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Desulfurization and reduction of siloxanes in biogas

2021-10-04 11:25:15

Desulfurization and reduction of siloxanes in biogas. Case Study: MCFC Project at CETAGUA (Mataró - Spain)

Reducing the carbon footprint of our society is essential. This can be achieved by capturing and confining anthropogenic CO2 emissions, as well as by replacing fossil fuels with renewable fuels.

MCFCs (Molten Carbonate Fuel Cells) are the only ones capable of doing both. Thanks to their principle of operation, CO2 can be extracted from a gas stream on the cathode side and fuels such as biogas can be converted into electricity on the anode side. However, the degradation caused by the pollutants present in these gases must be addressed. 

In this sense the project "MCFC catalyst and stack component degradation and lifetime: Fuel Gas Contaminant effects and Extraction strategies" aims to tackle this problem from two sides:

1) the investigation of the mechanisms of poisoning caused by fuels and to determine precisely the MCFC tolerance limits for long-term endurance;

2) optimization of fuel and gas cleaning to achieve adapted degrees of purification according to the operating conditions and MCFC tolerance.

CETaqua (Centro Tecnológico del Agua), a company belonging to the Suez group was involved in the project, where one of its main objectives was to test on a pilot scale, alternative adsorbent materials to activated carbons that were being conventionally used in most wastewater treatment plants (WWTP).

Fig 1: Biogas purification system located at the Mataró WWTP.

To this end, CETaqua contacted BION and a biogas purification project was carried out at the Mataró wastewater treatment plant (Barcelona), a project that was carried out in a two-stage system. The system consists of two identical lines composed of a first vessel filled with 3 mm BION SIGMA (formerly BION Fe) to remove H2S and a second step with a vessel filled with 4 mm BION AC for VOCs and extraction siloxanes (Figure 1).

The tests last about half a year and the results were evaluated at a rate of 10Nm3 / h, and the contaminant concentrations were in a range between 700-2000 ppmv and 4-5 mg/m3 for H2S and siloxanes, respectively.

Project results

In reference to H2S removal, the average results are summarized in Figure 2.

As can be seen, H2S was successfully removed in both lines and only during certain episodes, where peaks were measured, significant amounts of H2S were detected at the outlet of the first stage, but always maintaining removal efficiency values of more than 95% (Figures 2). Either way, the second vessel filled with BION AC, not only removes siloxanes and VOCs, but acted as a polishing stage that resulted in negligible H2S concentrations after the overall purification system.

Figure 3 clearly shows that BION SIGMA was depleted, as both colors can be distinguished before and after use.

Figure 3. DS B filled with BION SIGMA (a b). BION SIGMA in DS B (c).  DS A filled with BION SIGMA (d). BION SIGMA in DS B (top).

As for siloxanes, BION AC achieves removal efficiency values of about 30%, a value that might seem low, but there is a wide variety of siloxanes and not all of them are effectively removed with the same carbon quality. Therefore, depending on the siloxane to be removed, we could suggest one or another type of carbon. Taking into account that no characterization of siloxanes had been done before, the results obtained must be considered satisfactory.

 In summary, biogas purification system was successfully carried out and the biogas could be employed in fuel cells. 

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Efficient H2S Removal in Biogas

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Protect your biogas installations and reduce the maintenance costs

The conversion of biogas into green energy is not only environmentally friendly, but also contributes to the optimization of natural resources. More and more industries have biogas stations to take advantage of waste generated in these facilities, contributing to generate a circular economy where all available resources are exploited.   Biogas plants need to remove impurities before it is diverted to its final use (upgrading or cogeneration engines). In the case of upgrading, the need for purification is high due to the strict conditions required for methane purity.   The BION media ensures an effective removal of impurities at 99.5% efficiency.   BION medias: Protect and maintain the compressor by preventing the occurrence of corrosive atmosphere inside the compressor. Protect the membranes against fouling or pore blockage. Have very high adsorption capacity They are specially designed to give high performance in environments with low oxygen levels. Protect and maintain the installations   This becomes to reduced operating and maintenance costs and increased sorbent or adsorbent lifetime.   BION biogas purification solutions are the best return on investment because they They remove pollutant gases before they cause irreversible damage to membranes, compressors or cogeneration equipment. Enables compliance with biomethane grid injection input requirements Extends the lifetime of the pretreatment stage by reducing operating costs Avoid downtime by preventing costly unexpected repairs Eliminate ALL common contaminants other than H2S.

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Biogas Desulfurization at ETAR do Norte (Portugal)

The Wastewater Treatment Plant (ETAR) do Norte is one of the largest in the central region of Portugal, serving several municipalities. The infrastructure is located in the area of Coimbra, Leiria, occupying 6 hectares of land; it receives effluents from about 250,000 inhabitants of several municipalities.   It has the capacity to treat some 38,000 m3 of wastewater daily, of which 77% is domestic, 18% from industry and 5% is other effluents.   The biogas resulting from treatment is used as fuel for a cogeneration plant, where energy recovery is maximized through combined heat and power production.  The thermal energy is used to heat the sludge digesters, the building and the domestic hot water. The electrical energy produced, which can reach an output of 1.2 MW, is sold to the national power grid.   Biogas Desulfurization   Iron filings, one of the most widely used traditional methods, were used to reuse biogas for energy recovery. However, high construction costs and low efficiency led Simlis to look for other technologies to improve its process.   As an alternative, BION together with its distributor in Portugal, Equifluxo, proposed the use of BION Fe, a filter media regenerable with ambient air, capable of reaching a H2S removal capacity of up to 45% w/w. The use of this media would provide the following advantages over iron filings:   Save adding an iron chloride solution as a step prior to desulfurization. Reduce the number of media changes due to its high desulfurization capacity (45% w/w of BION Fe versus 12% w/w of iron filings). Achieve higher efficiencies. Reduce energy consumption due to the low pressure drop values generated. Depending on the final composition of the spent product and the regulations of each country, BION Fe could even be recoverable. On the other hand, the removal of water from the biogas, besides serving to promote the optimal operation of BiON Fe, has other advantages. The drying of the gas allows optimizing the combustion process in the cogeneration engine, reaching values between 2 and 5% more energy generation; it increases the efficiency of the engine and reduces the gas/fuel consumption; it allows reducing the contamination of the engine oil with the condensate, extending the life time of the oil from 400-500 hours to 2000-3000 hours. Finally, in the case of treating biogas with siloxanes, this dehumidification stage will help to slightly reduce the concentration of some of these recalcitrant compounds.   Bioconservacion Solution BION designed a reactor for biogas treatment with the following characteristics: Flow rate: 25 m3/h Temperature range: 35-40 ºC Relative humidity: 95-99 %. Composition: CH4 66 %, CO2 30 %, H2S 2500 ppm To carry out biogas desulfurization, Bioconservacion/Equifluxo designed a very versatile unit with a double fiberglass wall to reduce the effects of condensation, with a plenum that avoids the generation of preferential paths and therefore the use of the entire medium, as well as the generation of high pressure drop values. Over a period of 12 months, Bioconservacion/Equifluxo carried out exhaustive monitoring of the equipment's results, with technical visits every 45 days for the first 3 months and every 3 months thereafter. The results obtained were very positive, reaching efficiencies of over 99%, allowing full use of the energetic power of biogas (Figure 2).     Evolution of H2S concentration at the reactor inlet/outlet over time.

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