Patent Publication Number: US-2021179994-A1

Title: Digester comprising a porous inner wall

Description:
CROSS REFERENCE TO RELATED APPLCIATIONS 
     This application claims the benefit of priority under 35 U.S.C. § 119 (a) and (b) to French Patent Application No. 1914170, filed Dec. 11, 2019, the entire contents of which are incorporated herein by reference. 
     TECHNICAL FIELD 
     The present invention relates to a plant and a process for producing at least partly desulfurized biogas. 
     BACKGROUND 
     Biogas is the gas produced during the decomposition of organic matter in the absence of oxygen (anaerobic fermentation), also known as methanisation. The decomposition may be natural, as observed in swamps or in household rubbish dumps, though the production of biogas may also result from the methanisation of wastes in a dedicated reactor, under controlled conditions, known as a methaniser or digester, and then in a post-digester, which is similar to the digester and allows the methanisation reaction to be extended. 
     Biomass refers to any group of organic matter that can be converted into energy through this methanisation process: for example, treatment plant sludge, manures/slurries, agricultural residues, food wastes, etc. 
     The digester, namely the reactor dedicated to the methanisation of the biomass, is a dosed vessel, heated or not (operated at a set temperature, between the ambient temperature and 55° C.), the contents of said vessel, composed of the biomass, being mixed, continuously or sequentially. The conditions in the digester are anaerobic, and the biogas generated is found in the headspace of the digester (gas space), from where it is withdrawn. Post-digesters are similar to digesters. 
     Owing to its main constituents—methane and carbon dioxide—biogas is a powerful greenhouse gas; at the same time, it also constitutes a source of renewable energy, which is appreciable in the context of the increasing scarcity of fossil fuels. 
     Biogas contains predominantly methane (CH 4 ) and carbon dioxide (CO 2 ), in proportions which can vary according to the substrate and to the way in which the biogas is obtained; it may also contain, in smaller proportions, water, nitrogen, hydrogen sulfide (H 2 S), oxygen, and also other organic compounds, in the form of traces, including H2S, between 10 and 50 000 ppmv. 
     Depending on the organic matter which has undergone decomposition, and on the techniques used, the proportions of the components differ; on average, however, biogas comprises, on a dry gas basis, from 30% to 75% of methane, from 15% to 60% of CO 2 , from 0% to 15% of nitrogen, and from 0% to 5% of oxygen and trace compounds. 
     Biogas is made use of economically in various ways. It can, after a gentle treatment, be exploited close to the production site in order to supply heat, electricity or a mixture of both (cogeneration); the high carbon dioxide content reduces its calorific value, increases the costs of compression and of transportation and limits the economic advantage of making use of it economically to this use nearby. 
     More intensive purification of biogas allows it to be more widely used; in particular, intensive purification of biogas makes it possible to obtain a biogas which has been purified to the specifications of natural gas and which can be substituted for the latter; biogas thus purified is known as “biomethane”. Biomethane thus supplements natural gas resources with a renewable part produced within territories; it can be used for exactly the same uses as natural gas of fossil origin. It may supply a natural gas network or a vehicle filling station; it may also be liquefied for storage in the form of liquefied natural gas (bioLNG), etc. 
     Depending on the composition of the biomass, the biogas produced in the digestion contains hydrogen sulfide (H 2 S) in amounts of between 50 and 50 000 ppm. 
     Irrespective of the final commercial destination of the biogas, it proves to be vital to remove hydrogen sulfide, which is a toxic and corrosive impurity. Moreover, if the use of the biogas involves purifying it for injection of biomethane into the natural gas network, there are strict specifications limiting the permitted quantity of H 2 S. 
     A number of methods exist for removing H 2 S and are more or less widespread (beds of activated carbon, addition of iron compounds, physical or chemical absorption, water washing, biofilters, etc.). Removal is accomplished primarily by adsorption on a bed of activated carbon, outside the digester. In an increasing number of digesters, H2S abatement is accomplished in part by injecting air/enriched air/O 2  into the gas space of the digester, so constituting an in situ solution. With injection into the gas space at a low rate, solid sulfur is formed from the H 2 S and O 2  (eq. (1)), as performed by sulfur-oxidizing bacteria, e.g.  Thiobacillus . With a high rate of O 2  injected, the mixture is acidified (eq. (2)). The target reaction is therefore reaction (1). 
       H 2 S+0.5 O 2 →S+H 2 O   (1)
 
       H 2 S+2 O 2 →SO 4   2− +2 H+  (2)
 
     The amounts of O2 which need to be injected in practice are different from those expected from the stoichiometry of eq. (1): doses of 0.3%-3% O 2  relative to the biogas generated are most usually recommended, with doses of up to 12% being sometimes stated. 
     Presently, the in situ injection of air/enriched air/O 2  is not optimized, and the beds of activated carbon must therefore be maintained in order to remove all of the H 2 S. 
     From this basis, one problem which arises is that of providing an improved plant promoting greater removal of H 2 S. 
     SUMMARY 
     One solution of the present invention is a plant for producing at least partially desulfurized biogas, comprising a biomass digester and/or post-digester, the digester and/or post-digester comprising:
         a chamber comprising the biomass and the gas space, and   a means for introducing an oxidizing gas,
 
characterized in that the portion of the inner wall of the chamber situated at the level of the gas space is at least partly porous.
       

     “Gas space” refers to the space in the digester or post-digester that contains gas (as opposed to the space which contains the liquid). 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWING 
       For a further understanding of the nature and objects for the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawing, in which like elements are given the same or analogous reference numbers and wherein; 
         FIG. 1  is a horizontal schematic section through the chamber of the digester. 
     
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
       FIG. 1  is a horizontal schematic section through the chamber of the digester. Note that the section is made in the portion of the inner wall of the chamber situated at the level of the gas space. It highlights the porous part  1 . 
     The reactions between O 2  and H 2 S take place on a surface (not in the gas or liquid phase of the digester). The microorganisms needed for the reaction (sulfur-oxidizing bacteria such as  Thiobacillus ) are in the liquid phase, and the reagents are in the gas phase. A hydrophilic surface is required for contact between the liquid phase, the microorganisms, and the gas phase, the reagents. These surfaces are primarily the inner walls in the gas space, the gas/liquid interface of the digester or post-digester, and any other surface available in the gas space, e.g. fillets. If the surface areas available are insufficient, the H 2 S abatement reactions do not take place sufficiently, or even not at all. 
     In other words, the solution according to the invention is to increase the surface area of reaction between the liquid phase and the gas phase, by adding one or more porous parts to the surface of the inner wall of the chamber. This addition of porous mass allows an increase in the size of the reaction support and so promotes the greater removal of the H 2 S. 
     Depending on the case, the plant according to the invention may have one or more of the features below:
         the porosity of the portion of the inner wall of the chamber situated at the level of the gas space is between 75% and 95% of the volume,   the portion of the inner wall of the chamber situated at the level of the gas space comprises wall sub-portions having a porous surface.   the portion of the inner wall of the chamber situated at the level of the gas phase is divided into a first wall and a second wall, the two walls being side by side, and the second wall being opposite the interior of the chamber and having at least part of its surface porous.   the porous part of the portion of the inner wall of the chamber situated at the level of the gas phase is composed of a material which is resistant to a humid and corrosive atmosphere, for example certain stainless steels, PEEK, PTFE.   the plant comprises a mixing means which promotes transfer of the oxidizing gas to the inner wall of the chamber.       

     A further subject of the present invention is a process for producing at least partially desulfurized biogas, using a plant according to the invention, which comprises:
         injecting biomass into the digester;   injecting an oxidizing gas at the top of the digester; and   mixing the biomass.       

     The biomass is preferably mixed so as to promote transfer of the oxidizing gas to the inner wall of the chamber. 
     Note that the oxidizing gas might be oxygen or air or enriched air. Enriched air refers to air having a higher oxygen content than the oxygen content normally present in air. 
     Inside the digester, when hydrogen sulfide reacts with oxygen, the sulfur attaches to the inner wall of the chamber of the digester. After a certain time, the solid sulfur generated falls into the digestate and is evacuated with the latter. 
     The solution according to the invention produces a biogas stream containing less than 200 ppm of hydrogen sulfide. 
     The invention makes it possible to reduce the costs of purifying biogas by removal of hydrogen sulfide effectively, by increasing the reactivity of the oxygen already injected with the sulfur-containing products, by creating an additional reaction surface on the inner walls of the digester at the level of the gas space, with no need for complex engineering. 
     It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above. 
     While embodiments of this invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the composition and method are possible and within the scope of the invention. Accordingly the scope of protection is not limited to the embodiments described herein, but is only limited by the claims which follow, the scope of which shall include all equivalents of the subject matter of the claims.