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Making pressurized water scrubbing the ultimate biogas upgrading technology with the DMT Carborex PWS system.

Robert Lems*, Erwin Dirkse** *R&D manager, DMT Environmental Technology, Yndustrywei 3, 8501SN, Joure, The Netherlands (E-mail: ** Managing Director, DMT Environmental Technology. ( Abstract Biogas is one of the most promising energy sources for the future. Biogas is a waste product from e.g. landfill sites or digesters that can be applied as a green and renewable energy source with no global emissions on CO2 and hardly no local emissions on other pollutants. Currently most biogas is used at a CHP at which a large part of the energy is converted into heat which can not or only partly be used. This could result in an energy loss up to 60%. But biogas can also be upgraded to natural gas quality. As upgraded biogas, the gas can be used as vehicle fuel, injected into the gas grid or transported to more efficient energy production sites by which the total energy recovery can be close to 100%. Most important for biogas upgrading to natural gas quality is the removal of CO2 and H2S. A second important issue is the energy efficiency and methane losses. In this paper the advantages of pressurized water scrubbing compared to other available technologies are stressed out. In more detail innovations of the DMT Carborex PWS technology are explained. The possibilities for recovery of liquefied CO2 and the integration of heat-pump technology makes it the ultimate process for biogas upgrading. The result is an energy neutral plant without methane losses and even a reduction on global CO2 emissions (instead of being neutral). DMT will demonstrate the pressurized water scrubbing system in relation with the other upgrading processes by field experiences. Keywords Biogas, Biological desulphurization, CO2 recovery, Heat pump, Methane recovery, Natural gas, Pressurized water scrubbing, Upgrading system. Abbreviations upgrading: PSA: Pressure swing absorption, CA: Catalytic absorption, MS: Membrane separation, CL: Cryogenic liquefaction, PWS: Pressurized water scrubbing. Introduction Biogas is produced by fermentation of organic material in e.g. digesters but also at landfill sites. The gas contains high amount of methane which can be used as a green energy source with no global emissions on CO2 and hardly no 1 local emissions on other pollutants (see figure 1 for an example of vehicle fuel comparison). This makes biogas the most sustainable source of energy in the future comparable to solar-, wind- and water power.

Figure 1: Comparison of different vehicle fuels on global and local pollution emissions.

Currently most biogas is used in CHP or gas engines at which a large part of the energy is converted into heat from which usually only a small part can be used on site. This can result in energy losses up to 60%. But biogas can also be upgraded to natural gas quality or better. As upgraded green gas, the biogas can 2 be used as vehicle fuel , injected into the gas grid and/ or transported to more efficient energy production sites where the total energy recovery can be close to 100%.

For upgrading biogas to natural gas quality, the main function of the plant is the removal of CO2 and H2S (see table 1) to increase the energy content and reduce risk of corrosion. A second important aspect for the upgrading plant is the energy and methane efficiency to reach the desired final methane concentration. Most upgrading processes like pressurized water scrubbing have an energy efficiency between 90-96% and a methane slip of 0.5-2%. However, the DMT Carborex PWS system combines the PWS upgrading technology with the recovery of liquefied CO2 and the integration of highly advanced heat-pump technology. The result is an energy neutral plant with no methane loss and even a reduction on global CO2 emissions (instead of being neutral). Table 1: Raw biogas versus biogas at natural gas quality (The Netherlands/ UK/ German) and biogas at 3, 4 maximum quality for vehicle fuel use. Component Unit Biogas Natural gas Natural gas Vehicle fuel (Dutch) (German/ UK) CH4 v/v % 45-70 90-95 >95 >97 CO2 v/v % 30-45 <10% <5% <1 N2 v/v % 1-10 <10% <5% <2 O2 v/v % 0.2-1 <0.1% <0.2-0.5 <0.5 3 H2S mg/Nm 10-15.000 <5 <5 <5 3 CF mg/Nm 0-3000 <dew point <dew point <dew point H2O (dew point) C@70 bar Saturated -8 < -8 < -169 3 Caloric value kWh/Nm 5-7.7 8.8-10.8 8.4-13.1 10.7-11.6 3 Wobbe index kWh/Nm 4.8-8.4 12.0-12.3 12.8-15.7 14.1-14.8 Biogas upgrading processes. Several technologies exist for upgrading of biogas to natural gas quality . At this moment pressurized water scrubbing (PWS), pressure swing adsorption (PSA) and catalytic absorption (CA) are the most commonly applied processes. Other technologies which are still in development are cryogenic liquefaction (CL) and membrane separation (MS). Each process has its own advantages and disadvantages and maybe most suitable for a different raw biogas composition and desired upgraded gas quality. For example PSA can be used for landfill gas containing high concentrations of nitrogen gas because it is the only process capable of nitrogen removal. CA can be a good choice e at sites which have excess heat and require low pressure upgraded gas (<500mbar). CL has an advantage if CO2 recovery is required and the upgrade gas has to be liquefied. Finally membranes are the most compact but are only useful if the high methane loss (10-20%) can be used local for heating and power. The PWS technology is the most applicable process in most situations because it removes a wide range of pollutant (including CO2, H2S, alcohols etc) in one step. It has been the most implemented process world 6,7 wide with over 30 plants in Europe. (Data 2007 ) It is the most simple and robust technology, easy to operate and does not use any chemicals. At the same time it has a high energy efficiency and can produce a wide range of final gas qualities (90-99%) at fluctuating flow conditions. Furthermore both operational and 8 investment costs are the lowest compared to the other systems. Although PWS is the most applied process and in use for over 20 years, DMT proves that this technology is far from being a product without possibilities for further innovations. The improvements made by DMT are eliminating the weaknesses of the PWS system (e.g. methane slip, energy efficiency and emission of CO2) and turning it in unique advantages. What makes the DMT Carborex PWS the ultimate technology? The PWS process is based on the difference in solubility of CH4 and CO2 in water. The process is intensified by further improving the solubility of CO2 by pressurizing the absorption system to 8-10 bar. 9,10 (see figure 2 ) Also other water soluble pollutants like H2S will be washed out /absorbed into the circulation water.

Figure 2: solubility at different pressures. 2

The regeneration of water is provided by relief of the pressure to 2-4 bar at the flash vessel and subsequently stripping with air. At the flash vessel mainly traces of methane are escaping from the liquid, which are returned to the compressor. The CH4 enriched gas is dried and is ready for injection into the gas grid or other applications (see figure 3). To improve the PWS system, DMT developed different sub units which have been integrated into the 11 upgrading process. The result is the DMT Carborex PWS (pressurized water scrubbing) system which is the only system with zero methane loss, zero net energy demand and no chemical use for upgrading and desulphurization.

Figure 3: Schematic overview of the PWS system.

Biological desulfurization One of the pollutants in biogas which always has to be removed is H2S. H2S is a corrosive, toxic and bad smelling gas which is present in biogas in concentrations ranging from 10 ppm to 15.000 ppm or more. All upgrading processes require a pre-treatment for H2S removal which is usually done by a chemical process like activated carbon, Iron oxidation or alkaline scrubber. These processes always need chemicals and result in a discharge of chemical waste and high operational costs. The PWS technology is the only process which is capable to remove high concentrations of H2S from biogas at the same process like the CO2 absorption. Eventually the H2S will be emitted in the air with the CO2. DMT has already over 20 years of experience for H2S removal, both in gas and air streams. This experience has been used to integrate a biological desulphurization unit into the DMT Carborex PWS system. Depending on the original H2S concentration the H2S can be removed before compression or at the air exhaust. The H2S is biological converted to H2SO4 by the bacteria Acido Thiobacillus Thiooxidans (see 13 equation 1+2). H2SO4 is a part of the natural sulphur cycle and can be easily discharged to a WWTP. 14 Thiooxidans is an autotrophic bacteria which uses CO2 as carbon and H2S as energy source. The elevated CO2 concentration present in the exhaust increase the efficiency of the bacteria. This makes the DMT Carborex PWS the only system which is able to remove H2S without any chemical use. Biological oxidation of H2S . Equation 1) H2S + O2 S + 2H2O . Equation 2) S + 1O2 + H2O H2SO4

Figure 4: Picture of acido thiobacillus thiooxidans

Sterilized upgraded gas One of the concerns of the end-user about the upgraded gas is the possibility that pathogens (viruses/ bacteria) which may be present in the biogas will eventual come up in the final gas. The gas distributor could have concerns for corrosion of gas pipes by acido thiobacillus thiooxidans. Although this chance is very small and also natural gas can contain bacteria, DMT has incorporated a quadruple defence system into the DMT Carborex PWS system to ensure the upgraded gas is sterile. First the compressor is equipped with a sterilisation stage to kill pathogens from the incoming biogas at elevated (>150C) temperatures. The second defence is an UV sterilisation unit in the circulation water which eliminates any bacteria trying to survive in the system (e.g. coming from outside with the air stripper). This will also reduce maintenance on the system because the packing materials remain clean from bio fouling. The third step is the drying unit which eliminates the essential humidity for the bacteria followed by the last defence a HEPA (High efficiency particulate air) filter which are also used in for example clean-rooms. A HEPA filter will eliminate pathogens based on 3 mechanisms: Interception, impaction and diffusion which result in a >99.97% elimination of all particles of 0.3 15 micro meters or larger (see figure 5). Direct Catalytic oxidation of H2S and CH4 An important issue for biogas upgrading is the methane recovery from the biogas and green house emissions to the environment. The methane recovery should be near to 100% because it represents utilisable energy. But even more important is the methane emission which represents a strong green house 16 gas. Methane is about 23x stronger as green house gas than CO2. Therefore a methane slip of just 1% results in a greenhouse emission of 20% compared to total combustion of the biogas. All biogas upgrading processes experience a methane loss variation from 0.4 to 2% compared to the biogas input. CA and MS are the exceptions with a methane slip of about 0.1% (CA) respectively 20% (MS). The solution for these green house emissions is to oxidize the methane to carbon dioxide. This can be done by e.g. direct combustion or regenerative thermal oxidation (RTO). Most processes like direct combustion need a high concentration of methane and therefore (except with MS) the methane slip is too low and only RTO 17 is available. Even this process needs at least a methane concentration of 0.4% or higher (comparable to a methane slip of 1% or more due to air dilution) to function without adding extra fuel. Due to this the overall energy efficiency of conventional upgrading systems are deliberately lowered when methane emissions are handled (due to legislation like in Germany or from environmental view) by applying extra methane slip or using natural gas to keep the RTO in function. Normally PWS systems can be optimized to have a methane loss of 0.5-0.8% resulting in exhaust methane concentrations of 0.2-0.3%. To eliminate methane emissions but keep an optimum energy efficiency, DMT has developed and integrated an catalytic oxidation process, which is based on a platinum and palladium catalyst, into the DMT Carborex PWS system (see figure 5). This catalyser is able to autothermic oxidize methane at concentrations as low 0.2% in a very compact installation. The heat which is produced can be reused in the TSFigure 5: CRO unit PWS process (see Total energy control system). The catalyser is also unique in the fact that it can handle H2S concentrations up to 500 ppm. This means that in most cases no other H2S removal steps are necessary, eliminating any chemical or biological units and or wastes. With the CRO (catalytic regenerative oxidation) the methane emissions are reduced with >99% to 3 <20mg/Nm without reducing or even increasing the total energy efficiency. (see Total Energy Control System)

Figure 5: Working scheme HEPA

Total energy control system Besides the methane efficiency, the total energy efficiency is even more important. The energy efficiency is determined as the energy content of the upgraded gas (Q-CH4,out) minus the energy consumption of the upgrading unit (Qupgrading) divided by the energy content of the biogas input (Q-CH4,in). The energy needed for the biogas upgrading plant can be both electric and heat (e.g. for catalytic absorption) Equation 3) (Q-CH4,out Qupgrading)/ Q-CH4,in

Most processes have an energy consumption of 0.2-0.3 kWh/m upgraded gas. Only the CA has lower energy consumption if excess heat is available and if the gas is directly used at low pressure. However usually biogas is generated at digesters which demand rather than produce heat. Further more, the upgraded gas is usually used at pressures of 9, 43 or 250 bar. To optimize the total energy balance of a PWS system DMT has developed the TEC (Total Energy Control, see figure 6) system to optimize energy demand and converts heat and energy loss in heat gain to be used for e.g. the digester or facility heating. The core of the TEC is the EDi which is a sophisticated control system for a combination of a chiller and a heat-pump. The chiller is used to cool down excess heat from the biogas compressor, sterilisation, biogas input, condensation and Figure 6: Schematic drawing of the TEC system. environmental factors. The heat-pump converts the cooled energy into usable heat at temperatures between 55 to 80C. The heatpump capacity can be increased with heat from the methane oxidation unit and/ or the excess heat from the CO2 recovery unit (See next paragraph. In this way 80-110% of the digester heat can be supplied year round reducing heating costs with minimal 50.000 to 100.000 euro annual.) Because the chiller is a standard unit for any upgrading unit, the EDi does not require a higher quantity of installed power but due to the constant heat demand of the digester the EDi will be always in operation keeping the upgrading system at a low and constant temperature, increasing the stability and efficiency of the system. Further more the energy demand of the upgrading system (Qupgrading) is now positive making the total energy efficiency 100% or more. CO2 liquefaction CO2 is not only a green house gas and a waste gas but it is also a raw material for various industrial processes and is used in green houses to improve the crop yield. The market price for pure CO2 can range from 60 euro/ ton to 200 euro per ton depending on CO2 quality, fossil fuel price (which are usually used to generate CO2) and CO2 emission trade prices. The CL system is the only conventional upgrading process which results in CO2 recovery but at a high price and only at a purity of 99.6% with 0.4% methane pollution. The high price is not only literally the sales price but also a high energy consumption, complicated system, low CO2 quality (only admissible for green houses) and high green house emissions. The PWS system also emits a CO2 rich gas stream from the stripper tower. The gas stream can be adjusted to a CO2 concentration of 90-98% which can be directly used in green houses at low cost. But the DMT Carborex PWS system can be extended by incorporating a CO2 liquefaction unit. Due to the fact that the input of the DMT Carborex PWS, CO2 liquefaction unit is already a smaller and more concentrated CO2 stream than at the direct CL upgrading process, the recovery of CO2 is achieved by a much lower (investment and operational) price, lower energy demand and at much higher purity compared to cryogenic liquefaction. Figure 7: 3-D model of a CO2 liquefaction unit

The CO2 rich gas stream is pressurized to 12-16 bar and cooled down to minus 25-30C. At this point the CO2 condensates and is stored as liquid CO2 ready for transport. By applying different purification and drying steps a high CO2 quality can always be guaranteed. A purity of 99.98-99.9985% makes it possible to reuse the CO2 even within the food processing industry (e.g. beverage gasification). At the condenser the last traces of methane are now concentrated as non condensable This methane rich gas stream is redirected to the upgrading unit reducing the methane loss of the DMT Carborex PWS system to <0.001% making it the lowest of all systems. Due to the zero methane slip and reuse of CO2, the DMT Carborex PWS system is the system with the most reduction on global green house gas emissions. Field comparison There are a lot of comparison studies in the field of biogas upgrading . Different institutes and especially suppliers result in a various outcome mainly due to the selective use of different variable, definitions and system boundaries (e.g. available heat, final pressure, compressor included etc). Therefore we have made a comparison based on the literature studies and supplier information related to the most likely scenario of biogas production and use with the same system boundaries for each upgrading system. 3 The next scenario has been calculated for PSA, CA, MS, CL, PWS, DMT Carborex PWS: 550Nm /h biogas from a mesophilic (T=37-41C) digester with 60/40 v/v% CH4/CO2 and 100-500ppm H2S. The biogas is upgraded to natural gas quality (>95%) for main grid injection or vehicle fuel (minimum of 9 bar). As system boundaries the upgrading unit is calculated starting from raw biogas until gas at 9 bar and natural gas quality. There is no after treatment of methane emissions or other waste streams. For H2S removal activated carbon filters are calculated unless the process explicitly uses a different desulphurization technology. Heat for the digester and CA is supplied by means of natural gas combustion. The data for the DMT Carborex PWS system are based on an actual plant which is being built in Zwolle (NL) for Natuur gas Overijssel, one of the most important projects in the Netherlands at this moment. From table 2 it is clearly visible that PWS systems have the lowest investment and operational costs. The PWS system has to most references and also all process steps for the DMT Carborex PWS have a large range of references. At the same time it is the most flexible system, easiest to operate and the only system without any chemicals. For all other parameters the PWS system performs always in the top 2. By implementation of the DMT Carborex PWS system the investment cost increase (but only to about equal CA and PSA) but the cost of operation is lowered significant due to energy savings for the digester and profits from CO2 sales at food grade quality. A major benefit is also the reduction of methane slip to zero, so no methane and/or green house gas emissions.
18, 19, 20

Figure 8: Impression of biogas upgrading to vehicle fuel: Left, upgrading unit (Netherlands); top right, green gas bus; Bottom middle, Fuel storage; Bottom right, fuel station.

Table 2: Field data comparison for a biogas upgrading unit to natural gas quality for 550 Nm /h biogas. PSA MS CL CA PWS Carborex PWS unit 3 0.26 Energy consumption 0.22-0.25 0.5 0.3-0.4 0.3-0.4 0.2-0.3 kWh/m upgraded 80-85 >100 Energy efficiency 96-97 91-92 91-92 95-96 % 10-20 <0.001 Methane slip 1-3 0.5-0.8 0.1-0.2 0.6-0.8 % 98 Upgraded gas quality 98 90-95 98 99 98 % CH4 No No No FG CO2 recovery GH GH No, GH, FG Water/SH/AC Cat/water/AC Water/ S Chemical use AC/MS AC Water/ S ++ ++ Ease of operation + +/+/+ -, +/-, +, ++ ++ ++ Flexibility +/+/+ -, +/-, +, ++ ++ ++ References + + -, +/-, +, ++ 3 0.18 Operational cost 0.26 0.3-0.5 0.4 0.35 0.25 Euro/m upgraded 0.8 1.2-1.3 Investment costs 1.3-1.4 >1.5 1.4-1.5 1.1-1.3 Milj. euro GH= Green house quality; FG= Food grade quality; MS= Molecular Sieves; SH= Solvent enhancer; Cat= catalyst (amines/ PEG); AC= Activated carbon; S= Sulfur (solid or H2SO4)

Figure 9: 3-D drawings of the DMT Carborex PWS containerized system. Left control room and water distribution, middle gas drying/ post treatment, middle overview.

Advantages of standardization and the economy of scale One of the strengths of DMTs DMT Carborex PWS systems is that each sub-unit consists of standardized and containerized units. Due to this the total systems can be easily engineered (like blocks) to the customer demand with relative low costs. Each unit system is a world wide implemented and proven technology. DMT 3 is capable of delivering standards unit from 250 to 8000Nm /h and higher on request. For the smaller 3 systems (250-1000Nm /hr) the investment cost (0.6-1.2 milj. euro) are relative high compared to the operational cost (see figure 10). This is one of the reasons that smaller units are less economical viable in this setup (see next chapter). 3 250.000 0,12 Starting from 1000-2000Nm /h the operational cost are the biggest 0,1 200.000 expenses for upgrading biogas and investment investment cost are relative low 0,08 electricity (1.2-1.8 milj. Euro). The biggest cost 150.000 maintenance is the power demand. This power 0,06 operation could be locally generated by a water 100.000 0,04 nutrients small CHP unit which would also Price per m3 serve as a back-up/ complementary 50.000 0,02 heating for the digester. In this way centralized/ high flow upgrading 0 0 units would be the most optimal way 250 m3/h 500 m3/h 750 m3/h 1,000 m3/h 2,000 m3/h for energy utilization from biogas. Figure 10: Indicative graphical relation between cost and design flow. Small scale decentralised units for local use A large part of the investment price for the upgrading units is the process control, safety control and analysing systems with back-ups to guarantee a specific upgrade gas quality for injection in to the gas grid or to be used as vehicle fuel. However if the gas would be used locally near or at the biogas delivery site these parameters would be less important. For example, a farmer could use the upgraded gas for indoor heating, gas stove and his own fuel demand possible sharing with neighbours. In this case the final quality would be less important because these systems can operate between methane concentrations of 90-99% and there is no charge on exact kWh. By designing a system on these specific demands the upgrading unit can be simplified (see figure 11) to an absorber tower at 250 bar (4) with a simple 2-stage flash vessel (5) regeneration system which is only operated and controlled by an on/off switch. Both H2S and H2O removal can be accomplished with yearly exchangeable filters (1, 2 and 7). The upgraded gas will on average have a methane concentration of >97% and is stored in vessels (8) which can be easily transported to nearby sites. Due to this simplification and by the large amount of possible site (standardized production) these units can be economical feasible starting 3 from capacities as low as 50Nm /h.

Figure 11: Schematic view of small scale upgrading unit based on the PWS process.

Conclusion As proven technology, pressurized water scrubbing (PWS) is the oldest process for biogas upgrading to high quality methane gas. It is still the most used process today because it is the simplest process, has low operational and investment costs, and works at high energy efficiency and low methane slip. The PWS system is applicability in almost all cases of biogas supply and upgraded gas quality demand. In the last years DMT has shown that the PWS process still has opportunities for innovations. By integration of additional units like catalytic regenerative oxidation, sterilization and biological desulphurization the PWS process is continuously in development to remain the best technology in the market. With the new DMT Carborex PWS system, DMT also integrates a highly sophisticated energy optimisation system (TEC/EDi) and CO2 recovery process in the system. In this way the upgrading plant delivers heat for the digester, operates energy neutral with zero methane slip and produce not only enriched methane gas but also CO2 at food grade quality. This makes the DMT Carborex PWS the ultimate biogas upgrading technology now and in the future. Literature Jnsson, O., Persson, M., The potential of biogas as vehicle fuel in Europe. University of technology, Gteborg, Sweden, 2007 2, Coalition rijden op biogas (coalition driving on biogas). 3 DVFW-G 260 (D), GtS (NL), UKCS (UK) 4 Aansluit- en transportvoorwaarden gas, RNB, NMa 5 Lindenberg, A., Wellinger, A., Biogas upgrading and utilization. IAE Bioenergy. TASK 24: Energy from biological conversion of organic waste. Sailer Druck, Winterthur 2003. 6 Dirkse, E.H.M, Biogas upgrading using the DMT Carborex PWS technology, 2009 7 Eriksson, O. M. (2007) , The potential of biogas as vehicle fuel in Europe. University of Technology, Gteborg. 8 Report: Comparing different biogas upgrading techniques; July 2008 , Technical University of Eindhoven. 9 Lide, D.R., Handbook of chemistry and physics; 71th, 1990 10 Perry, R. H., Chemical engineers handbook, 50th, 1984 11 Brochure TS-PWS 12 Dirkse, E.H.M Biogas Desulphurisation using the DMT multiple stage Sulfurex process, 11th European Biosolids Conference, Manchester. (2006) 13 J. D. Butler, Air pollution Chemistry, The sulfur cycle in the biosphere, 1979 14 Germn Aroca et al, Comparison on the removal of hydrogen sulfide in biotrickling filters inoculated with thiobacillus thioparus and acidithiobacillus thiooxidans, Electronic journal of biotechnology, Vol.10 No 4 (2007) 15 16 17 R. Gay, Three ways to control VOC emissions, The free library, 1997 Air pollution control technology fact sheets, EPA-452/F-03-021 18 Creatieve Energy (creative Energy), senter novem, Brochure opwaarderen tot aardgaskwaliteit/ van biogas naar groen gas (upgrading to natural gas quality/ from biogas to green gas), 2009 19 E. Weidner et al., Technologien und Kosten der Biogasaufbereitung und Einspeisung in das Erdgasnetz. Ergebnisse der Markthebung 2007-2008. 20 Persson, M., Wellinger, A., Biogas upgrading and utilization. IAE Bioenergy. October 2006.

Figure 12: PWS, The Netherlands