WO2023222979A1 - Procédé de traitement d'eaux usées avec maximisation de la production de biogaz comprenant une étape d'electro-oxydation - Google Patents
Procédé de traitement d'eaux usées avec maximisation de la production de biogaz comprenant une étape d'electro-oxydation Download PDFInfo
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- WO2023222979A1 WO2023222979A1 PCT/FR2023/050707 FR2023050707W WO2023222979A1 WO 2023222979 A1 WO2023222979 A1 WO 2023222979A1 FR 2023050707 W FR2023050707 W FR 2023050707W WO 2023222979 A1 WO2023222979 A1 WO 2023222979A1
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- effluent
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- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 138
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000004065 wastewater treatment Methods 0.000 title claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 181
- -1 ammonium ions Chemical class 0.000 claims abstract description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 61
- 150000002826 nitrites Chemical class 0.000 claims abstract description 52
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 51
- 150000002823 nitrates Chemical class 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 230000029087 digestion Effects 0.000 claims abstract description 30
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 29
- 238000011282 treatment Methods 0.000 claims description 375
- 238000006243 chemical reaction Methods 0.000 claims description 118
- 241000894006 Bacteria Species 0.000 claims description 31
- 238000009434 installation Methods 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
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- 239000000126 substance Substances 0.000 claims description 26
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- 230000008030 elimination Effects 0.000 claims description 23
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- 229910002651 NO3 Inorganic materials 0.000 claims description 19
- 230000001651 autotrophic effect Effects 0.000 claims description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- 238000011144 upstream manufacturing Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- 238000006073 displacement reaction Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 13
- 238000005189 flocculation Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 230000016615 flocculation Effects 0.000 claims description 10
- 244000005700 microbiome Species 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 8
- 229910052567 struvite Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000005188 flotation Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 2
- 239000010802 sludge Substances 0.000 abstract description 48
- 238000005273 aeration Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 10
- 230000000696 methanogenic effect Effects 0.000 description 9
- 238000010908 decantation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000011221 initial treatment Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000001546 nitrifying effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007257 malfunction Effects 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- 239000001272 nitrous oxide Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 206010002660 Anoxia Diseases 0.000 description 2
- 241000976983 Anoxia Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 230000007953 anoxia Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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- 102100029974 GTPase HRas Human genes 0.000 description 1
- 101000584633 Homo sapiens GTPase HRas Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 230000002211 methanization Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 235000018343 nutrient deficiency Nutrition 0.000 description 1
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- 125000001477 organic nitrogen group Chemical group 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
Definitions
- Wastewater treatment process with maximization of biogas production including an electro-oxidation step
- the invention relates to a process for treating wastewater and associated sludge, in particular a carbon and nitrogen removal treatment with maximization of biogas production.
- wastewater treatment is a three-stage process: a primary treatment stage, a secondary treatment stage and a tertiary treatment stage.
- the first primary treatment stage generally makes it possible to reduce the solids and/or organic matter content of the wastewater to be treated.
- This is typically a settling stage, possibly assisted by a prior addition of coagulant and flocculant, during which the wastewater is placed in a holding tank or a settling basin.
- the solids contained in the wastewater thus settle to the bottom of the tank where they are collected and lighter substances such as fats and oils are collected on top of the wastewater present in the tank.
- This step thus produces so-called primary sludge and an effluent with a reduced solids content.
- These primary sludges are generally treated by anaerobic digestion to produce biogas, an energetic gas composed essentially of methane and carbon dioxide.
- the secondary treatment step makes it possible to reduce the carbon and/or nitrogen and/or phosphorus content of the effluent having a reduced solids content leaving the first treatment step.
- organic matter, nitrogen compounds and/or phosphorus compounds are assimilated or decomposed by aerobic and/or anaerobic and/or anoxia bacteria. It is therefore a biological treatment step, most often implemented in free culture reactors (so-called “activated sludge” process).
- the third stage of tertiary treatment is designed to further clean water when it is discharged into a sensitive ecosystem or for reuse. This step may involve the removal of phosphorus and/or micropollutants and/or disinfection and/or filtration.
- N/DN denitrification
- Nitrification is an aerobic oxidation reaction, requiring active aeration, in which a specialized group of autotrophic bacteria oxidizes ammonia nitrogen or ammonium, noted as NH4 or NH4 + , to:
- nitrous nitrogen also known as nitrite, NO2 or NO2
- nitrate nitrogen also known as nitrate, NO3 or NOs’.
- Denitrification consists of anoxic reduction, during which a specialized group of heterotrophic bacteria (which may be anaerobic) couple the oxidation of organic substrates with the reduction of nitrates to either nitrous oxide (N2O) or nitrogen gas (dinitrogen, N2).
- a specialized group of heterotrophic bacteria which may be anaerobic
- N2O nitrous oxide
- N2 nitrogen gas
- the nitrogen content must respect limits depending on the regulations, which can significantly impact the design of the treatment to be carried out.
- the lower the limit nitrogen content the longer the nitrification step must be and require strong aeration (high oxygen demand).
- Low nitrogen contents are also difficult to achieve by biological denitrification treatment, which also requires large quantities of biodegradable carbon often coming from an external supply when biodegradable carbon is not available in sufficient quantity in the effluent. to be treated in relation to the quantity of oxidized nitrogen to be denitrified.
- the sludge retention time (or SRT) is one of the key parameters for the design of the treatment chain because autotrophic nitrifying bacteria have a growth rate lower than the growth rate of heterotrophic microorganisms. denitrification, and must be maintained in the system in order to achieve effective nitrification. This growth rate further decreases with operating temperature. Thus, low temperatures and/or low nitrogen release limits require prolonged aeration as well as an increase in the age of the sludge produced, the sludge retention time and the hydraulic retention time, which conditions the sizing of the units. If a long sludge retention time allows good development of autotrophic nitrifying bacteria, the quantity of biomass formed under these conditions is reduced: the system is said to operate at low load. Conversely, a short sludge retention time limits, or even prevents, the development of nitrifying bacteria, and consequently denitrification, but allows the quantity of biomass formed to be increased: the system is said to operate under heavy load.
- Strict nitrogen discharge limits not only result in high construction costs due to sludge retention times and retention times high hydraulics, but also by high operating costs due in particular to the addition of reagent (addition of carbonates to increase alkalinity during autotrophic nitrification, addition of methanol as an external carbon source during heterotrophic denitrification, addition of a source of phosphate in case of nutrient deficiency), high oxygen demand (high aeration) and high pumping flows (internal and external recirculation).
- a downstream secondary treatment producing activated sludge at low load has a lower methanogenic potential than a downstream secondary treatment producing activated sludge at high load (called also “High Rate Activated Sludge” or “HRAS”), in which the carbon is not treated by a reactor carrying out biological nitrification.
- HRAS High Rate Activated Sludge
- the heterotrophic bacteria do not have enough food, they therefore consume from their reserve (endogenous respiration), which reduces the methanogenic potential.
- the sludge produced is therefore younger and the sludge production is greater, as is its methanogenic potential.
- biological nitrogen treatments are complex to control to the extent that the performance of these treatments is controlled indirectly: the activity of bacteria is typically regulated by the dissolved oxygen content in the medium, itself controlled by a air injection setpoint and therefore the flow rate of the blower. These treatments are also only effective after a period of biomass growth. Furthermore, during the biological nitrification step at low load, filamentous bacteria can be produced, likely to cause malfunctions (in particular loss of settleability of the sludge causing a leak of suspended matter at the clarification outlet) due to particularly swelling and foam formation.
- a first subject of the invention relates to a process for treating wastewater containing nitrogen in the form of ammonium ions and carbonaceous material, said process comprising:
- step (b) of said process is carried out without implementing biological nitrification under aerobic conditions and comprises at least one electro-oxidation step during which at least part of the ammonium ions contained in the first effluent are oxidized into nitrites and/or nitrates, and/or dinitrogen.
- Electro-oxidation is also a treatment with less risk of malfunction compared to a biological nitrification treatment (no risk of malfunction due to the production of filamentous bacteria, foam formation or sludge swelling).
- Electro-oxidation also makes it possible to achieve very low nitrogen levels in the treated water without being limited by an initial carbon content and makes it possible to reduce the production of nitrous oxide, a reaction intermediate in biological reactions of oxidation of ammoniacal nitrogen and reduction of nitrates, which is a greenhouse gas.
- step (a) of treating the waste water can be implemented under conditions in which the carbon content present in the second effluent is maximized, which makes it possible to optimize the production of biogas by anaerobic digestion during step (c).
- the treatment step (a) can comprise at least one step of treating the carbonaceous material chosen from a physical treatment step (al), optionally preceded by a physico-chemical treatment step (a2), and a biological treatment step (a3, a4) of the carbonaceous material.
- the physical and/or physico-chemical treatment makes it possible to reduce the content of the wastewater to be treated in solids, organic matter likely to flocculate and possibly phosphorus, to thus reduce the carbon content of the first effluent.
- the physical treatment step can be chosen from a decantation step, a flotation step and a filtration step
- the physicochemical treatment step can be chosen from a coagulation-flocculation step, a flocculation alone and an electrocoagulation step followed by flocculation, or a combination of these steps.
- the treatment step (a) may comprise at least one biological treatment step (a3) of the carbonaceous material, in particular carried out under conditions unfavorable to nitrification. This involves treating (i.e. eliminating) only the soluble biodegradable carbonaceous material (i.e. the non-particulate carbonaceous material) from the effluent to be treated in order to produce a first effluent with a reduced carbonaceous material content and a second effluent with increased carbon content.
- a3 biological treatment step of the carbonaceous material
- the biological treatment of carbonaceous material can be carried out in anoxic conditions or in oxic condition.
- step (b) may comprise a step of total electro-oxidation of at least part of the ammonium ions to dinitrogen.
- step (b) may comprise a partial electro-oxidation step (bl) of at least part of the ammonium ions to form nitrates and/or nitrites.
- At least part of the effluent produced by said partial electrooxidation step (bl) can be sent to treatment step (a), upstream or in an anoxic biological treatment step (a3) of the material. carbonaceous from step (a).
- the recirculation of part of the partially oxidized effluent in such an anoxic biological treatment step (a3) makes it possible to maximize denitrification and the elimination of carbon to achieve a production of sludge (forming the second effluent) with a potential high methanogen.
- the recirculation in the anoxic biological treatment step (a) (a3) allows the reduction of the carbon present in the wastewater entering the biological treatment step (a3), and possibly the carbon present in the part of the partially oxidized effluent recycled in this step (a3) made biodegradable by the partial electro-oxidation step, while providing the oxygen necessary for this reduction through the nitrates/nitrites produced during step (bl ) partial electro-oxidation, which makes it possible to reduce the need for aeration of said biological carbon treatment step (a3).
- step (b) may comprise the partial electro-oxidation step (bl) in which part of the ammonium ions are oxidized to nitrates and/or nitrites, for example where only half of the ammonium ions are oxidized to nitrates and/or nitrites, followed by a step (b3) of anoxic biological treatment by oxidation of ammonium ions by anaerobic autotrophic bacteria (Anammox step).
- the partial electro-oxidation step (b2) is then incomplete.
- step (bl) In the case where the incomplete partial electro-oxidation step (bl) is followed by this Anammox step (b3), at least part of the effluent produced by this step (b3) can be returned to the step (b3).
- An advantage of the Anammox step (b3) at the outlet of the incomplete partial oxidation step (bl) is to oxidize the remaining ammonium ions while reducing the amount of energy required compared to a step (b) not implementing only one or more electro-oxidation steps.
- step (b) may comprise the step of partial electro-oxidation (bl) of at least a part, preferably all, of the ammonium ions to nitrates and/or nitrites followed by a step of total electro-oxidation (b2) of at least a part, preferably all, of the nitrates and/or nitrites to dinitrogen.
- step (bl) may comprise the step of partial electro-oxidation (bl) of at least a part, preferably all, of the ammonium ions to nitrates and/or nitrites followed by a step of total electro-oxidation (b2) of at least a part, preferably all, of the nitrates and/or nitrites to dinitrogen.
- step (b) may comprise the step of partial electro-oxidation (bl) of a portion of the ammonium ions (for example half) to nitrates and/or nitrites followed by a step anoxic biological treatment by ion oxidation ammonium by anaerobic autotrophic bacteria (b3, Anammox step) then a step of total electro-oxidation (b2) of at least a part, preferably all, of the nitrates and/or nitrites to dinitrogen.
- the total electro-oxidation step (b2) of nitrates and/or nitrites to dinitrogen aims to complete the elimination of total nitrogen and to reach the total nitrogen limit targeted or regulated by legislation.
- the Anammox step (b3) aims to oxidize a portion of the ammonium ions, to thus reduce the energy consumption necessary for the electro-oxidation step. total (b2) of nitrates and/or nitrites into dinitrogen and reduce the overall energy consumption implemented during step (b) for the elimination of nitrogen.
- electrolysis of water present in the effluent can occur resulting in the production of dihydrogen at the cathode and dioxygen at the cathode. the anode.
- the treatment method can further comprise a step of treatment (d) of the third effluent produced by the treatment step (b) to produce a fourth effluent, this treatment step (d) comprising at least one treatment chosen from a treatment for eliminating suspended matter, a treatment for eliminating phosphorus compounds, a treatment for eliminating micropollutants (in particular organic and/or metallic pollutants) and a treatment for eliminating microorganisms.
- this treatment step (d) comprising at least one treatment chosen from a treatment for eliminating suspended matter, a treatment for eliminating phosphorus compounds, a treatment for eliminating micropollutants (in particular organic and/or metallic pollutants) and a treatment for eliminating microorganisms.
- the treatment stage (d) of the third effluent aims to further clean the water so that it meets discharge standards when discharged into a sensitive ecosystem or for reuse.
- the treatment method can also comprise a control step in which:
- a quantity of the at least one effluent to be extracted is determined to reach a limiting nitrogen content in the third or fourth effluent and said quantity of the at least one effluent to be extracted is extracted and it is mixed with the third or to the fourth effluent, and/or
- a quantity of the effluent resulting from the partial electro-oxidation step (bl) of the ammonium ions to be sent to an anoxic biological treatment step (a3) of step (a) is determined, this quantity corresponding to a nitrate and/or nitrite content necessary for an anoxic biological treatment for eliminating carbonaceous material, and we sends said quantity of this effluent to the anoxic biological treatment step (a3) of step (a).
- the control step comprising the sequence (il) (i2) aims to reduce the quantities of effluent treated by step (b) while respecting the standards for nitrogen discharge in the third effluent, which makes it possible to reduce the dimensions of installations and/or processing costs.
- the control step comprising the sequence (il) (i3) makes it possible to optimize the recirculation of the effluent produced by the partial electro-oxidation step (bl) so as to provide the necessary quantity of nitrates/nitrites for the reduction in step (a3) of the carbon initially contained in the wastewater.
- Step (il) may in particular also include a determination of the quantity of carbonaceous material contained in the wastewater to be treated entering step (a), and during step (i3), the quantity of effluent may be determined according to its nitrate and/or nitrite content and the carbon content of the wastewater to be treated.
- the control step comprising the sequence (il) (i3) also makes it possible to optimize the quantity of nitrogen to be treated by the total electro-oxidation step (b2) by minimizing it.
- the control step can implement the two sequences of steps (il) (i2) and (il) (i3) or only one of the two.
- the treatment process may further comprise at least one treatment step (e) of at least one part of a liquid fraction of the digestate produced by digestion step (c), this treatment step being chosen from a step (eO) of treatment by electrocoagulation, a step of treatment by electro-oxidation (el) during which at least part of the ammonium ions contained in said liquid fraction are oxidized to nitrites and/or nitrates, and/or to dinitrogen, a step (e2) of anoxic biological treatment by oxidation of ammonium ions by anaerobic autotrophic bacteria (Anammox step) and the succession of the two steps (el) (e2) preceded or not by step (eO).
- a treatment step (e) of at least one part of a liquid fraction of the digestate produced by digestion step (c) this treatment step being chosen from a step (eO) of treatment by electrocoagulation, a step of treatment by electro-oxidation (el) during which at least part of the ammonium ions
- the electrocoagulation treatment step (eO) may comprise a sub-step of precipitation of struvite by electrochemical dissolution of a sacrificial anode comprising magnesium, coupled with a sub-step of separation of the precipitated struvite.
- this treatment step (e) is to treat the nitrogen contained in the liquid fraction of the digestate produced by the ammonium-rich digestion step (c), which in particular makes it possible to return the treated liquid fraction to the line d. the main wastewater supply to the process, in step (a) or upstream of step (a).
- Another object of the invention relates to a wastewater treatment installation containing nitrogen in the form of ammonium ions and carbonaceous material, in particular for the implementation of the process according to the invention.
- the treatment installation according to the invention comprises:
- a first wastewater treatment unit comprising a wastewater supply pipe, a first pipe for evacuating a first effluent having a reduced carbonaceous content and a second pipe for evacuating a second effluent having an increased carbonaceous material content
- a second treatment unit comprising a supply pipe connected to the first pipe of the first treatment unit, a pipe for evacuating a third effluent having a reduced nitrogen content, the second treatment unit comprising at least an electro-oxidation treatment reaction zone and being devoid of an aerobic biological treatment reaction zone,
- the first unit may comprise at least one reaction zone chosen from a physical treatment reaction zone, optionally coupled to a physico-chemical treatment reaction zone, and a biological treatment reaction zone.
- the second processing unit may include:
- each second reaction zone being connected to a first reaction zone by a pipe for evacuating the effluent leaving the first reaction zone, or
- each second reaction zone being connected to a first reaction zone by a pipe for evacuating the effluent leaving (in particular produced by) the first reaction zone
- each third reaction zone being connected to a second reaction zone by a pipe for evacuating the effluent leaving the second reaction zone.
- the treatment installation may comprise a recirculation pipe connecting an outlet of the at least one first electro-oxidation treatment reaction zone or of the at least one second non-aerated biological treatment reaction zone to an inlet of a biological treatment reaction zone of the first unit.
- the second processing unit may comprise at least one discharge pipe from an electro-oxidation reaction zone chosen from a dihydrogen discharge pipe and a dioxygen discharge pipe.
- the treatment installation may also include at least one other treatment unit chosen from:
- a fourth treatment unit comprising a supply pipe connected to an evacuation pipe of the second treatment unit and a pipe for evacuating a fourth effluent, and comprising at least one selected reaction zone among a reaction zone for treatment of elimination of suspended matter, a reaction zone for treatment of elimination of phosphorus compounds, a reaction zone for treatment of elimination of micropollutants, a reaction zone for treatment of elimination of microorganisms,
- a fifth treatment unit comprising a supply pipe connected to a pipe for evacuating a liquid fraction of a digestate from the third unit and a pipe for evacuating an effluent, optionally connected to the pipe supply of the first unit, and comprising at least one reaction zone chosen from a reaction zone for treatment by electrocoagulation, a reaction zone for treatment by electro-oxidation, a reaction zone for non-aerated biological treatment by oxidation of ammonium ions by autotrophic bacteria anaerobes (Anammox reaction zone), and these last two reaction zones preceded or not by an electrocoagulation treatment reaction zone, an outlet of the electro-oxidation treatment reaction zone being connected to an inlet of the biological treatment reaction zone not ventilated.
- the electrocoagulation treatment reaction zone may in particular comprise an electrochemical reactor equipped with a sacrificial anode comprising magnesium and a solid-liquid separation device.
- the treatment installation can be equipped with a control system comprising at least one device for determining a content of ammonium and/or nitrate and/or nitrite ions, at least one fluid displacement device, and a control unit configured for:
- Anammox ANaerobic AMMOnium OXidation During this reaction, in anoxia conditions (in the absence of oxygen), rammonium is transformed into gaseous nitrogen using nitrites as an electron acceptor. This reaction is carried out in the presence of anaerobic autotrophic bacteria (they do not need free or dissolved O2).
- BMP methanogenic potential, corresponds to the maximum quantity of methane produced by a compound during its anaerobic degradation. It is generally expressed as the volume (NmL) of methane produced per gram of volatile substrate material.
- HRT Hydraulic retention time
- N/DN Nitrification / Denitrification.
- Refractory carbon carbon that cannot be removed by the purifying biomasses of wastewater treatment processes because the compound is too complex.
- Total electro-oxidation stage stage in which a total electrochemical oxidation of the species present is carried out (total oxidation of ammonium ions to dinitrogen, total oxidation of nitrites/nitrates to dinitrogen).
- Partial electro-oxidation stage stage in which a partial electrochemical oxidation of the species present is carried out, e.g. ammonium ions into nitrates and/or nitrites.
- An electro-oxidation step (total or partial) is incomplete when only part of the ions present in the effluent are oxidized.
- treatment in anoxic conditions we mean a treatment carried out in an environment to which no Ch is supplied (without aeration) but where oxygen is available in the environment in combined form, for example nitrates, sulfates or other.
- oxygen is available in the environment in combined form, for example nitrates, sulfates or other.
- treatment in oxic conditions is carried out in an environment to which oxygen O2 is supplied.
- Biological treatment can be carried out in fixed cultures where the bacteria develop in the form of a biofilm on the surface of a support material or in free cultures (also called activated sludge) where the bacteria develop freely in the enclosure (flocs) .
- the biological treatment is in free cultures (or “activated sludge”), it then includes a step of separating the bacterial culture (i.e. sludge) from the treated liquid effluent.
- the sludge is generally returned to biological treatment. Separation can be carried out in a clarifier (decanter) or in filters using microfiltration or ultrafiltration membranes.
- the separation of the biomass can be carried out downstream of the last reactor.
- wastewater we mean urban wastewater whose origin is essentially domestic but a part of which may be of industrial origin, or even industrial wastewater, in particular that coming from the agri-food industry or any other industry producing effluents loaded with carbonaceous matter and nitrogen.
- the wastewater will be municipal urban wastewater.
- Struvite is an ammonium-magnesium-phosphate salt with the chemical formula NH 4 MgPO 4 • 6 H 2 O.
- Figure 1 is a schematic representation of the treatment installation according to one embodiment of the invention.
- FIG. 2 is a schematic representation of the treatment installation according to a first alternative embodiment of the invention.
- FIG. 3 is a schematic representation of the treatment installation according to a second alternative embodiment of the invention.
- Figure 4 is a schematic representation of the treatment installation according to a third alternative embodiment of the invention.
- FIG. 5 is a schematic representation of the treatment installation according to a fourth alternative embodiment of the invention.
- FIG. 6 is a schematic representation of the treatment installation according to a fifth alternative embodiment of the invention.
- the process according to the invention is a process for treating wastewater containing nitrogen in the form of ammonium ions (NH 4 + ) and carbonaceous material, in other words a process for eliminating nitrogen and carbonaceous matter in wastewater.
- This wastewater often contains suspended particles which can also be eliminated by the process according to the invention.
- the nitrogen present in wastewater is mainly in the form of ammonium ions, however, it can also be present in the form of organic nitrogen which will ultimately be transformed by bacteria into ammonium ions through an ammonification reaction.
- the wastewater treatment process comprises a wastewater treatment step (a) producing a first effluent having a reduced carbonaceous material content and a second effluent having an increased carbonaceous material content, a treatment step (b) comprising at least one step of electro-oxidation of at least part of the first effluent to produce a third effluent having a reduced nitrogen content and a step (c) of anaerobic digestion of the second effluent to produce biogas and a digestate.
- Step (a) is thus a carbonaceous material elimination step while step (b) is a nitrogen elimination step and step (c) a biogas production step.
- step (b) is a carbonaceous material elimination step while step (b) is a nitrogen elimination step and step (c) a biogas production step.
- Wastewater treatment step (a) produces a first effluent having a reduced carbon content compared to the wastewater to be treated and a second effluent having an increased carbonaceous content compared to the wastewater to be treated.
- This treatment step (a) is a first treatment step which may comprise at least one treatment step chosen from a physical treatment step (al), optionally preceded by a physico-chemical treatment step (a2), and a step (a3, a4) of biological treatment, or a combination of these steps.
- the physical treatment step (al) can be chosen from a decantation step, a flotation step or a filtration step.
- the purpose of step (al) is to eliminate solid particles.
- the physical treatment step (al) thus produces sludge which corresponds to the second effluent having an increased carbonaceous material content and an effluent corresponding to the first effluent having a reduced carbonaceous material content.
- the physicochemical treatment step (a2) generally includes a coagulation (or electrocoagulation) step followed by a flocculation step.
- This type of treatment is typically carried out in the presence of chemical reagents, for example a coagulant and/or a flocculant.
- the coagulant can be added to the water to be treated or formed in situ (electrocoagulation).
- the flocculant is usually added to coagulated water.
- a flocculation step alone is also possible.
- the physico-chemical treatment step (a2) is implemented upstream of step (al) when it is present.
- the addition of a flocculant, or a coagulant and a flocculant, upstream of a physical treatment makes it possible to improve the separation of the first and second effluents, by also eliminating colloidal organic matter which may flocculate, and speed up the process, which will reduce the size of the installations.
- the physical treatment step (al) is a decantation step with or without prior physicochemical treatment step (a2), in particular with or without prior coagulation/flocculation.
- the treatment step (a) may also include at least one step (a3) of biological treatment of the carbonaceous material.
- the biological treatment step (a3) can be carried out under anoxic or oxic conditions adapted to eliminate the carbonaceous material present in the treated wastewater.
- Treatment in anoxic conditions makes it possible to eliminate biodegradable carbonaceous material by denitrification, that is to say without adding oxygen by aeration.
- part of the effluent produced by step (b) containing nitrates and/or nitrites is returned upstream of step (a) or in step (a), in upstream or in step (a3) of biological treatment in anoxic condition, which makes it possible to eliminate residual nitrogen during the biological treatment of carbon.
- Treatment in oxic conditions makes it possible to eliminate residual biodegradable carbonaceous material.
- the sequence of anoxic then oxic conditions makes it possible to limit the air intake for the overall elimination of carbon, and thus optimize the energy needs of said step (a3) of biological treatment.
- step (a3) of biological treatment is implemented in conditions limiting nitrification, i.e. using a low sludge age (low sludge retention time).
- the aim of this step is to only treat the carbonaceous material and not the nitrogen present in the waste water.
- those skilled in the art will be able to choose suitable conditions by controlling in particular one or more of the following parameters: residence time of the sludge (in particular chosen according to the temperature of the environment), hydraulic retention time, aeration, supply of oxygen, etc.
- the biological treatment step (a3) thus produces sludge which corresponds to the second effluent having an increased material content and an effluent corresponding to the first effluent having a reduced carbonaceous material content.
- step (a3) of biological treatment is carried out under anoxic conditions.
- step (a3) of biological treatment is carried out in two parts, the first being in anoxic condition and the second in oxic condition. Carrying out the biological treatment in anoxic conditions then in oxic conditions will make it possible to treat the residual biodegradable carbon and produce sludge with a high methanogenic potential.
- the treatment step (a) may also comprise at least one step (a4) of anaerobic biological treatment in free cultures of the carbonaceous material to advantageously biologically treat (eliminate) part of the phosphorus contained in the effluent.
- step (a4) is followed by step (a3), these steps are carried out in free cultures.
- step (a3) includes a separation step carried out for example in a clarifier. The separated activated sludge is then returned to step (a4).
- processing step (a) may include:
- step (al) of physical treatment or (a2) of physico-chemical treatment or the succession of at least one step (a2) of physico-chemical treatment and at least one step (al) of treatment physical (such as for example a preliminary decantation or filtration step with or without coagulation/flocculation),
- processing step (a) may include:
- step (a3) of biological treatment for eliminating the material carbon present in the effluent under anoxic and/or oxic conditions.
- the sludge from the physical treatment steps (a1) and/or (a2) physico-chemical treatment and the biological treatment steps (a3) (a4) are advantageously combined to form the second effluent having an increased carbonaceous material content.
- step (a) will be able to choose step (a), and in particular one or more of the steps (al), (a2), (a3), (a4) previously described, in the usual manner, depending on several factors, in particular the size of the plant, the quality of the wastewater to be treated and in particular its nitrogen and carbon content. He will also be able to choose appropriate implementation conditions for this step (a) to maximize the carbon content present in the second effluent.
- the first effluent from treatment step (a) is then treated by electro-oxidation to produce a third effluent having a reduced nitrogen content.
- step (b) at least part of the ammonium ions contained in the first effluent are oxidized to nitrites and/or nitrates, and/or to dinitrogen.
- Electro-oxidation also called anodic oxidation or electrochemical oxidation, is an advanced oxidation process. Electro-oxidation can be direct or indirect. Electro-oxidation is direct when electron exchanges take place directly between the surface of an electrode and the ions (ammonium ions) adsorbed on the surface of the electrode. Electro-oxidation is indirect when electrons are exchanged using intermediate oxidants. These oxidants can be generated on the surface of an electrode by transfer of electrons to ions present in water (chlorides, sulfates) or directly to water (electrolysis of water).
- the main oxidants generated on the surface of an electrode in wastewater are hydroxyl radicals (HO), sulfate radicals (SO4), hypochlorous acid (HC1O), or even ozone (O3) or peroxide. hydrogen (H2O2).
- HO hydroxyl radicals
- SO4 sulfate radicals
- HC1O hypochlorous acid
- O3 ozone
- hydrogen H2O2
- the treatment of ammonium ions can be carried out by oxidation of ammonium ions to nitrates and/or nitrites at the anode, while the reduction of nitrites and/or nitrates to N2 takes place at the cathode.
- ammonium ions can be directly oxidized to N2 at the anode.
- the electrolysis of water results in the production of H2 (gas) at the cathode and in the production of O2 (gas) at the anode. This electrolysis can occur whether the electro-oxidation is
- Electro-oxidation is a well-known process which will not be described in further detail. Electro-oxidation is typically controlled by varying the current density applied between the electrodes as well as the flow rate of effluent entering the electro-oxidation chamber (residence time).
- the organic material in particular the refractory carbonaceous material, and/or the organic micropollutants still present can be eliminated by partial or total indirect electro-oxidation, which makes it possible to achieve low carbon levels in treated water.
- reaction intermediates intermediate oxidants
- non-selective oxidants have an action on microorganisms, which makes it possible to achieve partial, or even total, disinfection of the treated water.
- Step (b) may comprise, or consist of, a step of total electro-oxidation of ammonium ions to dinitrogen.
- step (b) may comprise, or consist of, one or more electro-oxidation steps, for example a step of partial electro-oxidation of at least part of the ammonium ions to nitrates and/or nitrites followed by a step of total electro-oxidation of at least part of the nitrates and/or nitrites to dinitrogen, optionally with an intermediate Anammox step.
- electro-oxidation steps for example a step of partial electro-oxidation of at least part of the ammonium ions to nitrates and/or nitrites followed by a step of total electro-oxidation of at least part of the nitrates and/or nitrites to dinitrogen, optionally with an intermediate Anammox step.
- step (b) of nitrogen elimination can thus comprise a step of partial electro-oxidation (bl) of at least part of the ammonium ions to form nitrates and/or nitrites.
- Recycling is advantageously carried out upstream or in step (a3) of biological treatment of the carbonaceous material.
- this recycling is carried out upstream or in step (a3) of biological treatment in anoxic conditions.
- the presence of nitrites and/or nitrates in this recycling makes it possible to totally or partially eliminate the aeration usually necessary to reduce carbon through non-nitrifying biological treatment.
- the partial electro-oxidation step (bl) of the ammonium ions can then be followed by a total electro-oxidation step (b2) of at least part of the nitrates and/or nitrites to dinitrogen.
- a total electro-oxidation step (b2) of at least part of the nitrates and/or nitrites to dinitrogen.
- step (b2) at least part of the nitrates/nitrites are reduced to dinitrogen, however, part of the ammonium ions not oxidized during step (bl) can also be oxidized during this step.
- the total electro-oxidation step (b2) of at least part of the nitrates and/or nitrites aims to complete the elimination of the total nitrogen and to reach a limit content of total nitrogen predetermined by the operators or by discharge standards. This limit can be verified by direct measurement of the ammonium and/or nitrate and/or nitrite ion content with appropriate sensors and/or analyzers.
- step (b) may comprise the step of partial electro-oxidation (bl) of a portion of the ammonium ions followed by a step (b3) of biological treatment by oxidation of at least part of the ammonium ions by anaerobic autotrophic bacteria, also called Anammox, and optionally followed by a step of total electro-oxidation (b2) of at least part of the nitrates and/or nitrites to dinitrogen.
- the Anammox treatment step (b3) is thus coupled to the partial electro-oxidation step (bl) of the ammonium ions to nitrates/nitrites.
- Anammox treatment step (b3) involves anaerobic autotrophic bacteria which consume ammonium ions and nitrites to produce N2 without the need for oxygen and biodegradable carbon. It is therefore necessary as an input to the Anammox treatment step (b3) both ammonium ions and nitrites which are supplied by the incomplete partial oxidation step (bl).
- steps (bl) and (b3) makes it possible to reduce the overall energy consumption for nitrogen elimination, in particular, the optional step of total electro-oxidation (b2) of nitrates/nitrites located downstream then not having to oxidize all the ammonium ions not treated by step (bl) and all the nitrate/nitrite ions formed by step (bl).
- the partial electro-oxidation step (bl) can thus be implemented so as to obtain at the outlet an effluent presenting a ratio of nitrite/ammonium ion concentrations favoring its treatment by Anammox bacteria. This ratio is for example 0.8 to 1.8, preferably 1.1 to 1.5 gN/gN.
- the Anammox treatment step (b3) may not achieve a high ammonium ion removal rate, which would lead to a breakthrough of ammonium and nitrite ions at the treatment outlet, which must be converted to nitrates or even partially in N2 to comply with a strict discharge standard. It is then preferable to follow step (b3) of Anammox treatment with step (b2) of total electro-oxidation of at least part of the nitrates and/or nitrites and/or ammonium remaining as dinitrogen.
- step (b3) the H2 gas produced at the cathode during the electrolysis of water which can occur during the electrolysis step.
- the O2 gas produced at the anode during the electrolysis of water which can occur during the electro-oxidation step (b), and in particular during the partial electrooxidation steps (bl) of the ions ammoniums into nitrite/nitrite and/or total electro-oxidation (b2) of at least part of the nitrates and/or nitrites into dinitrogen can be recovered in order to be efficientlyzed, or reinjected into step (a3) of biological treatment for the elimination of carbonaceous matter to reduce the energy requirement when it is implemented partially or totally in oxic conditions.
- treatment step (b) is followed by a treatment step (d) of the third effluent produced.
- the treatment step (d) of the third effluent may comprise at least one treatment chosen from a treatment for eliminating materials in suspension, a treatment for the elimination of phosphorus compounds, a treatment for the elimination of micropollutants, a treatment for the elimination of microorganisms.
- the treatment step of removing suspended matter can be a physical or physico-chemical treatment as described in step (a). It may for example be a decantation, filtration or flotation step with or without, preferably with, prior coagulation/flocculation.
- the treatment step of eliminating phosphorus compounds can be a physical or physico-chemical treatment of the type previously described with the addition of a coagulant provided via a chemical reagent or by electrocoagulation with the aim of eliminating the phosphorus compounds.
- the treatment step of eliminating micropollutants or microorganisms may comprise at least one treatment chosen from electrocoagulation, advanced oxidation such as ozonation or electro-oxidation or by injection of a strong oxidant (e.g. ferrate ), an adsorption step on activated carbon, disinfection for example using oxidants (e.g. chlorine, peracids), ultraviolet rays, peracids or chlorine.
- a strong oxidant e.g. ferrate
- an adsorption step on activated carbon disinfection for example using oxidants (e.g. chlorine, peracids), ultraviolet rays, peracids or chlorine.
- the third effluent treatment step (d) is designed to further clean the water when it is discharged into a sensitive ecosystem or for reuse.
- Treatment step (d) makes it possible to produce a fourth effluent having a nitrogen and carbon content, micropollutant and/or microorganisms meeting specifications set by the operator or the legislation, and which can be discharged into nature. or reused.
- the treatment process may also include a step for controlling step (a) of wastewater treatment and step (b) of electro-oxidation treatment.
- the control step makes it possible to control the quantity of first effluent entering the treatment step (b) and/or one of the steps (bl), (b2) (b3) of step (b).
- the control step makes it possible to control the quantity of the effluent produced during the partial electro-oxidation step (bl) of the ammonium ions which can be recycled in step (a).
- a quantity of nitrogen present in the third effluent or the fourth effluent and in at least one effluent to be extracted chosen from the first effluent of step (a) is first determined.
- the effluent from the partial electro-oxidation step (bl) of ammonium ions and the effluent from step (b3) Anammox.
- the quantity of nitrogen can be measured directly by a sensor measuring the quantity of ammonium ions and/or nitrates/nitrites.
- the amount of nitrogen can also be measured indirectly by ammonia analyzers.
- a quantity of the at least one effluent to be extracted to reach a limiting nitrogen content in the third effluent or the fourth effluent and extract said quantity of the at least one effluent to be extracted and mix it. to the third effluent or to the fourth effluent.
- the quantity of nitrogen measured in the third or fourth effluent can be used to determine the quantity of the at least one effluent to be extracted so that combined with the third or fourth effluent, the total quantity of nitrogen of the latter does not exceed a limiting nitrogen content.
- the authorized nitrogen content limit particularly ammonium ions, can be chosen according to the nitrogen discharge limits authorized by legislation.
- a quantity of the effluent resulting from the electro-oxidation step -partial oxidation (bl) to be sent to the biological treatment step of step (a) is determined (i3).
- This quantity can be determined by measurement with nitrate/nitrite/ammonia sensors or by analyzers. This quantity corresponds to a nitrite and/or nitrate content making it possible to eliminate the carbonaceous material from the wastewater entering said biological treatment step (a3).
- This quantity of effluent is then sent to a biological treatment step (a3) of step (a), preferably, when this step is carried out in anoxic conditions. Recycling also makes it possible to reduce the energy required to be used during the second electro-oxidation step (b2).
- the second effluent from treatment step (a) is treated by an anaerobic digestion step (c) producing biogas and a digestate.
- Anaerobic digestion or methanization corresponds to a cascade of biochemical reactions allowing methanogenic bacteria to convert the organic matter present in a digester into biogas corresponding mainly to a mixture of carbon dioxide and methane.
- the remaining materials are called digestate.
- the conditions for implementing this step (c), in particular the temperature, pH and residence time, can advantageously be chosen in order to maximize the production of biogas.
- the anaerobic digestion step (c) may also include, or be followed by, a liquid-solid separation step of the digestate making it possible to separate the digestate into a solid fraction and a liquid fraction.
- This separation step can be a dehydration step of the digestate producing a solid fraction (dehydrated sludge) and a liquid fraction such as for example a centrifugation or filtration step.
- at least one pretreatment step of the second effluent upstream of step (c) of anaerobic digestion can be implemented to increase its yield.
- This pretreatment step can be chosen from a chemical, mechanical, biological and thermal pretreatment step.
- the chemical pretreatment step can be acidic or basic hydrolysis or advanced oxidation.
- the sludge can be heated to a temperature below 100°C.
- the mechanical pretreatment step can be an ultrasonic, microwave or electrokinetic disintegration step.
- the biological pretreatment step is for example a fermentation/hydrolysis step in mesophilic (30 - 42°C) or thermophilic (45 - 70°C) conditions with a residence time of around 1 to 3 days.
- the thermal pretreatment step can be a thermal hydrolysis process (THP).
- TTP thermal hydrolysis process
- the thermal hydrolysis process (THP) is a process consisting of heating sludge to a temperature generally between 140°C and 180°C with a treatment time of 30 minutes to 60 minutes.
- a post-treatment step can also be carried out at the outlet of step (c) of treatment by anaerobic digestion of the second effluent.
- the digested sludge resulting from step (c) of anaerobic digestion contains a large quantity of non-biodegradable organic matter usable for the production of additional energy.
- the post-treatment step is typically a hydrothermal carbonization (HTC) process. This process typically operates at temperatures between 180°C and 280°C for a period of several minutes to several hours in a non-oxidizing atmosphere.
- the wet dewatered sludge is treated with pressurized steam and the process produces a solid carbon fraction and a liquid fraction.
- the liquid fraction can be returned to step (c) of anaerobic digestion in order to increase biogas production.
- step (c) of anaerobic digestion of the second effluent can be followed by an additional treatment step (e) of at least a part of the liquid fraction of the digestate produced by step (c). ) of digestion.
- the effluent produced by the additional step (e) can then be returned to the process input stream to recycle the effluent. Recycling this flow makes it possible to optimize the process by treating the wastewater as much as possible and thus reducing the load contained in these returns.
- the additional treatment step (e) can be chosen from a step (eO) of treatment by electrocoagulation, a step (el) of treatment by electro-oxidation, a step (e2) of biological treatment by oxidation of ammonium ions by anaerobic autotrophic bacteria (Anammox treatment) and the succession of these last two stages (el) (e2) preceded or not by stage (eO).
- the solid fraction of biomass produced by this Anammox step (e2) can be returned as input to the digestion step (c).
- the additional step (e) makes it possible to treat a liquid fraction rich in ammonium ions in order to reduce its nitrogen content so that it is redirected into the main water pipe at the inlet of step (a) or into step (a).
- the step of treating the liquid fraction of additional step (e) is an electro-oxidation step which is a total oxidation of ammonium ions to dinitrogen.
- electro-oxidation would also oxidize dissolved carbon and should not be affected by variations in the capture rate of the sludge pretreatment process.
- the high temperature and the high nitrogen load also provide favorable conditions for the kinetics of electro-oxidation.
- the step of treating the liquid fraction of additional step (e) is an electro-oxidation step followed by an Anammox treatment step.
- the electro-oxidation step is an incomplete partial electro-oxidation step of ammonium ions to nitrates/nitrites.
- This implementation leads to better and stable control of the NH4/NOx ratio as explained during the description of step (b).
- the energy balance is also improved because only a part of the liquid fraction of the digestate undergoes electro-oxidation, which reduces the associated energy requirement.
- the additional step (e) comprises a step (eO) of treatment by electrocoagulation comprising a first sub-step of precipitation of the phosphorus and the ammonium contained in the liquid fraction of the digestate in the form of struvite by the implementation electrocoagulation by sacrificial anode comprising magnesium, coupled with a sub-step for separating the struvite formed which may for example be filtration or decantation.
- This step (eO) has the advantage of reducing the quantity of nitrogen to be oxidized by the subsequent steps, while producing a resource (struvite) with high agronomic added value (fertilizer), without the addition of an external chemical reagent because the Magnesium to provide for precipitation comes from electrocoagulation.
- the installation 100 for treating wastewater containing nitrogen mainly in the form of ammonium ions and carbonaceous material comprises a first unit 110 for treating wastewater adapted to the implementation of step (a) of the process, a second unit 120 for treatment by electro-oxidation adapted to the implementation of step (b) of the process, and a third unit 130 for treatment by anaerobic digestion adapted to the implementation implementation of step (c) of the process.
- the first wastewater treatment unit 110 is configured to be supplied by a supply pipe 1 for wastewater containing nitrogen partly in the form of ammonium ions and carbonaceous material and to produce a first effluent having a reduced carbonaceous material content discharged into a first discharge pipe 2 and a second effluent having an increased carbonaceous material content discharged into a second discharge pipe 3.
- the first treatment unit 110 can be a physical treatment unit, physico -chemical or biological.
- it may comprise one or more treatment reaction zones, chosen from a filtration reaction zone, a decantation reaction zone, a flotation reaction zone, a coagulation reaction zone, a zone flocculation reaction zone, an electrocoagulation reaction zone and a biological treatment reaction zone (with aeration for treatment in oxic conditions or without aeration for treatment in anoxic conditions).
- one or more reaction zones could be provided in parallel and/or in series for the implementation of each physical (al), physico-chemical (a2) or biological (a3, a4) treatment step.
- a reaction zone may include a reactor or a treatment enclosure.
- the reaction zone can then include a separation system by decantation (clarifier) or by filtration.
- the first unit 110 may comprise one or more biological treatment reaction zones, for example a single sequential reactor also called an SBR (Sequential Batch Reactor), a reactor with free cultures in suspension in continuous supply (activated sludge) or Biofilter reactor (reactor using thin and regularly renewed biological films) or several separate reactors, in particular with recirculation between them.
- SBR Simple Batch Reactor
- a reactor with free cultures in suspension in continuous supply activated sludge
- Biofilter reactor reactor using thin and regularly renewed biological films
- separate reactors allows continuous treatment of effluents.
- the invention is not limited by the number of reactors used, in particular several reactors each operating according to aerated/non-aerated cycles can be provided, or several continuously fed reactors or successive reactors comprising SBRs and continuous feed reactors.
- the first unit 110 when it contains an aerobic biological treatment reaction zone, will be sized so as not to carry out biological nitrification.
- the second electro-oxidation treatment unit 120 is configured to be supplied with first effluent by a supply pipe 4 connected to the first evacuation pipe 2 of the first treatment unit 110 and to evacuate via an evacuation pipe 5 a third effluent having a reduced nitrogen content.
- the second unit 120 comprises at least one electrooxidation reaction zone for carrying out the at least one electro-oxidation step.
- the second processing unit 120 comprises one or more electro-oxidation reaction zones connected in series and/or in parallel.
- the reaction zone(s) may in particular carry out total or partial oxidation.
- the second unit 120 also lacks an aerobic biological treatment reaction zone.
- the second unit 120 may also include a pipe 37 for evacuating dioxygen and a pipe 38 for evacuating dihydrogen from an electro-oxidation reaction zone.
- the first discharge pipe 2 and the supply pipe 4 are also connected, here by a valve 30, to an optional bypass pipe 13 (bypass pipe).
- the evacuation bypass pipe 13 is connected to the evacuation pipe 5 of the third effluent.
- the third anaerobic digestion treatment unit 130 comprises a pipe supply line 6 connected to the second pipe 3 of the first treatment unit 110, a biogas discharge pipe 7 and a digestate discharge pipe 8.
- the third unit 130 may comprise one or more anaerobic digestion reaction zones, in particular mounted in series and/or in parallel.
- Figures 2 and 3 present alternative configurations of the installation, in particular for the implementation of step (a) of wastewater treatment.
- Figures 2 and 3 respectively show a wastewater treatment installation 200 and 300 comprising a first wastewater treatment unit 110, a second electro-oxidation treatment unit 120 and a third anaerobic digestion treatment unit 130. These units 120 and 130 not being modified compared to Figure 1, the numbering remains the same for these units and the pipes concerned.
- the first wastewater treatment unit 110 comprises a unit 111 for physical and/or physico-chemical treatment of wastewater capable of implementing steps al) or a2) + al) and a biological treatment unit 112 capable of carrying out step a3) of the process.
- the biological treatment unit 112 comprises one or more reaction zones. If the biological treatment is carried out in free cultures, then the last reaction zone of the unit includes a biomass separation system such as a clarification enclosure, not shown in the figure.
- the physical and/or physico-chemical treatment unit 111 is supplied via the wastewater supply pipe 1 and comprises an evacuation pipe 9 for part of the second effluent and an evacuation pipe 11 for the effluent produced.
- the biological treatment unit 112 comprises a supply pipe 12 connected to the discharge pipe 11 of the unit 111. It is also connected to the first discharge pipe 2 of the first effluent and comprises a second discharge pipe evacuation 3 of part of the second effluent.
- the first evacuation pipe 2 is connected to the supply pipe 4 of the second unit 120 and optionally to a bypass pipe 13, as described with reference to Figure 1.
- the unit 112 can receive the dioxygen circulating in pipe 37 described with reference to Figure 1.
- Figure 3 differs from Figure 2 by the addition of an intermediate unit 113 between units 111 and 112 capable of implementing step a4) of the process by means of one or more biological treatment reaction zones.
- Unit 113 is an anaerobic biological treatment unit comprising a supply line 15 connected to the discharge line 11 of the unit 111 and a discharge line 16 connected to the supply line 12 of the unit 112
- the unit 112 also includes a sludge recirculation pipe 34 connected to the anaerobic biological treatment unit 113. Recirculation line 34 is only present if the biological treatments of units 112 and 113 are carried out in free cultures.
- Figures 4 and 5 present alternative configurations of the installation, in particular for the implementation of step (b) of treatment by electro-oxidation.
- Figures 4 and 5 show an installation 400 and 500 respectively for wastewater treatment comprising a first wastewater treatment unit 110, a second electro-oxidation treatment unit 120 and a third anaerobic digestion treatment unit 130. These units 110 and 130 not being modified compared to Figure 1, the numbering remains the same for these units and the pipes concerned.
- the second electro-oxidation treatment unit 120 comprises a unit 121 for partial electro-oxidation treatment of ammonium ions into nitrate/nitrite ions capable of implementing step b1) of the process and a unit 122 for treating total electro-oxidation of nitrate/nitrite ions into dinitrogen capable of implementing step b2) of the process.
- Each unit 121, 122 comprises one or more electro-oxidation reaction zones.
- the partial electro-oxidation treatment unit 121 is supplied with first effluent via the supply pipe 4 connected to the discharge pipe 2 of the unit 110, and comprises an effluent discharge pipe 17 output from step b1).
- the evacuation pipe 17 is connected, here by a valve 30, 32, to at least one pipe, here three pipes: a supply pipe 18 of the unit 122, an optional recirculation pipe 20 of part of the the effluent produced upstream of the unit 110 and a bypass pipe 19 for part of the effluent produced.
- the bypass pipe 19 is connected to the bypass pipe 13 and to the evacuation pipe 5 of the third effluent.
- the optional recirculation pipe 20 preferentially returns the effluent produced upstream of the treatment unit 112 implementing step a3) of the first treatment unit 110 (not shown in Figure 4).
- the total electro-oxidation treatment unit 122 comprises a supply pipe 18 connected to the discharge pipe 17 of the unit 121 and the third effluent that it produces leaves via the discharge pipe 5.
- Figure 5 differs from Figure 4 by the addition of an intermediate unit 123 located between units 121 and 122 and capable of implementing step (b3) of the process.
- Unit 123 includes one or more non-aerated biological treatment reaction zones.
- Unit 123 is an Anammox treatment unit and includes a supply line 21 connected to the discharge line 17 of unit 121 and a discharge line 22 connected to the supply line 18 of unit 122 and to the bypass pipe 19.
- the supply pipe 21 of the unit 123 is also connected to a by-pass pipe 33 of a part of the first effluent coming from the evacuation pipe 2 of the unit 110 .
- the installation shown in Figure 5 has a fourth optional unit 124 capable of implementing the treatment step (d) of the third effluent.
- the treatment unit 124 comprises a supply pipe 23 connected to the evacuation pipe 5 of the unit 122 and an evacuation pipe 24 of the fourth effluent.
- the fourth unit may comprise one or more treatment reaction zones connected in series and/or in parallel.
- Figure 6 shows an alternative configuration of the treatment installation, in particular downstream of the anaerobic digestion unit.
- Figure 6 shows an installation 600 wastewater treatment unit comprising a first wastewater treatment unit 110, a second electro-oxidation treatment unit 120 and a third anaerobic digestion treatment unit 130.
- These units 110, 120 and 130 not being modified compared to Figure 1, the numbering remains the same for these units and the pipes concerned, except for unit 130 which here includes an evacuation pipe 8 'of a liquid fraction of the digestate produced.
- the installation comprises a fifth unit 131 capable of implementing the additional step e) of the process.
- the fifth unit 131 comprises an optional electrocoagulation treatment unit 132 capable of carrying out step eO), an electro-oxidation treatment unit 133 capable of carrying out step el) and an optional Anammox treatment unit 134 capable of carrying out step e2).
- Each unit may include one or more appropriate treatment reaction zones connected in series and/or parallel.
- Unit 132 includes a supply pipe 25 connected to the discharge pipe 8' of unit 130 and a discharge pipe 26 for the effluent produced.
- the third unit 130 comprises a liquid-solid separation system (not shown) making it possible to separate the digestate into a solid fraction and a liquid fraction.
- the liquid fraction is then evacuated via the evacuation pipe 8’.
- this liquid-solid separation system could be external to the third unit 130 and located between it and the fifth unit 131.
- Unit 133 comprises a supply pipe 27 connected to the discharge pipe 26 of unit 132 and a discharge pipe 28 for the effluent produced.
- the unit 134 comprises a supply pipe 35 connected to the discharge pipe 28 of the unit 132 and a discharge pipe 36 for the produced effluent sending this effluent into the wastewater supply pipe 1.
- the treatment installations 100, 200, 300, 400, 500, 600 previously described may also include a process control system for implementing steps (il), (i2) and (i3) of the control step.
- the control system comprises at least one device 29 for determining a content of ammonium and/or nitrate and/or nitrite ions, at least one fluid displacement device 30 and a control unit 31.
- the control unit 31 is configured to implement:
- step (i2) from the quantities determined in step (il) and by controlling the at least one fluid displacement device 30,
- step (i3) from the quantities determined in step (il) and by controlling the at least one fluid displacement device 30.
- the at least one determination device 29 may be one or more sensors for the nitrogen content of the effluents.
- the at least one device 29 can be installed at the level of the evacuation pipe 5 of the third effluent or the evacuation pipe 24 of the fourth effluent and at the level of at least one pipe chosen from the first evacuation pipe 2 of the first effluent having a reduced carbonaceous material content, the evacuation pipe 17 of the effluent leaving the electro-step partial oxidation and optionally of the evacuation pipe 22 of part of the effluent produced by the Anammox step b3).
- the quantities measured by the at least one determination device 29 are sent to the control unit 31 which will calculate the quantity of fluid to be extracted through the bypass pipes and control the movement of this quantity.
- the control unit 31 may include a computer, or more generally at least one processor or any other type of digital calculator.
- the control unit 31 can also include a plurality of separate digital processors or computers, forming different means of the device, cooperating with each other.
- the at least one fluid displacement device 30 may comprise one or more valves, for example a three or four-way valve whose third way leads to the bypass pipe 13 and optionally to the bypass pipe 19.
- the at least one a device 30 can also include one or more positive displacement pumps (or any pump associated with a frequency variator and a flow meter to adjust the flow rate) capable of taking a calculated quantity of fluid to be extracted.
- the bypass pipes connected to the valves also form displacement devices within the meaning of the invention.
- the control system comprises a device 29 for determining a content of ammonium and/or nitrate ions and/or nitrites, a fluid displacement device 32 and the control unit 31.
- the determination device 29 can be a sensor for the nitrogen content of the effluents. It is installed here at the level of the evacuation pipe 17 of the effluent leaving the partial electro-oxidation treatment unit 121.
- the measured quantity is sent to the control unit 31 which will calculate the quantity of fluid to be recycled corresponding to a nitrate and/or nitrite content necessary for an anoxic biological treatment to eliminate carbonaceous material.
- the control unit 31 also controls the movement of the quantity of fluid to be recycled.
- the fluid displacement device 32 can be a three-way or four-way valve, one of the paths of which leads to the recirculation line 20.
- the device 32 can also be a positive displacement pump (or any pump associated with a frequency variator and a flow meter) capable of taking the calculated quantity to be recycled.
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- Environmental & Geological Engineering (AREA)
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Abstract
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CN202380039890.4A CN119183442A (zh) | 2022-05-19 | 2023-05-17 | 最大化沼气产量的包括电氧化步骤的废水处理方法 |
AU2023273260A AU2023273260A1 (en) | 2022-05-19 | 2023-05-17 | Wastewater treatment method with maximization of biogas production comprising an electro-oxidation step |
EP23730165.0A EP4526260A1 (fr) | 2022-05-19 | 2023-05-17 | Procédé de traitement d'eaux usées avec maximisation de la production de biogaz comprenant une étape d'electro-oxydation |
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FR2204775 | 2022-05-19 | ||
FR2204775A FR3135716A1 (fr) | 2022-05-19 | 2022-05-19 | Procédé de traitement d’eaux usées avec maximisation de la production de biogaz comprenant une étape d’électro-oxydation |
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CN (1) | CN119183442A (fr) |
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CN111646634A (zh) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | 一种超声耦合光电芬顿活化过硫酸盐水处理系统和处理水的方法 |
WO2021101366A1 (fr) * | 2019-11-20 | 2021-05-27 | Sime Darby Plantation Intellectual Property Sdn. Bhd. | Procédé de traitement d'un effluent d'huilerie de palme |
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- 2023-05-17 WO PCT/FR2023/050707 patent/WO2023222979A1/fr active Application Filing
- 2023-05-17 CN CN202380039890.4A patent/CN119183442A/zh active Pending
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WO2021101366A1 (fr) * | 2019-11-20 | 2021-05-27 | Sime Darby Plantation Intellectual Property Sdn. Bhd. | Procédé de traitement d'un effluent d'huilerie de palme |
CN111646634A (zh) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | 一种超声耦合光电芬顿活化过硫酸盐水处理系统和处理水的方法 |
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EP4526260A1 (fr) | 2025-03-26 |
CN119183442A (zh) | 2024-12-24 |
AU2023273260A1 (en) | 2024-11-07 |
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