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José Luiz de Medeiros
Lara de Oliveira Arinelli
Alexandre Mendonça Teixeira
Ofélia de Queiroz Fernandes Araújo
Offshore Processing
of CO2-Rich Natural
Gas with Supersonic
Separator
Multiphase Sound Speed, CO2 Freeze-
Out and HYSYS Implementation
Offshore Processing of CO2-Rich Natural Gas
with Supersonic Separator
José Luiz de Medeiros
Offshore Processing
of CO2-Rich Natural Gas
with Supersonic Separator
Multiphase Sound Speed, CO2 Freeze-Out
and HYSYS Implementation
123
José Luiz de Medeiros Alexandre Mendonça Teixeira
Escola de Química Escola de Química
Federal University of Rio de Janeiro (UFRJ) Federal University of Rio de Janeiro (UFRJ)
Rio de Janeiro, Brazil Rio de Janeiro, Brazil
Lara de Oliveira Arinelli Ofélia de Queiroz Fernandes Araújo

Escola de Química Escola de Química
Federal University of Rio de Janeiro (UFRJ) Federal University of Rio de Janeiro (UFRJ)
Rio de Janeiro, Brazil Rio de Janeiro, Brazil
ISBN 978-3-030-04005-5 ISBN 978-3-030-04006-2 (eBook)

https://doi.org/10.1007/978-3-030-04006-2
Library of Congress Control Number: 2018962390
© Springer Nature Switzerland AG 2019

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
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for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface
The supersonic separator (SS) is a recent new kind of separation unit operation,
whose working principles offer several difficulties for precise modeling and sim-
ulation, which have retarded the development of a reliable and systematic engi-
neering approach for efficient design of such operations. In this book, the authors
disclose a new and powerful approach based on rigorous process simulations
conducted by professional simulators like HYSYS to predict the performance of
supersonic separators, which can accomplish certain steps of CO2-rich natural gas
(NG) offshore processing, such as water removal for water dew-point adjustment
(WDPA), C3+ hydrocarbon removal for hydrocarbon dew-point adjustment
(HCDPA), and CO2 removal. Traditionally, these operations are conducted in the
offshore scenario of CO2-rich NG processing via well-known conventional tech-
nologies, respectively, glycol absorption (TEG absorption), Joule–Thomson
expansion (JTE) or propane refrigeration (C3-RFG), and membrane permeation
(MP) or chemical absorption (CA).
In this context, the book addresses the utilization of SS for offshore processing of
CO2-rich NG, as an alternative to JTE/C3-RFG, TEG absorption, and MP or CA
for the same finalities. To do this, the book is divided into four conceptually distinct
but complementary parts.
Part I, comprehending Chaps. 1, 2 and 3, discusses the general aspects of CO2-rich
NG offshore processing by conventional technologies and, introductorily, by the
unconventional supersonic separator (SS). Several technical and economic com-
parisons of performance involving conventional technologies and the SS are pre-
sented. Evidently, the conventional technologies have strong points; otherwise, they
would not be the conventional ones. But it is understandable that such debate natu-
rally entails to discuss the unavoidable contextualization of the comparative advan-
tages of SS in terms of costs and power consumption vis-à-vis the conventional
alternatives.
Part II, comprehending Chaps. 4 and 7, approaches aspects related to the ther-
modynamic infrastructure necessary to the engineering of CO2-rich NG processing
with/without the supersonic separator (SS). This discussion encompasses thermo-
dynamic frameworks to predict PVT properties, thermal properties, and mixed
v
vi Preface
PVT-thermal properties—like the thermodynamic sound speed property—of

vapor–liquid CO2-rich NG systems at high pressures and densities, and in critical
neighborhoods. This, naturally and vividly, brings equations of state (EOS) into the
discussion, but the same emphasis is not dedicated to excess solution models, the
other common category of thermodynamic models. In other words, CO2-rich NG
processing is typically a subject for EOS tools because the PVT facet is dominant as
NG processing only becomes economically feasible at high pressures and invari-
ably in the neighborhood of critical points, cricondenbars, cricondenterms, and
triple-points, which are not representable by excess solution models. Thus, Chap. 4
is dedicated to EOS frameworks, such as the common cubic EOS family (Peng–
Robinson EOS and Soave–Redlich–Kwong EOS), the cubic-plus-association
CPA-EOS a more complex framework suitable for associating systems like
water, alcohols, and glycols—the last two categories used as thermodynamic
hydrate inhibitors (THI) in NG systems—and the precise Span–Wagner EOS and
GERG-2008 EOS, which are oriented to specialized systems, such as pure CO2.
The thermodynamic infrastructure also comprises in Chap. 7, the thermodynamic
description of pure CO2 solid phase in order to address the modeling of CO2
freeze-out phenomenon, which has to be taken into account in SS processing of
CO2-rich NG. Chapter 7 also discusses algorithms for location of freeze-out
boundaries on the P T plane. Graphical examples are presented: (i) representation
of VLE locus and single-phase locus of several properties of CO2-rich NG with
Peng–Robinson EOS; (ii) three-dimensional diagrams of several properties of pure
CO2 including the solid, liquid, and gas domains, the VLE/SLE/SVE
one-dimensional loci and triple and critical points; and (iii) graphical determina-
tion of one-dimensional freeze-out boundaries SLE, SVE, and SVLE for several
CO2-rich NG systems.
Part III, comprehending Chaps. 5 and 6, is the core of the book. It is dedicated to
the theoretical fundamentals and HYSYS implementation of the supersonic separator
(SS) for condensing feeds (e.g., raw NG) including thermodynamic modeling of
multiphase equilibrium isentropic compressible flow; isentropic and non-isentropic
expansion/compression SS flow paths; normal shock modeling; the determination of
multiphase equilibrium sound speed property necessary for SS modeling; classical
analysis with the Landau Model on the asymptotic behavior of the sound speed in the
critical neighborhood; and the determination of the multiphase multi-reactive equi-
librium sound speed property necessary to address supersonic reactors. Certain
conventional separation operations not existing in professional process simulators—
such as membrane permeation (MP) units—are also modeled to become available on
HYSYS platform for classical processing of CO2-rich NG. As products of Part III,
four HYSYS unit operation extensions (UOE) are prepared for utilization in HYSYS
flowsheets processing CO2-rich NG, namely: (i) SS-UOE for rigorous thermody-
namic SS simulation and design; (ii) MP-UOE for MP simulation; (iii) PEC-UOE for
determination of the phase-equilibrium sound speed (c) property necessary in
SS-UOE; and (iv) REC-UOE for determination of the multiphase, multi-reactive
equilibrium sound speed (c) property for supersonic reactor modeling. Several
graphical examples are presented: (i) SS-UOE for CO2-rich NG processing;
Preface vii
(ii) SS-UOE for NG processing and the second law of thermodynamics; (iii) SS-UOE
validation with the literature; (iv) SS-UOE with several levels of adiabatic efficien-
cies; (v) PEC-UOE for the sound speed of multiphase NG systems, including critical
neighborhoods; (vi) PEC-UOE for sound speed of multiphase oil–gas–water sys-
tems; (vii) Landau Model analysis on asymptotic behavior of the sound speed in
critical neighborhoods; and (viii) REC-UOE for multi-reactive sound speed for
multiphase oxidation chemical reactors and pyrolysis chemical reactors.
Finally, Part IV, comprehending Chaps. 8 and 9, aims at process flowsheets
applications within HYSYS environment using the previously developed unit
operation extensions SS-UOE, PEC-UOE, and MP-UOE. Three major NG process
applications are considered: (i) technical assessment of CO2-rich NG processing
with conventional technologies TEG absorption, JT expansion, and MP CO2
removal, compared with alternative processing using SS for WDPA and HCDPA,
but with conventional MP CO2 removal; (ii) idem as before compared with alter-
native processing using TEG absorption WDPA, JT expansion HCDPA, but with
SS for CO2 removal; and (iii) technical assessment of raw NG processing con-
sidering saturation of thermodynamic hydrate inhibitor (THI) in the raw NG, via
conventional technologies TEG absorption and JT expansion compared with
alternative processing using the new proposed concept SS-THI-Recovery, which
prescribes SS with water injection for simultaneous WDPA, HCDPA, and THI
recovery from the raw NG producing lean NG, good grade LPG, and recovered
THI, which otherwise would be lost. In the last SS-THI-Recovery application, three
most common THIs are individually considered: methanol, ethanol, and MEG.
The main public of this book corresponds to the broad category of researchers.
Evidently, interested design and operation engineers, graduate students, professors,
and scientifically initiating undergraduate students with interests in this matter can
be included. This selection of public is not, obviously, our choice, as any author
would adore an audience as large as possible. Instead, it is determined by the
concept of the book, the way it is written and its contents. In this regard, the book is
eminently a scientific one focusing on frontier subjects related to CO2-rich NG
processing in offshore platforms. That is, the book is committed with the presen-
tation of a new kind of process separation for very specialized systems, where the
content comprises results of our researches in the last 5 years on this subject.
Rio de Janeiro, Brazil José Luiz de Medeiros

Contents
1 Offshore Processing of CO2-Rich Natural Gas and the Role

of Supersonic Separators—Introduction . . . . . . . . . . . . . . . . . . . . . . 1
Lara de Oliveira Arinelli, José Luiz de Medeiros,
Alexandre Mendonça Teixeira and Ofélia de Queiroz Fernandes Araújo
1.1 General Overview on Raw CO2-Rich Natural Gas Reserves
and Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Technologies for CO2 Capture from CO2-Rich Natural Gas . . . . 3
1.3 Supersonic Separator Application for CO2-Rich Natural Gas
Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Conventional Offshore Processing of CO2-Rich Natural Gas . . . ... 11
Ofélia de Queiroz Fernandes Araújo and José Luiz de Medeiros
2.1 Offshore Scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Topside Gas Processing of FPSO Units in Brazilian Pre-salt . . . . 12
2.3 Technologies for CO2 Separation in Ultra-Deepwater FPSOs . . . 17
2.3.1 CO2 Destination in Ultra-Deepwater FPSOs . . . . . . . . . . 19
2.4 Evaluation of Alternative Technologies . . . . . . . . . . . . . . . . . . . 19
2.4.1 Evaluated CO2 Removal Processes . . . . . . . . . . . . . . . . . 20
2.5 Equipment Sizing, Footprint Estimation,
and Economic Analysis Method . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5.1 Calculation of Operational and Capital Expenditures . . . . 30
2.5.2 Footprint Estimation . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.6 Process Performance Indicators . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.7 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.7.1 Mid-Point and End-Point Analyses . . . . . . . . . . . . . . . . . 34
2.7.2 Economic Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.8 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
ix
x Contents
3 Overview of Natural Gas Processing with Supersonic Separator ... 41

Ofélia de Queiroz Fernandes Araújo and José Luiz de Medeiros
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2 Comparison of Process Alternatives . . . . . . . . . . . . . . . . . . . . . . 42
3.2.1 Conventional Process: TEG + JT/LTS . . . . . . . . . . . . . . 44
3.2.2 Innovative Process: Supersonic Separator (SS) . . . . . . . . 45
3.3 Equipment Sizing and Economic Analysis . . . . . . . . . . . . . . . . . 46
3.4 Comparative Analysis: Results and Discussion . . . . . . . . . . . . . . 51
3.5 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4 Thermodynamic Modeling of CO2-Rich Natural Gas Fluid
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 55
José Luiz de Medeiros and Ofélia de Queiroz Fernandes Araújo
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.2 Cubic Equations of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.3 GERG-2004/2008 EOS and the Span–Wagner EOS . . . . . . . . . . 63
4.3.1 GERG-2004/2008-EOS . . . . . . . . . . . . . . . . . . . . . . . . . 64
4.3.2 Span–Wagner EOS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.4 CPA Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.5 Comments on EOS Performance for Applications
with CO2-Rich Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . ... 70
4.6 EOS Performance for Prediction of Physical Properties
of CO2-Rich Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . ... 73
4.6.1 Gas Density, Isobaric Heat Capacity, Enthalpy,
and Sound Speed . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 73
4.7 Performance of Other Equations of State with CO2-Rich NG
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 76
4.8 Comparison of PR-EOS with CO2–CH4 Systems Versus
Literature Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 76
4.9 VLE Envelopes and Thermodynamic Properties via PR-EOS
for CO2–CH4 Streams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 80
4.10 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 94
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 95
5 Thermodynamic Speed of Sound for Multiphase Multi-Reactive
Equilibrium Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 97
José Luiz de Medeiros, Lara de Oliveira Arinelli
and Ofélia de Queiroz Fernandes Araújo
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 97
5.2 Multiphase Sound Speed in the Literature . . . . . . . . . . . . . . ... 100
5.2.1 Multiphase Multi-Reactive Sound Speed
in the Literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 104
5.2.2 Outline of Incoming Sections . . . . . . . . . . . . . . . . . . ... 105
Contents xi
5.3 Sound Speed Property of Multiphase Multi-Reactive Streams . .. 105

5.3.1 Steady-State Equilibrium 1D Plug-Flow of Multiphase
Multi-Reactive Fluid Under Horizontal, Adiabatic
and Frictionless Conditions . . . . . . . . . . . . . . . . . . . . .. 106
5.3.2 Multiphase and Multi-Reactive Equilibrium Closed
System (ECS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 109
5.3.3 Traveling Fluid Element of Steady-State 1D Isentropic
Plug-Flow as ECS . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 110
5.3.4 Further Aspects of Sound Speed Property . . . . . . . . . . .. 114
5.3.5 Asymptotic Behavior of Sound Speed Property
in the Critical Neighborhood . . . . . . . . . . . . . . . . . . . .. 115
5.4 Computational Implementation of Multiphase Multi-Reactive
Sound Speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 126
5.4.1 Determination of the Phase Equilibrium Sound Speed:
PEC-UOE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 126
5.4.2 Determination of the Multiphase Multi-Reactive
Equilibrium Sound Speed via REC-UOE . . . . . . . . . . .. 127
5.5 Numerical and Graphical Results for the Multiphase
Multi-Reactive Sound Speed . . . . . . . . . . . . . . . . . . . . . . . . . .. 129
5.5.1 Sound Speed Calculation Inside the VLE Envelope
of Prudhoe Bay Natural Gas . . . . . . . . . . . . . . . . . . . . .. 129
5.5.2 Prudhoe Bay NG: Sound Speed Across
the Critical Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 131
5.5.3 Two-Phase and Three-Phase Equilibrium Sound Speeds
for Reservoir Oil with Water . . . . . . . . . . . . . . . . . . . .. 133
5.5.4 Sound Speed for Supersonic Separator with
Water-Saturated CO2-Rich Natural Gas . . . . . . . . . . . . .. 134
5.5.5 Determination of the Sound Speed in Two-Phase
Reactive O2+Methanol Streams . . . . . . . . . . . . . . . . . .. 140
5.5.6 Determination of Multi-Reactive Sound Speed
in Low-Pressure CH4 Pyrolysis . . . . . . . . . . . . . . . . . .. 144
5.6 Limit Conditions of Multiphase Multi-Reactive Compressible
Steady-State 1D Isentropic Plug-Flow with Variable Flow
Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 146
5.6.1 Temperature, Pressure and Velocity Profiles in 1D
Isentropic Compressible Flow with Variable
Flow Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 147
5.6.2 Sonic Singularities of Spatial Gradients of Temperature,
Pressure, and Velocity . . . . . . . . . . . . . . . . . . . . . . . . .. 150
5.6.3 Sonic Singularities of Spatial Gradients of
Thermodynamic Properties . . . . . . . . . . . . . . . . . . . . . .. 152
xii Contents
5.6.4 Summary of Sonic Singularities of Spatial Gradients

and Some Observations . . . . . . . . ................. 158
5.7 Final Remarks . . . . . . . . . . . . . . . . . . . . ................. 160
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................. 161
6 Modeling of Supersonic Separators and Membrane Permeation
Units for Processing of CO2-Rich Natural Gas with HYSYS
Implementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
6.2 Theoretical Building Blocks for CO2-Rich NG Processing
by Supersonic Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
6.2.1 Multiphase Sound Speed . . . . . . . . . . . . . . . . . . . . . . . . 168
6.2.2 Further Aspects of Multiphase Sound Speed . . . . . . . . . . 170
6.2.3 Supersonic Separation Modeling for Adjustment
of Natural Gas Dew-Points . . . . . . . . . . . . . . . . . . . . . . . 171
6.2.4 Membrane Permeation for CO2 Removal
from Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
6.2.5 Supersonic Separation for CO2 Removal
from Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
6.3 HYSYS SS and MP Unit Operation Extensions
for Natural Gas Conditioning . . . . . . . . . . . . . . . . . . . . . . . . . . 180
6.3.1 Membrane Permeation Modeling and Simulation:
MP-UOE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
6.3.2 Supersonic Separator Modeling and Simulation:
SS-UOE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.3.3 SS-UOE Examples and Validation . . . . . . . . . . . . . . . . . 193
6.3.4 Influence of Adiabatic Efficiencies on the Performance
of SS-UOE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
6.4 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
7 Modeling of CO2 Freeze-Out in the Processing of CO2-Rich
Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 215
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 215
7.2 CO2 Freeze-Out in the Literature . . . . . . . . . . . . . . . . . . . . . . .. 221
7.2.1 CO2 Freeze-Out in Industrial NG Processing . . . . . . . . .. 221
7.2.2 Thermodynamic Properties of Pure CO2
in the Solid State . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 223
7.2.3 Comparison of Calculated CO2 Freeze-Out Boundaries
with Experimental Data . . . . . . . . . . . . . . . . . . . . . . . .. 227
Contents xiii
7.3 Thermodynamic Modeling of CO2 Solid Phase for Freeze-Out

in CO2-Rich NG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 229
7.3.1 Fluid-Phase Modeling Definitions for CO2 Freeze-Out . .. 229
7.3.2 CO2DIAG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 230
7.3.3 Calibration of Pure CO2 Properties and Phase Diagrams
with CO2DIAG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 232
7.3.4 Three-Dimensional Wide-Range CO2 Phase Diagrams
with CO2DIAG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 243
7.4 Determination of Freeze-Out SLE-SVLE-SVE Boundaries
onto VLE Locus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 248
7.4.1 Remarks on Duhem Theorem for CO2-Rich NG
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 248
7.4.2 Remarks on Two-Dimensional CTC Loci . . . . . . . . . . .. 251
7.4.3 Remarks on Intersection of 1D Boundaries . . . . . . . . . .. 252
7.4.4 Calculation of Freeze-Out Boundaries for CTC Binary
CO2–CH4 Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
7.4.5 Calculation of Freeze-Out Boundaries for CTC
Multicomponent CO2-Rich NG . . . . . . . . . . . . . . . . . . . . 258
7.5 Results of Freeze-Out Calculations . . . . . . . . . . . . . . . . . . . . . . 262
7.5.1 System 10 mol% CO2 + 90 mol% CH4 . . . . . . . . . . . . . 264
7.5.4 System 4.45 mol% CO2 + 93.6 mol% CH4
+ 1.38 mol% C2H6 + 0.57 mol% C3H8 . . . . . . . . . . . . .. 269
7.5.5 System 50 mol% CO2 + 20 mol% CH4 + 30 mol%
C2H6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 269
7.5.6 The Invariant 1D SVLE Locus of Binary CO2–CH4
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 272
7.6 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 273
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 275
8 Supersonic Separators for Offshore Processing of CO2-Rich
Natural Gas: Comparison with Conventional Routes . . . . . . . . . . . . 277
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
8.2 CO2-Rich NG Processing Assumptions . . . . . . . . . . . . . . . . . . . 278
8.3 Description of CO2-Rich NG Processing Alternatives . . . . . . . . . 279
8.4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
8.4.1 Simulation Streams Results and Verification
of Goal-Attainments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
8.4.2 Power Demand Assessment . . . . . . . . . . . . . . . . . . . . . . 296
8.5 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
xiv Contents
9 Recovery of Thermodynamic Hydrate Inhibitors with Supersonic

Separators in Offshore Processing of Natural Gas: The Cases of
Methanol, Ethanol, and Monoethylene Glycol . . . . . . . . . . . . . . . .. 299
Alexandre Mendonça Teixeira, Lara de Oliveira Arinelli,
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
9.2 Technical Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
9.2.1 Natural Gas Hydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
9.2.2 Inhibition of Gas Hydrate Formation . . . . . . . . . . . . . . . 304
9.2.3 THI-Recovery Units (THI-RUs) . . . . . . . . . . . . . . . . . . . 307
9.2.4 Supersonic Separator Simulation, Operation,
and Control Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . 309
9.2.5 Cubic-Plus-Association Equation of State (CPA-EOS) . . . 312
9.3 SS-THI-Recovery Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
9.4 Simulation Scenario for SS-THI-Recovery Process . . . . . . . . . . . 318
9.5 Simulation Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
9.5.1 Methanol as THI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
9.5.2 Results of SS-THI-Recovery for Ethanol as THI . . . . . . . 329
9.5.3 Results of SS-THI-Recovery for MEG as THI . . . . . . . . . 335
9.5.4 Summary of Results and Discussion . . . . . . . . . . . . . . . . 342
9.6 Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Abbreviations
1D, 2D, 3D One, Two, and Three Dimensional

AAHI Anti-Agglomerating Hydrate Inhibitor
ADC Atmospheric Distillation Column
BIP Binary Interaction Parameter
BOP Blow-Out Preventer
C3+ Propane and Heavier Alkanes
CAM Cellulose Acetate Membrane
CCS Carbon Capture and Storage
CFD Computational Fluid Dynamics
ChW Chilled Water
CPA Cubic-Plus-Association
CPA-EOS Cubic-Plus-Association EOS
CPU Central Processing Unit
CSM Colorado School of Mines
CTC Constant Total Composition
CW Cooling Water
DEG Di-Ethylene Glycol
DLL Dynamic-Link Library
ECS Equilibrium Closed System
EOR Enhanced Oil Recovery
EOS Equation of State
EtOH Ethanol
FLS Flash Evaporator Vessel
FOB Freeze-Out Border
FPSO Floating Production Storage and Offloading
GFOB Grand Freeze-Out Border
GTL Gas to Liquids
HC Hydrocarbon
HCDP Hydrocarbon Dew-Point
HCDPA Hydrocarbon Dew-Point Adjustment
xv
xvi Abbreviations
HGR HYSYS Gibbs Reactor

HPS High-pressure Three-Phase Separator
HRWH Heat Recovery Water Heater
JTE Joule–Thomson Expansion
KHI Kinetic Hydrate Inhibitor
L Liquid
L+W Condensate with HCs + Water
LHS Left-Hand Side
LLE Liquid–Liquid Equilibrium
LLS Liquid–Liquid Separator
LM Landau Model
LNG Liquefied Natural Gas
LPG Liquefied Petroleum Gas
LTX Low-Temperature Separator
MDEA Methyl-Diethanolamine
MEA Monoethanolamine
MEG Monoethylene Glycol
MeOH Methanol
MMSm3/d Million Standard m3 per day
MP Membrane Permeation
MRU MEG Recovery Unit
NG Natural Gas
NGL Natural Gas Liquids
NRM Newton–Raphson Method
PFD Process Flow Diagram
PHW Pressurized Hot Water
PR Peng–Robinson
PR-EOS Peng–Robinson EOS
PVT Pressure, Volume, and Temperature
RGB Red, Green, and Blue True-color Pixel
RHS Right-Hand Side
S Solid
SAFT Statistical Associating Fluid Theory
SCF Supercritical Fluid
SDC Sub-atmospheric Distillation Column
SI International System of Units
SLE Solid–Liquid Equilibrium
SR Supersonic Reactor
SRK Soave–Redlich–Kwong
SRK-EOS Soave–Redlich–Kwong EOS
SS Supersonic Separator
SVE Solid–Vapor Equilibrium
SVLE Solid–Vapor–Liquid Equilibrium
SW Seawater
Abbreviations xvii
SW-EOS Span–Wagner EOS

TEG Triethylene Glycol
THI Thermodynamic Hydrate Inhibitor
THI-RU THI Recovery Unit
TP Triple-Point
UOE Unit Operation Extension
V Vapor
VB Visual Basic
VLE Vapor–Liquid Equilibrium
VLLE Vapor–Liquid–Liquid Equilibrium
VLWE Vapor–Liquid Water Equilibrium
WDP Water Dew Point
WDPA Water Dew Point Adjustment
WHRU Waste Heat Recovery Unit
Nomenclature
a Parameter of attractive term of cubic EOS (Pa.m6/mol2)

A Dimensionless attractive term of cubic EOS
A(x) Flow section area at axial position x (m2)
AðT; vÞ Molar Helmholtz free energy of pure fluid (J/mol)
A Molar Helmholtz free energy (J/mol)
Ai(T) Temperature-dependent terms of Landau Model free energy
Aij Coefficients for temperature influence on Landau
Model terms
AMP MP area (m2)
b Co-volume parameter of cubic EOS (m3/mol)
B Dimensionless co-volume term of cubic EOS
c Sound speed of multiphase multi-reactive fluid (m/s)
C P @H Molar heat capacity at const. P, Z of multiphase
@T P;Z
fluid (J/K.mol)
C V @U Molar heat capacity at const. V, Z of multiphase
@T V;Z
fluid (J/K.mol)
^ P @ H^
C ECS heat capacity at const. P, Z per mass unit (J/K.kg)
@T P;Z
S Molar isobaric heat capacity of compressed
C P;CO2 (T; P)
pure solid CO2 (J/K.mol)
S;SAT Molar isobaric heat capacity of saturated pure
C P;CO2 (T)
solid CO2 (J/K.mol)
D Internal diameter (m)
DI, DT, DO SS inlet/throat/outlet internal diameters (m)
E Total molar energy of multiphase fluid (J/mol)
fk Fugacity of pure species k (bar)
^fk Fugacity of species k in a mixture (bar)
fCO
S
2
(T; P) Fugacity of pure solid CO2 (bar)
S;SAT
fCO 2
(T) Fugacity of saturated pure solid CO2 (bar)
F Molar flow rate of multiphase fluid (mol/s)
xix
xx Nomenclature
^
G ECS Gibbs free energy per mass unit (J/kg)
H Molar enthalpy of multiphase fluid (J/mol)
^
H ECS enthalpy per mass unit (J/kg)
S Molar enthalpy of compressed pure solid CO2 (J/mol)
H CO2 (T; P)
S;SAT Molar enthalpy of saturated pure solid CO2 (J/mol)
H CO2 (T)
J Jacobian matrix of multiphase equilibrium equations
k Ratio of heat capacities
K Molar kinetic energy of multiphase fluid (J/mol)
Kij Binary interaction parameter of EOS
L MP permeate molar flow rate (mol/s)
L, LC, LD SS lengths: total, converging and diverging sections (m)
LLAVAL SS lengths: Laval nozzle (m)
LDiffuser, LDiff SS lengths: ending diffuser (m)
LShock = LLAVAL SS lengths: axial position just before shock and liquid
removal (m)
Ma = v/c Mach number
MaShock Mach number just before condensate withdrawal
and normal shock
MaBS Mach number just before shock and after condensate removal
MaAS Mach number just after normal shock
MM Molar mass of multiphase fluid (kg/mol)
N Total number of moles (mol)
N Vector (nc 1) of species mole numbers (mol)
nc Number of components
P Pressure (Pa, bar)
Pc, PTP Critical and triple-point pressures (bar, Pa)
Pout out
L , PV MP permeate and retentate pressures (bar)
in
PV MP gas feed pressure (bar)
PSAT (T) Saturation pressure (bar)
DPLN k MP log mean difference of partial pressures of species k (bar)
q Mass flow rate of multiphase multi-reactive stream (kg/s)
R Ideal gas constant (8.314 J/mol.K, Pa.m3/mol.K,
kPa.L/mol.K)
S Molar entropy of multiphase fluid (J/K.mol)
^
S ECS entropy per mass unit (J/K.kg)
T Absolute temperature (K)
TL, TV Temperatures of permeate and retentate (K)
Tc, TTP Critical and triple-point temperatures (K)
U Molar internal energy of multiphase fluid (J/mol)
[; \ Union and intersect operators
v Axial velocity of non-segregated multiphase flow (m/s)
vV, vL+W Axial velocities of segregated vapor and L + W two-phase
liquid (m/s)
Nomenclature xxi
V MP molar flow rate of retentate (mol/s)

v Molar volume in Landau Model (m3/mol)
V Molar volume (m3/mol)
^
V ECS volume per mass unit (m3/kg)
S;SAT
V CO2 (T) Molar volume of saturated pure solid CO2 (m3/mol)
S L V Critical and triple-point solid, liquid, and vapor molar
V c ; V TP ; V TP ; V TP
volumes (m3/mol)
V 00 Saturated molar volume of solid CO2 at the limit
T = 0 K (=25.800 cm3/mol)
x Flow axial position (m)
X, x Vector (nc 1) of liquid-phase mol fractions
Ykin , Ykout , Xkout Species k mol fraction in feed/retentate/permeate MP streams
Y;y Vector (nc 1) of vapor phase mol fractions
Z, z Vector (nc 1) of total multiphase-fluid mol fractions
Z Compressibility factor
Greek Symbols
a, b SS Converging and diverging wall angles for linear diameter

profiles (°)
a, b Positive constants of cubic EOS (Sect. 4.2)
a, b, η Molar fractions of liquid, vapor, and solid phases (Chap. 7)
dT; dP Positive perturbations for numerical derivatives (K, Pa)
dP ; dM ; dD Pressure step (Pa), Mach tolerance and spatial tolerance (m)
d Dimensionless reduced density in Span-Wagner EOS
D (vV − vL)/2vc Dimensionless difference of vapor and liquid molar volumes
Pk MP permeance of species k (MMSm3/d.m2.bar)
η Phase split mol fraction
ηEXP%,ηCMP% SS expansion/compression adiabatic efficiencies (%)
/k Fugacity coefficient of pure species k
^
/ Fugacity coefficient of species k in a mixture
k
U(T) Temperature-dependent term in cubic EOS
q ECS multiphase multi-reactive density (kg/m3)
q Density of multiphase fluid (kg/m3)
qc Critical density (kg/m3)
qS;SAT
CO2 (T)
Density of saturated pure solid CO2 (kg/m3)
qSTP ; qLTP ; qV
TP
Triple-point densities of solid, liquid,
and vapor phases (kg/m3)
c ¼ C P =C V Ratio of molar heat capacities of multiphase fluid
C Wall horizontal reaction force per length unit (N/m)
l Chemical potential of pure fluid (J/mol)
xxii Nomenclature
X Vector of multiphase equilibrium constraints

x Acentric factor
W Scalar property of multiphase fluid
R (vV + vL)/2vc Dimensionless sum of vapor and liquid molar volumes
h Vector of multiphase equilibrium variables
h Parameter of specification equation (Chap. 7)
s Dimensionless reduced temperature in Span–Wagner EOS
@q
NP @P ECS isothermal compressibility (derivative ∂q/∂P

T;Z at const. T, Z) (kg/Pa.m3)
NT @T@q ECS isobaric expansivity (derivative ∂q/∂P
P;Z at const. P, Z) (kg/K.m3)
Subscripts
AS Just after normal shock

BS Just before normal shock and after condensate withdrawal
c Critical point
C SS converging section
D SS diverging section
E SS entrance or excess property
I SS inlet
k Species index
L Liquid phase or permeate MP product
L+W Two-phase HC + Water condensate
O SS outlet
SAT Saturated
SLE Solid–liquid equilibrium
SVE Solid–vapor equilibrium
SVLE Solid–vapor–liquid equilibrium
T SS throat
TP Triple-point
V Vapor phase or retentate MP product
VLE Vapor–liquid equilibrium
W SS aqueous liquid at LShock
Superscripts
0
Ideal gas property
E Excess property
in, out Inlet, outlet
LAVAL Laval nozzle
Nomenclature xxiii
R Residual property
SAT Saturated
Shock Just before condensate withdrawal and normal shock
THROAT Relative to throat position in SS nozzle
* Sonic (choked) condition on steady-state 1D isentropic
plug-flow
* Ideal gas property of pure species at T and 1 atm
0 Ideal gas property for Span–Wagner EOS
VLE Vapor–liquid equilibrium
V, L, S Vapor, liquid, solid
Chapter 1
Offshore Processing of CO2-Rich
Natural Gas and the Role of Supersonic
Separators—Introduction

Alexandre Mendonça Teixeira and Ofélia de Queiroz
Fernandes Araújo
Abstract This chapter gives an overview on basic subjects that justify the exis-
tence of this book, the most important being the contextualization of offshore
processing of CO2-rich natural gas (NG), besides CO2 separation and destination.
A discussion and bibliographic review on alternatives for CO2 removal from CO2-
rich NG are included. Some basins worldwide have potential to produce oil with
associated gas, yet under high gas–oil ratios and high %CO2 ( 40 mol%) which
entails the onus of low-grade gas processing enchained to huge CO2 dispatch goals.
Here, the oil and gas industry meets great challenges, since the oil production, the
main revenue factor, is bounded to huge CO2-rich NG production with 10–80 mol%
CO2. Therefore, processing solutions are needed to turn high-capacity CO2-rich NG
processing rigs into feasible and safe operations, sometimes hundreds of kilometers
offshore. The supersonic separator (SS) is a promising technology that fits into this
context due to its capability of simultaneous adjustment of dew-points in a single
compact and low-footprint operation. Regarding CO2 removal, the most indicated
technology is membrane permeation, which besides being suitable for CO2 abate-
ment services, and is also compact and modular. On the other hand, the literature
already signalizes potential SS application for CO2 capture from CO2-rich NG.
1.1 General Overview on Raw CO2-Rich Natural Gas

Reserves and Processing
Environmental concerns on global warming and its effects on the planet implicate in
research and investment on alternative energy sources as a replacement of fossil
fuels on the world energy matrix. On the other hand, natural gas (NG) is a
worldwide growing fossil energy source due to its lower carbon emission rates in
comparison to traditional fuels like coal and oil (BP 2016). The conditioning
process of raw NG to fuel gas comprises a well-known set of operations that depend
on its composition and conditions, and which are generally applied on the following
order: (i) removal of H2S; (ii) water dew-point adjustment (WDPA) via
© Springer Nature Switzerland AG 2019 1

J. L. de Medeiros et al., Offshore Processing of CO2-Rich Natural Gas
with Supersonic Separator, https://doi.org/10.1007/978-3-030-04006-2_1
2 1 Offshore Processing Of CO2-Rich Natural Gas …
dehydration; (iii) hydrocarbon dew-point adjustment (HCDPA); and (iv) removal of

CO2. Over 10% of world NG proven reserves currently contain 15–80 mol% of
CO2, which is considered gas with high or ultra-high CO2 content (Burgers et al.
2011; BP 2016). A rich CO2 NG would imply %CO2 40 mol%, while an
ultra-rich CO2 NG has about 60–80 mol% CO2.
The CO2 removal step is not only important to reach NG specifications, but also
contributes to the reduction of CO2 emissions, being an important asset of carbon
capture and storage (CCS). Another remarkable benefit of CO2 separation is its
reinjection in oil fields to maintain well pressure for enhanced oil recovery (EOR).
The EOR strategy is economically positive as shown in a study by Shokri and
Babadagli (2017) with tests of CO2 injection and depletion for heavy oil recovery
after cold production with oil sands in Canada. In the case of non-associated gas
fields, CO2 could be separated and sent via pipelines to other nearby fields as EOR
agent, or stored in depleted gas fields or aquifers, such as in Sleipner, Snøhvit, and
In Salah fields in Indonesia, and Gorgon field in Australia (Burgers et al. 2011; IEA
2009).
The larger NG reserves with high and ultra-high CO2 contents are located in
Southeast Asia, Northwest Australia, Southeast Brazil, Central USA, Middle East,
and North Africa. The last four are oil-rich regions and thus present great potential
for EOR (Burgers et al. 2011). In SE-Brazil, the Pre-salt offshore oil accumulations
have a huge amount of associated gas with high CO2 content; hence, oil production
is tied to gas processing. Current oil and gas wells being explored in the Pre-salt
Lula field have about 10–20 mol% of CO2 in the gas, which is separated via
membrane permeation process in offshore platforms and reinjected in the reservoir
as early EOR agent (Honeywell 2012; Araújo et al. 2017). However, there are other
Pre-salt oil and gas fields where CO2 content is still higher. Jupiter field, discovered
in 2008, is reported to have a large gas cap with 79 mol% of CO2 and 55 mol% of
CO2 in the oil (Gaffney, Cline & Associates 2010). Libra field, discovered in 2010,
is the largest oil and gas reserve in Brazil so far, estimated to contain recoverable
resources of 4–15 billion bbl of oil, with huge gas–oil ratio of 400–600 Sm3/m3 and
%CO2 40% (Upstream 2016; Gaffney, Cline & Associates 2010). These giant
fields are not in full production yet due to the difficulty of processing such high flow
rate of CO2-rich/ultra-rich NG in offshore ultra-deepwater environment, over
200 km from the coast. On the other hand, LaBarge onshore gas field in Wyoming,
USA, produces NG with 65 mol% CO2, which is processed in Riley Ridge gas
treating facility and the majority of recovered CO2 is pipeline-transported and sold
to EOR operators nearby (Burgers et al. 2011).
In Asia and Oceania, there is a relative absence of significant oil accumulations
since most fields are of non-associated gas (Burgers et al. 2011). The East Natuna
offshore gas field, Natuna D-Alpha, is the largest reservoir in Southeast Asia,
estimated to have 1.3 trillion Sm3 of recoverable NG with 71 mol% CO2. Besides
the ultra-high CO2 content, which entails challenges related to costly offshore
processing with conventional technologies, the most indicated destination for CO2,
in this case, is stored in aquifers, not an economic motivation as when EOR agent
(Purwanto et al. 2016). Additionally, natural gas export to market would only be
1.1 General Overview on Raw CO2-Rich Natural Gas Reserves and Processing 3
economically feasible through subsea gas pipelines (already existent or planned)

connecting East Natuna to Indonesia, Malaysia, Thailand, and Singapore (OE
2017). There are also declining oil-producing regions in South Sumatra whose
fields could have extended lives with CO2 EOR provided by Natuna and other CO2-
rich NG fields in Peninsular Malaysia (%CO2 30–65 mol%) and in Sarawak (%
CO2 30–87 mol%) (Darman and Harun 2006; Isa and Azhar 2009; LEMIGAS
2011; Hadi et al. 2013; The Star 2014).
1.2 Technologies for CO2 Capture from CO2-Rich

Natural Gas
Common conventional technologies for CO2 removal from CO2-rich natural gas
comprise: (i) chemical absorption; (ii) physical absorption; (iii) membrane perme-
ation; (iv) gas–liquid membrane contactors; and (v) cryogenic distillation.
Chemical absorption (CA) process consists of an absorption column with
chemical solvent which is usually aqueous alkanolamines, such as MEA and
MDEA, and a second column for solvent regeneration at low pressure, with CO2 as
top product. The main issue of processing CO2-rich NG with this technology is the
high solvent recirculation rate and high heat duty for solvent regeneration.
Moreover, CO2 is extracted at low pressure, requiring large compression trains for
EOR purpose (Araújo et al. 2017).
Physical absorption (PA) also comprises steps of absorption at high pressure and
regeneration at low pressure; thus, similarly CO2 is captured as a low-pressure
stream. Physical solvents have a large capacity of CO2 absorption at high CO2
partial pressure; however, CO2/CH4 selectivity is rather low, implying high
hydrocarbon losses along with the CO2 product stream. There are issues of
high solvent recirculation rates for CO2-rich NG as well. The main PA solvents for
CO2 removal are methanol, propylene carbonate, and dimethyl ethers of poly-
ethylene glycol, respectively, of Rectisol, Fluor, and Selexol processes (Bagirov
et al. 2015).
Membrane permeation (MP) process is based on different permeance of com-
ponents through skin-dense membranes. Polymeric membranes such as cellulose
acetate membranes are the most used industrially for CO2/CH4 separation in two
main configurations: hollow fiber membrane or spiral wound membrane. This
technology is flexible concerning feed CO2 content; however, high %CO2 implies
high permeation area and high hydrocarbon losses, which can be reduced by
multistage configurations with a recycle compressor that increases power demand
and capital instead. The comparative advantages of MP are the relatively lower
footprint and its modularity implying easy scale-up. On the other hand, permeate is
a low-pressure CO2-rich gas that requires a large compression unit for EOR
(Arinelli et al. 2017). MP process is currently being used for CO2 capture in
offshore rigs receiving gas from Brazil Pre-salt fields with %CO2 up to 20 mol%
(Honeywell 2012). Araújo et al. (2017) report a full performance comparison

between chemical absorption (CA), physical absorption (PA), membrane perme-
ation (MP), and hybrid configurations (MP-CA, MP-PA, MP-MP) for offshore
processing of 6 MMSm3/d NG on floating production storage and offloading
platforms (FPSOs) at three %CO2 levels: 10, 30, and 50 mol%. The alternatives are
assessed according to multi-criteria performance indexes, such as power con-
sumption, specific CO2 emissions, specific hydrocarbon loss, specific footprint, and
NG production. It is assumed that heat duty for solvent regeneration in chemical
absorption is met by pressurized hot water (PHW), a utility produced in waste heat
recovery units (WHRUs) from power generation turboshafts. This cheap source of
heat clearly favors CA, which is concluded as the best alternative in a hybrid
MP-CA configuration, seconded by pure MP-MP alternative. Physical absorption
consistently presented poorest performances due to huge solvent recirculation and
low CO2/CH4 selectivity.
Closely related to chemical absorption (CA) and membrane permeation (MP),
there is a new operation, namely gas–liquid membrane contactor (GLMC), which
consists of a metallic shell with non-selective hollow fiber membranes axially
distributed inside. The CO2-rich NG can be fed in the shell side while an aqueous
amine solvent is admitted into the hollow fibers or vice versa, both schemes under
parallel or countercurrent contacts. Membrane contactors with MEA+MDEA
aqueous solvent were rigorously modeled by de Medeiros et al. (2013) for
high-pressure CO2 removal from NG with 10 mol% of CO2, showing that this
technology is feasible for FPSO flowsheets including the appropriate solvent
regeneration step, besides CO2 compression and dispatch trains. Recently, Kang
et al. (2017) confirmed the feasibility of high-pressure membrane contactors with
aqueous MDEA for CO2 removal from CO2 ultra-rich NG with 45% and 70 mol%
CO2 contents. Results show that CO2 capture per unit of feed increases by
increasing gas pressure and membrane area/feed ratio; however, it is bound to high
methane losses, a feature also previously reported by de Medeiros et al. (2013).
Cryogenic distillation (CD) is based on CO2 condensation at low temperatures,
producing a high-pressure liquid CO2 stream that demands less power for pumping
to EOR, thus a great advantage of this technology. There are several process
variants for CO2 removal from CO2-rich NG such as the Ryan Holmes and CFZ
processes. The former is the basis of commercial plants worldwide (Holmes et al.
1983). It is based on cryogenic distillation of CO2 avoiding the occurrence of CO2
freeze-out by adding or recycling a paraffinic solvent (such as C4+) that shifts the
freeze-out border to lower temperatures. However, the Ryan Holmes process usu-
ally involves three or more columns, entailing high footprint. The CFZ alternative
comprises a chamber for controlled CO2 freeze-out and melting in the middle of the
cryogenic column. Kelley et al. (2011) investigated an ExxonMobil CFZ pilot
plant, showing that CD columns are improved by incorporating the CFZ technol-
ogy. Other CD configurations have been studied for CO2-rich NG (Berstad et al.
2012; Langè et al. 2015; Hart and Gnanendran 2009). Langè et al. (2015) compared
a new dual-pressure cryogenic distillation with traditional MDEA chemical
absorption in terms of energy consumption and economic parameters, varying gas
1.2 Technologies for CO2 Capture from CO2-Rich Natural Gas 5
composition from 5 mol% to 65 mol% CO2 and from 0 mol% to 15 mol% H2S.
Results show that the cryogenic process is more profitable for NG with CO2 content
above 10 mol%, with great power savings and dispatching CO2 to EOR with lower
power demand comparatively with the chemical absorption counterpart.
1.3 Supersonic Separator Application for CO2-Rich

Natural Gas Processing
A relatively new operation for NG processing is the supersonic separator (SS). This
technology consists of expanding the gas to supersonic velocities through a con-
verging–diverging nozzle (Laval nozzle), resulting in a great temperature fall and
thus promoting condensation of heavier species in NG, like water and C3+. The
liquid drops are separated from the main flow by centrifugal swirling induced by
fixed vanes in SS inlet section (Arinelli et al. 2017). Figure 1.1 exhibits a general
SS scheme with swirling vanes, Laval nozzle, condensate collector, and ending
diffuser. The Mach number (Ma) describes the compressible flow along the device.
Flow is subsonic through the converging section (Ma < 1), sonic at nozzle throat
(Ma = 1), and supersonic through the diverging section (Ma > 1) until the normal
shock front. The supersonic flow is a metastable condition under higher discharge
pressures relative to the pressure profile in the diverging section. Consequently, the
flow is gradually becoming more unstable downstream the throat, as the pressure
gradient to SS outlet increases, eventually provoking the shock phenomenon. When
this sudden irreversible transition occurs, the supersonic flow collapses into sub-
sonic, sharply increasing pressure and temperature, producing entropy and reducing
flow velocity under conservation of mass, energy, and momentum. Therefore, the
condensed phases formed in the cold supersonic section of SS must be removed by
Condensate
Swirling Laval Nozzle
Collector Diffuser
Vanes
Throat
Subsonic Flow Supersonic Flow

Ma<1 Ma>1 Subsonic Flow
Normal
Sonic Flow Shock Ma<1
Ma=1 Front
Fig. 1.1 Scheme of a generic supersonic separator

condensate collectors upstream the normal shock front; otherwise, they will
revaporize through the shock transition, destroying separation. After shock, the flow
in the diffuser is subsonic, so lean gas is further decelerated, gaining pressure and
temperature until SS exit.
The supersonic technology has been already extensively investigated in NG
processing for water dew-point adjustment (WDPA), hydrocarbon dew-point
adjustment (HCDPA), and natural gas liquid (NGL) extraction (Schinkelshoek and
Epsom 2008; Machado et al. 2012; Cao and Yang 2015; Secchi et al. 2016; Castier
2016; de Medeiros et al. 2017; Arinelli et al. 2017). The main SS advantages against
conventional alternatives are lower footprint, better separation efficiency for the same
head loss or just slightly better separation with lower head loss and power demand.
On the other hand, SS application for CO2 removal from CO2-rich NG is a new
field of application. In this case, the raw gas should be previously treated in terms of
WDPA dehydration and HCDPA, not only to prevent gas hydrate or ice solids, but
most importantly to avoid water and C3+ condensation processes that hinder the deep
fall of temperature necessary for CO2 condensation. Moreover, in cases with high and
ultra-high CO2 contents, CO2 freeze-out must be avoided to prevent risk of equip-
ment obstruction and plugging. Hence, the flow path inside SS should be controlled,
guaranteeing that the CO2 freeze-out border is not crossed (Arinelli et al. 2017).
In December 2014, Petronas announced an agreement with Twister BV and
other companies to develop a SS unit for processing of CO2 ultra-rich NG from K5
offshore gas field (%CO2 70%) in Sarawak, Indonesia (TheStar 2014). Samawe
et al. (2014) investigated SS application for CO2 removal from NG with 70 mol%
of CO2. The authors built a SS prototype to obtain experimental pilot test data and
validate a CFD model. Despite succeeding in proving the concept of SS for CO2
capture, the achieved CO2 removal was very low: only 2.1%. Imaev et al. (2014)
proposed a new low-temperature process combined with SS for CO2 extraction
from CO2 ultra-rich NG. The first step comprises a high-pressure low-temperature
distillation column for CO2 bulk removal, while the column top vapor with 10 mol%
to 20 mol% CO2 goes through a SS unit, decreasing CO2 content to the desired
level ( 2 mol%) and refluxing CO2-rich condensate to the column.
Arinelli et al. (2017) investigated SS for treating a CO2-rich (44 mol%) NG
simultaneously in terms of WDPA and HCDPA and, alternatively, for CO2
removal. SS alternatives were compared with conventional technologies: WDPA
via TEG absorption, HCDPA via JT expansion, and CO2 removal via MP. Process
alternatives were assessed in terms of technical performance and power demand via
HYSYS simulation using Unit Operation Extensions for SS simulation (Arinelli
et al. 2017) and for determination of the multiphase sound speed (de Medeiros et al.
2017). Results show that SS is the best alternative for WDPA and HCDPA, as both
are executed simultaneously in a single operation, hence with lower footprint
regarding the conventional process, producing lean gas with better quality, lower
power demand and higher rate of NGL extraction. Regarding CO2 removal, the MP
process presented the best results in terms of technical performance, while the
performance of SS operation was limited by the premise of freeze-out avoidance,
resulting in lower CO2 capture. On the other hand, SS for CO2 removal has a great
1.3 Supersonic Separator Application for CO2-Rich Natural Gas Processing 7
advantage in terms of power consumption due to the production of a high-pressure

liquid CO2 stream, requiring much less power for EOR destination than the CO2-
rich low-pressure permeate generated in MP units.
Further, still concerning new fields of SS applications, Teixeira et al. (2018)
investigated the use of supersonic separators to treat raw NG contaminated with
thermodynamic hydrate inhibitor (THI), a common situation in offshore NG
industry when thermodynamic hydrate inhibition is required. This innovative
process performs a small injection of liquid water in SS inlet, and as a result, this SS
practically recovers all the THI trapped in the raw NG, besides the entire water and
also a good part of heavy hydrocarbons C3+, while lean NG with appropriate
WDPA and HCDPA and raw LPG with commercial value are produced. This new
conception of process presents several advantages, reducing at least 79% of THI
losses, and is effective even in the case of nonvolatile THIs like monoethylene
glycol (MEG).
1.4 Final Remarks
A contextualization of offshore processing of CO2-rich NG was presented. A brief

discussion and bibliographic review on alternatives for CO2 removal from CO2-rich
NG were included. The preferred scenario of this book is a typical huge oil–gas
offshore basin, located at long distances from shore, probably at deepwaters, with
the potential to produce oil with associated gas, under high gas–oil ratios and high
%CO2 ( 40 mol%), entailing the onus of low-grade gas offshore processing
enchained to huge CO2 dispatch goals constrained to the offshore aspect. Therefore,
new processing solutions are needed to turn high-capacity CO2-rich NG processing
rigs into feasible and safe operations.
It was shown that the supersonic separator (SS) is a promising technology with
potential to fit into this scenario due to its capability of simultaneous WDPA and
HCDPA in a single compact and low-footprint operation. Besides, SS has also
some potential for CO2 removal from CO2-rich NG, despite facing a hard com-
petition with membrane permeation, apparently the most indicated technology for
CO2 removal in such remote offshore scenarios.
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the structural, condition of the optic nerve. That such an influence
may be exerted is shown by cases of transverse myelitis low down in
the cord, which, according to Erb and Seguin, were complicated by
double optic-nerve atrophy. The second theory is that the involved
part of the cord and the optic nerve present a similar vulnerability to
the same morbid influences. This is illustrated in some cases of
chronic alcoholic and nicotine poisoning, in ergotism, and in the
spinal affections due to hereditary influences and developmental
defects.
To discuss the nature of the disturbing influence which is responsible

for the most characteristic evidence of the disease, the ataxia, would
be equivalent to reviewing almost every mooted question in spinal
physiology. It is to be borne in mind that ataxia is a collective term
designating any inco-ordination of movement which is independent
of motor paralysis. It may be due to abolition or impairment of tactile
perception; it may be due to loss of the muscular sense; it may be
due to hampered motor co-ordination; and, finally, it may be due to a
disturbance of the space-sense. In my opinion it is only in
exceptional cases that any one of these factors can be positively
excluded. Occasionally, one has been noted when the ataxia was
grave but the tactile sense was unimpaired, or where the muscular
sense was perfect but ataxia was well developed. The difficulty with
most such records is that no discrimination is made as to the kind of
ataxia present. That loss of skill which the patient shows when he
shuts his eyes and attempts to perform certain movements without
their aid is undoubtedly due to diminished sensation, either tactile or
muscular, and usually both. The inability to stand with the eyes
closed is probably a cerebellar phenomenon, and in this respect we
are on the way to return to Duchenne's opinion. It is true that the
cerebellar organ is healthy in most tabic subjects, but its centripetal
informer, the direct cerebellar tract, is either itself involved or affected
in its origin in the columns of Clarke. But, besides the static ataxia
and that motor ataxia which can be neutralized by the use of the eye,
there is another disturbance, which, as Erb and his followers hold,
cannot be accounted for on the strength of any sensory disturbance.
It consists in an interference with the proper succession and rhythm
of movement. It seems as if that automatic mechanism by which the
individual or grouped muscular contractions engaged in locomotion
follow each other with the smoothness of the action of perfectly-
fitting cog-wheels were disturbed; the correct after-movement is
hesitated over or skipped, or even takes place at the wrong moment,
neutralizing some other step in the co-ordination required. The
tendency of physiologists and pathologists is to attribute this form of
ataxia to the disease of the intrinsic co-ordinating apparatus of the
cord itself. The experiments of Tarchanoff on a headless duck, and
the determination of the existence of cursorial co-ordinating tracts
uniting the brachial and lumbar nuclei in mammals, as well as the
observations made on automatic co-ordinate movement in
decapitated criminals, demonstrate the existence in the cord of such
an apparatus. The combination of the ganglionic centres which
underlies this co-ordination is affected by the so-called short tracts of
the cord,48 and it is precisely a portion of these which are involved in
the lesion of the column of Burdach. A number of arguments have
been advanced against regarding the lesion of this column, or
indeed any of the lesions of the posterior column, as explaining the
ataxia-producing effect of tabes. Westphal has interposed some
potent objections. He holds that lesion of these columns will be
found more frequently when examinations shall no longer be limited
to those cases where disease is suspected because ataxia was
observed during life. He found extensive disease of the posterior
columns in sufferers from paretic dementia who did not exhibit the
characteristic ataxic gait of tabes. I believe this objection can be met
by the very cases cited by Westphal in its support. Where the spinal
disorder preceded the cerebral—that is, where paretic dementia
occurred as a complication of tabes dorsalis—true locomotor and
static ataxia had been present before the insanity exploded. On the
other hand, where the spinal disease followed the cerebral, typical
ataxia did not ensue. This would seem to indicate that the
destruction of cortical control is inimical to the development of typical
tabes. Leyden has made a suggestion in the same direction when he
attributes the lesser manifestness of locomotor ataxia in tabic
females to their inferior cerebral organization.49 A more convincing
proof of the correctness of this conclusion is furnished by the fact
that if the pathological process, after destroying the posterior
columns and producing ataxia, invades the voluntary motor tract, the
ataxic symptom becomes less palpable.50 This antagonism between
lateral-column and posterior-column lesion is frequently exemplified
in the combined forms of sclerosis. It would seem, then, that where
the brain is healthy and the controlling voluntary tracts are
unimpaired, the ataxia is aggravated, supporting the beautiful theory
of Adamkiewicz, which assumes that the locomotor ataxia is due to a
disturbance of the balance normally existing between the psycho-
motor centres and those controlling the muscular tone as well as
those mediating reflex excitability.51
48 Intersegmental tracts.
49 In one out of three female eases I found the active disturbance of gait as severe as
in males, but Leyden's observation is supported by all who have seen a sufficiently
large number of female cases.
50 Not because of paresis altogether, for it diminishes materially out of proportion to

the paresis.
51 Archiv für Psychiatrie, x. p. 545. There is another observation which bears in this
direction: James of Boston observed that absolute deaf-mutes in a large percentage
of cases are insusceptible to vertigo or to the allied phenomenon of sea-sickness.
Certainly, the auditory nerve is a space-sense nerve; its physiological elimination is,
however, accompanied by an immunity against a symptom which may be an evidence
of disturbed space-sense transmission. In like manner, the destruction of the central
perceptive and voluntary centres in the paretic dement inhibits the legitimate results of
posterior spinal sclerosis.
The degeneration of the crossed-pyramid tracts in typical tabes seem to be strictly an

atrophy from disuse, perhaps facilitated by the general malnutrition of the cord. It is
limited to that part supplying the most or solely affected extremities. Thus, where the
lower extremities are alone grossly involved it is totally degenerated in the lumbar
area, and only in its outer parts in higher levels. As if to fortify this comparison by
analogous observations from every great segment of the nervous axis, a similar
inhibiting influence of pyramid lesion on co-ordinating disturbance (muscular sense) is
noted in secondary degeneration of the interolivary layer; when uncomplicated with
pyramid lesion (Meyer and my own case,) ataxia is present; when so complicated
(Schrader, Homén) it is not observed, even if determinable.
Lissauer52 has recently determined the existence of a degeneration

of certain fine nerve-fibres, apparently derived from the outermost of
the radicles into which the posterior nerve-roots divide on entry. They
are situated on that border of the apex of the posterior horn which is
in contact with the lateral column, and were found degenerated in all
cases except such as were in the initial period. No symptomatic
relation has been claimed for this lesion.
52 Neurologisches Centralblatt, 1885, No. 11.
One of the most important questions which have grown out of the
pathological studies of tabes is the relationship between the lesions
and the not infrequently observed restoration of functions which had
been more or less seriously impaired in an earlier period of the
disease. Even those symptoms which ordinarily comprise the
continuous and essential clinical background of tabes may exhibit
remarkable changes in this direction. I have two well-established
observations—one of tabes of eight years' standing, the other of
more recent date—in which that symptom which, once established,
is the most constant, the reflex iridoplegia, disappeared, to reappear
in two months in one case where it had been associated with
myosis, and to reappear in eight months in the other, repeating this
oscillation the following year. I have now under observation a tabic
patient in the sixth year of his illness who two years ago had a return
of both knee-phenomena to a nearly normal extent, to lose them in
two months, and to regain the reflex on the left side four months ago,
retaining it up to the present. These three cases were of syphilitic
subjects. In a fourth advanced non-syphilitic tabic patient, whose
ataxia had reached a maximal degree, I found a return of both knee-
phenomena for three days after its absence had been established by
medical examiners for over a year, and had probably been a feature
for a much longer period. Hammond the younger and Eulenburg
have reported similar cases. Nothing is more surprising to those
unfamiliar with the progress of this disease than to find gross ataxia
or the electrical pains and anæsthesia to disappear or nearly so; and
the alleged success of more than one remedial measure is based on
the fallacious attributing to the remedy what was really due to the
natural remittence of the disease-process or of its manifestations.
The financial success of quacks and the temporary but rapidly
evanescent popularity of static electricity, Wilsonia belts, and like
contrivances are owing to the hopefulness inspired in the credulous
patient by the mere coincidence of spontaneous improvement and
the administration of a new remedy, supplemented, it may be, by the
influence of mind on body in his sanguine condition. It is to be
assumed that the influences which are at work in provoking the
trophic and visceral episodes of tabes are of an impalpable
character, and that all theorizing regarding the reason of their
preponderance in one and their absence in another case are as
premature as would be any speculation regarding their rapid
development and subsidence in the history of one and the same
case. But we have better grounds for explaining the remissions of
the ataxia and anæsthesia.
It is only in the most advanced stages of tabes that the destruction of

the axis-cylinder becomes absolute or nearly so. Contrary to the
opinion of Leyden,53 who held that the tabic sclerosis differs from
disseminated sclerosis in the fact that the axis-cylinder does not
survive the myelin disappearance, it is now generally admitted that a
certain number of exposed or practically denuded axis-cylinders may
be preserved in the sclerotic fields.54 It is on the theory that these
delicate channels may be oppressed at one time, perhaps by
inflammatory or congestive pressure, and relieved at another by its
subsidence, that we may assume them to be the channels through
which the now limited, now liberated, functions are mediated. It is
also reasonable to suppose that vicarious action may supplement
the impaired function, and to some extent overcome the disturbing
factors. This is illustrated by the controlling influence of the visual
function—yea, even of the unconscious and ineffectual co-operation
of completely amaurotic eyes—in neutralizing both locomotor and
static ataxia. One patient who was well advanced in the initial period
of tabes, and who had been encouraged to consider the medical
opinion to that effect as the result of an exaggerated refinement of
diagnosis, made repeated tests of the Romberg symptom in his own
case, and deluded himself into the belief that the physician was
mistaken because he succeeded in practically overcoming it with an
effort that too plainly told its own story; but still he overcame it.
Certain peripheral influences have the power of stimulating the
dormant activity of potentially vicarious tracts, and perhaps also the
blunted activity of those whose function is impaired. The outside
temperature, certain barometric conditions, all may exert an
influence in this direction for good or evil.
53 Op. cit., p. 328, vol. ii.
54 Babinski (Neurologisches Centralblatt, 1885, p. 324) notes this feature, and,

consistently with the findings of most modern observers, discovers much more
resemblance to disseminated sclerosis than to the systemic sclerosis with which
Strümpell and Westphal (in part) incline to classify tabes. Similar objections to the
system-disease theory are advanced by Zacher (Archiv für Psychiatrie, xv. p. 340). I
may not pass over in silence the fact that Babinski considers his observations to
militate also against regarding any phase of the tabic sclerosis as a secondary
process. But while it may fairly be asked that a sclerosis to be regarded as systemic
must be shown to be total, this is not necessary for a secondary process, unless the
primary involvement be total also; and that is not the case in tabes.
ETIOLOGY.—Authorities are now agreed that no single cause can be

regarded as the sole responsible factor in all cases of tabes, and that
a number of etiological influences are combined in the provocation of
this disease in most instances. When the distinctiveness of the
affection was first recognized it was customary to attribute it to
sexual excesses, and the unfortunate sufferer had frequently to bear
the implied reproach of having brought his misery on himself, in
addition to the hopeless prospect which those who followed
Romberg and other authorities of the day held out to him.55
55 This opinion survives in a large portion of the German laity and in French novels.
About the time that the poet Heine was dying from an organic spinal affection two
other prominent literary characters of Paris were affected with tabes. It so happened
that all three were popularly regarded as libidinous, and one of their leading
contemporaries, whose name escapes me, took occasion to issue a manifesto
addressed to the jeunesse dorée which closed with the apostrophe, “Gardons à nos
moelles.”
Heredity plays a very slight part in the etiology of tabes. Writers of

ten and fifteen years ago attributed a greater importance to it than is
now done. But this was due to the incorporation with tabes of the so-
called family form of locomotor ataxia—a disease which is now
regarded as a distinct affection.56
56 There is but one record of direct heredity (the father and son being affected nearly
at the same time), to my knowledge. It was observed at the Berlin Hospital by Remak
(Berliner klinische Wochenschrift, 1885, No. 7). Both father and son were syphilitic.
More importance may be attached to individual predisposition, but

thus far no distinct formulation of this factor has been attempted
except by Schmeichler,57 who offers the suggestion that there are
persons with a predisposition to the development of connective-
tissue proliferation in various organs of the body, and that in them
tabes and other sclerotic affections are consequently more frequent
than in others. This suggestion appears plausible, but it is
unconfirmed by positive observations.
57 Op. cit.
Sex appears on a superficial view to be one of the most important

elements. It is generally admitted that at most one female becomes
tabic for every ten males who do so. Of 81 cases in private practice,
I observed but 3 females. Rockwell, Seguin, Birdsall, and Putnam
give similar figures. This comparative immunity is probably due to
the fact that the female is less exposed to over-exertion, to surface
chilling of the feet, to the injurious consequences of sexual excess,
and to syphilis58 than the male. As a rule, the affection in females is
more insidiously developed, progresses more slowly, is less marked
by crises and trophic disturbances, and not accompanied by as
severe pains and profound disturbance of co-ordination as is the
corresponding affection in males.
58 Whether the shorter vitality of the syphilitic female as compared with that of the
male is a factor in diminishing the accumulation of chronic tertiary sequelæ in that
sex, or whether it be the lesser vulnerability of the inferior nervous system, I am
unable to decide from the facts at my disposal. In private and clinical experience I
have been struck by the fact that women affected with syphilis in the same way and
under similar circumstances with tabic syphilitic males develop symptoms of
functional disorder of the brain and cord, such as spinal and cerebro-spinal irritation.
My cases referred to had in no instance any indication of a syphilitic condition or
history, and a distinct and different cause was found in all three.
The most important element in creating an acquired predisposition to

tabes is undoubtedly the existence of constitutional syphilis. Some
difference of opinion still exists regarding the proportion of syphilitic
tabic patients, chiefly due to the neglect of Erb—when he first
announced the prevailing view, and which is generally attributed to
him—to differentiate between cases of demonstrated constitutional
syphilis and the so-called spurious or soft chancre. But although
there occurred a reaction against his view which went to as great an
extreme in the opposite direction, the careful and critically registered
statistics accumulated in the mean time strengthen the view that
there are more syphilitic subjects among the tabic than among any
class of sufferers from other nervous affections.59 Reumont, a
physician at Aix-la-Chapelle, to which place syphilitic patients in
general resort in large numbers, found that of 3400 cases of syphilis,
290 had nervous affections, 40 being afflicted with tabes. Bernhardt60
took occasion to examine a group of hospital patients who were free
from tabes, and found that not fully 16 per cent. were syphilitic, while
of 125 tabic patients, over 46 per cent. were determined to have had
positive syphilitic manifestations. Several of those observers who
have paid attention to the question of the syphilitic origin of tabes
have admitted that the more searching their inquiry the larger the
proportion of detected syphilitic antecedent histories. Thus, Rumpf's
earlier table shows 66, and his later 80, per cent. of such
antecedents. This latter figure exactly corresponds to the percentage
of syphilis in my private cases. At a discussion held by members of
the American Neurological Association in 1884, Webber gave 54,
Putnam 49, Rockwell 40, Birdsall 43,61 and Seguin 22 per cent.62 as
the proportion in their experiences.
59 Excepting always those having the distinctive and undisputed syphilitic character.
60 Archiv für Psychiatrie, xv. p. 862.
61 Derived from over five hundred cases which had presented themselves at the clinic
of the College of Physicians and Surgeons.
62 In the Archives of Medicine he tabulates 54 (private) cases as follows:
Chancre alone 23
Chancre followed by secondary symptoms 16
Total of those with history of chancre 39
No history of chancre in 15
Total 54
Of European writers, aside from those already mentioned, Berger

claims 43 per cent., and Bernhardt, in commenting on the increasing
percentage obtained by accurate investigation, reports an additional
series of 7 new cases in private practice, all of which were syphilitic.
Fournier, Voigt, Œhnhausen, and George Fisher estimate the
syphilitic tabic patients at respectively 93, 81, and 72 per cent. of the
whole number. The almost monotonous recurrence of a clear
syphilitic history in my more recent records is such that in private
practice I have come to regard a non-syphilitic tabic patient as the
exception. Among the poorer classes the percentage of discoverable
syphilitic antecedents is undoubtedly much less. The direct exciting
causes of tabes, exposure and over-exertion, are more common with
them and more severe in their operation.
The proof of a relationship between syphilis and tabes dorsalis does

not rest on statistical evidence alone. A number of observations
show that the syphilitic virus is competent to produce individual
symptoms which demonstrate its profound influence on the very
centres and tracts which are affected in tabes. Thus, Finger63
showed that obliteration of the knee-jerk is a frequent symptom of
the secondary fever of syphilis, and that the relation is so intimate
between cause and effect that after the return of the reflex, if there
be a relapse of the fever, the obliteration of the knee-jerk is repeated.
Both the permanent loss of the knee-jerk (Remak) and the peculiar
pupillary symptoms of tabes are sometimes found in syphilitic
subjects who have no other sign of nervous disorder; and Rieger and
Foster64 regard the syphilitic ocular disturbances, even when they
exist independently, as due, like those of tabes, to the spinal, and not
to a primarily cerebral, disturbance. Another argument in favor of the
syphilitic origin of tabes is derived from the occasional remedial
influence of antisyphilitic treatment. The force of this argument is
somewhat impaired by the fact that the same measures occasionally
appear to be beneficial in tabes where syphilis can be excluded. Still,
the results of the mixed treatment in a few cases of undoubted
syphilitic origin are sometimes unmistakable and brilliant.65 As some
cases, even of long standing, yield to such measures, while others,
apparently of lesser gravity and briefer duration, fail to respond to
them, the question as to whether syphilis is a direct cause or merely
a predisposing factor may be answered in this way: That in the
former class it must have been more or less directly instrumental in
provoking the disease, while in the latter class it is to be regarded as
a remote and predisposing factor, to which other causes, not
reached by antisyphilitic treatment, became added. The claim of Erb,
that “tabes dorsalis is probably a syphilitic disease whose outbreak is
determined by certain accessory provocations,” is not subscribed to
unreservedly by a single writer of eminence.
63 “Ueber eine constante nervöse Störung bei florider Syphilis der Secundärperiode,”
Vierteljahrschrift für Dermatologie und Syphilis, viii., 1882.
64 “Auge und Rückenmark,” Graefe's Archiv für Ophthalmologie, Bd. xxvii. iii.
65 In one case already referred to a return of both knee-phenomena and complete

disappearance of locomotor and static ataxia were effected after a duration of four
years. The treatment was neglected and the knee-jerks disappeared, and one has
now returned under the resumed treatment, but accompanied by lightning-like pains.
At a meeting of the Société médicale des Hôpitaux, held November 10, 1882,
Desplats reported a case in which even better results were obtained. Reumont
(Syphilis und Tabes nach eigenen Erfahrungen, Aachen, 1881) reports 2 out of 36
carefully observed syphilitic cases cured, and 13 as improved under antisyphilitic
treatment.
The question has been raised whether the influence of syphilis is

sufficiently great to justify a clinical demarcation between syphilitic
and non-syphilitic cases. A number of observers, including Reumont,
Leonard Weber, and Fournier, incline to the belief that there are
more atypical forms of tabes in the syphilitic group. Others, including
Rumpf, Krause, and Berger, are unable to confirm this, but the
former admits, what seems to be a general impression among
neurologists, that an early preponderance of ptosis, diplopia, and
pupillary symptoms is more common with syphilitic than with non-
syphilitic tabes. Fournier66 believes that syphilitic patients show more
mental involvement in the pre-ataxic period; but it is evident that he
has based this belief on a study of impure forms. The advent of
tabes in syphilitic cases does not in this respect differ from the rule.
The most protracted and severe diplopia I have yet encountered in a
tabic patient is one, now under observation, in the initial period of the
disease, syphilis being positively excluded as an etiological factor.
66 L'Éncephale, 1884, No. 6.
It seems to be a prevalent opinion that the cases of syphilis in which

tabes is developed include a large proportion of instances in which
the secondary manifestations were slight and unlike that florid
syphilis with well-marked cutaneous and visceral lesions which is
more apt to be followed by transitory or severe vascular affections of
the cord and brain.
Excesses in alcohol, tobacco, and abuse of the sexual function are

among the factors which frequently aggravate the tendency to tabes,
and one or more of them will usually be found associated with the
constitutional factor in syphilitic tabes. Both alcohol and nicotine
have a deleterious effect on nervous nutrition and on the spinal
functions, as is illustrated in the effect of the former in producing
general neuritis, and of both in provoking optic-nerve atrophy and
general paralysis of the insane, not to speak of the pupillary states
which often follow their abuse, and the undeniable existence of a
true alcoholic ataxia. Sexual excesses were, as stated, at one time
regarded as the chief cause: the reaction that set in against this
belief went to the extreme of questioning its influence altogether. It is
to-day regarded as an important aggravating cause in a large
number of cases, and this irrespective of whether it be the result of a
satyriacal irritation of the initial period or a precedent factor. In a
large number of my patients (18 out of 23 in whom this subject was
inquired into) the habit of withdrawing had been indulged in,67 and,
as the patients admitted, with distinct deleterious effects, such as
fulness and throbbing in the lumbo-sacral region, tremor and rigidity,
with tingling or numbness, in the limbs, blurred vision, and
sometimes severe occipital headache; in one case lightning-like
pains in the region of the anus ensued.68
67 Coitus reservatus, the real crime of the Onan of Scripture.
68 Leyden states that coitus in the upright position has been accused of producing
tabes, without mentioning his authority. I have no observation on this subject touching
tabes, but am prepared to credit its bad effect from the account of a masturbator, who
during the orgasm produced while standing felt a distinct shock, like that from a
battery, shooting from the lumbar region into his lower limbs, and causing him to fall
as if knocked down. He consulted me in great alarm—was scarcely able to walk from
motor weakness, and had no knee-phenomenon; in a few weeks it returned, and no
further morbid sign appeared. Masturbators of the worst type occasionally manifest
ataxia, and in three cases I have been able to establish the return of the knee-jerk,
together with other improvements in the spinal exhaustion of these subjects. The loss
and diminution of the patellar jerk, and the frequently associated urinary incontinence,
as well as certain of the peripheral pains found in masturbators, certainly prove that
undue repetition of the sexual act (be it natural or artificial) is competent to affect the
cord in a way that cannot but be injurious in case of a predisposition to tabes, if not
without the latter.
Of single causes, none exerts so direct and indisputable an influence

on the production of tabes as the action of cold and wet upon the
lower segment of the body. It is usually the case that such exposure
is frequently repeated and combined with over-exertion before the
disease is produced, but it is occasionally possible to trace the very
first symptom of the disease directly to a single exposure. A soldier
who stands up to his knees in a rifle-pit half full of water finds his
limbs numb or tingling; develops slight motor weakness, then
lightning-like pains, and ultimately a typical tabes. In the case of a
peddler who presented an advanced form of the disease, the first
symptoms had developed after a single wetting of his feet: while
walking along one of our watering-places with his wares the swell of
a steamer inundated the beach. He had been subject to perspiring
feet before that, and the perspiration remained checked from that
time on.69 The influence of surface chilling was remarkably manifest
in all three of my female cases. In one of them it was due to frequent
wetting of the feet; in the second, a midwife, the first symptoms
began immediately after standing on a cold hearthstone while
preparing some article needed in a lying-in case. In the third case, a
lady who contracted and safely passed through a scarlatina in her
twenty-eighth year was taken out driving while desquamation was
going on. She became thoroughly chilled, experienced numbness in
the fingers and toes, and from that day on developed a slowly
progressing tabes involving all extremities alike.70
69 Checking of habitual perspiration by violent measures is mentioned by the German
textbook writers as a frequent cause, but occurs quite rarely in the modern tables.
70 In view of the absence of spinal—or, in fact, any nervous—symptoms prior to the

exposure referred to, it does not seem necessary to insist that this was not an
instance of a true post-scarlatinal tabes; and possibly the case thus designated by
Tuczek (Archiv für Psychiatrie, xiii. p. 147) may have been really due to chilling of the
delicate body-surface after desquamation or during that process. The typical form of
myelitis and sclerosis after exanthematous fevers is rather of the disseminated type.
Spinal concussion has been mentioned by a number of authorities

as a possible cause for tabes, as for other forms of sclerotic spinal
disease. In 1 of 81 cases in my own observation the development of
the disorder could be distinctly traced to a railway injury; in 2 a
sudden aggravation was as distinctly referable to a similar cause.71
To what extent railroad travelling, with its attendant continual jarring
of the body, may predispose to the development of tabes or of other
spinal diseases is as yet a matter of mere conjecture. That railroad
travelling exerts a bad influence in some cases of the established
disease is evident; but in others the patients rather like the motion,
and claim to feel benefited by it.
71 A fall from a chair, striking on the back of the latter, while endeavoring to keep a
row of books from coming down in one case, and the shock of the Ashtabula disaster
in the other. The latter patient, the same one who is referred to as describing the
electric-storm sensation in an earlier part of this article, had his foot amputated in
consequence of that disaster; but, like one of the characters in Jacob Faithful, who felt
his toes when the weather changed, though he left both legs at Aboukir, he felt the
terrific pains of the disease in the absent foot as distinctly as in the other. Dumenil and
Petit (Archives de Névrologie, ix. Nos. 25 and 26) relate cases in which a spinal
concussion was the only ascertainable cause.
A number of toxic agents have been charged with producing tabes:

thus, Bourdon maintains this of absinthe; Oppenheim attributes one
case to poisoning by illuminating gas, the exposure to its influence
being immediately followed by a gastric crisis, and this by a
regulation tabes.72 It is supposed that most of the poisons acting on
the cord in this or a similar way, such as arsenic, cyanogen,73
barium, and chloral,74 do not produce a spinal lesion directly, but
through the medium of a secondary cachexia. Of no agent is the
effect in producing tabes so well studied as ergot of rye. It had long
been known that ergot-poisoning provoked certain co-ordinating,
motor, and sensory disturbances, but it was left for Tuczek75 to show
that this vegetable parasite produces a lesion of the spinal cord
which in its character and distribution apes typical posterior sclerosis
so closely as to justify the designation of a tabes ergotica. Possibly,
pellagra, which is sometimes manifested in a similar way,76 may yet
be shown to have a like influence.
73 Bunge, Archiv für experimentelle Pathologie, xii.

74 Transactions of the Clinical Society of London, xiii. p. 117, 1880.
75 Archiv für Psychiatrie, xiii. p. 148.
76 Bouchard, “Étude d'Anatomie pathologique sur un Cas de Péllagrie,” Gaz. méd. de

Paris, 1864, No. 39.
Among the occasional and exceptional causes of tabes, Leyden and

Jolly mention the puerperal state; Bouchut, diphtheria; and several
instances are recorded in which psychical shock was responsible for
the outbreak of the disease. In a small number of cases I found that
mental worry and anxiety coincided with the period of presumable
origin of the disease.
Age seems to have no special determining influence. It is true that

most sufferers from this disease are men in the prime of life or in the
period following it. But it is precisely at these periods that the
exposure to the recognized causes of tabes is greatest. It seems as
if there were very little liability to the development of tabes after the
fiftieth and before the twenty-fifth year; still, some cases of infantile
tabes have been recorded.77
77 Excluding the so-called family form of locomotor ataxia: 6 rather imperfectly
described cases are cited by Remak (loc. cit.), and 3 additional ones related by
himself. Of the latter, 2 had hereditary syphilis, and of 1 the father was both syphilitic
and tabic.
In the majority of cases tabes is due to a combination of a number of

the above-mentioned factors. The majority of tabic patients in the
middle and wealthy classes have had syphilis, and of these, in turn,
the majority have been guilty of sexual excesses or perverted sexual
acts, while excesses in tobacco and of alcohol are often superadded.
Among the poorer patients we find syphilis less frequently a factor,
but still present, according to various estimates, in from 20 to 60 per
cent. of the cases. Excesses in tobacco play a lesser, and excesses
in alcohol a larger, part in the supplemental etiology than in the other
class, while exposure to wet and cold and over-exertion are noted in
the majority; indeed, in a fair proportion they are the only assignable
causes.
DIAGNOSIS.—The recognition of advanced tabes dorsalis is one of the

easiest problems of neurological differentiation. The single symptom
which has given one of its names to the disease—locomotor ataxia
—is so manifest in the gait that even the sufferers from the affection
learn to recognize the disease in their fellow-sufferers by the peculiar
walk.78
78 At present I have six tabic patients under treatment, who are acquainted with each
other, and who have made each other's acquaintance in the singular way of
addressing one another on the strength of mutual suffering at Saratoga, at the Hot
Springs of Arkansas, and in New York City.
Although there are other chronic affections of the cord which

manifest ataxia, such as myelitis predominating in the posterior
columns, disseminated sclerosis in a similar distribution, and some
partially recovered cases of acute myelitis, the gait is not exactly like
that of tabes. The uncertainty may be as great, but the peculiarly
stamping and throwing motions are rarely present in these
affections. The clinical picture presented by the ataxic patient, aside
from his gait, is equally characteristic in advanced cases. Absence of
the knee-jerk and other deep reflexes, the bladder paralysis, sensory
disturbance, delayed pain-conduction, trophic disturbances, and
reflex iridoplegia are found in the same combination in no other
chronic disorder of the cord. It is supposable that an imperfect
transverse myelitis in the lumbar part of the cord might produce the
reflex, ataxic, sensory, sexual, and vesical symptoms of ataxia, but
the brachial symptoms found in typical tabes as well as gastric crises
would be absent. The pupillary symptoms would also fail to be
developed, in all probability. It is to be remembered that only
fascicular cord affections can produce a clinical picture exactly like
that of tabes in more than one important respect. In analyzing the
individual symptoms of the early stage the more important differential
features can be most practically surveyed.
The discovery of no single symptom of tabes dorsalis marks so
important an epoch in its study as Westphal's observation that the
knee-phenomenon is usually destroyed in it. Had this symptom not
been detected, so Tuczek admits, ergotin tabes would have eluded
recognition.79 It was claimed by a majority of neurologists at first that
this jerk is always abolished in tabes, but it is now recognized that
there are exceptions, as is shown by cases of Hirt,80 Westphal, and
others, not to mention some well-established cases of its return
during the progress of the disease.
79 It is not to be wondered that, like most new discoveries, that of the pathological
changes of the patellar reflex should have been made the basis of premature
generalizations. The attempt of Shaw (Archives of Medicine) to establish a relation
between disturbances of the speech-faculty and an increased knee-jerk has not met
with any encouragement or confirmation, and has been rebutted by Bettencourt,
Rodrigues (L'Éncephale, 1885, 2), and others.
80 Berliner klinische Wochenschrift, 1886, 10.
The knee-phenomenon is supposed to be a constant attribute of

physiological man. It is difficult to elicit it in children, and frequently
impossible to obtain it in young infants. It also disappears in old age,
without having any special signification, except that this occurrence
seems to be in direct relation to senile involution. In 2403 boys
between the ages of six and thirteen years, Pelizæus81 found it
absent in one only. It is customarily elicited by having the patient
while sitting in a chair throw one leg over the other; hereupon the
ligamentum patellæ is struck a short, quick blow. Under physiological
circumstances the leg is jerked outward involuntarily after an interval
of about one-fifth of a second—one that is scarcely appreciated by
the eye. But if it be found absent by this mode of examination, the
case is not to be regarded as one of absence of the jerk without
further ado. The patient is made to sit on a table, his legs dangling
down and his body leaning back, while he clenches his fists. By this
means the jerk will often be produced where it appears to be
impossible to evolve it by the ordinary means. It is also well to try
different parts of the ligament, and when comparing both sides to
strike on the corresponding spot and in the same direction. Many
subjects who appear to be irresponsive will respond very well when
a point on the outer edge near the tibial insertion is percussed. The
elbow reflex, which has the same signification for the upper extremity
that the knee-jerk has for the lower, is elicited in the same manner.
The absence of the knee-jerk is usually regarded as a suspicious

circumstance in persons of middle life; and where it can be
demonstrated that it has been present years previously and
subsequently disappeared, it is looked upon as of grave import. I,
however, published three years ago an authentic case of
disappearance of the knee-jerk in a physician now in active practice
in New York City who to this day enjoys excellent health and has
developed no other sign of spinal disease. The knee-jerk is also
abolished in a number of conditions not belonging to the domain of
strictly spinal diseases, such as diphtheria, diabetes, secondary
syphilis, and severe cases of intermittent fever. Of these, diabetes
alone can be possibly confounded with tabes dorsalis. The difficulty
of differentiating early tabes and diabetes is enhanced by the fact
that on the one hand there are often ataxic symptoms with diabetes,
while on the other both glycosuria and diabetes insipidus may
complicate tabes. Senator, Frerichs, Rosenstein, Leval-Piquechef,
Charcot, Raymond, Demange, Féré, Bernard, and T. A. McBride all
recognize the occasional presence of the ataxic gait, paræsthesia,
belt sensation, and even fulgurating pains, besides the abolition of
the jerk, in diabetes mellitus.82 In pure cases of diabetes, however, I
am not aware that spinal myosis or the reflex paralytic pupil has
been found.
82 I have now under observation a case of myelitis with predominating sclerosis of the
posterior columns of five years' standing in a merchant who has been under
antidiabetic treatment for eleven years.
Abolition of the knee-jerk is found in all organic diseases of the

spinal cord which destroy any part of the neural arch at the upper
lumbar level, where the translation of the reflex occurs, whether it be
in the posterior root-zones or in the gray matter of the origin of the
crural nerves. Thus, acute or chronic myelitis, disseminated sclerotic
foci of this level, may cause obliteration of the reflex at any time of
the disease; so may acute or chronic anterior poliomyelitis,
neoplasms, and amyotrophic lateral sclerosis of the anterior cornua
type if the destruction of the anterior cornua be complete enough. It
is also found abolished with all diseases of the peripheral nerves—
traumatic and neuritic—which produce absolute motor paralysis of
such nerves.
Among the sources of error possibly incurred in examining for this

important symptom the presence of rheumatism is one. There is
sometimes a tetanic rigidity of the joints which prevents the reflex
from becoming manifest. It is also sometimes found to be absent
immediately after severe epileptic attacks, according to Moeli.83
83 In three examinations after severe attacks of epilepsy I found it normal.
The condition of the pupil is perhaps a more constant sign of early

tabes than the loss of the knee-jerk; at least it has been found well
marked in cases where the jerk had not yet disappeared. It may be
regarded as a rule in neuro-pathology that wherever reflex
iridoplegia is at any time accompanied by other oculo-motor
disturbance, it is either of spinal origin or in exceptional cases due to
disease of the pons varolii. The peculiar character of the pupillary
disturbance of tabes furnishes us with a criterion for distinguishing it
from one affection which in common with it exhibits loss of the knee-
jerk—diphtheria. In diphtheria there is also a reflex disturbance of the
pupil, but it is the reverse of that of early tabes. In the latter reaction
to light is lost, but the accommodative contraction power is retained;
in diphtheria accommodative contraction power is lost, but reaction
to light is retained.
The bladder disturbance has already been described. It is found as a

marked symptom so prominently in no other systemic affection of the
cord, and in few of the non-systemic forms, of sclerosis. In none of
these is it associated with absence of the patellar jerk, reflex
iridoplegia, and fulminating pains, as in tabes, except there be also
some motor paresis. It is the combination of any two of the important
initial symptoms of tabes without paralysis or atrophy that is
regarded as indicative of the disease by most authorities. Thus the
swaying in closing the eyes, if associated with the Argyll-Robertson
pupil, is considered as sufficient to justify the diagnosis of incipient
tabes, even if the knee-jerk be present and fulminating pains and
bladder trouble absent. Undoubtedly, the tabic symptoms must begin
somewhere. But at what point it is justifiable to give a man the
alarming information that he is tabic is a question. I have a number
of neurasthenic subjects now under treatment who have had reflex
iridoplegia for years; in one the knee-jerk is slowly becoming
extinguished; in two it has been becoming more marked after
becoming less; in all the three mentioned there is slight swaying in
closing the eyes and some difficulty in expelling the last drops of
urine while micturating. I do not believe that such a condition justifies
a positive opinion, although the surmise that they are on the road to
developing tabes may turn out correct for all these and for some of
those who have merely reflex iridoplegia.
Incipient tabes cannot be readily confounded with any other chronic

disease of the spinal cord. Some of the cases produced by sudden
refrigeration resemble a beginning myelitis. But the absence of true
paralysis seems to distinguish it from the latter. In all the cases of so-
called acute locomotor ataxia of myelitic origin that I can find a
record of, paralytic symptoms were marked, if not throughout the
disease, at least in the initial period.
Other forms of sclerosis occasionally limited to the posterior columns

imitate the symptoms of tabes. It is unusual, however, for such
sclerosis to be distributed through so great an extent of the posterior
columns as to produce symptoms consistent with tabes in both the
upper and lower extremities. And even where this condition is
complied with, the typical progress so characteristic of tabes is not
adhered to. As previously stated, the progress is weakened by
variations in certain symptoms. Such variations are found in other
forms of sclerosis, but they are not as great, trophic disturbances not
so common, and visceral crises not so violent, as a rule.

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Offshore Processing of CO2 Rich

Natural Gas with Supersonic Separator

CO2-Reservoir Oil Miscibility Dayanand Saini

Fundamentals of Natural Gas Processing 3rd Edition

Handbook of Natural Gas Transmission and Processing

Chemo biological systems for CO2 utilization First

Data-Driven Analytics for the Geological Storage of Co2

Membrane Technology for CO2 Sequestration 1st Edition

Modeling, Control, and Optimization of Natural Gas

Advanced Coal Preparation and Beyond-CO2 Capture and

Lara de Oliveira Arinelli Ofélia de Queiroz Fernandes Araújo

ISBN 978-3-030-04005-5 ISBN 978-3-030-04006-2 (eBook)

Library of Congress Control Number: 2018962390

© Springer Nature Switzerland AG 2019

PVT-thermal properties—like the thermodynamic sound speed property—of

Rio de Janeiro, Brazil José Luiz de Medeiros

1 Offshore Processing of CO2-Rich Natural Gas and the Role

3 Overview of Natural Gas Processing with Supersonic Separator ... 41

5.3 Sound Speed Property of Multiphase Multi-Reactive Streams . .. 105

5.6.4 Summary of Sonic Singularities of Spatial Gradients

7.3 Thermodynamic Modeling of CO2 Solid Phase for Freeze-Out

9 Recovery of Thermodynamic Hydrate Inhibitors with Supersonic

1D, 2D, 3D One, Two, and Three Dimensional

HGR HYSYS Gibbs Reactor

SW-EOS Span–Wagner EOS

a Parameter of attractive term of cubic EOS (Pa.m6/mol2)

V MP molar flow rate of retentate (mol/s)

a, b SS Converging and diverging wall angles for linear diameter

X Vector of multiphase equilibrium constraints

AS Just after normal shock

Lara de Oliveira Arinelli, José Luiz de Medeiros,

1.1 General Overview on Raw CO2-Rich Natural Gas

© Springer Nature Switzerland AG 2019 1

dehydration; (iii) hydrocarbon dew-point adjustment (HCDPA); and (iv) removal of

economically feasible through subsea gas pipelines (already existent or planned)

1.2 Technologies for CO2 Capture from CO2-Rich

(Honeywell 2012). Araújo et al. (2017) report a full performance comparison

1.3 Supersonic Separator Application for CO2-Rich

Subsonic Flow Supersonic Flow

Fig. 1.1 Scheme of a generic supersonic separator

advantage in terms of power consumption due to the production of a high-pressure

1.4 Final Remarks

A contextualization of offshore processing of CO2-rich NG was presented. A brief

To discuss the nature of the disturbing influence which is responsible

50 Not because of paresis altogether, for it diminishes materially out of proportion to

The degeneration of the crossed-pyramid tracts in typical tabes seem to be strictly an

Lissauer52 has recently determined the existence of a degeneration

It is only in the most advanced stages of tabes that the destruction of

54 Babinski (Neurologisches Centralblatt, 1885, p. 324) notes this feature, and,

ETIOLOGY.—Authorities are now agreed that no single cause can be

Heredity plays a very slight part in the etiology of tabes. Writers of

More importance may be attached to individual predisposition, but

Sex appears on a superficial view to be one of the most important

The most important element in creating an acquired predisposition to

60 Archiv für Psychiatrie, xv. p. 862.

62 In the Archives of Medicine he tabulates 54 (private) cases as follows:

Of European writers, aside from those already mentioned, Berger

The proof of a relationship between syphilis and tabes dorsalis does

65 In one case already referred to a return of both knee-phenomena and complete

The question has been raised whether the influence of syphilis is

It seems to be a prevalent opinion that the cases of syphilis in which

Excesses in alcohol, tobacco, and abuse of the sexual function are

Of single causes, none exerts so direct and indisputable an influence