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Motor gasoline
Jet/DPK
Gas Oil
Fuel Oils
Bitumen
Sulphur
Separation
Conversion
Purification
Separation
Processing crude oil in the Refinery starts with distillation. (this process is covered in detail in
our Information brochure). This is a physical separation process which is undertaken under
different conditions as shown on the block flow scheme Fig. 1 by CD1 & 2 and HVU-2.
Another physical separation process is the Butane Deasphalting Unit (BDU). This solvent
extraction process makes a separation between distillate-type and asphaltic compounds of the
short residue. Solvent extraction is a more suitable process that high vacuum flashing where, in
order to avoid thermal cracking (temperature decomposition), impractically low pressures or
high temperatures would have to be used.
In the Butane Deasphalting process, short residue form a high vacuum distillation unit is
contacted with liquid butane under specified temperature and pressure conditions. Butane has
been selected as the optimum solvent because it provided the highest deasphalted oil yield with
good selectability at low solvent-to-feed ratios. The butane easily dissolves the lower boiling
hydrocarbons, but its solvent power is limited with respect to the higher boiling hydrocarbons,
especially aromatic and asphaltic compounds. The butane and short residue are mixed in an
extraction column at conditions close to the critical point of butane.
Two liquid phases are formed, one rich in butane containing the extracted oil (Deasphalted Oil DAO) the other of asphaltic compound with little butane and oil content (ASPHALT).
The extraction column operates isothermally, the butane-rich phase being continuous and the
asphaltic phase as dispersed droplets. The density difference between the phases drives the
dispersed phase downwards in a countercurrent flow to the continuous phase, so that an
interface level is formed in the bottom.
The extractor has perforated trays to enhance the contacting of the two liquid phases and the
butane solvent is recovered from the two phases (DAO and ASPHALT) by flashing and
stripping, to be recycled for reuse.
The DAO, along with the waxy distillate, is fed to the Hydrocracker. The asphalt is used as
Refinery fuel or blended with gas oil to make fuel oils.
E. Conversion (Upgrading)
The refining of oil into desirable products also uses catalytic upgrading techniques, where
chemical reaction with associated energy change results in products of better quality.
Several types of conversion processes are used.
The removal of sulphur from oil products by Desulphurisation through converting sulphur
compounds to hydrogen sulphide over a catalyst in the presence of hydrogen.
Catalytic reforming is restructuring of the oil molecules by aromisation and isomerisation
endothermic reactions over a platinum catalyst (Platforming).
The manufacture of bitumen uses the Air blowing technique of oxidation and polymerisation
to produce a harder product.
These processes are indicated in the refinery block flow scheme Fig. 1 as HDT, KHT and HDS,
PLAT and BITUMEN.
There are other conversion processes in the Refinery which came as part of the expansion.
The Hydrocracking process is a large complex of many units, which converts waxy distillate
and deasphalted oil (DAO) into predominantly kerosine and gas oil. The process id the 2-stage
Shell Hydrocracking system (Hydrocracker in fig. 1) and achieves almost 100% conversion.
Different catalysts are used in various stages. The first stage of the process reduces the
nitrogen, sulphur and oxygen content for protection of the second stage catalyst.
The second stage is predominantly hydrocracking.
The principle reactions occurring are:
1st Stage
Denitrogenation
Desulphurisation
Deoxygenation
Hydrogenation
Hydrocracking
Isomerisation
2nd Stage
Hydrogenation
Hydrocracking
Isomerisation
The
Products
The molecular types found in the main products from these reactions are:
i. Normal and iso paraffins
ii. Naphthenes
iii. Monoaromatics
The reaction products from the hydrocracking section (reactor effluent) are further separated by
fractional distillation into product streams and blended with other products of the Refinery (refer
Fig. 1).
An outline of the HCU process is given in Fig. 3.
The large consumption of hydrogen in the above reactions requires a separate production
source and for this the refinery has its own Hydrogen Manufacturing Unit (HMU).
The hydrogen is produced by converting hydrocarbons and steam into hydrogen with reaction
by-products of CO and CO2.
The CO is further converted to CO2 and removed by absorption (purification). The preferred
feedstock for hydrogen manufacture (HMU in Figure 1) is light hydrocarbon gases and butane.
The vaporised feed is de-sulphurised before the steam reforming reaction. The reactions which
occur during reformation are complex but can be simplified to the following equations:
For Methane: CH4 + H20 -> CO +3H2
Generally for Hydrocarbons: CnHm + H20 -> 2n + m . H2
2
Water gas shift reaction: CO + H2O > CO2 + H2
The process of reforming can be split into three phases of preheating, reaction and
superheating. The overall reaction is strongly endothermic and the design of the HMU reformer
is a careful optimisation between catalyst volume, furnace heat, transfer surface and pressure
drop.
In the preheating zone the steam/gas mixture is heated to the reaction temperature. It is at the
end of this zone that the highest temperatures are encountered.
The reforming reaction starts at a temperature of about 700C and, being endothermic cools the
process.
The final phase of the process, superheating and equilibrium adjustment, takes place in the
region where the tube wall temperature rises again.
The CO mixed with the hydrogen is then converted to CO2 in two stages, a high and low
temperature shift reaction.
CO + H2O > CO2 +H2
The CO2 produced by the shift reactions is removed by absorption but trace quantities of both
CO and CO2 do remain and the hydrogen stream is therefore passed through a methanator to
convert CO and CO2 to methane (CH4). The reactions are highly exothermic and take place as
follows:
CO +3H2 > CH4 + H2 O
CO2 +4H2 > CH4 + 2H2O
Finally, all produced hydrogen is cooled and sent to the Hydrocracker. Fig. 4 gives an outline of
the HMU process.
Crude oil, as received for refining, contains sulphur in levels up to a few percent weight. It is
removed from oil products mainly by the desulphurisation process described under toe
purification processes, which result in the formation of hydrogen sulphide. This H20 is further
converted by using the Claus process of partial combustion of H2S to form SO2 and then
reacting with the remaining H2S to produce sulphur. This Sulphur Recovery process takes
place in one thermal and two catalytic stages and has a total recovery of 95%. The final 1 or
2% volume of H2S in the tailgas from the last catalytic reactor is burnt in a separate incinerator
so that the effluent gas finally discharged to the atmosphere has an environmentally acceptable
H2S content of less than 5 ppm by volume.
In a Sulphur Recovery Unit (SRU), elemental sulphur is produced by the following reaction:
H2S + O2 <-> S + H2O + H2 O(1)
This overall reaction (1) is the sum of two exothermic reactions, the oxidation of H2S to SO2 (2)
and the subsequent reaction between H2S and SO3 (3) to form sulphur and water.
H2S +3/2 O2 <-> SO2 + H2O (2)
2H2S + SO2 <-> 3S + 2H2O (3)
In the first stage of the process enough air is supplied to convert one third of the H2S in the acid
feed gases to SO2 and H2O according to equation (2).
In addition to this, any hydrocarbons and NH3 in the feed gases are completely combusted:
C3H8 + 5O2 > 3CO2 + 4H2 O
2NH3 + 3/2 O2 > N2 +3H2 O
In the second and third stage of the process, more H2S is converted to sulphur according to
equation (3).
To shift the equilibrium of this reaction as far as possible to the right side, lower reaction
temperatures are applied to these stages. To assure sufficiently high reaction rates, the
reactions take place in the presence of a catalyst. Finally, the SRU tail gas is oxidised in a
catalytic incinerator at a temperature of approximately 400C. At this temperature, achieved by
burning fuel gas in addition to the process gases, the H2S and sulphur vapour/mist are
practically completely oxidised in the presence of a catalyst according to the reactions:
H2S + 3/2O2 > H2O + SO2 and S + O2 > SO2
The sulphur is produced in liquid form. Heated handling and loading facilities provide sulphur
storage before loading into road tankers for delivery to the fertiliser works. Fig. 5 is an outline of
the
SRU process.
Purification Processes
The treating or purification of the different refinery product streams is an important feature of the
refinery operation. Purification may be required in order to meet a final quality specification, or
necessary to avoid contamination or poisoning of a valuable catalyst in another refinery
process.
The removal of H2S from the various sour fuel gas streams produced by the refinery processes
allows sweet fuel gas to be burnt in the refinery furnaces without excessive SO2 emissions. The
Shell Adip process is applied, being a regenerable absorption process, with di-isopropanol
amine (DIPA) as the absorbant. The sour components react with the di-isopropanol (DIPA)
component of the Adip solution. The overall reaction can be represented as follows (-R
denotes the isopropanol group (CH3 CHOH CH2-)).
H2S + R2NH <-> R2N H2 + HS
The equilibrium of the above reaction lies at the right hand side of the equation at lower
temperatures and higher pressures (absorber conditions).
At higher temperatures and lower pressures (regenerator conditions) the reaction is reverses,
resulting in the removal of H2S from the solvent.
Fig. 6 outlines the Adip process of absorption and regeneration.
The normal DIPA
concentration in water of the Adip solution is 4 molar and the H2S concentration of the lean Adip
to the absorber is typically 80 ppm wt.
In the HMU, there is an example of a Non-Reversible Absorption Process applied to protect a
valuable catalyst. In this case, desulphurisation is by absorption of H2S by zinc oxide, according
to the equation:
ZnO + H2S > ZnS + H2O
The reaction is non-reversible and consequently the saturated absorbent must eventually be
discharged and replaced.
In other process of the Refinery, sulphur compounds (mainly H2S) and possible chlorine
compounds are removed from hydrocarbon gas streams by a Caustic Wash Process. Here,
the following typical reactions take place:
H2S + 2NaOH > Na 2s + 2 H2O
RSH + NaOH > RSNa + H2 O
HCI + NaOH > NaCI + H2O
Another significant purification process in the Refinery is the removal of CO from the hydrogen
product gas stream in the HMU.
Again, a Regenerable Absorption Process is applied by circulating a sulfinol solution.
This is a mixed solvent, consisting of: 50 wt% DIPA (CH3 CHOH CH2) 2NH 25 wt%
tetrahydro-thipothene-dioxide (Sulfolane): C 4H8O2S 25 wt% water.
is removed by absorption in the sulfinol at low temperatures and high pressure.
Subsequently, the fat sulfinol solution is regenerated by removal of CO2 at high temperature
and low pressure. The chemistry of the process is complex.
CO2
Economic Tools
The primary economic tool is that used by most refiners is a Linear Programme Model. This is a
mathematical representation of the Refinery which is optimised to maximise the Gross Refiners
Margin. It has a number of uses at NZRC, being used by the Oil Companies to select the
optimal feedstocks for a quarter, by the Refinery to see where synergies exist in summing all Oil
Company programmes into one, for month to month planning of the refinery processes, and at
the end of each quarter for dividing up the crude oil and products made between the Oil
Companies.
The Oil Industry also uses another optimising package for scheduling of the coastal tankers that
take product from the Refinery around the New Zealand coast, and bring indigenous feedstocks
to the Refinery.
Refining Costs
The total operating costs of the Refinery are around $2.90 per barrel of 1.9 cents per litre,
spread across all products. It is estimated that the refining cost of gasoline is around 3 cents
per litre, ie. about 3% of the total price paid at the pump.
The Refinery keeps a very close eye on its operating costs, which it compares every year with
its competitors. It leads the way within the Asia Pacific region with the low level of maintenance
costs versus replacement capital costs, all the time ensuring though that the assets are fully
kept up to date so that reliability is maintained.
In Conclusion
Now that you have a greater understanding of crude oil refining and its many useful products,
you begin to appreciate the importance of The Refinery to New Zealand our people, our
industry and our economy.
Our own Refinery makes us less vulnerable to the uncertainties of overseas supply, generates
revenue and employs New Zealanders.
The New Zealand Refining Company aims to ensure safe, efficient and profitable operation,
whilst preserving the environment.