UPGRADING THE TECHNOLOGY OF AMINE UNITS

AT SLOVNAFT BRATISLAVA REFINERY

Jn Bako, Paul Garland, Baijan Savalan
Technology Department, Slovnaft,
Vlie hrdlo, 824 12 Bratislava, Slovakia
tel. + 421 2 4055 8396; fax: + 421 2 4524 3635;
e-mail: jan.bakos@slovnaft.sk
email: bsavalan@brenntagoilandgas.com

Key words: Monoethanolamine, diethanolamine, methyldiethanolamine, hydrosulphide, absorption,

desorption.

INTRODUCTION

Process units using amines for gas treating have been around for a long time. First with
monoethanolamine (MEA), and later with diethanolamine (DEA), the industry became used to
getting the maximum possible performance out of these products. In the early 1980s methyldiethanolamine (MDEA) became a new amine considered for gas processing applications.

AMINE SYSTEM AT SLOVNAFT REFINERY

Technical study Exchange of MEA and DEA for MDEA was prepared at the Technology
Department in January 2002. Later, after discussion with representatives of Slovnaft Refinery the
following conclusions were approved:
To use (in the future) only MDEA solution for removal H2S from refinery gases
To operate existing amine solvent circles at blocks No 58 and 67 in order to enhance operation
reliability. Both circles will be interconnected in that way, which future maintenance operation
breaks at production units will include one of the absorption columns.
To exchange of MEA and DEA solvents for MDEA will diminish the volume of the circulating
amine solution that will facilitate usage of only 2 regeneration columns instead of current 4
columns.
In January 2002 there were two distribution circuits of absorbents grapping hydrosulphide
(H2S) from hydrocarbon gases.
DEA (23-25 wt. % solution in water) was an absorbent in newer, more up-to-date
distribution circuit. Hydrosulphide from VGH (Pretreater feed for FCC), RHC (LC Fining Reside
Hydrocracking unit) and FCC (Fluid Catalytic crack) units was absorbed in seven absorbers to
water solution of DEA. Regeneration of DEA saturated with H2S was performed in one
regeneration column C302. In the figure No 1 is technological scope of Amine regeneration unit.
MEA (13-15 wt. % solution in water) was an absorbent in older, more out-of-date
distribution circuit. Hydrosulphide from following units HDS 1-6 (Gas Oil Desulphurisation units),
HLO (Hydrotreating of Lube Oil), VGO Hydrocracker, Desulphurisation of Gases 1-2 (DoG) and
Desulphurisation of Liquid Gases (DoLG) was absorbed in ten absorbers to solution of MEA.
Regeneration of MEA saturated with H2S was performed in three regeneration columns D 121a,b
and C 5802.

SIMULATION CALCULATIONS
Simulation calculations were performed by means of CHEMCAD simulation programs.

Absorbers:
We prepared simulation calculations of all absorbers in which DEA was used as absorbent
according to design data and according to real status, too. Absorbers, in which MEA was used as
absorbent, were calculated only according to real status. It was not possible to complete design data
and to execute the simulation MEA distribution circuit.
The simulation of absorption in MDEA went according to following criteria:
Amount of H2S in the gas leaving individual absorbers was lower or at the level of amount
of H2S during the use of MEA/DEA solution.
Absorbent saturation. The degree of saturation of MDEA was lower or at the same level as
the degree of saturation of MEA/DEA
Concentrations of MDEA were 35, 40 or 50 wt.%
Desorbers:
Desorber C302 was calculated according to design data and real status too. Desorbers from
MEA distribution circuit were calculated only according to real status. The simulation of desorption
H2S from MDEA was prepared for every desorbers and for desorption of all H2S from MDEA only
in desorber C302 (connection of both distribution circuit), as well.

DESCRIPTION OF PROJECT

Backgrounds for preparation of the new project Exchange MEA and DEA for MDEA
were conclusions from simulation calculations and from technical economic evaluation.
The total cost of this project was 58.67mil. SK. The main items of cost were initial filling
charge of MDEA and modifications of equipments for improving operation mode. New separator of
hydrocarbons from Rich amine, mechanical and carbon filters, inert atmosphere for amine tanks,
amine recovery from liquid gases and new pumps were built.
We expected savings of steam for regeneration of Rich amine, cooling water for cooling
overhead stream from regenerator and electricity. Expected yearly benefit was 52.23mil. SK
(according to the prices and production hydrosulphide from year 2001).
Consistent absorbent (MDEA) for removal hydrosulphide brings along following positives:
Saving of energy required for regeneration of absorbent.
The specific absorption capacity will increase through the absorbent exchange this will
enable us to shutdown old desorbers (columns D 121a,b).
Through the shutdown of desorbers we will save the cooling water for condensation of
vapours outgoing from desorbers.
New absorbent is non-corrosive in comparison with MAE and DEA. It means lower
maintenance and repair costs.
Through the decrease of the number of equipments we will decrease also the maintenance
and innovation costs for measurement and control. Currently these equipments are out-ofdate and their status is not satisfactory.
The same absorbent in MOL and Slovnaft creates the conditions for a finance discount on
the purchase of absorbent (synergy effect).
-

Except the advantages mentioned above, a new absorbent brings also negative aspects:
The price of MDEA is significantly higher than the price of currently used MEA or DEA
Concentration of MDEA is higher than currently used MEA and DEA. Every loss of
absorbent in future will be higher through the price expression than it is now.
Technological mode of absorbers will have to be observed more strictly, the processing
during start-up and shutdown absorbers and desorbers must be revaluated to exclude the
possibility of absorbent losses during these technological procedures.

The tender for supply new amine was opened. Our requests were sent to five producers of
amine. The winner of tender was Brenntag Company, which offered GAS/SPECTM SS specialty
formulated of MDEA designed for the gas treating industry with lower foaming tendencies than
generic MDEA. GAS/SPECTM SS is less corrosive and less prone to degradation than MEA or
DEA. New amine reduces circulation rate and energy usage; this translates into lower operating
costs and increased capacity for existing equipment and reduced capital for new equipment.

EXECUTION OF EXCHANGE AMINES

Execution of exchange MEA and DEA for MDEA was prepared in two steps.
First step: Exchange DEA for MDEA:

This step was realised in June 2003 when from EFPA complex units were stopped after
three years of operation. All absorbers from units VGH, RHC and FCC, desorber and another
equipments as vessels, exchangers and reboilers were opened and cleaned also pipelines for
distribution rich and lean amine. We started using MDEA for removal H2S from gases at EFPA
complex. Initial concentration of MDEA was 35 wt. % and feed lean MDEA to absorbers was
default according to results from simulation calculations. Total circulation of MDEA was about
140t/h (DEA needed about 200t/h). After one month operation was prepared test run. The content of
MDEA was increased to 40 wt. % we changed the amounts of lean MDEA to absorbers and
observed the degree of saturation of MDEA and amount of H2S in the gas leaving individual
absorbers. We decreased total circulation to the range 115 120 t/h. Consumption of steam for
desorption was decreased from value about 17.5t/h (needed for using DEA) to 12 t/h. The saving of
steam in amount 5.5t/h was obtained after the exchange of DEA for MDEA.
After four months of using MDEA we had one negative experience. The gaskets in plate
exchangers (preheating of feed to regenerator), which were used for DEA, were not suitable for
MDEA. They started to leak in. After consulting with producer of plate exchangers we had to
change the brand of gaskets. New gaskets are from EPDM and we have a no problem experience
since April 2004.
New unit for deep hydrotreating components for production ultra low sulphur diesel (HDS 7)
started up in November 2004. Hydrosulphide from circulation gas and off gas from HDS 7 is
absorbed in MDEA. Flow rate of lean amine for this unit is about 30t/h.
Unit

Treating gas

VGH

Circulating gas
Off gas from VGH
Circulating gas
Off gas from PSA
Off gas from RHC
Fuel gas
LPG
Circulating gas
Off gas from HDS 7
Rich amine
Lean amine

RHC

FCC
HDS 7
AAR

Pressure
(MPa)
9.00
1.70
3.78
0.32
0.28
1.30
1.00
5.50
1.80

Consumption Consumption
of DEA
of MDEA
( t/h ) *
( t/h ) **
50.0 60.0
40.0 42.0
4.0 6.0
4.0 6.0
110.0 130.0
55.0 70.0
3.0 5.0
1.0 3.0
8.0 12.0
4.0 6.0
6.0 10.0
5.0 6.0
0.5 1.0
25.0 30.0
2.0 3.0
180.0 220.0

130.0 160.0

Loading of H2S
(mol H2S /
mol MDEA ) ***
0.230
0.277
0.324
0.011
0.211
0.016
-

0.330
0.304
0.275
0.006

* Consumption of DEA from year 2001

** Consumption of MDEA present day
*** Loading of hydrosulphide in MDEA (average year 2004)

Table No 1: Consumption of amines, loading of hydrosulphide, treating gas and process pressure at
absorbers from VGH, RHC and FCC units.

Second step: Exchange MEA for MDEA:

The execution of this step was more complicated than was first one. We needed to increase
technical status of MEA distribution circuit to the level of DEA distribution circuit. Before the
exchange MEA for MDEA was necessary to execute the following upgrade changes in technology
and equipment, which would secure lower operation costs, lower amine losses and higher security
and reliability in the future.
To install new air coolers at the regeneration column C 8502. This measure would cut
down cooling water consumption.
To construct a new tank for rich amine to separate hydrocarbons (three phases separator)
before desorption of hydrosulphide.
To filtrate of lean amine (mechanical and carbon filters). Filtration capacity is the same as
for DEA circuit.
To creation the inert atmosphere in tanks for fresh and lean amine
To install new pump for lean amine at unit HDS 6
To construct amine recovery at Desulphurisation of LPG according to Danube Refinery
solution.
Exchange MEA to MDEA was realised in April 2005 during turnaround Desulphurisation of
Gases units. After the exchange of amines regeneration of Rich amine is processed only in desorber
C 8502. The pair of desorbers D 121a,b were stopped.
Unit

Treating gas

HDS 1
HDS 5****
HDS 6
HLO****
VGO HC
DoG 1

Circulating gas
Circulating gas
Circulating gas
Circulating gas
Pressure gas
Sour pressure gas
Sour pressure gas
Low pressure gas
LPG
LPG
Rich amine
Lean amine

DoG 2
DoLG
AAR

Pressure
(MPa)
3.20
3.20
5.10
3.00
1.90
0.70
0.70
0.10
1.90
1.90

Consumption Consumption
of MEA
of MDEA
( t/h ) *
( t/h ) **
12.0 18.0
4.0 8.0
18.0 23.0
6.0 10.0
6.0 10.0
2.0 4.0
8.0 12.0
4.0 8.0
8.0 10.0
10.0 15.0
8.0 10.0
20.0 30.0
15.0 22.0
12.0 18.0
7.0 12.0
8.0 12.0
4.0 6.0
100.0 140.0

50.0 75.0

Loading of H2S
(mol H2S /
mol MDEA ) ***
0.034
-

0.124
-

0.226
0.335
-

0.147
0.275
0.235
0.149
0.025

* Consumption of MEA from year 2001

** Consumption of MDEA present day
*** Loading of hydrosulphide in MDEA (average Jun - August 2005)
*** HDS 5 and Hydrotreating of Lube Oil units were stopped in 2004

Table No 2: Consumption of amines, loading of hydrosulphide, treating gas and process pressure at
absorbers from HDS 1-6, HLO VGO HC and DoG 1-3 units.

COMPARISON OF REAL AND PLANNED PROFIT

The mainly profit from project the exchange of amines was the saving of low-pressured
(pressure level 0.4 MPa) and middle-pressured (pressure level 1.0 MPa) steams for regeneration of
amine. Low-pressured steam is used for amine regenerators C 302 and C 8502. Middle-pressured
steam was used for regenerators D 121a,b. Those two regenerators were processed only for MEA.
Project calculated with saving of steams on the rank 48.1 %.
The project calculated with 50 % saving of cooling water what means to stop processing the
regenerators D 121a,b. Another saving of cooling water brings change of water coolers (vapour
stream from overhead of regenerator and Lean amine) to new air coolers in November 2003.
Currently, cooling water is used only for cooling sulphur gases before inlet to absorbers in summer
season.
New air coolers increased consumption of electricity, but project calculated with saving of
electricity on the range 30 %.
The base year for evaluation of profit is year 2001. The prices all items (steams, cooling
water and electricity) are on present time higher than were in year 2001.
The evaluation of real profit was prepared after three months experience with using of
MDEA.

Production of
Hydrosulphide ( T )
Consumptions:
Steam 0.4 MPa ( T / T H2S )
Steam 1.0 MPa ( T / T H2S )
Total (steams 0.4 + 1.0 MPa)
Cooling water ( m3 / T H2S )
Electricity ( MWH / T H2S )
Cost for production 1 T H2S
( SK )

Jun Aug
2001*

Jun Aug
2005**

11269

16447

5.0176
1.9744
6.9920
163.91
0.1469

2.8842
0
2.8842
7.500
0.0955

0.5748
0.4125
0.0457
0.6496

3 539

1 840

1 699

Ratio
2005 / 2001

* Using MEA and DEA

** Using MDEA

Table No 3: Production of Hydrosulphide and consumptions of steams, cooling water

and electricity for three months period.

CONCLUSIONS

After very short period using MDEA for removal Hydrosulphide from hydrocarbon gases we
can say that expected targets from project Exchange MEA and DEA for MDEA were obtained.
The real total cost of this project was lower than planned. Saving of steams is about 10%
higher than was expected. The similar result is with electricity as well. Saving is about 5% higher
than was planned. Consumption of cooling water was decreased to 5 % of the value from year 2001.
The current production of Hydrosulphide is higher in comparison with year 2001 about 45 %.
The increase the prices of steams between years 2001 and 2005 was about 50%, cooling water
about 10% and electricity about 30%. The real cost (summary steams, cooling water and electricity
cost) for production 1 ton of Hydrosulphide in year 2001 was 3 539 SK. The same cost in year 2005
is 1 840 SK. The total benefit for period between Jun and August 2005 represents 27.94 mil.SK.

REFERENCES
1. Bako J, Feketeov J: The Exchange of MEA and DEA for MDEA Preliminary feasibility
study, January 2002.
2. Bako J, Feketeov J, Valach A: Proposal to exchange MEA and DEA for MDEA Analysis of
the existing H2S absorption process and proposal of technical and organizational changes to
facilitate introduction of a new solvent MDEA, July 2002.
3. Plaumann D, Stewward E, Kuroda R: Performance of specialty amines in gas processing, Gas
Technology, June 1999
4. Bako J: Amine system at Slovnaft refinery Report on activities and results, May 2005.