CLAUS TAIL GAS TREATING
Upgrade of Claus TGTUs
BASF has developed a new generation of promoter system compatible with MDEA solutions
named OASE® yellow. The new promoter system increases the selectivity and capacity of the
amine solvent, resulting in improved performance of tail gas treating units and allowing the
processing of more sour crudes. A. Kern and G. Vorberg of BASF discuss two case studies
demonstrating the benefits of OASE yellow.
R
efinery sulphur recovery units
Table 1: P
erformance gain by selective MDEA-based amine formulations in TGTUs
(SRUs) are faced with the chal-
lenge of processing increasingly Reboiler Sulphur Amine Operation at
sour crudes, while maintaining, or even duty specification circulation high lean amine
reducing, the level of sulphur emissions. rate temperatures
Higher sulphur loads need to be MDEA plain
treated by the Claus process and its tail –
Formulated/acidified MDEA x
gas treatment section. As a first meas-
OASE yellow (MDEA based) 3
ure, operators are exploring various ways
to improve the performance of the SRU
without incurring the additional costs
required for revamping. such systems are more prone to corrosion Case study 1 – A German refinery
Replacing the common MDEA-based incidents due to the (too) low residual acid
amine solution in the Claus TGTU can provide gas lean loading of the amine adversely This case study describes a commercial
a very cost-effective option, not only reducing affecting the corrosion protective layers refinery TGTU, previously running on MDEA,
emissions, but also allowing significant opex build up during plant operation. which converted to OASE yellow with the
savings as illustrated in this article. To overcome these constraints, BASF aim to reduce sulphur emissions.
has developed a new generation of pro- The tail gas to the amine absorber has
MDEA-based amine solvent in TGTUs moter system compatible with MDEA solu- a H2S content of 1.2 vol-% and a CO2 con-
tions, named OASE yellow, providing an centration of around 30 vol-%.
Methyl-diethanolamine (MDEA) is a ter- amine solvent with high selectivity and Within a timeframe of 72 hours the OASE
tiary amine, widely used in SRU TGTUs high capacity. yellow promoter was dosed into the TGTU
because of its natural selectivity towards An overview of selective MDEA-based amine loop by using a small dosing pump.
the removal of H2S. However, it is reach- amine formulations available and used in While the unit was running at full capacity,
ing its limits for more advanced acid gas tail gas treatment units is shown in Table 1. new operational settings were adjusted
removal requirements. Reduction of reboiler duty for the regen- accordingly, and the process was optimised.
First generations of promoter systems eration of the amine solution translates The effect of the amine conversion
(mainly comprising inorganic acid com- into opex savings. Reduction of the amine was visible instantaneously: The H2S con-
pounds) have been introduced. This so- circulation rate also translates into opex centration in the treated gas leaving the
called “acidification” of MDEA reduces savings with regard to the power consump- amine absorber and passing to the flare
the pH value of the amine solution, which tion of the amine pumps. decreased from 90 ppmv (start of the OASE
is beneficial for the regeneration step, The new generation, high selectivity, high yellow promoter addition) down to 15 ppmv
but has a negative effect on the absorp- capacity MDEA formulation can offer both. (end of the OASE yellow promoter addition).
tion capacity of the amine. It allows a Overall, the SO2 emission of the SRU
lower residual acid gas lean loading of Case studies TGTU system was reduced by 80%.
the amine. As a result, lower H2S concen- In parallel, the increased specific
trations and therefore sulphur emission The following two case studies demon- absorption capacity of the solvent allowed
reduction is achievable at lower reboiler strate the benefits of running the TGTU on the amine circulation rate to be reduced by
duties for regeneration. the new high selectivity and high capacity >25%. Fig. 1 summarises these findings.
However, acidified MDEA is lacking with amine solvent after successful introduction In a later optimisation stage, the lean
regard to absorption capacity and can lose of the innovative OASE yellow promoter to amine temperature was raised to the
its benefits when more sour crude is being existing MDEA systems. feed gas temperature in order to achieve
processed in the refineries leading to much Both conversions are carried out during an almost neutral water balance and
higher sulphur loads to the SRU and the 100% plant load, meaning no plant shut- subsequently no reflux bleed stream. The
respective tail gas sections. In addition, down and no process interruption. amine losses were thereby much reduced.
33 [Link] Sulphur 388 | May - June 2020
CLAUS TAIL GAS TREATING
Fig. 1: Reduction of H2S concentration in treated tail gas Fig. 2: Reduction of H2S concentration in treated tail gas
and opex by converting the MDEA to OASE yellow solution by converting the MDEA to OASE yellow solution
100 100 200 100
90 90 amine 90
H2S spec treated gas, ppmv
175
amine circulation rate, %
H2S spec treated gas, ppmv
circulation
amine circulation rate, %
80 80 80
70 150 rate, %
70 70
60 60 125 60
50 50 100 50
40 40 75 40
30 30 H2S spec 30
20 50
H2S spec 20 reboiler steam, t/h 20
10 10 25 10
amine circulation rate, %
0 0 0 0
conversion within 72 hours conversion within 26 hours
Case study 2 – A Korean refinery 150 ppmv can still be achieved while sig- By doing so, the sulphur emission issue is
nificantly reducing steam flow to 5.5 t/h. in effect converted into a wastewater treat-
In this case study a commercial refinery This translates into an outstanding steam ment task. Running a caustic wash unit is
TGTU previously running on acidified MDEA saving of 4 t/h (-40%). also an added cost and increases plant
solution was converted to OASE yellow with In addition, since the conversion of the complexity. Application of an innovative,
the aim to reduce opex costs. amine system the plant has been able to highly selective and high capacity solvent,
Due to oxygen enrichment in the burner run at 5-10 K higher lean amine tempera- such as OASE yellow, may allow the caus-
operation of the sulphur recovery unit, the tures, while still achieving the H2S spec. In tic wash unit to be mothballed.
tail gas to the amine absorber has a high combination with the reduced amine flow Both case studies showcase the per-
H2S content of 6.8 vol-%. The CO2 concen- rate, total lean amine cooling duty has formance gain of existing TGTUs that have
tration is 3.5 vol-%. been lowered to such an extent that the been converted to the new solvent. The
When processing more sour crude the lean amine air cooler is no longer required same benefits also apply to new TGTUs. In
sulphur emission can exceed the maximum and the plant is running a small amine addition, a grassroots design will be smaller
emission levels allowed. This can happen water cooler in its place. in size, therefore resulting in lower capex.
especially during hot summer months when Fig. 3 summarises provides data for the
lean amine temperatures are increasing optimisation process following the amine Conclusion
(e.g. due to limited air cooler duty) leading conversion.
to violation of the TGTU treated gas H2S OASE yellow solvent can reduce the opera-
spec. The OASE yellow system shows little Results and discussion tional cost and sulphur emissions of Claus
temperature sensitivity providing another TGTUs compared to plain MDEA or formu-
advantage compared to MDEA solutions. The upgrade i.e. conversion of the amine lated (acidified) MDEA solutions. Alterna-
Before OASE yellow promoter was intro- inventory can be carried out at any time tively, the capacity gain of OASE yellow can
duced to the TGTU amine loop, the treated while the TGTU system is in full operation also be used to increase the SRU load and
off gas going to the stack had an H2S con- and does not require a shutdown. TGTU throughput.
centration of 165 ppmv. The flow rate of tail In order to follow more stringent envi- Keeping the existing amine inventory
gas to the absorber was 10,030 Nm3/h. ronmental regulations, some TGTU sys- of the tail gas unit means no disposal of
The conversion was completed within tems have incorporated a caustic wash material is necessary, which is both eco-
26 hours and the H2S concentration in the unit downstream of the tail gas absorber. nomic, and very environmental-friendly. n
off-gas dropped to 35 ppmv. Meanwhile,
the amine circulation rate was reduced by Fig. 3: Optimisation step, reduction of steam flow for solvent regeneration while
>30%. Fig. 2 is illustrates the conversion keeping sulphur emission spec
process.
In a second step, following the conver- 200 16
recycled duty steam rate, t/h
sion, the optimisation phase started focus- 175 14
H2S spec treated gas, ppmv
maximum H2S spec
ing on opex savings. A key driver for lower 150 12
energy consumption and related cost is 125 10
the reduction of the low-pressure steam 100 8
used to regenerate the amine solution. 75 6
Without changes in the gas flow rates 50 4
H2S spec
and its composition, the steam flow to 25 2
reboiler steam, t/h
the reboiler was step-wise reduced start- 0 0
ing with 9.4 t/h. This in turn increased conversion optimisation
the H2S concentration in the treated tail
gas. However, the H2S spec of maximum
Sulphur 388 | May - June 2020 [Link] 33
