NATURAL GAS

Why?
- Abundant reserves
- Low cost
- Clean (less CO2 and NOx)  transition fuel
- Flexible
- Versatile
Uses?
- Electric power generation
- Heating
- Synthesis of chemicals
- Fuel for vehicles
Composition?
- Depends on location
- Mainly CH4 and light hydrocarbons (C1 – C6), CO2, N2, H2O, SOx, Hg
- Smell additive of “rotten eggs” since natural gas has no scent
Where?
- North America
- Australia
- Russia
- Iran
- Quatar
- Italy gets natural gas from: Northern Europe, Russia, Algeria, Lybia and USA (LNG).
Forms?
- Conventional NG, onshore and offshore
- Unconventional NG: Hydrates
Coal-Bed methane
Shale gas
Tight gas
Bio-gas
5 key question for the energy industry
1. How much more energy do we need?
2. When is global demand likely to stop growing – peak oil?
3. What can we expect about electric mobility?
4. How fast will energy from renewable grow?
5. Is the transition to lower carbon system fast enough?
GAS TREATMENT PLANTS

Specifications

HHV HHV Wobbe Index is the indicator of combustible

WI= =
ρfuel √ Specific Gravity interchangeability, all gas-fired equipment is designed for a WI
√ ρair range.
Common WI for natural gas is 48 – 53 MJ/Nm3
Natural gas contaminants
Natural gas must meet specifications also on contaminants content:

Measure Unit Pipelines NGL recovery plants

H2 S ppm vol <4 <4
CO2 % mol <2 < 0.005
N2 % mol Not specified < 1.4
Depends on
BTEX ppm vol < 10
equipment
H2O dew point °C < - 10 @70 barg < - 100 @ 70 barg
Water
Where? From formation water associated to the reservoir and from the upstream processes.
Why? Avoid condensation, corrosion, formation of hydrates and freezing in cryogenic NGL
recovery plants.
Admissible content? 0.1 – 150 ppmv.

Hydrates

Crystalline water-based solids with different structure, small gas molecules are trapped inside frozen
molecules of water.

Formation is possible only in presence of:

- Water
- Hydrate formers
- High pressure
- Low temperature

Inhibitors:

- MeOH or MEG, control the thermodynamic of the process. Lower hydrates formation
temperature.
- Control kinetic of the process.

Sulphur compounds
Why? Avoid SOx formation, toxicity and corrosivity of H2S.
Mercury
Forms?
- Dissolved elementary mercury
- Dissolved organic mercury
- Complexed mercury
- Inorganic mercury salts
- Suspended particles
Why? Avoid embrittlement and cracking of aluminium equipment (Heat Exchangers) causing
mechanical failure and gas leakage, avoid formation of amalgams with water, avoid poisoning of
catalysts, toxicity.
Admissible content? Removal below detectable limits, as much as possible.
Carbon dioxide
Why? Avoid corrosion problems and freezing.
BTEX
What are? Benzene, toluene, etilbenzene and xilene.
Why? Carcinogenic, avoid freezing.
Acid gas removal
Increased energy demand  need to use also sour reserves, not only sweet ones.
The removal of acid gases is a fundamental step, which can be carried out in different ways:

1. Amines
What are? Compounds with at least one hydroxyl group (OH) and one amino group (NH2).
OH increases water solubility and consequently reduces vapour pression
NH2 provides alkalinity and promotes reaction with acid gases
Types?
Commercial:
Primary amines = mono-ethanolamine MEA
di-glycolamine DGA Easily available in the market.
Secondary amines = di-ethanolamine DEA Performance can be predicted using
Tertiary amines = Methyl-di-ethanolamine MDEA simulation programs.

Tri-ethanolamine TEA
Proprietary:
- Licensed;
- Enhanced performances in acid gas removal and regeneration energy;
- Higher cost;
- Reduce equipment size and solvent circulation;
- Contemporary removal of sulphur components such as mercaptans, COS,… which cannot
be removed with amines;
- Amine performance cannot be predicted by using softwares.
Reactions?
The amine reacts both with CO2 and H2S:
𝐻2𝑆 + 𝑅1𝑅2𝑅3𝑁 ↔ 𝑅1𝑅2𝑅3𝑁𝐻+ + 𝐻𝑆− reacts giving amine hydrosulphide
𝐶𝑂2 + 𝐻2𝑂 + 𝑅1𝑅2𝑅3𝑁 ↔ 𝑅1𝑅2𝑅3𝑁𝐻+ + 𝐻𝐶𝑂3− (1) formation of bicarbonate, kinetically slow
𝐶𝑂2 + 2𝑅1𝑅2𝑁𝐻 ↔ 𝑅1𝑅2𝑁𝐻2+ + 𝑅1𝑅2𝑁𝐶𝑂𝑂− (2) formation of carbamate, kinetically fast
Reaction 2 requires the presence of H2, so can happen only with primary or secondary amines.
Tertiary amines are selective solvent for H2S absorption in the presence of CO2.
Process scheme?

Inlet separator = removal of particles and entrainments in feed gas.

Amine contactor = counter – current contactor.
P = 30 – 60 barg, defined by the feed gas.
Lean amine temperature is 5 – 10°C higher than feed gas temperature, to avoid
hydrocarbon condensation.
Wash water pump is used to reduce amine losses.
Sweet gas leaves the column via a demister.
Inter-stage cooling may be used to control the temperature.
Flash drum = Releases co-absorbed hydrocarbon.
P = 5 – 8 barg.
Lean/rich exchanger = pre-heating of the rich amine using the high temperature of regenerated
Lean amine
Can be shell & tube or plate & frame.
Rich amine is corrosive, must pass through tube side and not shell one.
Amine regenerator = Stripping with steam generated by boiling the amine solution in the reboiler.
The top gas is partially condensed, acid gases are removed and condensate
is recycled.
Reboiler = Kettle or thermosiphon.
Heat is supplied by low pressure steam (at least 3 – 5 barg).
Limited temperature to avoid amine degradation.
The higher the reboiler duty, the lower the residual lean amine acid load.
Ratio steam [kg] / solvent circulation (L) = 0.1 – 0.13.
Lean amine booster pump = increase regenerated lean amine pressure.
Lean amine cooler = cools the regenerated amine down to 40 – 60 °C.
Parameters?
Amine solution concentration =
- Higher concentration = less required solution circulation = saving CAPEX and OPEX
- High amine concentrations lead to different problems:
Increased corrosion problems
Increased viscosity, causes mass and heat transfer problems
Increased temperature of the absorber, due to the higher heat of reaction

- Typical amine concentrations:

MEA 15/20 %wt.
DEA 20/40% wt.
MDEA 40/55% wt.
Amine acid loading =
- Typical amine loading: mol CO 2+ mol H 2 S
MEA 0.35/0.40 mol/mol AAL=
mol AMINE
DEA 0.35/0.40 mol/mol
MDEA 0.45/0.50 mol/mol
- Solvent circulation must be high enough to guarantee this ranges.
- Higher values would cause corrosion.
Corrosion =
- Rate depends on: Type of amine
Amine concentration
Acid gas loading
Temperature
Presence of degradation products

- Corrosion cannot be eliminated, but it must be limited by a proper design:

Rich acid gas loading must be maintained within the loading range.
Velocity of rich amine must be limited to 1 – 5 m/s.
Alternatives to amine process:
1. Potassium carbonates
K2CO3 aqueous solution 30% wt.
Higher operating temperature (110°C) to keep the carbonate dissolved in the water.
Mainly used for CO2 removal.
Reactions:
𝐾2𝐶𝑂3 + 𝐶𝑂2 + 𝐻2𝑂 ↔ 2𝐾𝐻𝐶𝑂3 slow rate, necessity of speeding up with additives
𝐾2𝐶𝑂3 + 𝐻2𝑆 ↔ 𝐾𝐻𝑆 + 𝐾𝐻𝐶𝑂3 very difficult regeneration of KHS
2. Physical absorption
What is?
- Use of an organic solvent to absorb acid gases
- No reactions
- CO2 desorption by reducing the pressure in multi-stage flash
- If H2S is present, additional columns are required
- Gas separation is based only on different solubility
H2
CO2
H2S
Hexane
Benzene solubility

When is physical absorption more convenient?

- High concentrations of CO2
- Presence of gas impurities
- Low quantity of hydrocarbons (more soluble in water than CO2 and H2S)
 2. Membranes
How?
- Polymeric membrane through which only CO2, H2S and H2O pass. The components
dissolve into membrane surface and diffuse through it.

- Driving force = pressure difference (max 100 bar).

Types?
- Flat sheet combined in a spiral – wound element.
- Hollow fibers (filtra a manica) like a shell & tube exchanger.
When?
- High concentration of CO2, low concentration of H2S.
- Typically applied in offshore acid gas treatment installation.
Advantages?
- Static separation, no moving parts.
- Simple operation.
- Reduced footprint.
Disadvantages?
- Require pre – treatment section to remove water and heavy hydrocarbons, in order to
avoid damages due to condensation.
- Deep removal of CO2 is not possible, only bulk removal.
Inlet 30% CO2  Outlet 6% CO2
- Permeate gas is at low pressure, need to compress and spend money.
- Hydrocarbon losses.
Increase selectivity?
- Two stage membranes with inter – compression  $$$
- Hybrid system, membrane separator followed by amine absorber

3. Cryogenic distillation
Problems?
- CO2 /C2 azeotrope.
- CO2 freezing point: high operating pressure avoids CO 2 solidification, but in this condition
the CH4 rich gas is in critical conditions and CO2 removal is difficult.
Process?
Ryan Holmes cryogenic fractionation.

Characteristics:
- CO2 solidification and CO2/C2 azeotrope are avoided by means of an additive = butane.
- Ethane recovery = ethane separation
- Bulk CO2 recovery column = from the bottom liquid CO2 (90% purity) is recovered and
pumped into wells for enhanced recovery.
- Cryogenic demethaniser = production of sale gas which doesn’t require any additional
processing facility (50 ppm CO2, 4 ppm H2S)
- Additive recovery = recovery and recycle of butane, NGL recovery.

4. Liquid redox
What?
- H2S removal and conversion to solid elemental sulphur.
 - Iron catalysed

When?
- Small H2S quantities
Advantages?
- Very high efficiency >99%
- No hydrocarbon losses
Disadvantages?
- S not economically useful

5. H2S scavengers
What?
- H2S adsorption on solid non regenerable beds (Zinc zeolites)
- Contemporarily removal of H2S and CO2
Advantages?
- Very high efficiency
- Low capital cost
Disadvantages?
- High OPEX due to expensive adsorbent material and disposal of spent material

6. Molecular sieves
What?
- Alumina silicates with uniform pore crystalline structure
- They adsorb molecules that fit into pores
- The more the polarity, the easier the adsorption
When?
- Deep removal of H2S, not able to remove CO2 yet
Handling and valorisation of gas field by-products
Acid gas from gas fields:
- T = 40 – 50°C
- P = 0.2 – 1 barg
- May contain H2S or hydrocarbons such as BTEX  contaminants determine acid gas
destination
If no H2S is present:
- Released in the atmosphere, only if there are no BTEX
- Thermal oxidizers, obliged in presence of BTEX
If H2S is present:
- Sulphur recovery in order to cope with environmental regulation. Once sulphur has been
recovered, the gas is released in the atmosphere or burned.
- Re-injection into wells

Sulphur recovery unit

For high concentrations of H2S  60% mol

Claus process to convert H2S into liquid sulphur.
H2S/SO2 = 2
 1. Claus section

Catalytic region:
2 H2S + SO2  3/x Sx + 2 H2O Claus reaction
98% conversion
Equilibrium favoured by low temperature.
Al2O3 catalyst, deactivated by S condensation.
Thermal region:
H2S + 3/2 O2  SO2 + H2O Partial oxidation
2 H2S + SO2  3/2 S2 + 2 H2O Conversion to sulphur
70% conversion
HIGH T  LOW T
S2  S4  S6  S8

Firstly, sulphur is recovered in a thermal reactor (50 – 70 % S recovery):

- Burner control system to ensure H2S/SO2 = 2
There are 2 converters:
- First Claus converter = 230 – 240 °C
85 – 90 % S recovery
COS and CS2 produced in the burner are hydrolysed to H2S
Titania catalyst
Outlet temperature is higher than S dew point, there is the need for
condensation. It must be higher since S condensation can
deactivate
the catalyst.

- Second Claus converter = 210 – 220 °C

95 % S recovery
1. Tail Gas treating section
Still contains traces of H2S which shall be reduced to target ambient emission limits.
Treating section allows obtaining 99.9 % S recovery. Off-gas is sent to thermal oxidizer.
Hydrogenation reactor = SO2 and S (gas) are reduced to H2S  hydrogenation
COS and CS2 hydrolysis to H2S and CO2  hydrolysis
Quench tower = H2O separation.
Amine absorber and regenerator = H2S is separated by amine absorption and recycled back to
Clasu section.
 2. Degassing section
Liquid sulphur still contains vapour H2S, which must be separated to reduce toxic and explosive
hazards.
Sulphur can be sold as: liquid sulphur or solid granulated sulphur. Many applications: fertilizers,
chemicals, rubber, plastics, …
The principal sources of sulphur for industries are gas fields and oil sands.
Safety and environmental issues in handling sour gases
Prevention:
- Identificazione delle sostanze pericolose e caratteristiche principali
- Calcolo e confronto con i valori di soglia del pericolo
- Standard e regolamenti
- Obblighi ambientali
- Misure preventive (isolazione, depressurizzazione, distanze di sicurezza, …)
- Misure di protezione (protezione antincendio, apparati respiratori, …)
- Verifica della sicurezza dell’impianto e monitoraggio
Valori di soglia:
- LC50 = concentrazione letale che ucciderebbe il 50% dei soggetti esposti a un singolo
avvenimento
- IDHL (Immediately Dangerous to Life and Health)= massima concentrazione che permette
di scappare entro 30 minuti dall’evento senza ricorrere in pericoli o danni alla salute
- TLV (Threshold Limit Value) = TLV-STEL per esposizione continua per 15 minuti
TLV-TWA pesata per 8 ore lavorative al giorno
- Limiti di infiammabilità
- VOC
- TSP (Total Suspended Particles)
Nel caso dei gas acidi, i principali problemi sono dovuti a:
- HC = infiammabili
- H2S = tossico e infiammabile
- CO2 = asfissiante
- Hg = tossico

Obblighi ambientali:
- Contaminazione delle acque = evitare dissoluzione delle sostanze acide
- Contaminazione del suolo = evitare perdite di idrocarburi durante il processo e il trasporto
delle sostanze
- Efficienza energetica = aumentare l’efficienza per ridurre le emissioni
Natural Gas Dehydration

Glycol Dehydration Molecular Sieves Silica Gels

H2O
60 – 150 ppm mol 1 ppm mol 30 ppm mol
content
H2O dew
−10 °C −100 °C −40 °C
point
Very simple Ultra-high water removal Concurrent HC removal
Pros
Better economics Fixed bed operation Fixed bed operation
Solvent losses
Cyclic process
Affinity for BTEX Cyclic operation
High temperature
Cons Enhanced regeneration High temperature
required
required for ultra-high required
Licensed process $$$
purity

Dew point control units Dew point control units

Field Gas dehydration for NGL
Mild dehydration for Mild dehydration for
applications recovery and LNG plants
pipeline transportation pipeline transportation

Depending on the final purpose (admissible water content) one of the previous methods is chosen.
1. GLYCOL DEHYDRATION

Glycol = Alcohols with two hydroxyl groups. Polarity enhances combination with water.
High purity TEG is the most applied solvent.
150 ppm mol H2O
P = 30 – 50 barg
T = 30 – 60 °C

P = 0 – 0.5 barg
Glycol regeneration

T = 200 °C
Avoid TEG degradation
Better performance: ultra-high purity glycol by adding a stripping gas (same temperature, same
pressure, better purification).
Calculation procedure: with maps for first evaluation, then implementation on Aspen Hysis.
PROS:
- Low CAPEX/OPEX when mild dehydration is required
- Low energy requirements
- Possibility for modularization
- Low cost solvent
CONS:
- High affinity of glycol with water and other polar compounds (BTEX)
- Temperature limitations due to degradation

Glycol contactor
- Inlet water content
- Required water content (dew point)
- Operating temperature
- Required glycol purity
- Reboiler temperature

We obtain the number of trays (trayed column) or the packing height (packed column) of the
glycol contactor.

Glycol regeneration
More problematic: limit in temperature because of glycol degradation. Degradation temperature
limits the purity of the glycol, since for higher purity I should have higher temperatures.
Enhanced TEG regeneration systems
a. Stripping gas = usually fuel gas.
99.99 wt %
The more the gas, the more the purity, the bigger the column.
b. Vacuum = lowering the pressure decreases boiling temperature.
c. Licensed methods.

2. MOLECULAR SIEVES
Molecular sieves = solid zeolites (aluminium silicates) with uniform pore crystalline structure.
Usually provided as pellets.
Physical adsorption of gas molecules depends on:
- Molecule dimension
- Polarity = the higher the better

Molecular sieve unit = N-multiple beds working in sequence (cyclic process)

Adsorption phase at low temperature
Regeneration phase at high temperature: Heating, Cooling, Stand-by.
Concomitant removal of sulphur compounds and BTEX. Water is more
rapidly adsorbed than other contaminants
PROS:
- Ultra-high water removal
- Simultaneous removal of sulphur and BTEX
CONS:
- 10% of gas that should be treated is used for regeneration = auto-consumption
 - High temperature required for bed regeneration. Usually the bed is working in cryogenic
units!
- Cyclic process = peaks in temperature and composition profile
- Regeneration gas management

3. Silica gels
Silica gels = porous vitreous solid in form of beads. Higher pore size than molecular sieves.
Simultaneous adsorption of water (active surface) and heavy hydrocarbons (capillary condensation
inside the pores).
Similar process scheme of molecular sieves.
Mercury removal
Simple fixed bed adsorber, provided with an after filter to remove dust from the gas flow.

There are two types of equipment:

- Regenerative = Silver activated zeolites.
Can be put in molecular sieves, where both water and mercury are
removed.
Smaller volume.
Capacity depends on flow rate, concentration of mercury in feed stream,
time.
- Non-Regenerative = Based on chemical reactions between mercury and metal oxides.
6/9 years of operation.
Higher cost and bigger volume.
Based on sulphur (risk of sulphur dissolution) or metal oxides.
Different configurations:
- Regenerative = on the bottom of molecular sieves, no need to have an additional
equipment for mercury removal. In case of dust, add a downstream removal.
- Upstream = if content of mercury is very high and is dangerous for CO2 removal equipment.
If it enters CO2 removal equipment it enters the liquid phase.
- Downstream = no CO2, no H2O, pure mercury removal process.
NGL recovery
What? C2, C3, C4, C5 +
Why? Achieve requested specifications, produce feedstock for refineries or petrochemical plants.
If not recovered, it remains in the sales gas.
Why deep ethane recovery? Increase heating value, low amount of by-products (efficiency), value
as petrochemical/refinery feedstock.

Tolerance to inlet CO2:

CO2 content is one of the most critical

parameters.
Avoid freezing in the coldest section
of NGL recovery units.
The higher the CO2, the lower the
recovery.

Technologies:
Cooling based processes:
Joule – Thomson expansion
Most simple NGL recovery process.
Pre-cooling of the inlet stream.
Iso-enthalpic expansion valve cools the gas, liquid is
separated from the gas phase in the Low
Temperature Separator.
Limited recovery (30%).
High pressure drops, re-compression of the gas is
mandatory.
Turboexpansion Iso-entropic expansion in a turbine.
Work recovery (from turbine to
compressor).
More efficient.
New technology = active magnetic
bearings, uses magnetic field to
suspend the cylinder and avoid friction
limitations.

Mechanical refrigeration
Same scheme of Joule – Thomson expansion, but the external cooling is not provided by a valve
but a heat exchanger.
The refrigerant is usually propane.
Higher efficiency.
Requires an external refrigeration unit:
Process gas cooling is achieved by vaporization of
the refrigerant.
P, T chosen to minimize the exchange surface and
the compression power.
The higher the pressure, the better the
performance.

Technology comparison:

Technology selection depends on design

parameters:
Feed composition, flowrate, temperature
and pressure.
Impurity levels.
Maximum specific power requirements.
Enhanced NGL recovery processes:
Gas Sub-Cooled Process (GSP)
Recycle Split Vapour Process (RSV)
Additional reflux for higher recovery levels (> 99%).
Non-cooling based processes:
Silica gel adsorption for heavy hydrocarbon recovery.
Supersonic separation
Optimization of the recovery rate of
C2 and C3 (> 90%).
Part of the cold gas is fed to a
demethanizer column using a
turboexpander, while the remaining
is condensed and subcooled.
Condensation and sub-cooling are
possible thanks to the higher
pressure of the blue flow.
Use of a convergent – divergent nozzle to
cool and condensate the gas (pressure is
converted into kinetic energy).
Liquid droplets are collected on the walls
by centrifugal forces and removed in
dedicated vessels.
Limited flexibility, it is based on fluid
dynamics.
Sales gas compression
Sequence of centrifugal compressors driven by:
- Electric motor with fixed or variable speed.
- Steam turbines.
- Combustion gas turbines.

NGL fractionation
Why? NGL are valuable by-products of the raw natural gas processing. They are feedstock for
refineries or petrochemical plants and can be sold separately.
How? Fractionate distillation, many distillation columns in series which progressively separate NGL
basing on the boiling points.
Ethane
Propane
Butanes
Gasoline
De- ethanizer =

P = 25 – 35 bar

CO2, H2S, H2O concentrate in ethane stream

Ethane is condensed by means of a top reflux of ethane

itself.

De-propanizer = 15 – 22 bar
Propane is condensed by means of water/air.
De – butanizer =

P = 6 – 10 bar
Water/air condensers.
Iso-pentane problematics = it is too
heavy for the top stream and too
light for the bottom stream. It must
be removed otherwise it
accumulates inside the column.