FROM NG TO LIQUID AND SOLID

Why?
Conversion to higher value liquids/solids  adding value
Monetizing remote gas reserves
Crude oil prices are very high  alternative

Syngas
What is?
- Hydrogen
- CO
- CO2
NG is one of the main sources for syngas production.
Production?
Steam Reforming

- Most used technology

- Requires steam
- Endothermic process  heat provided by burning some of the feedstock gas
- WGS reaction to adjust CO/H2 ratio
- Catalytic
Partial Oxidation
 - Non-catalytic reaction
- Requires oxygen feedstock

Autothermal Reforming

- Combination of steam reforming and partial oxidation

- Catalytic reaction
- Autothermal  heat necessary for reforming is provided by partial oxidation
GAS TO LIQUIDS
Fischer Tropsch process

It is an alternative to crude oil refining to produce heavier hydrocarbons starting from syngas. It is
an exothermic and catalytic reaction. It is economically convenient when syngas comes from
refinery, nowadays the process of NG  syngas  FT is too expensive.

Product composition depends on:

- Operating conditions (Temperature, Pressure, H2/CO ratio)
- Type of catalyst
Main GtL products are:
- Diesel/gasoline
- Kerosene for aircraft
- Lubricants
Advantages compared to oil refining:
- Better thermal stability
- High cetane number
- Sulphur free process
- Zero aromatics
Methanol synthesis
Why methanol?
- Important chemical feedstock
- Gasoline blending substance, higher octane number than gasoline
- DME production as replacement of diesel
Haldor Topsoe process

80 bar

Hydrogenation and desulphurization

Why? S is poisonous for the reforming and methanol catalyst.

Both reactors contain catalyst.

Hydrogenation reactor uses H2 to convert SOx
into H2S.
Desulphurization reactor uses ZnO based catalyst
to stock S as ZnS.

Reforming
From the reforming train we obtain syngas. Three stages reforming:
- Adiabatic pre-reformer
- Primary reformer
- Autothermal catalytic secondary reformer fired with oxygen
Pre-reformer:
- Converts almost all heavy hydrocarbons
- No heat supplies  adiabatic
- T = 500°C
- Catalytic
- The aim is to reduce the load of the primary reformer and prolong the life of primary
reformer catalyst
Primary reformer:
- Heat provided by means of burners
- Catalytic
- T = 1100°C
Secondary reformer:
- Oxygen addiction
- Heat is supplied by combustion reaction
- Catalytic
- Residual methane conversion
Syngas cooling
Generation of high-pressure steam.
Syngas compression
Compression to 80 bar.
Methanol synthesis

- Exothermic and catalytic reactions

- Heat is used for steam generation
Methanol distillation

Methanol

Stabilized methanol,
Water and methanol
ù
water and higher alcohols
3-column distillation system:
- First column = removal of light components, used as fuel. From the bottom we obtain
stabilized methanol, containing water, ethanol and higher alcohols.
- Second column = removal of methanol from the top.
- Third column = final separation in liquid methanol, water and liquid off stream (higher
alcohols).
Ammonia synthesis
Desulphurization
Why? S is poisonous for the catalyst. Hydrogenation to H2S followed by sulphur fixation as ZnS
Reforming
The aim is the production of syngas.

Primary reformer:
- Catalytic
- Radiating section = reforming inside tubes, heat provided indirectly by burners
- Convective section = heat is provided directly by combustion reaction
Secondary reformer:
- Residual methane conversion
- Heat directly provided by combustion reactions
- Catalytic
- Air quantity is fixed to achieve H2/N2 = 3
Shift section
- Oxygen compounds are poisonous for ammonia catalyst
- WGS reaction
- Two adiabatic reactors: the first at High temperature and the second at Low Temperature
CO2 removal
- Physical adsorption with organic solvents (CH3OH)  Rectisol
- Chemical adsorption with inorganic solvents (K2CO3)
- MDEA chemical/physical adsorption  BASF
- Max 500 ppm mol
Methanation

Residual CO2 is converted into methane, inert gas in the ammonia synthesis. Max 5 ppm mol.
Ammonia synthesis
- High P (>250 bar)
- Low T (<200°C)
- Catalytic
- High equilibrium concentration of ammonia
- Reversible reaction  30% of N2 is converted, the unconverted are recycled after
separation of liquid ammonia
As by-products we obtain a lot of CO2, which can be combined with NH3 to produce urea.
Urea formation

CO2 and NH3 reacts to produce carbamate, a portion of which dehydrates to form urea and water.
The first reaction is completed, the second reaction is slow ad determines the reactor volume.
The fraction of carbamate that dehydrates is determined by:
- Reactant ratio
- Operating temperature (the higher the better)
- Residence time
Feedstock and utilities:
- Liquid NH3
- Gaseous CO2
- Steam as heat carrier
- Cooling water as condensing medium
- Power
Equilibrium reaction, to increase equilibrium conversion:
- Excess NH3
- Deficiency H2O
- Higher temperature and pressure
- Equilibrium reaction  conversion will never be unitary, need to recycle unconverted NH3
and CO2
Saipem – Snam process

Blue = carbamate

recovery
Recovery section
Each recovery section has the same scheme:
Decomposition of carbamate and urea concentration
Recovery of carbamate recycle from the section at lower pressure
Carbamate solution accumulation
Carbamate solution recycle to the section at higher pressure

Carbamate decomposition is the reverse of urea production reaction, so it is promoted by:

- Reducing pressure
- Provide heat
- Stripping agent = excess of NH3 and CO2
Liquid carbamate
Process scheme:

MP stripper for carbamate Carbamate collector

Ammonia collector
decomposition
MP absorber Heat exchanger, recovers
energy for NH3 condensation
1. CO2 compression
2. Urea synthesis reactor: T = 188°C
P = 155 bar
Liquid NH3 and carbamate are fed to the bottom from recycle
3. Stripper: carbamate decomposition helped by provision of heat and NH3 as motive fluid.
Stripper gases are condensed and recycled back.
P = 145 bar
4. Medium Pressure Decomposer: P = 17 bar. The purpose of this section is to partially strip
out the reactants, ammonia and carbon dioxide from the urea solution and, after their
condensation in water, to recycle the obtained solution to the reactor, together with the
ammonia and carbon dioxide aqueous solution resulting from the downstream sections of
the plant.
5. Medium Pressure Absorber: performs CO2 absorption and NH3 rectification. Liquid
carbamate from the bottom is recycled back to the stripper, ammonia vapours from the
top are condensed and sent to the ammonia collector.
6. Low Pressure Decomposer: P = 4 bar
7. Carbamate accumulator, from which carbamate is recycled to the MP section. Ammonia
and carbon dioxide are partially condensed in the shell of a preheater within the vacuum
section, thus recovering some energy in the form of 200 kg of steam per ton of urea, with
an investment cost that, even in existing plants, has a pay-back time of less than two years.
8. Vacuum Concentrator: aims to remove carbamate and water in different stages operating
under vacuum conditions. The urea solution leaving the LP section is about 70% and
contains small quantities of ammonia and carbon dioxide. The final concentration of the
urea solution 99.8%. Urea is heated with steam that vaporize water and increase urea
concentration. The necessary heat is provided by partial condensation of the vapours
(ammonia and carbon dioxide essentially) from the MP section evaporator.
9. Condensate treatment: a steam stripping column is used to remove NH3 and CO2 from the
condensate. Urea’s split is converted in NH3 and CO2. The reactants are recycled back to
LP section. The water leaving the unit can be recycled back.
10. Finishing: solidification of urea. The granulator is a fluidized bed, Molten urea (99.8% b.w.)
is sprayed at the top of the prilling tower. A rising draught of air inside the prilling tower is
the cooling medium that removes the solidification heat and cools the prills. Too much air
can entrain urea dust, creating a problem of increase in consumption and pollution. A
dedusting system is mandatory.
GAS TO SOLIDS

Raw Materials Basic Products

Petrochemicals

NG Ethylene Plastics
Virgin naphtha Propylene Elastomers
Coal Butadiene Resins
Aromatics Synthetic fibers

Polymers properties:
- Structure: crystalline-like regions mixed with amorphous domain. Crystallinity is related to
rigidity, strength and opacity.
- Molecular weight is given as average: unlike pure compounds, polymers are not composed
of identical molecules.

- Glass transition temperature: it is a property of the amorphous region, according to

temperature it can be either in glassy or rubbery state.

T < Tg Glass state  molecules are frozen, rigid and hard structure
T > Tg Rubbery state  softness, expansion

Differently from pure compounds, there is

no discontinuity between polymer and
liquid state.

Polymers classification:
Thermoplastic polymers = polymer resin that becomes soft when heated and becomes hard when
cooled, all without any chemical property change. Easily recycled.
Thermosetting polymers = amorphous polymers highly crosslinked, large 3D molecular network.
Hard and infusible structure.
Production chain:
Polyethylene:

HDPE:
- Biggest market, constant growing demand.
- Produced by a low-pressure polymerization.
- Very high crystalline grade due to the linear molecular structure.
LDPE:
- Low-Density Polyethylene
- Low degree of crystallization due to the presence of branching bonds.
- 60% amorphous structure
- Mainly used as “pellicola” and coating
- Produced by a high-pressure polymerization  3000 bar
LLDPE:
- Linear Low-Density Polyethylene produced by a low-pressure polymerization reaction like
HDPE
- Copolymer between ethylene and alfa-olefins (1-Butene, 1-Hexene and 1-Octane).
- The resulting structure is a mix of the linear structure of HDPE with the low density of
LDPE.
- The production process allows to obtain both HDPE and LLDPE  economic advantage
- The operating conditions are less critical compared with the LDPE process.
- It has a big market thanks to minor cost and better performance.
- LDPE is still better than LLDPE for what regards optical properties.
EVA:
- Ethylene Vinyl Acetate
- Used for greenhouse construction, medical applications,… thanks to its resistance to
ultraviolet radiation.
EVA PROCESS

Players:
Ethylene
Vinyl Acetate Monomer
Chain moderator
Peroxide initiator

Ethylene and low-pressure unreacted gas mixture of ethylene and vinyl acetate are compressed in
the primary compressor up to 300 bar. Fresh Vinyl Acetate Monomer, the chain moderator and
high-pressure recycle are added, the secondary compressor increases pressure up to 3000 bar.
Finally, peroxide initiator is fed to the reactor. The reactor can be a tubular reactor or an
autoclave. Tubolar reactors are more expensive but more efficient. Tubes are “pretensionati” to
avoid crack propagation due to high pressure stresses. Reactions are exothermic, so reaction heat
is removed by a cooling jacket. EVA is separated in two separators at different pressure.
The molten polymer is then sent to an extruder and a pelletizer.
The major capital investment is compression. In order to minimize the cost:
- Increase conversion Recycle gas minimization
- Select the lowest acceptable operating pressure Mass flow minimization
Conversion is mainly limited by the ability of removing heat. However, increasing of conversion
means increasing viscosity (higher polymer content), flow tends to laminar conditions (Reynolds
number) and heat transfer is limited. Optimization is mandatory!
HDPE GAS PHASE PROCESS

Inducing Condensing Agent

ISO C5

The gaseous feedstock needs to be purified from oxygen, acetate and sulphur compounds which
can poison the catalyst. The gas phase fluidized-bed reactor consists of a vertical pressure vessel
with an expanded upper section for de-entrainment of polymer particles. Typical operating
temperatures are 85 to 110 °C and a maximum operating pressure 24.1 bar. Liquid level inside the
reactor is kept constant by removing the product. Polymer powder is combined with additives and
processed in a compounding extruder. Pellets are produced in an underwater pelletizer and dried
in a pellet drier.
Alternatively, HDPE can be produced by:
HDPE ZIEGLER SLURRY PROCESS  Hexane dilution
The catalyst is diluted with hexane and fed to the polymerization reactor. There are three reactors
which operates in series and the catalyst is fed only to first reactor. The gas feed mixture consists
of ethylene, comonomer (butene-1), and hydrogen. Polymerization occurs at 5 – 10 bar and
temperature of 75 – 90 °C. The polymers suspension is separated by means of a decanter
centrifuge where the polymers powder is separated from hexane and the comonomer.
Hexane (diluent to reduce viscosity) allows operating at smaller temperature and pressure.
Styrene:

About 80% of styrene is produced by dehydrogenation of ethylbenzene to styrene. Benzene

production comes from reformate or pyrolysis gasoline.
GPPS:
- General Purpose Polystyrene
- Produced through free radical mechanism, no additives
- Easy to process
- Rigid
- Resistant to X-ray
- Used for plastic glasses, kitchen accessories, …
EPS:
- Expanded Polystyrene
- Copolymer with pentane or isopentane
- Light rigid foam
- Good thermal insulation and high impact resistance
- Excellent for packaging and for construction
HIPS:
- High Impact Polystyrene
- Copolymer with rubber
- Very high impact strength due to the addition of polybutadiene
- Used for windows shutters
SAN:
- Styrene-Acrylonitrile Copolymer
- Excellent mechanical properties in aggressive environments
ABS:
- Acrylonitrile-Butadiene-Styrene
- Good chemical resistance
- Low temperature toughness

GPSS PROCESS

Styrene, peroxide, additives (anti-sticking), chemicals (chain transfer), ethylbenzene (diluent to

mitigate viscosity) and recycle organic stream from reaction are fed to mixing tank. Two reactor
CSTR are need in order to allow the peroxide to work effectively (increase residence time) and the
to avoid the deactivation of the unconverted catalyst transferred to the devolatilization section
(200°C). Reaction temperature is between 100-150°C and the pressure is below 0 bar. Boiling of
the monomer and diluents is utilized to control the reactor temperature. The evaporated stream
in each of two reactors is condensed and recycled to the reactors.
After polymerization, the solution is first preheated to 200-240°C. The mixture of the two phase is
flashed in the first devolatilization vessel operating under vacuum. In order to reduce the
monomer concentration below 200 ppm, the polymer is sent to the second devolatilization which
is operated under higher vacuum. Non condensed vapor/inert gases from the vacuum system and
liquid organic purge from the condensation section are recovered as fuel in a furnace.
The molten polymer from the second devolatilization stage is pumped to the pelleting units where
will be cooled by water, pelletized, separated from water, dried and transferred to storage.
EPS PROCESS

First part of this process is similar to the GPPS already seen (polymerization and devolatilization
section). The blowing agent (pentane) required by formulation is added continuously, together
with other additive to enhance the thermal insulation property. Non condensed vapours/inert
gases from the vacuum system and the vent from the extruder will be sent to atmosphere passing
through the thermal oxidizer.
HIPS PROCESS

Rubber is dissolved in styrene in a proper section and then added with chemicals, peroxide and
ethylbenzene as diluent in a mixing section. Operating temperature is 60°C and the pressure is
almost atmospheric. The polymerization section is composed by a sequence of two/three plug-
flow reactors. At the end of the reaction train, the polymer solution is sent to a devolatilization
section, operated in two stages in series under vacuum conditions. Once the monomer and low
boiling compounds are removed, the polymer is sent to pelletizing unit.
Polypropylene:
- Homopolymer Polypropylene PP = biggest market
- Random Copolymer PP, contains 7% ethylene
- Heterophasic Impact Copolymeric PP, contains 25% ethylene

Conventionally produced from by-products of olefins production (steam cracking), but refineries
use it for gasoline  NG can become a necessity.
PP structure can be:
- Isostatic PP:
Most common
All methyl groups are attached to every other carbon atom on the same side of the chain

- Syndiotactic PP:
Methyl groups are attached to every other carbon atom, but alternate

- Atatic PP:
Methyl groups are attached randomly
There are three grades of PP:
- PP homopolymers:
High crystallinity and thermal resistance
Good mechanical properties
Textile industries applications (moquette)
 - PP random copolymers:
Ethylene as copolymer
Lower molecular regularity results in higher flexibility, impact-strength and transparency
Used for transparent bottles
- PP impact copolymers:
Ethylene in an heterophasic structure inside the semi-crystalline PP
Lower rigidity, improved impact resistance
Used for car components and electronic appliances

PP GAS PHASE PROCESS

The production of Impact Copolymers two reactors in series are required, while for the other
grades only one reactor is enough. Polymerization catalyst is very sensible to impurities (water,
oxygen, acetylene, sulphur compounds) which are removed. Fresh propylene is degassed to
remove impurities (CO and CO2). The reactor operates at around 33.8 bar and 55 °C.
As resin produced start to accumulate in the reactor, the level increase and an automatic
intermittent sequence is started to discharge the reactor to keep constant level in the reactor. The
second reactor operates in a similar way of reactor#1 but at lower pressure (20.7 bar).
Resin leaving the reactor contains dissolved hydrocarbons. The resin is transferred to Resin
Degassing unit from where the hydrocarbons are stripped using nitrogen and steam. They are sent
to Vent Recovery.
From Vent Recovery unit the feed stream is separated in three streams:
- Nitrogen and ethane  to convey gas in reactors for the resin discharge system, the excess
is rejected to prevent accumulation of inert.
- Liquid monomer stream (propylene, propane)  recycled in reactor(s) loop(s).
- Liquid propane  sent outside battery limit.
PP BULK PROCESS

Polymerization catalyst is very sensible to impurities (water, oxygen, acetylene, sulphur

compounds) which are removed. Fresh propylene is combined with recycled propylene and fed to
the loop reactor. Hydrogen and ethylene are also fed to the reactor.
The reactor operates at 80°C and 45 bar. In the loop reactor, a pump circulates the reaction slurry
mixture, containing 55 percent solids, at high velocity to avoid solids settlement and improve heat
transfer. Part of the circulating mixture is flashed into a high-pressure degasser (HP Degassing)
operated at 18 barg, where the powder separates from the monomer. After condensation in the
HP Degassing Section, the monomer is pumped back to the reactor passing through the
Purification Section. The polymer powder from the degasser, still containing some monomer,
flows to a LP Degassing operating at 0.7 barg.
The polymer from the LP Degassing is sent to a monomer Stripping System for the removal of
residual monomer. Here, steam strips all hydrocarbons, while wet polymer is dried by hot
nitrogen.
Polymer powder is combined with additives and processed in a compounding extruder. Pellets are
produced in an underwater pelletizer and dried in a pellet drier.