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Author: Erwin H.M. Dirkse, DMT Environmental Technology
Author: Erwin H.M. Dirkse, DMT Environmental Technology
hydroxide has decreased, solutions are introduced to deal with the waste water and continuous research
investigates new physical-chemical processes to re-use discharge water and regenerate the recirculation
fluid.
The latest in house development in the field of bio and landfill gas treatment is the biological
desulphurisation process known under the trade name of Bio-Sulfurex.
THE SULFUREX PROCESS
The selective process of desulphurisation.
There are many physical, physical / chemical, chemical and biological desulphurisation processes.
However, due to the capital costs, monitoring and operating costs involved most processes can only be
cost effective when used on large or very large gas throughputs. There are however many smaller
applications where traditional systems are just not cost effective and no business case can be made for
investment. It is in these smaller applications that the DMT Sulfurex Desulphurisation Process due to its
low capital and running costs has proven to be cost effective. The DMT Sulfurex Desulphurisation
Process has the following benefits:
simple, compact and robust construction;
low capital cost;
very flexible operating parameters;
simple low cost operation and maintenance;
low consumable usage;
no chemical waste;
economically viable for sulphur loads up to 10 25 tons a day depending on local site conditions
equipment assembled as transportable units
modular construction in optional insulated housings.
In the process the biogas is brought into intense contact with a circulating alkali liquid over an exchanger in
a single stage counter current process (gas scrubber). The H2S in the gas is absorbed by the alkali liquid
through several chemical reactions. Ultimately the hydrogen sulphide in the gas is almost totally converted
into NaHS and sodium bicarbonate using sodium hydroxide. The process is controlled by a sophisticated
H2S-detection and sampling system for very efficient operations and low chemical consumption. Selective
desulphurisation is possible due to the differences in the physical and chemical properties of H2S and CO2.
The course of this chemical process is further determined by chemical concentrations, pH values and the
temperature and pressure of the system. The following conditions should be taken into consideration:
the lower the final concentration of H2S in the purified gas, the higher the specific lye demand;
the higher the temperature and pressure of the system, the higher the specific lye demand;
the higher the CO2 content in the raw gas, the higher the lye demand;
the longer the gas remains in the scrubber, the higher the specific lye demand.
S p e c ific c o n s u m p tio n c a u s t ic s o d a
15
kg H2S
kg NaOH/
5 0 0 m 3 /u ,
35% CO 2, 30C
10
5 0 0 m 3 /u ,
15% CO 2, 30C
5 0 0 m 3 /u ,
15% CO 2, 10C
0
0
2500
5000
7500
10000
H 2 S c o n c e n tr a tio n (p p m )
The following design data is required in order to design a gas desulphurisation plant:
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gas flow in Nm /hour; maximum, minimum, average, current and future;
gas temperature in C. ;
gas pressure in mbar or Pa;
composition of gas ( CH4, CO2, H2S, other );
required efficiency; ppm H2S in the purified gas.
For optimal performance of the Sulfurex process the following conditions need to be considered:
3
fluctuations in gas flow preferably < 10 m /hr per minute;
system pressure preferably between - 250 and + 500 mmwg;
process temperature preferably between 2 and 50 C.
New developments
DMT Environmental Technology is constantly working on further improvements of the Sulfurex and the
Bio-Sulfurex processes. The main objectives of this research and development work are as follows:
Improvement in the selectivity of H2S absorption;
Savings on the consumption of sodium hydroxide;
Treatment of the spent lye solution if an aerobic waste water treatment is not available;
Regeneration or re-use of spent lye; studying several physical-chemical processes for the re-use or
regeneration of absorption fluid;
Pre-treatment of the biogas with activated sludge or wastewater effluent.
Pre-treatment of the biogas with activated sludge or wastewater effluent.
When utilising a pre-treatment stage in combination with the Sulfurex biogas desulphurisation unit
important savings can be achieved by reducing the consumption of sodium hydroxide. This is possible by
scrubbing the biogas with activated sludge from the aeration basin or effluent from an available biological
wastewater treatment plant.
The H2S is absorbed in the water or activated sludge and micro-biologically oxidised into sulphate when
the circulation fluid is returned to the aeration basin or the wastewater treatment plant. The efficiency
depends on the pH of the water and the amount of recirculation fluid available; at a pH level of approx. 7.5
an efficiency of 75 90 % on H2S can be achieved. The pre-treatment column can be situated near the
aeration basin and the chemical desulphurisation unit, placed on a skid complete with a circulation system.
Optimising the use of the spent lye.
The Sulfurex process is based upon the following chemical reactions:
H2S + NaOH (lye)
CO2 + 2NaOH
(1) and
(2)
Because of the selectivity in the process relatively less carbon dioxide is absorbed, nevertheless the
presence of CO2 will be apparent in the amount of sodium hydroxide that is required. Important savings
can be achieved via the following reaction:
Na2CO3 + H2S
This requires an extra absorption column in which the spent lye according to reaction (1) and (2) can be
used for the reaction (3). The pH level of the spent lye will then be reduced to 9-10 through the formation of
sodium bicarbonate instead of 10-11.5 without the re-use of the sodium carbonate. Theoretically it is
possible to save up to 60% of the lye consumption; in practice a lot of different process details are involved
and the likely savings will probably be more like 25-50 %.
Biogas outlet
Biogas inlet
Inertgas out
Inertgas out
Inertgas in
Inertgas in
First stage
Second stage
Ventilation
Drain
M1
M2
M1A
V1
M4
M2A
V2
M5
NaOH
Water supply
Chiller
Process Diagram
Operation
The biogas is fed into a vertical column with packing media in a counter current pattern. The packing media
provides sufficient contact surface area for the gas flow, nutrients and oxygen: it is also used as a carrier
for the bacteria. Oxygen is added to the gas in the form of compressed air. The compressed air is brought
into the column and when it moves up through the column, the bacterium treats the gas flow. An automatic
control system adjusts the amount of air flow according to the actual requirement which in turn is correlated
with the biogas flow. The amount of oxygen required depends on the amount of air and the oxygen already
present in the flow. The nutrients are sprayed on top of the medial and refreshed automatically as required.
Nutrients and trace elements can usually be sourced from the digested substrate or other natural sources
(e.g. landfill leachate) and need not to be added artificially.
Advantages of biological desulphurisation using the Bio-Sulfurex process.
High efficiency
> 95% reductions in of H2S for incoming biogas with up to 1 vol. % (10.000 ppm H2S).
Almost no utilities necessary.
No use of chemicals.
No waste flow requiring treatment or transportation.
Safe process. All equipment & instrumentation Ex-proof.
Compressed air supply linked to the biogas flow and oxygen demand.
Low capital and running costs (see table 3).
SAPPI PLANT, LANAKEN, BELGIUM.
South African Pulp and Paper Industries (SAPPI) paper mill in Lanaken, Belgium took delivery of a Sulfurex
process in 2004. The SAPPI mill is very large and has its own anaerobic wastewater treatment facility
producing biogas. Originally the biogas was used to fire a boiler. However SAPPI had two important
reasons for investing in a biogas desulphurisation plant: Firstly they were investing in a new CHP plant and
secondly they had to comply with new SO2 emission standards.
SAPPIs design data is as follows:
Biogas flow
Biogas volume
Biogas composition
H2S concentration
H2S out of the process
Efficiency of H2S removal
Biogas Temperature
Humidity
: 200 Nm / hour
3
: 1.750.000 m / year
: 78 % methane
20 % carbon dioxide
: max. 20.000 ppm
: max. 200 ppm
: > 99 %
: 35 C
: saturated
Because of the very high levels of H2S a physical / chemical process was preferred to a biological process;
therefore several Sulfurex process options were discussed. Table 2 shows the various options and their
respective running costs. SAPPI selected the most extensive option: a three stage process with an
activated sludge absorber as pre-treatment step followed by a two stage Sulfurex process including
cooling and drying of the biogas.
Process description
The SAPPI system consists of three scrubbing towers in which the four main process stages take place.
The first stage is an activated sludge absorber in which the biogas is pre-treated for initial H2S removal.
The soda utilization tower, in which soda formed in the third stage is re-circulated, is used for further H2S
removal. The third stage is a caustic scrubbing tower in which the caustic is dosed and used to remove the
final concentrations of H2S. The soda formed is transported to the second stage. The fourth stage process
is the cooling and drying of the biogas which is integrated within the total system.
Stage 1 - Activated sludge absorber, water scrubber, first biogas treatment stage.
The pre-cooled biogas enters the activated sludge absorber in a counter flow pattern. The absorber
consists of a scrubber with a special type of contact media, water-distribution system and a demister. In the
process activated sludge is used with a sludge concentration of 7 10 gram per litre.
5
The pH value of the effluent is very important in relation to the scrubbing efficiency of the activated sludge
absorber; therefore a pH measurement system is installed for adjusting the circulation flow over the
scrubber. The following processes take place in the absorber:
-
+
(aq)
(1)
(2)
(3)
(4)
(5)
2-
(6)
(7)
(8)
acids are present in the biogas in concentrations of 2 %, caustic soda consumption will increase to
approximately 50 % when compared to normal process conditions
Cooling and drying of the biogas.
Scrubbing of H2S is more efficient at lower process temperatures that consequently results in lower caustic
consumption. Reheating the biogas at the outlet reduces the relative humidity of the Biogas to 60%. The
cooling system begins with a chiller that cools a mixture of water and glycol from approximately 6C to 2C.
The water/glycol mixture is circulated by a pump. The cooling fluid is fed into the third stage scrubber and
increases in temperature, within the scrubber, from approximately 2C to 4C. At the same time the
circulation fluid has the cooling potential to reduce the temperature from 14C to 4C.
Secondly the cooling fluid enters the second stage. The cooling fluid in this section has a temperature gain
from approximately 4C to 6C. At the same time the circulation fluid cools from approximately 12C to 7C.
Optimisation of the cooling system according to the actual process conditions can be achieved by partially
bypassing or putting the heat exchangers in parallel..
The final stage of the cooling and drying system is the gas/gas heat exchanger in the outlet of the biogas
scrubber. The treated cold biogas is reheated with the untreated warm biogas. The untreated gas will cool
from approximately 30C to 27C and the treated gas will rise in temperature approximately 12C from
12C to 24C.
Waste water discharge
The spent lye discharged from the desulphurisation process needs to be disposed of. The waste water
consists of concentrations of 4 8 % by weight NaHS and NaHCO3, furthermore there are traces of
Na2CO3 and Na2S at a pH value of 9.5 to 11. Usually this stream is fed into the aeration stage of a waste
water treatment plant where the NaHS can be rapidly oxidised microbiologically into sulphate. If there is no
aeration stage available, waste water can alternatively be subjected to random oxidation. Extended
aeration results in NaHS being oxidised into sulphur, sulphate and poly-sulphur compounds.
Make-up water.
Make-up water is required in order to dilute the sodium hydroxide that is fed in (25 45 % solution) in order
to keep the compounds created soluble and to carry off heat from the chemical reactions taking place in
the process.
The make-up water should be free of hardness (zero) and iron (< 0.1 mg/l), as soda lye plus hard water
produces lime and hydrogen sulphide, plus iron produces black sulphide of iron, which may deposit in the
gas scrubber. Consequently, DMT stipulate the use of softened and de-ironed water and consequently
include a water treatment unit to provide de-ironing and softening. In the event that deposits still occur, they
can easily be dissolved by acidifying the gas scrubber. The materials of construction (PVC, PP, HDPE,
stainless steel) are acid-resistant.
45 C
30 C
15 C
Coagulation point curve
0 C
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
Weight-% NaOH
Caustic soda.
The DMT Sulfurex Desulphurisation Process requires chemically pure sodium hydroxide in order to avoid
clogging problems. Another important consideration is the selection of the correct concentration. Figure 3
shows the consequences of different concentrations of sodium hydroxide.
H2S detection and sample system.
A very important component in the DMT Sulfurex Desulphurisation Process is the H2S detection and
sample system. The total desulphurisation process is controlled by this unique and sophisticated system
for very efficient operations and low chemical consumption. The design is specially made by DMT for
efficient operation in gas scrubbers. Besides the necessary sample conditioning, the sample preparation
contains a dilution step. The dilution step makes it possible to measure wet gas in high ranges up to 500
1.000 ppm. The sensor itself operates in a lower measurement range but by dilution of the gas and heating
of the cabinet, water condensation is prevented. The sample flows via a fast loop back into the process.
The transport of the gas is handled by a heavy duty membrane pump. If instrument air is not available, the
dilution of the sample can be achieved with ambient air from the second head of the membrane pump.
Dilution of the sample has the extra benefit of low H2S emissions (max. 10 ppm). The air is also used, as a
safety measure, to purge the small cabinet to prevent high concentrations of dangerous gases. The design
of the system allows the use in control loops as the response time is short. The system was installed in a
zone 1 gas group IIC T4 area.
Measuring principle of the H2S sensor.
The sample gas diffuses through a hydrophobic, gas permeable membrane into the electrolyte of the
sensor. Located inside the sensor are measurement, reference and counter electrode components. A
potentiometer circuitry enforces a constant bias voltage between the measurement and reference
electrodes. The bias voltage, the electrolyte and the electrode material are selected in a way that the target
gas electro-chemically reacts with the measurement electrode. This reaction generates a current flow
through the sensor which is proportional to the gas concentration.
To compensate for temperature effects, a temperature sensor (NTC) is located directly inside the sensor
cell. The effects of temperature can therefore be compensated according to the actual sensor temperature.
Materials & installation of the unit
Materials used in the plant at SAPPI are as follows: all components were constructed from corrosion resistant materials such as plastics and/or
stainless steel;
the gas scrubbers were constructed as compact packaged units and then installed in a modular,
insulated housing system for easy transportation and erection on site;
The system was fully automated and controlled via a PLC control panel with optional remote
telemetry system
Scope of Supply
The scope of supply for the SAPPI Sulfurex desulphurisation plant included the design manufacture
supply installation and commissioning of the gas scrubber(s), instrumentation system, control system,
chemical storage tanks, make-up water system and water treatment unit, discharge of bleed-off,
interconnecting piping and cabling, modular insulated housing incl. ventilation, heating and CH4 / H2S
detection;
CONCLUSIONS
The Sulfurex desulphurisation plant installed at the SAPPI Plant has proven to be a robust and reliable
system for conditioning the biogas prior to it being fed to the CHP plant. The combination of physical,
biological and chemical processes provides optimum performance, reliability and low running costs.
Consequently maintenance and operational costs for the CHP plant since the installation of the system
have been significantly reduced of the engine over the last period were minimized and a very short pay
back period has been achieved
The Sulfurex desulphurisation plant has met its design targets: system efficiency was in accordance with
the process guarantees and process calculations that were made using the DMT developed design
program, caustic consumption was within the limits of the design process calculations with the scrubbers
8
overall performance being excellent. The efficiency of the pre-treatment stage by the activated sludge
scrubber was better than expected: calculated 75% removal had been expected at the design stage but
>85% removal was actually achieved. This is an interesting development in terms of lower caustic
consumption in the chemical stage of the plant.
During commissioning some problems were experienced when the contact media was in danger of
becoming clogged with calcium and bio sludge however this was quickly resolved by adjusting water levels
and cleaning.
Running costs of the Sulfurex desulphurisation plant were in line with those predicted at the design stage,
they were even better than originally predicted because of the higher efficiency of the pre-treatment of the
biogas by the activated sludge scrubber. The running costs of this plant are more comparable to those of a
purely biological plant.
The pay back period of the Sulfurex desulphurisation plant was less than two years which compares very
favourably to conventional biogas desulphurisation processes that utilise a single stage scrubber with
sodium hydroxide, iron oxide and activated carbon.
Figures 11 to 15 shows the consequences of sulphur damage to the gas engines, in terms of the
maintenance schedules
Table 1 Running costs for the Sulfurex system
5000 ppm H2S, 5000 ppm H2S,
Capacity plant (500 m3
30 C,
30 C,
gas/ hr), efficiency 200
15 vol % CO2
35 vol % CO2
ppm H2S, pressure 50
mbar
Costs of water
7.464
4.270
Costs of caustic soda
49.632
28.416
Costs of energy
525
525
Depreciation *)
20.361
20.361
Maintenance
2.000
2.000
Operation
4.160
4.160
Total cost in / year
84.000
60.000
Total cost per m3 biogas 0,0192
0,0137
10.000 ppm
H2S, 30 C,
35 vol % CO2
6.113
40.599
2.223
23.500
3.000
4.160
79.595
0,0182
10.917
72.680
525
21.361
2.000
4.160
112.000
0,0256
Table 2. Running costs for the proposed options at the SAPPI plant (/pa)
One stage
Two stage
Two stage
Sulfurex
Sulfurex
Sulfurex incl.
cooling / drying
Costs of water
Costs of caustic
soda
Costs of energy
Depreciation *)
Maintenance
Operation
Totalcost in /
year
Total cost per m3
biogas
4.000
65.000
5.000
32.500
5.000
25.000
Two stage
Sulfurex
incl. cooling /
drying pretreatment with
activated sludge
absorber
5.000
8.000
525
12.500
2.000
4.160
725
15.000
3.000
4.160
2.000
18.000
4.000
5.000
5.000
21.000
5.000
7.500
88.185
60.385
59.000
51.500
0,050
0,035
0,034
0,029
500 m3/hr,
5000 ppm H2S,
30 C,
35 vol % CO2
8.570
412
1250
25.791
5.000
10.400
500 m3/hr,
5000 ppm H2S,
30 C,
15 vol % CO2
8.570
412
1250
25.791
5.000
10.400
500 m3/hr,
5000 ppm H2S,
10 C,
35 vol % CO2
9.176
2.129
1250
28.000
6.000
10.400
Total cost in
51.000
51.000
56.955
Total cost per m3 biogas 0,0118
0,0118
0,0130
*) Costs of water can be 0,= if effluent out of WWTP is being used.
**) Costs of nutrients can be 0,= if effluent out of WWTP is being used...
***) At depreciation of 10 years and an interest of 5 %.
Electrolyte
500 m3/hr,
10.000 ppm
H2S, 30 C,
35 vol % CO2
14.823
653
2500
32.578
5.000
10.400
66.000
0,0151
Housing
Reference electrode
Measuring resistor
Gas
Reference electrode
signal
-U
Diffusion membrane
Measuring electrode
Temperature sensor
operational amplifier
Bias voltage
10
Figure 6. DMT two stage Sulfurex process, Mauri plant in Hull, Yorkshire, UK.
11
Figure 8. DMT three stage Sulfurex process, SAPPI plant in Lanaken, Belgium.
12
15