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Division 1.20.3 Sulphur oxides (SOX)

United Kingdom

Original text. Later amendments are not shown.

TechniqueDescription
Treatment of refinery fuel gas (RFG)Some refinery fuel gases may be sulphur-free at source (e.g. from catalytic reforming and isomerisation processes) but most other processes produce sulphur-containing gases (e.g. off-gases from the visbreaker, hydrotreater or catalytic cracking units). These gas streams require an appropriate treatment for gas desulphurisation (e.g. by acid gas removal — see below — to remove H2S) before being released to the refinery fuel gas system
Refinery fuel oil (RFO) desulphurisation by hydrotreatmentIn addition to selection of low-sulphur crude, fuel desulphurisation is achieved by the hydrotreatment process (see below) where hydrogenation reactions take place and lead to a reduction in sulphur content
Use of gas to replace liquid fuelDecrease the use of liquid refinery fuel (generally heavy fuel oil containing sulphur, nitrogen, metals, etc.) by replacing it with on-site Liquefied Petroleum Gas (LPG) or refinery fuel gas (RFG) or by externally supplied gaseous fuel (e.g. natural gas) with a low level of sulphur and other undesirable substances. At the individual combustion unit level, under multi-fuel firing, a minimum level of liquid firing is necessary to ensure flame stability
Use of SOX reducing catalysts additives

Use of a substance (e.g. metallic oxides catalyst) that transfers the sulphur associated with coke from the regenerator back to the reactor. It operates most efficiently in full combustion mode rather than in deep partial-combustion mode.

NB: SOX reducing catalysts additives might have a detrimental effect on dust emissions by increasing catalyst losses due to attrition, and on NOX emissions by participating in CO promotion, together with the oxidation of SO2 to SO3

HydrotreatmentBased on hydrogenation reactions, hydrotreatment aims mainly at producing low-sulphur fuels (e.g. 10 ppm gasoline and diesel) and optimising the process configuration (heavy residue conversion and middle distillate production). It reduces the sulphur, nitrogen and metal content of the feed. As hydrogen is required, sufficient production capacity is needed. As the technique transfer sulphur from the feed to hydrogen sulphide (H2S) in the process gas, treatment capacity (e.g. amine and Claus units) is also a possible bottleneck
Acid gas removal e.g. by amine treatingSeparation of acid gas (mainly hydrogen sulphide) from the fuel gases by dissolving it in a chemical solvent (absorption). The commonly used solvents are amines. This is generally the first step treatment needed before elemental sulphur can be recovered in the SRU
Sulphur recovery unit (SRU)

Specific unit that generally consists of a Claus process for sulphur removal of hydrogen sulphide (H2S)-rich gas streams from amine treating units and sour water strippers.

SRU is generally followed by a tail gas treatment unit (TGTU) for remaining H2S removal

Tail gas treatment unit (TGTU)

A family of techniques, additional to the SRU in order to enhance the removal of sulphur compounds. They can be divided into four categories according to the principles applied:

  • direct oxidation to sulphur

  • continuation of the Claus reaction (sub-dewpoint conditions)

  • oxidation to SO2 and recovering sulphur from SO2

  • reduction to H2S and recovery of sulphur from this H2S (e.g. amine process)

Wet scrubbing

In the wet scrubbing process, gaseous compounds are dissolved in a suitable liquid (water or alkaline solution). Simultaneous removal of solid and gaseous compounds may be achieved. Downstream of the wet scrubber, the flue-gases are saturated with water and a separation of the droplets is required before discharging the flue-gases. The resulting liquid has to be treated by a waste water process and the insoluble matter is collected by sedimentation or filtration

According to the type of scrubbing solution, it can be:

  • a non-regenerative technique (e.g. sodium or magnesium-based)

  • a regenerative technique (e.g. amine or soda solution)

According to the contact method, the various techniques may require e.g.:

  • Venturi using the energy from inlet gas by spraying it with the liquid

  • packed towers, plate towers, spray chambers.

Where scrubbers are mainly intended for SOX removal, a suitable design is needed to also efficiently remove dust.

The typical indicative SOx removal efficiency is in the range 85-98 %.

Non-regenerative scrubbing

Sodium or magnesium-based solution is used as alkaline reagent to absorb SOX generally as sulphates. Techniques are based on e.g.:

  • wet limestone

  • aqueous ammonia

  • seawater (see infra)

Seawater scrubbingA specific type of non-regenerative scrubbing using the alkalinity of the seawater as solvent. Generally requires an upstream abatement of dust
Regenerative scrubbingUse of specific SOX absorbing reagent (e.g. absorbing solution) that generally enables the recovery of sulphur as a by-product during a regenerating cycle where the reagent is reused