WO2017081354A1 - Procédé pour le traitement des eaux usées: processus flox - Google Patents
Procédé pour le traitement des eaux usées: processus flox Download PDFInfo
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- WO2017081354A1 WO2017081354A1 PCT/ES2016/070805 ES2016070805W WO2017081354A1 WO 2017081354 A1 WO2017081354 A1 WO 2017081354A1 ES 2016070805 W ES2016070805 W ES 2016070805W WO 2017081354 A1 WO2017081354 A1 WO 2017081354A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- iron
- addition
- lll
- ozone
- stage
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005345 coagulation Methods 0.000 claims abstract description 22
- 230000015271 coagulation Effects 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- -1 Fe(III) ions Chemical class 0.000 claims abstract 3
- 238000004064 recycling Methods 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 16
- 238000005189 flocculation Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 230000016615 flocculation Effects 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 150000007514 bases Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000701 coagulant Substances 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 description 22
- 238000006385 ozonation reaction Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Definitions
- the present invention relates to a process for the treatment of wastewater, and especially toxic or biorefractory wastewater with contaminants dissolved therein.
- the procedures that are most related to that which is the subject of the present invention are those that include oxidative methods of pollutants, usually comprising the addition to the waters to be treated of an oxidant, generally ozone or hydrogen peroxide; and including the process, in earlier or later stages, the addition of coagulants such as aluminum salts, iron salts or lime, to achieve a reduction in the final concentration, and the addition of flocculants in order to allow sedimentation and removal of the components in a final stage of filtration.
- pollutants usually comprising the addition to the waters to be treated of an oxidant, generally ozone or hydrogen peroxide; and including the process, in earlier or later stages, the addition of coagulants such as aluminum salts, iron salts or lime, to achieve a reduction in the final concentration, and the addition of flocculants in order to allow sedimentation and removal of the components in a final stage of filtration.
- ozone an oxidizing agent, since it is capable of participating in a large number of reactions with organic and inorganic compounds, providing a decrease in the color and turbidity of wastewater. It also acts as a disinfectant agent, given its biocidal properties.
- conventional ozonation processes consume at least stoichiometric amounts of ozone, which is an expensive oxidant, which is why they are only applied as a tertiary treatment or in dilute solutions, for example for the purification of mouth water. These stoichiometric amounts are governed by the Chemical Oxygen Demand (COD) of each wastewater.
- COD Chemical Oxygen Demand
- ozone is not able to mineralize in itself only to organic pollutants, so it is used by activating it, for example, with ultraviolet (UV) lamps to produce hydroxyl (OH) radicals.
- UV ultraviolet
- OH hydroxyl
- these wastewater treatment procedures include, at a stage before or after ozonation, coagulation and flocculation processes in which colloidal particles and suspensions of very fine particles are combined into agglomerates that can be separated via sedimentation, flotation, filtration, centrifugation or other separation methods.
- This separation is achieved by adding different chemical substances (coagulants and flocculants) that favor destabilization and agglomeration of individual colloidal particles.
- coagulation the colloidal particles and suspensions of very fine solids are destabilized, to begin to agglomerate in microflocols, if the conditions are appropriate; while in flocculation, the microflocles agglomerate forming macrophages, which can be filtered or separated by decantation.
- coagulation is not very efficient when it comes to eliminating contaminants dissolved in water (see example 2).
- Patent US5639379 a process for the removal of the color and odor of aqueous tributaries contaminated with textile dyes is described, the effluent being treated with permanganate, followed by a treatment with hydrogen peroxide, a coagulation and flocculation treatment maintaining a basic pH, a treatment with a water soluble polymer and the separation of the precipitated material.
- Patent US5679257 describes an industrial wastewater treatment in which ozone is used for the elimination of contaminants, combined with the application of ultrasound to cause coagulation and precipitation thereof. In a second stage, ozonation is combined with ultraviolet light.
- Ozone is produced "in situ" at high concentration through the interaction of electrolytically produced oxygen and ultraviolet light, being used to produce oxidation of pollutants.
- the by-products are subsequently removed by decantation, flocculation, coagulation or filtration.
- GB2056962 a process for the purification of wastewater containing coloring materials is described; said process comprising an oxidation phase in which hydrogen peroxide is used as an oxidizing agent and with coagulation, flocculation and decantation phases, before or after.
- Fenton process which consists in the oxidation of organic molecules through the use of hydrogen peroxide and a salt of Fe (ll), which is added, in small quantities, as a catalyst.
- This process is based on the generation of OH radicals by the catalytic decomposition of hydrogen peroxide in acidic medium. These radicals oxidize rapidly most organic substances to mineralizarlas, transforming them into C0 2, water and inorganic species. Oxidation processes that are based on the in situ generation of OH radicals from clean oxidants such as those mentioned above are generically called advanced oxidation processes.
- this process includes the simultaneous addition and at the same stage of a mixture of at least two oxidants between ozone, oxygen and / or hydrogen peroxide, so that ozone and / or hydrogen peroxide are added in sub-stoichiometric quantities with respect to the COD of the pollutants to be removed, and a Fe (lll) iron ion-supply substance in adequate amounts to produce coagulation and precipitation of ferric hydroxide to a pH between 3 and 7.
- a Fe (lll) iron ion-supply substance in adequate amounts to produce coagulation and precipitation of ferric hydroxide to a pH between 3 and 7.
- the coagulant comprises Fe ions (lll) given their ability to catalyze oxidation reactions with radical generation. Adsorbed radicals on the surface can help coagulation and flocculation of particles by coupling, reducing or eliminating the needs of flocculants.
- this procedure can be complemented by the addition of a flocculant, either in the initial stage of oxycoagulation or in a subsequent stage of flocculation and sedimentation in a decanter.
- the introduction of at least one oxidant in the gas phase can also produce the flotation of the polluting substances or their flocs, facilitating their separation from the treated water
- one of the oxidants used is oxygen
- this can be pure or in the form of a gas containing it, for example air, which substantially lowers the cost of the process compared to those that use pure gases.
- the amounts of iron suitable for oxycoagulation are not catalytic as in Fenton processes, but clearly higher, of the order of 1 gram / liter.
- the amount of ferric ions Fe (lll) that are supplied to the wastewater is greater than 0.1 grams / liter and preferably is between 0.2 and 2 grams / liter, although the optimum dose depends on each wastewater and should be studied on a case-by-case basis (see example 1).
- the process also contemplates, if the case requires, a neutralization and / or precipitation step by the addition of an alkaline compound, such as a hydroxide and / or a magnesium, calcium, sodium or potassium carbonate.
- an alkaline compound such as a hydroxide and / or a magnesium, calcium, sodium or potassium carbonate.
- the process culminates with a final stage of separation of the ferric hydroxide precipitate from the purified waters by a conventional system, such as decantation, flotation, centrifugation or filtration.
- a conventional system such as decantation, flotation, centrifugation or filtration.
- By-product can be recycled to the process after a heat treatment to oxidize contaminants entrained with it and subsequent acid redisolution.
- the iron can be added either in the form of iron compounds, for example Fe (III) salts such as sulfates or chlorides, or in the form of metallic iron or alloys containing it.
- Fe (III) salts such as sulfates or chlorides
- metallic iron or alloys containing it can be dissolved in the water to be treated by oxidative attack in acidic medium or by anodic solution.
- the addition of iron in any of these forms allows obtaining satisfactory results.
- the process of the invention can be carried out at any temperature between 0 e C. and 99 e C, preferably between 10 e C and 50 e C.
- its remarkable efficiency at room temperature and at atmospheric pressure allows to significantly reduce the costs of same.
- TOC total organic carbon
- COD chemical oxygen demand
- suspended materials color, odor, turbidity, ammoniacal nitrogen and toxicity.
- the treated waters are also disinfected by their germicidal action.
- the oxidants used are not toxic and are clean since their only reaction by-products are oxygen and water. DESCRIPTION OF THE FIGURES.
- Figure 1 shows a comparative graph of the results obtained in the treatment of water contaminated with phenol by a conventional ozonation process and in several experiments carried out according to the procedure object of this invention.
- Figure 2 shows a comparative graph of the results obtained from reduction of TOC and COD of contaminated water by conventional coagulation treatments (A), ozonation (B), coagulation with pre-ozonation (C) and by the method of the invention ( D) respectively.
- COD eliminations were even greater than those of COT. For example, after 60 minutes of reaction, 92% and 95% of COD were removed in experiments with molar ratios 1 and 2 respectively.
- the graph of Figure 2 compares the results of COD and COD reduction obtained in the previous experiment (D) with the results obtained under similar conditions by conventional coagulation (A), ozonation (B), and pre coagulation treatments -ozonation (C).
- the treatment was carried out on 750 mL of diluted solution of said waters in a 1/10 ratio, with a mixture of oxygen and ozone.
- the maximum gas flow used was 200L / h. With the application to the ozone generator of a current of 1 amp, a resulting flow of 13g / h of ozone is achieved.
- Fe (lll) in the form of hydrated iron sulfate was used for its treatment. 50g were weighed and dissolved in 150mL of hot millipore quality water and with the addition of sulfuric acid to pH 0.
- the solution was treated at room temperature (26 e C).
- foams were produced that were controlled by reducing the gas flow, but by adding Fe (lll) to the solution, the foams increased while the pH decreased.
- Fe (lll) By adding diluted NaOH the pH was increased to 6 and oxycoagulation occurred.
- H2SO4 the pH was reduced to 4 and the foams decreased.
- the gas flow rate was slowly increased for 15 minutes to the point where all the ozone could pass through the reactor.
- the pH continued to drop spontaneously, but was controlled between 3 and 4 during the rest of the experiment.
- 8 ml_ of Fe solution (lll) were fed into the system.
- TOC Total Organic Carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Le procédé selon l'invention comprend l'ajout simultané et lors d'une même étape d'un mélange d'au moins deux oxydants choisis parmi: l'ozone, l'oxygène et/ou le peroxyde d'hydrogène, et d'un coagulant comprenant des ions de Fe(III) dans des quantités adéquates pour produire la coagulation et la précipitation d'hydroxyde ferrique à un pH compris entre 3 et 7. Ledit procédé comprend une étape finale de séparation des eaux traitées des particules formées pendant le processus et, facultativement, l'ajout d'un floculant à l'étape d'oxydation/coagulation ou dans une étape suivante, une étape de neutralisation et/ou de précipitation, et une série d'étapes pour le recyclage de l'hydroxyde ferrique obtenu comme sous-produit.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201531646A ES2612380B1 (es) | 2015-11-13 | 2015-11-13 | Procedimiento para el tratamiento de aguas residuales: proceso FLOX |
| ESP201531646 | 2015-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2017081354A1 true WO2017081354A1 (fr) | 2017-05-18 |
Family
ID=58676836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ES2016/070805 WO2017081354A1 (fr) | 2015-11-13 | 2016-11-11 | Procédé pour le traitement des eaux usées: processus flox |
Country Status (2)
| Country | Link |
|---|---|
| ES (1) | ES2612380B1 (fr) |
| WO (1) | WO2017081354A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054319A (zh) * | 2019-05-11 | 2019-07-26 | 中铁二十一局集团第六工程有限公司 | 一种基于绿锈的隧道施工污水处理方法 |
| CN110152667A (zh) * | 2019-04-23 | 2019-08-23 | 同济大学 | 一种铁屑表面改性形成γ-FeOOH的方法 |
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| WO2002004360A1 (fr) * | 2000-07-07 | 2002-01-17 | Microbar Inc. | Procede de traitement d'eaux usees produites durant la fabrication de semi-conducteurs |
| US6596176B1 (en) * | 2001-06-26 | 2003-07-22 | Delozier Ii Gerald Edward | Potable water treatable process using hydrogen peroxide and metallic coagulant |
| WO2009101455A1 (fr) * | 2008-02-11 | 2009-08-20 | Pantelis Xynogalas | Procédé physico-chimique de traitement de déchets liquides et semi-solides d’huileries d’olive utilisant de l’ozone (o3) |
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- 2015-11-13 ES ES201531646A patent/ES2612380B1/es active Active
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2016
- 2016-11-11 WO PCT/ES2016/070805 patent/WO2017081354A1/fr active Application Filing
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| WO2002004360A1 (fr) * | 2000-07-07 | 2002-01-17 | Microbar Inc. | Procede de traitement d'eaux usees produites durant la fabrication de semi-conducteurs |
| US6596176B1 (en) * | 2001-06-26 | 2003-07-22 | Delozier Ii Gerald Edward | Potable water treatable process using hydrogen peroxide and metallic coagulant |
| WO2009101455A1 (fr) * | 2008-02-11 | 2009-08-20 | Pantelis Xynogalas | Procédé physico-chimique de traitement de déchets liquides et semi-solides d’huileries d’olive utilisant de l’ozone (o3) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152667A (zh) * | 2019-04-23 | 2019-08-23 | 同济大学 | 一种铁屑表面改性形成γ-FeOOH的方法 |
| CN110152667B (zh) * | 2019-04-23 | 2021-09-03 | 同济大学 | 一种铁屑表面改性形成γ-FeOOH的方法 |
| CN110054319A (zh) * | 2019-05-11 | 2019-07-26 | 中铁二十一局集团第六工程有限公司 | 一种基于绿锈的隧道施工污水处理方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2612380B1 (es) | 2018-07-27 |
| ES2612380A1 (es) | 2017-05-16 |
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