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    • 专利摘要:
    Biological denitrification process that allows the biological elimination of nitrites and nitrates in the water, also the biological elimination of sulfates in the water. The process includes the stages: - Raw water conditioning, by means of carbon source, nutrients and pH adjustment. - Denitrification: Filtering of the water through a closed filter of fixed bed in ascending flow and in anoxia situation. - Water refining filtration through a zeolite filter. - Filter washing. - Oxidation An oxidation stage will be added with two objectives: increase the oxidation-reduction potential and eliminate possible bacteria. The process allows the removal of sulfates from water, by means of a reduction-oxidation process using sulfate reducing bacteria (BSR), sulfate ions are eliminated. The process has a minimum maintenance cost, a simpler management of the plant and a lower environmental impact. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2738952A1
    申请号:ES201830763
    申请日:2018-07-25
    公开日:2020-01-27
    发明作者:Martin Joaquin Murria
    申请人:Ingenieria De Obras Zaragoza S L；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] OBJECT OF THE INVENTION
    [0005]
    [0006] It is the object of the present invention, as the title of the invention establishes, a denitrification process, that is to say the biological removal of nitrites and nitrates from the water that is carried out by a heterotrophic biological denitrification process.
    [0007]
    [0008] The present invention characterizes the special configuration and design of the means and stages of the process so that the process has a minimum maintenance cost, a simpler management of the plant and a lower environmental impact by not generating complex management waste .
    [0009]
    [0010] In addition, the process object of the invention also allows the removal of sulfates from water, since in the biological denitrification process object of the invention the pool of denitrifying bacteria also causes a reduction of sulfates, in the case of a high concentration of them in the water to be treated.
    [0011]
    [0012] Therefore, the present invention is circumscribed within the scope of denitrification processes.
    [0013]
    [0014] BACKGROUND OF THE INVENTION
    [0015]
    [0016] Currently, many municipalities have problems regarding the conditions of drinking water supply for use of supply, due to the water quality itself, which has high levels of nitrates (NO 3 ) and sulfates (SO 4 ), above the values limits established in RD 140/2003.
    [0017]
    [0018] The origin of such high levels of contamination may be natural, as a result of the dissolution of geological plasters in the percolation of water or artificial origin such as detergents and agricultural products.
    [0019] The Spanish technical-sanitary regulation (R.D. 140/2003) establishes the following maximum concentration values of such contaminants in drinking water:
    [0020] Sulfates: 250 mg / l
    [0021] Nitrates: 50 mg / l
    [0022]
    [0023] Biological denitrification is the reduction of nitrate ion (NO 3 "), present in the soil or in water, to nitrogen gas (N 2 ), the most abundant substance in the composition of the air, which will escape into the atmosphere. the biogeochemical cycle of nitrogen, by denitrification, nitrogen not consumed by plants is returned to the atmosphere.
    [0024]
    [0025] The reactions are produced by the intervention of heterotrophic anoxic bacteria. The absence of oxygen in the medium and the presence of organic matter as a source of carbon for synthesis are needed. Bacteria with the ability to perform denitrification take nitrate (or nitrite in some cases) as an electron acceptor in order to obtain the energy needed for growth.
    [0026]
    [0027] In the absence of dissolved O 2 or in limited concentrations, the nitrate reductase (enzyme) activity of the bacterium's electron transport chain is induced. This helps in the transfer of hydrogen and electrons to NO 3 "which acts as an electron acceptor.
    [0028]
    [0029] The steps that take place throughout the nitrate reduction process are presented below.
    [0030]
    [0031]
    [0032] Currently there are other processes of elimination of nitrates by biological route.
    [0033]
    [0034] - The Anammox process (anaerobic ammonium oxidation) can be considered as a shortcut in the natural nitrogen cycle where ammonium and nitrite are converted to nitrogen gas. This process is carried out by a group of autotrophic bacteria capable of oxidizing the ammonium to nitrogen gas using nitrite as an electron acceptor, without the need to provide organic matter or oxygen.
    [0035] In order to apply the Anammox process, it is necessary to have an effluent with adequate concentrations of nitrite and ammonium, so it is usually necessary to previously oxidize 50% of the ammonium to nitrite.
    [0036]
    [0037] The widespread application of Anammox-like processes has been limited due in large part to the low growth rate of Anammox bacteria and their sensitivity to high concentrations of dissolved oxygen, nitrites, free nitrous acid and free ammonia.
    [0038]
    [0039] The disadvantages of this denitrification process are:
    [0040]
    [0041] o Requires an oxygen supply for the oxidation of ammonite to nitrites.
    [0042] o They have to be done in an open tank.
    [0043]
    [0044] o This procedure requires a certain type of autotrophic bacteria.
    [0045]
    [0046] o Does not allow the elimination of sulfates.
    [0047]
    [0048] - Process based on UFBAF (Up-Flow Biological Aerated Filter) technology, and is a filtration process based on natural processes developed by microorganisms that modify chemical compounds.
    [0049]
    [0050] In this system the microorganisms are already found naturally in the waters to be treated and an appropriate environment for their development is favored.
    [0051]
    [0052] The process can be aerobic or anaerobic depending on the contaminants to be treated. Nitrates are eliminated by biological reduction, under anaerobic conditions, with the contribution of an external carbon source, transforming the nitrate to nitrogen gas, releasing it to the atmosphere. The metals are removed by biological oxidation, under aerobic conditions, that is, with the oxygen supply.
    [0053]
    [0054] The application of the process consists in the use of denitrifying bacteria for the reduction of nitrate to nitrogen gas under conditions of absence of oxygen.
    [0055]
    [0056]
    [0057] For a proper development of biomass, the process needs adequate conditions, including, among others, a power supply, lack of oxygen, as well as a support where microorganisms can be fixed and a reactor where the treatment is carried out.
    [0058]
    [0059] The disadvantages of this denitrification system are:
    [0060]
    [0061] o Requires a contribution or aeration with oxygen
    [0062]
    [0063] o Requires an active carbon filter
    [0064]
    [0065] o This process does not allow the elimination of sulfates.
    [0066]
    [0067] Therefore, it is the object of the present invention to overcome the specific drawbacks of particular requirements, limitation to a specific fixed bed filter, the non-possibility of sulfate removal, the need for an oxygen supply, developing a procedure such as that to It is described below and is reflected in its essentiality in the first claim.
    [0068]
    [0069] DESCRIPTION OF THE INVENTION
    [0070]
    [0071] The object of the present invention is a biological denitrification process that reproduces the denitrification process as it occurs in nature.
    [0072]
    [0073] The system is composed of a fixed-bed biological filter where biological denitrification develops, a physical filter where suspended matter is retained and possible water turbidity and an oxidant addition, in addition to the equipment washing system.
    [0074]
    [0075] The designed system, in addition to denitrifying, allows the elimination of a variable percentage of sulfates dissolved in raw water, in addition to solids and suspended particles.
    [0076]
    [0077] The procedure has the following stages:
    [0078] - Raw water conditioning, by means of carbon source, nutrients and pH adjustment.
    [0079] - Denitrification: Filtering of the water through a closed filter of fixed bed in ascending flow and in anoxia situation. At this stage the reduction of nitrate to atmospheric nitrogen occurs.
    [0080] - Water refining filtration through a zeolite filter. At this stage the levels of organic solids, odors and flavors are reduced.
    [0081] - Filter washing. The water resulting from the washings can be poured into the municipal sanitation network.
    [0082] - Oxidation An oxidation stage with two objectives will be added:
    [0083] • Increase the oxidation-reduction potential (ORP) of the product water.
    [0084] • Eliminate possible bacteria or organic matter remaining in the water, in order to guarantee safe water for consumption, while avoiding increasing the consumption of disinfection chlorine.
    [0085]
    [0086] The process object of the invention also allows the removal of sulfates from water.
    [0087]
    [0088] In the denitrification process it has been observed that the pool of denitrifying bacteria also causes a reduction of sulfates, in the case of a high concentration thereof in the water to be treated.
    [0089]
    [0090] Biological desulphation is a reduction-oxidation process that occurs naturally by reducing sulfate bacteria (BSR) in which sulfate ions are removed
    [0091]
    [0092] Unless otherwise indicated, all technical and scientific elements used herein have the meaning normally understood by a person skilled in the art to which this invention pertains. In the practice of the present invention methods and materials similar or equivalent to those described herein can be used.
    [0093]
    [0094] Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the The invention will be derived partly from the description and partly from the practice of the invention.
    [0095]
    [0096] PREFERRED EMBODIMENT OF THE INVENTION.
    [0097]
    [0098] Next, a preferred embodiment of the proposed invention.
    [0099]
    [0100] - Gross Water Conditioning.
    [0101]
    [0102] Biological denitrification equipment requires for its operation the contribution of the elements that microorganisms need to perform the transformation of nitrate (NO 3 ") to nitrogen gas (N 2 ). These elements are a source of carbon and nutrients.
    [0103]
    [0104] In terms of biological denitrification, the carbon source can be:
    [0105]
    [0106] • The soluble biodegradable organic matter present in the water to be treated. In general, it is low in the water supply.
    [0107] • Soluble biodegradable organic matter produced during endogenous decay (endogenous respiration).
    [0108] • An external carbon source can use acetic or lactic acid.
    [0109]
    [0110] The reaction that describes the action of microorganisms having NO 3 "as an electron acceptor dosing acetic acid as a carbon source is:
    [0111]
    [0112] 0.85 CH 3 COOH NO 3 - H + ^ 0.1 C 5 H 7 NO 2 + 2.1 H 2 O 0.45 N 2 T
    [0113]
    [0114] The energy obtained from this process will be used by microorganisms for bacterial growth.
    [0115]
    [0116] The denitrification reaction is carried out in a pH range, so the pH of the raw water must be regulated by the addition of the corresponding reagents.
    [0117] Therefore, the products used for the conditioning of raw water and nutrient supply are the following:
    [0118]
    [0119] Acetic or lactic acid
    [0120] Phosphoric Acid or Orthophosphate
    [0121] Sodium hydroxide
    [0122]
    [0123] The adaptation of the raw water is carried out by means of a system of dosing pumps that directly inject these components with a flow rate according to the characterization of the raw water and the quality requirements of the outlet water.
    [0124]
    [0125] - Denitrification
    [0126]
    [0127] After the process of adaptation of the raw water, it passes through the denitrification filter where the process of reducing nitrates to nitrogen gas is carried out.
    [0128]
    [0129] The denitrification filter will be a closed-pressure, upstream pressure filter with a fixed bed. An atmosphere of absence of oxygen will be created to favor the development of families of suitable bacteria.
    [0130]
    [0131] Expanded aluminosilicate exclusively is used as a bacterial support material, since the porosity and granulometry characteristics allow rapid development of the bacterial colony.
    [0132]
    [0133] In this filter bed is the adhered biomass where the optional denitrifying bacteria carry out the transformation of nitrate into atmospheric nitrogen. Denitrifying bacteria in the filter come from the inoculation of a culture of the following families of bacteria:
    [0134]
    [0135] Bacillus megaterium, Bacillus polymyxa, Bacillus subtilus, Bacillus licheniformis, Bacillus thuringiensis, Pseudomonas putida, Saccharomyces cerevisiae, and Trichodermaresei.
    [0136] All these microorganisms of the compound inoculated in the filter are classified Agents of the RISK GROUP I according to the Risk Groups of the World Health Organization.
    [0137]
    [0138] - Refinement Filtration
    [0139]
    [0140] After the denitrification process, the water will pass through a closed upflow filter where a more fine filtration of the solids of organic matter, possible odors and / or flavors and adsorption of other types of possible contaminants will be carried out. The filter medium of this stage is natural zeolite.
    [0141]
    [0142] This bed complies with filtration and physical retention, so that the filler material has been selected so that a development of bacteria does not occur.
    [0143]
    [0144] The sizing of the refining filter has been carried out in order to obtain a filtration rate of less than 1 m3 / m2.h, so that the passage speed is not very high, which would cause the filter bed to be dragged.
    [0145]
    [0146] The refining filters have a set of valves that allow insulating any of said filters, as well as being able to perform periodic backwashing to eliminate retained matter.
    [0147]
    [0148] - Filter washing
    [0149]
    [0150] Within the biological process of eliminating nitrates and sulfates it is necessary to carry out backwashing of the filters and eliminate the generated sludge and dead bacteria.
    [0151]
    [0152] The washing process of the equipment filters is carried out every 24 hours or due to the difference in pressure reached. Each wash sequence requires a water consumption of between 5% and 10% of the maximum daily water volume treated by the equipment.
    [0153]
    [0154] The water to be used in the washings can be raw water without conditioning and from the header tank or treated water can also be used, as long as the concentration of free chlorine does not exceed 2 ppm.
    [0155] The water resulting from the washes is a water with an organic matter content of the biological and affinity filtration phases. The characterization of this water is a domestic residual with a weak concentration of COD, BOD5 and SS. This wash water is of sufficient quality to be discharged directly to the municipal collector without the need for any previous treatment or as irrigation water for the field.
    [0156]
    [0157] - Oxidation
    [0158]
    [0159] After refining filtration, an oxidation stage is arranged to increase the oxidation-reduction potential and, if necessary, eliminate possible bacteria or organic matter remaining in the water, in order to guarantee a safe water for consumption. to avoid increasing the consumption of chlorine disinfection.
    [0160]
    [0161] A dosage of hydrogen peroxide is chosen as the oxidizing phase.
    [0162]
    [0163] - Desulphation
    [0164]
    [0165] The process object of the invention also allows the removal of sulfates from water, a step that can be carried out immediately after denitrification and before refining.
    [0166]
    [0167] Biological desulphation is a reduction-oxidation process that occurs naturally by reducing sulfate bacteria (BSR) in which sulfate ions are removed.
    [0168]
    [0169] Sulfate reducing bacteria (BSR) are anaerobic microorganisms that use sulfur-based molecules as final electron acceptors to perform their metabolic functions.
    [0170]
    [0171] They are adaptable bacteria that are usually found in anoxic environments with high concentrations of sulfates (sewage, sulphide deposits, oil wells, ...). Traditionally, two groups are distinguished with respect to the way of oxidizing organic matter: a first group that partially oxidizes matter, consisting of genera such as Desulfovibrio, Desulfomonas, Desulfotomaculum, Desulfobulbus and Thermodesulfobacterium and a second group that reduces the rest of the matter to CO 2 , which are the bacteria Desulfobacter, Desulfococcusa, Desulfosarcin, Desulfonema and Desulfobacterium. Both groups, apart from partially or totally degrading organic matter, produce hydrogen sulfide as a byproduct.
    [0172]
    [0173] These bacteria can reduce sulfates to sulphides and finally to hydrogen sulphide under anaerobic conditions.
    [0174]
    [0175] In the described procedure it has been observed that the pool of denitrifying bacteria defined in the previous section, also causes a reduction of the sulfates, in the case of a high concentration thereof in the water to be treated. In this way, by feeding the reactor with a stream of water with a high concentration of sulfates, offering a means for the growth and retention of bacteria and adding the necessary carbon source, the conversion of sulfates into hydrogen sulphide can be promoted together with the denitrification processes already described.
    [0176]
    [0177] For the elimination of sulfates in water, better yields will be obtained by including several groups of previously defined sulphoreductive bacteria in the pool of inoculated bacteria.
    [0178]
    [0179] As a byproduct of the biological process, hydrogen sulfide will be generated, giving that characteristic smell of rotten eggs at concentrations greater than 2 ppm.
    [0180]
    [0181] For its elimination we have an aeration tower following the biological desulphation process.
    [0182]
    [0183] In the aeration towers, the water is put in contact with the air, with the aim of modifying the concentration of volatile substances or eliminating remaining gases. In our case, the objective is to eliminate hydrogen sulfide produced in biological desulphation.
    [0184]
    [0185] The aeration process in the tower fulfills the objective of water purification as a complementary system of the sulfate reduction process of water, by means of the dragging or sweeping of volatile substances, normally caused by mixing turbulent water with the air of the environment and the process of oxidation of metals and gases. This means increasing the oxygen content and decreasing the content of carbon dioxide, methane, hydrogen sulfide and volatile organic compounds. In the gas exchange that occurs in this process, they take place simultaneously: aeration / absorption and gas transfer / desorption.
    [0186]
    [0187] We have opted for the implementation of a cascade aerator, for its zero energy consumption. In this type of aerators the water is dropped, in thin sheets or layers on one or more steps or trays to produce turbulence where the water comes into intimate contact with the air creating the gas transfer. In view of its use in treatment plants for small or medium flows, the proposed system is economical, no additional energy is required and maintenance is simple.
    [0188]
    [0189] The gases generated in the aeration process will be circulated through a chamber with activated carbon beads, which absorb and accumulate the hydrogen sulphide generated.
    [0190]
    [0191] Describing sufficiently the nature of the present invention, as well as the manner of putting it into practice, it is stated that, within its essentiality, it may be implemented in other embodiments that differ in detail from that indicated by way of example. , and which will also achieve the protection sought, provided that it does not alter, change or modify its fundamental principle.
    权利要求:
    Claims (9)
    [1]
    1. - Biological denitrification procedure characterized by comprising the following stages:
    - conditioning of raw water, by means of carbon source, nutrients and pH adjustment;
    - denitrification: filtration of water through a closed fixed bed filter based exclusively on expanded aluminosilicate in upstream and anoxia situation; at this stage the reduction of nitrate to atmospheric nitrogen occurs;
    - filtration of water refining through an up-flow filter where a more fine filtration of the solids of organic matter, possible odors and / or flavors and adsorption of other types of possible contaminants will be performed using a zeolite filter;
    - filter washing; the water resulting from the washes can be poured into the municipal sanitation network;
    - oxidation; an oxidation stage with two objectives will be added:
    • increase the oxidation-reduction potential (ORP) of the product water;
    • eliminate possible bacteria or organic matter left in the water, in order to ensure safe water for consumption, while avoiding increasing the consumption of disinfection chlorine.
    [2]
    2. - Biological denitrification method according to claim 1 characterized in that the carbon source is:
    • the soluble biodegradable organic matter present in the water to be treated; in general, it is low in the supply water;
    • soluble biodegradable organic matter produced during endogenous decay (endogenous respiration);
    • an external carbon source, you can use acetic or lactic acid;
    and the nutrients are some or combination of the following:
    Acetic or lactic acid
    Phosphoric Acid or Orthophosphate
    Sodium hydroxide
    [3]
    3. - Biological denitrification process according to claim 1 or 2, characterized in that expanded bacterinosilicate is used as bacterial support material and the existing denitrifying bacteria in the filter come from the inoculation of a culture of the following bacterial families:
    Bacillus megaterium, Bacillus polymyxa, Bacillus subtilus, Bacillus licheniformis, Bacillus thuringiensis, Pseudomonas putida, Saccharomyces cerevisiae, and Trichodermaresei.
    [4]
    4. - Biological denitrification method according to claim 1 or 2, characterized in that the sizing of the filter used in the refinement filtration stage has been carried out in order to obtain a filtration rate of less than 1 m3 / m2.
    [5]
    5. - Biological denitrification process according to any of the preceding claims characterized in that the oxidation takes place by means of a dosage of hydrogen peroxide.
    [6]
    6. - Biological denitrification method according to any of the preceding claims, characterized in that it allows a desulphation to be carried out following denitrification by reducing sulfate bacteria.
    [7]
    7. - Biological denitrification method according to claim 6 characterized in that the reducing sulfate bacteria (BSR) is carried out with one or both of the following groups of bacteria:
    - first group that partially oxidizes matter, consisting of genera such as Desulfovibrio, Desulfomonas, Desulfotomaculum, Desulfobulbus and Thermodesulfobacterium and
    - a second group that reduces the rest of the matter to CO2, which are the bacteria Desulfobacter, Desulfococcusa, Desulfosarcina, Desulfonema and Desulfobacterium;
    where both groups, apart from partially or totally degrading organic matter, produce hydrogen sulfide as a byproduct.
    [8]
    8. Equipment for denitrification according to the denitrification process according to any of claims 1 to 7 characterized in that it comprises a fixed bed biological filter where biological denitrification develops, a physical filter where the suspended matter is retained and possible turbidity of water and an oxidant addition, in addition to the equipment washing system.
    [9]
    9. Equipment for denitrification and desulphation according to claim 8, characterized in that it also comprises an aeration tower following the biological desulphation process, wherein said aeration tower is a cascade aeration tower.
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    同族专利:
    公开号 | 公开日
    ES2738952B2|2020-06-01|
    引用文献:
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    WO2005047187A2|2003-11-07|2005-05-26|Severn Trent Water Purification, Inc.|Biologically active reactor system and method for treating wastewater|
    CN102173533A|2011-02-28|2011-09-07|桂林理工大学|Efficient anaerobic ammonium oxidation sewage treatment method|
    CN103241835A|2013-05-30|2013-08-14|南开大学|High-efficiency stable short-range nitration-anaerobic ammonia oxidation biological denitrification method|
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