BIOGAS DESULPHURISATION USING THE DMT MULTIPLE STAGE SULFUREX PROCESS Author: Erwin H.M.

Dirkse, DMT Environmental Technology ABSTRACT Global rising energy costs are focusing efforts by many industrial and municipal entities to find new sources of energy. Generating electricity from Biogas is of course nothing new however the cost of cleaning up certain Biogas streams with excessive levels of Hydrogen Sulphide (H2S) has previously proven to be financially unsustainable. Rising energy costs combined with improvements and cost reductions in desulphurisation systems have increased the number of potential biogas streams that can be efficiently and cost effectively treated to provide the end user with a lucrative additional revenue stream from their anaerobic digestion process. DMT a Dutch based manufacture of odour control and Biogas desulphurisation systems, is also offering the Sulfurex process in the UK. The first UK system is installed in the summer of 2006 at the Mauri plant in Hull, Yorkshire. This system is designed to reduce the level of incoming Biogas from 20,000 ppm down to 135 ppm prior to it being fed into the CHP plant. The Sulfurex process is a multiple stage scrubbing process based on the selective absorption of H2S in a solution of sodium hydroxide. Numerous Sulfurex systems are operational throughout Europe. Despite the success of the system it has been significantly improved in recent years, the key developments are as follows: Improved selective absorption of H2S Reduced consumption of sodium hydroxide Treatment of spent lye Regeneration of spent lye Biogas pre-treatment with activated sludge or waste water. Pre-treatment of Biogas using activated sludge can significantly reduce the consumption of sodium hydroxide and thereby lower operational costs. Selective absorption reduces the amount of CO2 absorbed and consequently reduces the volume of sodium hydroxide required. The second stage scrubbing process of the Sulfurex system in which the spent lye can be used to further improve the rate of absorption. The Sulfurex system is capable of reducing the H2S levels, up to 20,000 ppm in the incoming Biogas stream by more than 99%. Further developments also include the potential for desulphurisation without using any chemicals at all, this system is known as the Biosulfurex process and utilises a purely biological approach. When a limited amount of Oxygen is dosed into the Biogas flow Thiothrix & Thiobacillus bacteria oxidise H2S to elemental sulphur and sulphate, dependant on process conditions, or sulphuric acid. In order for the bacteria to oxidise effectively Oxygen, nutrients, and a contact surface are required. Oxygen is provided by a compressed air supply, nutrients from activated sludge and the contact surface from the media within the scrubber itself. This paper will describe the operation and performance of both the Sulfurex and Biosulfurex systems, detailing system efficiencies, capital costs, running costs and payback periods. KEY WORDS Biogas desulphurisation, Sulfurex, DMT, selective absorption INTRODUCTION DMT Environmental Technology has developed considerable know-how and experience within the very specific area of desulphurisation of biogas and landfill gasses. In the mid 1980s DMT developed a desulphurisation process and registered it under the name of Sulfurex. This process is based upon selective absorption of H2S in a solution of sodium hydroxide. Since 1985 , DMT has been supplying desulphurisation systems worldwide on a variety of projects including paper mills, breweries, fertiliser plants, landfill sites, sludge-digestion facilities, waste water treatment plants and potato factories where anaerobic treatment processes produce biogas or landfill gas containing H2S. Recently DMT has improved the Sulfurex process and adapted the process to incorporate the latest technologies; the selectivity of H2S adsorption has been improved, the specific consumption of sodium 1

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

5 0 0 m 3 /u , 35% CO 2, 30C

kg NaOH/

kg H2S

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 )

Figure 1. Caustic Soda consumption based on H2S concentrations 2

The following design data is required in order to design a gas desulphurisation plant: 3 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 NaHS (Sodium hydrogen sulphide) + H2O Na2CO3 (Sodium Carbonate) + H2O (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 NaHS + NaHCO3 (Sodium hydrogen carbonate) (3)

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

Biogas sample take-off system Clean air Analizer M3

Inertgas in First stage

Ventilation

Inertgas in Second stage

Drain M1 M2 V1 M1A M2A M4 M5

V2

NaOH

Water supply

Chiller

Process Diagram

Two stage combined biogas drying and -desulphurization plant

Figure 2. Typical P & I D for a two stage Sulfurex system. Cooling and drying the biogas. It is advisable to have the biogas dried before it enters the CHP engine because of potential for condensate formation, consequently DMT have developed a very compact vertical biogas drying system, combining the removal of water and H2S in one process. The biogas conditioner is based on direct contact between biogas and the scrubber fluid, within a packed column. The scrubber fluid is cooled over an integrated plate type heat exchanger running at less than 5 prior to it entering the top of the scrubber column. The water C. in the biogas (RH of 100 %) will condenses on contact with the surface of the packing material. The condensate and scrubber fluid is collected in the circulation basin of the scrubber. Surplus fluid is drained out of the tank. The treated biogas passes through a demister to remove droplets and is heated by an integrated gas / gas heat exchanger at the top of the scrubber column or by a separate heater fed with engine cooling water at +/- 90 The removal efficiency of these type of plants for sulphur is very high; C. the relative humidity of the biogas is reduced from 100 % to 60 %. As a result the reliability of the gas engine or steam turbine can be increased considerably. Consequently down time and maintenance cost can be significantly reduced. Running costs Running costs will vary according to make up of the Biogas, various examples are shown in Fig 3, but 3 typically for a 500 m /hr biogas plant running at 5000 ppm H2S and a target level of 200 ppm H2S the 3 running costs will be less than 0.02 per m biogas treated. (Based on depreciation over 10 years and interest at 5%) BIOLOGICAL DESULPHURISATION - BIOSULFUREX It is also possible to remove H2S form Biogas or landfill gas using a biological system. The DMT BioSulfurex system is a very cost effective method and yet still provides efficient removal of H2S. The process is fully biological, requiring no (or in some cases minimal) chemicals or external utilities. When a limited quantity of air is added to the biogas, specific aerobic bacteria such as Thiothrix and Thiobacillus will oxidize the H2S into elemental sulphur and/or depending on the environmental conditions into sulphuric acid. These bacteria require: Oxygen Nutrients and trace elements Growth area

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
3

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: 2 H2S(g) + H2O(l) 2 CO2(g) + OH (aq) H2S(aq) + HS (aq) + H3O CO2(aq) + HCO3 (aq)
+ (aq)

(1) (2)

(1) Dissolution of H2S in water with a specific pH. (2) Dissolution of CO2 in water. Except for the reactions mentioned above various other chemical reactions of sulphide compounds also occur, depending on the composition of the activated sludge. By scrubbing the biogas the pH value of the activated sludge decreases; the higher the pH value the better the scrubbing process operates. Stage 2- Soda utilisation stage, soda scrubber. In the second step the biogas flows through the scrubbing tower in a counter flow pattern; before passing to stage 3. A soda solution is sprayed over the scrubbing tower column. In the circulation system there is a heat exchanger as the lower temperatures provide enhanced scrubbing and the biogas is therefore cooled from approximately 30 to 8 C C. The following reactions will take place in the second stage: 2 H2S(g) + H2O(l) H2S(aq) + HS (aq) + H3O (aq) H2S(aq) + Na2CO3(aq) NaHS(aq) + NaHCO3(aq) CO2(g) + Na2CO3(aq) + H2O(l) 2 NaHCO3-(aq) (3) Dissolution of H2S in water (4) Chemical reaction between H2S and soda. (5) Dissolution and reaction of CO2 in water by soda Stage 3 -Caustic stage, caustic scrubber. In the third stage the biogas from stage 2 enters the tower in a counter flow pattern. The medium that is sprayed over the column consists of a caustic solution which is formed by addition of a caustic solution into the circulation flow. Make-up water is also added. In this way the total concentration of caustic added should not be more than 3-4 %, because of the danger of clogging the system (crystallisation of sodium bicarbonate ). In the water circulation system is a heat exchanger, which cools the circulation water from approximately 14 to 4 degrees C. The lower temperatures in the scrubbing column, enhances the reaction. The caustic is added through a dosing system. The volume of caustic is adjusted by increasing or decreasing the pump frequency. This is controlled by a DMT purpose designed H2S sampling and take-off system. The waste water drains via an overflow system back into the second stage scrubber. The following reactions will mainly take place in the third stage: 3 H2S(g) + 3OH (aq) H2S(aq) + HS (aq) + S (aq)+ 3H2O(l) 2HS (aq) + S (aq)+ 3H2O(aq) 2H2S(aq) 23 CO2(g) + 3 OH (aq) CO2(aq) + HCO3 (aq) + CO3 (aq) + H2O(l) (6) Chemical reaction between H2S and soda. (7) Dissolution of H2S in water (8) Dissolution and reaction of CO2 in water by caustic DMT bases its guarantees on caustic consumption using in house developed design programs and process calculations; checked and adjusted with field data from operational systems. Biogas emanating from processes for which DMT has no previous experience or data may have significantly different compositions should these compounds have a catalytic effect on the absorption of carbon dioxide, the specific caustic consumption could be significantly higher than those where the Biogas composition is known. Potential unknown compounds could be alcohols, aldehydes, fatty acids and similar structures. To ascertain if these compounds are present the biogas should be sampled using gas chromatography analysis. If alcohols and or acids are present in the biogas in concentrations of 50 100 ppm, caustic soda consumption will increase by 1 3 % when compared to normal process conditions. If alcohols and or 6
2+

(3) (4) (5)

(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 2 C. 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 2 to 4C. At the same time the C circulation fluid has the cooling potential to reduce the temperature from 14 to 4 C C. Secondly the cooling fluid enters the second stage. The cooling fluid in this section has a temperature gain from approximately 4C to 6 At the same time the circulation fluid cools from approximately 12 to 7 C. C C. 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 30 to 27C and the treated gas will rise in temperature approximately 12 from C C 12 to 24 C C. 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.
Dilution effects of water free sodium hydroxide
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 0 -20 -30 -40

Boiling point curve

End temperature, degrees Celsius

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

Figure 3. The effects of diluting pure sodium hydroxide. 7

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

5000 ppm H2S, 10 C, 35 vol % CO2 6.113 40.599 2.223 23.500 3.000 4.160 79.595 0,0182

10.000 ppm H2S, 30 C, 35 vol % CO2 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 65.000 525 12.500 2.000 4.160 88.185 0,050

5.000 32.500 725 15.000 3.000 4.160 60.385 0,035

5.000 25.000 2.000 18.000 4.000 5.000 59.000 0,034

Two stage Sulfurex incl. cooling / drying pretreatment with activated sludge absorber 5.000 8.000 5.000 21.000 5.000 7.500 51.500 0,029

Table 3. Running costs for a Bio-Sulfurex process for varying parameters Capacity plant (m3 gas / hr), efficiency 200 ppm H2S , pressure 50 mbar Costs of water *) Costs of energy Costs of nutrients **) Depreciation ***) Maintenance Operation 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 10.400 500 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

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

Housing Reference electrode

Measuring resistor

Gas
Reference electrode

signal

-U Diffusion membrane Measuring electrode Temperature sensor operational amplifier Bias voltage

Figure 4. General arrangement of Hydrogen Sulphide measurement system

Figure 5. DMT BIOSULFUREX biological biogas desulphurisation plant

10

Figure 6. DMT two stage Sulfurex process, Mauri plant in Hull, Yorkshire, UK.

Figure 7. Interior of a H2S detection and sampling unit

11

Figure 8. DMT three stage Sulfurex process, SAPPI plant in Lanaken, Belgium.

Figure 9. DMT BIOSULFUREX biological biogas desulphurisation plant

12

Figure 10. Illustration of a Sulfurex plant

Figure 11. Effect of sulphur on gas engine maintenance schedule 1 13

Figure 12. Effect of sulphur on gas engine maintenance schedule 2

Figure 13. Effect of sulphur on gas engine maintenance schedule 3 14

Figure 14. Effect of sulphur on gas engine maintenance schedule 4

Figure 15. Effect of sulphur on gas engine maintenance schedule 5

15