Natural Gas Sweetening

Membrane Separation
Preference of Membrane over Absorption?
CO2 Separation
•The content of carbon dioxide in natural gas and hydrocarbon gases is variable and can
be as high as 40-60% in cases with predictions as high as 80% as hydrocarbon
capacities decline.
•These high content CO2 gases can often arise from the practice of enhanced oil
recovery (EOR). In miscible-flood EOR, the oil bearing strata is injected with CO 2 to
stimulate oil recovery. Gas released by this process at the well head is therefore heavily
laden with CO2 and is in need of treatment.
•All appropriate gas permeation membranes show much higher affinities for carbon
dioxide than methane with permeability ratios greater than 20.
•This therefore enables effective CO 2 removal from hydrocarbons. Modules used for
separation are hollow fibre designs with double-ended tube sheets.
• The feed gas is introduced to the outside of the fibre bundle with the CO 2 rich stream
permeating to the inside of the fibres and the hydrocarbon rich steam flowing to the
central core of the module where it is piped away.
• The application of the membrane units depends
upon the scale of the operation.
• Single stage membrane units are suitable for
low flow rate application but with higher
flowrates multiple module designs with gas
recycle are used to minimize losses of
hydrocarbons.
• In this operation the permeate gas (CO2 rich)
has sufficient calorific value to be used as a
fuel.
 Enhanced oil recovery by CO2
•Enhanced oil recovery processes are often used to
increase production from depleted fields. High pressure
CO2 is pumped into the ground at the periphery of the
field and diffuses through the formation to drive residual
oil towards the oil wells.
•Large quantities of CO2 are required in the initial stages
of the process.
•In time the CO2 arrives at the well head and the
concentration of CO2 in the gas associated with the well
will increase to values as high as 70% to 90%. The
objective of the gas separation is to recover the natural
gas and also the CO2.
•The CO2 is recompressed and re-used in the process. The
variable composition of CO2 in the gas makes membrane
separation more attractive than amine absorption, and
especially when high CO2 concentrations are
encountered.
•The operation of the system requires optimization of the
permeate pressure- high permeate pressure minimizes
recompression costs but decreases membrane efficiency.
Membrane carbon dioxide removal from
NGL
• A membrane gas-processing technology for CO2 removal has been developed that lowers
operating costs by reducing membrane surface-area requirements using "sweep gas"
technology.
• The process treats the separated NGL stream instead of the raw inlet-gas.
• The gas plant extracts NGLs from sweet natural gas produced at various offshore platforms. The
plant uses cryogenics to extract up to 86% of the incoming C2 and virtually all C3+ fractions.
• The CO2 concentrates in the liquid ethane product becomes overly contaminated therefore out
of sales specification.
• As the boiling points of CO2 and C2 are similar so the plant was operated with a warmer than
desired bottom reboiler temperature to remove the CO2 which also removed part of the
ethane product liquid.
• If operation is performed at lower temperature then the concentration of methane will be
limited.
How to avoid this problem?
Membrane Separation set up
• In a typical setup for semi-permeable membrane separation, the
stream to be purified is introduced at high pressure on the exterior
(shell side) of the membrane fibre.
• The higher permeable components like CO2 travel through the fibre
wall and are collected at low pressure in the centre bore as a gas.
• This gas in the bore then flows out both ends of the membrane unit at
approximately atmospheric pressure ‘ in order to maximise the
pressure difference across the membrane fibre to increase the driving
force across the fibre wall.
Conti…
• The membrane unit was modified so that the low pressure permeate may be
purged and diluted by a flow of fuel gas countercurrent to the flow of the high-
pressure stream.
• Pressure regulators are arranged so that the flow of fuel through the membrane
unit is maintained. The outlet of the permeate side of the membrane, which will
contain a mixture of permeated impurities and fuel gas, is operated at a pressure
just sufficient to enter the plant' s fuel system serving plant boilers, engines or
other fuel users.
• Despite the higher total back-pressure on the permeable membrane, the dilution
effect actually reduces the partial pressure to the extent that overall driving force
across the membrane is increased.
Conti…
• In the case of an NGL feed stream, the driving force for the CO2 is increased by
a greater proportion than that for the hydrocarbon, thereby improving membrane
selectivity, or separation factor.
• In a fuel gas sweep of 15% of the molar flow rate of liquid is used, the driving force for
CO2 removal is increased by approximately 17%, whereas the driving force for product
hydrocarbon loss by permeation remains relatively unchanged.
• As the ratio of molar flow-rate of fuel-gas sweep to molar flow-rate of liquid product is
further increased, the partial pressure on the permeate side of the membrane is further
reduced, causing an even greater driving force.
• In the actual application, the liquid would go into a pipeline after being treated.
The sweep gas was introduced on the tube side of the device and the permeate
stream drawn off near the bottom of the case.
Conti…
• The resulting permeate gas volume is small and is sent to the flare. In the
actual application, this permeate gas would be sent back to the fuel-gas
system.
• The membrane system operated at liquid feed pressures up to 1000 psig
while the permeate pressure was at 100 psig.
• The analysis of the permeate gas samples consistently showed negligible,
if any, heavy hydrocarbon constituents, confirming that the membrane
device is operating successfully.
Separation of Hydrogen Sulphide and Water Vapor
Natural gas is often saturated with water at the well head and this has important
implications in subsequent pipeline transport.
- Under high pressure, water reacts with methane to form solid methane hydrate
which could lead to blocking of the pipeline if left unchecked.
- In the presence of CO2 and/or H2S condensation of water in pipelines will lead to
the formation of aqueous S2-ions and carbonic acid which will react with and thus
corrode pipelines.

• The formation of methane hydrate can occur at temperatures below approximately 13C at
typical pipeline pressures of 70 bar.
• Prevention of this requires removing as much water as possible and adding an inhibitor,
e.g. ethylene glycol or methanol. Glycols are also useful dehydration agents and are used
to remove water.
• This may also include the use of a silica gel or molecular sieve solid bed adsorption
(dehydration) unit. Glycol used in dehydration in offshore platforms, requires regeneration
in situ for re-use. This is normally achieved by heating at reduced pipeline pressure.
Dehydration by Gas Permeation
• Gas permeation is a possible method of dehydration as most
membranes are very permeable to water vapour
with reported selectivities over CO2 of greater than 100 (up to 1,000
for cellulose acetate).