Biogas Purification and Methane-Enrichment For Industrial/Vehicular use

The approximate composition of a biogas from anaerobic digesters is: CH4 ...55-75% CO2.25-45% Water vapor Fully Saturated Traces of H2S..Up to 1% Removal of impurities According to application: Application Gas heater (boiler) Vehicle fuel Gas grind H2S <1000 ppm Yes Yes CO2 No Yes Yes H2O No Yes Yes Traces Yes Yes Yes

Purification methods: Absorption (scrubbing) Pressure Swing Absorption (PSA) Cryogenics Gas membranes

Carbon Dioxide Removal For the removal of carbon dioxide we need: Increased calorific value of the gas Consistent gas quality, similar to natural gas

Removal options: Absorption Pressure Swing Absorption (PSA) Cryogenic separation Membrane technology

Benefits of absorption removal method:

Simultaneous removal of H2S and CO2 Most common solvent used in water Efficiency of scrubbing depends on the solubility, which depends on: o Temperature o Pressure o pH of water

Pressure Swing Absorption (PSA) process: Adsorbents such as activated carbon and molecular sieves are used Selectivity of adsorption is based on different molecular weight and molecular size Adsorption is carried out at a high pressure Desorption is carried out at a low pressure

Advantages of PSA process: Simple design & operation Consistent purity of gas is achieved Clean process requiring very less floor area Dry product gas is produced Simultaneous removal of various impurities

Cryogenic separation: Boling point: o CH4 (-) 160 Celsius o CO2 (-) 79 Celsius Removal of CO2 in liquid form by cooling biogas to critical temperature at critical pressure Expensive, only tested in pilot plants Requires cryogenic vessels to store and transport Recovery of CO2 is possible

Removal of water: Mostly achieved by: o Condensation by cooling at low temperatures o Drying over silica gel or Al2O3, if low dew points need to be achieved Alternative o Absorption in glycol or hyroscopic salts

Removal of H2S: By catalytic removal (Chemical process)

Absorption on activated carbon (Physical process) Microorganisms (Biological process)

Principle of PSA Biogas purification

PSA biogas purification system is the gas separation system with specially designed adsorbent This adsorbent is called Molecular Sieves (MS) having a micro pore on its surface and adsorbs CO2, N2, H2S, and H2O molecules selectively under a certain pressure. After adsorption process, adsorbent is regenerated by depressurizing. These PSA systems produce the Purified Methane enriched gas continuously by repeating above absorption and regeneration process.

Biogas Compression & Storage Storage pressure Low (up to 0.2 Barg) Low Medium (up to 20 Barg) High (up to 250 B0arg) Storage device Water sealed gas golder Gas bag Similar to propane/LPG tank Commercial gas cylinders Material of construction Steel Rubber, plastic, vinyl Steel Alloy steel

Methane producing-system proposition: We propose to develop a new purification system using magnetic nanoparticles of iron oxides, biogas produced in anaerobic digesters used for the treatment of solid and liquid waste generated in hog production systems and dairy cattle. Some anaerobic purification methods: Absorption dependent on pressure, temperature and pH of the liquid from the digester Absorption Pressure employs activated carbon, which method has been shown that the capture efficiency H2S and SO2 increases if the reaction temperature increases from 125 C coal with a high air flow and the adsorption process is brought to an elevated pressure and the desorption process is brought to low pressure so that pressure difference must have a system which constantly pressurize the system if the biogas has a 2400 ppm concentration of the absorptive capacity of the activated carbon is estimated to be 0,062 kg of absorbent H2S/Kg and the value is considered presenting a low capacity removal of 5%; within such systems has been used volcanic rock and has demonstrated acceptable efficiency to levels of 200 g/m3 in 81 seconds but the saturation of the system to 1500 ppm of H2S can be maintained only by 90 days Cryogenic system: it is an expensive but if it supplies a significant amount of refrigerant can reduce cooling costs Membrane: membranes are commercially available with pore size of 5 A.

Alternative (currently used) methods: Activated carbon impregnated with potassium iodide has been shown to be an alternative for the removal of H2S from biogas digesters in small pig farms but depends on the size of the digester to be effective, since removal using this technology has a cost very high operating. An alternative method may be inexpensive magnetic nanoparticles of iron oxide (Fe3O4) supported on alumina, as the pore diameter is 15 Amstrong with an adsorption of 1.38X10-3 (cc / A / G) and which is greater in this type of particles which make them attractive for the removal of CO2 and H2S. The surface area of the nanoparticles is higher so the deal flow of biogas can be high, the main idea is that just by using a moisture separator between the digester and the filter is used to develop a cost-effective method for the capacity to adsorb sulfur and carbon dioxide for subsequent cleaning with special solutions that alter the pH of the nanoparticles causing impurities are removed from the biogas without changing the filter cartridge frequently.

Problem According to the Census of Agriculture, Livestock and Forestry INEGI 2008, Mexico has a population of over pig heads 15.2 million. Of its production is estimated that 10.8% is backyard, a semi-tech 32.3% while 56.9% is technical. The state of Guanajuato, Jalisco and Michoacn along with reach 30% of pork

production nationwide in 2008, classifying small-scale farms, medium farms, and large farms. Like all anthropogenic activity, production of pigs, has consequences for the quality of the environment, due to the generation of wastewater and excreta. In 2004-2008, the pig population has remained in the range of 14.5 and 15.5 million heads nationwide. In 2008 there was a herd of 2.34 million head of cattle producing milk. The state of Jalisco is ranked first inventory with 311,700 heads, contributing 13.32%, the state of Durango had 249.687 and represented 10.67%, meanwhile the state of Chihuahua had 245.917 heads and represented 10.51%, Coahuila followed with 10.39%, 243.183 meant cattle. The rumen is a complex foregut where grazing grasses are stored for anaerobic fermentation. Gases are produced during the fermentation in the rumen and are discharged into the atmosphere by animals which typically contain 30-40% with the other compounds and traces of N2, CO2, H2S and H2. This amount of methane is produced in the in vitro fermentation is about 15-20%. The amount and composition of the gas varies with the type of animal and the type of food. Discarded organic waste to increase the amount of soil nutrients such as nitrogen (N), phosphorus (P) and potassium (K) that can be beneficial for fertility. An alternative for waste management is the use of digesters that have gained a lot of interest mainly for its contribution to energy saving and environmental care, but from the environmental point of view, has been the case that are considered as a unique option to mitigate the pollution potential of organic wastes such as animal manures from. To be successful in the field biodigesters should generate economic benefits, social and environmental. The predominant technology of biodigestion systems are: lagoon systems (94%), modular (4%), and those of bio-bag and ferrocement (1% each). The systems have the following problems: System Oversizing. Failure agitation systems Faults in the burner The maintenance is not performed regularly. Owners are not sufficiently familiar with the operation of the systems.

With the conditions that were discussed above, biogas has a composition as follows: 60% CH4, 35% CO2, 4% H2 and H2S 1%, which means that its use is limited in potential alternatives. Methods We produce a H2S removal system consisting of a filter made of magnetite nanoparticles obtained via chemical coprecipitation. The methane produced in the digesters is treated by filtering magnetic nanoparticles supported on alumina, as the pore size present in the nanoparticles is greater than in present technologies used for filtering the biogas from the digesters. 1) Synthesis and characterization of magnetic nanoparticles.

1.1) Synthesis of nanoparticles The magnetic nanoparticles are synthesized by the chemical coprecipitation method, proving an easy and economical method for producing magnetite nanoparticles. Conducted solutions of ferric chloride hexahydrate and ferrous chloride tetra hydrated distilled water separately and with constant stirring to ensure uniformity of the solution after the mixture is made of solutions with a 2:1 stoichiometry relationship between the chloride and ferric chloride ferrous respectively, agitation of the solutions is carried out at 1500 RPM with constant heating to a temperature of 70 C, and add NH4OH (ammonium hydroxide) serving as a precipitating agent and the stirring speed increased to 4000 RPM and maintain constant agitation speed and temperature during 20 minutes. After stopping the synthesis of the nanoparticles is due to perform the separation of the nanoparticles from the waste solution containing undesirable for the use of nanoparticles, super magnets are positioned underneath the containing vessel and for performing a subsequent decanting washed with tridistilled water to pH fitting that we ensure that they are free of residues of NH4OH. 1.2) Characterization of magnetic nanoparticles After completing the synthesis of the nanoparticles must ensure that the magnetic material is a single phase, which is free of impurities, checking the size of the nanoparticles, the pore size measure, measure pH to perform these analyzes include the following techniques: Elemental analysis. IR spectroscopy. X-rays Transmission and scanning electron microscopy. ICP mass. Adsorption of gases. vibrating sample magnetometry. 2) Characterization of commercial alumina Acquisition is performed for characterization of alumina chemical and physical analysis to be used as support material of magnetic nanoparticles, the characterization is by the following techniques: Elemental analysis. IR spectroscopy. X-rays Transmission and scanning electron microscopy..

 ICP mass. Adsorption of gases. Once a mixture will be characterized with magnetic nanoparticles in wet and drying with subsequent gradual increase of temperature up to 70 C and maintaining that temperature for 4 days in a mold with a column length of 1 m, diameter of 0.3 m on the outside and on the inside 0.1m stainless steel after heat treatment and to generate the filter to use in removing impurities contained in the biogas to completely remove the moisture will be a compaction process hydraulic exert a force of 10 tons, once this process will be to characterize the pore size present in the nanoparticles that are on the surface of alumina by electron microscopy technique neighborhood gas adsorption to know the filter pore size and total surface area to size the capacity of the filter in relation to the biogas stream. Tests for pore size in the filter because this measure will enable us to treat biogas more efficiently. 3) Design Biofilter The design of the biofilter will be based on the daily function of operating digesters and energy required to achieve complete degradation of organic material and generating biogas. Methane to have a carbon and four hydrogens is due to perform a mass balance to know from where the carbon and hydrogen release is made more quickly, as the cow dung has a low percentage of solids ( 10%) like biodigesters, process is performed in a moist environment mainly. 4) Proof of biofilter with magnetic nanoparticles The implementation of the biofilter will be in existing digester and known conditions to control power in a more efficient biogas leaving the digester and measuring its heat capacity and the amount of waste removed after the filter. It is important that no pressure is required to increase, increasing the temperature or adding substances to the biogas separation of impurities from passing through the biofilter, represents an important advantage to the other currently known technologies. It is also important to mention that the CO2 this can be reduced until only 2% of the total volume of biogas is not a batch process and continuous but its size will not saturate in short periods of time. To perform this activity will use a digesters fed the same stool and one of them will place a solid matter separator that ensures that the particle size between the digester is about 2 mm in diameter, there will be a trap stainless steel of dimensions L = 2 m, a = 1.2 m H = 0.8 m, which is capable of removing solids to a constant volume of 2 m3. After the filtration is performed residues are passed to a stirrer mechanical, which is moved by a pair of 3 HP electric motors each to provide a stirring speed of 1500 RPM. The output will place the biofilter packed with magnetic nanoparticles in a column of 1 m in length, 0.3 m in diameter of the part 0.1m outside and on the inside, to ensure a constant flow of gas which must be a maximum of 25 L / min, for this must be placed a baffle with flow control valve stainless steel to reduce the diameter of digester output and maintain laminar flow before the entry of the biofilter, the biofilter will be capable of removal based on the mass that it passes through and is governed by: Q =

mass load / VxSin, where Q is the flow m3 / s, V is the volume in m3 and Sin is the concentration of pollutants at the entrance, the parameters to be taken into account for the efficiency of the biofilter is moisture saturation, saturation time of impurities present in the biofilter, and operating temperature of the biofilter. A biofliter output meter is placed sulfides an ATX-612 chromatograph Model 700 on-line sampling of hydrogen sulfide (H2S) before and after the filter for measuring the removal efficiency. There will be three devices to measure the heat capacity present: An electric generator, which will monitor the amount of kWh produced based on the volume of the digester gas supplied by a model AC-250 meter with a digital IMAC pulses; gas quality will be tested weekly for one year with an environmental sensor IR 30M An internal combustion engine which measured the following parameters: maximum power, maximum feel, engine temperature and amount of fuel consumed per hour working and connected loa. The engine will work in three loading rates (empty, full load and maximum load) to make use of purified biogas engine must perform methane gas compression to achieve 2000 psi pressure d. A diffuser burner for the combustion process must be performed in low pressure burners (5 psi), it should perform an adaptation of conventional burners able to use methane and thus improve the combustion parameters to measure the efficiency and the relationship between heat generated and transferred to the bodies subjected to direct flame burners. At the digester without biofilter will be placed sulfides meter before the three devices and assess the biogas without filtration, using gas chromatography. In the proposed systems will measure the amount of fuel consumed per hour and make a comparison with the price of fossil fuels to demonstrate the savings that could be generated in a place that has digesters.

Successful removal will use methane in automotive applications which will help reduce the costs generated by the consumption of fossil fuels used in agricultural areas of the world. So if you stop using fossil fuels and use methane as fuel automotive will gain large enough that some activities in the agricultural sector become more profitable