WO2013093155A1 - Biofilter comprising black slag from an electric arc furnace and uses thereof - Google Patents
Biofilter comprising black slag from an electric arc furnace and uses thereof Download PDFInfo
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- WO2013093155A1 WO2013093155A1 PCT/ES2012/070874 ES2012070874W WO2013093155A1 WO 2013093155 A1 WO2013093155 A1 WO 2013093155A1 ES 2012070874 W ES2012070874 W ES 2012070874W WO 2013093155 A1 WO2013093155 A1 WO 2013093155A1
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- gaseous pollutant
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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
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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
-
- 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
- B01D2257/304—Hydrogen sulfide
-
- 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
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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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
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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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 contaminated gases with biodegradable gaseous pollutants.
- the invention relates to a biofilter comprising black slag from an electric arc furnace as filler material, to eliminate or reduce the content of biodegradable gaseous pollutants present in a polluted gaseous stream containing at least one of said pollutants, thus as with a biofiltration method comprising the use of said biofilter.
- Hydrogen sulfide is extremely harmful to health, 20-50 ppm in the air is enough to cause acute discomfort that leads to suffocation and can lead to death from overexposure.
- Carbon disulfide (CS 2 ) constitutes a highly dangerous pollutant due mainly to its harmful effects on human health. Prolonged exposure to CS 2 vapors causes symptoms of intoxication ranging from reddening 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.
- VOCs Volatile organic compounds
- US EPA The American Protection Agency Environmental
- VOCs encompass a wide range of chemical compounds, including aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, aldehydes, ketones, ethers, acids and alcohols, many of which may have adverse effects on the human or animal health, as well as the environment in general, in the short or long term.
- VOCs have been identified as one of the main sources in the formation of photochemical smog by reacting with other air pollutants (for example, nitrogen oxides) and with sunlight, which can cause respiratory problems, eye irritation, pain head, etc., and damage to flora and animal life.
- air pollutants for example, nitrogen oxides
- sunlight which can cause respiratory problems, eye irritation, pain head, etc., and damage to flora and animal life.
- biolavadores bioscrubber
- biotrickling filter drained bed bioreactors
- biofilter fixed bed biofilters
- biofilters employ microorganisms that are fixedly adhered in a porous medium to degrade contaminants present in a gaseous stream that flows through the bed. Said microorganisms grow in a biofilm supported on the surface of the medium. When the gas passes through the bed, the contaminants of the gas phase are absorbed in the biofilm that surrounds the environment, where they are biodegraded. Therefore, biofilters basically 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. 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. The absence of a mobile aqueous phase makes these bioreactors ideal for the treatment of contaminants that are not very soluble in water.
- the selection of the support material is a fundamental factor for the proper functioning of conventional biofilters, since it influences both the ability to remove the contaminant (microbial activity) and the final cost of the biofiltration system (replacement frequency of the depleted support and its subsequent management, load losses associated with bed compaction, etc.).
- the biomass responsible for the degradation of pollutants must be developed on its surface, certain important physical-chemical characteristics must be taken into account: high specific surface area, high porosity, low apparent density, high water retention capacity and availability of essential nutrients for correct development of microbial metabolism.
- microorganisms capable of degrading CS 2 are microorganisms of the genus Paracoccus (P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (eg, Thiobacillus strain TJ330; T. thioparus strain TK-m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (eg, T. ramose, etc. ), etc.
- P. denitrificans, etc. microorganisms of the genus Paracoccus (P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibri
- blast furnace slags as a bed of a laboratory-scale biopercolator filter for the independent treatment of various contaminants: toluene [yield greater than 90% for contaminant ingress loads greater than 30 gm "3 h " 1 and 3 minutes of residence time], styrene [yield greater than 95% for contaminant inlet loads less than 30 gm "3 h " 1 and 1.07 minutes of residence time] or 1.3 -butadiene [elimination capacity less than 5 gm "3 h " 1 for contaminant inlet charges less than 25 gm "3 h " 1 and residence times around 1.89-5.04 minutes].
- the authors of the present invention have developed a fixed bed biofiltration method to purify (ie, eliminate or reduce) the amount of biodegradable gaseous pollutants present in a gaseous stream contaminated with at least one of said pollutants efficiently;
- biodegradable gaseous pollutants include VOCs, H 2 S, and CS 2 .
- This method is based on the use of black slag from an electric arc furnace or EAFS [of English, "Electric Are Furnace Slag”] as a biofilter filler, and in the use of microorganisms capable of degrading such contaminants, and provides various advantages over traditional methods and with other biological methods described in the state of the art, mainly due to its physical-chemical characteristics that allow continuous operation for long periods of time without suffering erosion and / or deterioration.
- this residue (EAFS) adequately serves as support for them, which form a biofilm of microorganisms around it, thus enabling the purification of the contaminated gas stream.
- the invention relates to a biofilter comprising black arc furnace slag (EAFS) as filler material ("biofilter of the invention").
- said biofilter also comprises microorganisms capable of degrading the biodegradable gaseous pollutant that it is desired to eliminate, for example, one or more VOCs, H 2 S, CS 2 , etc. Said microorganisms are inoculated into the filler material (EAFS) of the biofilter.
- EAFS black arc furnace slag
- the invention relates to an installation for the purification of gaseous streams contaminated with at least one biodegradable gaseous pollutant comprising at least one biofilter of the invention.
- the invention in another aspect, relates to a method for purifying a gaseous stream containing at least one biodegradable gaseous pollutant, by means of biofiltration, which comprises passing said gaseous stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention which also comprises microorganisms capable of degrading said biodegradable gas contaminant (s).
- the invention relates to the use of black arc furnace slag (EAFS) as a filler material in a fixed bed biofilter for the purification of gaseous streams, in particular, gaseous streams contaminated with at least one gaseous pollutant. biodegradable.
- EAFS black arc furnace slag
- Figure 1 represents a particular embodiment of a continuous acclimatization system for obtaining inoculum for starting a biofilter of the invention.
- FIG. 2 is a schematic representation of a particular embodiment of an installation suitable for the implementation of a biofiltration method of biodegradable gaseous pollutants, for example, VOCs, according to the present invention.
- the invention relates to a fixed bed biofilter, hereinafter "biofilter of the invention", which comprises black arc furnace slag (EAFS) as filler material.
- biofilter of the invention can be used to purify contaminated gases containing at least one biodegradable gaseous pollutant (eg, a chemical compound that can be decomposed by the action of biological agents), for example, a volatile organic compound (VOC), hydrogen disulfide (H 2 S), carbon sulfide (CS 2 ), etc.
- a biodegradable gaseous pollutant eg, a chemical compound that can be decomposed by the action of biological agents
- VOC volatile organic compound
- H 2 S hydrogen disulfide
- CS 2 carbon sulfide
- the biofilter of the invention is used to purify gases contaminated with one or more VOCs, H 2 S and / or CS 2 , by biofiltration, that is, to eliminate or reduce the amount of VOCs, H 2 S and / or CS 2 , present in a gas stream containing VOCs, H 2 S and / or CS 2 .
- the biofilter of the invention is used to purify, by biofiltration, gases contaminated with one or more VOCs.
- the filler material (support) contained in the biofilter of the invention black slag from an electric arc furnace (EAFS), is a waste from the steel industry legally considered as an inert waste [Official Gazette of the Basque Country (BOPV), 1994 ; No 239, Decree 423/1994] and is obtained as an unwanted by-product during the manufacture of steel from scrap iron and / or steel as raw material in electric arc furnaces.
- Steel productions, worldwide and European, in 2008 were 1,327 and 198 million tons (mt), respectively, while Spanish production in 2009 was 14.4 mt.
- This steel manufacturing generates a large amount of industrial waste that represents between 15% and 20% of the total steel production [150-200 kg of slag per ton produced of steel], the black slag being an electric arc furnace (EAFS) the quantitatively most important industrial by-product in the manufacture of common steels. Due to the high generation and accumulation in outdoor deposits of these black slags (EAFS), their use has been authorized as a final product on roads and public or private roads of traffic as one of the structural layers, as raw material in the cement manufacturing and as aggregate for structural concrete.
- EAFS electric arc furnace
- the black slag of electric arc furnace mainly comprises calcium silicates, ferrites and metal oxides.
- the main mineralogical phases present are dicalcium silicate (lamite, ⁇ - Ca 2 Si04), dicalcium ferrite (2CaOFe 2 03) and wustite (iron oxide (II), FeO).
- common minerals may also be present, such as olivine (Mg 2 Si04), mervinite (Ca 2 Mg (Si04) 2 ), tricalcium silicate (3CaOSi0 2 ), brown millerite (NiS), etc., as well as various oxides, for example, free calcium oxide (CaO), free magnesium oxide (MgO), silica (Si0 2 ), ferrous oxide (FeO), aluminum oxide or alumina (A1 2 0 3 ), manganese oxide ( MnO), phosphorus pentoxide (P 2 0 5 ), etc.
- olivine Mg 2 Si04
- mervinite Ca 2 Mg (Si04) 2
- brown millerite NaS
- various oxides for example, free calcium oxide (CaO), free magnesium oxide (MgO), silica (Si0 2 ), ferrous oxide (FeO), aluminum oxide or alumina (A1 2 0 3 ),
- said EAFS comprises CaO (35-60%), Si0 2 (9-20%), FeO (15-30%), MgO (5-15%), A1 2 0 3 (2-9% ), MnO (3-10%) and P 2 0 5 (0, 1-2%)), where the% are percentages by weight with respect to the total.
- the chemical composition of the EAFS that can be used in the biofilter of the invention may vary depending on the starting materials used in the production of steel, the type of steel manufactured, the conditions of the oven, cooling system, etc.
- Black slags of electric arc furnace have been commonly used as aggregates for road construction, as raw material in the Cement manufacturing process, as landfill in forest tracks, and, currently, are used in structural concrete for construction with 80% of the steel aggregate.
- EAFS as a filler or support material for fixed bed biofilters for the treatment of contaminated gaseous streams, which contain at least one biodegradable gaseous pollutant, for example, VOCs, H 2 S, CS 2 , etc.
- contaminated gaseous streams which contain at least one biodegradable gaseous pollutant, for example, VOCs, H 2 S, CS 2 , etc.
- Said EAFS can be used as it is produced, that is, without the need for any prior conditioning except prior screening of EAFS particles to use the appropriate / desired size fraction.
- EAFS particles can vary within a wide range; however, in a particular embodiment, at least 50%, typically at least 60%, advantageously at least 70%, preferably at least 80%, more preferably at least 90%, even more preferably at least 95 %, and even more preferably, 96%, 97%, 98% 99% or 100% of the EAFS particles have an average diameter equal to or less than 20 mm, typically equal to or less than 10 mm, usually between about 4 mm and approximately 7 mm, preferably between approximately 5 mm and approximately 6.5 mm.
- the implementation of the biofiltration method provided by this invention requires the inoculation of EAFS with microorganisms capable of degrading the contaminant or biodegradable contaminants that it is desired to be removed.
- microorganism as used herein includes bacteria, fungi, yeasts, protozoa, etc. Numerous microorganisms capable of degrading biodegradable contaminants, possibly present in gaseous streams, are known, for example, VOCs, H 2 S, CS 2 , etc.
- the biodegradable gaseous pollutant present in the gaseous stream is a VOC.
- a "volatile organic compound” or “VOC” is an organic compound that has a vapor pressure greater than 0.1 mm Hg under standard conditions (25 ° C and 760 mm Hg), and encompasses a wide range of chemical compounds, including aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, aldehydes, ketones, ethers, acids and alcohols, many of which may have adverse effects for human or animal health, as well as the environment in general, in the short or long term.
- VOCs include benzene, chlorobenzene, ethylbenzene, toluene, styrene, xylene, pentane, ethylene, ethanol, phenol, butylacetate, ethyl acetate, dichloromethane, dimethyl sulfide, etc.
- the biofilter of the invention comprises a microorganism capable of degrading VOCs.
- a "microorganism capable of degrading VOCs” is a microorganism that has the ability to use a VOC as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or For the enviroment.
- Said microorganism can be a bacterium, a fungus, a yeast, a protozoan, etc.
- microorganisms capable of degrading VOCs include fungi and yeasts of the genera Exophiala, Scedosporium, Paecilomyces, Cladosporium, Cladophialophora, Fusarium or Phanerochaete Chrysosporium (Garc ⁇ a-Pe ⁇ a et al, 2009. Dynamic numerical reconstruction of a fungal biofiltration system using differential neural network. J. Process Control. 19, 1103-1110; Zhao et al., 2010. Isolation and identification of black yeasts by enrichment on atmospheres of monoaromatic hydrocarbons. Microb. Ecol.
- bacteria from genera Acinetobacter, Alcaligenes (eg, A. xylosoxidans strain Y234, etc.), Bacillus (eg, B. sphaericus, etc.), Burkholderia (eg, B. vietnamiensis strain G4, etc.), Corynebacterium, Hyphomicrobium, Pseudomonas (eg , P. aeruginosa; P. putida strain Fl; etc.), Rhodococcus (eg, R. fascians, R. pyridinovoran, R. rhodochrous, etc.), or Xanthobacter (Malhautier et al., 2005.
- Alcaligenes eg, A. xylosoxidans strain Y234, etc.
- Bacillus eg, B. sphaericus, etc.
- Burkholderia eg, B. vietnamiensis strain G4, etc.
- the biofilter of the invention contains microorganisms capable of degrading VOCs belonging to a single genus or to a single species of microorganisms capable of degrading VOCs; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading VOCs belonging to different genera and / or species of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
- the biodegradable gaseous pollutant present in the gaseous stream is H 2 S; in that case, the biofilter of the invention comprises a microorganism capable of degrading H 2 S.
- a "microorganism capable of degrading H? S" is a microorganism that has the ability to use H 2 S as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or for the environment.
- Said microorganism can be a bacterium, a fungus, a yeast, a protozoan, etc.
- microorganisms capable of degrading H 2 S include microorganisms of the genus Acidthiobacillus (eg, A. thiooxidans strain AZ11, etc.), Beggiatoa, Macromonas, Pseudomonas (eg, P. acidovorans strain DMR-11; P Putida strain CH11, etc.), Sulfolobus (eg, S. Metallicus, etc.), Thiobacterium, Thiobacillus (eg, T. sp., T. denitrificans; T. novellus strain CH3; T. thioparus strain CH11, T.
- Acidthiobacillus eg, A. thiooxidans strain AZ11, etc.
- Beggiatoa Macromonas
- Pseudomonas eg, P. acidovorans strain DMR-11; P Putida strain CH11, etc.
- Sulfolobus eg, S. Metallicus
- the biofilter of the invention contains microorganisms capable of degrading H 2 S belonging to a single genus or to a single species of microorganisms capable of degrading H 2 S; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading H 2 S belonging to different genera and / or species of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
- the biodegradable gaseous pollutant present in the gaseous stream is CS 2 ; in that case, the biofilter of the invention comprises a microorganism capable of degrading CS 2 .
- a microorganism capable of degrading CS It 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 for the environment.
- Said microorganism can be a bacterium, a fungus, a yeast, a protozoan, etc.
- microorganisms capable of degrading CS 2 include microorganisms of the genera Paracoccus (P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (eg, Thiobacillus strain TJ330; T. thioparus strain TK-m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (eg, T. ramose, etc.), etc. (Pol et al, 2007. Isolation of a carbon disulfide utilizing Thiomonas sp. And its application in a biotrickling filter. Appl. Microbiol. Biotechnol. 74, 439-446).
- Thioalkalimicrobium e
- the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to a single genus or 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 of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
- microorganisms to be inoculated in the biofilter filler material of the invention will be chosen according to the biodegradable pollutant present in the gas stream to be purified. Such microorganisms will have the potential capacity to degrade said biodegradable contaminants.
- microorganisms capable of degrading biodegradable contaminants useful for the implementation of the present invention are commercially available or in crop collections.
- the person skilled in the art can find and identify, by conventional methods, other microorganisms capable of degrading said biodegradable contaminants from various sources.
- microorganisms that tolerate the biodegradable contaminant in question eg, VOCs, H 2 S, CS 2 , etc.
- can live in samples from sites contaminated with said contaminant for example, areas or facilities wherein gaseous streams containing said biodegradable contaminants, soils contaminated with said contaminants, activated sludge, composting, etc .; are used or generated.
- the ability of a microorganism to degrade a biodegradable pollutant can be determined by any conventional procedure, known to those skilled in the art, that allows to know if a microorganism uses said contaminant biodegradable, for example, by contacting a culture of said microorganism with said biodegradable contaminant (eg, one or more VOCs, H 2 S, CS 2 , etc.) and incubating under appropriate conditions for the development and growth of the microorganism in question; Under these conditions, the decrease in the amount of said biodegradable contaminant (eg, one or more VOCs, H 2 S, CS 2 , etc.) is indicative that the analyzed microorganism is capable of degrading said biodegradable contaminant.
- a biodegradable pollutant for example, VOCs, H 2 S, CS 2 , etc.
- the amount of biodegradable contaminant can be determined by conventional methods, for example, by chromatography (eg, gas chromatography, etc.).
- the microorganism may be supported on a filler material of the type used in the biofilter of the invention (EAFS) and the biodegradable contaminant may be contained in a stream of air, preferably saturated with water vapor in water before contacting it with the microorganism.
- EAFS filler material of the type used in the biofilter of the invention
- the biofilter of the invention comprises a reservoir, in which the filler material and microorganisms capable of degrading the biodegradable pollutant (s) (eg, one or more VOCs, H 2 S, CS 2 , etc.) are located. .) as well as means for the entry of the gas stream containing said contaminant or contaminants, suitably saturated in water vapor previously, and means for the exit of the gas stream totally or partially discharged from said or said biodegradable contaminants.
- the biofilter is also preferably provided with irrigation means to periodically provide nutrients to the microorganisms.
- devices can be included to measure the inlet temperature of the gas stream containing the biodegradable contaminants to be treated since it can affect the metabolic process of microorganisms capable of degrading said biodegradable contaminants, or to measure the pH since during the operation of the biofiltration method provided by this invention acid products can be generated that can adversely affect the activity of the biofilter.
- load loss meters can be included, since excess biomass can fill up and render the biofiltration system useless.
- the biofilter of the invention can be designed in various shapes and dimensions, using the appropriate materials for it.
- the structural simplicity of the biofilter 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 biofilter 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 in series, 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, similarly , the gaseous outflow of said second biofilter of the invention is introduced into the third of the biofilters of the invention, and so on until the definitive exit of the gaseous stream totally or partially discharged from biodegradable contaminant.
- the biofilter of the invention can be used to purify gases contaminated with one or more biodegradable contaminants by biofiltration. Therefore, in another aspect, the invention relates to a method for purifying a gas stream containing at least one biodegradable gaseous pollutant by biofiltration, hereinafter "biofiltration method of the invention", which comprises passing said gas stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention, that is, a biofilter comprising black arc furnace slag (EAFS) as filler material and microorganisms capable of degrading said biodegradable pollutant.
- biofiltration method of the invention comprises passing said gas stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention, that is, a biofilter comprising black arc furnace slag (EAFS) as filler material and microorganisms capable of degrading said biodegradable pollutant.
- EAFS black arc furnace slag
- the expression "purifying a gaseous stream containing at least one biodegradable gaseous pollutant” includes both the virtually total elimination of the biodegradable gaseous pollutant (or pollutants) present in a gaseous stream containing said pollutant as reducing the amount of said biodegradable gaseous pollutant (or pollutants) present in a gaseous stream that contains said pollutant to levels permitted by legislation or that are not harmful to human or animal health and / or the environment.
- biodegradable refers to a chemical compound that can be decomposed by the action of biological agents, for example, a microorganism, etc. Therefore, a “biodegradable gaseous pollutant” is a chemical compound considered as a pollutant, in a gaseous state, which can be decomposed by the action of biological agents, for example, a microorganism.
- biodegradable gaseous pollutants include volatile organic compounds (VOCs), hydrogen disulfide (H 2 S), carbon sulphide (CS 2 ), etc.
- the biofiltration method of the invention can be used to purify a gaseous stream contaminated with one or more biodegradable gaseous pollutants.
- the biofiltration method of the invention is used to purify a gaseous stream contaminated with a single gaseous pollutant. biodegradable.
- the biofiltration method of the invention is used to purify a gaseous stream contaminated with two or more biodegradable gaseous pollutants.
- biodegradable gaseous pollutant is selected from the group consisting of VOCs, H 2 S, CS 2 , and any combination thereof. Therefore, in a particular embodiment, said polluted gaseous stream to be purified comprises one or more VOCs. In another particular embodiment, said contaminated gas stream to be purified comprises H 2 S.
- said contaminated gas stream to be purified comprises CS 2 .
- said polluted gaseous stream to be purified comprises one or more VOCs, and a biodegradable gaseous pollutant selected from H 2 S and CS 2 .
- said polluted gas stream to be purified comprises at least one biodegradable gaseous pollutant selected from H 2 S and CS 2 , and, optionally, one or more VOCs.
- said polluted gas stream to be purified comprises one or more VOCs, H 2 S and CS 2 .
- the biofiltration method of the invention comprises performing a previous step of inoculating the EAFS (biofilter filler material of the invention) with microorganisms capable of degrading the biodegradable contaminant (s) to be treated, with the aim of forming a biofilm of said microorganisms on the biofilter filler material of the invention that enables the purification of the contaminated gaseous stream to be purified.
- the inoculation of the EAFS can be carried out directly with microorganisms capable of degrading the standardized biodegradable pollutant (s) or pollutants (s), or with an inoculum obtained preliminary by acclimatization of a given biomass to the contaminant or contaminants to be treated.
- acclimatization can be carried out in any suitable installation, for example, in the biofilter of the invention itself, or, alternatively, in a laboratory or in a plant pilot, using a continuous or discontinuous acclimatization reactor.
- acclimatization comprises contacting a biomass rich in microorganisms, such as biological sludge from a wastewater treatment plant (WWTP), with a gaseous stream containing the biodegradable pollutant (s) to treat, so that an optimal population of microorganisms capable of degrading said contaminant (s) is developed.
- WWTP wastewater treatment plant
- the amount of biodegradable gaseous pollutant (s) present in said gaseous stream can be increased, if desired, as the acclimatization of the microorganisms to said biodegradable gaseous pollutant (s) increases ( s).
- the person skilled in the art can generate, by conventional methods, gaseous streams containing different concentrations of pollutant or biodegradable pollutant (s) to be analyzed, and select the one that provides a better acclimatization of the microorganisms present in the biological medium chosen at pollutant or contaminants.
- the conditions for acclimatizing the microorganisms initially contained in the biomass to said biodegradable pollutant (s) or pollutants (s) depend, in general, on various factors, for example, on the biodegradable gaseous pollutant or pollutant content (s) (s) in the gas stream used, residence time, duration of treatment, etc.
- a nutrient solution in order to favor Metabolism of microorganisms capable of degrading said pollutant (s) or biodegradable gaseous pollutant (s).
- the contribution of said nutrient solution can be carried out by irrigation in the case of acclimatization in the biofilter or by addiction / replacement to the liquid medium in the case of acclimatization in an acclimatization reactor.
- said acclimatization takes place outside the biofilter itself, and, in particular, in a continuous acclimatization system.
- said acclimatization comprises the bubbling on a liquid medium rich in microorganisms in constant agitation (for example, a sludge from an WWTP) of a gas stream comprising one or more biodegradable gaseous pollutants in an amount equal to or less than about 100 ppmv, typically between 25 ppmv and 100 ppmv, continuously, with a flow rate that provides a residence time equal to or less than 3 minutes, typically between 2 and 3 minutes approximately, for at least 30 days, preferably for approximately 60 days.
- a particular embodiment of a continuous acclimatization system for obtaining inoculum for starting the biofilter of the invention provided with: (1) gaseous current inlet, (2) sampling point, (3) is shown in Figure 1. liquid medium under stirring, (4) sampling point and (5) gaseous current outlet.
- a "activated" liquid medium is obtained, that is, a liquid medium containing the microorganism or microorganisms capable of degrading the contaminant or biodegradable gas contaminants (s) in question, which is used to inoculate the SAIs.
- the inoculation is carried out in the biofilter itself, previously loaded with the filler material, for example, by irrigation with said "activated” liquid medium. After successive irrigation, the biofilm of microorganisms is formed, so that the biofilter is now ready for the purification of gaseous streams contaminated with the biodegradable pollutant (s) in question.
- the acclimatization process initiated outside the biofilter continues in the biofilter itself. To do this, after inoculating the biofilter previously loaded with filler material, it is fed for a short period (typically 2 weeks) with currents with low pollutant concentrations, normally not exceeding 100 ppmv.
- the entire acclimatization process takes place in the biofilter itself.
- the watering of the filler material contained in the biofilter with a liquid medium that presents various populations of microorganisms, such as biological sludge from an WWTP, together with the passage of a gas stream containing at least one biodegradable gaseous pollutant, preferably in a relatively low amount also leads to the formation of the biofilm of microorganisms on the filler material, responsible for purification.
- the biofiltration method of the invention comprises passing said gas stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention.
- the amount or concentration of biodegradable pollutant (s) or pollutant (s) present in said gaseous stream to be purified may vary within a wide range.
- said gaseous stream to be purified contains at least one biodegradable gaseous pollutant in an amount between about 50 ppmv and about 250 ppmv.
- the amounts or concentrations of biodegradable gaseous pollutant expressed refer to total amounts or concentrations of biodegradable gaseous pollutant. , so that if there is more than one biodegradable gaseous pollutant in the polluted gaseous stream to be purified, the total amount or concentration results from the sum of the amounts or concentrations of each of them. Also, the residence time, or average amount of time that the gaseous stream can remain that contains at least one biodegradable gaseous pollutant to be cleaned in contact with the filler material (EAFS) of the biofilter of the invention can vary over a wide range.
- EAFS filler material
- said residence time is between about 10 seconds and about 80 seconds, typically about 60 seconds.
- the gaseous stream containing at least one biodegradable gaseous pollutant to be purified by the biofiltration method of the invention can come from various pollutant sources, for example, from process facilities that use or generate said pollutants, such as fiber manufacturing facilities. of cellulose, synthetic wrap food industry, pharmaceutical industry, chemical industry, paint manufacturing, etc.
- the biofiltration method of the invention comprises a step of humidifying the gas stream containing at least one biodegradable pollutant to be purified, for which said gas stream is contacted with an aqueous medium. , for example, water, before being introduced into the biofilter.
- the aqueous medium used in 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 gas stream containing at least one contaminant. biodegradable gas the necessary humidity, located before of the biofilter.
- 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 saturation of the gas stream containing the less a biodegradable gaseous pollutant to purify and minimize system maintenance.
- the relative humidity of the gas stream containing at least one biodegradable gaseous pollutant entering the biofilter of the invention is equal to or greater than 70%, usually equal to or greater than 80%, advantageously equal to or greater than 90% , preferably equal to or greater than 95%, even more preferably equal to or greater than 99%.
- the gaseous stream containing at least one biodegradable pollutant to be purified passes through the filler material that supports the growing microorganisms capable of degrading said gaseous pollutant (s). biodegradable (s).
- the degradation of said pollutant (s) occurs, in general, after transferring the gas stream containing at least one biodegradable gaseous pollutant to a liquid medium where it is used as a source of carbon and / or energy.
- the use of said contaminant implies a series of chemical reactions that lead to the decomposition or degradation of the contaminant, for example, to its partial or total oxidation, as well as the production of biomass capable of degrading said contaminant (s), with what the biofiltration method of the invention results in a practically complete degradation of the biodegradable pollutant or gaseous pollutants (s) generating non-hazardous (harmless) products for human or animal health and / or the environment and a current Total or partially discharged gas in said pollutant (s) or biodegradable gaseous pollutant (s).
- the biofiltration method of the invention includes the possibility of passing the gas stream containing at least one biodegradable gaseous pollutant through one or more biofilters of the invention.
- the biofiltration method of the invention comprises passing the gaseous stream containing at least one biodegradable gaseous pollutant to be purified through a single biofilter of the invention.
- the biofiltration method of the invention comprises passing the gas stream containing at least one biodegradable gaseous pollutant to be purified through two or more biofilters of the invention, for example 2, 3, 4, or even more, operationally connected to each other; in this case, the gaseous stream containing at least one biodegradable pollutant to be purified is passed through the first of the biofilters of the invention and the gaseous outlet of said first biofilter of the invention, which will be at least partially discharged in said biodegradable gaseous pollutant (s), it is passed through the second biofilter of the invention, and, similarly, the gaseous outflow of said second biofilter of the invention, which it will be even more discharged in said biodegradable gas contaminant (s), is passed through the third biofilter of the invention, and so on until the final exit of the total or partially discharged gas stream from said biodegradable gaseous pollutant (s).
- the biofiltration method of the invention allows to achieve an efficiency of elimination of said biodegradable pollutant (s) of 100%, or very close to 100%, in relation to the amount of said biodegradable gaseous pollutant (s) present in the gaseous stream containing at least one biodegradable gaseous pollutant to be purified.
- the stable operation of the biofilter of the invention may require 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; an amount of 5 was added 3 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 -4H 2 0.60 mg / dm 3 of CuCl 2 , 50 mg / dm 3 of ZnCl 2 , 50 mg / dm 3 of H 3 B0 3 , 2 g / dm 3 of HC0 3 Na, 90 mg / dm 3 ( ⁇ 4) 6 7 0 24 ⁇ ⁇ 4 ⁇ 2 0, 1 g /
- the buffering (buffer effect) of the pH of the biofilm where the microorganisms reside is favored and carry potential degradation intermediates (acids) generated as unwanted by-products of the degradation reaction of said biodegradable gas contaminant (s).
- the good pH regulating characteristics as well as the good characteristics for retaining moisture by the SAIs used as a biofilter filler material used in the biofiltration method of the invention minimize the need for watering very continuous
- the period of time between two consecutive irrigations may vary within a wide range, depending on numerous factors (eg, need to provide nutrients, need to moisten the support, etc.), in a particular embodiment, the period of time between two consecutive waterings is between approximately 1 and 5 days, typically between approximately 1 and 2 days.
- carbon dioxide / carbonic acid could be generated, for example, when the biodegradable gaseous pollutant comprises a VOC, in practice, in general, it is not necessary to use additional reagents to neutralize said acid. from the oxidation of said contaminants.
- 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 one or more gaseous pollutants. biodegradable contained in a gas stream containing said contaminant (s).
- 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 with moisture) gas stream containing at least one biodegradable gaseous pollutant is passed, for example, one or more VOCs, H 2 S, CS 2 , etc., or combinations thereof, through the filler material contained in the biofilter of the invention wherein said gaseous pollutant (s) (s) ) biodegradable (s) is / are degraded by microorganisms capable of degrading said contaminant (s).
- a moistened (eg, saturated with moisture) gas stream containing at least one biodegradable gaseous pollutant is passed, for example, one or more VOCs, H 2 S, CS 2 , etc., or combinations thereof, through the filler material contained in the biofilter of the invention wherein said gaseous pollutant (s) (s) ) biodegradable (s)
- a gaseous stream containing at least one biodegradable gaseous pollutant (2) from a pollutant source (1) is introduced into a humidification system (3) containing water in order to moisten said gaseous stream containing at least one biodegradable gaseous contaminant before entering a bioreactor (5).
- the moistened gaseous stream containing at least one biodegradable gaseous pollutant (4) is introduced into said bioreactor (5) which contains 2 biofilters of the invention (6a and 6b); each of which comprises a filler material and microorganisms capable of degrading said biodegradable gaseous contaminant (s), wherein said filler material comprises EAFS.
- the 2 biofilters of the invention (6a and 6b) are arranged vertically and operatively connected to each other so that the output current of the first biofilter (6a) feeds the second biofilter (6b) from which the practically discharged gas stream from said ( s) biodegradable gas contaminant (s) (7).
- the nutrients contained in the irrigation system (8) are supplied to the biofilters of the invention by irrigation in order to maintain the metabolism of microorganisms capable of degrading said gaseous pollutant (s) (s) biodegradable (s).
- the biofiltration method of the invention can be carried out in a suitable installation comprising at least one biofilter of the invention, that is, a biofilter comprising black electric arc furnace slag (EAFS) as filler material and microorganisms capable of degrading the biodegradable pollutant or gaseous pollutants to be eliminated, such as VOCs, H 2 S, CS 2 , etc.
- EAFS black electric arc furnace slag
- the installation of the invention may contain one or more biofilters of the invention.
- the installation of the invention comprises a single biofilter 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 series); in this case, the gas stream containing at least one biodegradable gaseous pollutant (eg, one or more VOCs, H 2 S, CS 2 , etc., or combinations thereof) to be purified is passed through the first biofilter of the invention and the gaseous outflow of said first biofilter of the invention is passed through the second biofilter of the invention, and, similarly, the gaseous outflow of said second biofilter of the invention is passed through of the third biofilter of the invention, and so on until the definitive exit of the total or partially discharged gas stream of said biodegradable gas contaminant (s).
- biodegradable gaseous pollutant eg, one or more VOCs, H 2 S, CS 2 , etc
- the modular design of the installation of the invention allows the biofilters of the invention further away from the entrance of the gaseous stream containing at least one biodegradable gaseous pollutant to receive very low concentrations of said gaseous pollutant (s). biodegradable (s) but sufficient for the adaptation of microorganisms capable of degrading said gaseous pollutant (s) biodegradable (s).
- the modular design allows biodegradation of said biodegradable gaseous pollutant (s) in the first biofilter of the invention while the remaining biofilters can act as a reserve, which guarantees the efficiency of the system even with sudden increases in pollutant load.
- 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 at least a biodegradable gaseous pollutant the necessary moisture, 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 at least a biodegradable gaseous pollutant the necessary moisture, located before the biofilter of the invention.
- the installation of the invention includes suitable means for transporting the gas stream to be purified, 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 said Biodegradable gaseous contaminant (s) 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 at least one biodegradable gaseous pollutant to be purified, means for measuring the pH in inside the biofilter, and means for measuring the amount of biodegradable gaseous pollutant (s) present in the gaseous outflow of the biofilter of the invention.
- the installation of the invention in addition to at least one biofilter of the invention, may contain one or more different biofilters in which the biofilter filler material is not EAFS but another material of an inorganic nature or of an organic nature for example, compost , peat, acid peat, pine bark, a mixture of compost, sawdust and perlite, or 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 biofilter filler material is not EAFS but another material of an inorganic nature or of an organic nature for example, compost , peat, acid peat, pine bark, a mixture of compost, sawdust and perlite, or 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.
- 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 2 biofilters (6a and 6b), placed vertically, with an approximate total volume of 4.5 L, built in polyvinyl chloride (PVC) and with downward gas flow; the biofilters (6a and 6c) are operatively connected to each other and, inside, is the filling material comprising EAFS, which acts as a support material on which the biomass (microorganisms) responsible for the degradation of toluene (biodegradable gaseous pollutant contained in the polluted gaseous stream to be purified) is developed.
- EAFS acts as a support material on which the biomass (microorganisms) responsible for the degradation of toluene (biodegradable gaseous pollutant contained in the polluted gaseous stream to be purified) is developed.
- the inoculum was obtained from the biological sludge of a wastewater treatment plant (WWTP).
- the acclimatization process of the biomass contained in the mud was carried out in an acclimatization reactor built in PVC 4.5 L), as shown in Figure 1.
- feeding with gaseous streams containing toluene, with toluene concentrations between 25 and less than 100 ppmv, and, with residence times of approximately 3 minutes, which bubbled over the sample of sludge while stirring it was possible to obtain, after about 30 days, the liquid medium necessary for the inoculation of the black slag of electric arc furnace (EAFS).
- EAFS electric arc furnace
- the EAFS was introduced into the modular bioreactor ( Figure 2) and irrigated with the acclimatized inoculum, forming a biofilm containing the active biomass, that is, the microorganisms capable of degrading toluene.
- the utility of the system was evaluated with a gas stream with a toluene content of approximately 50-150 ppmv. With this current the efficiency of the treatment of purification of toluene was greater than 90% for residence times of approximately 60 s.
- the maintenance of moisture in the biofilter filler material (EAFS) was achieved by daily irrigation with the nutrient solution required for active biomass metabolism.
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Abstract
The invention relates to a biofilter comprising black slag from an electric arc furnace as a filler material and micro-organisms capable of breaking down one or more pollutant substances such as volatile organic compounds (VOCs), hydrogen disulphide (H2S), carbon sulphide (CS2) and any combination of same. The invention also relates to a method for purifying a gas stream containing at least one biodegradable gaseous pollutant by means of biofiltration in which the gas stream containing at least one biodegradable gaseous pollutant is made to pass through the biofilter.
Description
BIOFILTRO QUE COMPRENDE ESCORIA NEGRA DE HORNO DE ARCO ELÉCTRICO Y SUS APLICACIONES BIOFILTER THAT INCLUDES BLACK ESCORIA OF ELECTRIC ARC OVEN AND ITS APPLICATIONS
CAMPO DE LA INVENCIÓN FIELD OF THE INVENTION
La presente invención se relaciona, en general, con la depuración de gases contaminados con contaminantes gaseosos biodegradables. En particular, la invención se relaciona con un biofiltro que comprende escoria negra de horno de arco eléctrico como material de relleno, para eliminar o reducir el contenido en contaminantes gaseosos biodegradables presentes en una corriente gaseosa contaminada que contiene al menos uno de dichos contaminantes, así como con un método de biofiltración que comprende el empleo de dicho biofiltro. The present invention relates, in general, to the purification of contaminated gases with biodegradable gaseous pollutants. In particular, the invention relates to a biofilter comprising black slag from an electric arc furnace as filler material, to eliminate or reduce the content of biodegradable gaseous pollutants present in a polluted gaseous stream containing at least one of said pollutants, thus as with a biofiltration method comprising the use of said biofilter.
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. Existen infinidad de gases que se liberan a la atmósfera y que pueden ser calificados como contaminantes; tales como, por ejemplo, sulfuro de hidrógeno, disulfuro de carbono, compuestos orgánicos volátiles, amoníaco etc. The increasing emission of pollutants into the environment and the consequent deterioration of the latter has led to legal control over their emission. There are countless gases that are released into the atmosphere and that can be qualified as pollutants; such as, for example, hydrogen sulfide, carbon disulfide, volatile organic compounds, ammonia etc.
El sulfuro de hidrógeno (H2S) es extremadamente nocivo para la salud, bastan 20-50 ppm en el aire para causar un malestar agudo que lleva a la sofocación y puede llevar a la muerte por sobreexposición. Hydrogen sulfide (H 2 S) is extremely harmful to health, 20-50 ppm in the air is enough to cause acute discomfort that leads to suffocation and can lead to death from overexposure.
El disulfuro de carbono (CS2) constituye un contaminante altamente peligroso debido principalmente a sus efectos perjudiciales sobre la salud humana. La exposición prolongada a vapores de CS2 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. Carbon disulfide (CS 2 ) constitutes a highly dangerous pollutant due mainly to its harmful effects on human health. Prolonged exposure to CS 2 vapors causes symptoms of intoxication ranging from reddening 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.
Los compuestos orgánicos volátiles (COVs) constituyen un tipo de contaminantes altamente peligrosos. La Agencia Americana de Protección
Medioambiental (US EPA) define los COVs como todo compuesto orgánico que tenga una presión de vapor superior a 0, 1 mm Hg en condiciones estándar (25°C y 760 mm Hg). Así, bajo esta definición, los COVs engloban una amplia gama de compuestos químicos, entre los que se incluyen hidrocarburos alifáticos, hidrocarburos aromáticos, hidrocarburos clorados, aldehidos, cetonas, éteres, ácidos y alcoholes, muchos de los cuales pueden tener efectos adversos para la salud humana o animal, así como sobre el medio ambiente en general, a corto o largo plazo. Asimismo, los COVs han sido identificados como una de las fuentes principales en la formación del "smog' fotoquímico al reaccionar con otros contaminantes atmosféricos (por ejemplo, óxidos de nitrógeno) y con la luz solar, pudiendo causar problemas respiratorios, irritación ocular, dolor de cabeza, etc., y daños a la flora y la vida animal. Volatile organic compounds (VOCs) constitute a type of highly hazardous contaminants. The American Protection Agency Environmental (US EPA) defines VOCs as any organic compound that has a vapor pressure greater than 0.1 mm Hg under standard conditions (25 ° C and 760 mm Hg). Thus, under this definition, VOCs encompass a wide range of chemical compounds, including aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, aldehydes, ketones, ethers, acids and alcohols, many of which may have adverse effects on the human or animal health, as well as the environment in general, in the short or long term. Likewise, VOCs have been identified as one of the main sources in the formation of photochemical smog by reacting with other air pollutants (for example, nitrogen oxides) and with sunlight, which can cause respiratory problems, eye irritation, pain head, etc., and damage to flora and animal life.
Por ello, ha sido necesario desarrollar procesos destinados a controlar la emisión de este tipo de contaminantes 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 y grandes caudales. 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 de dichos contaminantes (H2S, CS2 y/o COVs). Therefore, it has been necessary to develop processes aimed at controlling the emission of this type of pollutants 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 and large flows. 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 such contaminants (H 2 S, CS 2 and / or VOCs).
A lo largo de los últimos años, las tecnologías biológicas de depuración de corrientes gaseosas contaminadas han tomado fuerza como alternativa a las tecnologías físico-químicas, ya que son procesos más limpios y económicos, eliminan muchas de las desventajas asociadas con los sistemas físico-químicos tradicionales, por ejemplo, generación de nuevos residuos, etc., y resultan especialmente útiles cuando los caudales a tratar son grandes y las concentraciones de contaminantes (e.g., H2S, CS2 y/o COVs) son bajas. 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. Las tecnologías biológicas se fundamentan en una serie de reacciones
metabólicas microbiológicas que conducen a la degradación de los contaminantes presentes en la corriente gaseosa. A través de reacciones oxidativas y, en menor lugar, reductivas, los contaminantes pueden ser transformados en subproductos como por ejemplo C02, vapor de agua, nitratos, sulfates y nueva biomasa, entre otros productos. Over the last few years, biological technologies for the purification of contaminated gaseous streams have gained strength as an alternative to physical-chemical technologies, since they are cleaner and cheaper processes, eliminating many of the disadvantages associated with physical-chemical systems. traditional, for example, generation of new waste, etc., and are especially useful when the flows to be treated are large and the concentrations of pollutants (eg, H 2 S, CS 2 and / or VOCs) are low. 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. Biological technologies are based on a series of reactions Microbiological metabolics that lead to the degradation of pollutants present in the gas stream. Through oxidative and, to a lesser extent, reductive reactions, pollutants can be transformed into by-products such as C0 2 , water vapor, nitrates, sulfates and new biomass, among other products.
Aunque existe un gran número de diferentes configuraciones, los sistemas biológicos de purificación de corrientes gaseosas más utilizados pueden clasificarse en tres grandes grupos: biolavadores ("bioscrubber"), bioreactores de lecho escurrido ("biotrickling filter") y biofiltros de lecho fijo ("biofilter") [Delhomenie, MC. et al. 2005. Biofiltration of Air: A Review. Critica! Reviews in Biotechnology, 25:53-72]. Los mecanismos básicos de eliminación del contaminante son similares en todos los casos, difiriendo unos de otros en la presencia o ausencia de un soporte, la naturaleza del soporte utilizado, la presencia o ausencia de una fase liquida móvil, y/o la capacidad de tratar diferentes contaminantes. Although there are a large number of different configurations, the most commonly used biological gas purification systems can be classified into three large groups: biolavadores ("bioscrubber"), drained bed bioreactors ("biotrickling filter") and fixed bed biofilters (" biofilter ") [Delhomenie, MC. et al. 2005. Biofiltration of Air: A Review. Review! Reviews in Biotechnology, 25: 53-72]. The basic mechanisms for removing the contaminant are similar in all cases, differing from each other in the presence or absence of a support, the nature of the support used, the presence or absence of a mobile liquid phase, and / or the ability to treat Different pollutants
En concreto, los biofiltros convencionales de lecho fijo emplean microorganismos que están adheridos fijos en un medio poroso para degradar los contaminantes presentes en una corriente gaseosa que atraviesa el lecho. Dichos microorganismos crecen en una biopelícula soportada sobre la superficie del medio. Al pasar el gas a través del lecho, los contaminantes de la fase gaseosa se absorben en la biopelícula que rodea al medio, donde son biodegradados. Por tanto, los biofiltros básicamente 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. 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. La ausencia de una fase acuosa móvil hace que estos bioreactores sean ideales para el tratamiento de contaminantes muy poco solubles en agua. Specifically, conventional fixed-bed biofilters employ microorganisms that are fixedly adhered in a porous medium to degrade contaminants present in a gaseous stream that flows through the bed. Said microorganisms grow in a biofilm supported on the surface of the medium. When the gas passes through the bed, the contaminants of the gas phase are absorbed in the biofilm that surrounds the environment, where they are biodegraded. Therefore, biofilters basically 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. 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. The absence of a mobile aqueous phase makes these bioreactors ideal for the treatment of contaminants that are not very soluble in water.
La selección del material de soporte es un factor fundamental para el correcto funcionamiento de los biofiltros convencionales, ya que influye tanto en la capacidad de eliminación del contaminante (actividad microbiana) como en el coste final del sistema de biofiltración (frecuencia de sustitución del soporte agotado y su gestión posterior, pérdidas de carga asociadas a la compactación del lecho, etc.). Igualmente, al
desarrollarse sobre su superficie la biomasa responsable de la degradación de los contaminantes, deben tenerse en cuenta ciertas características físico-químicas importantes: alta área superficial específica, alta porosidad, baja densidad aparente, alta capacidad de retención de agua y disponibilidad de nutrientes esenciales para un correcto desarrollo del metabolismo microbiano. The selection of the support material is a fundamental factor for the proper functioning of conventional biofilters, since it influences both the ability to remove the contaminant (microbial activity) and the final cost of the biofiltration system (replacement frequency of the depleted support and its subsequent management, load losses associated with bed compaction, etc.). Likewise, at The biomass responsible for the degradation of pollutants must be developed on its surface, certain important physical-chemical characteristics must be taken into account: high specific surface area, high porosity, low apparent density, high water retention capacity and availability of essential nutrients for correct development of microbial metabolism.
Se conocen numerosos microorganismos capaces de degradar H2S pertenecientes a los géneros Acidthiobacillus (e.g., A. thiooxidans strain AZ11, etc.), Beggiatoa, Macromonas, Pseudomonas (e.g., P. acidovorans strain DMR-11 ; P. putida strain CH11, etc.), Sulfolobus (e.g., S. Metallicus, etc.), Thiobacterium, Thiobacillus (e.g., T. sp., T. denitrificans; T. novellus strain CH3; T. thioparus strain CH11, T. thioparus strain DW44, etc.), Thiomicrospira, Thiomonas, Thiospira, Thiosphaera, etc. Numerous microorganisms capable of degrading H 2 S belonging to the genera Acidthiobacillus (eg, A. thiooxidans strain AZ11, etc.), Beggiatoa, Macromonas, Pseudomonas (eg, P. acidovorans strain DMR-11; P. putida strain CH11, are known, etc.), Sulfolobus (eg, S. Metallicus, etc.), Thiobacterium, Thiobacillus (eg, T. sp., T. denitrificans; T. novellus strain CH3; T. thioparus strain CH11, T. thioparus strain DW44, etc. .), Thiomicrospira, Thiomonas, Thiospira, Thiosphaera, etc.
Entre los microorganismos capaces de degradar el CS2 se encuentran microorganismos del género Paracoccus (P. denitrificans, etc.), Thioalkalimicrobium (e.g., T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (e.g., T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (e.g., Thiobacillus strain TJ330; T. thioparus strain TK- m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (e.g., T. ramose, etc.), etc. Among the microorganisms capable of degrading CS 2 are microorganisms of the genus Paracoccus (P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (eg, Thiobacillus strain TJ330; T. thioparus strain TK-m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (eg, T. ramose, etc. ), etc.
Por otra parte, es conocido el tratamiento de corrientes gaseosas contaminadas con COVs mediante biofiltros rellenos con diversos tipos de soporte. A modo ilustrativo, Dorado y col. [A comparative study based on physical characteristics of suitable packing materials in biofiltration. Environ. Technol. 31(2)(2010): 193-204] comparan diez materiales comúnmente usados como soporte en biofiltración, tanto de naturaleza orgánica (por ejemplo, fibra de coco, hojas de pino, compost, etc.) como inorgánica o sintéticos (por ejemplo, espuma de poliuretano, lignita, roca de lava, etc.). Entre otras características, se evalúa su capacidad para adsorber tolueno de una corriente gaseosa. No obstante, a pesar de los distintos tipos de material de relleno conocidos, resulta conveniente disponer de una mayor gama de tales materiales de relleno con el fin de disponer de más recursos a la hora de seleccionar el material más apropiado en función de las características particulares de la depuración (contaminantes presentes, concentración, etc.). On the other hand, the treatment of gaseous streams contaminated with VOCs by means of biofilters filled with various types of support is known. By way of illustration, Dorado et al. [A comparative study based on physical characteristics of suitable packing materials in biofiltration. Environ. Technol 31 (2) (2010): 193-204] compare ten materials commonly used as biofiltration support, both organic in nature (for example, coconut fiber, pine leaves, compost, etc.) and inorganic or synthetic (for example , polyurethane foam, lignite, lava rock, etc.). Among other features, its ability to adsorb toluene from a gas stream is evaluated. However, despite the different types of filler material known, it is convenient to have a greater range of such filler materials in order to have more resources when selecting the most appropriate material based on the particular characteristics of purification (contaminants present, concentration, etc.).
Por otro lado, Chou y col. [Treatment of 1,3-butadiene in an air stream by a biotrickling filter and a biofilter. J. Air & Waste Manage. Assoc. 48 (1998):711-720;
Treatment of styrene-contaminated airstream in biotrickling filter packed with slags. J. Environ. Eng. 124 (9) (1998):844-850; Treatment of toluene in an air stream by a biotrickling filter packed with slags. J. Air & Waste Manage. Assoc. 49 (1999): 386- 398] han empleado escorias de alto horno como lecho de un filtro biopercolador a escala de laboratorio para el tratamiento independiente de diversos contaminantes: tolueno [rendimiento superior al 90% para cargas de entrada de contaminante superiores a 30 g m"3 h"1 y 3 minutos de tiempo de residencia], estireno [rendimiento superior al 95% para cargas de entrada de contaminante inferiores a 30 g m"3 h"1 y 1,07 minutos de tiempo de residencia] ó 1,3-butadieno [capacidad de eliminación inferior a 5 g m"3 h"1 para cargas de entrada de contaminante menores a 25 g m"3 h"1 y tiempos de residencia entorno 1,89-5,04 minutos]. Una desventaja asociada con estos sistemas es que precisan de una gestión adecuada del medio líquido que se recircula continuamente a través del material de relleno. Adicionalmente, muchos autores han demostrado que los bioreactores de filtro escurrido o "filtros biotrickling" dan lugar a una acumulación excesiva de biomasa, lo que conduce a una pérdida de eficacia en la filtración. Asimismo, la conjunción de costes operacionales relativamente elevados y restricciones en cuanto a la solubilidad de los COVs suponen un claro inconveniente en comparación con los biofiltros. On the other hand, Chou et al. [Treatment of 1,3-butadiene in an air stream by a biotrickling filter and a biofilter. J. Air & Waste Manage. Assoc. 48 (1998): 711-720; Treatment of styrene-contaminated airstream in biotrickling filter packed with slags. J. Environ. Eng. 124 (9) (1998): 844-850; Treatment of toluene in an air stream by a biotrickling filter packed with slags. J. Air & Waste Manage. Assoc. 49 (1999): 386-398] have used blast furnace slags as a bed of a laboratory-scale biopercolator filter for the independent treatment of various contaminants: toluene [yield greater than 90% for contaminant ingress loads greater than 30 gm "3 h " 1 and 3 minutes of residence time], styrene [yield greater than 95% for contaminant inlet loads less than 30 gm "3 h " 1 and 1.07 minutes of residence time] or 1.3 -butadiene [elimination capacity less than 5 gm "3 h " 1 for contaminant inlet charges less than 25 gm "3 h " 1 and residence times around 1.89-5.04 minutes]. A disadvantage associated with these systems is that they require proper management of the liquid medium that is continuously recirculated through the filling material. Additionally, many authors have shown that drained filter bioreactors or "biotrickling filters" result in excessive accumulation of biomass, which leads to a loss of filtration efficiency. Also, the conjunction of relatively high operational costs and restrictions regarding the solubility of VOCs is a clear drawback compared to biofilters.
Por tanto, sigue existiendo la necesidad de encontrar métodos alternativos para tratar corrientes gaseosas contaminadas con contaminantes gaseosos biodegradables, or ejemplo, COVs, H2S, CS2, etc., sencillos y fiables, que, preferentemente, resuelvan al menos alguno de los problemas de los métodos de biofiltración de corrientes gaseosas contaminadas con dichos contaminantes descritos en el estado de la técnica. Therefore, there is still a need to find alternative methods for treating gaseous streams contaminated with biodegradable gaseous pollutants, for example, VOCs, H 2 S, CS 2 , etc., simple and reliable, which, preferably, solve at least some of the problems of the biofiltration methods of gaseous streams contaminated with said contaminants described in the prior 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 (es decir, eliminar o reducir) de manera eficiente la cantidad de contaminantes gaseosos biodegradables presentes en una corriente gaseosa contaminada con al menos uno de dichos contaminantes; ejemplos ilustrativos, no limitativos de dichos contaminantes gaseosos biodegradables incluyen COVs, H2S, y CS2. Dicho método se basa en la utilización de escoria negra de horno de arco eléctrico
o EAFS [del inglés, "Electric Are Furnace Slag"] como material de relleno del biofiltro, y en el empleo de microorganismos capaces de degradar dichos contaminantes, y proporciona diversas ventajas frente a los métodos tradicionales y frente a otros métodos biológicos descritos en el estado de la técnica, debido principalmente a sus características físico-químicas que permiten una operación en continuo durante largos periodos de tiempo sin sufrir erosión y/o deterioro. Tras una etapa previa de inoculación con microorganismos capaces de degradar el contaminante o contaminantes, este residuo (EAFS) sirve adecuadamente como soporte a los mismos, los cuales forman una biopelícula de microorganismos a su alrededor, posibilitando así la depuración de la corriente gaseosa contaminada. The authors of the present invention have developed a fixed bed biofiltration method to purify (ie, eliminate or reduce) the amount of biodegradable gaseous pollutants present in a gaseous stream contaminated with at least one of said pollutants efficiently; Illustrative, non-limiting examples of such biodegradable gaseous pollutants include VOCs, H 2 S, and CS 2 . This method is based on the use of black slag from an electric arc furnace or EAFS [of English, "Electric Are Furnace Slag"] as a biofilter filler, and in the use of microorganisms capable of degrading such contaminants, and provides various advantages over traditional methods and with other biological methods described in the state of the art, mainly due to its physical-chemical characteristics that allow continuous operation for long periods of time without suffering erosion and / or deterioration. After a previous stage of inoculation with microorganisms capable of degrading the contaminant or contaminants, this residue (EAFS) adequately serves as support for them, which form a biofilm of microorganisms around it, thus enabling the purification of the contaminated gas stream.
Así, en un aspecto, la invención se relaciona con un biofiltro que comprende escoria negra de horno de arco eléctrico (EAFS) como material de relleno ("biofiltro de la invención"). Para su puesta en operación, dicho biofiltro comprende, además, microorganismos capaces de degradar el contaminante gaseoso biodegradable que se desea eliminar, por ejemplo, uno o más COVs, H2S, CS2, etc. Dichos microorganismos se inoculan en el material de relleno (EAFS) del biofiltro. Thus, in one aspect, the invention relates to a biofilter comprising black arc furnace slag (EAFS) as filler material ("biofilter of the invention"). For commissioning, said biofilter also comprises microorganisms capable of degrading the biodegradable gaseous pollutant that it is desired to eliminate, for example, one or more VOCs, H 2 S, CS 2 , etc. Said microorganisms are inoculated into the filler material (EAFS) of the biofilter.
En otro aspecto, la invención se relaciona con una instalación para la depuración de corrientes gaseosas contaminadas con al menos un contaminante gaseoso biodegradable que comprende, al menos, un biofiltro de la invención. In another aspect, the invention relates to an installation for the purification of gaseous streams contaminated with at least one biodegradable gaseous pollutant comprising at least one biofilter of the invention.
En otro aspecto, la invención se relaciona con un método para depurar una corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable, mediante biofiltración, que comprende hacer pasar dicha corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a través de un biofiltro de la invención que comprende, además, microorganismos capaces de degradar dicho(s) contaminante(s) gaseoso(s) biodegradable(s). In another aspect, the invention relates to a method for purifying a gaseous stream containing at least one biodegradable gaseous pollutant, by means of biofiltration, which comprises passing said gaseous stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention which also comprises microorganisms capable of degrading said biodegradable gas contaminant (s).
En otro aspecto la invención se relaciona con el uso de escoria negra de horno de arco eléctrico (EAFS) como material de relleno en un biofiltro de lecho fijo para la depuración de corrientes gaseosas, en particular, corrientes gaseosas contaminadas con al menos un contaminante gaseoso biodegradable. In another aspect the invention relates to the use of black arc furnace slag (EAFS) as a filler material in a fixed bed biofilter for the purification of gaseous streams, in particular, gaseous streams contaminated with at least one gaseous pollutant. biodegradable.
BREVE DESCRIPCIÓN DE LAS FIGURAS
La Figura 1 representa una realización particular de un sistema de aclimatación en continuo para la obtención de inóculo para el arranque de un biofiltro de la invención. BRIEF DESCRIPTION OF THE FIGURES Figure 1 represents a particular embodiment of a continuous acclimatization system for obtaining inoculum for starting a biofilter of the invention.
La Figura 2 es una representación esquemática de una realización particular de una instalación adecuada para la puesta en práctica de un método de biofiltración de contaminantes gaseosos biodegradables, por ejemplo, COVs, según la presente invención. Figure 2 is a schematic representation of a particular embodiment of an installation suitable for the implementation of a biofiltration method of biodegradable gaseous pollutants, for example, VOCs, according to the present invention.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN DETAILED DESCRIPTION OF THE INVENTION
Biofiltro de la invención Biofilter of the invention
En un aspecto, la invención se relaciona con un biofiltro de lecho fijo, en adelante "biofiltro de la invención", que comprende escoria negra de horno de arco eléctrico (EAFS) como material de relleno. El biofiltro de la invención puede ser utilizado para depurar gases contaminados que contienen, al menos, un contaminante gaseoso biodegradable (e.g., un compuesto químico que puede ser descompuesto por acción de agentes biológicos), por ejemplo, un compuesto orgánico volátil (COV), disulfuro de hidrógeno (H2S), sulfuro de carbono (CS2), etc. En una realización particular, el biofiltro de la invención se utiliza para depurar gases contaminados con uno o más COVs, H2S y/o CS2, mediante biofiltración, es decir, para eliminar o reducir la cantidad de COVs, H2S y/o CS2, presente en una corriente gaseosa que contiene COVs, H2S y/o CS2. En otra realización particular y preferida, el biofiltro de la invención se utiliza para depurar, mediante biofiltración, gases contaminados con uno o más COVs. In one aspect, the invention relates to a fixed bed biofilter, hereinafter "biofilter of the invention", which comprises black arc furnace slag (EAFS) as filler material. The biofilter of the invention can be used to purify contaminated gases containing at least one biodegradable gaseous pollutant (eg, a chemical compound that can be decomposed by the action of biological agents), for example, a volatile organic compound (VOC), hydrogen disulfide (H 2 S), carbon sulfide (CS 2 ), etc. In a particular embodiment, the biofilter of the invention is used to purify gases contaminated with one or more VOCs, H 2 S and / or CS 2 , by biofiltration, that is, to eliminate or reduce the amount of VOCs, H 2 S and / or CS 2 , present in a gas stream containing VOCs, H 2 S and / or CS 2 . In another particular and preferred embodiment, the biofilter of the invention is used to purify, by biofiltration, gases contaminated with one or more VOCs.
El material de relleno (soporte) contenido en el biofiltro de la invención, escoria negra de horno de arco eléctrico (EAFS), es un residuo de la industria siderúrgica considerado legalmente como un residuo inerte [Boletín Oficial del País Vasco (BOPV), 1994; No 239, Decreto 423/1994] y se obtiene como subproducto no deseado durante la fabricación de acero a partir de chatarra de hierro y/o acero como materia prima en hornos de arco eléctrico. Las producciones de acero, a nivel mundial y europeo, en el año 2008 fueron de 1.327 y 198 millones de toneladas (mt), respectivamente, mientras que la producción española en el año 2009 fue de 14,4 mt.
Esta fabricación de acero genera una gran cantidad de residuos industriales que representan entre el 15% y 20% de la producción total de acero [150-200 kg de escoria por cada tonelada producida de acero], siendo la escoria negra de horno de arco eléctrico (EAFS) el subproducto industrial cuantitativamente más importante en la fabricación de aceros comunes. Debido a la alta generación y acumulación en depósitos al aire libre de estas escorias negras (EAFS), se ha autorizado su uso como producto final en carreteras y vías públicas o privadas de tráfico rodado como una de las capas estructurales, como materia prima en la fabricación de cemento y como árido para el hormigón estructural. Ahora se ha encontrado que también puede ser utilizado como material de relleno en biofiltros destinados a la depuración, mediante biofiltración, de corrientes gaseosas contaminadas con al menos un contaminante gaseoso biodegradable, por lo que la presente invención contribuye a resolver, además, el problema generado por el exceso de estas escorias (EAFS), proponiendo una aplicación novedosa para ese residuo. The filler material (support) contained in the biofilter of the invention, black slag from an electric arc furnace (EAFS), is a waste from the steel industry legally considered as an inert waste [Official Gazette of the Basque Country (BOPV), 1994 ; No 239, Decree 423/1994] and is obtained as an unwanted by-product during the manufacture of steel from scrap iron and / or steel as raw material in electric arc furnaces. Steel productions, worldwide and European, in 2008 were 1,327 and 198 million tons (mt), respectively, while Spanish production in 2009 was 14.4 mt. This steel manufacturing generates a large amount of industrial waste that represents between 15% and 20% of the total steel production [150-200 kg of slag per ton produced of steel], the black slag being an electric arc furnace (EAFS) the quantitatively most important industrial by-product in the manufacture of common steels. Due to the high generation and accumulation in outdoor deposits of these black slags (EAFS), their use has been authorized as a final product on roads and public or private roads of traffic as one of the structural layers, as raw material in the cement manufacturing and as aggregate for structural concrete. It has now been found that it can also be used as a filler material in biofilters intended for the purification, by means of biofiltration, of gaseous streams contaminated with at least one biodegradable gaseous pollutant, whereby the present invention also contributes to solving the problem generated for the excess of these slags (EAFS), proposing a novel application for that residue.
Mineralógicamente, la escoria negra de horno de arco eléctrico (EAFS) comprende principalmente silicatos de calcio, ferritas y óxidos metálicos. En general, las principales fases mineralógicas presentes son el silicato dicálcico (lamita, β- Ca2Si04), la ferrita dicálcica (2CaOFe203) y la wustita (óxido de hierro (II), FeO). Además de estas fases mineralógicas también pueden estar presentes minerales comunes, tales como olivino (Mg2Si04), mervinita (Ca2Mg(Si04)2), silicato tricálcico (3CaOSi02), millerita marrón (NiS), etc., así como diversos óxidos, por ejemplo, óxido de calcio (CaO) libre, óxido de magnesio (MgO) libre, sílice (Si02), óxido ferroso (FeO), óxido de aluminio o alúmina (A1203), óxido de manganeso (MnO), pentóxido de fórforo (P205), etc. En una realización particular, dicha EAFS comprende CaO (35- 60%), Si02 (9-20%), FeO (15-30%), MgO (5-15%), A1203 (2-9%), MnO (3-10%) y P205 (0, 1-2%)), donde los % son porcentajes en peso respecto al total. No obstante, el experto en la materia entenderá que la composición química de la EAFS que puede ser utilizada en el biofiltro de la invención puede variar dependiendo de los materiales de partida utilizados en la producción de acero, el tipo de acero fabricado, las condiciones del horno, el sistema de enfriamiento, etc. Mineralogically, the black slag of electric arc furnace (EAFS) mainly comprises calcium silicates, ferrites and metal oxides. In general, the main mineralogical phases present are dicalcium silicate (lamite, β- Ca 2 Si04), dicalcium ferrite (2CaOFe 2 03) and wustite (iron oxide (II), FeO). In addition to these mineralogical phases, common minerals may also be present, such as olivine (Mg 2 Si04), mervinite (Ca 2 Mg (Si04) 2 ), tricalcium silicate (3CaOSi0 2 ), brown millerite (NiS), etc., as well as various oxides, for example, free calcium oxide (CaO), free magnesium oxide (MgO), silica (Si0 2 ), ferrous oxide (FeO), aluminum oxide or alumina (A1 2 0 3 ), manganese oxide ( MnO), phosphorus pentoxide (P 2 0 5 ), etc. In a particular embodiment, said EAFS comprises CaO (35-60%), Si0 2 (9-20%), FeO (15-30%), MgO (5-15%), A1 2 0 3 (2-9% ), MnO (3-10%) and P 2 0 5 (0, 1-2%)), where the% are percentages by weight with respect to the total. However, the person skilled in the art will understand that the chemical composition of the EAFS that can be used in the biofilter of the invention may vary depending on the starting materials used in the production of steel, the type of steel manufactured, the conditions of the oven, cooling system, etc.
Las escorias negras de horno de arco eléctrico (EAFSs) se han utilizado habitualmente como áridos para la construcción de carreteras, como materia prima en el
proceso de elaboración de cemento, como relleno en pistas forestales, y, actualmente, se utilizan en el hormigón estructural para construcción con un 80% del árido siderúrgico. Black slags of electric arc furnace (EAFSs) have been commonly used as aggregates for road construction, as raw material in the Cement manufacturing process, as landfill in forest tracks, and, currently, are used in structural concrete for construction with 80% of the steel aggregate.
Por tanto, la utilización de la EAFS como material de relleno o soporte de biofiltros de lecho fijo para el tratamiento de corrientes gaseosas contaminadas, que contienen al menos un contaminante gaseoso biodegradable, por ejemplo, COVs, H2S, CS2, etc., supone una aplicación novedosa para ese residuo de la industria siderúrgica. Dicha EAFS, además, puede ser utilizada tal como se produce, es decir, sin necesidad de tener que realizar ningún acondicionamiento previo salvo un tamizado previo de las partículas de EAFS para utilizar la fracción de tamaño adecuado/deseado. Therefore, the use of EAFS as a filler or support material for fixed bed biofilters for the treatment of contaminated gaseous streams, which contain at least one biodegradable gaseous pollutant, for example, VOCs, H 2 S, CS 2 , etc. , supposes a new application for this waste of the steel industry. Said EAFS, moreover, can be used as it is produced, that is, without the need for any prior conditioning except prior screening of EAFS particles to use the appropriate / desired size fraction.
El empleo de EAFS en biofiltros de lecho fijo, para depurar corrientes gaseosas contaminadas mediante biofiltración presenta numerosas ventajas, entre las que merece la pena destacar su estabilidad frente a largos periodo de operación en régimen continuo, su carácter inerte frente a las distintas corrientes gaseosas a tratar, su capacidad de regulación del pH debido a su composición química, en particular, a su contenido en CaO, su mínimo coste y su gran disponibilidad. Además, su utilización contribuye a la revalorización de un residuo muy abundante. The use of EAFS in fixed-bed biofilters, to purify gaseous streams contaminated by biofiltration has numerous advantages, among which it is worth noting its stability against long periods of operation in a continuous regime, its inert character compared to the different gaseous streams at treat, its ability to regulate pH due to its chemical composition, in particular, its CaO content, its minimum cost and its high availability. In addition, its use contributes to the revaluation of a very abundant residue.
El tamaño de las partículas de la EAFS puede variar dentro de un amplio intervalo; no obstante, en una realización particular, al menos el 50%, típicamente al menos el 60%, ventajosamente al menos el 70%, preferentemente al menos el 80%, más preferentemente al menos el 90%, aún más preferentemente al menos el 95%, y todavía más preferentemente, el 96%, 97%, 98% 99% o 100% de las partículas de EAFS tienen un diámetro medio igual o inferior a 20 mm, típicamente igual o inferior a 10 mm, habitualmente comprendido entre aproximadamente 4 mm y aproximadamente 7 mm, preferentemente entre aproximadamente 5 mm y aproximadamente 6,5 mm. The size of EAFS particles can vary within a wide range; however, in a particular embodiment, at least 50%, typically at least 60%, advantageously at least 70%, preferably at least 80%, more preferably at least 90%, even more preferably at least 95 %, and even more preferably, 96%, 97%, 98% 99% or 100% of the EAFS particles have an average diameter equal to or less than 20 mm, typically equal to or less than 10 mm, usually between about 4 mm and approximately 7 mm, preferably between approximately 5 mm and approximately 6.5 mm.
Tal como se ha mencionado anteriormente, la puesta en práctica del método de biofiltración proporcionado por esta invención requiere la inoculación de las EAFS con microorganismos capaces de degradar el contaminante o contaminantes biodegradables que se desea(n) eliminar. El término "microorganismo", tal como aquí se utiliza incluye bacterias, hongos, levaduras, protozoos, etc. Se conocen numerosos microorganismos capaces de degradar contaminantes biodegradables eventualmente presentes en corrientes gaseosas, por ejemplo, COVs, H2S, CS2, etc.
En una realización particular, el contaminante gaseoso biodegradable presente en la corriente gaseosa es un COV. En el sentido utilizado en esta descripción un "compuesto orgánico volátil" o "COV", de acuerdo con la definición de la US EPA, es un compuesto orgánico que tiene una presión de vapor superior a 0,1 mm Hg en condiciones estándar (25°C y 760 mm Hg), y engloba una amplia gama de compuestos químicos, entre los que se incluyen hidrocarburos alifáticos, hidrocarburos aromáticos, hidrocarburos clorados, aldehidos, cetonas, éteres, ácidos y alcoholes, muchos de los cuales pueden tener efectos adversos para la salud humana o animal, así como sobre el medio ambiente en general, a corto o largo plazo. Ejemplos ilustrativos, no limitativos, de COVs incluyen benceno, clorobenceno, etilbenceno, tolueno, estireno, xileno, pentano, etileno, etanol, fenol, butilacetato, etilacetato, diclorometano, dimetil sulfuro, etc. Cuando el contaminante gaseoso biodegradable presente en la corriente gaseosa es un COV, el biofiltro de la invención comprende un microorganismo capaz de degradar COVs. En el sentido utilizado en la presente invención, un "microorganismo capaz de degradar COVs" es un microorganismo que presenta la capacidad de utilizar un COV como fuente de energía y transformarlo en un producto inocuo o menos nocivo para la salud humana o animal y/o para el medio ambiente. Dicho microorganismo puede ser una bacteria, un hongo, una levadura, un protozoo, etc. Ejemplos ilustrativos, no limitativos, de microorganismos capaces de degradar COVs incluyen hongos y levaduras de los géneros Exophiala, Scedosporium, Paecilomyces, Cladosporium, Cladophialophora, Fusarium o Phanerochaete Chrysosporium (García-Peña et al, 2009. Dynamic numerical reconstruction of a fungal biofiltration system using differential neural network. J. Process Control. 19, 1103-1110; Zhao et al, 2010. Isolation and identification of black yeasts by enrichment on atmospheres of monoaromatic hydrocarbons. Microb. Ecol. 60, 149-156), bacterias de los géneros Acinetobacter, Alcaligenes (e.g., A. xylosoxidans strain Y234, etc.), Bacillus (e.g., B. sphaericus, etc.), Burkholderia (e.g., B. vietnamiensis strain G4, etc.), Corynebacterium, Hyphomicrobium, Pseudomonas (e.g., P. aeruginosa; P. putida strain Fl; etc.), Rhodococcus (e.g., R. fascians, R. pyridinovoran, R. rhodochrous, etc.), o Xanthobacter (Malhautier et al., 2005. Biofiltration of volatile organic compounds, Appl. Microbiol. Biotechnol. 68, 16 - 22), etc.
Ejemplos adicionales de microorganismos capaces de degradar COVs, y, por tanto, útiles en el contexto de la presente invención, incluyen los microrganismos mencionados por Delhomenie y col. [Delhomenie et al, 2005. Biofiltration of Air: A Review. Critica! Reviews in Biotechnology, 25:53-72 (véase la Tabla 3)]. En una realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar COVs pertenecientes a un único género o a una única especie de microorganismos capaces de degradar COVs; alternativamente, en otra realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar COVs pertenecientes a distintos géneros y/o especies de microorganismos; en una realización particular, dichos microorganismos forman un consorcio de microorganismos. As mentioned above, the implementation of the biofiltration method provided by this invention requires the inoculation of EAFS with microorganisms capable of degrading the contaminant or biodegradable contaminants that it is desired to be removed. The term "microorganism" as used herein includes bacteria, fungi, yeasts, protozoa, etc. Numerous microorganisms capable of degrading biodegradable contaminants, possibly present in gaseous streams, are known, for example, VOCs, H 2 S, CS 2 , etc. In a particular embodiment, the biodegradable gaseous pollutant present in the gaseous stream is a VOC. In the sense used in this description a "volatile organic compound" or "VOC", according to the US EPA definition, is an organic compound that has a vapor pressure greater than 0.1 mm Hg under standard conditions (25 ° C and 760 mm Hg), and encompasses a wide range of chemical compounds, including aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, aldehydes, ketones, ethers, acids and alcohols, many of which may have adverse effects for human or animal health, as well as the environment in general, in the short or long term. Illustrative, non-limiting examples of VOCs include benzene, chlorobenzene, ethylbenzene, toluene, styrene, xylene, pentane, ethylene, ethanol, phenol, butylacetate, ethyl acetate, dichloromethane, dimethyl sulfide, etc. When the biodegradable gaseous pollutant present in the gaseous stream is a VOC, the biofilter of the invention comprises a microorganism capable of degrading VOCs. In the sense used in the present invention, a "microorganism capable of degrading VOCs" is a microorganism that has the ability to use a VOC as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or For the enviroment. Said microorganism can be a bacterium, a fungus, a yeast, a protozoan, etc. Illustrative, non-limiting examples of microorganisms capable of degrading VOCs include fungi and yeasts of the genera Exophiala, Scedosporium, Paecilomyces, Cladosporium, Cladophialophora, Fusarium or Phanerochaete Chrysosporium (García-Peña et al, 2009. Dynamic numerical reconstruction of a fungal biofiltration system using differential neural network. J. Process Control. 19, 1103-1110; Zhao et al., 2010. Isolation and identification of black yeasts by enrichment on atmospheres of monoaromatic hydrocarbons. Microb. Ecol. 60, 149-156), bacteria from genera Acinetobacter, Alcaligenes (eg, A. xylosoxidans strain Y234, etc.), Bacillus (eg, B. sphaericus, etc.), Burkholderia (eg, B. vietnamiensis strain G4, etc.), Corynebacterium, Hyphomicrobium, Pseudomonas (eg , P. aeruginosa; P. putida strain Fl; etc.), Rhodococcus (eg, R. fascians, R. pyridinovoran, R. rhodochrous, etc.), or Xanthobacter (Malhautier et al., 2005. Biofiltration of volatile organic compounds , Appl. Microbiol. Biotechnol 68, 16-22), etc. Additional examples of microorganisms capable of degrading VOCs, and therefore useful in the context of the present invention, include the microorganisms mentioned by Delhomenie et al. [Delhomenie et al, 2005. Biofiltration of Air: A Review. Review! Reviews in Biotechnology, 25: 53-72 (see Table 3)]. In a particular embodiment, the biofilter of the invention contains microorganisms capable of degrading VOCs belonging to a single genus or to a single species of microorganisms capable of degrading VOCs; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading VOCs belonging to different genera and / or species of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
En otra realización particular, el contaminante gaseoso biodegradable presente en la corriente gaseosa es H2S; en ese caso, el biofiltro de la invención comprende un microorganismo capaz de degradar H2S. En el sentido utilizado en la presente invención, un "microorganismo capaz de degradar H?S" es un microorganismo que presenta la capacidad de utilizar H2S como fuente de energía y transformarlo en un producto inocuo o menos nocivo para la salud humana o animal y/o para el medio ambiente. Dicho microorganismo puede ser una bacteria, un hongo, una levadura, un protozoo, etc. Ejemplos ilustrativos, no limitativos, de microorganismos capaces de degradar H2S incluyen microorganismos de los géneros Acidthiobacillus (e.g., A. thiooxidans strain AZ11, etc.), Beggiatoa, Macromonas, Pseudomonas (e.g., P. acidovorans strain DMR-11 ; P. putida strain CH11, etc.), Sulfolobus (e.g., S. Metallicus, etc.), Thiobacterium, Thiobacillus (e.g., T. sp., T. denitrificans; T. novellus strain CH3; T. thioparus strain CH11, T. thioparus strain DW44, etc.), Thiomicrospira, Thiomonas, Thiospira, Thiosphaera, etc. (Omri et al, 2011. H2S gas biological removal efficiency and bacterial community diversity in biofilter treating wastewater odor. Bioresour. Technol. 102, 10202 - 10209; Aroca et al., 2007. Comparison on the removal of hydrogen sulfide in biotrickling filters inoculated with Thiobacillus thioparus and Acidithiobacillus thiooxidans. EJB. 10 (4), 514 - 520).
En una realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar H2S pertenecientes a un único género o a una única especie de microorganismos capaces de degradar H2S; alternativamente, en otra realización particular, el biofiltro de la invención contiene microorganismos capaces de degradar H2S pertenecientes a distintos géneros y/o especies de microorganismos; en una realización particular, dichos microorganismos forman un consorcio de microorganismos. In another particular embodiment, the biodegradable gaseous pollutant present in the gaseous stream is H 2 S; in that case, the biofilter of the invention comprises a microorganism capable of degrading H 2 S. In the sense used in the present invention, a "microorganism capable of degrading H? S" is a microorganism that has the ability to use H 2 S as a source of energy and transform it into a harmless or less harmful product for human or animal health and / or for the environment. Said microorganism can be a bacterium, a fungus, a yeast, a protozoan, etc. Illustrative, non-limiting examples of microorganisms capable of degrading H 2 S include microorganisms of the genus Acidthiobacillus (eg, A. thiooxidans strain AZ11, etc.), Beggiatoa, Macromonas, Pseudomonas (eg, P. acidovorans strain DMR-11; P Putida strain CH11, etc.), Sulfolobus (eg, S. Metallicus, etc.), Thiobacterium, Thiobacillus (eg, T. sp., T. denitrificans; T. novellus strain CH3; T. thioparus strain CH11, T. thioparus strain DW44, etc.), Thiomicrospira, Thiomonas, Thiospira, Thiosphaera, etc. (Omri et al, 2011. H2S gas biological removal efficiency and bacterial community diversity in biofilter treating wastewater odor. Bioresour. Technol. 102, 10202-10209; Aroca et al., 2007. Comparison on the removal of hydrogen sulfide in biotrickling filters inoculated with Thiobacillus thioparus and Acidithiobacillus thiooxidans. EJB. 10 (4), 514-520). In a particular embodiment, the biofilter of the invention contains microorganisms capable of degrading H 2 S belonging to a single genus or to a single species of microorganisms capable of degrading H 2 S; alternatively, in another particular embodiment, the biofilter of the invention contains microorganisms capable of degrading H 2 S belonging to different genera and / or species of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
En otra realización particular, el contaminante gaseoso biodegradable presente en la corriente gaseosa es CS2; en ese caso, el biofiltro de la invención comprende un microorganismo capaz de degradar CS2. En el sentido utilizado en la presente invención, un "microorganismo capaz de degradar CS?" es un microorganismo que presenta la capacidad de utilizar CS2 como fuente de energía y transformarlo en un producto inocuo o menos nocivo para la salud humana o animal y/o para el medio ambiente. Dicho microorganismo 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 (P. denitrificans, etc.), Thioalkalimicrobium (e.g., T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (e.g., T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (e.g., Thiobacillus strain TJ330; T. thioparus strain TK-m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (e.g., T. ramose, etc.), etc. (Pol et al, 2007. Isolation of a carbón disulfide utilizing Thiomonas sp. and its application in a biotrickling filter. Appl. Microbiol. Biotechnol. 74, 439 - 446). In another particular embodiment, the biodegradable gaseous pollutant present in the gaseous stream is CS 2 ; in that case, the biofilter of the invention comprises a microorganism capable of degrading CS 2 . In the sense used in the present invention, a "microorganism capable of degrading CS?" It 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 for the environment. Said microorganism 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 (P. denitrificans, etc.), Thioalkalimicrobium (eg, T. aerophilum, T. sibericum, etc.), Thioalkalivibrio (eg, T. versutus, T. nitratis, T. denitrificans, etc.), Thiobacillus (eg, Thiobacillus strain TJ330; T. thioparus strain TK-m; T. sp. strain DSM 8985, etc.), Thiomonas, Thiothrix (eg, T. ramose, etc.), etc. (Pol et al, 2007. Isolation of a carbon disulfide utilizing Thiomonas sp. And its application in a biotrickling filter. Appl. Microbiol. Biotechnol. 74, 439-446).
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 microorganismos 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 de microorganismos; en una realización particular, dichos microorganismos forman un consorcio de microorganismos. In a particular embodiment, the biofilter of the invention contains microorganisms capable of degrading CS 2 belonging to a single genus or 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 of microorganisms; In a particular embodiment, said microorganisms form a consortium of microorganisms.
El experto en la materia entenderá que los microorganismos a inocular en el material de relleno del biofiltro de la invención serán elegidos en función del
contaminante biodegradable presente en la corriente gaseosa a depurar. Dichos microorganismos tendrán la capacidad potencial para degradar dichos contaminantes biodegradables. The person skilled in the art will understand that the microorganisms to be inoculated in the biofilter filler material of the invention will be chosen according to the biodegradable pollutant present in the gas stream to be purified. Such microorganisms will have the potential capacity to degrade said biodegradable contaminants.
Algunos de dichos microorganismos capaces de degradar contaminantes biodegradables útiles para la puesta en práctica de la presente invención se encuentran disponibles comercialmente o en colecciones de cultivos. Asimismo, el experto en la materia puede encontrar e identificar, por métodos convencionales, otros microorganismos capaces de degradar dichos contaminantes biodegradables a partir de diversas fuentes. Efectivamente, el experto en la materia reconoce que pueden vivir microorganismos que toleran el contaminante biodegradable en cuestión (e.g., COVs, H2S, CS2, etc.) en muestras procedentes de sitios contaminados con dicho contaminante, por ejemplo, áreas o instalaciones en donde se usan o generan corrientes gaseosas que contienen dichos contaminantes biodegradables, suelos contaminados con dichos contaminantes, lodos activados, compostaje, etc.; por tanto, mediante una selección de los cultivos de los microorganismos presentes en dichas muestras y/o un periodo de aclimatación al contaminante es posible encontrar cepas de microorganismos capaces de degradar el contaminante biodegradable en cuestión. Some of said microorganisms capable of degrading biodegradable contaminants useful for the implementation of the present invention are commercially available or in crop collections. Likewise, the person skilled in the art can find and identify, by conventional methods, other microorganisms capable of degrading said biodegradable contaminants from various sources. Indeed, the person skilled in the art recognizes that microorganisms that tolerate the biodegradable contaminant in question (eg, VOCs, H 2 S, CS 2 , etc.) can live in samples from sites contaminated with said contaminant, for example, areas or facilities wherein gaseous streams containing said biodegradable contaminants, soils contaminated with said contaminants, activated sludge, composting, etc .; are used or generated. therefore, by selecting the cultures of the microorganisms present in said samples and / or a period of acclimatization to the contaminant it is possible to find strains of microorganisms capable of degrading the biodegradable contaminant in question.
La capacidad de un microorganismo de degradar un contaminante biodegradable, por ejemplo, COVs, H2S, CS2, etc., puede determinarse por cualquier procedimiento convencional, conocido por los técnicos en la materia, que permita conocer si un microorganismo utiliza dicho contaminante biodegradable, por ejemplo, poniendo en contacto un cultivo de dicho microorganismo con dicho contaminante biodegradable (e.g., uno o más COVs, H2S, CS2, etc.) e incubando bajo condiciones apropiadas para el desarrollo y crecimiento del microorganismo en cuestión; bajo esas condiciones, la disminución de la cantidad de dicho contaminante biodegradable (e.g., uno o más COVs, H2S, CS2, etc.) es indicativa de que el microorganismo analizado es capaz de degradar dicho contaminante biodegradable. La cantidad de contaminante biodegradable puede ser determinada por métodos convencionales, por ejemplo, mediante cromatografía (e.g., cromatografía de gases, etc.). Si se desea, el microorganismo puede encontrarse soportado sobre un material de relleno del tipo utilizado en el biofiltro de la invención (EAFS) y el contaminante biodegradable puede
estar contenido en una corriente de aire, preferentemente saturada en vapor de agua en agua antes de ponerla en contacto con el microorganismo. The ability of a microorganism to degrade a biodegradable pollutant, for example, VOCs, H 2 S, CS 2 , etc., can be determined by any conventional procedure, known to those skilled in the art, that allows to know if a microorganism uses said contaminant biodegradable, for example, by contacting a culture of said microorganism with said biodegradable contaminant (eg, one or more VOCs, H 2 S, CS 2 , etc.) and incubating under appropriate conditions for the development and growth of the microorganism in question; Under these conditions, the decrease in the amount of said biodegradable contaminant (eg, one or more VOCs, H 2 S, CS 2 , etc.) is indicative that the analyzed microorganism is capable of degrading said biodegradable contaminant. The amount of biodegradable contaminant can be determined by conventional methods, for example, by chromatography (eg, gas chromatography, etc.). If desired, the microorganism may be supported on a filler material of the type used in the biofilter of the invention (EAFS) and the biodegradable contaminant may be contained in a stream of air, preferably saturated with water vapor in 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 el contaminante o contaminantes biodegradable(s) (e.g., uno o más COVs, H2S, CS2, etc.) así como unos medios para la entrada de la corriente de gaseosa que contiene dicho contaminante o contaminantes, adecuadamente saturada en vapor de agua previamente, y unos medios para la salida de la corriente gaseosa descargada total o parcialmente de dicho o dichos contaminantes biodegradables. El biofiltro está provisto también de manera preferente con medios de riego para aportar de manera periódica nutrientes a los microorganismos. Opcionalmente, si se desea, se pueden incluir dispositivos para medir la temperatura de entrada de la corriente gaseosa que contiene los contaminanbtes biodegradables a tratar ya que puede afectar al proceso metabólico de los microorganismos capaces de degradar a dichos contaminantes biodegradables, o para medir el pH ya que durante la operación del método de biofiltración proporcionado por esta invención se pueden generar productos ácidos que pueden afectar adversamente a la actividad del biofiltro. Adicionalmente, se pueden incluir medidores de pérdida de carga, ya que un exceso de biomasa puede llegar a colmatar e inutilizar el sistema de biofiltración. El biofiltro 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 the biodegradable pollutant (s) (eg, one or more VOCs, H 2 S, CS 2 , etc.) are located. .) as well as means for the entry of the gas stream containing said contaminant or contaminants, suitably saturated in water vapor previously, and means for the exit of the gas stream totally or partially discharged from said or said biodegradable contaminants. The biofilter is also preferably provided with irrigation means to periodically provide nutrients to the microorganisms. Optionally, if desired, devices can be included to measure the inlet temperature of the gas stream containing the biodegradable contaminants to be treated since it can affect the metabolic process of microorganisms capable of degrading said biodegradable contaminants, or to measure the pH since during the operation of the biofiltration method provided by this invention acid products can be generated that can adversely affect the activity of the biofilter. Additionally, load loss meters can be included, since excess biomass can fill up and render the biofiltration system useless. The biofilter of the invention can be designed in various shapes and dimensions, using the appropriate materials for it.
La simplicidad estructural del biofiltro 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 biofiltro 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 en serie, 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 biofiltro 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 contaminante biodegradable.
Método de biofiltración de la invención The structural simplicity of the biofilter 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 biofilter 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 in series, 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, similarly , the gaseous outflow of said second biofilter of the invention is introduced into the third of the biofilters of the invention, and so on until the definitive exit of the gaseous stream totally or partially discharged from biodegradable contaminant. Biofiltration method of the invention
El biofiltro de la invención puede ser utilizado para depurar gases contaminados con uno o más contaminantes biodegradables mediante biofiltración. Por tanto, en otro aspecto, la invención se relaciona con un método para depurar una corriente gaseosa que contiene, al menos, un contaminante gaseoso biodegradable mediante biofiltración, en adelante "método de biofiltración de la invención", que comprende hacer pasar dicha corriente gaseosa que contiene, al menos, un contaminante gaseoso biodegradable a través de un biofiltro de la invención, es decir, un biofiltro que comprende escoria negra de horno de arco eléctrico (EAFS) como material de relleno y microorganismos capaces de degradar dicho contaminante biodegradable. The biofilter of the invention can be used to purify gases contaminated with one or more biodegradable contaminants by biofiltration. Therefore, in another aspect, the invention relates to a method for purifying a gas stream containing at least one biodegradable gaseous pollutant by biofiltration, hereinafter "biofiltration method of the invention", which comprises passing said gas stream containing at least one biodegradable gaseous pollutant through a biofilter of the invention, that is, a biofilter comprising black arc furnace slag (EAFS) as filler material and microorganisms capable of degrading said biodegradable pollutant.
En el sentido utilizado en esta descripción, la expresión "depurar una corriente gaseosa que contiene, al menos, un contaminante gaseoso biodegradable" incluye tanto la eliminación prácticamente total del contaminante (o contaminantes) gaseoso biodegradable presente en una corriente gaseosa que contiene dicho contaminante como la reducción de la cantidad de dicho contaminante (o contaminantes) gaseoso biodegradable presente en una corriente gaseosa que contiene dicho contaminante hasta niveles permitidos por la legislación o que no resulten nocivos para la salud humana o animal y/o para el medio ambiente. In the sense used in this description, the expression "purifying a gaseous stream containing at least one biodegradable gaseous pollutant" includes both the virtually total elimination of the biodegradable gaseous pollutant (or pollutants) present in a gaseous stream containing said pollutant as reducing the amount of said biodegradable gaseous pollutant (or pollutants) present in a gaseous stream that contains said pollutant to levels permitted by legislation or that are not harmful to human or animal health and / or the environment.
El término "biodegradable", tal como aquí se utiliza, se refiere a un compuesto químico que puede ser descompuesto por acción de agentes biológicos, por ejemplo, un microorganismo, etc. Por tanto, un "contaminante gaseoso biodegradable" es un compuesto químico considerado como contaminante, en estado gaseoso, que puede ser descompuesto por acción de agentes biológicos, por ejemplo, un microorganismo. Ejemplos ilustrativos, no limitativos, de contaminantes gaseosos biodegradables incluyen compuestos orgánicos volátiles (COVs), disulfuro de hidrógeno (H2S), sulfuro de carbono (CS2), etc. The term "biodegradable", as used herein, refers to a chemical compound that can be decomposed by the action of biological agents, for example, a microorganism, etc. Therefore, a "biodegradable gaseous pollutant" is a chemical compound considered as a pollutant, in a gaseous state, which can be decomposed by the action of biological agents, for example, a microorganism. Illustrative, non-limiting examples of biodegradable gaseous pollutants include volatile organic compounds (VOCs), hydrogen disulfide (H 2 S), carbon sulphide (CS 2 ), etc.
El método de biofiltración de la invención puede ser utilizado para depurar una corriente gaseosa contaminada con uno o más contaminantes gaseosos biodegradables. En una realización particular, el método de biofiltración de la invención se utiliza para depurar una corriente gaseosa contaminada con un único contaminante gaseoso
biodegradable. En otra realización particular, el método de biofiltración de la invención se utiliza para depurar una corriente gaseosa contaminada con dos o más contaminantes gaseosos biodegradables. The biofiltration method of the invention can be used to purify a gaseous stream contaminated with one or more biodegradable gaseous pollutants. In a particular embodiment, the biofiltration method of the invention is used to purify a gaseous stream contaminated with a single gaseous pollutant. biodegradable. In another particular embodiment, the biofiltration method of the invention is used to purify a gaseous stream contaminated with two or more biodegradable gaseous pollutants.
Aunque prácticamente el método de biofiltración de la invención puede ser utilizado para depurar una corriente gaseosa contaminada con cualquier contaminante gaseoso biodegradable, es decir, con cualquier contaminante gaseoso que puede ser descompuesto por acción de un agente biológico, tal como un microorganismo capaz de degradar dicho contaminante gaseoso, en una realización particular, dicho contaminante gaseoso biodegradable se selecciona del grupo formado por COVs, H2S, CS2, y cualquier combinación de los mismos. Por tanto, en una realización particular, dicha corriente gaseosa contaminada a depurar comprende uno o más COVs. En otra realización particular, dicha corriente gaseosa contaminada a depurar comprende H2S. En otra realización particular, dicha corriente gaseosa contaminada a depurar comprende CS2. En otra realización particular, dicha corriente gaseosa contaminada a depurar comprende uno o más COVs, y un contaminante gaseoso biodegradable seleccionado entre H2S y CS2. En otra realización particular, dicha corriente gaseosa contaminada a depurar comprende, al menos, un contaminante gaseoso biodegradable seleccionado entre H2S y CS2, y, opcionalmente, uno o más COVs. En otra realización particular, dicha corriente gaseosa contaminada a depurar comprende uno o más COVs, H2S y CS2. Although practically the biofiltration method of the invention can be used to purify a gaseous stream contaminated with any biodegradable gaseous pollutant, that is, with any gaseous pollutant that can be decomposed by the action of a biological agent, such as a microorganism capable of degrading said Gaseous pollutant, in a particular embodiment, said biodegradable gaseous pollutant is selected from the group consisting of VOCs, H 2 S, CS 2 , and any combination thereof. Therefore, in a particular embodiment, said polluted gaseous stream to be purified comprises one or more VOCs. In another particular embodiment, said contaminated gas stream to be purified comprises H 2 S. In another particular embodiment, said contaminated gas stream to be purified comprises CS 2 . In another particular embodiment, said polluted gaseous stream to be purified comprises one or more VOCs, and a biodegradable gaseous pollutant selected from H 2 S and CS 2 . In another particular embodiment, said polluted gas stream to be purified comprises at least one biodegradable gaseous pollutant selected from H 2 S and CS 2 , and, optionally, one or more VOCs. In another particular embodiment, said polluted gas stream to be purified comprises one or more VOCs, H 2 S and CS 2 .
En una realización particular, el método de biofiltración de la invención comprende la realización de una etapa previa de inoculación de las EAFS (material de relleno del biofiltro de la invención) con microorganismos capaces de degradar el contaminante o contaminantes biodegradable(s) a tratar, con el objetivo de formar una biopelícula de dichos microorganismos sobre el material de relleno del biofiltro de la invención que posibilite la depuración de la corriente gaseosa contaminada a depurar. La inoculación de las EAFS se puede realizar directamente con microorganismos capaces de degradar el contaminante o contaminantes gaseoso(s) biodegradable(s) estandarizados, o bien, con un inoculo obtenido preliminarmente mediante aclimatación de una determinada biomasa al contaminante o contaminantes a tratar. 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, utilizando un reactor de aclimatación continuo o discontinuo. En general, la aclimatación comprende poner en contacto una biomasa rica en microorganismos, como por ejemplo lodo biológico de una estación depuradora de agua residual (EDAR), con una corriente gaseosa que contiene el contaminante o contaminantes gaseoso(s) biodegradable(s) a tratar, de tal modo que se desarrolle una población óptima de microorganismos capaces de degradar dicho(s) contaminante(s). La cantidad de contaminante o contaminantes gaseoso(s) biodegradable(s) presente en dicha corriente gaseosa puede variar dentro de un amplio intervalo; no obstante, en la práctica se suele empezar utilizando una corriente gaseosa que contiene el contaminante o contaminantes gaseoso(s) biodegradable(s) a tratar en una cantidad relativamente baja, generalmente igual o inferior a 100 partes por millón en volumen (ppmv) [1 ppmv = 1 μg x mi-1], típicamente comprendida entre 25 y 100 ppmv. La cantidad de contaminante o contaminantes gaseoso(s) biodegradable(s) presente en dicha corriente gaseosa puede ir aumentándose, si se desea, a medida que aumenta la aclimatación de los microorganismos a dicho(s) contaminante o contaminantes gaseoso(s) biodegradable(s). El experto en la materia puede generar, por métodos convencionales, corrientes gaseosas conteniendo diferentes concentraciones de contaminante o contaminantes gaseoso(s) biodegradable(s) a analizar, y seleccionar aquélla que proporcione una mejor aclimatación de los microorganismos presentes en el medio biológico elegido al contaminante o contaminantes. Asimismo, caudales de dicha corriente gaseosa que proporcionen un tiempo de residencia [en inglés, "EBRT" (empty bed residence time), que relaciona el caudal de la corriente gaseosa con el tamaño del biofiltro según la fórmula EBRT = Vf / Q, donde Vf es el volumen del biofiltro vacío y Q es el caudal de la corriente gaseosa, y da una idea del tiempo de tratamiento] igual o inferior a 3 minutos, típicamente, entre 2 y 3 minutos aproximadamente, suelen ser adecuados durante la etapa de aclimatación. Las condiciones para aclimatar los microorganismos contenidos inicialmente en la biomasa a dicho(s) contaminante o contaminantes gaseoso(s) biodegradable(s) dependen, en general, de diversos factores, por ejemplo, del contenido en contaminante o contaminantes gaseoso(s) biodegradable(s) en la corriente gaseosa utilizada, del tiempo de residencia, de la duración del tratamiento, etc. Durante esta etapa de aclimatación previa, al igual que durante la biofiltración propiamente dicha, puede ser necesario aportar una solución de nutrientes con el fin de favorecer el
metabolismo de los microorganismos capaces de degradar dichos(s) contaminante o contaminantes gaseoso(s) biodegradable(s). El aporte de dicha solución de nutrientes puede realizarse mediante riego en el caso de la aclimatación en el biofiltro o mediante adicción/remplazo al medio líquido en el caso de la aclimatación en un reactor de aclimatación. In a particular embodiment, the biofiltration method of the invention comprises performing a previous step of inoculating the EAFS (biofilter filler material of the invention) with microorganisms capable of degrading the biodegradable contaminant (s) to be treated, with the aim of forming a biofilm of said microorganisms on the biofilter filler material of the invention that enables the purification of the contaminated gaseous stream to be purified. The inoculation of the EAFS can be carried out directly with microorganisms capable of degrading the standardized biodegradable pollutant (s) or pollutants (s), or with an inoculum obtained preliminary by acclimatization of a given biomass to the contaminant or contaminants to be treated. Said acclimatization can be carried out in any suitable installation, for example, in the biofilter of the invention itself, or, alternatively, in a laboratory or in a plant pilot, using a continuous or discontinuous acclimatization reactor. In general, acclimatization comprises contacting a biomass rich in microorganisms, such as biological sludge from a wastewater treatment plant (WWTP), with a gaseous stream containing the biodegradable pollutant (s) to treat, so that an optimal population of microorganisms capable of degrading said contaminant (s) is developed. The amount of biodegradable gaseous pollutant (s) present in said gaseous stream can vary within a wide range; however, in practice it is usually started using a gaseous stream containing the biodegradable pollutant (s) to be treated in a relatively low amount, generally equal to or less than 100 parts per million by volume (ppmv) [ 1 ppmv = 1 μg x mi -1 ], typically between 25 and 100 ppmv. The amount of biodegradable gaseous pollutant (s) present in said gaseous stream can be increased, if desired, as the acclimatization of the microorganisms to said biodegradable gaseous pollutant (s) increases ( s). The person skilled in the art can generate, by conventional methods, gaseous streams containing different concentrations of pollutant or biodegradable pollutant (s) to be analyzed, and select the one that provides a better acclimatization of the microorganisms present in the biological medium chosen at pollutant or contaminants. Likewise, flows of said gaseous stream that provide a residence time [in English, "EBRT" (empty bed residence time), which relates the flow of the gaseous stream with the size of the biofilter according to the formula EBRT = V f / Q, where V f is the volume of the empty biofilter and Q is the flow rate of the gas stream, and gives an idea of the treatment time] equal to or less than 3 minutes, typically, approximately 2 to 3 minutes, are usually adequate during the stage acclimatization The conditions for acclimatizing the microorganisms initially contained in the biomass to said biodegradable pollutant (s) or pollutants (s) depend, in general, on various factors, for example, on the biodegradable gaseous pollutant or pollutant content (s) (s) in the gas stream used, residence time, duration of treatment, etc. During this stage of previous acclimatization, as during the biofiltration itself, it may be necessary to provide a nutrient solution in order to favor Metabolism of microorganisms capable of degrading said pollutant (s) or biodegradable gaseous pollutant (s). The contribution of said nutrient solution can be carried out by irrigation in the case of acclimatization in the biofilter or by addiction / replacement to the liquid medium in the case of acclimatization in an acclimatization reactor.
Con objeto de acelerar el arranque del biofiltro se prefiere que la aclimatación tenga lugar fuera del propio biofiltro, y, en particular, en un sistema de aclimatación continuo. En este sentido, aunque las condiciones para aclimatar pueden variar ampliamente, en una realización particular, dicha aclimatación comprende el borboteo sobre un medio líquido rico en microorganismos en constante agitación (por ejemplo, un lodo de una EDAR) de una corriente gaseosa que comprende uno o más contaminantes gaseosos biodegradables en una cantidad igual o inferior a aproximadamente 100 ppmv, típicamente comprendida entre 25 ppmv y 100 ppmv, de manera continua, con un caudal que proporciona un tiempo de residencia igual o inferior a 3 minutos, típicamente, entre 2 y 3 minutos aproximadamente, durante aproximadamente al menos 30 días, preferentemente durante aproximadamente 60 días. En la Figura 1 se representa una realización particular de un sistema de aclimatación en continuo para la obtención de inoculo para el arranque del biofiltro de la invención provisto de: (1) entrada de corriente gaseosa, (2) punto de muestreo, (3) medio líquido bajo agitación, (4) punto de muestreo y (5) salida de corriente gaseosa. In order to accelerate the biofilter startup, it is preferred that the acclimatization takes place outside the biofilter itself, and, in particular, in a continuous acclimatization system. In this sense, although the conditions for acclimatization can vary widely, in a particular embodiment, said acclimatization comprises the bubbling on a liquid medium rich in microorganisms in constant agitation (for example, a sludge from an WWTP) of a gas stream comprising one or more biodegradable gaseous pollutants in an amount equal to or less than about 100 ppmv, typically between 25 ppmv and 100 ppmv, continuously, with a flow rate that provides a residence time equal to or less than 3 minutes, typically between 2 and 3 minutes approximately, for at least 30 days, preferably for approximately 60 days. A particular embodiment of a continuous acclimatization system for obtaining inoculum for starting the biofilter of the invention provided with: (1) gaseous current inlet, (2) sampling point, (3) is shown in Figure 1. liquid medium under stirring, (4) sampling point and (5) gaseous current outlet.
Una vez que se han desarrollado los microorganismos capaces de degradar dicho contaminante o contaminantes gaseoso(s) biodegradable(s), se obtiene un medio líquido "activado", es decir, un medio líquido que contiene el microorganismo o microorganismos capaces de degradar el contaminante o contaminantes gaseoso(s) biodegradable(s) en cuestión, el cual se utiliza para inocular las EAFS. De manera preferente, la inoculación se lleva a cabo en el propio biofiltro, cargado previamente con el material de relleno, por ejemplo, mediante riego con dicho medio líquido "activado". Tras riegos sucesivos, se forma la biopelícula de microorganismos, con lo que el biofiltro ya está listo para la depuración de corrientes gaseosas contaminadas con el contaminante o contaminantes gaseoso(s) biodegradable(s) en cuestión.
En una variante de la invención, se contempla que el procedimiento de aclimatación iniciado fuera del biofiltro continúe en el propio biofiltro. Para ello, tras inocular el biofiltro previamente cargado con material de relleno, se alimenta durante un periodo breve (típicamente 2 semanas) con corrientes con concentraciones de contaminantes bajas, normalmente no superiores a 100 ppmv. Once the microorganisms capable of degrading said biodegradable pollutant (s) have been developed, a "activated" liquid medium is obtained, that is, a liquid medium containing the microorganism or microorganisms capable of degrading the contaminant or biodegradable gas contaminants (s) in question, which is used to inoculate the SAIs. Preferably, the inoculation is carried out in the biofilter itself, previously loaded with the filler material, for example, by irrigation with said "activated" liquid medium. After successive irrigation, the biofilm of microorganisms is formed, so that the biofilter is now ready for the purification of gaseous streams contaminated with the biodegradable pollutant (s) in question. In a variant of the invention, it is contemplated that the acclimatization process initiated outside the biofilter continues in the biofilter itself. To do this, after inoculating the biofilter previously loaded with filler material, it is fed for a short period (typically 2 weeks) with currents with low pollutant concentrations, normally not exceeding 100 ppmv.
En otra realización alternativa, se contempla que todo el procedimiento de aclimatación tenga lugar en el propio biofiltro. Así, el regado del material de relleno contenido en el biofiltro con un medio líquido que presente diversas poblaciones de microorganismos, como por ejemplo lodo biológico de una EDAR, junto al paso de una corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable, preferentemente en una cantidad relativamente baja, también conduce a la formación de la biopelícula de microorganismos sobre el material de relleno, responsable de la depuración. In another alternative embodiment, it is contemplated that the entire acclimatization process takes place in the biofilter itself. Thus, the watering of the filler material contained in the biofilter with a liquid medium that presents various populations of microorganisms, such as biological sludge from an WWTP, together with the passage of a gas stream containing at least one biodegradable gaseous pollutant, preferably in a relatively low amount also leads to the formation of the biofilm of microorganisms on the filler material, responsible for purification.
Diversas estrategias de aclimatación útiles en biofiltros convencionales se encuentran descritas en el estado de la técnica [Elias, A. y col. (2010). J. Air & Waste Manage. Assoc. 60: 959-967]. Various acclimatization strategies useful in conventional biofilters are described in the prior art [Elias, A. et al. (2010). J. Air & Waste Manage. Assoc. 60: 959-967].
El método de biofiltración de la invención comprende hacer pasar dicha corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a través de un biofiltro de la invención. La cantidad o concentración de contaminante o contaminantes gaseoso(s) biodegradable(s) presente en dicha corriente gaseosa a depurar puede variar dentro de un amplio intervalo. No obstante, en una realización particular, dicha corriente gaseosa a depurar contiene al menos un contaminante gaseoso biodegradable en una cantidad comprendida entre aproximadamente 50 ppmv y aproximadamente 250 ppmv. Dado que la corriente gaseosa contaminada a depurar puede contener uno o más contaminantes gaseosos biodegradables, en la presente invención, a menos que se indique lo contrario, las cantidades o concentraciones de contaminante gaseoso biodegradable expresadas se refieren a cantidades o concentraciones totales de contaminante gaseoso biodegradable, de tal modo que si existe más de un contaminante gaseoso biodegradable en la corriente gaseosa contaminada a depurar, la cantidad o concentración total resulta de la suma de las cantidades o concentraciones de cada uno de ellos.
Asimismo, el tiempo de residencia, o cantidad promedio de tiempo que puede permanecer la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar en contacto con el material de relleno (EAFS) del biofiltro de la invención puede variar dentro de un amplio intervalo. No obstante, en una realización particular, dicho tiempo de residencia está comprendido entre aproximadamente 10 segundos y aproximadamente 80 segundos, típicamente alrededor de 60 segundos aproximadamente. Midiendo la concentración del contaminante o contaminantes gaseoso(s) biodegradable(s) en cuestión a la salida del biofiltro de la invención se puede comprobar el funcionamiento del material de relleno y de los microorganismos capaces de degradar dicho(s) contaminante o contaminantes gaseoso(s) biodegradable(s), de manera que, en caso de que la eficacia del biofiltro decaiga, tomar las medidas oportunas para aumentar la eficacia, por ejemplo, regando 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 at least one biodegradable gaseous pollutant through a biofilter of the invention. The amount or concentration of biodegradable pollutant (s) or pollutant (s) present in said gaseous stream to be purified may vary within a wide range. However, in a particular embodiment, said gaseous stream to be purified contains at least one biodegradable gaseous pollutant in an amount between about 50 ppmv and about 250 ppmv. Since the contaminated gaseous stream to be purified may contain one or more biodegradable gaseous pollutants, in the present invention, unless otherwise indicated, the amounts or concentrations of biodegradable gaseous pollutant expressed refer to total amounts or concentrations of biodegradable gaseous pollutant. , so that if there is more than one biodegradable gaseous pollutant in the polluted gaseous stream to be purified, the total amount or concentration results from the sum of the amounts or concentrations of each of them. Also, the residence time, or average amount of time that the gaseous stream can remain that contains at least one biodegradable gaseous pollutant to be cleaned in contact with the filler material (EAFS) of the biofilter of the invention can vary over a wide range. . However, in a particular embodiment, said residence time is between about 10 seconds and about 80 seconds, typically about 60 seconds. By measuring the concentration of the biodegradable gaseous pollutant (s) in question at the exit of the biofilter of the invention, the operation of the filler material and the microorganisms capable of degrading said gaseous pollutant (s) can be checked ( s) biodegradable (s), so that, if the effectiveness of the biofilter declines, take appropriate measures to increase the effectiveness, for example, watering the filler material with a nutrient solution, as mentioned below. , to recover normalcy.
La corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar mediante el método de biofiltración de la invención puede proceder de diversos focos contaminantes, por ejemplo, de instalaciones de procesos que utilizan o generan dichos contaminantes, tales como las instalaciones de fabricación de fibras de celulosa, industria alimentaria de envoltura sintética, industria farmacéutica, industria química, fabricación de pinturas, etc. The gaseous stream containing at least one biodegradable gaseous pollutant to be purified by the biofiltration method of the invention can come from various pollutant sources, for example, from process facilities that use or generate said pollutants, such as fiber manufacturing facilities. of cellulose, synthetic wrap food industry, pharmaceutical industry, chemical industry, paint manufacturing, etc.
En la práctica resulta conveniente que la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar esté húmeda, o sea saturada en vapor de agua, 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 al menos un contaminante gaseoso biodegradable a depurar, 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 al menos un contaminante gaseoso biodegradable la humedad necesaria, situada antes
del biofiltro. 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 saturación de la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar y minimizar el mantenimiento del sistema. En una realización particular, la humedad relativa de la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable de entrada al biofiltro de la invención es igual o superior al 70%, habitualmente igual o superior al 80%, ventajosamente igual o superior al 90%, preferentemente igual o superior al 95%, aún más preferentemente igual o superior al 99%. In practice, it is convenient that the gas stream containing at least one biodegradable pollutant gas to be purified is moist, or saturated in water vapor, since the humidity of said gas stream 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 gas stream containing at least one biodegradable pollutant to be purified, for which said gas stream is contacted with an aqueous medium. , for example, water, before being introduced into the biofilter. The aqueous medium used in 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 gas stream containing at least one contaminant. biodegradable gas the necessary humidity, located before of the biofilter. 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 saturation of the gas stream containing the less a biodegradable gaseous pollutant to purify and minimize system maintenance. In a particular embodiment, the relative humidity of the gas stream containing at least one biodegradable gaseous pollutant entering the biofilter of the invention is equal to or greater than 70%, usually equal to or greater than 80%, advantageously equal to or greater than 90% , preferably equal to or greater than 95%, even more preferably equal to or greater than 99%.
Durante el proceso de biofiltración, la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar pasa a través del material de relleno que sirve de soporte a los microorganismos en crecimiento capaces de degradar dicho(s) contaminante(s) gaseoso(s) biodegradable(s). La degradación de dicho(s) contaminante(s) ocurre, en general, previa transferencia de la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a un medio líquido en donde es utilizado como fuente de carbono y/o energía. La utilización de dicho contaminante implica una serie de reacciones químicas que conducen a la descomposición o degradación el contaminante, por ejemplo, a su oxidación parcial o total, así como la producción de biomasa capaz de degradar dicho(s) contaminante(s), con lo que el método de biofiltración de la invención da lugar a una degradación prácticamente completa del contaminante o contaminantes gaseoso(s) biodegradable(s) 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 dicho(s) contaminante o contaminantes gaseoso(s) biodegradable(s). During the biofiltration process, the gaseous stream containing at least one biodegradable pollutant to be purified passes through the filler material that supports the growing microorganisms capable of degrading said gaseous pollutant (s). biodegradable (s). The degradation of said pollutant (s) occurs, in general, after transferring the gas stream containing at least one biodegradable gaseous pollutant to a liquid medium where it is used as a source of carbon and / or energy. The use of said contaminant implies a series of chemical reactions that lead to the decomposition or degradation of the contaminant, for example, to its partial or total oxidation, as well as the production of biomass capable of degrading said contaminant (s), with what the biofiltration method of the invention results in a practically complete degradation of the biodegradable pollutant or gaseous pollutants (s) generating non-hazardous (harmless) products for human or animal health and / or the environment and a current Total or partially discharged gas in said pollutant (s) or biodegradable gaseous pollutant (s).
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 al menos un contaminante gaseoso biodegradable a través de uno o más biofiltros de la invención. Así, en una realización particular, el método de biofiltración de la invención comprende hacer pasar la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar 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 al menos un contaminante gaseoso biodegradable a depurar 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 al menos un contaminante gaseoso biodegradable a depurar se hace pasar a través del primero de los biofiltros de la invención y la corriente gaseosa de salida de dicho primer biofiltro de la invención, que estará al menos parcialmente descargada en dicho(s) contaminante(s) gaseoso(s) biodegradable(s), se hace pasar a través del segundo biofiltro de la invención, y, de manera similar, la corriente gaseosa de salida de dicho segundo biofiltro de la invención, que estará aún más descargada en dicho(s) contaminante(s) gaseoso(s) biodegradable(s), 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 dicho(s) contaminante(s) gaseoso(s) biodegradable(s). Por tanto, el método de biofiltración de la invención permite alcanzar una eficacia de eliminación de dicho(s) contaminante(s) gaseoso(s) biodegradable(s) del 100%, o muy próxima al 100%, en relación con la cantidad de dicho(s) contaminante(s) gaseoso(s) biodegradable(s) presente en la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a depurar. The person skilled in the art will understand that the biofiltration method of the invention includes the possibility of passing the gas stream containing at least one biodegradable gaseous pollutant through one or more biofilters of the invention. Thus, in a particular embodiment, the biofiltration method of the invention comprises passing the gaseous stream containing at least one biodegradable gaseous pollutant to be purified through a single biofilter of the invention. In other Particular embodiment, the biofiltration method of the invention comprises passing the gas stream containing at least one biodegradable gaseous pollutant to be purified through two or more biofilters of the invention, for example 2, 3, 4, or even more, operationally connected to each other; in this case, the gaseous stream containing at least one biodegradable pollutant to be purified is passed through the first of the biofilters of the invention and the gaseous outlet of said first biofilter of the invention, which will be at least partially discharged in said biodegradable gaseous pollutant (s), it is passed through the second biofilter of the invention, and, similarly, the gaseous outflow of said second biofilter of the invention, which it will be even more discharged in said biodegradable gas contaminant (s), is passed through the third biofilter of the invention, and so on until the final exit of the total or partially discharged gas stream from said biodegradable gaseous pollutant (s). Therefore, the biofiltration method of the invention allows to achieve an efficiency of elimination of said biodegradable pollutant (s) of 100%, or very close to 100%, in relation to the amount of said biodegradable gaseous pollutant (s) present in the gaseous stream containing at least one biodegradable gaseous pollutant to be purified.
Durante la realización del método de biofiltración 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 era3 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 H3B03, 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 el/loscontaminante(s) gaseoso(s) biodegradable(s) a tratar, con dicho riego se favorece el tamponamiento (efecto buffer) del pH del biofilm donde residen los microorganismos y se arrastran los posibles intermedios de degradación (ácidos) generados como sub-productos no deseados de la reacción de degradación de dicho(s) contaminante(s) gaseoso(s) biodegradable(s). En cualquier caso, las buenas características reguladoras del pH así como las buenas características para retener la humedad por parte de las EAFS utilizadas como material de relleno del biofiltro utilizado en el método de biofiltración 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 soporte, etc.), en una realización particular, el periodo de tiempo comprendido entre dos riegos consecutivos está comprendido entre aproximadamente 1 y 5 días, típicamente entre aproximadamente 1 y 2 días. During the realization of the biofiltration method of the invention, the stable operation of the biofilter of the invention may require 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; an amount of 5 was added 3 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 -4H 2 0.60 mg / dm 3 of CuCl 2 , 50 mg / dm 3 of ZnCl 2 , 50 mg / dm 3 of H 3 B0 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 metabolism (growth and maintenance) of microorganisms capable of degrading the biodegradable gas contaminant (s) to be treated, with such irrigation the buffering (buffer effect) of the pH of the biofilm where the microorganisms reside is favored and carry potential degradation intermediates (acids) generated as unwanted by-products of the degradation reaction of said biodegradable gas contaminant (s). In any case, the good pH regulating characteristics as well as the good characteristics for retaining moisture by the SAIs used as a biofilter filler material used in the biofiltration method of the invention minimize the need for watering very continuous Although the period of time between two consecutive irrigations may vary within a wide range, depending on numerous factors (eg, need to provide nutrients, need to moisten the support, etc.), in a particular embodiment, the period of time between two consecutive waterings is between approximately 1 and 5 days, typically between approximately 1 and 2 days.
Aunque durante la operación del método de biofiltración de la invención se pudiera generar dióxido de carbono/ácido carbónico, por ejemplo, cuando el contaminante gaseoso biodegradable comprende un COV, en la práctica, en general, no es necesario utilizar reactivos adicionales para neutralizar dicho ácido procedente de la oxidación de dichos contaminantes. Although during the operation of the biofiltration method of the invention, carbon dioxide / carbonic acid could be generated, for example, when the biodegradable gaseous pollutant comprises a VOC, in practice, in general, it is not necessary to use additional reagents to neutralize said acid. from the oxidation of said contaminants.
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 las EAFS utilizadas en la elaboración del material de relleno del biofiltro utilizado en el método de biofiltración de la invención, debido a sus buenas características físico-químicas, no sufren un deterioro (o erosión) significativo tras más de 12 meses de operación y es esperable que alcance incluso los 10 años. Por tanto, la presente invención proporciona un método estable y duradero para la depuración (eliminación o reducción de la cantidad) de uno o más contaminantes gaseosos
biodegradables contenidos en una corriente gaseosa que contiene dicho(s) contaminante(s). Tests carried out by the inventors on a continuous basis have shown that the SAIs used in the preparation of the biofilter filler material used in the biofiltration method of the invention, due to their good physical-chemical characteristics, do not suffer deterioration (or erosion) significant after more than 12 months of operation and is expected to reach even 10 years. Therefore, the present invention provides a stable and durable method for the purification (elimination or reduction of the amount) of one or more gaseous pollutants. biodegradable contained in a gas stream containing said contaminant (s).
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 al menos un contaminante gaseoso biodegradable, por ejemplo, uno o más COVs, H2S, CS2, etc., o combinaciones de los mismos, a través del material de relleno contenido en el biofiltro de la invención en donde dicho(s) contaminante(s) gaseoso(s) biodegradable(s) es/son degradados por los microorganismos capaces de degradar dicho(s) contaminante(s). Brevemente, una corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable (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 al menos un contaminante gaseoso biodegradable antes de su entrada en un biorreactor (5). La corriente gaseosa humedecida que contiene al menos un contaminante gaseoso biodegradable (4) es introducida en dicho biorreactor (5) el cual contiene 2 biofiltros de la invención (6a y 6b); cada uno de los cuales comprende un material de relleno y microorganismos capaces de degradar dicho(s) contaminante(s) gaseoso(s) biodegradable(s), en donde dicho material de relleno comprende EAFS. Los 2 biofiltros de la invención (6a y 6b) están dispuestos verticalmente y operativamente conectados entre sí de manera que la corriente de salida del primer biofiltro (6a) alimenta al segundo biofiltro (6b) del que sale la corriente gaseosa prácticamente descargada de dicho(s) contaminante(s) gaseoso(s) biodegradable(s) (7). En caso necesario, los nutrientes contenidos en el sistema de riego (8) se aportan a los biofiltros de la invención mediante riego con el fin de mantener el metabolismo de los microorganismos capaces de degradar dicho(s) contaminante(s) gaseoso(s) biodegradable(s). 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 with moisture) gas stream containing at least one biodegradable gaseous pollutant is passed, for example, one or more VOCs, H 2 S, CS 2 , etc., or combinations thereof, through the filler material contained in the biofilter of the invention wherein said gaseous pollutant (s) (s) ) biodegradable (s) is / are degraded by microorganisms capable of degrading said contaminant (s). Briefly, a gaseous stream containing at least one biodegradable gaseous pollutant (2) from a pollutant source (1) is introduced into a humidification system (3) containing water in order to moisten said gaseous stream containing at least one biodegradable gaseous contaminant before entering a bioreactor (5). The moistened gaseous stream containing at least one biodegradable gaseous pollutant (4) is introduced into said bioreactor (5) which contains 2 biofilters of the invention (6a and 6b); each of which comprises a filler material and microorganisms capable of degrading said biodegradable gaseous contaminant (s), wherein said filler material comprises EAFS. The 2 biofilters of the invention (6a and 6b) are arranged vertically and operatively connected to each other so that the output current of the first biofilter (6a) feeds the second biofilter (6b) from which the practically discharged gas stream from said ( s) biodegradable gas contaminant (s) (7). If necessary, the nutrients contained in the irrigation system (8) are supplied to the biofilters of the invention by irrigation in order to maintain the metabolism of microorganisms capable of degrading said gaseous pollutant (s) (s) biodegradable (s).
Instalación de la invención Installation of the invention
El método de biofiltración de la invención puede realizarse en una instalación adecuada que comprende al menos un biofiltro de la invención, es decir, un biofiltro que comprende escoria negra de horno de arco eléctrico (EAFS) como material de relleno y
microorganismos capaces de degradar el contaminante o contaminantes gaseosos biodegradables que se desea eliminar, como, por ejemplo, COVs, H2S, CS2, etc. Dicha instalación, en adelante "instalación de la invención", constituye un aspecto adicional de esta invención. The biofiltration method of the invention can be carried out in a suitable installation comprising at least one biofilter of the invention, that is, a biofilter comprising black electric arc furnace slag (EAFS) as filler material and microorganisms capable of degrading the biodegradable pollutant or gaseous pollutants to be eliminated, such as VOCs, H 2 S, CS 2 , etc. 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. Así, en una realización particular, la instalación de la invención comprende un único biofiltro 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, ó incluso más, operativamente conectados entre sí (en serie); en este caso, la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable (e.g., uno o más COVs, H2S, CS2, etc., o combinaciones de los mismos) a depurar se hace pasar a través del primer biofiltro de la invención y la corriente gaseosa de salida de dicho primer biofiltro de la invención se hace pasar a través del segundo biofiltro 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 dicho(s) contaminante(s) gaseoso(s) biodegradable(s). The installation of the invention may contain one or more biofilters of the invention. Thus, in a particular embodiment, the installation of the invention comprises a single biofilter 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 series); in this case, the gas stream containing at least one biodegradable gaseous pollutant (eg, one or more VOCs, H 2 S, CS 2 , etc., or combinations thereof) to be purified is passed through the first biofilter of the invention and the gaseous outflow of said first biofilter of the invention is passed through the second biofilter of the invention, and, similarly, the gaseous outflow of said second biofilter of the invention is passed through of the third biofilter of the invention, and so on until the definitive exit of the total or partially discharged gas stream of said biodegradable gas contaminant (s).
El diseño modular de la instalación de la invención permite que los biofiltros de la invención más alejados de la entrada de la corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable reciban concentraciones muy bajas de dicho(s) contaminante(s) gaseoso(s) biodegradable(s) pero suficientes para la adaptación de los microorganismos capaces de degradar dicho(s) contaminante(s) gaseoso(s) biodegradable(s). Asimismo, el diseño modular permite la biodegradación de dicho(s) contaminante(s) gaseoso(s) biodegradable(s) en el primer biofiltro de la invención mientras que los restantes biofiltros pueden actuar como reserva, lo que garantiza la eficacia del sistema incluso con incrementos repentinos de carga contaminante. The modular design of the installation of the invention allows the biofilters of the invention further away from the entrance of the gaseous stream containing at least one biodegradable gaseous pollutant to receive very low concentrations of said gaseous pollutant (s). biodegradable (s) but sufficient for the adaptation of microorganisms capable of degrading said gaseous pollutant (s) biodegradable (s). Likewise, the modular design allows biodegradation of said biodegradable gaseous pollutant (s) in the first biofilter of the invention while the remaining biofilters can act as a reserve, which guarantees the efficiency of the system even with sudden increases in pollutant load.
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 al menos un contaminante gaseoso biodegradable 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 a depurar, 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 dicho(s) contaminante(s) gaseoso(s) biodegradable(s) 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 at least a biodegradable gaseous pollutant the necessary moisture, located before the biofilter of the invention. Additionally, the installation of the invention includes suitable means for transporting the gas stream to be purified, 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 said Biodegradable gaseous contaminant (s) 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 al menos un contaminante gaseoso biodegradable a depurar, medios para medir el pH en el interior del biofiltro, y medios para medir la cantidad de contaminante(s) gaseoso(s) biodegradable(s) presente en la corriente gaseosa de salida del biofiltro de la invención. 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 at least one biodegradable gaseous pollutant to be purified, means for measuring the pH in inside the biofilter, and means for measuring the amount of biodegradable gaseous pollutant (s) present in the gaseous outflow of the biofilter of the invention.
La instalación de la invención, además de al menos un biofiltro de la invención, puede contener uno o más biofiltros diferentes en los que el material de relleno del biofiltro no es EAFS sino otro material bien de naturaleza inorgánica como de naturaleza orgánica por ejemplo, compost, turba, turba ácida, corteza de pino, una mezcla de compost, serrín y perlita, o 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. The installation of the invention, in addition to at least one biofilter of the invention, may contain one or more different biofilters in which the biofilter filler material is not EAFS but another material of an inorganic nature or of an organic nature for example, compost , peat, acid peat, pine bark, a mixture of compost, sawdust and perlite, or 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.
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 tolueno Design of a toluene 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 2 biofiltros (6a y 6b), 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 y 6c) están conectados operativamente entre sí y, en su interior, se encuentra el material de relleno
que comprende EAFS, que actúa como material de soporte sobre el que se desarrolla la biomasa (microorganismos) responsable de la degradación del tolueno (contaminante gaseoso biodegradable contenido en la corriente gaseosa contaminada a depurar). 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 2 biofilters (6a and 6b), placed vertically, with an approximate total volume of 4.5 L, built in polyvinyl chloride (PVC) and with downward gas flow; the biofilters (6a and 6c) are operatively connected to each other and, inside, is the filling material comprising EAFS, which acts as a support material on which the biomass (microorganisms) responsible for the degradation of toluene (biodegradable gaseous pollutant contained in the polluted gaseous stream to be purified) is developed.
El inoculo se obtuvo a partir de lodo biológico de una estación depuradora de agua residual (EDAR). El proceso de aclimatación de la biomasa contenida en el lodo se llevó a cabo en un reactor de aclimatación construido en PVC
4,5 L), tal como se representa en la Figura 1. En esta etapa inicial de aclimatación, alimentando con corrientes gaseosas que contenían tolueno, con concentraciones de tolueno comprendidas entre 25 y menos de 100 ppmv, y, con tiempos de residencia de aproximadamente 3 minutos, que borboteaban sobre la muestra de lodo en agitación, se llegó a obtener, al cabo de unos 30 días aproximadamente, el medio líquido necesario para la inoculación de la escoria negra de horno de arco eléctrico (EAFS). The inoculum was obtained from the biological sludge of a wastewater treatment plant (WWTP). The acclimatization process of the biomass contained in the mud was carried out in an acclimatization reactor built in PVC 4.5 L), as shown in Figure 1. In this initial stage of acclimation, feeding with gaseous streams containing toluene, with toluene concentrations between 25 and less than 100 ppmv, and, with residence times of approximately 3 minutes, which bubbled over the sample of sludge while stirring, it was possible to obtain, after about 30 days, the liquid medium necessary for the inoculation of the black slag of electric arc furnace (EAFS).
La EAFS se introdujo en el biorreactor modular (Figura 2) y se regó con el inoculo aclimatado, formándose una biopelícula que contenía la biomasa activa, es decir, los microorganismos capaces de degradar tolueno. The EAFS was introduced into the modular bioreactor (Figure 2) and irrigated with the acclimatized inoculum, forming a biofilm containing the active biomass, that is, the microorganisms capable of degrading toluene.
La utilidad del sistema se evaluó con una corriente gaseosa con un contenido en tolueno de aproximadamente 50-150 ppmv. Con dicha corriente la eficacia del tratamiento de depuración de tolueno fúe superior al 90% para tiempos de residencia de aproximadamente 60 s. El mantenimiento de la humedad en el material de relleno del biofiltro (EAFS) se consiguió mediante un riego diario con la solución de nutrientes exigida para el metabolismo de la biomasa activa. The utility of the system was evaluated with a gas stream with a toluene content of approximately 50-150 ppmv. With this current the efficiency of the treatment of purification of toluene was greater than 90% for residence times of approximately 60 s. The maintenance of moisture in the biofilter filler material (EAFS) was achieved by daily irrigation with the nutrient solution required for active biomass metabolism.
El proceso de depuración de dicha corriente gaseosa que contiene tolueno como contaminante no generó lixiviados en el sistema, lo que eliminó la necesidad de tener que realizar un tratamiento posterior de los mismos.
The purification process of said gaseous stream containing toluene as a pollutant did not generate leachates in the system, which eliminated the need for subsequent treatment.
Claims
1. Un biofiltro de lecho fijo que comprende escoria negra de horno de arco eléctrico (EAFS) como material de relleno. 1. A fixed bed biofilter comprising black electric arc furnace slag (EAFS) as filler material.
2. Biofiltro según la reivindicación 1, que además comprende microorganismos capaces de degradar al menos un contaminante gaseoso biodegradable. 2. Biofilter according to claim 1, further comprising microorganisms capable of degrading at least one biodegradable gaseous pollutant.
3. Biofiltro según la reivindicación 2, en el que dicho contaminante gaseoso biodegradable se selecciona del grupo formado por compuestos orgánicos volátiles (COVs), disulfuro de hidrógeno (H2S), sulfuro de carbono (CS2), y cualquier combinación de los mismos. 3. Biofilter according to claim 2, wherein said biodegradable gaseous pollutant is selected from the group consisting of volatile organic compounds (VOCs), hydrogen disulfide (H 2 S), carbon sulfide (CS 2 ), and any combination thereof. same.
4. Una instalación que comprende, al menos, un biofiltro según cualquiera de las reivindicaciones 1 a 3. 4. An installation comprising at least one biofilter according to any one of claims 1 to 3.
5. Un método para depurar una corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable mediante biofiltración que comprende hacer pasar dicha corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable a través de un biofiltro según la reivindicación 1, comprendiendo dicho biofiltro, además de escoria negra de horno de arco eléctrico (EAFS) como material de relleno, microorganismos capaces de degradar dicho al menos un contaminante gaseoso biodegradable. 5. A method for purifying a gaseous stream containing at least one biodegradable gaseous pollutant by means of biofiltration comprising passing said gaseous stream containing at least one biodegradable gaseous pollutant through a biofilter according to claim 1, said biofilter, in addition to black arc furnace slag (EAFS) as filler material, microorganisms capable of degrading said at least one biodegradable gaseous pollutant.
6. Método según la reivindicación 5, en el que dicho contaminante gaseoso biodegradable se selecciona del grupo formado por compuestos orgánicos volátiles (COVs), disulfuro de hidrógeno (H2S), sulfuro de carbono (CS2), y cualquier combinación de los mismos. 6. The method of claim 5, wherein said biodegradable gaseous pollutant is selected from the group consisting of volatile organic compounds (VOCs), hydrogen disulfide (H 2 S), carbon sulphide (CS 2 ), and any combination thereof. same.
7. Método según la reivindicación 5 ó 6, en el que dicha corriente gaseosa contiene al menos un contaminante gaseoso biodegradable en una cantidad comprendida entre aproximadamente 50 partes por millón en volumen (ppmv) y aproximadamente 250 ppmv. 7. A method according to claim 5 or 6, wherein said gas stream contains at least one biodegradable gaseous pollutant in an amount between about 50 parts per million by volume (ppmv) and about 250 ppmv.
8. Método según cualquiera de las reivindicaciones 5 a 7, en el que el caudal de dicha corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable se selecciona de manera tal que el tiempo de residencia está comprendido entre aproximadamente 10 s y aproximadamente 80 s. A method according to any one of claims 5 to 7, wherein the flow rate of said gaseous stream containing at least one biodegradable gaseous pollutant is selected such that the residence time is between about 10 s and about 80 s.
9. Método según la reivindicación 5, que comprende la inoculación previa del material de relleno del biofiltro con microorganismos capaces de degradar al menos un contaminante gaseoso biodegradable. 9. A method according to claim 5, comprising prior inoculation of the biofilter filler material with microorganisms capable of degrading at least one biodegradable gaseous pollutant.
10. Método según la reivindicación 9, en el que dicha inoculación comprende la aclimatación previa de una muestra de un lodo biológico. 10. The method according to claim 9, wherein said inoculation comprises the previous acclimation of a sample of a biological sludge.
11. Método según la reivindicación 10, en el que dicha muestra de lodo biológico procede de una estación depuradora de agua residual (EDAR). 11. The method according to claim 10, wherein said biological sludge sample is from a wastewater treatment plant (WWTP).
12. Método según cualquiera de las reivindicaciones 10 ú 11, en el que dicha aclimatación comprende el tratamiento de lodo biológico con una corriente gaseosa que contiene al menos un contaminante gaseoso biodegradable en una cantidad igual o inferior a aproximadamente 100 ppmv, de manera continua, con un caudal que proporciona un tiempo de residencia igual o inferior a 3 minutos, durante aproximadamente al menos 30 días. 12. A method according to any of claims 10 or 11, wherein said acclimatization comprises the treatment of biological sludge with a gaseous stream containing at least one biodegradable gaseous pollutant in an amount equal to or less than about 100 ppmv, continuously, with a flow rate that provides a residence time equal to or less than 3 minutes, for at least 30 days.
13. Uso de escoria negra de horno de arco eléctrico (EAFS) como material de relleno de un biofiltro para biofiltración en sistemas de lecho fijo de corrientes gaseosas contaminadas con al menos un contaminante gaseoso biodegradable. 13. Use of black arc furnace slag (EAFS) as a biofilter filling material for biofiltration in fixed bed systems of gaseous streams contaminated with at least one biodegradable gaseous pollutant.
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ES201132043A ES2409156B1 (en) | 2011-12-19 | 2011-12-19 | BIOFILTER THAT INCLUDES BLACK ESCORIA OF ELECTRIC ARC OVEN AND ITS APPLICATIONS. |
ESP201132043 | 2011-12-19 |
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EP3395429A1 (en) * | 2017-04-26 | 2018-10-31 | Bonno Koers | Filter material, device and method for purifying gases and liquids |
US10981112B2 (en) | 2017-04-26 | 2021-04-20 | Bonno Koers | Filter material, device and method for purifying gases and liquids |
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