the surface of the cerebrum. Minute hæmorrhages were found often
underneath the arachnoid membrane, but the largest hæmorrhages
were always found at the base of the brain, and spreading down into
the spinal canal along the medulla.
On removing the cord, minute hæmorrhages were found along the
surface, irregular in distribution, and never very large. On section the
brain and cord appeared normal.
Histology.—A large number of sections were prepared from the
animals developing symptoms of poisoning; the various tissues are
described seriatim:
Muscles.—These appear to have undergone general fatty
degeneration. The individual muscle fibres are indistinct in outline,
and show irregular areas stained by hæmatoxylin. Some infiltration
may be seen here and there between the muscle fibres, and minute
hæmorrhages are occasionally detected, the chief appearance being
that of general atrophy. The heart muscle shows similar
degeneration, and the tendency of the sarcolemma to break down
and stain irregularly is apparent. In many areas the muscle fibres
stain poorly, if at all. Occasionally minute hæmorrhages are found,
passing between the muscle fibres.
Liver.—The hepatic cells show varied degeneration; the vessels
passing between the cells are engorged with blood, the cells being
frequently much distorted from their general arrangement, and here
and there completely obliterated by small areas of exudation as well
as actual hæmorrhages.
Spleen.—The parenchyma shows masses of irregular spaces
filled with recently-shed blood; the individual cells show a granular
degeneration, with occasional basophile staining, the general
appearance being one of chronic congestion. Here and there cloudy
swelling may be seen.
Intestine.—Sections across the small intestine show atrophy of the
intestinal wall, slight degeneration of the muscular coats, with
infiltration and minute hæmorrhages.
Large Intestine.—Here similar minute hæmorrhages are found, in
no case large enough to be seen by the naked eye. Areas of necrotic
tissue are also seen in which considerable quantities of lead
sulphide particles are found.
PLATE I
Fig. 1.—Section of Large

Intestine of Animal
poisoned by Inhalation of
White Lead, showing
Excretion of Lead by
Tissues. (Stained Eosin and
Hæmatoxylin.) × 250.
The whole of the large intestine
was stained black, the staining
commencing at the ileo-cæcal
valve. No staining is
observable in the small
intestine; the line of
demarcation is sharp.
Fig. 2.—Intestinal Ulceration
in Turpentine Poisoning.
(Stained Eosin and
Hæmatoxylin.) × 250.
Fig. 3.—Section of Anterior

Crural Nerve from Animal
poisoned by Inhalation of
White Lead Dust, showing
Hæmorrhage in Nerve.
(Stained Hæmatoxylin and
Eosin.) × 250.
There was paralysis of the
quadriceps extensor on the
right side; the left leg was
unaffected and the left anterior
crural nerve was unaffected.
PLATE II
Fig. 1.—Section of Lung of
Animal exposed to
Inhalation of White Lead
Dust, showing Mass of Lead
in the Lung Substance.
Eosin, and treated with
H2S.) × 250.
Fig. 2.—Lung of Animal

exposed to Turpentine
Vapour. (Stained
Hæmatoxylin and Eosin.) ×
250.
Fig. 3.—Lung of Animal
exposed to Inhalation of
White Lead Dust, showing
Chronic Inflammation with
Exudation and Capillary
Leakage and Hæmorrhage.
Eosin.) × 250.
Lung.—Red or grey hepatization may be found, or a general

appearance of broncho-pneumonia, where the dust used contained
angular or insoluble substances. In animals subjected to prolonged
inhalation, particles of lead could be demonstrated in the alveolar
cells, and in the tissue beyond, either by staining with chromic acid
or by means of iodine. Staining by sulphuretted hydrogen is not very
satisfactory, as most animals resident in a large city show masses of
carbon situated in various parts of the alveolar cells. If, however, a
section be treated by means of iodine or chromic acid, and watched
under the microscope during the process, the particles of carbon are
easily differentiated from those of lead compounds.
Nervous System.—Sections of the brain and spinal cord, and of
the nerve supplying the paralyzed muscles, all exhibited the same
phenomena of minute hæmorrhages. In later cases some change in
the cells is found, but as a rule, beyond a slight increase of the
intracellular substance, little or no change is found in the cellular
elements of the brain; but in the region of the surface minute
hæmorrhages may be constantly traced, spreading over the surface
of the cortex. In the cord, sections made in various situations failed
to show any very definite degeneration, and little or no hæmorrhage
was observed amongst the cells of the cord. Hæmorrhages could
occasionally be seen on the surface.
In a number of animals the anterior crural nerves supplying the
paralyzed quadriceps extensor muscles were examined carefully
both for degeneration and for hæmorrhages. Very few degenerated
nerve fibres were found, not more than would be accounted for by
the minute hæmorrhages, which were found passing in between the
nerve bundles, and here and there producing pressure on the nerve
bundles themselves.
Kidney.—In the kidneys minute microscopical hæmorrhages,
some of them quite large, were found in the cortex. The
hæmorrhages are diffuse and irregular, and apparently due here, as
in other situations in the body, to the breaking down of minute
venioles rather than arterioles. In many cases the change is
capillary. Parenchymatous nephritis may be seen, probably resulting
from the transudation taking place from the vessel walls.
The chief view brought out in the histological examination of the
various organs is one of capillary hæmorrhage. This phenomenon is
not peculiar to lead poisoning, but, from the work of Moore of
Liverpool[4], it would seem that all heavy metals, such as bismuth,
mercury, not excepting iron, tend to produce a curious generalized
yielding of the minuter vessel walls. Armit[5] has demonstrated a
similar effect with nickel. The phenomena is, however, typically
associated with lead poisoning, and may, we think, be regarded as
the definite factor of chronic lead poisoning.
For the purposes of controlling the experiments of inhalation, two
other series of experiments were undertaken. In one instance an
animal was fed for two years on white lead; the animal was given 0·1
gramme per day, and this was increased up to 0·5 gramme, and
ultimately 1 gramme. This animal exhibited no symptoms whatever
of lead poisoning, and when it was killed, at the end of the time of
experiment, showed no apparent lesion, with the exception of very
marked staining of the colon and vermiform appendix. This staining
of the large intestine and the appendix, the engorgement of the
vessels, particularly of the omentum and mesentery, the
enlargement of the lymphatic glands in the neighbourhood of the
colon, ileo-cæcal valve, and appendix, suggest the absorption of
lead in the upper part of the intestine, and its discharge or
elimination into the large intestine. That lead is absorbed into the
upper part of the intestine was demonstrated in the following
manner:
An animal was anæsthetized, an incision made, and a loop of
intestine pulled up and clamped off, a solution of lead chloride being
run into the loop by means of a hypodermic syringe. The mesenteric
vein passing from this loop of intestine was then carefully secured, a
small opening made in it, and the blood collected drop by drop until
some 40 c.c. had been collected, the time occupied being about
three-quarters of an hour. The blood thus collected was submitted to
chemical examination, and lead was demonstrated to be present.
Lead therefore passes direct from the intestine into the portal
circulation.
In only one of the feeding experiments with solid compounds of
lead was any definite symptom of lead poisoning produced, and in
this instance the compound used was dust collected from the flues of
a blast-furnace. This dust was afterwards found to contain a
considerable quantity of arsenic. The experiment cannot therefore be
regarded as conclusive. With the more soluble salts of lead,
however, such as the acetate, lead poisoning may be set up by
means of lead administered via the intestinal canal: 1 gramme of
lead acetate administered by means of a hypodermic syringe
through a catheter passed into the stomach of a cat produced
abortion in ten days, and death in three weeks. Four grammes of
acetate produced a similar effect in a dog in four weeks.
PLATE III
Fig. 1.—Kidney of Animal
poisoned with White Lead
(Inhalation), showing
Microscopical
Hæmorrhages. (Stained
250.
Fig. 2.—Kidney of Man dying

of Chronic Lead Poisoning.
Eosin.) × 250.
Fig. 3.—Brain of Young
Woman dying of Acute Lead
Encephalopathy, showing
Small Cerebral
Hæmorrhages. (Stained
250.
The two following cases, in which both chemical and histological

examination has been carried out on the tissues of persons who had
been employed in occupations which rendered them exposed to
absorption of lead, and who died with symptoms directly suggestive
of lead poisoning, may be added, as they confirm the experimental
results given above in all particulars:
Case 1.—A woman aged twenty-one, employed in a litho-transfer
works, who died after a short illness during which the chief
symptoms were headache and mental clouding.
At the post-mortem examination no pathological lesions were
discoverable with the exception of a small gland which had become
calcareous, situated near the right bronchus. The brain was injected
over the left cerebral hemisphere, but no hæmorrhages were to be
seen with the naked eye. There were no other pathological signs. A
portion of the brain showing the injection and congestion were
submitted to histological and chemical analysis. Histologically the
brain tissue was found to be normal, with the exception of slight
chromatolysis of some of the larger cells; but interspersed about the
whole section in the slides examined, but more particularly in the
area of the cortex, minute microscopical hæmorrhages were found
(see Fig. 3). Here and there these hæmorrhages were seen related
to the expanded capillaries, all of which showed considerable
engorgement with blood. The arteries and veins themselves were, in
addition, considerably distended. There was no interstitial
degeneration of the neuroglia noticed. A few patches were found
which apparently represented old hæmorrhages undergoing gradual
fibroid degeneration. In no case were the hæmorrhages of a size
that could be detected by the naked eye.
Two hundred and fifty grammes of the injected area of the brain
were submitted to chemical examination by the moist process
described in the chapter on Chemical Analysis. The nitric acid filtrate
from the electrolytic deposition gave a well-marked precipitate with
sulphuretted hydrogen, which was filtered off and recognized as
lead. There was only the merest trace of iron present. By colorimetric
estimation the quantity of lead found present in the brain estimated
as Pb was 0·0143 gramme. The quantity found in 250 grammes of
brain substance examined from the injected area was 0·0041
gramme.
Case 2.—A man who had been employed in an electrical
accumulator works for a considerable time, and who had had a
history of several attacks of lead colic and one of lead paresis
affecting both hands.
The man’s work in connection with lead ceased from the time of
the paresis, but some three years subsequently he died with cerebral
hæmorrhage.
Portions of the organs, brain, kidney, liver, and spleen, were
examined histologically, stained in the ordinary way with
hæmatoxylin and eosin. In the brain the same marked microscopical
hæmorrhages were observed as described in the previous case, and
in addition many more areas of old fibroid scars, very minute, but
apparently corresponding to earlier minute hæmorrhages. The
kidney showed definite interstitial hæmorrhage (see Plate III., Fig. 2),
as did the liver and spleen.
A portion of the brain was further submitted to chemical
examination, and 0·0014 gramme of lead was determined as
present.
The importance of this confirmatory evidence is undoubted, as the
presence of the capillary hæmorrhage existing in the tissues of a
person dying under suspicious circumstances when employed in a
lead process is confirmed by the chemical determination of lead in
the tissues.
The following tables, arranged under three headings, give some of
the experimental results obtained by submitting animals to the effect
of compounds of lead.
Table XI. gives the inoculation experiments.
The materials used in these experiments were those used in the
inhalation and feeding experiments. The experiments are also
arranged in such a manner that each series is a control one of the
other.
The amount of substance used for the inoculation gives some
rough idea of the dose required to produce poisoning in an animal;
but even this question of dose in absolute quantities, administered
hypodermically, shows considerable variation in the degree of
poisonous effect. The first animal in Table XI. was inoculated with
acetate, this being one of the more soluble lead compounds, and
was given it in three small doses. The animal received 0·3 gramme
per kilogramme of body weight, whereas in No. 35 2 grammes of
washed frit—that is to say, lead glaze formed by fusing together
litharge and silica—actually did produce symptoms, but of a mild
nature. Animal No. 33 only had 0·16 gramme, being 0·05 gramme
per kilogramme of body weight; and this caused acute symptoms.
0·35 gramme of white lead in a 3·500 kilogramme animal (No. 31)
produced no symptoms at all. In the list of the inoculation
experiments, three animals only exhibited no symptoms—one of
these (No. 31) which was given white lead hypodermically, and Nos.
41 and 42, which were inoculated with lead silicate or lead frit, which
had been previously treated with acetic acid or water.
Several practical points arise from these experiments, notably with
regard to the frits, as it is seen that a considerable amount of the
toxic properties contained in frit are removed by washing—most by
washing with acetic acid and water, but also to some extent by
washing with hot water alone, showing that in the ordinary
production of lead frit for pottery purposes a certain amount of lead
in a soluble condition as regards the body tissues was still present.
This is no doubt entangled in the true silicates in the forms of oxides,
or even as carbonate. Further, the toxicity of the lead compounds
used may certainly be arranged in the order of their solubility with
regard to the animal tissues, the acetate being the most poisonous,
and the frit, when washed, the least; but unwashed frit, even in
relatively small doses, may produce poisoning. This point is still
further emphasized in Table XIII. Animal No. 42, four months after
previous inoculation, showed no signs of poisoning. Lead nitrate in
water was therefore given in quantities of 0·01 gramme per diem;
one month later this animal developed poisoning.
Table XII. deals with the feeding experiments.
In these experiments acetate was given in one case only, and then
in the form of pills coated with keratin. It is impossible to say,
however, whether the animal ever received any soluble lead, as on
one or two occasions the keratin pills passed right through the
animal without dissolving. On the other hand, feeding with nitrate of
lead in water produced symptoms, but when the nitrate was given in
milk no symptoms appeared. It will be noticed it took a cat four
months to show any signs of poisoning taking 0·1 gramme per day;
whereas the animal receiving subcutaneous doses of 0·16 gramme
of acetate showed paralysis in fifteen days, and in twenty-two days
was so ill that it had to be destroyed under an anæsthetic. The same
relationship in time also obtains in the case of the animals fed on dry
white lead. In practically no instance did definite or severe poisoning
follow the feeding on dry white lead alone, even when quite large
quantities were taken. On reference to the inoculation experiments of
Table XI., it will be seen that the inoculation of 2 grammes of dry
white lead produced definite symptoms, although the feeding cats
had an amount very largely in excess of this. The only animals fed
on white lead or frit exhibiting signs of lead poisoning were those
which were given alcohol in addition to the lead compound.
A comparison of the results given in Tables XI. and XII. shows that
animals which received lead compounds subcutaneously suffered
much more than the animals which received the lead via the gastro-
intestinal canal, even when the doses given via the mouth were
exceedingly large. It will follow, then, that the actual contact with the
more intimate fluids of the body, rather than the digestive juices,
determines the solubility and general distribution of the lead
compound in the body. This is confirmed by a recent paper by
Straub[6].
The animals experimented upon by feeding were kept in the
laboratory under the same conditions as the inhalation animals, but
were so placed that under no circumstance could they obtain any
lead dust by inhalation. These animals were used as control to the
breathing experiments, the substance fed to the animals being in all
cases the same substance as was used for the various inhalation
experiments; but in addition a certain number of the animals were
given alcohol, which are referred to in Table XII. Alcohol was also
given to animal No. 6 in the inhalation series.
The animals fed with lead were fed with the same compound
which was used for the inhalation experiments, 0·4 to 1 gramme
being given daily; so that during the period these animals were
exposed to lead dust the other animals were taking the same
compound via the intestinal canal, but in much larger quantities, and
yet they exhibited no signs of lead poisoning.
TABLE XI.—INOCULATION.
Date of
No. of Total Compound used Number of First
Animal. Weight. and Quantity. Inoculations. Symptoms. Duratio
Kgs.
16 3·200 0·91 grm. lead 3 Forty-fifth day 47 days
acetate: (1) 0·16; encephalopathy
(2) 0·5; (3) 0·25
25 3·350 Fritted lead: (1) 0·6; 2 Twenty-sixth day 26 days
(2) 2·0 = 2·6 grms. slight paralysis
of left hind-limb
28 3·050 2 grms. white lead 1 Fourth day 23 days
aborted
31 3·450 0·35 grm. white lead — No symptoms 1 year

32 2·900 0·3 grm. frit 1 Eleventh day stiff 28 days
joint; stepping
not normal
33 3·150 0·16 grm. PbO as 1 Fifteenth day 22 days
acetate paralysis
35 3·750 2·0 grms. water- 1 Ninth day aborted 1 year
washed frit
40 3·050 1·0 grm. unwashed 1 Forty-seventh day 58 days
frit some muscular
weakness
41 3·000 1·0 grm. acetic acid 1 No symptoms 5 month
and water-washed
frit
42 2·800 1·0 grm. water- 1 No symptoms 4 month
washed frit
43 2·900 Lead nitrate in water: — Thirtieth day 5 month
0·01 grm. per diem encephalopathy
TABLE XII.—FEEDING EXPERIMENTS.
Total
Duration
No. of Compound of Other First Appearance of of
Animal. Weight. Pb used. Substance. Poisoning Symptoms. Experiment.
Kgs.
2 2·750 0·5 to 0·1 None Vomited fifth day; no 2 months
grm. flue other symptoms
dust (55
per cent.
PbO) from
blast-
furnace
flue
9a 3·500 0·5 grm. dry None Vomited fifth day; no 2 months —
white lead other symptoms
11a 3·850 0·8 grm. None None 8 months —
3·900 After 8 50 c.c. 1 month 2 months
months alcohol
given (port
alcohol wine)
12 3·800 0·8 grm. dry 50 c.c. port 1 month slight 38 days
white lead wine paralysis
13 3·400 0·8 grm. dry None None 18 months
white lead
14 3·650 0·4 grm. low- None None 8 months G
solubility
frit
3·730 0·4 grm. low- 50 c.c. port 6 months 1 year
solubility wine encephalopathy
frit and
alcohol
23 4·100 1 grm. high- None None 1 year
solubility
glaze
4·600 Given lead None None 5 months
nitrate,
0·01 to 0·1
grm.
24 2·900 1 grm. high- None None 6 months
solubility
glaze
46 2·150 0·1 grm. lead None 4 months 4 months
nitrate in opisthotonus
water
47 2·100 0·1 grm. lead None None 4 months
nitrate in
milk
49 2·500 2 grs. None None 3 months
acetate in
keratin pill
15 2·950 Control no None None 1 year
lead
[A] Increased in weight.
TABLE XIII.—INHALATION EXPERIMENTS.

Compound of Lead in Dust and
No. of Average Quantity in Air Number of Day
Animal. Weight. during Experiment. Method. Inhalations. First Sym
Kgs.
1 3·000 0·007 to 0·01 grm. flue dust A 11 of 1 13 days (4
from blast-furnace flue hour inhalati
2 3·580 0·007 to 0·01 grm. litharge A 12 15 days (

dust inhalati
4 4·100 0·001 to 0·007 grm. white lead A 12 37 days (

dust inhalati
6 5·200 0·001 to 0·007 grm. white lead A 12 12 days (4

(alcohol: 50 c.c. port wine inhalati
daily in milk)
7 3·000 0·001 to 0·007 grm. white lead; A 11 30 days (
no alcohol inhalati
10 4·500 0·0001 to 0·001 grm. white B 40 of 20 120 days
lead minutes inhalati
11 3·750 0·0001 to 0·001 grm. white B 40 of 20 120 days
lead minutes inhalati
21 3·900 0·001 to 0·09 grm. low- B 14 of 1 42 days (
solubility glaze hour inhalati
22 3·900 0·001 to 0·09 grm. low- B 26 60
solubility glaze
30 3·500 0·001 to 0·09 grm. low- B 14 45
solubility glaze
The experiments definitely bring out one all-important fact—

namely, that lead dust circulating in the air is many times more
dangerous than lead actually swallowed; for even if the animals
which were exposed to the inhalation of dust swallowed the whole of
the quantity contained in the respired air, they would only obtain one-
tenth of the amount the other fed animals were getting. It is, of
course, impossible to suppose that the whole of the lead contained
in the inhaled air reached the lung. It can only have been the smaller
particles which did so. Therefore the ratio is many more than ten
times between the fed and the inhaling animal; in all probability only
one-tenth of the contained lead in the respired air reaches the lung.
Under these circumstances the ratio of poisoning via the lung to
poisoning via the intestinal canal is as 100 : 1.
Table XIII. deals with the question of inhalation.
Every care was taken during these experiments to avoid any
vitiation of such experiments by the actual swallowing of lead dust by
the animals exposed to breathing. Moreover, all the animals were
carefully controlled, in that an animal of somewhat similar weight at
the same time was subjected to the ingestion of the same lead
compound, but in much bigger quantities, via the mouth.
It will be seen immediately, on comparing Tables XI. and XII. with
Table XIII., that the rate of poisoning by means of dust is greatly in
excess of the rate of poisoning by feeding, even where poisoning by
feeding actually occurred. Also that the amount of dust present in the
air inhaled shows a marked correlation with the date of appearance
of the first symptoms of poisoning, and that where the quantity of
dust is very much reduced the poisoning was delayed longer than
might have been expected, and that when poisoning did appear the
symptoms were much less pronounced than with the more dusty
atmospheres; and this although the quantity of lead obtained would
be relatively the same over the range of time the animals were
exposed.
The knowledge gained in dealing with industrial poisoning clinically
receives very strong corroboration from these inhalation
experiments, for it is a well-known fact that many persons engaged
in dusty trades exhibit a species of immunity to lead poisoning. It is
true that some susceptible persons, as has already been pointed
out, very rapidly show signs of poisoning, even with a dosage
producing no effect in other persons working under similar
conditions; and it is highly probable that these persons have arrived
at a species of equilibrium by which they are able to excrete the lead
ingested, and so prevent any accumulation and general damage to
their tissues. Directly, however, the dosage is increased, signs of
poisoning come on, as in the case of animals Nos. 10 and 11. For
some seventy to eighty days little or no sign of poisoning was seen
with the small dosage commenced with. At the end of this time, as
no symptoms appeared, the quantity of lead in the air was increased,
with the result that poisoning rapidly became manifest.
We have also in these inhalation experiments, in Cases 21 and
22, definite evidence that a low-solubility glaze—that is to say, glaze
containing fritted lead—is capable of setting up lead poisoning when
taken via the lung, as when such glaze is inoculated, although it
produces no such symptoms when given via the mouth, except,
perhaps, when it is complicated by excessive alcohol.
Symptoms exhibited by Experimental Animals.—The cat is
peculiarly susceptible to lead poisoning. In lead works it is
impossible to keep a cat any length of time, as it rapidly dies of
poisoning.
All the animals subjected to lead absorption, and definitely
suffering from symptoms of lead poisoning, exhibited the following
symptoms:
1. Slight increase of weight over the first period of poisoning,
lasting from one to three weeks.
2. A progressive diminution in weight, progressing until the animal
exhibited definite signs of poisoning.
3. Wasting, especially of the spinal muscles (the erector spinæ
and in the lumbar region), out of proportion to the determined loss of
weight; pinched facies, with frequent exhibition of running from the
eyes and nose, even when not exposed to the action of lead dust,
merely by inoculation.
4. Various types of paralysis, particularly in the cat; the muscles of
the back and of the quadriceps extensor of the hind-legs show signs
of paralysis. In the cat the quadriceps extensor is paralyzed sooner
than the extensor communis digitorum in man. The cats show loss of
power in the hind-limbs by inability to jump. The reflexes, particularly
the knee-jerks and elbow-jerks, are first of all increased, and latterly
become lost.
The chief and main sign which was noted in the histological
examination of the animals inoculated was one of minute

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Flow Assurance.

Volume II Qiwei Wang

For Information on all Gulf Professional Publishing publications

Publisher: Charlotte Cockle

CHAPTER 2 Paraffin management.................................................. 85

CHAPTER 3 Asphaltene management........................................... 185

3.5.2 Deposition tests ............................................................... 201

CHAPTER 5 Inorganic mineral scale mitigation.......................... 287

5.5.4 The importance of appropriate core flood testing

CHAPTER 6 Sand control completion using in-situ resin

CHAPTER 7 Condensate and water blocking removal ................ 503

CHAPTER 8 Foam-assisted liquid lift ........................................... 541

8.7.1 Batch foam-assisted lift trial........................................... 569

CHAPTER 9 Corrosion inhibition .................................................. 609

9.5.4 Monte Carlo simulations................................................. 632

CHAPTER 10 Microbial control ...................................................... 709

Gas hydrate management

Gaurav Bhatnagar and Shawn Gao

Flow Assurance. DOI: https://doi.org/10.1016/B978-0-12-822010-8.00009-X

1.9.4 Remediation of hydrate plug in west Africa deepwater floating

1.2 Fundamentals of hydrate

Table 1.1 Characteristics of hydrate cages of different structures.

Small Large Small Large Small Medium Large

With the advancement of experimental technologies and continuous research

form an orthorhombic structure, in which water molecules form 14-hedra cages

1.2.3 Phase behavior

Fresh Water 10wt% NaCl 20wt% NaCl 20vol% MEOH

8000 Hydrate Risk

2000 Hydrate Free Region

1.2.4.1 Mechanical properties

1.2.4.2 Self-preservation during dissociation

1.2.4.3 Large gas-to-hydrate volume ratio

1.3 Hydrate formation

1.3.1.2 Cold restart

1.3.1.3 Steady state

1.3.1.4 Gas injection, gas lift, or gas export

1.3.2 Hydrate formation mechanism

1.4 Hydrate management in production systems

1.4.1 Risk assessment

1.4.2 Hydrate modeling

Fig. 1.—Section of Large

Fig. 3.—Section of Anterior

Fig. 2.—Lung of Animal

Lung.—Red or grey hepatization may be found, or a general

Fig. 2.—Kidney of Man dying

The two following cases, in which both chemical and histological

31 3·450 0·35 grm. white lead — No symptoms 1 year

TABLE XII.—FEEDING EXPERIMENTS.

[A] Increased in weight.

TABLE XIII.—INHALATION EXPERIMENTS.

2 3·580 0·007 to 0·01 grm. litharge A 12 15 days (

4 4·100 0·001 to 0·007 grm. white lead A 12 37 days (

6 5·200 0·001 to 0·007 grm. white lead A 12 12 days (4

The experiments definitely bring out one all-important fact—

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