WO2012056081A1 - Biofilter and biofiltration-based method for the purification of a gas stream containing carbon disulfide - Google Patents
Biofilter and biofiltration-based method for the purification of a gas stream containing carbon disulfide Download PDFInfo
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- WO2012056081A1 WO2012056081A1 PCT/ES2011/070748 ES2011070748W WO2012056081A1 WO 2012056081 A1 WO2012056081 A1 WO 2012056081A1 ES 2011070748 W ES2011070748 W ES 2011070748W WO 2012056081 A1 WO2012056081 A1 WO 2012056081A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
- B01D53/85—Biological processes with gas-solid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/95—Specific microorganisms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates, in general, to the purification of gases contaminated with a contaminant, and, in particular, with a bio filter to eliminate or reduce the content of carbon disulfide (CS 2 ) present in a gas stream contaminated by that compound, as well as with the corresponding bio filtration method.
- CS 2 carbon disulfide
- carbon disulfide (CS 2 ) a volatile, colorless and very easily flammable liquid, constitutes a highly dangerous pollutant due mainly to its harmful effects on human health.
- Prolonged exposure to carbon sulfide vapors causes symptoms of intoxication ranging from redness of the face and euphoria to loss of consciousness, coma and breathing paralysis.
- Chronic intoxication causes headache, loss of sleep, impaired vision, memory and hearing, nerve inflammation and vascular damage.
- Biolavadores bioscrubber
- biotrickling drained bed bioreactors
- fixed bed biofilters biofilters
- bioscrubber constitute a technology of treatment in two stages. In the first, the contaminated gas comes into contact with a liquid phase that absorbs the contaminants. After the contaminants have been absorbed, the liquid is treated by a traditional biological process (for example, by an activated sludge process). Biolavadores have as their main drawback their inability to treat poorly soluble compounds, so they are not good candidates in the case of CS 2 .
- Drained bed bioreactors require the continuous feeding of a liquid medium onto a bed of inorganic support material (eg, polyethylene, polypropylene, PVC or lava rock).
- inorganic support material eg, polyethylene, polypropylene, PVC or lava rock.
- This technology is mainly controlled by the mass transfer between the gas phase and the liquid phase, which is a disadvantage because the gaseous CS 2 is very poorly soluble in water.
- Another disadvantage associated with continuous liquid feeding consists in obtaining a liquid medium that must be properly managed.
- the inorganic nature of the support material forces the system to be inoculated with the appropriate biomass for biodegradation.
- US patents US 4968622, US 5747331 and US 5236677 describe drained bed bioreactors for the biological degradation of CS 2 .
- Biofilters (“fixed bed bioreactors”) constitute, in Europe, the most used biological gas treatment technology for the elimination of odors and volatile organic compounds (VOCs) and sulphides (VSCs). Despite their name, they are not "filtration” units in the strict sense of the word, but instead encompass a combination of several basic processes: absorption, adsorption, biodegradation and desorption. Basically, biofilters consist of a compartment that contains a filler or support material (filter material) that serves as a carrier of the biomass responsible for the biodegradation of contaminants.
- the biomass or population of microorganisms capable of degrading the contaminant constitutes, in all cases, a decisive element for the effective functioning of the system. Its biodiversity depends on the composition of the fed gas, the bed. support and, in general, environmental conditions. Microorganisms capable of degrading CS 2 are not as abundant as microorganisms capable of degrading other pollutants (eg, hydrogen sulfide (H 2 S)), possibly due to the fact that CS 2 possesses fungicidal properties since the breakage of its double bonds require more energy [Yang, Y. et al. (1997).
- H 2 S hydrogen sulfide
- Thiobacillus TJ330 [Hartikainen, T. et al. (2000). Physiology and taxonomy of Thiobacillus strain TJ330, which oxidizes carbon disulphide (CS 2 ). J. Appl.
- Thiobacillus thioparus TK [Smith, N.A. et al. (1988). Oxidation of carbon disulphide as the soli source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m. J. Gen. Microbiol. 134: 3041-3048];
- the nature of the support material of the microorganisms is also a fundamental factor for the proper functioning of the bioreactors, since it influences both the ability to eliminate the contaminant and the cost of the system.
- the ideal support should meet various characteristics such as, for example, having a high moisture and biomass retention capacity, a high contact surface, a suitable bed porosity (to avoid load losses and system collapse), low economic cost , long life time, etc. In addition, once exhausted, it should be easy to manage to avoid generating an added problem.
- biofilters with specially designed inorganic supports have been described, the use of supports of an organic nature provides several advantages, among which it is worth noting the possibility of containing indigenous biomass (bacteria, fungi, protozoa, algae, etc.) and nutrients, although, on the other hand, this type of supports undergoes greater degradation over time than some of the synthetic materials.
- indigenous biomass bacteria, fungi, protozoa, algae, etc.
- this type of supports undergoes greater degradation over time than some of the synthetic materials.
- compost Yang, Y. et al. (1994). Oxidative destruction of carbon disulfide vapors using biofiltration In: Air & Waste Management Association's 87th Annual Meeting & Exhibition, Cincinnati, Ohio], peat [Hartikainen, T. et al. (2001).
- the authors of the present invention have developed a fixed bed biofiltration method to efficiently purify (eliminate / reduce) the amount of CS 2 present in a gaseous stream contaminated with said compound (CS 2 ).
- Said method based on the use as filler material of the biofilter of a product commonly used as compost, provides several advantages over traditional methods and other biological methods described in the state of the art, mainly due to its physical characteristics. -chemistry.
- the invention relates to a biofilter comprising a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30 -70% by weight of animal waste, and (ii) 70-30% by weight of plant waste.
- the invention in another aspect relates to a method for purifying a gas stream containing CS 2 by biofiltration comprising passing said gas stream containing CS 2 through said biofilter.
- the invention in another aspect relates to an installation for the purification of a gaseous composition comprising CS 2 comprising at least one of said bio filters.
- the invention relates to a method for acclimatizing to CS 2 microorganisms capable of degrading CS 2 contained in a compost, wherein said compost is obtainable by aerobic-anaerobic decomposition of a mixture that It comprises (i) 30-70% by weight of animal waste, and (ii) 70-30%> by weight of plant waste, which comprises contacting said compost containing microorganisms capable of degrading CS 2 with a gaseous stream that it comprises CS 2 in an amount less than about 100 ppmv, with a residence time of less than about 120 seconds, continuously, for at least 100 days.
- the invention relates to a method for generating a population of microorganisms capable of degrading CS 2 which comprises combining: a) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) in weight of animal waste and (ii) 70-
- Figure 1 is a photograph showing a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%> by weight of animal waste, and (ii) 70-30%> by weight of plant waste , in the form of pellets.
- Figure 2 is a schematic representation of a particular embodiment of an installation suitable for the implementation of the CS 2 biofiltration method according to the present invention.
- the invention relates to a biofilter of carbon disulfide (CS 2 ), hereinafter "biofilter of the invention", which comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste, and (ii) 70-30%> by weight of plant waste.
- Said biofilter of the invention can be used to purify gases contaminated with CS 2 by bio filtration, that is, to reduce the amount of, or eliminate, the amount of CS 2 present in a gaseous stream containing CS 2 .
- the filler material present in the biofilter of the invention comprises a product of an organic nature, in particular, a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising from 30%> to 70%> by weight of animal waste and of the 70%> to 30%> by weight of plant waste.
- animal residues suitable for the production of compost used in the biofiltration method of the invention include pig purines, poultry residues, cattle residues, etc., and combinations thereof.
- plant residues include leaves, branches, pieces of wood, sawdust, etc., and combinations thereof.
- a product commonly used for agricultural purposes can also be used advantageously as filler material (filter material) in a CS 2 biofilter due, among other reasons, to its characteristics physicochemical such as, for example, high moisture retention capacity, high porosity, high contact surface, good ability to regulate pH, adaptable and diverse biomass, low investment cost and long duration (mechanically resistant and chemically inert and stable).
- Said filler material (compost) of the biofilter of the invention serves as support for microorganisms capable of degrading CS 2 and provides the necessary nutrients for the metabolism of said microorganisms capable of degrading CS 2 although, at times, it may be necessary to make a contribution additional nutrients for the maintenance and growth of the microorganisms present in said filler material.
- the compost used as filler material of the biofilter of the invention can be used without compacting, that is, in the form of more or less loose granules of different granulometry, or, advantageously, in compacted form.
- said compost is in the form of compacted particles, preferably in the form of pellets ( Figure 1).
- the size of said pellets may vary within a wide range; however, in a particular embodiment, said compost pellets have an average diameter between about 5 mm and about 12 mm, preferably between about 6 mm and about 8 mm.
- the size of the compost pellets together with the high porosity of the compost provide a large surface area that favors the contact of microorganisms capable of degrading CS 2 with said contaminant.
- the morphological regularity of the compost pellets constituting the biofilter filler material of the invention ensures a very homogeneous distribution of the filler material in the biofilter of the invention, which minimizes the development of preferential paths that limit the contact time. actual between the gas stream containing CS 2 to be treated and the active surface of the filler material comprising the microorganisms capable of degrading CS 2 .
- the biofilter filler material of the invention has a good water retention capacity, which is very favorable since microorganisms require a significant amount of water to grow and the process is exothermic.
- the moisture content of the filler material can vary over a wide range, in a particular embodiment, the moisture content of the biofilter filler material of the invention is between 30% and 70%, preferably between 35% o and 50% or A low moisture content in the filler material reduces the thickness of the biofilm and adversely affects the activity of microorganisms capable of degrading CS 2 , and, consequently, the activity of the biofilter.
- a high degree of humidity can create saturation, causing anaerobic areas or increase the loss of load.
- the biofilter of the invention comprises, in addition to said filler material, microorganisms capable of degrading CS 2 .
- a microorganism capable of degrading CS 2 is a microorganism that has the ability to use CS 2 as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or the environment, for example, in sulfate [see, for example, Smith, NA et al. (1988); Revah et al. (1994); Alcantara et al. (1999), cited above].
- Said microorganism capable of degrading CS 2 can be a bacterium, a fungus, a yeast, a protozoan, etc.
- microorganisms capable of degrading CS 2 include microorganisms of the genera Paracoccus (eg, P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. denitrificans, T. nitratis, T. versutus, etc.), Thiobacillus (eg, Thiobacillus TJ330, T.
- Paracoccus eg, P. denitrificans, etc.
- Thioalkalimicrobium eg, T. aerophilum, T. sibericum, etc.
- Thioalkalivibrio eg, T. denitrificans, T. nitratis, T. versutus,
- the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to a single genus or to a single species of microorganisms capable of degrading CS 2 ; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to different genera and / or species.
- microorganisms capable of degrading CS 2 useful for the implementation of the present invention are commercially available or in crop collections.
- the person skilled in the art knows that, in general, microorganisms that tolerate the contaminant in question (CS 2 ) live in samples from sites contaminated with said contaminant, for example, areas or facilities where gas streams are used or generated containing CS 2 , etc .; therefore, by selecting the cultures of the microorganisms present in said samples it is possible to find strains of microorganisms capable of degrading the contaminant in question (CS 2 ).
- said filler material contains microorganisms of a very diverse nature, and, among said microorganisms there are microorganisms capable of degrading CS 2 which can be identified and isolated by conventional methods of selecting microorganisms known to those skilled in the art.
- the biomass indigenous (native microorganisms) of the compost that constitutes the biofilter filler material of the invention is adaptable, since in contact with gaseous streams containing CS 2 , advantageously moistened previously with water, the population of microorganisms present in said compost is self- regulated to proliferate microorganisms capable of degrading CS 2 and incapable of degrading microorganisms are repressed CS 2.
- the implementation of the bio filtration method provided by this invention does not require initial inoculation with microorganisms capable of degrading CS 2 since these are present in the filler material (compost) of the biofilter used in said bio filtration method; however, if desired, in a particular embodiment, said compost can be inoculated with a culture of microorganisms capable of degrading CS 2 .
- the ability of a microorganism to degrade CS 2 can be determined by any conventional procedure, known to those skilled in the art, which allows to know if a microorganism uses CS 2 , for example, by contacting a culture of said microorganism with CS 2 and incubating under appropriate conditions; Under these conditions, the detection of hydrogen sulfide, an intermediate product of the oxidation of CS 2 , or the production of sulfate, a final product of the oxidation of CS 2 , is indicative that the analyzed microorganism is capable of degrading CS 2 ; if desired, the microorganism may be supported on a filler material of the type used in the biofilter of the invention (compost) and the CS 2 may be contained in a stream of air, preferably moistened with water before contacting it with the microorganism.
- the biofilter of the invention comprises a reservoir, in which the filler material and microorganisms capable of degrading CS 2 are found , as well as means for entering the gas stream containing CS 2 , optionally moistened previously, and means for the output of the gas stream totally or partially discharged from CS 2 .
- devices can be included to measure the inlet temperature of the gas stream containing CS 2 to be treated since it can affect the metabolic process of microorganisms capable of degrading CS 2 , or to measure the pH since During the operation of the bio filtration method provided by this invention, acid products can be generated that can adversely affect the activity of the biofilter.
- the bio filter of the invention can be designed in various shapes and dimensions, using the appropriate materials for it.
- bio filter of the invention facilitates the design of bioreactors containing one or more biofilters of the invention.
- the invention contemplates the development of a bioreactor comprising a single bio filter of the invention, while, in another particular embodiment, the invention contemplates the development of a bioreactor comprising two or more biofilters of the invention.
- the bio filter of the invention can be used to purify gases contaminated with CS 2 by bio filtration.
- the invention relates to a method for purifying a gas stream containing CS 2 by bio filtration, hereinafter "biofiltration method of the invention", which comprises passing said gas stream containing CS 2 to through a biofilter of the invention, that is, a biofilter comprising a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste, and (ii) 70-30% by weight of plant waste.
- biofiltration method of the invention comprises passing said gas stream containing CS 2 to through a biofilter of the invention, that is, a biofilter comprising a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste, and (ii) 70-30% by weight of plant waste
- the expression "purify gases contaminated with CS 2" includes both the almost total elimination of CS 2 present in a gaseous stream containing CS 2 and the reduction of the amount of CS 2 present in a gaseous stream It contains CS 2 up to levels permitted by legislation or that are not harmful to human or animal health, and / or to the environment.
- the gaseous stream containing CS 2 to be treated by the biofiltration method of the invention can come from various polluting sources, for example, from process facilities that use or generate CS 2 , such as the cellulose fiber manufacturing sectors, industry synthetic wrap food, etc.
- the biofiltration method of the invention comprises passing said gas stream containing CS 2 through a biofilter of the invention, the characteristics of which have already been mentioned previously.
- the amount of CS 2 present in said gaseous stream to be treated may vary within a wide range, as can the residence time or average amount of time that the gaseous stream containing CS 2 to be treated remains in contact with the filling material. .
- said gaseous stream to be treated contains CS 2 in an amount between about 50 ppmv and about 250 ppmv and the residence time is between about 10 seconds and about 80 seconds Measuring the concentration of CS 2 a
- the output of the biofilter can be checked for the operation of the filler material and of the microorganisms capable of degrading CS 2 so that, in the event that the efficiency of the biofilter decreases, in the first instance it would be enough to water the filler material with a solution of nutrients, as mentioned below, to restore normalcy.
- the biofiltration method of the invention comprises a step of humidifying the gaseous stream containing CS 2 to be treated, for which said gaseous stream is contacted with an aqueous medium, for example, water, before being introduced into the biofilter.
- the aqueous medium used at this stage may be present in a humidification system, such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gaseous stream containing CS 2 the necessary humidity, located before the bio filter.
- a humidification system such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gaseous stream containing CS 2 the necessary humidity, located before the bio filter.
- said humidification system comprises a single column of aqueous medium (eg, water); in another particular embodiment said humidification system comprises at least two, for example, 2, 3, 4 or even more, columns of aqueous medium (eg, water), in order to guarantee a correct humidification of the gas stream containing CS 2 to treat and minimize system maintenance.
- the relative humidity of the gas stream containing CS 2 entering the bio filter is equal to or greater than 90%, preferably equal to or greater than 95%, even more preferably equal to or greater than 99%.
- a compost with a moisture content of between 35% and 50% as a filler material of the bio filter of the invention used in the biofiltration method of the invention offers good results.
- the gaseous stream containing CS 2 to be treated passes through the filler material that supports the growing microorganisms capable of degrading CS 2 .
- the degradation of CS 2 occurs, in general, after transferring the gas stream containing CS 2 to a liquid medium where it is used as a source of carbon and energy.
- CS 2 contaminant
- the biofiltration method of the invention comprises performing a previous stage of acclimatization to CS 2 of the microorganisms initially contained in said compost.
- This step is particularly interesting when the corresponding microorganisms initially contained in the compost used as filler material of the biofilter of the invention used in the bio-filtration method of the invention are to be used as microorganisms capable of degrading CS 2 ; in fact, this stage of previous acclimatization could be avoided if the compost was inoculated with microorganisms capable of degrading standardized CS 2 .
- Said acclimatization can be carried out in any appropriate installation, for example, in the biofilter of the invention itself, or, alternatively, in a laboratory or in a pilot plant, and, in general, comprises contacting said compost, which contains a population of indigenous microorganisms (indigenous biomass), some of which are capable of degrading CS 2 , with a gaseous stream containing CS 2 .
- the amount of CS 2 present in said gaseous stream containing it may vary within a wide range; however, in practice it is usually started using a gas stream containing CS 2 in a relatively low amount, generally equal to or less than 100 ppmv, typically between 20 and 100 ppmv.
- the amount of CS 2 present in said gaseous composition can be reduced, if desired, as the acclimatization of the microorganisms to CS 2 increases .
- the person skilled in the art can generate, by conventional methods, gaseous streams containing different concentrations of CS 2 , and select that which provides a better acclimatization of the microorganisms present in the compost to CS 2 .
- the conditions for acclimating to the CS 2 the microorganisms initially contained in the compost used as filler material in the biofilter of the invention used in the implementation of the bio-filtration method of the invention depend, in general, on various factors, for example, of the content in CS 2 in the gas stream used, the residence time, the duration of the treatment, etc.
- said acclimatization comprises treating said compost with a gas stream comprising CS 2 in an amount equal to or less than about 100 ppmv, with a residence time equal to or less than about 120 seconds, continuously, for approximately at least 100 days, preferably approximately 200 days.
- said step of acclimatization to the CS 2 of the microorganisms initially contained in the compost used as a filler material of the bio filter of the invention used in the biofiltration method of the invention is carried out with a gas stream comprising CS 2 in an amount between about 25 ppmv and about 100 ppmv, the residence time being between about 20 seconds and about 120 seconds, continuously, for at least 100 days.
- a nutrient solution such as the one mentioned previously, in order to maintain the metabolism of microorganisms capable of degrading CS 2 .
- the contribution of said nutrient solution to the compost can be done by irrigation, as previously mentioned.
- the biomass developed on the compost which comprises microorganisms capable of degrading CS 2
- the biomass developed on the compost can be used as inoculum of other bio filters, for example, bio filters of the invention, thus obtaining very fast starts with high debugging efficiencies (elimination or reduction) of CS 2 practically from startup.
- the biofiltration method of the invention includes the possibility of passing the gas stream containing CS 2 through one or more bio filters of the invention.
- the biofiltration method of the invention comprises passing the gaseous stream containing CS 2 to be treated through a single biofilter of the invention.
- the biofiltration method of the invention comprises passing the gas stream containing CS 2 to be treated through two or more biofilters of the invention, for example, 2, 3, 4, or even more, operatively connected to each other; in this case, the gaseous stream containing CS 2 to be treated is passed through the first of the biofilters of the invention and the gaseous outflow of said first bio filter of the invention, which will be at least partially discharged into CS 2 , is passed through the second bio filter of the invention, and, similarly, the gaseous stream of said second bio filter of the invention, which will be even more shameless in CS 2 , is passed through the third bio filter of the invention, and so on until the final exit of the total or partially discharged gas stream of CS 2 . Therefore, the bio filtration method of the invention allows to achieve a removal efficiency of CS 2 of 100%, or very close to 100%, in relation to the amount of CS 2 present in the gaseous stream containing CS 2 to be treated .
- the filler material present in the biofilter of the invention can supply the nutrients necessary for the metabolism of microorganisms capable of degrading CS 2
- the stable operation of the biofilter of the invention can require the irrigation of the filler material with a nutrient solution.
- Appropriate macronutrients must contain N, P, K, completed to a lesser extent with micronutrient elements such as Fe or Ni, among others [Barona, A., et al. (2007). Additional determinations in a potential support material for toluene biofiltration: adsorption and partition in the nutrient solution. Chem. Biochem. Eng. Q. 21 (2): 151-157].
- the nutrient solution contains 100 mg of KH 2 P0 4 , 400 mg of K 2 HP0 2 , 27 mg of MgS0 4 -7H 2 0, 10 mg of CaS0 4 -2H 2 0, 10 mg of FeS0 4 7H 2 0 and 500 g of (NH 4) 2 S0 4 in 1 L of water; a quantity of 5 cm 3 of micronutrient solution containing 2 g / dm 3 of FeCl 2 -4H 2 0, 2 g / dm 3 of CoCl 2 -6H 2 0, 0.5 g / dm 3 of MnCl 2 is added -4H 2 0.60 mg / dm 3 of CuCl 2 , 50 mg / dm 3 of ZnCl 2 , 50 mg / dm 3 of H 3 BO 3 , 2 g / dm 3 of HC0 3 Na, 90 mg / dm 3 ( ⁇ 4) 6 7 0 24 ⁇ ⁇ 4 ⁇ 2 0, 1 g
- the good pH regulatory characteristics as well as the Good characteristics for retaining moisture by the compost used as a filler material of the bio filter used in the bio filtration method of the invention minimize the need for watering very continuously.
- the period of time between two consecutive irrigations can vary within a wide range, depending on numerous factors (eg, need to provide nutrients, need to moisten the compost, etc.), in a particular embodiment, the period of time between two consecutive waterings is approximately 60 days, typically approximately 40 days.
- Sulfate or sulfuric acid is generated during the biofiltration method of the invention; however, in general, it is not necessary to use additional reagents to neutralize sulfuric acid from the oxidation of CS 2 .
- the generation of leachate associated with the implementation of the biofiltration method of the invention is minimal and, in general, of little or no environmental impact, so it is not necessary to perform any management with said leachate.
- the present invention provides a stable and durable method for the purification (elimination or reduction of the amount) of the CS 2 contained in a gaseous stream containing said contaminant.
- FIG. 2 An illustrative scheme of a particular embodiment of the biofiltration method of the invention is shown in Figure 2, in which it can be seen that a moistened (eg saturated moisture) gas stream containing CS 2 is passed through the material of filler contained in the biofilter of the invention wherein CS 2 is degraded by microorganisms capable of degrading CS 2 .
- a gaseous stream containing CS 2 (2) from a contaminating source (1) is introduced into a humidification system (3) that contains water in order to moisten said gaseous stream containing CS 2 before entering a bioreactor (5).
- the humidified gas stream containing CS 2 (4) is introduced into said bioreactor (5) which contains 3 biofilters of the invention (6a, 6b and 6c); each of which comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of waste from animals and (ii) 70-30% by weight of plant residues.
- the 3 biofilters of the invention (6a, 6b and 6c) are arranged vertically and operatively connected to each other so that the output current of the first bio filter (6a) feeds the second bio filter (6b) and the output current of said Second bio filter (6b) feeds the third bio filter (6c) from which the gaseous stream practically discharged from CS 2 (7) comes out.
- the nutrients contained in the nutrient store (8) are supplied to the biofilters of the invention by irrigation in order to maintain the metabolism of microorganisms capable of degrading CS 2 .
- the bio filtration method of the invention can be carried out in a suitable installation comprising at least one bio filter of the invention, that is, a bio filter comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material It comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) by weight of animal waste and (ii) 70-30%) by weight of plant waste.
- Said installation hereinafter “installation of the invention" constitutes an additional aspect of this invention.
- the installation of the invention may contain one or more biofilters of the invention whose characteristics have been previously defined. Therefore, in a particular embodiment, the installation of the invention comprises a single bio filter of the invention. In another particular embodiment, the installation of the invention comprises two or more biofilters of the invention, for example, 2, 3, 4, or even more, operatively connected to each other; in this case, the gaseous stream containing CS 2 to be treated is passed through the first bio filter of the invention and the gaseous stream of said first bio filter of the invention is passed through the second bio filter of the invention, and, similarly, the gaseous outflow of said second Biofilter of the invention is passed through the third biofilter of the invention, and so on until the final exit of the total or partially discharged gas stream of CS 2 .
- the installation of the invention comprises a single bio filter of the invention.
- the installation of the invention comprises two or more biofilters of the invention, for example, 2, 3, 4, or even more, operatively connected to each other; in this case, the gaseous stream containing
- the modular design of the installation of the invention allows biofilters farther from the entrance of the gas stream containing CS 2 to receive very low concentrations of CS 2 but sufficient for the adaptation of microorganisms capable of degrading CS 2 .
- the modular design allows the biodegradation of CS 2 in the first biofilter while the remaining biofilters can act as a reserve, which guarantees the efficiency of the system even with sudden increases in pollutant load (CS 2 ).
- the installation of the invention advantageously includes, if desired, a humidification system, such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gas stream containing CS 2 the necessary humidity, located before the biofilter of the invention.
- a humidification system such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gas stream containing CS 2 the necessary humidity, located before the biofilter of the invention.
- the installation of the invention includes suitable means for transporting the gas stream and, if desired, a source of nutrients in case it is necessary to contribute to the biofilter of the invention to maintain the metabolism of microorganisms capable of degrading CS 2 present in the biofilter of the invention.
- the installation of the invention may include means for measuring and / or controlling the inlet temperature to the biofilter of the invention of the gas stream containing CS 2 to be treated, means for measuring the pH inside the biofilter. , and means for measuring the amount of CS 2 present in the gas stream of the biofilter.
- the invention contemplates that, after the acclimatization period, the biomass developed on the compost, which comprises microorganisms capable of degrading CS 2 , is used as inoculum of other biofilters, for example, biofilters of the invention, thus obtaining very fast starts with high purification efficiencies (elimination or reduction) of CS 2 practically from the start.
- the acclimatization to the CS 2 of the microorganisms capable of degrading CS 2 can be carried out by means of a treatment comprising contacting the compost that contains a population of native microorganisms (indigenous biomass), some of which are capable of degrading CS 2 , with a gas stream containing CS 2 , as previously mentioned in relation to the implementation of the bio filtration method of the invention.
- the invention relates to a method for generating a population of microorganisms capable of degrading CS 2 which comprises combining: a) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70 % by weight of animal waste and (ii) 70-30% by weight of plant waste, which comprises microorganisms capable of degrading CS 2 acclimatized to CS 2 according to the acclimatization method defined above (acclimatized compost), with
- a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) by weight of animal waste and (ii) 70-30% or by weight of plant waste (fresh compost),
- FIG. 2 shows a schematic representation of an installation suitable for the implementation of the biofiltration method of the invention.
- said installation basically consists of a humidification system (3) and a bioreactor (5) containing 3 biofilters (6a, 6b and 6c), placed vertically, with an approximate total volume of 4.5 L, built in chloride polyvinyl (PVC) and with downward gas flow; the biofilters (6a, 6b and 6c) are operatively connected to each other and, inside, there is the filling material comprising a compost in the form of pellets (supplied by the company SLIR), which acts as a support material on the The biomass responsible for the degradation of CS 2 (microorganisms capable of degrading CS 2 ) is developed.
- Said compost has been obtained by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste and (ii) 70-30% by weight of plant waste.
- Table 1 shows some physicochemical properties of the pelletized compost used.
- CS 2 this can be used to treat gaseous streams containing CS 2 (bio-filter feed stream), with an amount of CS 2 between approximately 50 ppmv and approximately 250 ppmv, with residence times of approximately 10 seconds to approximately 80 seconds.
- the maintenance of moisture in the filling material of the bio-filter (compost) is achieved by monthly irrigation with the nutrient solution required for the metabolism of active biomass.
- the effectiveness of the treatment of purification of CS 2 is greater than 90% in the first third of design volume [bio-filter (6a)], with the remaining 2/3 parts [bio filters (6b and 6c)] being the reserve system by that pass very low concentrations of CS 2 , which guarantee its acclimatization and potential purification activity of CS 2 . Therefore, said reserve system can be used as inoculum to start up new bioreactors for the purification of gaseous streams containing CS 2 as a contaminant.
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Abstract
Description
BIOFILTRO Y MÉTODO PARA DEPURAR MEDIANTE BIOFILTRACIÓN UNA CORRIENTE GASEOSA QUE CONTIENE DISULFURO DE CARBONO BIOFILTER AND METHOD TO CLEAN THROUGH A BIOFILTRATION A GASEOUS CURRENT CONTAINING CARBON DISULFIDE
CAMPO DE LA INVENCIÓN FIELD OF THE INVENTION
La presente invención se relaciona, en general, con la depuración de gases contaminados con un contaminante, y, en particular, con un bio filtro para eliminar o reducir el contenido en disulfuro de carbono (CS2) presente en una corriente gaseosa contaminada por ese compuesto, así como con el correspondiente método de bio filtración. The present invention relates, in general, to the purification of gases contaminated with a contaminant, and, in particular, with a bio filter to eliminate or reduce the content of carbon disulfide (CS 2 ) present in a gas stream contaminated by that compound, as well as with the corresponding bio filtration method.
ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION
La emisión cada vez mayor de contaminantes al medio ambiente y el consecuente deterioro de éste, ha llevado a un control legal sobre la emisión de los mismos. En concreto, el disulfuro de carbono (CS2), un líquido volátil, incoloro y muy fácilmente inflamable, constituye un contaminante altamente peligroso debido principalmente a sus efectos perjudiciales sobre la salud humana. La exposición prolongada a vapores de sulfuro de carbono provoca síntomas de intoxicación que van desde el enrojecimiento de la cara y la euforia hasta la pérdida del conocimiento, coma y parálisis de la respiración. La intoxicación crónica produce dolor de cabeza, pérdida de sueño, disfunciones de la visión, la memoria y el oído, inflamación de los nervios y daños vasculares. The increasing emission of pollutants into the environment and the consequent deterioration of the latter has led to legal control over their emission. Specifically, carbon disulfide (CS 2 ), a volatile, colorless and very easily flammable liquid, constitutes a highly dangerous pollutant due mainly to its harmful effects on human health. Prolonged exposure to carbon sulfide vapors causes symptoms of intoxication ranging from redness of the face and euphoria to loss of consciousness, coma and breathing paralysis. Chronic intoxication causes headache, loss of sleep, impaired vision, memory and hearing, nerve inflammation and vascular damage.
Por ello, ha sido necesario desarrollar procesos destinados a controlar la emisión de dicho contaminante (CS2) al medio ambiente. La mayoría de dichos procesos se basan en principios físico-químicos. No obstante, dichos procesos presentan diversos inconvenientes ya que generalmente requieren diversos equipos para la separación y eliminación completa del contaminante, lo que los hace costosos y con grandes exigencias de energía, y, en ocasiones, resultan ineficientes, particularmente cuando el contaminante se encuentra en bajas concentraciones. Por ello, ninguna de las tecnologías físico-químicas tradicionales (oxidación térmica, procesos termocatalíticos, incineración, hidrogenación, hidrólisis, condensación, adsorción, etc.) representa en la actualidad una opción apropiada para el tratamiento del CS2. Therefore, it has been necessary to develop processes aimed at controlling the emission of said pollutant (CS 2 ) into the environment. Most of these processes are based on physical-chemical principles. However, these processes have several drawbacks since they generally require various equipment for the complete separation and elimination of the contaminant, which makes them expensive and with high energy requirements, and, sometimes, they are inefficient, particularly when the contaminant is in low concentrations Therefore, none of the traditional physicochemical technologies (thermal oxidation, thermocatalytic processes, incineration, hydrogenation, hydrolysis, condensation, adsorption, etc.) currently represents an appropriate option for the treatment of CS 2 .
A lo largo de los últimos años, las tecnologías biológicas de limpieza de corrientes gaseosas contaminadas han tomado fuerza como alternativa a las tecnologías físico-químicas, ya que son procesos más limpios y económicos, que eliminan muchas de las desventajas asociadas con los sistemas físico-químicos tradicionales, y resultan especialmente útiles cuando los caudales a tratar son grandes y las concentraciones de contaminantes (e.g., CS2) son bajas. Over the past few years, biological technologies for cleaning contaminated gas streams have gained strength as an alternative to physicochemical technologies, since they are cleaner and more economical processes, which eliminate many of the disadvantages associated with physical systems. traditional chemicals, and are especially useful when the flow rates to be treated are large and the concentrations of pollutants (eg, CS 2 ) are low.
Los sistemas biológicos de purificación de corrientes gaseosas pueden clasificarse en tres grandes grupos: biolavadores ("bioscrubber"), bioreactores de lecho escurrido ("biotrickling") y biofiltros de lecho fijo [Delhomenie, MC. y col. 2005. Biofiltration of Air: A Review. Critical Reviews in Biotechnology, 25:53-72]. Biological gas stream purification systems can be classified into three main groups: biolavadores ("bioscrubber"), drained bed bioreactors ("biotrickling") and fixed bed biofilters [Delhomenie, MC. et al. 2005. Biofiltration of Air: A Review. Critical Reviews in Biotechnology, 25: 53-72].
Los biolavadores ("bioscrubber") constituyen una tecnología de tratamiento en dos etapas. En la primera, el gas contaminado entra en contacto con una fase líquida que absorbe los contaminantes. Después de haber absorbido los contaminantes, el líquido es tratado mediante un proceso biológico tradicional (por ejemplo, mediante un proceso de lodos activados). Los biolavadores tienen como principal inconveniente su incapacidad para tratar compuestos poco solubles en agua, por lo que no son buenos candidatos en el caso del CS2. The biolavadores ("bioscrubber") constitute a technology of treatment in two stages. In the first, the contaminated gas comes into contact with a liquid phase that absorbs the contaminants. After the contaminants have been absorbed, the liquid is treated by a traditional biological process (for example, by an activated sludge process). Biolavadores have as their main drawback their inability to treat poorly soluble compounds, so they are not good candidates in the case of CS 2 .
Los bioreactores de lecho escurrido ("filtros biotrickling") requieren la alimentación continua de un medio líquido sobre un lecho de material de soporte inorgánico (por ejemplo, polietileno, polipropileno, PVC o roca de lava). Esta tecnología está principalmente controlada por la transferencia de masa entre la fase gaseosa y la fase líquida, lo que constituye una desventaja debido a que el CS2 gaseoso es muy poco soluble en agua. Otra desventaja asociada con la alimentación continua de líquido consiste en la obtención de un medio líquido que debe ser gestionado adecuadamente. Además, la naturaleza inorgánica del material de soporte obliga a inocular el sistema con la biomasa adecuada para la biodegradación. Las patentes norteamericanas US 4968622, US 5747331 y US 5236677 describen bioreactores de lecho escurrido para la degradación biológica de CS2. Los biofiltros ("bioreactores de lecho fijo") constituyen, en Europa, la tecnología de tratamiento biológico de gas más utilizada para la eliminación de olores y compuestos volátiles orgánicos (VOCs) y sulfurados (VSCs). A pesar de su nombre, no son unidades de «filtración» en el sentido estricto de la palabra, sino que abarcan una combinación de varios procesos básicos: absorción, adsorción, biodegradación y desorción. Básicamente, los biofiltros consisten en un compartimento que contiene un material de relleno o soporte (material filtrante) que sirve como portador de la biomasa responsable de la biodegradación de los contaminantes. Drained bed bioreactors ("biotrickling filters") require the continuous feeding of a liquid medium onto a bed of inorganic support material (eg, polyethylene, polypropylene, PVC or lava rock). This technology is mainly controlled by the mass transfer between the gas phase and the liquid phase, which is a disadvantage because the gaseous CS 2 is very poorly soluble in water. Another disadvantage associated with continuous liquid feeding consists in obtaining a liquid medium that must be properly managed. In addition, the inorganic nature of the support material forces the system to be inoculated with the appropriate biomass for biodegradation. US patents US 4968622, US 5747331 and US 5236677 describe drained bed bioreactors for the biological degradation of CS 2 . Biofilters ("fixed bed bioreactors") constitute, in Europe, the most used biological gas treatment technology for the elimination of odors and volatile organic compounds (VOCs) and sulphides (VSCs). Despite their name, they are not "filtration" units in the strict sense of the word, but instead encompass a combination of several basic processes: absorption, adsorption, biodegradation and desorption. Basically, biofilters consist of a compartment that contains a filler or support material (filter material) that serves as a carrier of the biomass responsible for the biodegradation of contaminants.
El fundamento de todos los procesos biológicos se basa en la capacidad que tienen algunos microorganismos para degradar los contaminantes y transformarlos en productos inocuos o menos nocivos para la salud humana o animal y/o el medio ambiente. En el caso concreto del CS2, la degradación trascurre según la siguiente secuencia de reacciones [Smith, N. A. et al. (1988). Oxidation of carbón disulphide as the solé source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m. J. Gen. Microbiol, 134:3041-3048]: The foundation of all biological processes is based on the ability of some microorganisms to degrade contaminants and transform them into products that are harmless or less harmful to human or animal health and / or the environment. In the specific case of CS 2 , degradation occurs according to the following sequence of reactions [Smith, NA et al. (1988). Oxidation of carbon disulphide as the solé source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m. J. Gen. Microbiol, 134: 3041-3048]:
1. S=C=S + H20→ 0=C=S + H2S 1. S = C = S + H 2 0 → 0 = C = S + H 2 S
2. 0=C=S + H20→ C02 + H2S 2. 0 = C = S + H 2 0 → C0 2 + H 2 S
3. H2S + 202→ H2S04 + Energía 3. H 2 S + 20 2 → H 2 S0 4 + Energy
Otros autores, Revah y col. [Revah et al. (1994). Air biodesulphurisation in process plants. In: Bioremediation: The TOKYO '94 Workshop, OECD Publishing, París] y Alcántara y col. [Alcántara et al. (1999) Carbón disulfide oxidation by a microbial consortium from a tricking filter. Biotechnol. Lett., 21 :815-819] proponen otros pasos adicionales intermedios en la degradación posterior del sulfuro de hidrógeno: Other authors, Revah et al. [Revah et al. (1994). Air biodesulphurisation in process plants. In: Bioremediation: The TOKYO '94 Workshop, OECD Publishing, Paris] and Alcántara et al. [Alcantara et al. (1999) Carbon disulfide oxidation by a microbial consortium from a tricking filter. Biotechnol Lett., 21: 815-819] propose other additional intermediate steps in the subsequent degradation of hydrogen sulfide:
S + H20 + 3/2 02^ H2S04 S + H 2 0 + 3/2 0 2 ^ H 2 S0 4
A pesar de las diferentes configuraciones de los reactores biológicos, la biomasa o población de microorganismos capaces de degradar el contaminante, constituye, en todos los casos, un elemento decisivo para el funcionamiento eficaz del sistema. La biodiversidad de la misma depende de la composición del gas alimentado, el lecho- soporte y, en general, de las condiciones ambientales. Los microorganismos capaces de degradar el CS2 no son tan abundantes como los microorganismos capaces de degradar otros contaminantes (e.g., sulfuro de hidrógeno (H2S)), debido posiblemente al hecho de que el CS2 posee propiedades fungicidas y a que la rotura de sus dobles enlaces requiere más energía [Yang, Y. et al. (1997). Biofiltration for control of carbón disulfide and hydrogen sulfide vapors, for presentation at the "Air and waste management association's 90th annual meeting & exhibition", Toronto, Canadá]. De hecho, tal como refleja la siguiente lista, el número de cepas capaces de degradar CS2 es muy limitado: In spite of the different configurations of the biological reactors, the biomass or population of microorganisms capable of degrading the contaminant constitutes, in all cases, a decisive element for the effective functioning of the system. Its biodiversity depends on the composition of the fed gas, the bed. support and, in general, environmental conditions. Microorganisms capable of degrading CS 2 are not as abundant as microorganisms capable of degrading other pollutants (eg, hydrogen sulfide (H 2 S)), possibly due to the fact that CS 2 possesses fungicidal properties since the breakage of its double bonds require more energy [Yang, Y. et al. (1997). Biofiltration for control of carbon disulfide and hydrogen sulfide vapors, for presentation at the "Air and waste management association's 90th annual meeting &exhibition", Toronto, Canada]. In fact, as the following list reflects, the number of strains capable of degrading CS 2 is very limited:
Thiobacillus TJ330 [Hartikainen, T. et al. (2000). Physiology and taxonomy of Thiobacillus strain TJ330, which oxidizes carbón disulphide (CS2). J. Appl.Thiobacillus TJ330 [Hartikainen, T. et al. (2000). Physiology and taxonomy of Thiobacillus strain TJ330, which oxidizes carbon disulphide (CS 2 ). J. Appl.
Microbiol. 89: 580-586]; Microbiol 89: 580-586];
Thiothrix ramosa [Odintsova, E.V. et al. (1993). Chemolithoautotrophic Growth of Thiotrix Ramosa. Archives of Microbio logy, 160: 152-157]; Thiothrix ramosa [Odintsova, E.V. et al. (1993). Chemolithoautotrophic Growth of Thiotrix Ramosa. Archives of Microbio logy, 160: 152-157];
- una cepa sin identificar de la especie Thiobacillus [Pías, C. et al. (1993). - an unidentified strain of the Thiobacillus species [Pías, C. et al. (1993).
Degradation of carbón disulphide by a Thiobacillus isolate. Appl. Microbiol. Degradation of carbon disulphide by a Thiobacillus isolate. Appl. Microbiol
Biotechnol. 38: 820-823]; Biotechnol 38: 820-823];
Thiobacillus thioparus TK [Smith, N.A. et al. (1988). Oxidation of carbón disulphide as the solé source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m. J. Gen. Microbiol. 134: 3041-3048]; Thiobacillus thioparus TK [Smith, N.A. et al. (1988). Oxidation of carbon disulphide as the solé source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m. J. Gen. Microbiol. 134: 3041-3048];
- Paracoccus denitrificans KS1, KS2 y KS2 [Jordán, S.L. et al. (1995). Novel eubacteria able to grow on carbón disulfide. Arch. Microbiol. 163: 131-137; Jordán, S.L. et al. (1997). Autotrophic growth on carbón disulfide is a property of novel strains of Paracoccus denitrificans. Arch. Microbiol. 168: 225-236]; - Paracoccus denitrificans KS1, KS2 and KS2 [Jordán, S.L. et al. (nineteen ninety five). Novel eubacteria able to grow on carbon disulfide. Arch. Microbiol. 163: 131-137; Jordán, S.L. et al. (1997). Autotrophic growth on carbon disulfide is a property of novel strains of Paracoccus denitrificans. Arch. Microbiol. 168: 225-236];
Thioalkalivibrio [Sorokin, D.Y. et al. (2001). Thioalkalimicrobium aerophilum gen. nov., sp. nov. and Thioalkalimicrobium sibericum sp. nov., andThioalkalivibrio [Sorokin, D.Y. et al. (2001). Thioalkalimicrobium aerophilum gene. nov., sp. Nov. and Thioalkalimicrobium sibericum sp. nov., and
Thioalkalivibrio versutus gen. nov., sp. nov., Thioalkalivibrio nitratis sp. nov. and Thioalkalivibrio denitrificans sp. nov., novel obligately alkaliphilic and obligately chemolithoautotrophic sulfur-oxidizing bacteria from soda lakes. Int. J. Syst. Evol. Microbiol. 51 : 565-580]; y Thioalkalivibrio versutus gen. nov., sp. Nov., Thioalkalivibrio nitratis sp. Nov. and Thioalkalivibrio denitrificans sp. Nov., novel obligately alkaliphilic and obligately chemolithoautotrophic sulfur-oxidizing bacteria from soda lakes. Int. J. Syst. Evol Microbiol 51: 565-580]; Y
- Thiomonas [Pol, A. et al. (2007). Isolation of a carbón disulfide utilizing Thiomonas sp. and its application in a biotrickling filter. Appl. Microbiol. Biotechnol. 74:439-446]. - Thiomonas [Pol, A. et al. (2007). Isolation of a carbon disulfide utilizing Thiomonas sp. and its application in a biotrickling filter. Appl. Microbiol Biotechnol 74: 439-446].
Por otra parte, la naturaleza del material de soporte de los microorganismos también constituye un factor fundamental para el correcto funcionamiento de los bioreactores, ya que influye tanto en la capacidad de eliminación del contaminante como en el coste del sistema. El soporte ideal debería cumplir diversas características tales como, por ejemplo, poseer una alta capacidad de retención de humedad y biomasa, una elevada superficie de contacto, una porosidad de lecho adecuada (para evitar pérdidas de carga y colapso del sistema), bajo coste económico, tiempo de vida largo, etc. Además, una vez agotado, debería ser fácil de gestionar para evitar la generación de un problema añadido. On the other hand, the nature of the support material of the microorganisms is also a fundamental factor for the proper functioning of the bioreactors, since it influences both the ability to eliminate the contaminant and the cost of the system. The ideal support should meet various characteristics such as, for example, having a high moisture and biomass retention capacity, a high contact surface, a suitable bed porosity (to avoid load losses and system collapse), low economic cost , long life time, etc. In addition, once exhausted, it should be easy to manage to avoid generating an added problem.
Aunque se han descrito biofiltros con soportes inorgánicos especialmente diseñados, la utilización de soportes de naturaleza orgánica aporta diversas ventajas, entre las que merece la pena destacar la posibilidad de contener biomasa indígena (bacterias, hongos, protozoos, algas, etc.) y nutrientes, aunque, por otra parte, este tipo de soportes sufre una mayor degradación a lo largo del tiempo que algunos de los materiales sintéticos. Entre los materiales de soporte de origen natural de los biofiltros se encuentran el compost [Yang, Y. et al. (1994). Oxidative destruction of carbón disulfide vapors using biofiltration In: Air & Waste Management Association's 87th Annual Meeting & Exhibition, Cincinnati, Ohio], turba [Hartikainen, T. et al. (2001). Carbón Disulfide and Hydrogen Sulfide Removal with a Peat Bio filter. J Air & Waste Manag. Assoc, 51 :387-392], turba ácida [US 5747331], corteza de pino o una mezcla de compost, serrín y perlita [Vaith, K. et al. (1997). Comparison of Biofilter Performance for Hydrogen Sulfide, Methyl Mercaptan, Carbón Disulfide, and Dimethyl Disulfide Removal. In proceedings of Control of odors and VOC emissions specialty conference, Houston]. Although biofilters with specially designed inorganic supports have been described, the use of supports of an organic nature provides several advantages, among which it is worth noting the possibility of containing indigenous biomass (bacteria, fungi, protozoa, algae, etc.) and nutrients, although, on the other hand, this type of supports undergoes greater degradation over time than some of the synthetic materials. Among the naturally occurring support materials of biofilters are compost [Yang, Y. et al. (1994). Oxidative destruction of carbon disulfide vapors using biofiltration In: Air & Waste Management Association's 87th Annual Meeting & Exhibition, Cincinnati, Ohio], peat [Hartikainen, T. et al. (2001). Carbon Disulfide and Hydrogen Sulfide Removal with a Peat Bio filter. J Air & Waste Manag. Assoc, 51: 387-392], acid peat [US 5747331], pine bark or a mixture of compost, sawdust and perlite [Vaith, K. et al. (1997). Comparison of Biofilter Performance for Hydrogen Sulfide, Methyl Mercaptan, Carbon Disulfide, and Dimethyl Disulfide Removal. In proceedings of Control of odors and VOC emissions specialty conference, Houston].
Muchos de los sistemas de biofiltración de corrientes gaseosas que contienen CS2 propuestos hasta la fecha requieren una etapa previa de inoculación del material de soporte con cultivos microbio lógicamente puros de microorganismos capaces de degradar CS2 para conseguir que el sistema degrade el CS2. Otras limitaciones de los sistemas de biofiltración de CS2 conocidos, que complican su funcionamiento e incrementan el coste asociado a los mismos, incluyen las exigencias relativas al mantenimiento (ajuste de pH, consumo de reactivos, riego, etc.) así como el deterioro del material de soporte. Many of the gas stream biofiltration systems containing CS 2 proposed to date require a previous stage of inoculation of the support material with logically pure microbe cultures of microorganisms capable of degrading CS 2 to make the system degrade CS 2 . Other limitations of known CS 2 biofiltration systems, which complicate their operation and increase the cost associated with them, include the requirements related to maintenance (pH adjustment, reagent consumption, irrigation, etc.) as well as the deterioration of the support material.
Por tanto, sigue existiendo la necesidad de encontrar métodos alternativos para tratar corrientes gaseosas contaminadas con CS2, sencillos y fiables, que, preferentemente, resuelvan al menos alguno de los problemas de los métodos de biofiltración de corrientes gaseosas contaminadas con CS2 descritos en el estado de la técnica. Therefore, there is still a need to find alternative methods for treating gaseous streams contaminated with CS 2 , simple and reliable, which, preferably, solve at least some of the problems of the biofiltration methods of gaseous streams contaminated with CS 2 described in the state of the art
COMPENDIO DE LA INVENCIÓN SUMMARY OF THE INVENTION
Los autores de la presente invención han desarrollado un método de biofiltración sobre lecho fijo para depurar (eliminar/reducir) de manera eficiente la cantidad del CS2 presente en una corriente gaseosa contaminada con dicho compuesto (CS2). Dicho método, basado en la utilización como material de relleno del biofiltro de un producto habitualmente empleado como abono (compost), proporciona diversas ventajas frente a los métodos tradicionales y a otros métodos biológicos descritos en el estado de la técnica, debido principalmente a sus características físico-químicas. The authors of the present invention have developed a fixed bed biofiltration method to efficiently purify (eliminate / reduce) the amount of CS 2 present in a gaseous stream contaminated with said compound (CS 2 ). Said method, based on the use as filler material of the biofilter of a product commonly used as compost, provides several advantages over traditional methods and other biological methods described in the state of the art, mainly due to its physical characteristics. -chemistry.
Así, en un aspecto la invención se relaciona con un biofiltro que comprende un material de relleno y microorganismos capaces de degradar CS2, en donde dicho material de relleno comprende un compost obtenible por descomposición aeróbica- anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales, y (ii) 70-30% en peso de residuos vegetales. Thus, in one aspect the invention relates to a biofilter comprising a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30 -70% by weight of animal waste, and (ii) 70-30% by weight of plant waste.
En otro aspecto la invención se relaciona con un método para depurar una corriente gaseosa que contiene CS2 mediante biofiltración que comprende hacer pasar dicha corriente gaseosa que contiene CS2 a través de dicho biofiltro. In another aspect the invention relates to a method for purifying a gas stream containing CS 2 by biofiltration comprising passing said gas stream containing CS 2 through said biofilter.
En otro aspecto la invención se relaciona con una instalación para la depuración de una composición gaseosa que comprende CS2 que comprende, al menos, uno de dichos bio filtros. In another aspect the invention relates to an installation for the purification of a gaseous composition comprising CS 2 comprising at least one of said bio filters.
En otro aspecto, la invención se relaciona con un método para aclimatar al CS2 microorganismos capaces de degradar CS2 contenidos en un compost, en donde dicho compost es obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales, y (ii) 70-30%> en peso de residuos vegetales, que comprende poner en contacto dicho compost que contiene microorganismos capaces de degradar CS2 con una corriente gaseosa que comprende CS2 en una cantidad inferior a aproximadamente 100 ppmv, con un tiempo de residencia inferior a aproximadamente 120 segundos, de manera continua, durante aproximadamente al menos 100 días. In another aspect, the invention relates to a method for acclimatizing to CS 2 microorganisms capable of degrading CS 2 contained in a compost, wherein said compost is obtainable by aerobic-anaerobic decomposition of a mixture that It comprises (i) 30-70% by weight of animal waste, and (ii) 70-30%> by weight of plant waste, which comprises contacting said compost containing microorganisms capable of degrading CS 2 with a gaseous stream that it comprises CS 2 in an amount less than about 100 ppmv, with a residence time of less than about 120 seconds, continuously, for at least 100 days.
En otro aspecto, la invención se relaciona con un método para generar una población de microorganismos capaces de degradar CS2 que comprende combinar: a) un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70%) en peso de residuos de animales y (ii) 70-In another aspect, the invention relates to a method for generating a population of microorganisms capable of degrading CS 2 which comprises combining: a) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) in weight of animal waste and (ii) 70-
30%o en peso de residuos vegetales, que comprende microorganismos capaces de degradar CS2 aclimatados al CS2 según el método de aclimatación anteriormente definido (compost aclimatado), con 30% by weight of vegetable waste, comprising microorganisms capable of degrading CS 2 CS 2 acclimatized by the method defined above acclimation (acclimatized compost), with
b) un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70%> en peso de residuos de animales y (ii) 70- b) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%> by weight of animal waste and (ii) 70-
30%o en peso de residuos vegetales (compost fresco), 30% or by weight of vegetable waste (fresh compost),
en una proporción (compost aclimatado): (compost fresco) comprendida entre aproximadamente 1 : 1 y aproximadamente 5: 1, en peso. in a proportion (acclimatized compost): (fresh compost) between approximately 1: 1 and approximately 5: 1, by weight.
BREVE DESCRIPCIÓN DE LAS FIGURAS BRIEF DESCRIPTION OF THE FIGURES
La Figura 1 es una fotografía que muestra un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70%> en peso de residuos de animales, y (ii) 70-30%> en peso de residuos vegetales, en forma de pellets. Figure 1 is a photograph showing a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%> by weight of animal waste, and (ii) 70-30%> by weight of plant waste , in the form of pellets.
La Figura 2 es una representación esquemática de una realización particular de una instalación adecuada para la puesta en práctica del método de biofiltración de CS2 según la presente invención. DESCRIPCIÓN DETALLADA DE LA INVENCIÓN Figure 2 is a schematic representation of a particular embodiment of an installation suitable for the implementation of the CS 2 biofiltration method according to the present invention. DETAILED DESCRIPTION OF THE INVENTION
Bio filtro de la invención Bio filter of the invention
En un aspecto, la invención se relaciona con un biofiltro de disulfuro de carbono (CS2), en adelante "biofiltro de la invención", que comprende un material de relleno y microorganismos capaces de degradar CS2, en donde dicho material de relleno comprende un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales, y (ii) 70-30%> en peso de residuos vegetales. Dicho biofiltro de la invención puede ser utilizado para depurar gases contaminados con CS2 mediante bio filtración, es decir, para reducir la cantidad de, o eliminar, la cantidad de CS2 presente en una corriente gaseosa que contiene CS2. In one aspect, the invention relates to a biofilter of carbon disulfide (CS 2 ), hereinafter "biofilter of the invention", which comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste, and (ii) 70-30%> by weight of plant waste. Said biofilter of the invention can be used to purify gases contaminated with CS 2 by bio filtration, that is, to reduce the amount of, or eliminate, the amount of CS 2 present in a gaseous stream containing CS 2 .
El material de relleno presente en el biofiltro de la invención comprende un producto de naturaleza orgánica, en concreto, un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende del 30%> al 70%> en peso de residuos de animales y del 70%> al 30%> en peso de residuos vegetales. Ejemplos ilustrativos, no limitativos, de residuos de animales apropiados para la producción del compost utilizado en el método de biofiltración de la invención, incluyen purines de cerdo, residuos de aves de corral, residuos de ganado bovino, etc., y sus combinaciones. Ejemplos ilustrativos, no limitativos, de residuos vegetales incluyen hojas, ramas, trozos de madera, serrín, etc., y sus combinaciones. Los autores de la presente invención han encontrado que un producto comúnmente utilizado con fines agrícolas (abono), también puede ser empleado de manera ventajosa como material de relleno (material filtrante) en un biofiltro de CS2 debido, entre otras razones, a sus características físico-químicas tales como, por ejemplo, alta capacidad de retención de humedad, elevada porosidad, elevada superficie de contacto, buena capacidad para regular el pH, biomasa adaptable y diversa, bajo coste de inversión y larga duración (mecánicamente resistente y químicamente inerte y estable). Dicho material de relleno (compost) del biofiltro de la invención sirve de soporte para los microorganismos capaces de degradar CS2 y proporciona los nutrientes necesarios para el metabolismo de dichos microorganismos capaces de degradar CS2 aunque, en ocasiones, pudiera ser necesario efectuar un aporte adicional de nutrientes para el mantenimiento y crecimiento de los microorganismos presentes en dicho material de relleno. The filler material present in the biofilter of the invention comprises a product of an organic nature, in particular, a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising from 30%> to 70%> by weight of animal waste and of the 70%> to 30%> by weight of plant waste. Illustrative, non-limiting examples of animal residues suitable for the production of compost used in the biofiltration method of the invention, include pig purines, poultry residues, cattle residues, etc., and combinations thereof. Illustrative, non-limiting examples of plant residues include leaves, branches, pieces of wood, sawdust, etc., and combinations thereof. The authors of the present invention have found that a product commonly used for agricultural purposes (fertilizer) can also be used advantageously as filler material (filter material) in a CS 2 biofilter due, among other reasons, to its characteristics physicochemical such as, for example, high moisture retention capacity, high porosity, high contact surface, good ability to regulate pH, adaptable and diverse biomass, low investment cost and long duration (mechanically resistant and chemically inert and stable). Said filler material (compost) of the biofilter of the invention serves as support for microorganisms capable of degrading CS 2 and provides the necessary nutrients for the metabolism of said microorganisms capable of degrading CS 2 although, at times, it may be necessary to make a contribution additional nutrients for the maintenance and growth of the microorganisms present in said filler material.
El compost utilizado como material de relleno del biofiltro de la invención puede utilizarse sin compactar, es decir, en forma de gránulos más o menos sueltos de diversa granulometría, o, ventajosamente, en forma compactada. En una realización particular, dicho compost se encuentra en forma de partículas compactadas, preferentemente en forma de pellets (Figura 1). El tamaño de dichos pellets puede variar dentro de un amplio intervalo; no obstante, en una realización particular, dichos pellets de compost tienen un diámetro medio comprendido entre aproximadamente 5 mm y aproximadamente 12 mm, preferiblemente entre aproximadamente 6 mm y aproximadamente 8 mm. El tamaño de los pellets de compost junto con la elevada porosidad del compost, proporcionan una gran área superficial que favorece el contacto de los microorganismos capaces de degradar CS2 con dicho contaminante. Asimismo, la regularidad morfológica de los pellets de compost constituyentes del material de relleno del biofiltro de la invención asegura una distribución muy homogénea del material de relleno en el biofiltro de la invención, lo que minimiza el desarrollo de caminos preferenciales que limiten el tiempo de contacto real entre la corriente gaseosa que contiene CS2 a tratar y la superficie activa del material de relleno que comprende los microorganismos capaces de degradar CS2. The compost used as filler material of the biofilter of the invention can be used without compacting, that is, in the form of more or less loose granules of different granulometry, or, advantageously, in compacted form. In a particular embodiment, said compost is in the form of compacted particles, preferably in the form of pellets (Figure 1). The size of said pellets may vary within a wide range; however, in a particular embodiment, said compost pellets have an average diameter between about 5 mm and about 12 mm, preferably between about 6 mm and about 8 mm. The size of the compost pellets together with the high porosity of the compost, provide a large surface area that favors the contact of microorganisms capable of degrading CS 2 with said contaminant. Likewise, the morphological regularity of the compost pellets constituting the biofilter filler material of the invention ensures a very homogeneous distribution of the filler material in the biofilter of the invention, which minimizes the development of preferential paths that limit the contact time. actual between the gas stream containing CS 2 to be treated and the active surface of the filler material comprising the microorganisms capable of degrading CS 2 .
El material de relleno del biofiltro de la invención presenta una buena capacidad de retención de agua, lo que resulta muy favorable ya que los microorganismos requieren de una importante cantidad de agua para crecer y el proceso es exotérmico. Aunque el grado de humedad del material de relleno puede variar dentro de un amplio intervalo, en una realización particular, el grado de humedad del material de relleno del biofiltro de la invención está comprendido entre 30% y 70%, preferentemente, entre 35%o y 50%o. Un bajo contenido de humedad en el material de relleno reduce el espesor de la biopelícula y afecta adversamente a la actividad de los microorganismos capaces de degradar CS2, y, por consiguiente, a la actividad del biofiltro. Por otro lado, un elevado grado de humedad puede crear una saturación, provocando zonas anaerobias o incrementar la pérdida de carga. El biofiltro de la invención comprende, además de dicho material de relleno, unos microorganismos capaces de degradar CS2. En el sentido utilizado en la presente invención, un microorganismo capaz de degradar CS2 es un microorganismo que presenta la capacidad de utilizar el CS2 como fuente de energía y transformarlo en un producto inocuo o menos nocivo para para la salud humana o animal y/o el medio ambiente, por ejemplo, en sulfato [véase, por ejemplo, Smith, N. A. et al. (1988); Revah et al. (1994); Alcántara et al. (1999), citados supra]. Dicho microorganismo capaz de degradar CS2 puede ser una bacteria, un hongo, una levadura, un protozoo, etc. Ejemplos ilustrativos, no limitativos, de microorganismos capaces de degradar CS2 incluyen microorganismos de los géneros Paracoccus (e.g., P. denitrificans, etc.), Thioalkalimicrobium (e.g., T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (e.g., T. denitrificans, T. nitratis, T. versutus, etc.), Thiobacillus (e.g., Thiobacillus TJ330, T. thioparus, etc.), Thiomonas, Thiothrix (e.g., T. ramosa, etc.), etc. En una realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar CS2 pertenecientes a un único género o a una única especie de microorganimos capaces de degradar CS2; alternativamente, en otra realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar CS2 pertenecientes a distintos géneros y/o especies. The biofilter filler material of the invention has a good water retention capacity, which is very favorable since microorganisms require a significant amount of water to grow and the process is exothermic. Although the moisture content of the filler material can vary over a wide range, in a particular embodiment, the moisture content of the biofilter filler material of the invention is between 30% and 70%, preferably between 35% o and 50% or A low moisture content in the filler material reduces the thickness of the biofilm and adversely affects the activity of microorganisms capable of degrading CS 2 , and, consequently, the activity of the biofilter. On the other hand, a high degree of humidity can create saturation, causing anaerobic areas or increase the loss of load. The biofilter of the invention comprises, in addition to said filler material, microorganisms capable of degrading CS 2 . In the sense used in the present invention, a microorganism capable of degrading CS 2 is a microorganism that has the ability to use CS 2 as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or the environment, for example, in sulfate [see, for example, Smith, NA et al. (1988); Revah et al. (1994); Alcantara et al. (1999), cited above]. Said microorganism capable of degrading CS 2 can be a bacterium, a fungus, a yeast, a protozoan, etc. Illustrative, non-limiting examples of microorganisms capable of degrading CS 2 include microorganisms of the genera Paracoccus (eg, P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. denitrificans, T. nitratis, T. versutus, etc.), Thiobacillus (eg, Thiobacillus TJ330, T. thioparus, etc.), Thiomonas, Thiothrix (eg, T. ramosa, etc.), etc. In a particular embodiment, the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to a single genus or to a single species of microorganisms capable of degrading CS 2 ; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to different genera and / or species.
Algunos de dichos microorganismos capaces de degradar CS2 útiles para la puesta en práctica de la presente invención se encuentran disponibles comercialmente o en colecciones de cultivos. No obstante, el experto en la materia conoce que, en general, viven microorganismos que toleran el contaminante en cuestión (CS2) en muestras procedentes de sitios contaminados con dicho contaminante, por ejemplo, áreas o instalaciones en donde se usan o generan corrientes gaseosas que contienen CS2, etc.; por tanto, mediante una selección de los cultivos de los microorganismos presentes en dichas muestras es posible encontrar cepas de microorganismos capaces de degradar el contaminante en cuestión (CS2). Por tanto, debido a la diversidad de residuos utilizados en la elaboración del material de relleno utilizado en el biofiltro de la invención, dicho material de relleno (compost) contiene microorganismos de naturaleza muy diversa, y, entre dichos microorganismos existen microorganismos capaces de degradar CS2 los cuales pueden ser identificados y aislados por métodos convencionales de selección de microorganismos conocidos por los técnicos en la materia. Efectivamente, la biomasa indígena (microorganismos autóctonos) del compost que constituye el material de relleno del biofiltro de la invención es adaptable, ya que en contacto con corrientes gaseosas que contienen CS2, ventajosamente humedecidas previamente con agua, la población de microorganismos presente en dicho compost se auto-regula de manera que proliferan los microorganismos capaces de degradar CS2 y se reprimen los microorganismos incapaces de degradar CS2. Por tanto, en una realización particular, la puesta en práctica del método de bio filtración proporcionado por esta invención no requiere la inoculación inicial con microorganismos capaces de degradar CS2 ya que estos están presentes en el material de relleno (compost) del biofiltro utilizado en dicho método de bio filtración; no obstante, si se desea, en una realización particular, se puede inocular dicho compost con un cultivo de microorganismos capaces de degradar CS2. Some of said microorganisms capable of degrading CS 2 useful for the implementation of the present invention are commercially available or in crop collections. However, the person skilled in the art knows that, in general, microorganisms that tolerate the contaminant in question (CS 2 ) live in samples from sites contaminated with said contaminant, for example, areas or facilities where gas streams are used or generated containing CS 2 , etc .; therefore, by selecting the cultures of the microorganisms present in said samples it is possible to find strains of microorganisms capable of degrading the contaminant in question (CS 2 ). Therefore, due to the diversity of waste used in the preparation of the filler material used in the biofilter of the invention, said filler material (compost) contains microorganisms of a very diverse nature, and, among said microorganisms there are microorganisms capable of degrading CS 2 which can be identified and isolated by conventional methods of selecting microorganisms known to those skilled in the art. Indeed, the biomass Indigenous (native microorganisms) of the compost that constitutes the biofilter filler material of the invention is adaptable, since in contact with gaseous streams containing CS 2 , advantageously moistened previously with water, the population of microorganisms present in said compost is self- regulated to proliferate microorganisms capable of degrading CS 2 and incapable of degrading microorganisms are repressed CS 2. Therefore, in a particular embodiment, the implementation of the bio filtration method provided by this invention does not require initial inoculation with microorganisms capable of degrading CS 2 since these are present in the filler material (compost) of the biofilter used in said bio filtration method; however, if desired, in a particular embodiment, said compost can be inoculated with a culture of microorganisms capable of degrading CS 2 .
La capacidad de un microorganismo de degradar CS2 puede determinarse por cualquier procedimiento convencional, conocido por los técnicos en la materia, que permita conocer si un microorganismo utiliza CS2, por ejemplo, poniendo en contacto un cultivo de dicho microorganismo con CS2 e incubando bajo condiciones apropiadas; bajo esas condiciones, la detección de sulfuro de hidrógeno, un producto intermedio de la oxidación del CS2, o la producción de sulfato, un producto final de la oxidación del CS2, es indicativa de que el microorganismo analizado es capaz de degradar CS2; si se desea, el microorganismo puede encontrarse soportado sobre un material de relleno del tipo utilizado en el biofiltro de la invención (compost) y el CS2 puede estar contenido en una corriente de aire, preferentemente humedecida en agua antes de ponerla en contacto con el microorganismo. The ability of a microorganism to degrade CS 2 can be determined by any conventional procedure, known to those skilled in the art, which allows to know if a microorganism uses CS 2 , for example, by contacting a culture of said microorganism with CS 2 and incubating under appropriate conditions; Under these conditions, the detection of hydrogen sulfide, an intermediate product of the oxidation of CS 2 , or the production of sulfate, a final product of the oxidation of CS 2 , is indicative that the analyzed microorganism is capable of degrading CS 2 ; if desired, the microorganism may be supported on a filler material of the type used in the biofilter of the invention (compost) and the CS 2 may be contained in a stream of air, preferably moistened with water before contacting it with the microorganism.
Estructuralmente, el biofiltro de la invención comprende un depósito, en el que se encuentra el material de relleno y los microorganismos capaces de degradar CS2, así como unos medios para la entrada de la corriente de gaseosa que contiene CS2, opcionalmente humedecida previamente, y unos medios para la salida de la corriente gaseosa descargada total o parcialmente de CS2. Opcionalmente, si se desea, se pueden incluir dispositivos para medir la temperatura de entrada de la corriente gaseosa que contiene CS2 a tratar ya que puede afectar al proceso metabólico de los microorganismos capaces de degradar el CS2, o para medir el pH ya que durante la operación del método de bio filtración proporcionado por esta invención se pueden generar productos ácidos que pueden afectar adversamente a la actividad del biofiltro. El bio filtro de la invención puede ser diseñado en diversas de formas y dimensiones, utilizando los materiales adecuados para ello. Structurally, the biofilter of the invention comprises a reservoir, in which the filler material and microorganisms capable of degrading CS 2 are found , as well as means for entering the gas stream containing CS 2 , optionally moistened previously, and means for the output of the gas stream totally or partially discharged from CS 2 . Optionally, if desired, devices can be included to measure the inlet temperature of the gas stream containing CS 2 to be treated since it can affect the metabolic process of microorganisms capable of degrading CS 2 , or to measure the pH since During the operation of the bio filtration method provided by this invention, acid products can be generated that can adversely affect the activity of the biofilter. The bio filter of the invention can be designed in various shapes and dimensions, using the appropriate materials for it.
La simplicidad estructural del bio filtro de la invención facilita el diseño de bioreactores que contienen uno o más biofiltros de la invención. Así, en una realización particular, la invención contempla el desarrollo de un bioreactor que comprende un único bio filtro de la invención, mientras que, en otra realización particular, la invención contempla el desarrollo de un bioreactor que comprende dos o más biofiltros de la invención, por ejemplo, 2, 3, 4 ó incluso más, operativamente conectados entre sí, de manera que la corriente gaseosa de salida del primero de dichos biofiltros de la invención es introducida en el segundo de los biofiltros de la invención, y, de manera similar, la corriente gaseosa de salida de dicho segundo bio filtro de la invención es introducida en el tercero de los biofiltros de la invención, y así sucesivamente hasta la salida definitiva de la corriente gaseosa total o parcialmente descargada de CS2. The structural simplicity of the bio filter of the invention facilitates the design of bioreactors containing one or more biofilters of the invention. Thus, in a particular embodiment, the invention contemplates the development of a bioreactor comprising a single bio filter of the invention, while, in another particular embodiment, the invention contemplates the development of a bioreactor comprising two or more biofilters of the invention. , for example, 2, 3, 4 or even more, operatively connected to each other, so that the gaseous outflow of the first of said biofilters of the invention is introduced into the second of the biofilters of the invention, and, so similarly, the outlet gas stream of said second bio filter of the invention is introduced into the third of the biofilters of the invention, and so on until the final exit of the total or partially discharged gas stream of CS 2 .
Método de la invención Invention Method
Como se ha mencionado previamente, el bio filtro de la invención puede ser utilizado para depurar gases contaminados con CS2 mediante bio filtración. As previously mentioned, the bio filter of the invention can be used to purify gases contaminated with CS 2 by bio filtration.
Por tanto, en otro aspecto, la invención se relaciona con un método para depurar una corriente gaseosa que contiene CS2 mediante bio filtración, en adelante "método de biofiltración de la invención", que comprende hacer pasar dicha corriente gaseosa que contiene CS2 a través de un biofiltro de la invención, es decir, un biofiltro que comprende un material de relleno y microorganismos capaces de degradar CS2, en donde dicho material de relleno comprende un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales, y (ii) 70-30% en peso de residuos vegetales. Therefore, in another aspect, the invention relates to a method for purifying a gas stream containing CS 2 by bio filtration, hereinafter "biofiltration method of the invention", which comprises passing said gas stream containing CS 2 to through a biofilter of the invention, that is, a biofilter comprising a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste, and (ii) 70-30% by weight of plant waste.
En el sentido utilizado en esta descripción, la expresión "depurar gases contaminados con CS2" incluye tanto la eliminación prácticamente total del CS2 presente en una corriente gaseosa que contiene CS2 como la reducción de la cantidad de CS2 presente en una corriente gaseosa que contiene CS2 hasta niveles permitidos por la legislación o que no resulten nocivos para la salud humana o animal, y/o para el medio ambiente. La cantidad de CS2 presente en dicha corriente gaseosa que contiene CS2 puede variar dentro de un amplio intervalo; no obstante, en una realización particular la cantidad de CS2 presente en dicha corriente gaseosa a tratar mediante el método de bio filtración de la invención está comprendida entre aproximadamente 50 partes por millón en volumen (ppmv) [1 ppmv = 1 μg x mi 1] y aproximadamente 250 ppmv. La corriente gaseosa que contiene CS2 a tratar mediante el método de biofiltración de la invención puede proceder de diversos focos contaminantes, por ejemplo, de instalaciones de procesos que utilizan o generan CS2, como son los sectores de fabricación de fibras de celulosa, industria alimentaria de envoltura sintética, etc. In the sense used in this description, the expression "purify gases contaminated with CS 2 " includes both the almost total elimination of CS 2 present in a gaseous stream containing CS 2 and the reduction of the amount of CS 2 present in a gaseous stream It contains CS 2 up to levels permitted by legislation or that are not harmful to human or animal health, and / or to the environment. The amount of CS 2 present in said gaseous stream containing CS 2 can vary within a wide range; however, in a particular embodiment the amount of CS 2 present in said gaseous stream to be treated by the bio filtration method of the invention is comprised between approximately 50 parts per million by volume (ppmv) [1 ppmv = 1 μg x ml 1 ] and approximately 250 ppmv. The gaseous stream containing CS 2 to be treated by the biofiltration method of the invention can come from various polluting sources, for example, from process facilities that use or generate CS 2 , such as the cellulose fiber manufacturing sectors, industry synthetic wrap food, etc.
El método de biofiltración de la invención comprende hacer pasar dicha corriente gaseosa que contiene CS2 a través de un biofiltro de la invención, cuyas características ya han sido mencionadas previamente. La cantidad de CS2 presente en dicha corriente gaseosa a tratar puede variar dentro de un amplio intervalo, al igual que el tiempo de residencia o cantidad promedio de tiempo que permanece la corriente gaseosa que contiene CS2 a tratar en contacto con el material de relleno. No obstante, en una realización particular, dicha corriente gaseosa a tratar contiene CS2 en una cantidad comprendida entre aproximadamente 50 ppmv y aproximadamente 250 ppmv y el tiempo de residencia está comprendido entre aproximadamente 10 segundos y aproximadamente 80 segundos Midiendo la concentración del CS2 a la salida del biofiltro se puede comprobar el funcionamiento del material de relleno y de los microorganismos capaces de degradar CS2 de manera que, en caso de que la eficacia del biofiltro decaiga, en primera instancia bastaría con regar el material de relleno con una solución de nutrientes, tal como se menciona más adelante, para recuperar la normalidad. The biofiltration method of the invention comprises passing said gas stream containing CS 2 through a biofilter of the invention, the characteristics of which have already been mentioned previously. The amount of CS 2 present in said gaseous stream to be treated may vary within a wide range, as can the residence time or average amount of time that the gaseous stream containing CS 2 to be treated remains in contact with the filling material. . However, in a particular embodiment, said gaseous stream to be treated contains CS 2 in an amount between about 50 ppmv and about 250 ppmv and the residence time is between about 10 seconds and about 80 seconds Measuring the concentration of CS 2 a The output of the biofilter can be checked for the operation of the filler material and of the microorganisms capable of degrading CS 2 so that, in the event that the efficiency of the biofilter decreases, in the first instance it would be enough to water the filler material with a solution of nutrients, as mentioned below, to restore normalcy.
En la práctica resulta conveniente que la corriente gaseosa que comprende CS2 a tratar esté húmeda, o sea previamente humedecida, ya que la propia humedad de dicha corriente gaseosa colabora en el desarrollo adecuado de los microorganismos presentes en el material de relleno del biofiltro de la invención. Por tanto, en una realización particular, el método de biofiltración de la invención comprende una etapa de humidificación de la corriente gaseosa que contiene CS2 a tratar, para lo cual, dicha corriente gaseosa se pone en contacto con un medio acuoso, por ejemplo, agua, antes de ser introducida en el biofiltro. El medio acuoso utilizado en esta etapa puede estar presente en un sistema de humidificación, tal como, por ejemplo, una o más columnas de medio acuoso (e.g., agua), que cede(n) a la corriente gaseosa que contiene CS2 la humedad necesaria, situada antes del bio filtro. En una realización particular, dicho sistema de humidificación comprende una única columna de medio acuoso (e.g., agua); en otra realización particular dicho sistema de humidificación comprende al menos dos, por ejemplo, 2, 3, 4 ó incluso más, columnas de medio acuoso (e.g., agua), con el fin de garantizar una correcta humidificación de la corriente gaseosa que contiene CS2 a tratar y minimizar el mantenimiento del sistema. En una realización particular, la humedad relativa de la corriente gaseosa que contiene CS2 de entrada al bio filtro es igual o superior al 90%, preferentemente igual o superior al 95%, aún más preferentemente igual o superior al 99%. De este modo, el empleo de un compost con un grado de humedad comprendido entre el 35% y el 50% como material de relleno del bio filtro de la invención utilizado en el método de biofiltración de la invención, ofrece buenos resultados. In practice it is convenient that the gaseous stream comprising CS 2 to be treated is wet, or previously moistened, since the humidity of said gaseous stream itself contributes to the proper development of the microorganisms present in the biofilter filler material of the invention. Therefore, in a particular embodiment, the biofiltration method of the invention comprises a step of humidifying the gaseous stream containing CS 2 to be treated, for which said gaseous stream is contacted with an aqueous medium, for example, water, before being introduced into the biofilter. The aqueous medium used at this stage may be present in a humidification system, such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gaseous stream containing CS 2 the necessary humidity, located before the bio filter. In a particular embodiment, said humidification system comprises a single column of aqueous medium (eg, water); in another particular embodiment said humidification system comprises at least two, for example, 2, 3, 4 or even more, columns of aqueous medium (eg, water), in order to guarantee a correct humidification of the gas stream containing CS 2 to treat and minimize system maintenance. In a particular embodiment, the relative humidity of the gas stream containing CS 2 entering the bio filter is equal to or greater than 90%, preferably equal to or greater than 95%, even more preferably equal to or greater than 99%. Thus, the use of a compost with a moisture content of between 35% and 50% as a filler material of the bio filter of the invention used in the biofiltration method of the invention offers good results.
Durante el proceso de biofiltración, la corriente gaseosa que contiene CS2 a tratar pasa a través del material de relleno que sirve de soporte a los microorganismos en crecimiento capaces de degradar CS2. La degradación del CS2 ocurre, en general, previa transferencia de la corriente gaseosa que contiene el CS2 a un medio líquido en donde es utilizado como fuente de carbono y energía. La utilización de dicho contaminante (CS2) implica la oxidación parcial o total del CS2 y la producción de biomasa (microorganismos capaces de degradar CS2) y con lo que el proceso de biofiltración de la invención da lugar a una descomposición prácticamente completa del CS2 generando productos no peligrosos (inocuos) para la salud humana o animal y/o el medio ambiente y una corriente gaseosa total o parcialmente descargada en CS2. During the biofiltration process, the gaseous stream containing CS 2 to be treated passes through the filler material that supports the growing microorganisms capable of degrading CS 2 . The degradation of CS 2 occurs, in general, after transferring the gas stream containing CS 2 to a liquid medium where it is used as a source of carbon and energy. The use of said contaminant (CS 2 ) implies the partial or total oxidation of CS 2 and the production of biomass (microorganisms capable of degrading CS 2 ) and with which the biofiltration process of the invention results in a practically complete decomposition of the CS 2 generating non-hazardous (harmless) products for human or animal health and / or the environment and a total or partially discharged gas stream in CS 2 .
Aunque no es estrictamente necesario, en ocasiones puede resultar ventajoso, antes de hacer pasar la corriente gaseosa que contiene CS2 a tratar a través del biofiltro de la invención, someter los microorganismos contenidos inicialmente en el compost utilizado como material de relleno del biofiltro de la invención utilizado en el método de biofiltración de la invención, a una etapa previa de aclimatación al CS2. Although it is not strictly necessary, it can sometimes be advantageous, before passing the gas stream containing CS 2 to be treated through the biofilter of the invention, subjecting the microorganisms initially contained in the compost used as filler material of the biofilter of the invention used in the biofiltration method of the invention, at a previous stage of acclimatization to CS 2 .
Por tanto, en una realización particular, el método de biofiltración de la invención comprende la realización de una etapa previa de aclimatación al CS2 de los microorganismos contenidos inicialmente en dicho compost. Esta etapa es particularmente interesante cuando se van a utilizar como microorganismos capaces de degradar CS2 los microorganismos correspondientes contenidos inicialmente en el compost utilizado como material de relleno del biofiltro de la invención utilizado en el método de bioñltración de la invención; de hecho, esta etapa de aclimatación previa podría evitarse si se inoculara el compost con microorganismos capaces de degradar CS2 estandarizados. Dicha aclimatación puede realizarse en cualquier instalación apropiada, por ejemplo, en el propio biofiltro de la invención, o, alternativamente, en un laboratorio o en una planta piloto, y, en general, comprende poner en contacto dicho compost, que contiene una población de microorganismos autóctonos (biomasa indígena), algunos de los cuales son capaces de degradar CS2, con una corriente gaseosa que contiene CS2. La cantidad de CS2 presente en dicha corriente gaseosa que lo contiene puede variar dentro de un amplio intervalo; no obstante, en la práctica se suele empezar utilizando una corriente gaseosa que contiene CS2 en una cantidad relativamente baja, generalmente igual o inferior a 100 ppmv, típicamente comprendida entre 20 y 100 ppmv. La cantidad de CS2 presente en dicha composición gaseosa puede ir reduciéndose, si se desea, a medida que aumenta la aclimatación de los microorganismos al CS2. El experto en la materia puede generar, por métodos convencionales, corrientes gaseosas conteniendo diferentes concentraciones de CS2, y seleccionar aquélla que proporcione una mejor aclimatación de los microorganismos presentes en el compost al CS2. Las condiciones para aclimatar al CS2 los microorganismos contenidos inicialmente en el compost utilizado como material de relleno en el biofiltro de la invención utilizado en la puesta en práctica del método de bioñltración de la invención dependen, en general, de diversos factores, por ejemplo, del contenido en CS2 en la corriente gaseosa utilizada, del tiempo de residencia, de la duración del tratamiento, etc. En este sentido, aunque las condiciones para aclimatar al CS2 los microorganismos contenidos inicialmente en el compost presente en el material de relleno del biofiltro de la invención utilizado en la puesta en práctica del método de bioñltración de la invención pueden variar ampliamente, en una realización particular, dicha aclimatación comprende el tratamiento de dicho compost con una corriente gaseosa que comprende CS2 en una cantidad igual o inferior a aproximadamente 100 ppmv, con un tiempo de residencia igual o inferior a aproximadamente 120 segundos, de manera continua, durante aproximadamente al menos 100 días, preferentemente aproximadamente 200 días. En una realización aún más particular, dicha etapa de aclimatación al CS2 de los microorganismos contenidos inicialmente en el compost utilizado como material de relleno del bio filtro de la invención utilizado en el método de biofiltración de la invención se realiza con una corriente gaseosa que comprende CS2 en una cantidad comprendida entre aproximadamente 25 ppmv y aproximadamente 100 ppmv, estando el tiempo de residencia comprendido entre aproximadamente 20 segundos y aproximadamente 120 segundos, de manera continua, durante aproximadamente al menos 100 días. Therefore, in a particular embodiment, the biofiltration method of the invention comprises performing a previous stage of acclimatization to CS 2 of the microorganisms initially contained in said compost. This step is particularly interesting when the corresponding microorganisms initially contained in the compost used as filler material of the biofilter of the invention used in the bio-filtration method of the invention are to be used as microorganisms capable of degrading CS 2 ; in fact, this stage of previous acclimatization could be avoided if the compost was inoculated with microorganisms capable of degrading standardized CS 2 . Said acclimatization can be carried out in any appropriate installation, for example, in the biofilter of the invention itself, or, alternatively, in a laboratory or in a pilot plant, and, in general, comprises contacting said compost, which contains a population of indigenous microorganisms (indigenous biomass), some of which are capable of degrading CS 2 , with a gaseous stream containing CS 2 . The amount of CS 2 present in said gaseous stream containing it may vary within a wide range; however, in practice it is usually started using a gas stream containing CS 2 in a relatively low amount, generally equal to or less than 100 ppmv, typically between 20 and 100 ppmv. The amount of CS 2 present in said gaseous composition can be reduced, if desired, as the acclimatization of the microorganisms to CS 2 increases . The person skilled in the art can generate, by conventional methods, gaseous streams containing different concentrations of CS 2 , and select that which provides a better acclimatization of the microorganisms present in the compost to CS 2 . The conditions for acclimating to the CS 2 the microorganisms initially contained in the compost used as filler material in the biofilter of the invention used in the implementation of the bio-filtration method of the invention depend, in general, on various factors, for example, of the content in CS 2 in the gas stream used, the residence time, the duration of the treatment, etc. In this sense, although the conditions for acclimatizing to CS 2 the microorganisms initially contained in the compost present in the biofilter filler material of the invention used in the implementation of the bio-filtration method of the invention can vary widely, in one embodiment. in particular, said acclimatization comprises treating said compost with a gas stream comprising CS 2 in an amount equal to or less than about 100 ppmv, with a residence time equal to or less than about 120 seconds, continuously, for approximately at least 100 days, preferably approximately 200 days. In an even more particular embodiment, said step of acclimatization to the CS 2 of the microorganisms initially contained in the compost used as a filler material of the bio filter of the invention used in the biofiltration method of the invention is carried out with a gas stream comprising CS 2 in an amount between about 25 ppmv and about 100 ppmv, the residence time being between about 20 seconds and about 120 seconds, continuously, for at least 100 days.
En general, durante la etapa de aclimatación se desarrollan inicialmente sobre el compost hongos coloreados, que son los responsables en un principio de la degradación del CS2. Posteriormente, desaparece de la superficie la coloración de los hongos, y entonces parecen ser las bacterias las encargadas de la degradación del CS2. A partir de dicho momento, el compost está preparado para recibir concentraciones crecientes de CS2 y degradarlo de manera eficiente. In general, during the acclimatization stage, colored fungi are initially developed on the compost, which are primarily responsible for the degradation of CS 2 . Subsequently, the coloration of the fungi disappears from the surface, and then the bacteria appear to be responsible for the degradation of CS 2 . As of that moment, the compost is prepared to receive increasing concentrations of CS 2 and degrade it efficiently.
Durante esta etapa de aclimatación previa (en su caso) puede ser necesario aportar al compost una solución de nutrientes, tal como la mencionada previamente, con el fin de mantener el metabolismo de los microorganismos capaces de degradar CS2. El aporte de dicha solución de nutrientes al compost puede realizarse mediante riego, tal como se ha mencionado previamente. During this stage of previous acclimatization (if applicable) it may be necessary to provide the compost with a nutrient solution, such as the one mentioned previously, in order to maintain the metabolism of microorganisms capable of degrading CS 2 . The contribution of said nutrient solution to the compost can be done by irrigation, as previously mentioned.
Tras el periodo de aclimatación, la biomasa desarrollada sobre el compost, que comprende microorganismos capaces de degradar CS2, puede ser utilizada como inoculo de otros bio filtros, por ejemplo, bio filtros de la invención, obteniéndose de este modo arranques muy rápidos con elevadas eficacias de depuración (eliminación o reducción) del CS2 prácticamente desde el arranque. After the acclimatization period, the biomass developed on the compost, which comprises microorganisms capable of degrading CS 2 , can be used as inoculum of other bio filters, for example, bio filters of the invention, thus obtaining very fast starts with high debugging efficiencies (elimination or reduction) of CS 2 practically from startup.
El experto en la materia entenderá que el método de biofiltración de la invención incluye la posibilidad de hacer pasar la corriente gaseosa que contiene CS2 a través de uno o más bio filtros de la invención. Así, en una realización particular, el método de biofiltración de la invención comprende hacer pasar la corriente gaseosa que contiene CS2 a tratar a través de un único biofiltro de la invención. En otra realización particular, el método de biofiltración de la invención comprende hacer pasar la corriente gaseosa que contiene CS2 a tratar a través de dos o más biofiltros de la invención, por ejemplo, 2, 3, 4, o incluso más, operativamente conectados entre sí; en este caso, la corriente gaseosa que contiene CS2 a tratar se hace pasar a través del primero de los biofiltros de la invención y la corriente gaseosa de salida de dicho primer bio filtro de la invención, que estará al menos parcialmente descargada en CS2, se hace pasar a través del segundo bio filtro de la invención, y, de manera similar, la corriente gaseosa de salida de dicho segundo bio filtro de la invención, que estará aún más descarada en CS2, se hace pasar a través del tercer bio filtro de la invención, y así sucesivamente hasta la salida definitiva de la corriente gaseosa total o parcialmente descargada de CS2. Por tanto, el método de bio filtración de la invención permite alcanzar una eficacia de eliminación del CS2 del 100%, o muy próxima al 100%, en relación con la cantidad de CS2 presente en la corriente gaseosa que contiene CS2 a tratar. The person skilled in the art will understand that the biofiltration method of the invention includes the possibility of passing the gas stream containing CS 2 through one or more bio filters of the invention. Thus, in a particular embodiment, the biofiltration method of the invention comprises passing the gaseous stream containing CS 2 to be treated through a single biofilter of the invention. In another particular embodiment, the biofiltration method of the invention comprises passing the gas stream containing CS 2 to be treated through two or more biofilters of the invention, for example, 2, 3, 4, or even more, operatively connected to each other; in this case, the gaseous stream containing CS 2 to be treated is passed through the first of the biofilters of the invention and the gaseous outflow of said first bio filter of the invention, which will be at least partially discharged into CS 2 , is passed through the second bio filter of the invention, and, similarly, the gaseous stream of said second bio filter of the invention, which will be even more shameless in CS 2 , is passed through the third bio filter of the invention, and so on until the final exit of the total or partially discharged gas stream of CS 2 . Therefore, the bio filtration method of the invention allows to achieve a removal efficiency of CS 2 of 100%, or very close to 100%, in relation to the amount of CS 2 present in the gaseous stream containing CS 2 to be treated .
Aunque el material de relleno presente en el biofiltro de la invención puede suministrar los nutrientes necesarios para el metabolismo de los microorganismos capaces de degradar CS2, durante la realización del método de bio filtración de la invención, la operación estable del biofiltro de la invención puede requerir el riego del material de relleno con una solución de nutrientes. Los macronutrientes apropiados deben contener N, P, K, completados en menor proporción con elementos micronutrientes como el Fe o Ni, entre otros [Barona, A., et al. (2007). Additional determinations in a potential support material for toluene biofiltration: adsorption and partition in the nutrient solution. Chem. Biochem. Eng. Q. 21 (2): 151-157]. En una realización particular, la solución de nutrientes contiene 100 mg de KH2P04, 400 mg de K2HP02, 27 mg de MgS04-7H20, 10 mg de CaS04-2H20, 10 mg de FeS04-7H20 y 500 g de (NH4)2S04 en 1 L de agua; se añade una cantidad de 5 cm3 de solución de micronutrientes que contiene 2 g/dm3 de FeCl2-4H20, 2 g/dm3 de CoCl2-6H20, 0,5 g/dm3 de MnCl2-4H20, 60 mg/dm3 de CuCl2, 50 mg/dm3 de ZnCl2, 50 mg/dm3 de H3BO3, 2 g/dm3 de HC03Na, 90 de mg/dm3 (ΝΗ4)6Μο7024·4Η20, 1 g/dm3 de ácido etilentetraaminodiacético (EDTA), 0,1 g/dm3 de Na2Se03, 50 mg/dm3 de NiCl2 H20. Además de aportar nutrientes para favorecer el metabolismo (crecimiento y mantenimiento) de los microorganismos capaces de degradar CS2, con dicho riego se arrastra el sulfato (S04 2~) generado como producto de la reacción de degradación del CS2. En cualquier caso, las buenas características reguladoras del pH así como las buenas características para retener la humedad por parte del compost utilizado como material de relleno del bio filtro utilizado en el método de bio filtración de la invención minimizan la necesidad de tener que efectuar riegos de forma muy continuada. Aunque el periodo de tiempo que transcurre entre dos riegos consecutivos puede variar dentro de un amplio intervalo, dependiendo de numerosos factores (e.g., necesidad de aportar nutrientes, necesidad de humedecer el compost, etc.), en una realización particular, el periodo de tiempo comprendido entre dos riegos consecutivos es de aproximadamente 60 días, típicamente de aproximadamente 40 días. Although the filler material present in the biofilter of the invention can supply the nutrients necessary for the metabolism of microorganisms capable of degrading CS 2 , during the performance of the bio filtration method of the invention, the stable operation of the biofilter of the invention can require the irrigation of the filler material with a nutrient solution. Appropriate macronutrients must contain N, P, K, completed to a lesser extent with micronutrient elements such as Fe or Ni, among others [Barona, A., et al. (2007). Additional determinations in a potential support material for toluene biofiltration: adsorption and partition in the nutrient solution. Chem. Biochem. Eng. Q. 21 (2): 151-157]. In a particular embodiment, the nutrient solution contains 100 mg of KH 2 P0 4 , 400 mg of K 2 HP0 2 , 27 mg of MgS0 4 -7H 2 0, 10 mg of CaS0 4 -2H 2 0, 10 mg of FeS0 4 7H 2 0 and 500 g of (NH 4) 2 S0 4 in 1 L of water; a quantity of 5 cm 3 of micronutrient solution containing 2 g / dm 3 of FeCl 2 -4H 2 0, 2 g / dm 3 of CoCl 2 -6H 2 0, 0.5 g / dm 3 of MnCl 2 is added -4H 2 0.60 mg / dm 3 of CuCl 2 , 50 mg / dm 3 of ZnCl 2 , 50 mg / dm 3 of H 3 BO 3 , 2 g / dm 3 of HC0 3 Na, 90 mg / dm 3 (ΝΗ 4) 6 7 0 24 · Μο 4Η 2 0, 1 g / dm 3 etilentetraaminodiacético acid (EDTA), 0.1 g / dm 3 of Na 2 SE0 3, 50 mg / dm 3 of NiCl 2 H 2 0 In addition to providing nutrients to promote the metabolism (growth and maintenance) of microorganisms capable of degrading CS 2 , with this irrigation the sulfate (S0 4 2 ~ ) generated as a product of the degradation reaction of CS 2 is carried away . In any case, the good pH regulatory characteristics as well as the Good characteristics for retaining moisture by the compost used as a filler material of the bio filter used in the bio filtration method of the invention minimize the need for watering very continuously. Although the period of time between two consecutive irrigations can vary within a wide range, depending on numerous factors (eg, need to provide nutrients, need to moisten the compost, etc.), in a particular embodiment, the period of time between two consecutive waterings is approximately 60 days, typically approximately 40 days.
Durante la operación del método de biofiltración de la invención se genera sulfato o ácido sulfúrico; no obstante, en general, no es necesario utilizar reactivos adicionales para neutralizar el ácido sulfúrico procedente de la oxidación del CS2. Sulfate or sulfuric acid is generated during the biofiltration method of the invention; however, in general, it is not necessary to use additional reagents to neutralize sulfuric acid from the oxidation of CS 2 .
Por otra parte, la generación de lixiviado asociada con la puesta en práctica del método de biofiltración de la invención es mínima y, en general, de escaso o nulo impacto medioambiental, por lo que no es necesario realizar ninguna gestión con dicho lixiviado. On the other hand, the generation of leachate associated with the implementation of the biofiltration method of the invention is minimal and, in general, of little or no environmental impact, so it is not necessary to perform any management with said leachate.
Ensayos realizados por los inventores en régimen continuo han puesto de manifiesto que el compost utilizado en la elaboración del material de relleno del bio filtro utilizado en el método de biofiltración de la invención, debido a sus buenas características físico-químicas, no sufre un deterioro (o erosión) significativo tras más de 12 meses de operación y es esperable que sobrepase los 24 meses. Por tanto, la presente invención proporciona un método estable y duradero para la depuración (eliminación o reducción de la cantidad) del CS2 contenido en una corriente gaseosa que contiene dicho contaminante. Tests carried out by the inventors in a continuous regime have shown that the compost used in the preparation of the filler material of the bio filter used in the biofiltration method of the invention, due to its good physical-chemical characteristics, does not suffer deterioration ( or erosion) significant after more than 12 months of operation and is expected to exceed 24 months. Therefore, the present invention provides a stable and durable method for the purification (elimination or reduction of the amount) of the CS 2 contained in a gaseous stream containing said contaminant.
En la Figura 2 se muestra un esquema ilustrativo de una realización particular del método de biofiltración de la invención, en el que puede apreciarse que se hace pasar una corriente gaseosa humedecida (e.g., saturada de humedad) que contiene CS2 a través del material de relleno contenido en el biofiltro de la invención en donde el CS2 es degradado por los microorganismos capaces de degradar CS2. Brevemente, una corriente gaseosa que contiene CS2 (2) procedente de un foco contaminante (1) es introducida en un sistema de humidificación (3) que contiene agua con el fin de humedecer dicha corriente gaseosa que contiene CS2 antes de su entrada en un biorreactor (5). La corriente gaseosa humedecida que contiene CS2 (4) es introducida en dicho bioreactor (5) el cual contiene 3 biofiltros de la invención (6a, 6b y 6c); cada uno de los cuales comprende un material de relleno y microorganismos capaces de degradar CS2, en donde dicho material de relleno comprende un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales y (ii) 70-30% en peso de residuos vegetales. Los 3 biofiltros de la invención (6a, 6b y 6c) están dispuestos verticalmente y operativamente conectados entre sí de manera que la corriente de salida del primer bio filtro (6a) alimenta al segundo bio filtro (6b) y la corriente de salida de dicho segundo bio filtro (6b) alimenta al tercer bio filtro (6c) del que sale la corriente gaseosa prácticamente descargada de CS2 (7). En caso necesario, los nutrientes contenidos en el depósito de nutrientes (8) se aportan a los biofiltros de la invención mediante riego con el fin de mantener el metabolismo de los microorganismos capaces de degradar CS2. An illustrative scheme of a particular embodiment of the biofiltration method of the invention is shown in Figure 2, in which it can be seen that a moistened (eg saturated moisture) gas stream containing CS 2 is passed through the material of filler contained in the biofilter of the invention wherein CS 2 is degraded by microorganisms capable of degrading CS 2 . Briefly, a gaseous stream containing CS 2 (2) from a contaminating source (1) is introduced into a humidification system (3) that contains water in order to moisten said gaseous stream containing CS 2 before entering a bioreactor (5). The humidified gas stream containing CS 2 (4) is introduced into said bioreactor (5) which contains 3 biofilters of the invention (6a, 6b and 6c); each of which comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of waste from animals and (ii) 70-30% by weight of plant residues. The 3 biofilters of the invention (6a, 6b and 6c) are arranged vertically and operatively connected to each other so that the output current of the first bio filter (6a) feeds the second bio filter (6b) and the output current of said Second bio filter (6b) feeds the third bio filter (6c) from which the gaseous stream practically discharged from CS 2 (7) comes out. If necessary, the nutrients contained in the nutrient store (8) are supplied to the biofilters of the invention by irrigation in order to maintain the metabolism of microorganisms capable of degrading CS 2 .
Instalación de la invención Installation of the invention
El método de bio filtración de la invención puede realizarse en una instalación adecuada que comprende al menos un bio filtro de la invención, es decir, un bio filtro comprende un material de relleno y microorganismos capaces de degradar CS2, en donde dicho material de relleno comprende un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70%) en peso de residuos de animales y (ii) 70-30%) en peso de residuos vegetales. Dicha instalación, en adelante "instalación de la invención", constituye un aspecto adicional de esta invención. The bio filtration method of the invention can be carried out in a suitable installation comprising at least one bio filter of the invention, that is, a bio filter comprises a filler material and microorganisms capable of degrading CS 2 , wherein said filler material It comprises a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) by weight of animal waste and (ii) 70-30%) by weight of plant waste. Said installation, hereinafter "installation of the invention", constitutes an additional aspect of this invention.
La instalación de la invención puede contener uno o más biofiltros de la invención cuyas características han sido definidas previamente. Por tanto, en una realización particular, la instalación de la invención comprende un único bio filtro de la invención. En otra realización particular, la instalación de la invención comprende dos o más biofiltros de la invención, por ejemplo, 2, 3, 4, o incluso más, operativamente conectados entre sí; en este caso, la corriente gaseosa que contiene CS2 a tratar se hace pasar a través del primer bio filtro de la invención y la corriente gaseosa de salida de dicho primer bio filtro de la invención se hace pasar a través del segundo bio filtro de la invención, y, de manera similar, la corriente gaseosa de salida de dicho segundo biofiltro de la invención se hace pasar a través del tercer biofiltro de la invención, y así sucesivamente hasta la salida definitiva de la corriente gaseosa total o parcialmente descargada de CS2. The installation of the invention may contain one or more biofilters of the invention whose characteristics have been previously defined. Therefore, in a particular embodiment, the installation of the invention comprises a single bio filter of the invention. In another particular embodiment, the installation of the invention comprises two or more biofilters of the invention, for example, 2, 3, 4, or even more, operatively connected to each other; in this case, the gaseous stream containing CS 2 to be treated is passed through the first bio filter of the invention and the gaseous stream of said first bio filter of the invention is passed through the second bio filter of the invention, and, similarly, the gaseous outflow of said second Biofilter of the invention is passed through the third biofilter of the invention, and so on until the final exit of the total or partially discharged gas stream of CS 2 .
El diseño modular de la instalación de la invención permite que los biofiltros más alejados de la entrada de la corriente gaseosa que contiene CS2 reciban concentraciones muy bajas de CS2 pero suficientes para la adaptación de los microorganismos capaces de degradar CS2. Asimismo, el diseño modular permite la biodegradación del CS2 en el primer biofiltro mientras que los restantes biofiltros pueden actuar como reserva, lo que garantiza la eficacia del sistema incluso con incrementos repentinos de carga contaminante (CS2). The modular design of the installation of the invention allows biofilters farther from the entrance of the gas stream containing CS 2 to receive very low concentrations of CS 2 but sufficient for the adaptation of microorganisms capable of degrading CS 2 . Likewise, the modular design allows the biodegradation of CS 2 in the first biofilter while the remaining biofilters can act as a reserve, which guarantees the efficiency of the system even with sudden increases in pollutant load (CS 2 ).
La instalación de la invención incluye, ventajosamente, si se desea, un sistema de humidificación, tal como, por ejemplo, una o más columnas de medio acuoso (e.g., agua), que cede(n) a la corriente gaseosa que contiene CS2 la humedad necesaria, situada antes del biofiltro de la invención. Adicionalmente, la instalación de la invención incluye los medios adecuados para transportar la corriente gaseosa y, si se desea, una fuente de nutrientes por si fuera necesario aportar al biofiltro de la invención para mantener el metabolismo de los microorganismos capaces de degradar CS2 presentes en el biofiltro de la invención. The installation of the invention advantageously includes, if desired, a humidification system, such as, for example, one or more columns of aqueous medium (eg, water), which yields (n) to the gas stream containing CS 2 the necessary humidity, located before the biofilter of the invention. Additionally, the installation of the invention includes suitable means for transporting the gas stream and, if desired, a source of nutrients in case it is necessary to contribute to the biofilter of the invention to maintain the metabolism of microorganisms capable of degrading CS 2 present in the biofilter of the invention.
Asimismo, si se desea, la instalación de la invención puede incluir medios para medir y/o controlar la temperatura de entrada al biofiltro de la invención de la corriente gaseosa que contiene CS2 a tratar, medios para medir el pH en el interior del biofiltro, y medios para medir la cantidad de CS2 presente en la corriente gaseosa de salida del biofiltro. Likewise, if desired, the installation of the invention may include means for measuring and / or controlling the inlet temperature to the biofilter of the invention of the gas stream containing CS 2 to be treated, means for measuring the pH inside the biofilter. , and means for measuring the amount of CS 2 present in the gas stream of the biofilter.
Inoculación de microorganismos capaces de degradar CS? Inoculation of microorganisms capable of degrading CS?
Como se ha mencionado previamente, la invención contempla la posibilidad de que, tras el periodo de aclimatación, la biomasa desarrollada sobre el compost, que comprende microorganismos capaces de degradar CS2, sea utilizada como inoculo de otros biofiltros, por ejemplo, biofiltros de la invención, obteniéndose de este modo arranques muy rápidos con elevadas eficacias de depuración (eliminación o reducción) del CS2 prácticamente desde el arranque. La aclimatación al CS2 de los microorganismos capaces de degradar CS2 puede realizarse mediante un tratamiento que comprende poner en contacto el compost que contiene una población de microorganismos autóctonos (biomasa indígena), algunos de los cuales son capaces de degradar CS2, con una corriente gaseosa que contiene CS2, tal como se ha mencionado previamente en relación con la puesta en práctica del método de bio filtración de la invención. As previously mentioned, the invention contemplates that, after the acclimatization period, the biomass developed on the compost, which comprises microorganisms capable of degrading CS 2 , is used as inoculum of other biofilters, for example, biofilters of the invention, thus obtaining very fast starts with high purification efficiencies (elimination or reduction) of CS 2 practically from the start. The acclimatization to the CS 2 of the microorganisms capable of degrading CS 2 can be carried out by means of a treatment comprising contacting the compost that contains a population of native microorganisms (indigenous biomass), some of which are capable of degrading CS 2 , with a gas stream containing CS 2 , as previously mentioned in relation to the implementation of the bio filtration method of the invention.
Por tanto, en otro aspecto, la invención se relaciona con un método para generar una población de microorganismos capaces de degradar CS2 que comprende combinar: a) un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales y (ii) 70- 30% en peso de residuos vegetales, que comprende microorganismos capaces de degradar CS2 aclimatados al CS2 según el método de aclimatación anteriormente definido (compost aclimatado), con Therefore, in another aspect, the invention relates to a method for generating a population of microorganisms capable of degrading CS 2 which comprises combining: a) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70 % by weight of animal waste and (ii) 70-30% by weight of plant waste, which comprises microorganisms capable of degrading CS 2 acclimatized to CS 2 according to the acclimatization method defined above (acclimatized compost), with
b) un compost obtenible por descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70%) en peso de residuos de animales y (ii) 70- 30%o en peso de residuos vegetales (compost fresco), b) a compost obtainable by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70%) by weight of animal waste and (ii) 70-30% or by weight of plant waste (fresh compost),
en una proporción (compost aclimatado): (compost fresco) comprendida entre aproximadamente 1 : 1 y aproximadamente 5: 1, en peso, preferentemente, de 3: 1 aproximadamente . in a proportion (acclimatized compost): (fresh compost) between approximately 1: 1 and approximately 5: 1, preferably by weight, approximately 3: 1.
El siguiente ejemplo ilustra la invención y no debe ser considerado en sentido limitativo de la misma. The following example illustrates the invention and should not be considered in a limiting sense thereof.
EJEMPLO 1 EXAMPLE 1
Diseño de un sistema de biofiltración de CS2 Design of a CS2 biofiltration system
La Figura 2 muestra una representación esquemática de una instalación adecuada para la puesta en práctica del método de biofiltración de la invención. Tal como se puede apreciar, dicha instalación consta básicamente de un sistema de humidificación (3) y un bioreactor (5) que contiene 3 biofiltros (6a, 6b y 6c), colocados verticalmente, con un volumen total aproximado de 4,5 L, construido en cloruro de polivinilo (PVC) y con flujo de gas descendente; los biofiltros (6a, 6b y 6c) están conectados operativamente entre sí y, en su interior, se encuentra el material de relleno que comprende un compost en forma de pellets (suministrado por la empresa SLIR), que actúa como material de soporte sobre el que se desarrolla la biomasa responsable de la degradación de CS2 (microorganismos capaces de degradar CS2). Dicho compost ha sido obtenido mediante la descomposición aeróbica-anaeróbica de una mezcla que comprende (i) 30-70% en peso de residuos de animales y (ii) 70-30% en peso de residuos vegetales. La Tabla 1 muestra algunas propiedades físico-químicas del compost pelletizado utilizado. Figure 2 shows a schematic representation of an installation suitable for the implementation of the biofiltration method of the invention. As can be seen, said installation basically consists of a humidification system (3) and a bioreactor (5) containing 3 biofilters (6a, 6b and 6c), placed vertically, with an approximate total volume of 4.5 L, built in chloride polyvinyl (PVC) and with downward gas flow; the biofilters (6a, 6b and 6c) are operatively connected to each other and, inside, there is the filling material comprising a compost in the form of pellets (supplied by the company SLIR), which acts as a support material on the The biomass responsible for the degradation of CS 2 (microorganisms capable of degrading CS 2 ) is developed. Said compost has been obtained by aerobic-anaerobic decomposition of a mixture comprising (i) 30-70% by weight of animal waste and (ii) 70-30% by weight of plant waste. Table 1 shows some physicochemical properties of the pelletized compost used.
Tabla 1 Table 1
Propiedades físico-químicas del compost utilizado Physicochemical properties of the compost used
[ufe: unidades formadoras de colonia] [ufe: colony forming units]
[σ Desviación estándar] [σ Standard deviation]
En una etapa inicial de aclimatación en planta piloto de laboratorio, la biomasa indígena del compost se alimenta de corrientes gaseosas contaminadas con CS2 y saturadas en humedad (>90%) generadas en el laboratorio, con concentraciones no superiores a 100 ppmv de CS2 aproximadamente y con un tiempo de residencia inferior a 120 segundos aproximadamente, de manera continua, durante 24 horas al día. Este periodo no requiere ningún tratamiento adicional del compost (e.g., inoculación de microorganismos capaces de degradar CS2). In an initial stage of acclimatization in a pilot laboratory plant, indigenous compost biomass feeds on gaseous streams contaminated with CS 2 and saturated in moisture (> 90%) generated in the laboratory, with concentrations not greater than 100 ppmv of CS 2 approximately and with a residence time of less than approximately 120 seconds, continuously, for 24 hours a day. This period does not require any additional compost treatment (eg, inoculation of microorganisms capable of degrading CS 2 ).
Una vez aclimatada la biomasa activa (microorganismos capaces de degradar Once the active biomass is acclimatized (microorganisms capable of degrading
CS2), esta puede utilizarse para tratar corrientes gaseosas que contienen CS2 (corriente de alimentación al bioñltro), con una cantidad de CS2 comprendida entre aproximadamente 50 ppmv y aproximadamente 250 ppmv, con tiempos de residencia de aproximadamente 10 segundos a aproximadamente 80 segundos. El mantenimiento de la humedad en el material de relleno del bioñltro (compost) se consigue mediante un riego mensual con la solución de nutrientes exigida para el metabolismo de la biomasa activa. CS 2 ), this can be used to treat gaseous streams containing CS 2 (bio-filter feed stream), with an amount of CS 2 between approximately 50 ppmv and approximately 250 ppmv, with residence times of approximately 10 seconds to approximately 80 seconds. The maintenance of moisture in the filling material of the bio-filter (compost) is achieved by monthly irrigation with the nutrient solution required for the metabolism of active biomass.
La eficacia del tratamiento de depuración de CS2 es superior al 90 % en el primer tercio de volumen de diseño [bioñltro (6a)], constituyendo las 2/3 partes restantes [bio filtros (6b y 6c)] el sistema de reserva por el que pasan concentraciones muy bajas de CS2, las cuales garantizan su aclimatación y potencial actividad depuradora de CS2. Por tanto, dicho sistema de reserva puede ser utilizado como inoculo para poner en marcha nuevos bioreactores para la depuración de corrientes gaseosas que contienen CS2 como contaminante. The effectiveness of the treatment of purification of CS 2 is greater than 90% in the first third of design volume [bio-filter (6a)], with the remaining 2/3 parts [bio filters (6b and 6c)] being the reserve system by that pass very low concentrations of CS 2 , which guarantee its acclimatization and potential purification activity of CS 2 . Therefore, said reserve system can be used as inoculum to start up new bioreactors for the purification of gaseous streams containing CS 2 as a contaminant.
El proceso de depuración de dicha corriente gaseosa que contiene CS2 como contaminante no genera lixiviados en el sistema, lo que elimina la necesidad de tener que realizar un tratamiento posterior de los mismos. The process of purification of said gaseous stream containing CS 2 as a contaminant does not generate leachates in the system, which eliminates the need for subsequent treatment.
Claims
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201031602A ES2386221B1 (en) | 2010-10-29 | 2010-10-29 | BIOFILTER AND METHOD TO CLEAN THROUGH A BIOFILTRATION A GASEOUS CURRENT CONTAINING CARBON DISULFIDE |
| ESP201031602 | 2010-10-29 |
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| WO2012056081A1 true WO2012056081A1 (en) | 2012-05-03 |
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| PCT/ES2011/070748 Ceased WO2012056081A1 (en) | 2010-10-29 | 2011-10-28 | Biofilter and biofiltration-based method for the purification of a gas stream containing carbon disulfide |
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| WO (1) | WO2012056081A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701433A (en) * | 2012-05-31 | 2012-10-03 | 中国环境科学研究院 | Biological filter deodorization filler and preparation method |
| CN112870947A (en) * | 2021-02-03 | 2021-06-01 | 中国环境科学研究院 | Composite device for removing compost volatile sulfides |
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| US20060051856A1 (en) * | 2004-09-03 | 2006-03-09 | Maga Gerardo F | Bioreactor system for biological degradation of oily sludge |
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| CN102701433A (en) * | 2012-05-31 | 2012-10-03 | 中国环境科学研究院 | Biological filter deodorization filler and preparation method |
| CN102701433B (en) * | 2012-05-31 | 2014-02-12 | 中国环境科学研究院 | A kind of biological filter deodorizing filler and preparation method thereof |
| CN112870947A (en) * | 2021-02-03 | 2021-06-01 | 中国环境科学研究院 | Composite device for removing compost volatile sulfides |
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| Publication number | Publication date |
|---|---|
| ES2386221B1 (en) | 2013-05-28 |
| ES2386221A1 (en) | 2012-08-13 |
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