Note: Descriptions are shown in the official language in which they were submitted.
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REMOVING CONTAMINANTS FROM NATURAL GAS BY COOLING
This application is a divisional of co-pending
Canadian Patent Application No. 2,515,139 filed
February 4, 2004.
The present invention relates to a process and
apparatus for removing a contaminant from a natural gas feed
stream by forming a solid of the contaminant and suitably
subsequently melting the solid contaminant.
When the contaminant is water, the present
invention relates particularly, though not exclusively, to a
process and apparatus for dehydrating a natural gas feed
stream.
When the contaminant is a sour species, for
example hydrogen sulphide or carbon dioxide, the present
invention relates particularly, though not exclusively, to a
process and apparatus for sweetening the natural gas feed
stream.
The present invention also relates particularly,
though not exclusively, to a process and apparatus for
sequentially dehydrating and sweetening the natural gas feed
stream.
Natural gas from~either production reservoirs or
storage reservoirs typically contains water, as well as
other species, which form solids during the liquefaction to
produce liquefied natural gas (LNG). It is common practice
for the natural gas to be subjected to a dehydration process
prior to the liquefaction.' Water is removed to prevent
hydrate formation occurring in pipelines and heat exchangers
upstream of the liquefaction vessel.
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If water is not removed, solid hydrates may form
in pipe work, heat exchangers and/or the liquefaction
vessel. The hydrates are stable solids comprising water and
natural gas having the outward appearance of ice,
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with the natural gas stored within the crystal lattice of
the hydrate.
The formation of natural gas hydrates was
historically seen as an undesirable result that should be
avoided. However, processes have been developed to
encourage natural gas hydrate formation such as
International patent applications No. 01/00 755 and
No. 01/12 758. In the first of these International patent
applications, a method and apparatus is described whereby
natural gas and water are combined in the presence of an
agent adapted to reduce the natural gas water interfacial
tension to encourage natural gas hydrate formation. In
the second of these International patent applications, a
production plant is described, including a convoluted
flow path to cause mixing of water and natural gas as a
first step prior to reducing the temperature to produce,
natural gas hydrate.
Methods of dehydrating natural gas feed streams known
in the art include absorption of water in glycol or
adsorption of the water using a solid such as hydrated
aluminium oxide, silica gels, silica-alumina gels and
molecular sieves.
Natural gas also typically contains sour species,
such as hydrogen sulphide (HZS) and carbon dioxide (COZ).
Such a natural gas is classified as "sour gas~'. When the
HZS and COZ have been removed from the natural gas feed
stream, the gas is then classified as "sweet". The term
"sour gas" is applied to natural gases including HZS
because of the bad odour that is emitted even at low
concentrations from an unsweetened gas. HAS is a
contaminant of natural gas that must be removed to
satisfjr legal requirements, as HZS and its combustion
products of sulphur dio~_ide and sulphur trioxide are also
toxic. Furthermore, HzS is corrosive to most metals
normally associated with gas pipelines so that processing
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and handling of a sour gas may lead to premature failure
of such systems.
Like dehydration, gas sweetening processes are known
in the art, such processes typically include adsorption
using solid adsorption processes or absorption using
amine processes, molecular sieves, etc. Existing
dehydration and gas sweetening processes are extremely
complex and expensive.
The present invention represents an improvement on
the process and device discussed in International patent
application publication No~. D3/062 725.
To this end the process for removing contaminants
from a natural gas feed stream including water according
to the present invention comprises the steps of cooling
the natural gas feed stream in a first vessel to a first
operating temperature at which hydrates are formed; and
removing from the first vessel a stream of dehydrated
gas.
An essential feature of the process of the present
invention is that on purpose hydrates are formed in order
to remove water. Normally formation of hydrates is
prevented.
When the natural gas feed stream further includes
sour species, the process according to the present
invention suitably further comprises the steps of cooling
the dehydrated gas in a second vessel to a second
operating temperature at which solids of the sour species
are formed or at oahich the sour species dissolve in a
liquids and removing from the second vessel a stream of
dehydrated sweetened gas.
The term "operating temperature" is used to refer to
a temperature below the solid/liquid transition
temperature for the contaminant at a given pressure of
operation of the first or second vessel.
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In this specification a "warm" liquid stream can be
any compatible stream of liquid having a temperature
above the solid/liquid transition temperature of the
contaminant for a given pressure of operation of the
first or second vessel. The warm liquid stream has thus a
temperature that is sufficiently high to cause melting of
the solids of the contaminant. The warm liquid may or may
not take the contaminant fully into solution.
The invention will now be described in more detail
with reference to the accompanying drawings, wherein
Figure 1 shows schematically a process flow diagram
of a first embodiment of the invention: and
Figure 2 shows schematically a process flow diagram
of a further embodiment of the invention.
Reference is now made to Figure 1. Figure 1 shows an
apparatus 10 for carrying out the process of the present
invention. The apparatus 10 comprises a first vessel 12.
The contaminant removed in the first vessel 12 is water
and thus the gas exiting the first vessel 12 is dry. Also
heavy hydrocarbons are removed as a consequence of this
process, and thus the gas stream exiting the first
vessel 12 is dew pointed for hydrocarbons to an extend
determined by the conditions in the first vessel 12. The
water dew point of the gas exiting the first vessel 12,
however, is lower than its equilibrium dew point due to
the formation of hydrates.
In the embodiment as illustrated in Figure 1, wet
feed gas from a wellhead is fed through conduit 15 to a
first flash tank 16 in r.~hich condensate is separated from
the feed gas. The pressure and temperature conditions
within the first flash tank 16 would typically be in the
order of 75 to 130 bar and between 25 and 90 °C (about 5
to 10 °C above the hydrate formation temperature). The
condensate liquid stream exiting the first flash
vessel 16 through conduit 17 is "a warm liquid" as
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defined above. The condensate consists of liquid
hydrocarbons that are produced. together with natural gas.
The gas stream separated from the sour wet feed gas in
the first flash tank 16 enters the first vessel 12 via
wet sour gas feed stream inlet 20. An intermediate heat
exchanger 22 may be used to cool the wet sour gas between
the first flash tank 16 and the first vessel 12. The
intermediate heat exchanger 22 drops the temperature of
the wet sour gas to a temperature just above the hydrate
formation temperature for the particular pressure of this
feed stream. The hydrate formation temperature for the
particular pressure of the feed stream is the maximum
value of the first operating temperature, which is the
operating temperature in the first vessel 12.
The wet gas feed stream fed to the first vessel 12 is
expanded using a Joule-Thompson valve 29 or other
suitable a}:pansion means such as a turbo expander to
further cool the stream as it enters the first vessel 12.
The Joule-Thompson valve 29 may alternatively define the
inlet 20 to the first vessel 12. Upon expansion of the
wet sour gas feed stream into the first vessel 12, the
gas pressure-temperature conditions within the vessel 12
allow hydrates to form. The necessary degree of cooling
is achieved by the degree of expansion of the wet sour
gas feed stream through the Joule-Thompson valve 29.
The first operating temperature and the pressure in
the first vessel 12 are maintained at a level whereby
hydrates are formed. The natural gas feed stream entering
downstream of the Joule-Thompson valve 24 into the first
vessel 12 is at the first operating temperature.
If the natural gas feed stream also contains sour
species, the first operating temperature to which the
feed gas in the first vessel 12 is cooled is below the
temperature at which hydrates are formed but above the
temperature at which solids of sour species, such as H25
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and C02, are formed. This is done to produce hydrates and
to prevent the formation of solids of sour species in the
first vessel 12.
Dry sour gas exits the first vessel 12 via dry sour
gas outlet 39. Typically the dry sour gas exiting the
first vessel 12 would have a nominal pressure of 10 to
30 bar lower than the pressure upstream of the e~;pansion
device 29 and a temperature of 10 to 25°C lower than the
temperature just upstream of the expansion device 24. The
term "dry gas" is used to~refer to water-free gas.
A hydrate-containing liquid stream is remotTed from
the first vessel 12 via water condensate outlet 28, and
passed through conduit 29 to a separator 30. The water is
separated from the condensate in the water condensate
separator 30. Such a separator is for example a baffled
gravity separation unit. As water is heavier than the
condensate, any suitable gravity separation techniques
may be used. The separated condensate is removed through
conduit 31 and the separated water is rempved through
conduit 33.
The natural gas feed stream entering into the first
vessel 12 was cooled to the first operating temperature.
Alternatively, the natural gas feed stream can be cooled
using one or more sprays of a sub-cooled liquid
introduced via sub-cooled liquid inlet 26. In a further
alternative embodiment, the natural gas feed stream is
cooled by both the Joule-Thompson valve 29 and the sub-
cooled liquid supplied through inlet 26. In case of spray
cooling, the natural gas feed stream can enter into the
first vessel 12 at a temperature that is at or above the
hydrate-formation temperature.
The sub-cooled liquid inlet 26 should be located in
the first vessel 12 above the inlet 20 of the ~,~et sour
gas feed stream. In the illustrated embodiment, the sub-
cooled liquid inlet 26 is a plurality of spray nozzles.
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The particular sub-cooled liquid is condensate recycled
from the process and sprayed into the first vessel 12.
Sprays are used in order to maximise the contact area of
the sub-cooled liquid and the gas and thus the cooling
effect of contact of the sub-cooled liquid with the wet
sour gas.
The dry sour gas at a pressure of 10 to 30 bar lower
than the pressure upstream of the expansion device 24 and
at the operating temperature of the,first vessel 12 is
directed via second heat exchanger 36 in conduit 35 to a
second flash tank 40. It~is cooled in the second heat
exchanger 36 to form a two-phase mixture of gas and
condensate at a .temperature higher than -56 °C. Not shown
is that additional cooling may be provided by indirect
25 heat exchange with a refrigerant that is circulated
through an external refrigeration cycle, for example a
propane refrigeration cycle. In the second flash tank 40,
condensate is separated from the dry sour gas stream. The
liguid stream exits the second flash tank 90 via liquid
outlet 42 and is sufficiently cooled to satisfy the
criteria of a sub=cooled liquid that may be fed to the
sub-cooled liquid inlet 26 of the first vessel 12. The
sub-cooled liquid is supplied through conduit 43,
provided with a pump 94 to the sub-cooled liquid
inlet 26.
The dry sour gas exits the second flash tank 40 via
gas outlet 47 and is fed through conduit 45 to the
intermediate heat exchanger 22 and from there to an end
user (not shown).
As observed earlier, the present invention relates to
dehydrating natural gas by forming hydrates. To prevent
hydrates from blocking outlet 28 and conduit 29, the
condensate present in the lower portion of the first
vessel 12 is preferably heated. This is suitably done by
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introducing a warm liquid into the first vessel 12 below
the level at which the feed stream is introduced.
A portion of the stream of warm condensate separated
in the first flash tank 16 is fed through conduit 17 and
inlet 1B to the first vessel 12. The warm condensate is
sufficiently warm to liquefy hydrate formed in the first
region of the first vessel 12. As the hydrates melt, the
gas trapped in the hydrate lattice is liberated and the
water goes into solution with the condensate. In addition
at least a portion of thq condensate separated in the
water/condensate separator 30 can be recycled for use as
the warm liquid used for heating the solids of the
freezable species in the first vessel 12 through
conduit 37 (after heating, not shown).
Any gas present within the water condensate separator
may be recycled to the first vessel 12. Alternatively or
additionally, a portion of the gas separated in the
water/condensate separator 30 may be recycled to the wet
sour gas feed stream entering the first vessel 12 via
inlet 20.
Suitably the liquid that is sprayed into the first
vessel through inlets 26 is a natural gas liquid, which
natural gas liquid is a mixture of C2, liquefied
petroleum gas components, Cg and Cq and C5+ hydrocarbon
components.
Suitably, the warm liquid that is introduced into the
first vessel through inlet 1B is also a natural gas
liquid.
Reference is now made to Figure 2 showing a further
embodiment of the present invention. In this further
embodiment dehydrated gas is treated to remove sour
components from it. The dehydration process is discussed
with reference to Figure 1, and will not be repeated
here. Farts having the same function as parts shown in
rigure 1 get the same reference numeral.
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The dry sour gas exits the second flash tank 90 via
gas outlet 97 and is fed to a,second vessel 14 via dry
sour gas inlet 46. As with the first vessel 12, the dry
sour gas being fed to the second vessel 19 may be
expanded through a Joule-Thompson valve 98 or other
suitable expansion means, such as a turbo expander, in
order to further cool the gas. As before with the first
vessel 12, the Joule-Thompson.valve may define th.e dry
sour gas inlet 46. The temperature of the dry gas
entering into the second vessel 14 is at a second
operating temperature. The second operating temperature
is the maximum temperature at which solids of the sour
species are formed or the temperature at which the sour
species dissolve in a liquid.
The gas exiting the second vessel 14 via outlet 62 is
dehydrated and sweetened. The dry sweetened gas would
typically be at a pressure of between 20 and 50 bar and a
temperature of not lower than -85 °C. This product stream
of sweetened dry gas is typically transported to the end
user at ambient temperature.
The product stream of dry sweetened gas can be
further cooled by allowing the gas to expand in expansion
device &3, and the further cooled dry sweetened gas is.
used in one or more of the heat exchangers 38, 36 or 22
to effect cooling of one or more of the other process
streams within the apparatus 10. Please note that the
temperature to which the dry gas is cooled in heat
exchanger 36 is greater than that at which the solids of
the sour species form for the given line pressure.
Through outlet 52 a liquid is removed that contains
the sour species.
The dry sour gas was cooled to the second operating
temperature by allowing the gas to expand in Joule-
Thompson valve 98. P.lternative,l_y, the dry sour gas can be
'5 cooled using one or more sprays of a sub-cooled liquid
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.supplied through inlet 49. In a further alternative
embodiment, the natural gas feed stream is cooled by both
the Joule-Thompson valve 48 and the sub-cooled liquid
supplied through inlet 99. In case of spray cooling, the
dry gas can enter into the second vessel 14 at a
temperature that is at'or above the temperature at which
solids of the sour species are formed or the temperature
at which the sour species dissolve in a liquid.
The sub-cooled liquid inlet 49 should be located in
the second vessel 14 above the dry sour gas inlet 46. In
the illustrated embodiment the sub-cooled liquid inlet 49
is a plurality of spray nozzles. The temperature and
pressure conditions in the second vesse1.14 are adjusted
so as to form solids of the freezable species_ For
sweetening of a gas, the temperature-pressure conditions
need only be adjusted to form solids of hydrogen sulphide
(H2S) and carbon dioxide (C02). However; the process
conditions within the second vessel are sufficient to
cause the formation of solids of the freezable species of
other hydrocarbons such as benzene; toluene, ethylbenzene
and xylene.
Suitably, the sub-cooled liquid is part of the liquid
passing through conduit 43. In order to reduce the
temperature the liquid is passed through conduit 50 to
the heat exchanger 38 where it is, cooled by indirect heat
exchange with dry sweetened gas. The dry sweetened gas is
then passed through conduit 65 to heat exchanger 36 for
cooling the dry sour gas from the first vessel 12.
The dry sweetened gas is then fed to the intermediate
heat exchanger 22 and from there to an end user (not
shown).
Applicant had found that in particular the
concentration of C2-C4 hydrocarbon components in the
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liquid should be in the range of from 0.5 to 1.5 mol per
mol of C02 in the feed gas. The liquid in the second
vessel 14 is the liquid sprayed in the vessel through the
inlet 49. Thus the concentration of C2-C4 hydrocarbon
components in th.e sub-cooled liquid should be in the
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specified range. It will be understood that if the
concentration of C2-Cq hydrocarbon components in the
liquid stream in conduit 50 is too low, additional C~-Cq
hydrocarbon components can be added to this stream.
To prevent sour species from blocking outlet 52, the
condensate present in the lower portion of the second
vessel 19 is preferably heated. This is suitably done by
introducing a warm liquid through warm condensate
inlet 56 into the second vessel 14 below the level at
which the feed stream is introduced. A suitable liquid is
liquid passing through conduit 50. Alternatively liquid
passing through conduit 31 can be used.
Further optimisation of the above discussed flow
schemes to improve heat integration is possible. For
example part of the hydrocarbon liquid stream leaving the
second vessel 14 through outlet 52 can be recycled to
inlet 26 of the first vessel 12. In order to do so a
separation vessel (not shown) is used to separate a
stream of liquid enriched in sour species from the
hydrocarbon stream that is recycled.
