Production, Liquefaction and Transport

of Low-Processed Natural Gas

Haakon Andreas Hveding

Master of Science in Product Design and Manufacturing

Submission date: July 2010
Supervisor: Truls Gundersen, EPT
Co-supervisor: Jostein Pettersen, Statoil
Arne Olav Fredheim, Statoil

Norwegian University of Science and Technology

Department of Energy and Process Engineering
Problem Description
The main objective for this Master thesis is to make a systematic survey and analysis of value
chains for natural gas based on un-processed or low-processed natural gas in liquid phase
(possibly with a solid fraction). The survey should evaluate and focus on energy efficiency,
complexity (both in development, design and operation), uncertainty elements, need for technology
qualification and the realism of the concepts.

1. A high level survey of different published, known, patented as well as possible/imaginable

concepts for production and transport of un-processed or low-processed natural gas.
2. An evaluation of different solutions for processes and equipment related to such concepts
for gas transport with emphasis on gas pre-treatment and liquefaction. This will also require a
search in the patent literature.
3. To establish energy and material balances for relevant concepts and value chains based
on process modeling tools (process simulators). The level of detail should be increased for the
more promising concepts.
4. To analyze and discuss the results (see the objective section) and compare with realistic
figures for conventional production and transport solutions.

Assignment given: 11. February 2010

Supervisor: Truls Gundersen, EPT
Production, Liquefaction & Transport of Low-Processed Natural Gas

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 Production, Liquefaction & Transport of Low-Processed Natural Gas

Preface

This Master Thesis was written as the final work in the last semester of the quinquennial
Product Design and Manufacturing program at the institute of Energy and Processing, NTNU,
in the spring of 2010.

As the thesis is not a continuation of the project assignment in autumn 2009, a great deal of
time was spent on getting an overview and gather and evaluating different patents from the
concepts described, as well as patents that potentially could have been used.

I would like to express my gratitude to my supervisor Truls Gundersen at NTNU for great
follow-up and always being available for consultation. I would also like to thank the industrial
contacts at Statoil, Jostein Pettersen and Arne Olav Fredheim for giving me input and
information during the semester, and taking the time to arranging feedback meetings along the
way. In addition I would like to thank Petter Nekså, Jacob Stang and Yves Ladam for input on
the LUWS concept status and Longman Zhang for calculations and advice on freeze out
concentration limits for water and CO2.

Trondheim, 06.07.2010

____________________

Haakon A. Hveding

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 Production, Liquefaction & Transport of Low-Processed Natural Gas

Summary in English

The pre-processing and liquefaction of LNG is very energy demanding in addition to having a
high level of complexity. This motivates for finding alternative value chains and technologies
for gas transportation and various concepts have been proposed based on natural gas in liquid
phase. These can be split into two main principles; liquefaction with solids formation, and
storage under pressure. Due to the increased temperature and solubility, freezable components
will not form solids as easily in the pressurized concepts allowing less pre-treatment of the
gas. The evaluated concepts in this thesis are Liquefied Unprocessed Well Stream (LUWS)
with controlled solids formation, and three pressurized storage concepts; Aker Solutions’
Heavy Liquid Gas (HLG), ExxonMobil’s Pressurized Liquefied Natural Gas (PLNG) and
Chevron’s Liquefied Heavy Gas (LHG). All are presented in a high level survey together with
similar ideas and patents in the first part of the thesis.

Value chain evaluations are carried out for the different concepts and positive contributions,
uncertainty and possible difficulties are discussed. The different patents filed, with solutions
to some of the difficulties associated with the concepts, are also explained and presented. As
the different gas products will have a less pure composition compared to LNG, the gas
treating part of the value chains will be moved downstream of the liquefaction for all the new
concepts.

Through simplified simulations in PRO/II, energy requirements and specifications of the

product liquid for the different concepts are found. The gas composition is adjusted to avoid
freeze out of any kind for the pressurized liquids. The power needs for liquefaction are
drastically decreased with increased pressure, giving smaller and less complex liquefaction
plants. For a HLG concept at 20 bars, the power need is around halved, while for LHG at 50
bars it is between 25-39% compared to LNG, depending on the amount of heavy
hydrocarbons in the LHG. The amount of flash gas needed for power production is as a direct
result reduced by 70%.

Water removal will still be necessary for all the concepts as hydrates will form easily at high
pressures and low temperatures. The only exception is for the LUWS concept, where a
smaller amount of water possibly could be allowed to form hydrates in a controlled way
together with hydrocarbons and CO2.

The reduced requirements for the gas means alternative processes for pre-treatment can be
utilized and the thermal energy needs for these decreased at the liquefaction site. CO2 removal
may be done by a membrane system or similar as the CO2 concentration can be around 1,4
and 6 mole% for a pressure of 12 and 50 bars respectively without the forming of solids. At
the receiving site, a system similar to the CRYEX process can be implemented to remove the
CO2 and allow storage of gas as LNG at atmospheric pressure.

Estimations of the weight of the steel pressure vessels have been calculated for all the
pressure levels. Due to the extremely high weight and the large amount of steel needed, the
vessels must be constructed by an alternative building material for the high pressure ranges. A
fiber reinforced plastic is suggested used with a steel or aluminum liner retaining the liquid. If
successfully manufactured, these vessels would significantly reduce the weight and make
HLG/LHG possible to implement.

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Sammendrag på norsk

Før-prosesseringen og flytendegjøringen av LNG er veldig energikrevende i tillegg til å ha en

høy grad av kompleksitet. Dette gir motivasjon til å finne alternative verdikjeder og
teknologier for gasstransport og ulike konsepter har blitt lagt frem basert på naturgass i
flytende form. Disse kan deles inn i to hovedgrupper; flytendegjøring med utfrysning, og
transport under trykk. På grunn av forhøyet temperatur og løselighet vil komponenter som
vanligvis ville frøset ut kunne forbli i væskeform i de trykksatte konseptene, som igjen
reduserer kravene til før-prosessering av gassen. De drøftede konseptene i denne oppgaven er:
Liquefied Unprocessed Well Stream (LUWS) med kontrollert utfrysning, samt tre trykksatte
konsepter; Aker solutions Heavy Liquid Gas (HLG), ExxonMobils Pressurized Liquefied
Natural Gas (PLNG) og Chevrons Liquefied Heavy Gas (LHG). Alle blir presentert i en
oversikt sammen med lignende ideer og patenter i begynnelsen av oppgaven.

Verdikjedebetraktninger for de ulike konseptene har blitt utført og positive virkninger,

usikkerhet samt mulige vanskeligheter blitt diskutert. Forskjellige patenter med mulige
løsninger til nevnte vanskeligheter forbundet med konseptene har også blitt presentert og
gjennomgått. Siden den transporterte væsken vil ha en mindre ren komposisjon enn LNG,
gassbehandlingsdelen av verdikjeden vil bli flyttet nedstrøms av produksjonen og
flytendegjøringen for alle de nye konseptene.

Gjennom forenklede simuleringer i PRO/II har energibehov og spesifikasjoner for

væskeproduktene til de forskjellige konseptene blitt funnet. Gasskomposisjonen blir justert
slik at ingen utfrysning finner sted i de trykksatte væskene. Kraftbehovet for flytendegjøring
blir drastisk redusert med økning i trykknivå noe som gir mindre prosessanlegg og reduserer
kompleksiteten på dem. For HLG konseptet ved 20 bar blir kraftbehovet rundt det halve,
mens LHG ved 50 bar gir et krav på mellom 25-39% i forhold til LNG varierende med
mengden tyngre hydrokarboner i væskeproduktet.

Fjerning av vann før flytendegjøringen vil fremdeles være nødvendig for alle konseptene da
gasshydrater lett vil oppstå ved høye trykk og lave temperaturer. Eneste unntak er for LUWS
konseptet hvor en mindre mengde vann muligens kan tillates å forme hydrater på en
kontrollert måte sammen med hydrokarboner og CO2.

Det reduserte kravene til renhet på gassen fører til at alternative prosesser til førprosessering
kan bli tatt i bruk og de termiske energibehovene redusert ved prosesseringsanlegget. CO2
fjerning kan bli utført ved hjelp av en membran eller lignende siden CO2-konsentrasjonen kan
være rundt 1,4% og 6% for trykk ved henholdsvis 12 og 50 bar uten å danne fast stoff. Ved
mottagsstedet, kan et system ikke ulikt CRYEX prosessen bli brukt til å fjerne CO2 og dermed
tillate lagring av noe av gassen som LNG ved atmosfærisk trykk.

Noen estimat for vekten av trykkbeholderene laget av stål er satt opp for alle trykknivåer.
Grunnet den ekstremt høye vekten og den store mengden stål, må trykkbeholderene bli utført i
et alternativ byggemateriale for de høyeste trykkene. Fiberarmert plastikk beholdere med et
foringsmateriale av aluminium eller stål er foreslått. Hvis disse blir vellykket produsert til en
rimelig pris vil dette muliggjøre realisering av konsepter slik som HLG/LHG.

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Table of Contents

Preface ........................................................................................................................................I
Summary in English ................................................................................................................ II
Sammendrag på norsk .......................................................................................................... III
Table of Contents ................................................................................................................... IV
Nomenclature .......................................................................................................................... VI
Index of Tables ..................................................................................................................... VII

1 Introduction ....................................................................................................................... 1
1.1 Objective ...................................................................................................................... 1
1.2 Background .................................................................................................................. 1
1.3 Limitations ................................................................................................................... 2
2 Conventional LNG production ........................................................................................ 3
3 Survey of Concepts ........................................................................................................... 7
3.1 LUWS .......................................................................................................................... 7
3.2 Idaho National Laboratory: "Compact High Efficiency Natural Gas Liquefier" ..... 10
3.3 Cool Energy Limited and the MicroCell/CryoCell technology................................. 11
3.4 PLNG - Pressurized Liquefied Natural Gas .............................................................. 12
3.5 HLG - Heavy liquefied gas ........................................................................................ 15
3.6 Chevron LHG ............................................................................................................ 17
4 Untraditional Separator Technologies .......................................................................... 18
4.1 3S - Super Sonic Separator Technology .................................................................... 18
4.2 CRYEX - Cryogenic Extraction ................................................................................ 20
4.3 CryoCell..................................................................................................................... 21
5 Evaluation of processes and equipment ........................................................................ 22
5.1 Concept groups .......................................................................................................... 22
5.2 Value chain for LUWS .............................................................................................. 23
5.2.1 Dehydration ........................................................................................................ 24
5.2.2 Liquefaction ....................................................................................................... 24
5.2.3 Storage ................................................................................................................ 25
5.2.4 Transportation .................................................................................................... 26

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5.2.5 Receiving facilities ............................................................................................. 26
5.2.6 Other pre-processing units ................................................................................. 27
5.2.7 Post processing and CO2 disposal ...................................................................... 27
5.2.8 Slurry behavior in Storage.................................................................................. 28
5.2.9 Possible LUWS approaches ............................................................................... 30
5.3 Value chain for HLG/PLNG/LHG ............................................................................ 32
5.3.1 CO2 removal requirements ................................................................................. 33
5.3.2 Dehydration ........................................................................................................ 35
5.3.3 Reduced HHC scrubber requirements ................................................................ 35
5.3.4 Power requirements ............................................................................................ 35
5.3.5 Loading systems ................................................................................................. 36
5.3.6 Storage tanks and Transportation ....................................................................... 36
5.3.7 Receiving facilities ............................................................................................. 38
5.3.8 Post processing ................................................................................................... 39
5.3.9 End User Alternatives ........................................................................................ 40
6 Process simulations ......................................................................................................... 42
6.1 Assumptions .............................................................................................................. 42
6.2 Freeze out Temperatures ........................................................................................... 44
6.3 An approximation of the Amine treatment energy needed ........................................ 46
6.4 Results and discussion ............................................................................................... 47
6.4.1 Concept results ................................................................................................... 47
6.4.2 Calculated example ............................................................................................ 52
6.5 Pressure vessel calculations ....................................................................................... 54
6.6 Water content limits................................................................................................... 58
6.7 Comparison of Concepts ........................................................................................... 61
6.8 Further work .............................................................................................................. 65
7 Conclusion ....................................................................................................................... 67
8 References ........................................................................................................................ 68
9 Appendix ........................................................................................................................... A

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Nomenclature

LNG Liquefied Natural Gas

NGL Natural Gas Liquids
LPG Liquid petroleum Gases
PLNG Pressurized LNG
HLG Heavy Liquid Gas
LHG Liquid Heavy Gas
LUWS Liquefied Unprocessed Well Stream
FPSO Floating Production Storage and Offloading
HHV Higher Heating Value
GCV Gross Calorific Value
HHC Heavy Hydrocarbons
DP Dew Point
JT Joule-Thomson
MEA Mono ethanol amine
FRP Fiber Reinforced Plastic
ppm Parts per million
C1 Methane
C2 Ethane
C3 Propane
iC4 I-Butane
nC4 N-Butane
iC5 I-Pentane
nC5 N-Pentane
C6 Hexane
CX+ Hydrocarbons over X C-atoms
Hg Mercury
s Specific entropy
e Specific exergy
h Specific enthalpy

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Index of Tables

Table 1: LNG Specifications ...................................................................................................... 4

Table 2: Power production end user ......................................................................................... 40
Table 3: Simulation results I .................................................................................................... 48
Table 4: Simulation Results II .................................................................................................. 49
Table 5: Liquids Composition .................................................................................................. 50
Table 6: Freezable components Concentrations ....................................................................... 51
Table 7: Example Calculations I .............................................................................................. 52
Table 8: Example Calculations II ............................................................................................. 52
Table 9: Steel Vessel Calculations ........................................................................................... 55
Table 10: Containment Vessel Comparison ............................................................................. 57
Table 11: Fiber Reinforces Plastic Calculations ...................................................................... 58
Table 12: Pros and Cons; LNG LUWS .................................................................................... 61
Table 13: Pros and Cons; HLG, PLNG, LHG.......................................................................... 62
Table 14: Comparison of Concepts .......................................................................................... 65

Table of Figures

Figure 1: LNG General Value Chain ......................................................................................... 3

Figure 2: LNG Tanker ................................................................................................................ 4
Figure 3: LNG cost distribution ................................................................................................. 5
Figure 4: LNG Value Chain Diagram ........................................................................................ 5
Figure 5: LNG Receiving Facility.............................................................................................. 6
Figure 6: LUWS Patent diagram ................................................................................................ 8
Figure 7: LUWS Patent PH diagram .......................................................................................... 9
Figure 8: Idaho Process Flow Diagram .................................................................................... 11
Figure 9: MicroCell Patent Vessel ........................................................................................... 11
Figure 10: PLNG Ship.............................................................................................................. 13
Figure 11: PLNG Reduced Space Requirements .................................................................... 13
Figure 12: PLNG delivery Chain ............................................................................................. 14
Figure 13: US Patent No. 6,378,330 ........................................................................................ 14
Figure 14: US Patent No. 5,956,971 ........................................................................................ 15
Figure 15: US Patent No. 6,539,747 ........................................................................................ 15
Figure 16: HLG Patent Figure .................................................................................................. 16
Figure 17: HLG FPSO.............................................................................................................. 16
Figure 18: HLG Topside .......................................................................................................... 16
Figure 19: HLG Receiving facility........................................................................................... 16
Figure 20: LHG Patent Diagram .............................................................................................. 17

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Figure 21: Twister Separator .................................................................................................... 18

Figure 22: Twister Separator Stages ........................................................................................ 19
Figure 23: CRYEX Flow Diagram ........................................................................................... 20
Figure 24: CryoCell Flow Diagram ......................................................................................... 21
Figure 25: Concept P-T diagram .............................................................................................. 22
Figure 26: LUWS Value Chain Diagram ................................................................................. 23
Figure 27: LUWS Settling....................................................................................................... 26
Figure 28: Mechanical Solids Separation................................................................................. 27
Figure 29: Solids Return Tranport Diagram ............................................................................ 28
Figure 30: Possible LUWS Solution ........................................................................................ 30
Figure 31: Solution: Flow Diagram of possible LUWS ........................................................... 31
Figure 32: HLG Value Chain Diagram .................................................................................... 32
Figure 33: Membrane Separator. .............................................................................................. 34
Figure 34: PLNG Unloading .................................................................................................... 36
Figure 35: PLNG Vessel Prototype ......................................................................................... 37
Figure 36: Spherical Composite ............................................................................................... 38
Figure 37: Cylindrial Composite .............................................................................................. 38
Figure 38: Unloading pressurized Liquefied Gas into LNG storage facilities ......................... 39
Figure 39: SLV diagram for Methane-CO2 . ............................................................................ 45
Figure 40: CO2 solubility in CH4 ............................................................................................ 45
Figure 41: Minimum Theoretical Work ................................................................................... 47
Figure 42: Density Chart .......................................................................................................... 49
Figure 43: Moss type ................................................................................................................ 55
Figure 44: Cylindrical Pressure Vessel .................................................................................... 55
Figure 45: Total Steel Vessel Weight ...................................................................................... 56
Figure 46: Hydrate Formation Curve ....................................................................................... 59
Figure 47: Water Content at hydrate equilibrium .................................................................... 59

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1 Introduction

1.1 Objective
The main objective for this thesis is to give an overview of concepts and alternative processes
for production, liquefaction and transport of low-processed natural gas in a liquid phase. The
value chains for such concepts are to be presented and evaluated with special emphasis on
pretreatment and liquefaction, so that a basis of the feasibility and complexity can be given
for the different concepts.

The energy requirements for liquefaction and recompression in addition to the compositions
of the different products are to be found through simple simulations in PRO/II. The results of
these will then be compared to a conventional LNG process. Estimations of transport vessel
sizes and weights will also be calculated and the different vessel options and building material
discussed.

1.2 Background

A large amount of natural gas around the world is currently not being produced because of its
economic, physical or geographic unsuitable qualities [1]. This gas, so called stranded gas,
has a huge potential of becoming a future energy source once the technical difficulties are
mastered. Known areas today are found all around the world e.g. Alaska, Siberia and Brazil,
with different complications varying heavily. Many possible future discoveries are situated in
arctic areas and under the ice cap of the North Pole. With the receding ice layers experienced
today, options for developing energy resources in these regions must be evaluated and
improved.

Regions far away from gas markets depend today mostly on LNG as the transportation
method due to the alternative of building a gas pipe, would be too costly. Traditional LNG
however, can be impractical in many cases because of the necessary pre-processing of the
natural gas and the consequential cost of the equipment. This is especially the case for
offshore liquefaction plants (FPSO’s), where the space used for processing also has a high
expense and should be limited to an absolute minimum.

To make field developments more economical feasible, different methods for alternative
storage and transportation have been developed. Among these are Compressed Natural Gas
(CNG), Natural Gas Hydrates (NGH), Gas To Liquids (GTL), Liquefied Unprocessed Well
Stream (LUWS) and Pressurized Liquefied Natural Gas (PLNG). There are advantages and
disadvantages for all of them and some are more suited for various areas than others.

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The two alternatives involving gas in a liquid cryogenic phase are LUWS and pressurized
LNG. These can both also be liquefied with a reduced, or no requirement for pre-processing
of the gas stream depending on the feed gas composition. The advantages of this are obvious
resulting in a lower equipment count and space requirements. In addition, the latter will
dramatically reduce the power requirements for liquefaction.

1.3 Limitations
There are a lot of unpredictable variables in all the concepts and the comparison between
them will not be a correct depiction of what the actual outcome might be, if they are allowed
to be realized. However, since the simulations will be done on the same assumptions, the
numerical values of these will be comparable, even though they are simplified and not
optimized. The technical difficulties associated with them are discussed, but since there is
high uncertainness with regard to many aspects of these, there cannot be drawn absolute
conclusions in the comparison.

As there are many different alternatives and aspects to go through, the analyses will have a
more high level character than one on a specific part of a process. A lot of time was used for
finding and getting insight in the different patents and concepts. This limited the time
available for thorough process simulations.

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2 Conventional LNG production

In 1941, the first commercial LNG plant started liquefying gas in Cleveland, Ohio, and in
1959, the first trans-Atlantic LNG shipment proved the possibility of a large scale global trade
of natural gas. Since then, and especially in the last ten years, there has been an extensive
expansion in worldwide production and demand. At the end of 2008, the total produced LNG
reached 377,4 million m3 (172 mill. tons) and the number of transport vessels passed 300 [2].
The future projections predict an annual increase of natural gas demand of 1,6% per year until
2030 [2].

The high level value chain for LNG will consist of the five sections shown in Figure 1.

Figure 1: LNG General Value Chain

The delivered gas composition will need to be adjusted to the market it is delivered to and the
requirements vary around the world. The requirements include:
• Heating value
• Wobbe Index
• Water Dew Point
• Hydrocarbon Dew Point
• Nitrogen Content
• CO2 Content
• H2S Content

The specification in this thesis is set to EASEE’s Harmonized Pipeline Specifications and can
be found in the appendix.

The liquefaction of gas requires a much purer gas than the pipe specifications due to freeze
out at low temperatures. Some of the concentration limits are extremely low and the design of
the plant becomes a great deal more complex than a pipe gas treatment facility. The result of
this is an extensive pre-processing procedure that all LNG plants will have implemented in
some way or the other. The typical gas specifications before liquefaction are presented in
Table 1.

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CO2 H2O HHC Hg H2S

50-100 ppm 0,1-0,5 ppm 1-10 ppm 0,01μg/Nm3 4 ppm

Table 1: LNG Specifications

Transportation of LNG is for the most part done by large well insulated tankers, but it can
also be distributed with tank trucks or by train to smaller customers. Practically all transport
of LNG today is done under atmospheric pressure and at a temperature of about -160°C. The
liquefaction reduces the volume to around 1/600 compared to transportation in a gaseous
state, making worldwide shipment possible at competitive costs.

Figure 2: LNG Tanker [4]

Site specific variations

The technical installations will have to be adjusted depending on site specific variables:

• The available ambient cooling water or air temperature can vary greatly between arctic
conditions and the tropics influencing the work requirements. In warmer climates, the
daily variation may also be big.

• The well stream composition will affect the choice of processes for treatment. This
can be the amount of heavy hydrocarbons, but especially the CO2 and H2S amounts
are important as these can vary widely.

• CO2 recovery and disposal obligations will vary with the geographical placement of
the plant and the political agreements here. This is especially true where a high CO2
content is present in the feed.

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The diagram in Figure 3 shows the cost distribution associated with the LNG value chain
with both a minimum and maximum percentage wherein the cost usually lies. As we can see,
the LNG plant including gas treating, liquefaction, LPG extraction and storage takes up a
large fraction of the total cost. In addition, the LNG shipping costs can vary between 10 and
30% of the total, and may in some cases have a large influence on the total cost [3].

45
40
35
30
25
Max
20
15 Min
10
5
0
Gas Lng plant Shipping Receiving
production terminal

Figure 3: LNG cost distribution

An extended value chain for LNG can be represented by a simple box diagram shown in
Figure 4. This includes both the extensive pre-processing as well as the treatment at the
receiving site.

Figure 4: LNG Value Chain Diagram

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When the gas arrives at the inlet facilities, both the temperature and the pressure have been
reduced from the well heads. This results in condensation of both water and heavy
hydrocarbons (HHC’s) which are removed from the stream and treated separately. In addition,
the hydrate inhibitors injected at the wellhead are regenerated here and sent back to the well.

The next step is removing the acid gases CO2 and H2S. This can be done in numerous
different ways with amine treatment and molecular sieves being the most common. Amines
are usually solved in water which means that the gas is saturated with it after the sour gas
treatment. Therefore, the dehydration of the gas in most cases has to be placed subsequent to
this process.

Water removal is for LNG plants mostly done by molecular sieves which can take the gas to
extreme dryness. All of these steps ensure, in addition to the sales specifications, that there is
no freeze out during the liquefaction.

Also, mercury (Hg) removal is especially needed for LNG production due to the corrosive
effects it has on aluminum. Most LNG heat exchangers are made of aluminum and the
presence of Hg will strongly effect the lifetime of these. The recommended maximum amount
of Hg in the gas is typically set to ten nano-grams per cubic meter [4].

The last step of the pre-processing is the removal of heavy hydrocarbons. This can be done by
a simple refrigeration cycle and a separator or by more complex fractionation processes. The
more thorough removal of the smaller droplets is done by a scrubber.

The gas is then cooled down below the dew point by an appropriate cooling cycle. The
selection of the type of cooling process will be carefully evaluated as this is heavily dependent
on location, size and power supply among others. Some nitrogen rich gas is flashed off at the
end for fuel before the liquid is stored in tanks.

Arriving at the receiving terminal the LNG is pumped to storage tanks. A high pressure pump
increases the pressure of the liquid to the pipeline specifications before it is vaporized by
either air or water heated vaporizers. The last part of the delivery chain consists of
measurements and quality control before it is sold to the customer. A flow diagram of a
typical LNG receiving facility is shown in Figure 5 [5].

Figure 5: LNG Receiving Facility [5]

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3 Survey of Concepts

As there are numerous patents, publications and possible solutions associated with the
different concepts, a brief summary of these will be presented in this chapter and will be more
thoroughly dealt with further on.

Liquefaction with solids formation

Methods have been suggested of liquefying gas directly from the well stream without any, or
with only marginal pre-processing. The liquid produced will contain solids of various
substances e.g. CO2 and C6+, depending on the gas specifications. In the most extreme ideas,
the product will also contain solids of water and even sand. In this way the amount of
equipment required for liquefaction is significantly reduced, resulting in a less complex and
less expensive process. The main obstacle for this concept is the method of handling the
generation of solids in the actual liquefaction. Some suggested solutions have been presented
but the technology verification of the method however, is not yet satisfactory and the
commercial applications are still unclear. In addition, the total profitability when considering
transportation, storing and post-processing adds to the uncertainness.

3.1 LUWS
Liquefied Unprocessed Well Stream, or LUWS for short, is the result of a knowledge building
project (KMB) funded by the Research Council of Norway in cooperation with IFE, NTNU,
SINTEF and Statoil. Guttorm Olav Endrestøl is the project leader of this study which started
in summer 2006 and is due to finish within 2010. A post doc position, employing Andre
Fettouhi at the Technical University of Denmark, is funded by the same financiers and
commenced in 2007 supervised by Kaj Thomsen. Fettouhi has mostly done work on
developing software for freeze out issues in connection with the project. The basis of the
concept-patent filed in 2003 in connection with this project is shown in Figure 6 and
illustrates the basic steps for obtaining the specified liquid natural gas.

With this concept it would be possible to liquefy and transport the well stream gas without
any pre-processing at all. The transported weight and volume might then include sand, water,
HHC’s, CO2 and the light liquid hydrocarbons. The substances that will freeze out are
allowed to do so but in a controlled way and in a predicted location in the process. By not
needing to separate the water, removing the CO2 content and other prerequisites as one need
for conventional LNG, the process would be a great deal less complicated. The reduced
processing equipment might make smaller gas fields possible to develop with special

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emphasis on utilizing FPSO’s. Part of the cooling for liquefaction would come from an
expansion of the well stream by decreasing the pressure down to atmospheric levels. In the
patent, a few possible patented expanders are mentioned that could handle the solids forming
during the expansion. The mentioned are a dynamic expander with patent No. 4,771,612, and
two static ones with patent No. 5,083,429 and 6,372,019 [6]. The latter is a Supersonic
Separator described later. None of the expanders have been proven to handle solids.

Additional cooling will be required even for the highest well pressures as expansion does not
deliver enough cooling to liquefy the whole stream. This can either be achieved by
recompressing the remaining gas phase, cooling and expanding again or by solely cooling
through a heat exchanger and an external cooling loop. The main focus for the KMB has been
on heat exchanger freeze out and a test rig has been built for this purpose. The rig can handle
pressures up to 500 bars and temperatures down to -170°C covering all possible areas of
interest [7]. The key problem to the tests is related to the water content in the feed and has
proved to be a difficult element to handle and predict.

The original thought for cooling is depicted in a ph-diagram in Figure 7. State 6 shows the
wellhead conditions before the stream is expanded through 3 and ending at state 2. Part of the
stream will here be liquefied and the remaining gas cooled to storage state 1.

Figure 6: LUWS Patent diagram [6]

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An alternative route has been proposed aiming at avoiding the phase envelope entirely and
expanding the product in liquid phase thus preventing some of the challenges associated with
the gas phase. Water however, is still a problem here and the formation of gas hydrates is of
great concern.

Figure 7: LUWS Patent PH diagram [6]

LUWS process description

The unprocessed well stream is led through a cooling loop to set the temperature to a few
degrees above the temperatures at which hydrates would start forming. The typical range
would be 10-30°C depending on the pressure of the stream. This cooling can be achieved by
leading the gas through extra coiled pipes on the seabed or a similar arrangement. After
entering the processing plant or FPSO, the stream is expanded and cooled through a multi
stage expander resulting in parts of the gas condensing. This expansion is done in multiple
stages and at each stage liquid is drained off. All the drained liquids from the expansion are
routed to a mixing vessel.

The remaining gas, which will consist of the lighter components and mostly methane, is fed to
a heat exchanger where it is further cooled and liquefied by an external cooling device. All the
liquids are collected in a storage tank before it is shipped ashore. The expansion can power a
generator that can supply the cooling cycle and reduce the amount of external energy required
for liquefaction further.

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3.2 Idaho National Laboratory: "Compact High Efficiency Natural Gas

Liquefier"

Idaho National Laboratory, INL, has developed a method for producing LNG directly from
transmission lines without the need for pre-treating the gas e.g. removing CO2 and lowering
the water dew point. This technology is very compact and in the patent being claimed to be
competitive with some of the major LNG plants around the world. In 2000, INL went into a
Cooperative Research and Development Agreement with Pacific Gas and Electric and
Southern California Gas Company. In this cooperation, the construction of a 38m3 per day
prototype plant took place and the tests of it verified the efficiency and uses. This method was
mainly thought to be of small scale, but could just as easily be applied to bigger plants
according to the patent. In addition, it was meant to be placed at a pressure let-down station
where the high pipeline pressure is decreased to fit the transportation pressures downstream.
Utilizing the power and the cooling on expansion, this method indicates a possibility of
liquefying some of the gas without the need for further removal of contaminants. The well
stream is in this concept mixed with methanol or a similar water absorbing substance to
prevent hydrates from forming during the cool down. CO2 is allowed to freeze out during the
expansion to form a slurry comprising of liquefied gas and solid CO2. The slurry is then
separated by a hydro cyclone to form the LNG product and a thick slush of mostly solid CO2.
Although this patent suggests removing all the solids for reinjection or venting, one could
imagine the possibility of transporting the slurry without any further processing mixed with
the liquefied gases.

On May 5th 2005, Battelle Energy Alliance filed for a patent on the invention and the uses of
it. Patent No. US 7,219,512 B1 [8].

Idaho Process description

Feed gas is firstly filtrated to remove any objects of some size (e.g. sand or other solids),
which can obstruct the flow in the plant. The feed is then split into two separate streams, one
cooling stream and one process stream. The cooling stream is expanded through a turbo
expander giving a cold, low pressure stream. The power generated from the expander is used
to further compress the process stream. The process stream is then cooled down by the
cooling stream in a heat exchanger giving a cold, high pressure stream for further processing.

The process stream is then again split into a second cooling stream, CS2, and the process
stream. The CS2 is expanded and further cools the process stream. The final product stream is
then expanded to form a mixture of liquid, vapor and solids. This mixture can again be
separated and the product will be a liquid-solid mixture comprising of CO2, HHC and LNG.
The expansion valve in this patent is a Joule-Thomson valve. However, the patent does not
suggest or point out any manufacturers of such a valve. Nor does it indicate how the valve
may cope with the formation of solids following the pressure decrease. The process flow
diagram is shown in Figure 8.

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Figure 8: Idaho Process Flow Diagram [8]

3.3 Cool Energy Limited and the MicroCell/CryoCell technology

In January 1999, Professor Robert Amin working at Curtin University, Australia, began
research on a method for removing CO2 from a well stream as a part of the cryogenic process
of liquefying natural gas. This study resulted in a process called MicroCell or Curtin
Contamination Tolerant Process (CCTP). This process would remove CO2 and other freezable
components like H2S by letting them form solids in a specially designed contactor vessel after
being expanded through a JT-valve. His work on the topic in cooperation with Mr. Tony
Kennaird of Core Laboratories made the basis of what became CryoCell in 2005 [9].The
patent for the early work done by professor Amin claimed
the use of separating these contaminants in US patent No.
7,325,415 [10]. This patent describes a possible device for
liquefying natural gas without pre-processing shown in
Figure 9. The basic principal for the device is having a
vessel constructed of a non adhesive material and
expanding the gas stream into this. In addition, a vortex
inside the container is provoked by injecting a sub stream
of LNG for controlling the freeze zone. Successful tests of
the device have been completed in conjunction with the
filed patent.

The technology is now under ownership of Cool Energy

Limited with Shell Technology Ventures Fund 1 as the
major stock holder and is still being developed further
under the name CryoCell [9]. Although the CryoCell Figure 9: MicroCell Patent
technology is primarily designed as a CO2 removal process, it Vessel [10]
would also allow the production of a LNG-slurry for
transportation.
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Liquefied Natural Gas under pressure

LNG under pressure is a new concept for transportation of natural gas and some value chains
for this have been proposed by different parties. The motivation for production of LNG under
pressure is the decrease of power requirements for liquefaction. Depending on the level of
increased pressure, the saturation temperature will be higher than that of gas at atmospheric
conditions. In addition, it has the positive side effect of increasing the solubility of the
contaminants liquid resulting in a lower requirement for pre-processing without running the
risk of freeze out. The main difficulties in connection with this concept are the means of
containment in storage and transportation. Due to the low temperatures, ordinary steel
container walls would need to be thick in addition to running the risk of rupturing due to the
low temperature. A couple of companies have evaluated the possibility of implementing such
gas transportation method resulting in numerous patents. ExxonMobil has especially put
down a substantial effort in the evaluation, but also Aker Solutions and Chevron have their
own processes and patents.

3.4 PLNG - Pressurized Liquefied Natural Gas

Pressurized Liquefied Natural Gas, or PLNG, is ExxonMobil’s name for their new
transportation method for natural gas involving above atmospheric pressures. Their first
patent referring to PLNG was filed in 1998 and since then many solutions to various
difficulties have been suggested and patented.

Unlike conventional LNG production, the whole delivery chain of PLNG is done under
pressure. The pressure can be in the range of 1-7,6 MPa, but ExxonMobil suggests an optimal
selection to be around 1,7 MPa corresponding to a -115°C dew point. The liquefaction can
either be done by a refrigeration system and heat exchangers or by and expansion process.
Because of the increased temperature of the product, the required power for liquefaction is
about halved compared to conventional methods, again depending on the pressure. This
results in a substantial reduction in expensive equipment i.e. heat exchangers, compressors
and turbines, making the production less expensive.

The greatest savings might come from the reduction or possible elimination of CO2 treating
by an amine process. The increased pressure and elevated temperatures increases the
solubility of CO2 to about 2% when stored at 1,7 MPa. With a well stream containing less
than this amount the amine treatment would be superfluous. The reductions in space and heat
requirements due to this can be extensive. The solubility of aromatics and HHC’s are also
increased and the usually required scrub tower might also be unnecessary. The potential
reduction in process equipment is represented in Figure 11, where the yellow areas represent
the potential reductions.

Due to the plants compactness it would be ideal for implementing on an FPSO where space is
costly. It could also make smaller gas fields more attractive to develop.

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The PLNG is proposed transported in a 220x33x49 meter single insulated compartment on a
specially designed ship shown in Figure 10.

Figure 10: PLNG Ship [11]

Figure 11: PLNG Reduced Space Requirements [11]

The high pressures at the cryogenic temperatures require special containers for storage and
transportation. Ordinary cryogenic steels do not have the strength for handling these pressures
without having a large wall thickness, resulting in a massively heavy ship. ExxonMobil has
developed and patented a so called High Strength, Low Temperature steel, or HSLT steel, for
this purpose and claims to be able to produce this at a relatively low cost. A prototype of the
new containers has been built and tests of it have been successful [11].

ExxonMobil presented the technology at the GasTech convention in Bilbao, Spain in 2005
and the delivery chain from this presentation is shown in Figure 12.

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Figure 12: PLNG delivery Chain [11]

The main difference from a conventional LNG chain is the import terminal. This will need to
be specially designed for PLNG which again sends the gas into a pipeline. This can be placed
on a barge or a ship as to make the trading of the gas more flexible and can be positioned near
a LNG terminal for ensuring gas supply between shipments. Another option that has been
looked into is the possibility of storing the gas underground in salt caverns. The PLNG is then
vaporized at the import terminal and injected into the caverns for storage. This would give a
steady gas supply in addition to reducing storage costs.

A large number of patents have been filed by ExxonMobil Upstream Research Company with
M. Minta and R. Bowen as the main contributors during their evaluation of the technology.
Some of the main patents are shown below with connected flow diagrams.

Process for making pressurized liquefied natural gas from pressured natural gas using
expansion cooling:

Figure 13: US Patent No. 6,378,330 B1 Apr. 30, 2002

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Process for liquefying a natural gas stream containing at least one freezable component

Figure 14: US Patent No. 5,956,971 Sept. 28, 1999

Process of manufacturing pressurized liquid natural gas containing heavy hydrocarbons

Figure 15: US Patent No. 6,539,747, B2 Apr. 1, 1999

3.5 HLG - Heavy liquefied gas

In 1992 Ugland Engineering filed patent US 5,199,266 “Unprocessed petroleum gas
transport” which is shown in Figure 16 below. The patent explains a method for producing
what is called heavy liquefied gas, or HLG, with minimal pre-processing and is similar to
ExxonMobil’s PLNG. The well stream entering the plant is here removed of its solids and
liquids before it is dried and cooled. The cooling is done under pressure and produces a liquid
natural gas with a temperature above -120°C. The HLG is then stored at a pressure of between
10-30 bars corresponding to temperatures of -100°C to -120°C. Transportation must be done
in a suitable vessel specially made to withstand the pressures. A concept diagram from the
patent is shown in Figure 16.

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In recent years Aker Kværner, now Aker Solutions, has pursued the method based on Ugland
Engineering’s work and from 2007 - 2009 the Norwegian Science Council has been funding
the project. In addition, Statoil, Vigor and DNV have also participated in the development.

Figure 16: HLG Patent Figure

In connection with the project a case study was done based on producing 4 Mill Sm2 gas per
day and transporting it 1000 nautical miles for further processing. A suggested FPSO is
modeled in Figure 17 containing both liquefaction, storage and offloading system. The case
study concluded that HLG is competitive with pipeline transport above 1000nm if
compression and dehydration facility is available and 500 if not. The topside area was
estimated to be 5000m2 depicted in Figure 18 [12].

Figure 17: HLG FPSO [12]

Figure 18: HLG Topside [12]

A suggested receiving terminal was also modeled shown in Figure 19. The storage capacity of
this is 32000 m2 constructed in 9% nickel steel.

Figure 19: HLG Receiving facility [12]

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3.6 Chevron LHG

Chevron filed for a patent (Application No. 20090095020) in 2008, regarding a method for
producing liquefied gas from the associated gas generated during crude oil production. The
liquefied product is called Liquid Heavy Gas or LHG. Where the practice has been to flare
these gases, this method aims at utilizing them. The main mechanisms are drawn in Figure 20
showing the path from the oil field to the LHG storage tank. The end pressure suggested in
the method is between 15 and 52 bars and the temperature above -48°C. At these conditions
the process can handle CO2 concentrations up to 5mole% with a 2% concentration being
preferred. This again will eliminate the need for CO2 removal allowing for a more economical
production in remote areas. The LHG will according to the invention consist of between 30%
to 70% methane and ethane, or C2÷ components. The high concentration of heavy
hydrocarbons in the gas mixture will result in the condensation pressures and temperatures of
C2÷ to be moderate compared to the other mentioned processes.

The relatively high temperatures make the use of ordinary transportation vessels for Liquid
Petroleum Gases (LPG) possible for the LHG. These tankers have the capability of
transporting liquids with a temperature above -48°C at pressures under 34 bars according to
the patent. Consequentially the cost for developing transportation containers is significantly
reduced. The LHG is shipped to an onshore processing plant for fractionation to pipeline gas
and LPG’s. All of the associated methane and ethane can however not be transformed to
liquids for the LHG process for most fields without lowering the dew point too much. The
surplus light hydrocarbons will be used as fuel for turbines and compressors at the production
site as well as other utility energy demands like a refrigeration cycle. If there still is leftover
gas this is suggested compressed to CNG or similar for storage or transportation. The
proposed gas chilling for the process can be any expansion process (JT process, turbo
expansion) or an external refrigeration process.

Figure 20: LHG Patent Diagram

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4 Untraditional Separator Technologies

The new concepts can radically change the conditions of the end liquid product as well as the
gas purity requirements. This will open for replacing the pre-processing technologies usually
utilized today with new untraditional ones or even develop new custom technologies to be
implemented. Presented in this chapter are some processes thought suitable for separating
water and removing acid gas from the feed stream in the low processed gas value chains.

4.1 3S - Super Sonic Separator Technology

A new expansion process concept has been developed called Super Sonic Separation or SSS.
The expansion in this device is near isentropic, not unlike known turbo-expanders, but
combine these qualities in a way that make separation of the gasses and liquids formed during
expansion it possible. Whereas the usual configuration for expansion is using a turbo-
expander to right above the dew point and then expanding through a JT valve, the SSS
technology can handle the formation of liquids. Since the JT expansion valve is an isenthalpic
process, the product temperature is higher than the minimum attainable for an isentropic
process like the turbo-expander. The main difference for the SSS process is that the expansion
work is not transformed to shaft work but to kinetic energy in the form of a vortex in the tube
as presented in Figure 21. After entering the SSS tube, the gas flow is transformed into a high
vorticity, concentric swirl by static guide vanes. A Laval nozzle will then expand the gas to a
supersonic velocity at low temperatures resulting in water and HHC’s condensing in the
stream. The concentric swirl in the tube makes it easy to remove the liquids as they are
heavier than the gasses and will be forced to the walls.

Figure 21: Twister Separator [13]

To recover the pressure allowing for a higher dry gas value, the streams are slowed down in
diffusers before being discharged. The diffusers can recover around 80% of the free pressure
in the stream [13].

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The SSS technology has been developed by two separate parties with TransLang
Technologies Ltd. on one side and Twister BV on the other. This has resulted in two different
devices; 3S and Twister respectively. Both apparatuses rely on the same principles and are
similar in construction. Twister is the result of a joint venture between Shell Technology
Ventures and other investors with co-funding from the EU and The Netherlands. The
separator has been vigorously tested and has now been successfully commissioned at two gas
plants, one at the offshore B11 plant in Malaysia (2003) and one at the onshore Okoloma
plant in Nigeria in 2009. Both the plants have six Twister tubes in parallel to support various
mass flows engaging the amount of tubes required for a given flow [13].

Future potential for SSS Technology

Twister BV is now looking into the possibilities of extending their application of the device to
new areas of gas processing. Studies are being executed on the possibility of CO2, H2S as well
as mercury removal with the device in addition to installation subsea [9]. Having more tubes
in series opens for extracting different substances in each processing step, avoiding problems
with freeze out. This process line up might also require recompression between the stages. If a
more durable device is manufactured, even solid formation within the gas vortex maybe
tolerated expanding the area of use to concepts like LUWS.

Figure 22: Twister Separator Stages [13]

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4.2 CRYEX - Cryogenic Extraction

CRYEX is Chicago Bridge and Iron Company’s (CB&I) patented process for separation of
CO2. This method is based on letting the CO2 remain in the gas when it is dried and liquefied
for later to be extracted as small solid particles on expansion. The main difference for the
actual condensation part of the plant is that it has to be done under high pressure as opposed
to conventional LNG production. The first commercially utilized CRYEX process was at the
Newport LNG plant in Oregon in 1977 [14]. The technology is well proven with four peak
shaving plants successfully installed in the USA.

The CRYEX Process

The CRYEX process needs a dehydrated feed gas as it cannot handle the formation of gas
hydrates. Therefore, a water removal plant needs to be installed upstream of the CRYEX
process. The condensation is done under pressure to raise the solubility of CO2 in the liquid
and to avoid the deposit of solids in the same way as for HLG/PLNG/LHG. The maximum
concentration depends as mentioned earlier on the pressure levels and corresponding
temperature as well as the composition of other components present. This creates an upper
limit of the possible amount of CO2 present in the feed gas which is approximately 5 mol%
corresponding to a 42 bar pressure. When the gas is in a liquid state with dissolved CO2 it is
expanded trough a JT valve decreasing the pressure to atmospheric levels and thus lowering
the temperature to around -160°C. This pressure let-down is done in a specially designed
CRYEX vessel where the CO2 is allowed to form small solid particles. At the bottom of this
drum the solids deposit and a slurry of CO2 and LNG can be extracted. This slurry will consist
of between 20-28 mol% CO2 and based on plant specifications and energy demand is either
separated or evaporated and used as fuel gas [15].

When depressurizing into the Cryex vessel, the mixture will move down into the phase
envelope evaporating some of the LNG. This gas will have to be recompressed and mixed
with the feed gas before again being condensed. At the top of the CRYEX vessel the product
LNG is drawn off and pumped into a storage container. This LNG will have around 350 ppm
CO2, which is higher than conventional LNG and very small solid particles will float around
in it [15]. This is however not a problem for the downstream shipping and processing. The
schematics for the CRYEX process can be in Figure 23.

Figure 23: CRYEX Flow Diagram [15]

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4.3 CryoCell

CryoCell is a novel CO2 separation process patented by Cool Energy Limited based on the
Micro-Cell technology mentioned earlier. The process has been tested in a demonstration
plant at the AWE Xyris site and the results look promising for reducing costs and complexity
of acid gas treating. Cool Energy is currently cooperating with Great Artesian Limited and
Beach Petroleum Limited for a CryoCell plant in the Cooper Basin which will handle
20MMcsfd of gas [16]. The plant schematics are shown in Figure 24 and show how the gas is
cooled before it is expanded through a JT-valve and into a container. Here CO2 freezes and
falls to the bottom of the column where it is heated and melted to a liquid before extracted.
The liquid CO2 can then easily be pumped up to the CO2 storage pressure and sent for
reinjection.

Due to the simplicity of the process, the capital costs can be reduced as much as 20-40%
depending on the CO2 content compared to conventional amine treatment [17]. The heat
demand associated with the regenerative process in an amine plant is also eliminated saving
huge amounts of thermal energy. Even though it can handle a wide range of CO2 content, the
process requires a very dry feed gas, so dehydration of the gas is an absolute necessity.
Currently, the commercialized plant design can only reduce the CO2 content to pipe
specifications, but future development for LNG pre-treatment is anticipated [17]. The
minimum CO2 content achieved is around 200 ppm which is by far enough for a pressurized
LNG product like PLNG or HLG that can tolerate 1-3 mol percent CO2. The maximum
successfully tested feed CO2 concentration is 60% [9].

Figure 24: CryoCell Flow Diagram [9]

The technology is still under development and its durability and reliability is not yet tested in
a large scale production site. This makes the device less attractive when considering
integration with the low processed gas value chain and especially combined with other
unproven applications.

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5 Evaluation of processes and equipment

The different concepts will have a wide range of variables which will influence the value
chains in positive as well as negative ways. The number of units of equipment will vary
heavily and the complexity and uncertainty elements are also important factors to consider. In
this chapter the value chains for the different concepts will be discussed and elements in them
evaluated.

5.1 Concept groups

The concepts described in the earlier chapters can be categorized into groups. One group will
consist of liquid hydrocarbons transported at elevated pressure and include HLG, PLNG and
LHG. The value chains for these will be similar in structure even though LHG in some cases
may be significantly simplified in the pre-processing step. The second group will be where the
freezable components are allowed to form solids in a controlled manner. Here, this will
include LUWS or any other possible arrangements which include solids discussed previously.
The different concepts are plotted in Figure 25: Concept P-T diagram together with
conventional LNG and a compressed natural gas option. The HLG concept has been divided
into two pressure levels; one at 12 bars and another at 20. This can of course be optimized
when the final gas composition etc is known. Even though we operate at relatively high
pressures for the LHG concept, we can see that it is far from getting close to the CNG
pressure which is around 200 bars.

Figure 25: Concept P-T diagram

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5.2 Value chain for LUWS

The original idea for the LUWS concept was to liquefy and transport all of the substances that
come from the well and in this way eliminate all the pre-processing equipment. The product
would then contain even sand, mud and water. As the well stream can contain a large portion
of these unwanted contaminants and the removal of some of them is fairly straight forward,
separation of at least sand and mud is seen as a necessity [7].

As we see in the box diagram in Figure 26, the operations usually found in the pre-processing
stage for LNG is now shifted further down the chain at the receiving site. This will have a
large impact on the value chain and the considerations when evaluating it. In the diagram, the
red colored boxes are the areas with possibly the most difficulties and uncertainty, while the
green area is the reduced requirements, compared to LNG.

The main area of application for LUWS is not proposed to be big base-load plants, but smaller
remotely situated gas fields where the available infrastructure is scarce. The plant could be
installed on a FPSO or onshore, with a floating alternative being the most practical for
extracting gas from smaller reservoirs.

Figure 26: LUWS Value Chain Diagram

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5.2.1 Dehydration

Removing the water content from the feed stream was not part of the original idea for LUWS
as this would complicate the process. Nevertheless, the problems arising dealing with natural
gas alongside water at low temperatures, might cause bigger problems than the savings when
excluding it. Typical water content for the well stream is around 3% so including the water in
the transported product will directly reduce the useful products accordingly [4]. At least the
condensed water before cooling should be removed leaving only water saturated gas at around
20°C. Removing the water will contribute to a more profitable shipping part in the chain, but
the most important motivation for dehydration is the prevention of gas hydrates formation. In
the presents of water, gasses in the feed will form gas hydrates under certain conditions. At -
161°C formation of such hydrates will take place under any pressure and can constitute large
problems when doing so. Removing the water will also eliminate the most challenging
component in regard of freeze out during the liquefaction.

While for LNG the water content should be reduced to under 150-50 ppm, it may be possible
to leave more water in the gas for a LUWS concept. As we are already prepared for solids
formation in the liquefaction, a small amount of water could be allowed to form hydrates
without causing problems. This opens for larger options when selecting the dehydration
process and a vigorous adsorption system may not be required. The hydrates will form early
during the cooling and will make the freeze out difficult to predict.

In the case of a glycol absorption process like Tri-Ethylene Glycol (TEG), problems will arise
for a process with as little pre-processing as LUWS. Acid gas and condensate is normally
removed before the dehydration, but because we want to leave these in the product they will
be at least partially present through the absorption. Both acid gas and aromatic hydrocarbons
will be absorbed along with the water and would have to be handled when regenerating the
glycol [18]. Since CO2 and HHC’s are a significant part of the feed stream to the dehydration,
a large amount of these substances will have to be separated from the condensed water. In
addition, the liquid hydrocarbons entering the process will cause extensive chemical foaming
in the unit.

5.2.2 Liquefaction

The main obstacle for accomplishing a technically feasible LUWS chain lies in the
liquefaction part of the process and how to predict and control the freeze zone. This has also
been the main area of research [7]. In principle, there are two ways of removing the heat from
the gas; heat exchange or an expansion cycle.

Heat exchange

Cooling the gas down to -160°C will require a system similar to well proven LNG systems,
but the heat exchangers will need to be significantly changed to handle the solid formation.
The build material of the heat exchangers should be changed by one that limits the adhesion
of passing solids as well as frosting of the components on the cold surfaces inside. A non-
sticky surface with a high heat transfer coefficient is needed or the solid formation should take
place away from any surface.

Heat exchangers are built with relatively small tubing sizes to maximize the contact surface
and reducing the size of the unit. The small tubing will cause problems if there are solids

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flowing are over a certain size. Together, these can merge and form a solid blockage in the
heat exchanger which would lead to downtime.

Another possibility is to keep the pressure at a high level throughout the liquefaction
preventing the temperature dropping below the freeze out points. After all the feed is
condensed it can be sub-cooled and expanded through a valve letting solids form in much the
same way as a CRYEX process. This would require the same dehydration as for conventional
LNG.

Expansion process

A way to avoid having freeze-out problems in the heat exchangers is to provide the cooling
through expansion cooling. Utilizing a Joule-Thomson valve or a turbo expander, the
temperature will drop and a part of the gas will liquefy. A near isentropic expander should be
used in preference to a valve, as is gives a bigger temperature drop.

The gas will have a higher inlet pressure than for other processes due to the absence of pre-
processing requirements such as the amine stripper. This gives a lot of free energy for cooling
but is far from being enough to liquefy more than a small fraction of the gas. The remaining
warm flash gas will again need to be cooled by heat exchange or by recompression and
expansion. This gas will now consist of the lighter components, mainly methane and nitrogen,
and far less of the freezable ones as these will form solids at higher temperatures. An
arrangement with a contactor vessel like the MicroCell could control the freeze out zone.

5.2.3 Storage

The produced product is thought to be stored close to atmospheric pressures and therefore the
tanks will have a lot in common with conventional LNG storage tanks. The temperature will
also be in the same region, about -160°C. As LNG tanks have undergone vigorous testing and
studies, the knowledge of them can be transferred to the new LUWS tanks. LUWS will
however, contain a large portion of solids, e.g. 10-20%, and it will have to be taken into
account when designing the vessel.

Solid CO2, or dry ice, will have a density of around 1,562 kg/dm3 [19]. Because natural gas
will have a density similar to liquid methane, which again is 0,422 kg/dm3, the dry ice might
settle at the bottom of the tank quite quickly [19]. If H2S is not removed either, this will form
a solid fraction with a density of about 1,1 kg/dm3. As the H2S fraction is small this will be
negligible compared to the other solids. In addition there will be approximately 6 mole%
HHC’s in the gas mix that will form solids at -160°C resulting in yet more species of solids.
The solids might not cause problems as long as they are mixed with the liquids, forming a
slurry, but as soon as they divide into layers they can make the loading and unloading
complex. If they are left immovable over a period of time the layers made up of small solid
particles may form form larger solid layers, making solids suspension in the liquid less
feasible. If practical, a circulation system that inhibits the solids to cluster could be installed in
the tanks. However, the large differences in density for the liquid and solid fraction, in
addition to having over 10 mole% solids can make this an ineffective and costly measure. If
the phase separation is unwanted is also an issue as solids removal options are evaluated at the
receiving site.

Usually the presence of water and CO2 will pose a threat to corrosion in a steel tank [20] . The
free water will react with the carbon forming carbonic acid, or H2CO3, which again corrodes

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the steel forming corrosion products like FeCO3 among others [20] . In the one option of
LUWS without pre-processing dehydration, there will be both CO2 and water present, but
both the substances will be in solid phase preventing the reactions to take place. However,
there are times in the LUWS process where the temperatures are above the hydrate formation
limits. This can be when loading/unloading the shipping vessel or when the gas is evaporated.

5.2.4 Transportation

In theory, the LUWS product can be shipped in ordinary LNG tanks with only minor design
modifications. There are however major differences that might cause problems in the
utilization. The new tanks would have to withstand solids in contact with the container walls
during transportation. In difference to the storage tanks at the production site, the content of
the containers used under transportation will be moving and exposed to sloshing. The solids in
the containers will then consequentially touch and scrape the walls exposing the wall
materials to a possible erosion problem. Measures that could be taken include reinforcing of
the walls or a more resistant building material.

A LNG shipment that has a duration of 20 days or so will have a substantial amount of boil-
off gas as heat leaks into the containers. This amount is usually around 5% of the cargo [4].
Since it is the liquid components that will vaporize first during transportation and since this
liquid is similar to conventional LNG, the boil-off gas should not be very different from what
the industry is used to today. A standard small re-liquefaction unit could therefore be installed
on a LUWS vessel.

Usually, the boil-off gas will result in ageing of the gas when the more volatile components
vaporize. This will increase the Gross Calorific Value (GCV) during the transportation time
and one must take measures to ensure the requirements at arrival still are satisfied. This will
not be a problem for the LUWS concept since this will need post processing at the receiving
point in any case and adjustments may be done then.

5.2.5 Receiving facilities

If the product is a fine slurry with free floating solids in suspension, the use of ordinary
pumps may be possible. But arriving at the delivery site, the product species may be in
separated layers, thus inhibiting the use of conventional unloading systems. A typical
distribution of components in the shipping tanks could look like the one in
Figure 27, if the layers are allowed to settle.

Figure 27: LUWS Settling

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Cryogenic separation of CO2

As the solids accumulate at the bottom of the storage tank, the liquid light-end hydrocarbons
can be extracted with a cryogenic pump. The pump must tolerate some degree of solid as the
liquid may have debris floating around in it. When there are mostly solids left in the tank a
heat source should be utilized to increase the temperature in the tank thus melting the heavy
hydrocarbons like Figure 28 shows. The maximum temperature should be kept well below the
freezing point of carbon dioxide and in this way avoid this being vaporized. As CO2 has a
normal boiling point below the freezing point, the only CO2 leaving the tank will be in gas
phase and could be sent to the pipeline sales gas for heating value reduction.

Figure 28: Mechanical Solids Separation

Reaching the target temperature, the solids will contain a large concentration of CO2 and
smaller of heavy hydrocarbons from C8+ and aromatics. These will need to be separated by
other means or shipped back to the liquefaction plant for re-gasified re-injection.

5.2.6 Other pre-processing units

Mercury may become a problem for the LUWS concept if not removed. As mentioned,
mercury will react with aluminum in the heat exchangers, forming mercury amalgams. A
possible approach will be to have a different build material for the heat exchangers and avoid
the problem or a simple Hg removal unit will have to be installed. Means would typically
include activated charcoal-sulfur bed systems.

5.2.7 Post processing and CO2 disposal

As there is no treatment of the gas before liquefaction, all the necessary processing will have
to be done at the receiving site. LPG’s and NGL’s should be extracted and the CO2 fraction
lowered to comply with the sales specifications.

The gas at the receiving end of the chain will contain all the carbon dioxide from the well
stream when it is vaporized. The maximum CO2 content in the end product can only be 2,5%
in compliance with the pipeline specifications, so all the excess gas must be disposed of .
Since the receiving terminal usually is far away from any reservoir, the carbon dioxide cannot
be re-injected at site and must therefore be transported for disposal elsewhere. Building a
pipeline exclusively for this purpose would be costly and would be an unrealistic measure for
reducing the CO2 emissions.

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One possible solution would be to transport the CO2 back to the production site with the same
ship it came in on since this is practically empty on the return trip. A proposed value chain for
a CO2 return-shipment for conventional LNG has been proposed by Aspelund and Gundersen
and much of the same principles may be utilized for LUWS [21]. The CO2 cold when heated
may be used for pre-cooling of the well stream. A simplified value chain is shown in Figure
29 where the solids are returned with the shipping vessel for reinjection.

Figure 29: Solids Return Tranport Diagram

As the phases can already easily be separated at the production site mechanically, it might
favorable to remove the CO2 there instead of transporting it first. This will save around 2,5%
of the cargo space and avoid having solid CO2 in the tanks on the return trip. However, this
would need to be evaluated for the site specific cases.

5.2.8 Slurry behavior in Storage

The freeze out components will together with the lighter liquid fractions make up a slurry
with some solid particles in possible suspension. The slurry can either be of a settling or a
non-settling type [22]. A non-settling type will consist of solid particles floating practically
uniformly in the liquid or it could settle so slowly that for transportation purposes could be
regarded as non-settling. This type can have a Newtonian flow behavior and may be pumped
in a laminar fashion. The settling type will consist of larger solid particles at lower

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concentrations and will after a while settle above or below the liquid, depending on the
densities. The solids will in this case not affect the viscosities of the liquids as the layers are
separated. Settling slurries may be pumped, or influenced by a jet stream, to form a turbulent
flow in which the solids may appear non-settling.

How the slurry behaves will largely be dependent on the solid particle size and densities of
both the liquid and solids. Predicting the particle size may be difficult as it is dependent on
numerous variables [23]. For LUWS, this will include how the solids are formed in the
liquefaction cycle by either expansion cooling or heat exchangers. Particles will most likely
be different in the different solutions selected.

Some parameters affecting the solid particle sizes in a storage tank are [23]:

Attrition

Attrition is the mechanism where the solids in moving slurry become smaller either due to
breakage or abrasion. Breakage is when the crystals are broken up into smaller crystals due to
collisions with the walls or other obstacles it may run into. Abrasion is when small fragments
from larger crystals are removed. Breakage will need much higher collision energy than
abrasion.

Agglomeration

When two smaller crystals form a larger one, we have agglomeration. The speed at which this
happens is again dependant on crystal size, slurry distribution and temperature. CO2 in LUWS
may have a lower agglomeration speed due to the low stickiness of the solids at -160°C.

Ostwald ripening

When stored for relatively long periods of time, solids may experience what is known as
Oswald ripening. This is when large solid crystals grow in size taking mass from smaller
crystals. This will happen as the molecules on a surface are energetically less stable than in
the interior [23]. Large particles with a low surface to volume ratio will therefore increase in
size while the smaller ones decrease. This effect might not be of big concern for LUWS as the
liquid can have a short storage time.

Due to the major temperature differences in the liquid and the ambient, around 185°C, there
will be a potentially large amount of heat entering the vessel in the same way as for LNG.
During transportation, some of the light hydrocarbons and nitrogen, will vaporize due to this
heat flux and will manipulate the movement of the solid particles in the tanks. If this effect is
large enough, a circulation system may not be needed and the solids not settle at the bottom of
the tanks.

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5.2.9 Possible LUWS approaches

As the main obstacle for the LUWS concept is the freeze out during liquefaction, a thought
solution for this is proposed. Instead of utilizing a heat exchanger or an expansion process as
the cooling means, a simple bubble column reactor without trays could suffice. The
unprocessed gas stream would be injected into the column where it mixes with LNG at around
-160°C. The gas should be distributed through a fine mesh to spread the gas flow over the
whole column. This would ensure the gas bubbles to become sufficiently small as shown in
Figure 30. The gas will here be cooled down well below the freeze out temperature for the
freezable components which will form solids making a slurry. The column size should be
designed in such a way that the freezable component will have time to be cooled and form
solids. The injected gas stream will have a slightly elevated pressure, e.g. 2 bars, while the
produces LUWS will be at 1 atm.

Figure 30: Possible LUWS Solution

As the solids form, heat from the well stream gas will vaporize part of the LNG in the tank
which will leave the column at the top. As this boil off gas is almost pure methane, this can be
re-liquefied in a conventional LNG process with no modifications of the heat exchangers and
sent back to the column. LUWS will be drawn off for shipment at the bottom of the column
and will contain both a part solids and a larger part LNG. If too much liquid is drawn off,
some of this should be sent back into the column. Many units in parallel would be necessary
for a large production rate and the columns may be impractically high for giving the gas time
to be cooled. In this method, all the cooling is provided at -160°C which means the
temperature lift is unnecessary high which again will lead to a badly performing process,
energy wise. A possibility would be to have a different cooling medium than LNG, e.g. one
with a vaporization temperature close to the freeze out temperatures, and separate this from
the lean gas in a second processing unit. It is also of high importance that the injected gas
does not come into contact with the column walls, as this would lead to solid deposits here.

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A simple PRO/II simulation has been done as shown in Figure 31. This shows that the energy
consumption will be greatly increased compared to the other processes with a specific energy
consumption of around 0,87 kWh/kg or 6,55% of the higher heating value. This is not
acceptable for large optimized liquefaction plants, but for the smallest reservoirs with a
remote location the alternative of a full scale preprocessing may just as well be as costly. This
method would also open for the possibility of leaving the water in the feed leaving only the
liquefaction process and the column arrangement. The large amount of CO2 produced from
the power plant could be re-injected into the well, or separated and injected into the column
for transport in the LUWS. The conditions and assumptions for the simulation are given in
chapter 6.1.

Figure 31: Solution: Flow Diagram of possible LUWS

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5.3 Value chain for HLG/PLNG/LHG

Both HLG, PLNG and to some extent LHG, will be treated under the same chapter as these
are all fairly similar in construction and the boundaries of how they differ can be unclear. The
names used for the concepts in this chapter depend on the patents or origin, but the topics
covered are interchangeable. A general value chain for HLG or similar, will not be entirely
different from a conventional LNG chain and will under most circumstances include all the
same parts.

The main value chain steps will however comprise of different systems and requirements
depending on the well stream specifications and the location of the gas field. A detailed block
diagram of the whole process is illustrated in Figure 32 below where one can follow the
processing steps from the well stream to the delivery to a pipeline with the required
specifications. Again the green colored boxes represent a simplified or improved part while
the red indicates a possible complication or uncertainty. In this section we will go through the
different steps and evaluate solutions for processes and equipment.

Figure 32: HLG Value Chain Diagram

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5.3.1 CO2 removal requirements

A major advantage of producing and shipping LNG at elevated pressure is the increased
solubility of CO2 in the liquid product which reduces the concentration limit for solid
formation risk. The concentration limit the HLG will be able to solve will strongly be affected
by the pressure and the resulting temperature. This will increase with rising pressure and
especially when increasing the temperature to -130°C or about 7 bars from 1 bar. At the
typical proposed pressure for HLG, a CO2 concentration of around 2% can be tolerated
without formation of solids [11]. In the circumstance of processing a CO2-lean gas reservoir
below this limit, the acid gas treatment requirements may altogether be eliminated, resulting
in vast reduction in heat requirements for the liquefaction plant.

For many gas fields in operation, the CO2 content is relatively low e.g. < 2%, but with
depleting resources the accepted content for initiating development is bound to increase.
Because of this, a HLG liquefaction plant will in most cases have to have some form of CO2
removal process to reduce the concentration below the preset limit.

In any case, the extent of the removal will be less profound and this opens for installing other
removal processes than the ones usually employed in existing plants. This could be any
process able of reducing the concentration to the specific level which most of the
commercially available processes are.

Selecting the correct gas sweetening means should be carefully considered and some of the
main variables are:

• Feed gas concentration of impurities

• Hydrocarbon composition
• Operating conditions
• Capital and operating costs
• Sweet gas CO2 concentration requirements

For HLG, these conditions may be very different from conventional LNG resulting in other
terms for selection. For instance, the HHC part of the gas will be much higher which will have
an effect on some of the absorption processes especially. If the used absorption solvent has a
strong affinity to HHC’s the loss of these will constitute a great waste in the produced value
of the feed and will have to be recovered resulting in a higher energy need and space
requirement.

Usually, the CO2-removal process is based on a water soluble absorption process making the
gas saturated with water. This results in the dehydration necessarily being placed subsequent
to this. Because of the decreased requirements for CO2-removal and the options in selecting
removing processes, the dehydration may in some cases be placed prior to this for a HLG
plant extending the options for integration.

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Membrane CO2 removal

Another possibility would be to install a membrane CO2 removal unit instead of a

regenerative process. A membrane removal unit works by having a semi-permeable and thin
barrier that selectively lets some compounds through while others not [24]. In variation to a
solvent removal process, membranes have a different effect on their size with respect to the
thoroughness of the removal. While the size of the first is directly linked to the amount of
CO2 removed from the gas, the latter will be dependent on the percentage of the CO2
removed. A reduction from 10% - 5% will therefore require a just as large system as a
reduction from 20% - 10% [24]. With a starting value of 5% and a HLG specification of 2%
the total removed percentage will therefore be 60%. The membrane system will eliminate the
thermal power needs as it only needs a pressure gradient to operate.

A membrane system will also need some pre-treatment due to some gas specification
restrictions. The membrane cannot handle liquids as these will lead to swelling in addition to
HHC’s over C15 can coat the membrane surface. These will have to be removed prior to the
treatment. As the membrane decreases the pressure of the gas, it will cool down in the same
way as a traditional valve due to the Joule-Thomson effect. This will cause some of the
content to condensate so the pre-treatment stage will have to include a dew point control
system. This will set the dew point well below the lowest temperature through the membrane.
An example of a membrane system is shown in Figure 33.

Figure 33: Membrane Separator [46].

The advantages of membrane systems are

• Lower capital costs

• Lower space requirements

• Lower operating costs and energy demand

• Low complexity

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5.3.2 Dehydration

Even though the increased temperature will allow slightly higher water content before
liquefaction, the requirements will still be restricted by the limit where gas hydrates will form.
A molecular sieve adsorption process is therefore also required for HLG pre-processing in the
same way as for conventional LNG. The water content limit is discussed later together with
the process simulations.

5.3.3 Reduced HHC scrubber requirements

Independent of the gas field, production of LNG will always require removal of HHC’s before
liquefaction due to higher freezing points of these than the product storage temperature.
Higher temperatures will allow a greater amount of aromatic and heavy hydrocarbons to
maintain in the product without freezing. Again, depending on the well stream composition,
the fractionation system to separate these may not be needed for some cases of HLG and
especially for the high pressure LHG. Where some smaller amount of heavy hydrocarbons
needs to be removed, a supersonic separator technology like the Twister could be utilized to
set the preferred HC dew point.

5.3.4 Power requirements

A higher product temperature will result in lower power consumption for liquefaction.
Because removing heat at cryogenic temperatures require an increasingly large amount of
power per removed kilowatt, the most expensive cooling can be avoided by setting the
condensation temperature at a higher level. The higher the pressure is set, the lower the power
consumption will be resulting in a smaller amount of gas used for power production and a
larger amount of produced HLG delivered to the customer. The largest savings will be in the
lowest temperature areas so an increase from -160°C to -120°C will constitute a substantial
amount of the total power requirements. The exact work requirements are discussed in the
simulation chapter. The reduced work is the foremost reason for considering the HLG/PLNG
solution and has the potential of making the gas delivery more competitive for where a full
scale LNG plant is unprofitable.

Usually the heat recovered from the power producing gas turbines is not lost but is utilized in
the regenerative processes of water and CO2 removal. For HLG these heat requirements can
be reduced quite significantly with possibly eliminating the acid gas treatment process. The
heat produced would also be reduced due to the lower compressor work in the liquefaction
stage and so less heat would be wasted.

In the case where the CO2-content in the field gas is below the permitted level the largest
thermal power consumer is lost. One can in this case evaluate if running the liquefaction
compressors on electrical power from the grid instead of gas turbines is suitable. This might
help reduce the total CO2 emissions which in turn can save costs for the operators. Because
one in this case will have no recovered heat source, you will be forced to produce the needed

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heat supply with a boiler or similar to feed the regenerator in the molecular sieve process
during dehydration.

5.3.5 Loading systems

As the product liquid is pressurized, the loading systems from the production site to the
shipping tanks have to be specially designed. A system for loading and unloading PLNG has
been proposed and patented by ExxonMobil in US Patent No. 6,237,347 B1of May 29, 2001.
“Method for loading pressurized liquefied natural gas into containers.”

Figure 34: PLNG Unloading

The system consists of multiple storage compartments where the liquid is stored as shown in
figure 34. When unloading the tanks, a methane rich gas is compressed and injected into the
compartments, pressuring out the liquid. When loading, the gas is displaced by the entering
liquid and sent to the liquefaction facilities. The empty return shipment will contain some
compressed gas reducing the total delivered amount.

5.3.6 Storage tanks and Transportation

Conventional LNG ships can of course not be utilized in HLG/PLNG transportation so design
and construction of a high pressure containment system will also be required for this concept.
Because of the low temperatures, special concern should be taken when selecting the material
for the vessels due to brittleness at low temperatures. Using ordinary cryogenic carbon steels
will be very costly and will make the total weight of the ship unacceptably high as the
thickness of the tank walls need to be increased. Development of new steel or other material
types would be necessary. In US Patent no. 6,085,528, such a steel is described, claiming to
withstand temperatures of between -62°C and -123°C at pressures between 10,35 bar and

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75,90 bar [25]. This HSLT steel has a Nickel content of around 9 wt%, giving it properties to
withstand the harsh conditions. The amount of Nickel would depend on the operating
conditions and should be kept at a minimum for limiting the expenses associated with the
costly material. A 17m tall prototype of the container constructed with this new steel has been
built for ExxonMobil by Kawasaki Heavy Industries and is shown in Figure 35.

Figure 35: PLNG Vessel Prototype [11]

Alternatively, a glass fiber composite reinforced vessel might contribute to limit the weight
and lower the production costs. Several designs for such a vessel are presented in US patent
no. 7,147,124 [26]. In this patent an inner self supporting liner will contain the cryogenic
liquid and would be made of a material able to handle the low temperatures. This could be
any suitable material, but aluminum or a cryogenic steel type is proposed used [26]. This liner
would be impermeable, preventing the liquid in coming in contact with other parts of the
container. Around the liner a load bearing vessel made of a composite material is laid capable
of withstanding the high pressure. In this way the inner layer would not need to support the
high stress. This vessel is proposed made of carbon, glass, Kevlar or other suitable materials.
The advantages of this proposed containment vessels are many over the HSLT steel
mentioned above. In addition to being less heavy, the production process for the vessel is
simpler and the insulation requirements are reduced. The form of the vessel can either be a
large semi-spherical container or many smaller cylindrical. Both schematics of the proposed
design forms in the patent are shown in Figure 36 and Figure 37.

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Figure 36: Spherical Composite

Figure 37: Cylindrial Composite

The cost of shipment for HLG will undoubtedly be much higher than transport at atmospheric
pressures in the development stages and will make out a large portion of the increased
expenses. The key to commercialization of HLG lies in making of an economically
reasonable system which can be mass produced reducing the cost for each unit.

5.3.7 Receiving facilities

The consumers of gas rely on a steady supply and not only when the shipments of liquid gas
arrive. Due to this, the liquid arriving ashore on delivery will have to be unloaded to storage
tanks as a buffer, waiting to be re-gasified. For LNG, this is normally not a problem since the
pressure at which it is stored is at approximately atmospheric. For these new concepts
however, a specially designed receiving facility will have to be constructed in order to deal
with the increased pressure. The complexity of these receiving facilities will be higher than
the ones used for LNG today, and will also amount to a larger portion of the total investment
costs in the value chain.

Today there are well established receiving facilities for LNG, making shipments and trading
routes flexible and easily rearranged. Getting the same flexibility for HLG would be difficult
without building high pressure facilities at all the possibly desired destinations. This would
also be costly as the worlds LNG marked is expanding rapidly and new receiving facilities
also will need to be able to handle LNG.

Another possibility would be to have additional transportation ships in the delivery chain,
unloading the HLG directly to the re-gasification plant. This will avoid the construction of
new receiving facilities and making the delivery chain more dynamic and flexible. Some of
the cold energy recovered when heating and expanding the HLG may even be used to produce
some amount of LNG at 1 bar for storage in the existing LNG storage tanks. This would
however require further processing and removal of CO2 and HHC’s as these would freeze out

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at such low temperatures. This could be done in a cryogenic separation process like the
CRYEX process where the freezable components are allowed to form solids after being
expanded in a liquid state through a valve. In the same way, the existing LNG receiving
facilities could be retrofitted with a HLG-terminal and the pressure tanks for storage would
not be needed. The flash gas after the expansion could be fed to the sales-gas pipeline directly
or be liquefied or compressed for storage.

Such a system is described in US Patent No. 6,560,988 B2 patented in May 13, 2003, and a
flow diagram of the invention is shown in Figure 38.

Figure 38: Unloading pressurized Liquefied Gas into LNG storage facilities

As seen in the diagram, the pressurized liquid is led through a series of turbo expanders
decreasing the pressure in stages. After each expansion, some vapor will be produced when
moving down into the liquid-vapor phase envelope. This gas is flashed off for recompression
and distribution in pipelines. The turbo expanders will create some mechanical work which
may be utilized in the recompression of the vapor. After the last expansion step the
temperature will be the same as for conventional LNG but at atmospheric pressures, making
storage in LNG tanks possible. The produced amount of LNG compared to the shipping load
is around 51% giving the possibility of storing half of the shipment onshore for a longer
period of time [27]. This will liberate the shipping vessels from expensive port time reducing
the required number of vessels. The patent however, does not mention the complications of
changing solubility of CO2 and HHC’s in the liquid at the different pressures. These
components will run the risk of freeze out when the temperature and pressure is decreased.

5.3.8 Post processing

Depending on the selected process and the resulting pre-processing at the liquefaction site, the
liquid product may need conditioning before the sale specifications are satisfied.

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Due to the wide range of accepted heating values, staying within these limits is not the
greatest concern. However, removal of heavy hydrocarbons will be necessary for reducing the
HC dew point to -2°C or lower as required by EASEE [28].
The maximum CO2 content in the sales gas is 2,5% and acid gas removal may be needed. The
need for reduction of the CO2-content at the receiving site is not necessary for the cases of
HLG where the gas is sweetened below the 2,5% limit at the liquefaction site. For the lowest
HLG pressures, this limit will need to be subceded to prevent freeze out, avoiding this
problem altogether. When operating at temperatures allowing more than the pipeline
limitations, it could be advantageous to remove more CO2 than needed to avoid the need for
post removal and transport. This would limit the gas sweetening units in the value chain to
only one place. Eliminating the need for a heat source at the receiving site is advantageous as
there is not as much waste heat from power production here compared to the liquefaction
plant. Some utility heat may also be required to operate the regenerative processes if installed.

5.3.9 End User Alternatives

The natural gas produced with the lowest level of pre-processing will need a large unit for
post-processing which will question the economical feasibility. This will only be the case if
the gas is to be delivered at pipe gas specifications, but some alternative end user may be
more suitable. For instance, having a large power plant running on the delivered gas from a
LUWS or a LHG concept, may altogether eliminate the need for post processing and the
resulting value chain is considerably simplified. Other end users may be large petrochemical
industries where methanol, ammonium, hydrogen etc is produced. The amount of delivered
gas from a liquefaction plant may however exceed the needed gas amount for these alternative
end users substantially.

The largest power production today from a single natural gas power station is the Kawagoe
power station in Japan with a total of 4802 MW production [29]. A reasonably sized well
stream for LNG production is around 2,1 million tons per year, or around 60 kg/s. With a
heating value of roughly 50 MJ/kg the total produced power would be 1500 MW as Table 2
shows.

Heating Turbine Combined Mass Flow Mass Flow Power

Value Efficiency cycle MM Tons/ Produced
MJ/kg Efficiency year Kg/s MW

Power
Plant 50 35% 50% 2,1 60 1500

Table 2: Power production end user

The plant efficiency used is of combined cycle and is well below the maximum achieved for a
similar plant [30].

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As we can see from the table, the resulting electrical power is in the obtainable region for a
natural gas power plant. Nevertheless, as the gas is delivered in a liquid state, and for some
concepts stored under pressure, the fuel storage and supply becomes more complex than
coming from a pipeline. A conversion from pressurized to non-pressurized liquid would be
needed or pressure containers onshore would have to be built. Alternatively, the shipping
vessel could deliver gas directly to the plant while in dock as discussed earlier.

NGL & LPG recovery

Extracting heavier hydrocarbons at the receiving site is one of the means to adjust the gas
properties. In addition, the heavier components such as propane, has a higher market price
than LNG and should if possible be sold separately. Other means of adjusting the properties
are mixing with other gas streams or injecting an inert gas, typically nitrogen. As nitrogen
injection is expensive, HHC removal is preferred when mixing streams are unavailable [5].
For the new concepts, a larger amount of HHC’s will need to be extracted. For LHG, which
has practically all its LPG/NGL solved, this amount will make out around 20-25 percent of
the total liquid delivered as the calculations in chapter 8 shows. This would require a much
larger infrastructure for handling and transporting the different products.

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6 Process simulations
For evaluating the energy requirements and the degree of influence by the variables, some
non-extensive energy and material balances have been established for the new liquefaction
processes and receiving sites. The process layouts can be seen in the appendix.

The acid gas removal, dehydration and other pre-processing stages have not been simulated in
this thesis due to their complexity and the widespread study of these in previous papers.
Instead, some estimates have been done to get comparable data for energy needs and gas
properties. The calculations are done for five different types of transportation liquids. These
are all liquids at the dew point temperature with varying transportation pressures:

• Conventional LNG
• LUWS concept with solids

• HLG concept at 12 bars pressure

• HLG concept at 20 bars pressure

• LHG concept at 50 bars pressure

The LHG concept was originally thought to produce a liquid with a much higher HHC
fraction than in the selected well stream gas. As we have set a specific gas composition for all
cases, this is will be lower, resulting in a lower dew point temperature than proposed in the
LHG patent.

6.1 Assumptions
Cooling requirements

The cooling requirement for LNG production can either come from an expansion process or
through a refrigeration process with heat exchangers removing the heat from the feed gas.
In the simulations, the cooling loops are not simulated fully but instead approximated with a
set exergy efficiency. The duty of the heat exchanger cooling is taken directly as the enthalpy
difference at the inlet and outlets of the heat exchanger.

Minimum theoretical work for liquefaction

The ideal minimum work can be expressed as an infinite number of Carnot cycles each
removing an indefinitely small amount of heat from each temperature level. Wmin can
therefore be expressed in the equation below. This correlation can however be very difficult to
find for a mixed gas composition.

 T0 
=
Wmin ∫ δ q 1 − T 

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For a stream at a given starting condition, the theoretical amount of energy needed for
liquefaction can be found by evaluating the thermo-mechanical exergy changes before and
after the cooling. This is given by exergy change equation below and is only dependent on the
starting and ending conditions as well as the temperature T0, where the heat is delivered. In
the simulations this equation is used with T0 set as sea water cooling at 15°C for all concepts.

∆e= (h2 − h1 ) − T0 ( s2 − s1 )

Because below around -130°C thermal cooling is more valuable than mechanical energy, one
should expect a substantial reduction in the minimum work for a HLG process with the end
product temperature above this level.

Approximation of actual work requirements

Obtaining reasonable results for the liquefaction processes, based on establishing full and
energy and material balances will require a lot of work. This is especially true if one wants to
optimize the processes to obtain energy requirements in the range of operating LNG plants.
As the objective of this thesis is not to look into different cooling processes, an approximation
between the required cooling and the work for heat removal will be used.

The specific power consumption of the Snøhvit LNG plant is 0,23 kWh/kg giving it an exergy
efficiency slightly under 50% [31]. The exergy efficiency of 50% will be used for all
processes in the simple energy and material balances. It is important to remember that this
efficiency will decrease for the simpler processes e.g. the PRICO process used for smaller
reservoirs or on FPSO’s in addition to not being necessarily constant for all temperature
levels.

Liquefaction pressure

The pressure where the liquefaction is done will greatly affect the needed power for the
process. This can be shown in Appendix 7, where the minimum work for different pressures is
shown. The higher the liquefaction pressure the lower the energy requirement. This is
especially true for a pressure right above 1 bar and less so when having high enough pressure
to stay clear of the gas-liquid phase envelope, around 60 bars. All liquefaction is done at this
pressure level for all the concepts before being depressurized to the storage pressure.
Conserving the feed pressure throughout the pre-processing stage would be a big advantage
but is not always easily done as many acid gas removal processes require a relatively low
pressure, e.g. in amine strippers.

End flash gas fraction

The feed stream will contain some nitrogen that will have a lower saturation temperature than
the other components. Having the whole fraction of nitrogen remaining in the product will not
only demand a lower end temperature, but also decrease the heating value and increase the
transportation volumes. Some gas will therefore be flashed off after expansion. This nitrogen
rich methane gas could be used as fuel gas or a nitrogen removal system could be installed
sending the methane fraction back for liquefaction. When considering all the different power

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consumers in the process a typical LNG plant will need between 5 and 10 percent of the feed
gas for power production [4].

For the concept examples, a minimal amount of flash gas will be produced. The flash gas will
be used for power generation in a gas turbine with a presumed constant energy efficiency of
35 percent of the gross heating value. Due to solubility differences of nitrogen under different
pressures in addition to the flash gas amount, it is not equal in all the cases but will consist of
around 75% methane and 25% nitrogen. For HLG and LHG more nitrogen could have been
solved in the product stream without flashing off gas. In these cases, the necessary fuel could
have been taken from the well stream or from the gas before liquefaction.

In all the cases a JT-valve is utilized for pressure reduction. An expander would in optimized
cycles be used to right above the bubble point as these give a higher temperature fall and can
produce some work. These are for simplicity however, left out in the simulations.

Gas Composition

Real well stream gas compositions will consist of a huge number of different components but
for simplicity an approximation is given at which the calculations have been done and is
shown in Appendix 3: Gas composition. The results can therefore not be transferred directly
to other compositions without adjustments. This is especially true for the LHG concept which
heavily depends on the heavier hydrocarbon content for lowering its dew point. The CO2
fraction can also exceed the 5% assumed in this thesis which again would affect the pre-
processing requirements.

Equation of state
For all the calculations, a SRK Equation of State has been used. The simulations have been
tested with other equations to verify the results are within a reasonable range.

6.2 Freeze out Temperatures

Carbon Dioxide
As the temperature is increased, the liquid can contain a higher percentage of carbon dioxide.
Finding the exact limit temperature for which the freeze out will occur can be complicated
when there are other components present in the mixture.
For finding the maximum allowed amount of CO2 in the end product, a binary Methane-CO2
system can be used as a basis. This is shown in the Solid-Liquid-Vapor diagram, (SLV) in
Figure 39: SLV diagram for Methane-CO2 [32].This will not however, describe the accurate
limit value at where CO2 will form solids due to the influence of the other components. The
presence of nitrogen will slightly increase the CO2 freezing temperature while light-end
hydrocarbons like ethane and propane will lower the CO2 freezing temperature [32].

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Figure 39: SLV diagram for Methane-CO2 [32].

The Solid-Liquid line in the diagram is, as we can see in Figure 39, not very dependent on the
liquid pressure with the freezing point only slightly decreasing with increased pressure. Due
to this, a good approximation of the allowable CO2 mole-percent can be found with a
solubility curve for a CO2-CH4 system shown in Figure 40. For typical pressures of HLG the
CO2 mole% will be in the range of 1-2% while a Chevron LHG liquid might be able to
contain a percentage as high as 5-6%. The phase diagram Appendix 4 indicates that at 50 bars
the CO2 freeze out temperature is over -60°C and any CO2 over the solubility limit will then
form solids. A gas-solid transition may still occur.

Figure 40: CO2 solubility in CH4 [32]

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Heavy Hydrocarbons

The heavier hydrocarbons will also form solids for most of the temperatures in the simulation
cases. The feed gas specifications in the simulations contain components from Cyclo-Hexane,
with a normal freezing point of over 6°C, to hexane with -95,3°C which will all form solids
under atmospheric pressures. The mole fraction of these will have to be reduced in a
hydrocarbon scrubber to satisfy the freeze out concentration limits if over the solubility.

In order to find the maximum allowable mole fractions for the various temperature and
pressure states, a non-equilibrium simulation program called NeqSim has been used [33]. This
predicts the freeze out temperatures for the mixture based on SRK EOS for the liquid phase,
and a solid fugacity model for the solid phase. See the appendix for equations and further
explanation. The solids are assumed formed only in sub-cooled liquid so a further evaluation
of potential frosting in gas phase should be done for a more extensive prediction.

The program has been used to find the boundary cases for three different systems of LNG
under pressure with resulting temperatures. These are HLG at 12 bars, HLG at 20 bars and a
LHG case at 50 bars. The results are shown in Appendix 10. The LHG case does not form
solids even without any pre-processing of the specified well stream composition at the set
conditions.

Post processing and recompression

All the compressors in the calculations are assumed to have a polytropic efficiency of 80%
while the efficiency of the pumps is set to 80%. Inter-cooling of the compressors is not taken
into account, but should be integrated with the vaporization heat exchanger. Hydrocarbon dew
point control is done by setting the cricondentherm to -2°C by flashing the gas during
vaporization.

6.3 An approximation of the Amine treatment energy needed

There is a large heating demand associated with an amine process for removing acid gas. Due
to the corrosive effects of high concentration of amines, the maximum allowed weight
fraction (WF) is between 0,20-0,55 depending on the type used. For this simple
approximation Mono-ethanolamine, or MEA, is used as this is cheaper than MDEA and less
corrosive than DEA [18]. MEA will typically have a WF of around 20% and an acid gas
loading of 0,33 mol acid gas/mol MEA [18]. The approximate heat duty for the amine re-
boiler is set to 300 kJ/L amine and the amount of amines can roughly be found by the
equation:

QMEA = MEA kg / s
M MEA CO2 = mol CO2 / s
CO2  M MEA = g / mol
M CO2
QMEA = M CO2 = g / mol
( AG WF )
AG = Acid gas loading
WF = Weight fraction

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Assuming a linear energy requirement independent of the acid gas concentration of the feed
gas, the heat requirement can be calculated to 6200 kW per kg CO2 removed. In comparison,
although using MDEA, Melkøya LNG at 4,3 Mtpa needs 69 MW of hot oil at 190°C equal to
around 5400 kW/kg removed CO2 [34].

Because the heat requirements for a certain amount of CO2 rich amine with a particular load is
given, the heat needed for regeneration is directly linked to the removed CO2. This means that
a system decreasing the acid gas content from 6 to 3% will require approximately the same
amount of energy as a system from 3 – 0%.

The amine-stripper condenser will require cooling but this is usually obtained through air or
seawater heat exchange as the required temperature is only around 55-60°C [18]. The energy
consumption for this then only comes from the cooling water pump.

6.4 Results and discussion

6.4.1 Concept results

Even though the results obtained through the simulations and calculations are simplified, they
will give us some comparable data for evaluating them based on the same assumptions as will
be presented in this chapter.

The theoretical work for a liquefaction process based on the given gas specifications given are
shown in Figure 41 and is calculated based on exergy change. The graph shows rapidly
decreasing energy consumption for the low range pressure increase up to 6 bars. An increase
between 1 and 6 bars gives a power reduction of over 30%. This is as expected as the most
expensive cooling is in the lowest temperature regions and the dew point temperature is a
function of pressure. The work requirement is then decreasing more linearly down to the
highest regions of the HLG pressure range below 0,06 kWh/kg.

Figure 41: Minimum Theoretical Work

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Process Energy Energy % of HC dew WI Temperature Pressure

Consumption % of HHV point [kWh/m3] [°C] [Bar]
[kWh/kg] LNG [°C]
LNG 0,2300 100 1,536 -2 15,26 -162,42 1,1
LUWS 0,1803 78,39 1,371 130 15,37 -161,66 1,1
HLG 12 0,1309 56,91 0,920 20 14,77 -121,17 12
HLG 20 0,1003 43,61 0,729 45 14,63 -107,27 20
LHG 0,0570 24,78 0,438 130 15,13 -77,97 50
Table 3: Simulation results I

The results of energy requirements and some liquid properties for the liquefaction processes
based on the previously mentioned assumptions are shown in Table 3 and Table 4.

As expected, the energy consumption decreases with increased pressure with LNG consuming
0,23 kWh/kg of produced liquid and HLG12 and HLG20 0,1309 and 0,1003 respectively. The
LNG energy consumption is identical for Melkøya LNG due to the exergy efficiency taken
from this plant, but this also verifies the models and assumptions used.

The LHG concept has very low energy consumption with only 0,057 kWh/kg. LNG needs
over 404 percent more than this which gives the LHG concept a large advantage. The low
consumption is due to two factors:

• Higher dew point temperature because of the pressure

• Higher content of components with a high dew point temperature

As all the CO2 and HHC’s liquefy or solidify at high temperatures, the concepts containing
some or all these components in the liquid will have abnormally low power consumption.
This will be especially true for the LHG and LUWS concepts where none of these
components are extracted. The percentage of the heating value used for liquefaction will also
be influenced by this as LPG is drawn off for individual sale in the other three concepts. This
is the reason why the percentage of the heating value used for liquefaction of LNG, is only
350% higher than that of LHG. The LUWS concept has a specific work requirement which is
lower than that of LNG. This is misleading as liquids are drawn off from conventional LNG
before cooling, resulting in a smaller amount of produced cryogenic liquid. In this case, a
more correct comparison can be made in the calculated example presented in chapter 6.4.2.

The LPG/NGL fraction drawn off at the liquefaction plant will vary with the largest possible
amounts solved in the liquid product. The higher the solubility is, the lower the LPG fraction
becomes. However, this amount could be increased if this is practical to the downstream
processing facility’s availability and costs. The amount is in these examples set to an
approximate minimum, assuming the removal is more costly at the liquefaction site.

The HC dew point for LNG will not be entirely correct as the maximum HHC amount in the
gas should be 1-10 ppm to avoid freeze out. As we do not simulate the scrubber in the pre-
processing, this amount is left in the liquid but would in a real case increase the LPG fraction
and decrease the amount of delivered pipe gas.

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Process HHV Density Density LPG I End Amine

MJ/kg Kg/m3 Percent fraction of flash regeneration
of LNG well stream frac.* kWh/kg LNG
LNG 53,91 461,6 100 0,260 0,0591 795
LUWS 47,36 576,8 125 0 0,0604 0
HLG 12 51,22 418,6 90,7 0,238 0,0316 563
HLG 20 49,51 406,9 88,2 0,193 0,0248 356
LHG 46,81 417,0 90,3 0 0,0163 0
*Fraction of mass flow through the heat exchangers
Table 4: Simulation Results II

The liquid densities will also be influenced by the different factors giving a span of 170 kg/m3
between 576,8 for LUWS and 406,9 for HLG20. This difference will have a large impact on
the size or the number of transportation vessels needed for the same volume of transported
gas. The transport volume for LHG will have to be 41,7% larger than for LUWS while the
two HLG concept will need 10,3% and 13,7% larger volume than LNG. An overview of the
needed transport volumes is shown in Figure 42 which indicates that all the pressurized
concepts have around the same need for extra shipping volumes per weight.

120

110
Volumes [% of LNG]

100

90

80

70

60
LNG LUWS HLG 12 HLG 20 LHG

Concept type

Figure 42: Density Chart

The total mass of transported product will of course be the same for all concepts except for
the removed CO2 and the flash gas used for fuel. LPG produced on the liquefaction site will
require a LPG transportation vessel from here, while the concepts where this is included in the
liquefaction stream, does not. Whether it is best suited to remove the high end liquids at the
producing or receiving site will need to be evaluated specifically for each development based
on cost, availability and sales markets.

The last column in Table 4: Simulation Results II shows the regeneration heat for the amines
in the CO2 removal process. This is as expected highest for LNG where all the acid gases are
removed and nonexistent for LHG and LUWS. This only represents the regeneration heat at
the liquefaction site and it is important to take into account the removal at the receiving site as
well when considering the whole value chain. This is better represented in the example in
chapter 6.4.2.

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The liquid product compositions for the concepts are shown in Table 5: Liquids Composition.

Composition LNG LUWS HLG HLG LHG

[mole %] 12 bars/-121°C 20bars/-107°C 50 bars/-78°C

CO2 0,0000000* 5,3191416 1,4285300 2,695933 5,049991

Methane 90,6853214 80,2175696 88,1478902 85,80425 79,82015
Ethane 5,4373723 5,3211878 5,2649753 5,275842 5,063532
Propane 1,7824487 2,1286006 1,7957381 1,947102 2,030505
I-Butane 0,6690971 1,0643007 0,7155577 0,866179 1,015923
I-Pentane 0,3367910 1,0643007 0,4211510 0,644057 1,016356
Hexane 0,0886523 0,5321504 0,1658628 0,351701 1,016469
Heptane 0,0110768 0,5321504 0,0359488 0,093204 0,508251
Octane 0,0020720 0,5321504 0,0146955 0,044734 0,508257
Nonane 0,0003314 0,5321504 0,0059663 0,020692 0,508259
Decane 0,0000446 0,5321504 0,0022923 0,008946 0,50826
Benzene 0,0348156 0,5321504 0,0684914 0,150482 0,508235
CH 0,0308994 0,6276966 0,0645207 0,143539 0,508235
N2 0,9210798 1,0643007 1,8683683 1,95332 1,937576
*Value based on total CO2-removal.
Table 5: Liquids Composition

Again, we can see that the C5+ components are present in the LNG composition. The total
amount of these make out 0,5 mole% when in reality with a scrubber installed in the pre-
processing, this would be around 0,01 mole% (100ppm). As the difference is quite small and
specially for the heaviest compounds, we choose to ignore the effects this has on the gas.

The CO2 content for LNG should be 50-100ppm and not non-existent as here, but is not
present in the feed gas for simplifications. All the other concepts will need acid gas treatment
except for HLG at 12 bars which has 1,43 mole% CO2 which is well below the requirements.
As the HLG20 has only slightly more CO2 than the pipe gas specifications, it would be
reasonable to remove some more of it at the liquefaction plant to avoid having two separate
removal processes at both the liquefaction and vaporization sites.

The LUWS and LHG composition will be almost the same as these are both unprocessed well
streams. There will however be a slight difference as the energy needed for liquefaction will
be higher for the LUWS concept. The nitrogen content in LUWS will be around half of that
for LHG due to this, because the flash gas consists of around 25% N2. The ethane will also be
quite stable at just over 5 mole%. This will not be drawn off as liquid nor will it be part of the
end flash fraction.

As we can see from EASEE’s gas pipeline specifications in the appendix, the hydrocarbon
dew point needs to be -2°C or lower between 1-70 bara. This is not satisfied for any of the
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four new liquefied gas products and dew point control will therefore have to be part of the
post processing at the receiving site. This is in the simulations obtained by removing liquids
during the heating in the evaporator.

The Wobbe-Index requirements are according to EASEE, to be between 13,60 and 15,81
kWh/m3. This is a very wide range of acceptable values and none of the products will deliver
gas outside these even without any post processing. However, since the gas will need to be
processed to comply with other specifications, the index will be influenced by the removal of
CO2 and heavy hydrocarbons among others.

Composition HLG HLG

Limit Limit
% 12 bars/-121°C 20bars/-107°C

CO2 1,4285300 1,48717 2,695933 2,84697

Methane 88,1478902 84,4877 85,80425 82,7123
Ethane 5,2649753 5,28047 5,275842 5,16952
Propane 1,7957381 2,11218 1,947102 2,0678
I-Butane 0,7155577 1,0561 0,866179 1,0339
I-Pentane 0,4211510 1,0561 0,644057 1,0339
Hexane 0,1658628 1,0561 0,351701 1,0339
Heptane 0,0359488 0,528047 0,093204 0,516952
Octane 0,0146955 0,127118 0,044734 0,360942
Nonane 0,0059663 0,345105 0,020692 0,516952
Decane 0,0022923 0,0128439 0,008946 0,0444435
Benzene 0,0684914 0,0330198 0,150482 0,0776918
CH 0,0645207 0,305844 0,143539 0,516952
N2 1,8683683 2,11218 1,95332 2,0678
Table 6: Freezable components Concentrations

In Table 6: Freezable components Concentrations, the two HLG concepts and their freezable
component concentration compared to the limits calculated in NeqSim are shown. The
concentrations and freeze out limits will vary with the concentration of all the components in
the liquid and has a complex coherence. The limits are therefore not absolute and a safety
margin should be established. A good insight is however obtained showing which
components to specially take precaution against.

The yellow colored rows in Table 6 make up the freezable components in the temperature
ranges in which we operate. For all the products, the freezable components are below the
maximum allowed limits with the exception of benzene. Benzene will form solids in both the
HLG cases and will therefore need to be removed in a pre-processing unit. This could be a
selective benzene removal unit or the hydrocarbon dew point may be lowered. In addition the

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CO2 in HLG12 is too close to the freeze out limit to handle any fluctuations and some more
should be removed in the amine process.

6.4.2 Calculated example

As an example of a typical liquefaction plant, a 2,1 million tons well stream per year example
is calculated. The results are shown in Table 7 and Table 8.

Concept Pipe Pipe LPG LPG Liquefac Power Re-

gas sale gas amount I amount tion % of compression
sale II power LNG power

Kg/sec m3/sec Kg/sec Kg/sec MW % MW

LNG 37,9600 47,26 14,2247 0 31,428 100,0 1,566
LUWS 40,6530 48,54 0 14,313 37,284 118,63 13,615
HLG 12 40,6152 49,34 13,3539 0,911 19,570 62,27 6,516
HLG 20 42,0269 50,20 11,1172 3,158 16,381 52,12 6,590
LHG 41,7185 51,59 0 15,405 12,236 38,93 9,382
Table 7: Example Calculations I

Concept End CO2 Amine CO2 Amine Pipe gas

flash Removed regeneration Removal regeneration HC dew
for fuel on site heat required* heat point

Kg/Sec Kg/s MW Kg/s MW °C

LNG 2,5067 5,6815 35,2 0 0,0 -2,0
LUWS 2,9401 0 0,0 2,463 15,27 -2,03
HLG 12 1,2844 4,2043 26,1 0 0,0 -2,07
HLG 20 1,0271 2,8408 17,6 0,199 1,2 -2,02
LHG 0,7351 0 0,0 2,510 15,56 -2,06
*Removal at receiving site
Table 8: Example Calculations II

The well stream flow without acid gas removal is equal to 60,368 kg/sec. As the different
concepts have different requirements for CO2 content and the amine processes are not
simulated in this thesis, the CO2 concentrations are set for each case and the flow rate
decreased corrected accordingly.

The LHG concept is by far the least energy demanding concept in addition to being the
simplest for this gas composition. For a reasonably sized production rate as in this example,
the power requirement for liquefaction is only just over 12 MW. This is very low, reducing
the need for a large power producing unit considerably. In addition, the acid gas removal
process is unnecessary before liquefaction and LGP/NGL is shipped solved in the LHG
product. This high LPG/NGL fraction will also have a negative effect on the power
consumption for LHG as more liquid is cooled down than for LNG. From Table 7: Example
Calculations I, we see the liquefaction power for LHG is 39% compared to LNG. This could

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be reduced additionally if liquids are drawn off at ambient temperatures before liquefaction
and stored and shipped in a separate vessel than the LHG product. This would then also
reduce the amount of CO2 possible solved in the product liquid and a removal process should
be installed. The work requirement is still well below all the other concepts. For LUWS, an
increase of 18,6% is observed due to the larger amount of gas needed to be cooled to the
storage temperature.

The amine regeneration heat will only be half that of LNG for the LUWS and LHG concept as
these have a 2,5 mole% of CO2 left in the sales gas. The need for this regeneration heat will
however be at the receiving site where there might not be a surplus of heat for power
production. The best alternative may be to remove just enough CO2 for the sales gas to have
the maximum allowed specifications of 2,5 mole% before liquefaction. This could be done for
HLG20, LHG and LUWS. There will also then not be any abundant removed CO2 at the
receiving site which needs to be disposed of as all the CO2 is sold as pipe-gas. If the heat is to
be produced from combustion of some the gas the amount would be around 0,5 kg/s LHG
with a thermal efficiency of 70%. This heat could of course be produced in connection with
producing power for the recompression.

All the concepts will have a total LPG/NGL production of around 14,3 kg/s except LHG
which has 15,4 kg/s extraction at the receiving site. This elevated amount is due to the high
concentration of C5+ which must be remover to satisfy the 2°C HC dew point. LHG will have
both a higher percentage of HHC and nitrogen resulting in a lower methane concentration.
Both HLG20 and LHG will deliver around the same mass flow of pipe gas at 42 kg/s while
the other two has equally 40,6 kg/s. The low 38 kg/s for LNG is due to the total removal of
CO2 from the pipe-gas, but this could be adjusted to increase the gas value adding to this flow
rate. The mole-percent nitrogen will be just under 2 for the pressurized concepts while for
LNG and LUWS approximately 1.

The power needed for recompression is based on recompression of evaporated liquid, as well
as pumping work of the liquid. The end pump pressure is set to a pressure such that extraction
of liquids needed for hydrocarbon dew point control is possible. The vapor is recompressed
using a compressor with an efficiency of 80%. There do exist some NGL and LPG recovery
processes that allow the pressure increase to be done by a pump, utilizing the cold in the
liquid streams [5]. This could reduce the power requirement by as much as 90%, but are in
these concepts not simulated. As hydrocarbon extraction can be done more energy efficient,
the power needed for recompression should not be weighted too heavily in the comparison.

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6.5 Pressure vessel calculations

Comparable weight estimates have been calculated for all the concepts to find the
containment vessel weights for both steel and composite material.

Yield strength is the stress limit where the steel will start to deform plastically and therefore
will change shape permanently. As the containers will have a wall thickness of less than one
tenth of the diameter, the simplified equations for the maximum stresses can be found from a
net force balance and are [35]:

∑F y =0

σ A A − pAe =0 =σ Aπ ( r02 − r 2 ) − pπ r 2

With r0 = r + t, this becomes:

pπ r 2 pπ r 2 p 2r
σA = =
(
π [r + t ] − r
2 2 π r 2
) (
+ 2rt + t 2 − r 2 )
π 2rt + t 2 ( )
Since t2 will be much smaller than t due to the size of t, this expression can be simplified to:

Pd
Axial Stress: σA =
4t
The hoop stress is found in a similar manner to form equation:

Pd
Hoop Stress: σH =
2t
The ambient pressure containers for LNG and LUWS are of Moss type while the pressurized
vessels have a cylindrical shape. For the spherical LNG tanks there is only axial stress and the
maximum stress can be twice that of a cylindrical vessel. As there is a technical limit to the
maximum thickness of the plates, this is set to a constant 150mm for the pressure vessels. The
diameter of the vessels is calculated from this criterion and at a set height of 40m. The area of
the ends of the cylinder is set to two half spheres with the same diameter.

σ max t 2
d=
p
Simplified steel mass calculation: Surface Area x Thickness x Density:

Cylinder: Sphere:

=m ( 2π rh + 4π r )t  ρ
2
m = 4π r 2  t  ρ

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Figure 43: Moss type

Figure 44: Cylindrical Pressure Vessel

The same Cr-Ni Austenitic Stainless Steel 304 is assumed used for all the containers as this
covers the whole temperature range for all the concepts [36].

From Appendix 8 we find the yield stress for the 9% Nickel steel to be 215 MPa. With a
factor of safety of 4, the allowable stress limit is:

σ y 215MPa
σ Allow
= = = 5375
. MPa
η 4
The factor of safety should be quite high as the weakest areas of the vessels can be found in
the welding seams, allowing a much lower stress. The resulting dimensions and weights for
the four concepts are shown in Table 9 below.

LNG HLG 12 HLG 20 LHG

Safety factor 4 4 4 4
Yield [Mpa] 215 215 215 215
Total volume [m3] 150000 150000 150000 150000
Steel density [kg/m3] 8000 8000 8000 8000
Pressure [Mpa] 0,3 1,2 2 5
Thickness [mm] 124,30 150 150 150
Diameter [m] 44,54 13,44 8,06 3,23
Height [m] - 40 40 40

TYPE Sphere Cylinder Cylinder Cylinder

Volume per tank [m3] 37500 5672,7 2042,2 326,7

No of tanks 4 26 73 459
Steel volume per tank [m3] 774,65 338,38 182,61 65,69
Mass per tank [tons] 6197,2 2707,0 1460,9 525,5
Steel volume total [m3] 3098,6 8947,7 13412,8 30157,0
Steel weight total [tons] 24789 71581 107302 241256
Table 9: Steel Vessel Calculations

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As we see from the simple calculations, the total weight of the shipping containment system is
increasing rapidly with the elevated pressure. To compare the results, the weight of an
operating LNG tanker is around 55000 tons in total, plus the weight of the cargo [37]. This
agrees with the total steel weight in Table 9 with the tanks weighing 24789 tons in total. The
LUWS tanks will have a similar weight as the LNG tanks as these are both at 1 bar. The
proposed PLNG tank in the concept description by ExxonMobil has a dimension of 10m in
diameter and a height of 46m [11].

250000

200000
Weight [Tons]

150000

100000

50000

0
LNG HLG 12 HLG 20 LHG

Figure 45: Total Steel Vessel Weight

HLG12 and to some extent HLG20, might both have a tolerable total weight of shipping
vessel even though far heavier than conventional LNG carriers with three and four times the
weight respectively. The diameters of the cylinder containers decrease very fast, thus
increasing the number of containers to give the same volume cargo space. One solution could
be to decrease the tonnage and increase the number of ships. At 241000 tons, the LHG vessels
constructed of steel will be too heavy to be on a reasonably sized ship and this design will
have to be abandoned. The total steel weight per kilogram of LHG liquid is almost 3,86kg
compared to 0,36kg for LNG as shown in Table 10. This means a substantial amount of steel
will have to be transported as deadweight increasing the capital and operating expenses.
Instead, an optional build material should be considered as the temperature in LHG is only
-78°C.

The calculations are done with a constant freight volume equal 150000m3, but as the densities
and heating values of the liquids are dissimilar, the delivered pipe gas and net calorific value
for the shipments will be different. A comparable measure is the transported energy per ton of
vessel weight, but one should also keep in mind that in this value lays both the heating value
and the density differences. The transported energy per ton of vessel is 12,44 times higher for
LHG than for LHG, with a lower HHV of LHG contributing to this.

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Pressure Cargo Density Full HHV Energy Kg

Vessels capacity Liquid trans. per vessel steel/kg
Weight
vessels weight cargo

Tons m3 Kg/m3 Kg/m3 MJ/kg MJ/ton Kg/Kg

LNG 24789 150000 461,6 165,3 53,91 150,6 0,35802

LUWS 24789 150000 576,8 165,3 47,36 165,3 0,28651

HLG 12 71581 150000 418,6 477,2 51,22 44,9 1,14001

HLG 20 107302 150000 406,9 715,3 49,51 28,2 1,75804

LHG 241256 150000 417,0 1608,4 46,81 12,1 3,85701

Table 10: Containment Vessel Comparison

Glass fiber reinforced pressure vessel

For the heavier pressure vessels, a composite material relieving the steel from the hoop stress
would make the total weight become acceptable as mentioned previously. A metal inner liner
will then contain the liquid while a composite overwrap will absorb all the stress. The liner
should have a construction and thickness to minimize the resulting weight, but tolerate a
fluctuation in pressure.

As the tanks will only need to withstand pressure forces from the tank, it is assumed that all
loads are taken up by the fibers only and that the resin in the composite is only there to keep
the fibers in place and distribute the forces evenly. Typical tensile strength of a fiber
reinforced plastic, or FRP, is between 550-1700 MPa depending on the ratio of fibers to resin
[38]. Because the pressure vessels will need limited compressive strengths, a high fiber
fraction can be utilized giving a tensile strength in the upper levels of this. In addition, the
FRP at low temperatures will gain strength and become less brittle than at room temperature
which is an obvious advantage for these vessels [38]. The resin however becomes brittle and
must be chosen with care. A moderate 1000 MPa tensile strength is assumed and with a factor
of safety of 4, the thickness of the spherical FRP is calculated.

A conservative estimate for the specific weight is set at 2,5 tons/m3 with generic E-glass Fiber
having a density of 2,54-5,6 tons/m3 [36]. With the same tanks and volumes as the steel
design and with the same tonnage, the specifications of the FRP vessels are shown in Table
11. The steel liners are set to withstand a pressure of 3 bars regardless of the concept
pressures, resulting in different liner thicknesses due to the different shape and sized of the
pressure vessels. The result is a decreasing thickness of the liner from over 9mm in the
HLG12 tanks to 2,25mm in the 50bar LHG concept.

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HLG 12 HLG 20 LHG

Factor of safety 4 4 4
Yield Mpa [Mpa] 1000 1000 1000
Total volume [m3] 150000 150000 150000
3
Frp density [kg/m ] 2500 2500 2500
Pressure [Mpa] 1,2 2 5
Thickness [mm] 32,25 32,25 32,25
Diameter [m] 13,44 8,06 3,23
Height [m] 40 40 40

TYPE Cylinder Cylinder Cylinder

Volume per tank m3 [m3] 5672,7 2042,2 326,7

No of tanks 26 73 459
FRP volume per tank [m3] 72,75 39,26 14,12
Mass per tank [tons] 181,9 98,2 35,3
FRP volume total [m3] 1923,8 2883,8 6483,8
FRP weight total [tons] 4809 7209 16209
Steel liner thickness [mm] 9,375 5,625 2,25
Steel liner weight [tons] 4474 4024 3619
Total weight [tons] 9283 11233 19828

Table 11: Fiber Reinforces Plastic Calculations

While the steel tanks in the highest range of pressures gave an intolerable amount of steel and
resulting weight, the FRP tanks show great potential for reducing the ship size and weight. As
we compare Table 9: Steel Vessel Calculations and Table 11, it becomes clear that it might be
possible to construct a LHG ship carrying the same amount of liquid as a conventional LNG
carrier with around the same weight using fiber reinforced plastics.

6.6 Water content limits

In the presence of free water, light hydrocarbons, and in some cases other gases like CO2 will
form gas hydrates under the right conditions. At high pressures e.g. 200 bars, the hydrate
formation temperature limit can be as high as 25°C while in a typical HLG pressure range,
10-50 bars with the typical limit is between -40°C and -30°C [39]. As we can see from Figure
46, LNG at -160°C will unquestionably form hydrates at any pressure above ambient and
must therefore contain no more water than that solved in the liquid hydrocarbons. The new
concepts will both differ in temperature and pressure and the requirements for dehydration
will change. The conditions however, will not be inside the safe zone of the hydrate formation
curve so no free water can be present in any of the compositions.

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Figure 46: Hydrate Formation Curve

For any condition, hydrate formation is very complex and both kinetics and phase equilibrium
contribute to the solid formation. Due to the kinetics, the formation of solids will not occur
even though the water content is higher than the equilibrium concentration. With increased
liquid temperature, the water removal limit may be increased. However, with increased
pressure, the phase equilibrium for water-hydrate is influenced and less water can be present
in the liquid as shown in Figure 47. The effect is particularly large when going from
atmospheric to about 50 bars. The consequence of this will be a requirement of thorough
dehydration for all the pressurized concepts if hydrate is to be avoided. This should be done in
a molecular sieve adsorption process. For the LUWS concept, a small hydrate formation rate
may be permitted. In any case, the delivered pipe gas will need to have a water dew point of -
8°C or lower to comply with the EASEE’s harmonized gas specifications.

Figure 47: Water Content at hydrate equilibrium (E.Solbraa)

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Molecular Sieve Dehydration

Molecular sieves, or mol-sieves, have been utilized for dehydration and other gas purification
processes for many years and are well proven. The mol-sieves are crystalline hydrated metal
alumino-silicates and are synthetically manufactured [40]. This crystalline has an enormous
amount of cavities which were formed during the production, giving them an extremely large
surface area and resulting pore volumes. It is in these cavities water or other substances will
be adsorbed. When heated, these cavities will be emptied without damaging the structure. A
typical chemical composition of the sieves is;

AK2O- B Na2O- Al2O3- C SiO2-D H2O

Where A, B, C and D are constants.

The molecular sieves may be classified by the size of the cavities and can be specified in the
form X A, where X is a numerical value of the opening and A stands for the unit Ångström.
The size of the cavities can be controlled by altering the fraction of substances in the
crystalline giving different mol sieves for adsorption of different substances. The most
common is 4A which is used for dehydration of air while the larger 5A can adsorb larger
molecules like H2S and CO2. The smaller 3A will exclude most molecules other than water
[40]. The theoretical equilibrium water capacity of the sieves is around 20-25%, depending on
the sieve type. The regeneration temperature is between 200 – 350°C depending on the
wanted speed of regeneration.

The silicates are usually placed in fixed packed beds where the gas stream is lead through and
adsorbs the water. Gas pre-treatment for LNG production is usually done by a number of
molecular sieve beds in parallel. These are arranged in a way that some may be regenerated
while others are operative, giving a continuous process.

For some of the concepts of unprocessed liquefied gas, the whole well stream is intended
liquefied without removal of any liquids, except water. However, as the molecular sieves
needed for dehydration will be severely reduced by high boiling hydrocarbons, all the free
liquids will need to be separated thoroughly in advance. The dew point of the entering gas
should also be lower than the minimum internal temperature through the adsorber. This
temperature may decrease as a result of the pressure drop over the adsorption beds. Even so,
special attention should be taken when considering a system without a hydrocarbon stripper
prior to the mol sieve process. Olefins and aromatics etc can enter the system as aerosols if
not filtered properly and may polymerize inside the pores of the molecular sieves. When this
occurs, the polymer molecules are too big to leave the pores during regeneration resulting in
degradation of the performance [41]. Removal of aromatics and other heavy molecules from
the cavities can be achieved by burn-off where the mol sieves are heated to high temperatures
and injected with a small amount of oxygen.

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6.7 Comparison of Concepts

There will be negative and positives sides to the different concepts depending on the various
assumptions. As an overview of the most important aspects, tables of pros and cons are shown
in Table 12 and Table 13.

There will be many good reasons for selecting conventional LNG as the preferred
transportation method over the new, unconventional ones. The most obvious reason being the
uncertainty of the other concepts as these have not been fully tested in a commercial way.
Even for the largest oil companies in the world with solid finances, being the first to make use
of some of these concepts would involve a risk that might not be worth the savings if
successful. Choosing a method that turns out to be non-functional or problematic would inflict
a heavy financial loss. Once a concept is proven and is successfully and economically
delivering gas, the risk will be greatly reduced. This again will result in other companies
wanting to utilize the same technology.

Pros Cons

Conventional LNG Well proven technology High equipment count

Established receiving Extensive pre-treatment

facilities
High flexibility in market High power consumption for
liquefaction
Low pressure transport High complexity for high
performance
High boil-off rate
Low temperature
Low equipment count at Freeze out problems
liquefaction site
LUWS Low pressure transport Low technical verification
Transportation in Low flexibility in market
conventional LNG ships
possible
Possibility of mechanical Need for mechanical
separating methods at separation of solids or
receiving site melting at receiving
Possibly low complexity High power consumption for
liquefaction
Very little pre-processing Unproven commercialization
Table 12: Pros and Cons; LNG LUWS

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Conventional LNG is a well proven and a safe option to choose but has high power
consumption for liquefaction due to its low storage temperature. All the pressurized concepts
will decrease this considerably. LUWS does not offer a lower power consumption in reality,
as the whole well stream needs to be cooled to around -160°C, whereas LNG will have a
LPG/NGL fraction removed before the cooling loop. From the calculated example in Table 7,
this extra amount of liquid results in an increase in the net power need of around 18%
compared to LNG. The only savings of energy demand for LUWS will be in the form of a
decreased heat requirement for the regeneration processes and the fractionation of heavy
hydrocarbons. As the energy consumption goes up for this concept, there will be more heat
available from the power production even though the need for it is decreased. The only
savings then will be in the form of a reduced number of equipment at the liquefaction site. For
reducing the power consumption, the LPG could be stored and shipped in separate vessels.

With the increased focus on CO2 capture and storage, the LUWS concept would be suitable
for small reservoirs and where CO2 re-injection is impossible. Having CO2 solids in the
transported product will avoid a second transportation method for this from the production
site. The CO2 would have to be separated at the receiving site and shipped for disposal.

Pros Cons
Low power consumption High pressure storage
HLG for liquefaction
Increased tolerance for Lower flexibility in market
CO2
Decreased Scrubber Unproven
requirements Commercialization
Potentially less expensive Heavier transportation
ships vessels
Possibility of steel pressure Pre-processing needed.
vessels
Very low power Very high storage pressure
LHG consumption for
liquefaction
Option of not extracting Need for alternative
LPG/NGL at production building material for
site storage vessels
Possibility of no acid gas Safety issues associated
removal at production site with high pressure
High transportation Unproven
temperature Commercialization
Potentially less expensive Lower flexibility in market
ships

Table 13: Pros and Cons; HLG, PLNG, LHG

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In addition to the increased energy needs, LUWS has a number of difficulties connected to the
controlled freeze out of CO2 and HHC’s which none of the other concepts have. The extent of
these difficulties is not yet fully been investigated, giving the LUWS concept a high
uncertainty. The testing of this, both in small and big scale, will need to be successful before
this concept can be considered a genuine option. If successful, it could prove to be
competitive for smaller reservoirs where high specific power consumption is traded off in
exchange of a simple process. For large optimized liquefaction plants the power consumption
will have a larger impact on the value chain and a LUWS option will be less attractive.

LUWS would probably be able to utilize a transportation vessel designed for LNG but with
specially fitted pumps and jetties for handling solids. This would make it less expensive to
implement as soon as the technical difficulties with freeze out are solved. The other concepts
would require building of new, specially designed tanker. This may be more expensive for the
first vessels produced due to the design costs, but with larger number produced the cost might
drop and turn out to be less expensive than LNG tankers. The reduction in cost the smaller
pressure vessels can be manufactured separately from the hull decreasing the total delivery
time for a ship order. Yet another possibility for small scale production is to retrofit an
existing shipping vessel e.g. a dry bulk ship, to transport the relatively small containers for the
pressurized liquid in smaller quantities.

The buildup of the value chain for LUWS will be similar to the one for LHG in many ways.
They both will have their gas purification processes downstream at the receiving site with
only dehydration and other minimal pre-processing before liquefaction. This is only true in
the cases where a relatively CO2 and HHC-lean gas is to be liquefied. According to the
solubility diagram for CO2, the 50 bar LHG should be able to contain at least 6 mole% of it. If
the amount of contaminants exceed the amount the liquid can dissolve, a removal unit will be
required. This can consist of a dew point control device like the Twister, and a CO2 removal
membrane. All the removed components will need to be re-injected or shipped by other means
and will complicate the value chain. LHG will also need pressure vessels constructed of a
light-weight material as steel would be too heavy. Some uncertainty regarding the cost,
building methods and the fatigue life of these will also be a factor to consider. LUWS will
have a power requirement for liquefaction of over three times that of LHG, giving large
incentives for selecting LHG in preference to LUWS. Choosing LHG would also reduce the
space needed for power production with around one third which would make it suitable for
installation on a floating vessel in remote areas.

Today, there are a large number of receiving facilities for LNG in operation. The market is
relatively flexible and producers can deliver the gas where they get the best price. For all the
new concepts, a rebuild or extension of the receiving facilities is necessary as the delivered
gas is not fulfilling the pipe-gas requirements. Retrofitting one receiving terminal may not be
too expensive, but changing all is. Therefore, the new concepts will lose some of its flexibility
in the gas market compared to LNG. The result of this will be entering long-term contracts
for delivery to a specific site in the same way as pipe gas contracts.

All the concepts as presented in this thesis will need some conditioning at the receiving site.
However, adjusting the amount of pre-processing so the post-processing is minimized is an
option. Reducing the CO2 content below 2,5 mole% and setting the hydrocarbon dew point
below -2°C could eliminate the need for post-processing. The biggest saving will then be the
power consumption for liquefaction, but still a large reduction of the pre-processing stages
occurs. For the HLG12 presented here, just a slight increase in CO2 removal and a lower
hydrocarbon dew point at liquefaction would be sufficient for the gas to be sold directly as

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pipe gas. This sweetening should be done by a membrane to decrease the complexity and both
the capital and operating expenses. If other components are exceeding the limits for pipe gas
e.g. O2 and H2S, some minor processing units may still be needed, but could be easily dealt
with.

Using components from conventional LNG, or components from this with minor alterations,
will reduce the cost for research and development. All the non freeze-out concepts should be
able to use ordinary LNG heat exchangers as these usually have an operating pressure of
around 60 bars. Mercury removal will be necessary however, as the aluminum will corrode
when in contact with it. The heavier hydrocarbons that might deposit on the heat exchanger
walls will need to be removed prior to liquefaction, but may not constitute a problem for all
gas reservoirs. The LUWS concept will need a totally different design with larger tubing for
solid formation. For the high pressure concepts, new fittings downstream of liquefaction will
be needed in addition to a loading system to storage tanks and between this and the
transportation vessel. Due to this similarity with LNG in the liquefaction, LHG and HLG
could be tested and implemented at a reduced cost compared to LUWS giving another
incentive for selecting one of these.

The total weight of the pressurized vessels will be greatly increased compared to LNG if
constructed of steel. For LHG, the total weight of just the pressure vessels will be over
200 000 tons given a factor of safety of 4. The resulting ship would need to be 5-8 times the
size of a conventional LNG tanker to bear the weight of both the pressure vessels and the
cargo. For this heavy pressure, an alternative building material is necessary to limit the weight
below an acceptable level. Prototypes for a fiber reinforced plastic pressure vessel of
considerable size must be built and tested before the LHG concept could be an option. These
would need to withstand low temperatures and comply with safety regulations. For the lower
pressures in HLG, steel containment could prove viable, but still with an increase in weight
and size compared to LNG.

Recently developed as well as unconventional equipment and processing systems may aid in
the implementation of the new concepts. Because they do not need as thorough pre-treatment
as LNG, all open for alternative CO2 and HHC removal. Separating technologies like the
Twister and 3S show potential for simplifying the dew point control as well as possibilities of
simplifying CO2 extraction in the future with further development. The CRYEX system fits
perfectly with the potential pressure reduction at the receiving site for HLG/LHG, separating
the CO2 as a solid. In this way, parts of all the pressurized concepts can be stored at
atmospheric pressures in existing LNG storage facilities.

A high level comparison chart of the new concepts together with CNG and LNG is shown in
Table 14: Comparison of Concepts. The complex and negative red squares for LNG in the
early stages of the value chain represent the thorough pre-processing and energy demanding
liquefaction. These are changed to much more satisfying ones for all the new concepts. The
exception is the energy demand for LUWS. Further down the value chain where conventional
LNG is competitive and well established, the new concepts show noticeably less positive
properties. The pressurized containment vessels make up a key barrier to making the new
concepts more attractive. If these are provided, the comparison chart becomes more in favor
of these and especially LHG. Shipped directly to a power plant for combustion with minimal
post processing, this concepts becomes extremely attractive with only elements of uncertainty
and technology qualification left as possible show stoppers.

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Post processing
Pre-processing

Containment

Qualification
requirement

Uncertainty
Liquefaction

Complexity

Technology
Equipment

Receiving
Energy

Vessels

facility
count
LNG

HLG

LHG

LUWS

CNG

Table 14: Comparison of Concepts

6.8 Further work

Deciding to modify the value chains for gas transportation worldwide is not a decision to
handle leniently. In the case of the presented concepts, a huge amount of investments must be
done before a well working and profitable delivery chain can be realized. In addition, the risks
involved in some of the concepts may become too high for most companies to participate.

Pressure vessel material

For the high pressure concepts HLG and LHG, the main technical difficulty is the weight of
the containment vessels if they are to be made of ordinary Nickel steel. The option of a
composite material should be looked into further and evaluated thoroughly under cryogenic
temperatures.

Economical analysis of HLG/PLNG/LHG

An economical analysis should be carried out for the concepts of increased pressure. As the
technical differences from LNG would require new production techniques for the needed
equipment and storage, the first units would be very expensive. A number of liquefaction
plants and transportation vessels must be produced before the concept would be economically
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profitable. Finding this limit when comparing to other alternatives for profitability, is a major
undertaking with huge uncertainty, but should be looked into.

Optimal Pressure Selection

The optimal pressure for the HLG and LHG concepts would depend greatly on the gas
reservoir which is to be developed due to the increased solubility of contaminants in the gas.
Therefore, a case study with an existing potential reservoir with specific data for this site
should be explored. The delivered liquid hydrocarbons could be used for a thought power
plant where this is suitable. The number of transporting vessels, HLG and LPG, should be
found in addition to the potential cost of these compared to LNG. Avoiding almost all the
contaminants removal at the production site will save a lot of space and simplify the potential
FPSO on which the process is installed. If the increased building costs and complexity of high
pressures will justify the lower equipment count for this specific reservoir should be
discussed.

Solid particles in suspension

An evaluation of the particle sizes and how they will behave in a specific gas composition
over a shipping period of 20 days should be done. As this behavior is highly complex, a test
rig may be needed for observation. The solid particles should be generated in both a heat
exchanger and through expansive cooling to get the correct solid particle sizes. The test
should be done in a similar composition as gas from a potential reservoir.

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7 Conclusion

Alternative value chains to LNG based on natural gas in liquid form, have been proposed and
patented by many parties over the last decades. The most studied are Liquefied Unprocessed
Well Stream (LUWS) Aker solutions Heavy Liquid Gas (HLG), ExxonMobil’s Pressurized
Liquefied Natural Gas (PLNG) and Chevron’s Liquefied Heavy Gas (LHG).

The work required for liquefaction is reduced for all the new concepts except LUWS, where
an increase of 18,6% is observed. This increase is due to the larger amount of gas cooled to
storage temperature. The two simulated HLG concepts at 12 and 20 bars consumed 62 and 52
percent respectively compared to conventional LNG. The 50 bar LHG concept would only
need 39 percent, but this could be lowered if liquids where drawn off and stored and shipped
separately. This would however make the value chain more complex, but could be a possible
option depending on the cost of the shipping vessels.

Dehydration is required for all the concepts as hydrate formation during cool down would
cause severe problems. CO2 removal can be reduced significantly reducing the thermal energy
need and complexity of the liquefaction plants. For LUWS and LHG, all the CO2 may remain
in the gas with freeze-out in LUWS, while dissolved in LHG. The two HLG concepts would
require some acid gas treatment with a maximum limit of 1,4 and 2,7 mole% respectively. As
the thoroughness of acid gas removal is considerably reduced, alternative removal processes
such as membranes may be utilized.

New pressure vessel designs are needed to transport cryogenic liquids in large quantities.
Steel would make the shipping vessel too heavy for LHG, but a fiber reinforced plastic with a
metal liner shows potential in reducing this. If successfully built at an acceptable cost, LHG or
a high pressure HLG is likely to be a favorable option compared to LNG in terms of
complexity and energy requirements.

As a transition and as a trial study, an end consumer such as a power plant is suggested for the
concepts with high concentrations of CO2 and HHC’s. In this way, post processing may be
excluded giving a simple and energy efficient value chain. Due to the lowest work
requirement and possibly no acid gas removal, the 50 bar LHG concept should be used. The
main obstacle for implementing this is the pressure vessels which must be built in a light
material.

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8 References

[1]. Gerald M. G., CB&I. LNG: Proven Technology for Monetizing Stranded Gas, World
Energy Magazine, Vol.7, No.4

[2]. Website of U.S Energy Information Administration (EIA). Available at:

www.eia.doe.gov [Cited: 08.04.2010]

[3]. EIA website, The Global LNG market: Status and outlook. Report #:DOE/EIA-0637
December 2003. Available at:
http://www.eia.doe.gov/oiaf/analysispaper/global/lngindustry.html [Cited: 01.04.2010]

[4]. Course material forSpezialization course at NTNU, Trondheim: TEP08, autumn 2009.

[5]. Cuellar K. T., Economical options for recovering NGL / LPG at LNG receiving
terminals. 86th Annual Convention of the Gas Processors Association, San Antonio,
2007

[6]. US Patent No. 7,503,186 LUWS: Method and system for condensation of unprocessed
well stream from offshore gas or gas condensate field, March 2009.

[7]. Stang, J., SINTEF. Meeting March 23, 2010.

[8]. US Patent No. 7,219,512 Apparatus for liquefaction of natural gas and methods
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[9]. Website of CoolEnergy., Available at:

http://www.coolenergy.com.au/demonstration.php. [Cited: 08.04.2010]

[10]. US Patent No. No. 7,325,415, Process and device for production of LNG by removal
of freezable solids, May, 2008

[11]. Bowen, R. et.al, Pressurized Liquefied Natural Gas (PLNG) A New Gas
Transportation Technology. GasTech, Bilbao, Spain, 2005

[12]. Lund J. T., HLG – Heavy Liquefied Gas: A promising technology for production of
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Park Hotel, 2006 November.

[13]. Website of Supersonic gas solutions, Available at http://twisterbv.com

[Cited: 04 10, 2010.]

[14]. Gullberg, R. W., NWNG's Newport LNG Facility, First user of cryex purification.
Pipeline and Gas Journal, Vol. 206, No. 13

[15]. SPE News ISSUE. Vol. 108, September 2007. Available at

http://wa.spe.org/images/wa/articles/67/spe108_finalweb.pdf [Cited: 06.04.2010]

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[16]. Brendeng. E., Cryex-prosessen for utskilling av CO2 fra naturgass, SINTEF
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9 Appendix

Appendix 1: EASEE Harmonized pipeline specifications for natural gas ................................ B

Appendix 2: Gas composition after CO2 Removal .................................................................... B
Appendix 3: Gas composition.................................................................................................... B
Appendix 5: Chemical compound Properties . .......................................................................... C
Appendix 4: CO2 Phase diagram ............................................................................................... C
Appendix 6: Water content of Natural Gas................................................................................ D
Appendix 7: TS diagram for liquefaction .................................................................................. E
Appendix 8: Cr-Ni Steel Properties ........................................................................................... E
Appendix 9: NeqSim Equations................................................................................................. F
Appendix 10: NeqSim Results HLG12...................................................................................... G
Appendix 11: NeqSim Results HLG20...................................................................................... G
Appendix 12: CO2 Solubility in CH4........................................................................................ H
Appendix 13: Theoretical Boiling Point of NG ......................................................................... H
Appendix 14: Hydrate Equilibrium curves ................................................................................ H
Appendix 15: Process Flow Diagram ......................................................................................... I

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Appendix A – Gas Properties

Appendix 3: Gas composition Appendix 2: Gas composition after CO2 Removal

Appendix 1: EASEE Harmonized pipeline specifications for natural gas

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Appendix 4: CO2 Phase diagram ( Prof. Shakhashiri 2008)

Tc °C Pc bar NB °C NF °C
Cyclo hexane 81 7
Benzene 80 6
Decane 174,2 -29,7
Nonane 150,8 -51
CO2 -31,05 73,8 -78,45 -56,4
Octane 126 -56,8
H2S 100 89,37 -60,35 -85,55
Heptane 98 -91
Hexane 69 -95
Ibutane 134,9 36,48 -11,7 -159,55
Ipentane 28 -160
Methane -82,55 49,2 -161,3 -182,45
Ethane -32,25 48,8 -88,5 -183,25
Propane -96,65 42,25 -41,9 -187,65
N2 -147 33,999 -195,9 -210
Appendix 5: Chemical compound Properties [42].

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Appendix 6: Water content of Natural Gas (GPSA)

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Appendix B: Miscellaneous

Appendix 7: TS diagram for liquefaction

Cr-Ni Austenitic Stainless Steel 304

Density 8,00 g/cc

Hardness, Brinell 123
Hardness, Knoop 138
Hardness, Rockwell B 70
Hardness, Vickers 129
Tensile Strength, Ultimate 505 Mpa
Tensile Strength, Yield 215 Mpa
Elongation at Break 70,0 %
Modulus of Elasticity 193-200 Gpa
Poissons Ratio 0,29
Charpy Impact 325 J
Shear Modulus 86,0 GPa
Carbon <=0,080 %
Chromium 18,0-20,0 %
Nickel 8,0-10,5 %

Appendix 8: Cr-Ni Steel Properties [36]

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Appendix 9: NeqSim Equations [33].

Liquid phase: SRK EOS

SRK EOS is one of the most often used cubic equations of state, which is:
NRT a (1)
= p +
V − b V (V + b)
p is the pressure, N is the total amount of the component, R is the gas constant, T is the
temperature of the system, V is the volume of the system, the parameters a and b are
determined by critical temperature Tc , critical pressure Pc and acentric factor ω , .
The Van der Waals 1-fluid mixing rule is used for the mixture, which is:
N = ∑ ni (2)
i

=a ∑ij
ai a j (1 − kij )ni n j (3)

b = ∑ bi ni (4)
i

where i and j denote for component i and j in the mixture, n is the number of moles of
each component, and kij is the binary interaction parameter.

Solid Phase: Solid fugacity model based on assumed sub-cooled liquid

The solid phase appears in the mixture is assumed to contain only pure hexane. The solid
fugacity is expressed as:
∆H − Ti melt ∆C p 1 1 ∆C p T ( p − patm )∆V (6)
fi = fi
solid liquid
exp(−( )( − melt ) + ln( melt ) − )
R T Ti R Ti RT
fi solid is the fugacity of pure solid component i , f i liquid is the fugacity of the same component
as a pure liquid at the same pressure p and temperature T (calculated from the fluid phase
model), ∆H , ∆C p and ∆V are the changes in molar enthalpy, molar heat capacity and molar
volume respectively on fusion at the melting point, Ti melt is the normal melting point
temperature of component i , and patm is the atmospheric pressure.

Regeneration heat in the sweetening process:

LNG:
Weight percent CO2 after LPG extraction: 0,1282
Regeneration heat= 0,1282*6200 kW/kg CO2= 795 kW/kg produced LNG

HLG12:
0,09076 kg CO2 removed for every kg produced HLG12
Regeneration heat= 0,09076*6200 kW/kg CO2= 563 kW/kg produced HLG12

HLG20
0,0574 kg CO2 removed for every kg produced HLG20
Regeneration heat= 0,0574*6200 kW/kg CO2= 356 kW/kg produced HLG20

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Appendix C: Simulation Results

HLG 12 bar minus 125 oC HLG HLG 20 bar minus 115 oC

Phase Fraction Phase Fraction

Solid-CO2 0,0359182 Solid-CO2 0,0224639
Solid-n-Octane 0,003796333 Solid-n-Octane 0,001508954
Solid-n-Nonane 0,00173224
Solid-n-Decane 0,004570138
Solid-n_decane 0,004878383
Solid-n_benzene 0,00424856
Solid-benzene 0,004687332
Solid-c-Hexane 0,002114393
liquid 0,967208449
liquid 0,946873119

Liquid Mole Fraction

CO2 0,0284697
Liquid mole concentration
CO2 0,0148717 methane 0,827123

methane 0,844877 ethane 0,0516952

ethane 0,0528047 propane 0,020678

propane 0,0211218 i-butane 0,010339
i-butane 0,010561 i-pentane 0,010339
i-pentane 0,010561 n-hexane 0,010339
n-hexane 0,010561 n-heptane 0,00516952
n-heptane 0,00528047 n-octane 0,00360942
n-octane 0,00127118 n-nonane 0,00516952
n-nonane 0,00345105 nC10 0,000444435
nC10 0,000128439
benzene 0,000776918
benzene 0,000330198
c-hexane 0,00516952
c-hexane 0,00305844
nitrogen 0,020678
nitrogen 0,0211218

Appendix 10: NeqSim Results HLG12 Appendix 11: NeqSim Results HLG20

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Appendix 14: Hydrate Equilibrium curves (E. Solbraa)

Appendix 12: CO2 Solubility in CH4 (Aker Kværner)

Appendix 13: Theoretical Boiling Point of NG (Aker Kværner)

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Appendix D: Simulation flow diagrams

Appendix 15: PRO/II Process Flow Diagram

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