EP4240698A1 - Procédé de traitement de liquide et source d'ajout pour celui-ci - Google Patents
Procédé de traitement de liquide et source d'ajout pour celui-ciInfo
- Publication number
- EP4240698A1 EP4240698A1 EP21801850.5A EP21801850A EP4240698A1 EP 4240698 A1 EP4240698 A1 EP 4240698A1 EP 21801850 A EP21801850 A EP 21801850A EP 4240698 A1 EP4240698 A1 EP 4240698A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substance
- suspension
- less
- mol
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000011282 treatment Methods 0.000 title claims description 14
- 239000000126 substance Substances 0.000 claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 230000005484 gravity Effects 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 230000008093 supporting effect Effects 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 preferably kaolin Chemical compound 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000012088 reference solution Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 239000004411 aluminium Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000010801 sewage sludge Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000000700 radioactive tracer Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000006335 Phosphate-Binding Proteins Human genes 0.000 description 1
- 108010058514 Phosphate-Binding Proteins Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910020169 SiOa Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical class [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 1
- 229960000623 carbamazepine Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- 239000002609 medium Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012927 reference suspension Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
Definitions
- the invention relates to a treatment of a liquid consisting predominantly of water in order to influence the concentration of a substance contained therein.
- Such treatments are well known, for example from waste water treatment in sewage treatment plants.
- micropollutants from treated wastewater in particular microplastics and pharmaceuticals
- process engineering approaches such as ozonization, membrane separation processes, biological degradation or adsorption using activated carbon with an elimination performance comparable to ozonization famous.
- Such an additional cleaning step is commonly referred to as a 4th cleaning stage.
- 4th purification stages with additional settling basins are to be regarded as very reliable and robust compared to other approaches compared to membrane processes in operation and are often regarded as a promising approach with a view to future legal requirements regarding micropollutants in the treated water.
- DE 10 2012 019 709 A1 discloses an agent in which an aluminum compound, e.g. B. AI 2 (OH) 5 CI, is used in a form as a flocculant in which their basicity is between 35 and 50%.
- an aluminum compound e.g. B. AI 2 (OH) 5 CI
- additional advantageous effects are to be exerted on the aqueous media to be treated, particularly when adjusting the pH of the treated medium.
- the invention is based on the object of further developing a method of the type mentioned at the outset with a view to a satisfactory combination of effectiveness, reliability and simplicity.
- This object is achieved by the invention from a procedural point of view by a method for changing the concentration of at least one organic second substance (the micropollutants) contained in a liquid consisting predominantly of water and containing a first substance containing phosphate in particular (the micropollutants) in the liquid by adsorption of particles of the second Substance to a third substance added to the liquid, consisting predominantly and in particular to more than 80 percent by weight of carbon and having an inner surface area of more than 100 m 2 /g, under a movement of the adsorbing third substance with movement direction component in the direction of gravity supporting effect through a product a precipitation of the first substance with a fourth substance added to the liquid, containing or consisting of a metal salt containing iron and/or aluminum, in which the addition of the fourth substance and the addition of de s already before this addition in a manner counteracting its later movement in the liquid with a movement component against the direction of gravity pretreated third substance in close temporal and spatial coupling.
- the addition of coordinated amounts of the third and fourth substances should be no more than 10 minutes, preferably no more than 5 minutes, in particular no more than 1 minute apart, and spatially no more than 1.4 r*, preferably no more than r*, in particular no more than 0.7 r*, where r* is equal to the cube root of 0.75 V/TT and V is the volume of liquid treated in one minute.
- the inner surface of the third substance is at least partially wetted as a result of the pretreatment. Compared to the dry form of activated carbon, this increases its effective specific weight after addition, which counteracts the adsorbent floating.
- the third substance/the activated carbon is preferably not too fine in terms of its particle size, so a d 50 of not less than 10 ⁇ m, preferably not less than 17 ⁇ m, in particular 20 ⁇ m, is preferred. This also provides an advantageous growth surface for bacteria.
- this wetting and the addition of the third substance are more than 20 seconds apart, preferably more than 1 minute, more preferably more than 10 minutes, in particular more than one hour apart. This promotes the degree of wetting of the inner surface and reduces air inclusions in the porous adsorbent.
- the wetting is realized by providing a suspension in which the third substance is suspended.
- the third substance is added in the form of adding a suspension in which the third substance is suspended.
- the suspension contains a fifth substance that inhibits sedimentation of the third substance in the suspension.
- the fifth substance preferably has or consists of, in particular, finely divided silicon dioxide. This is particularly advantageous when more than 12 hours, in particular more than 48 hours, even more than 10 days, lie between the wetting of the third substance and its addition.
- the fourth substance preferably has one or more from the group of aluminum chloride, including polyaluminum chloride, iron chloride or iron sulfate, or consists at least predominantly of it; alternatively or additionally, other metal salts can also be used, such as aluminum sulfate.
- the quantitative ratio of the fourth and third substance is determined by a common addition source. Dosing is particularly simple in this way, and an undesired change in the intended quantity ratio caused by operating errors can be reliably avoided.
- the common addition source is present in the form of a suspension containing the fourth substance and the third substance.
- the liquid containing the second substance is waste water, and the change in the concentration of the second substance preferably takes place in the third cleaning stage of a sewage treatment plant.
- the second substance adsorbed by the activated carbon can be in the form of micropollutants, such as microplastics and/or pharmaceuticals. Sedimentation of the activated charcoal adsorbing these micropollutants occurs through sinking of the activated charcoal, which sinking is favored by mechanical entrainment of gelatinous flakes, to the formation of which e.g. phosphate precipitated by the fourth substance (as a component of the first substance or first substance) contribute. In this way, an improved removal of such micro-contaminants is already possible in the third purification stage, without requiring the structural complexity of a fourth purification stage previously considered for such a removal of micro-contaminants.
- the micropollutants accumulate in the sewage sludge and produce a comparatively high concentration of micropollutants there, while the liquid in the tank has a lower concentration of micropollutants than before the addition of the suspension.
- the sewage sludge can then be removed from the tank as usual and then, for example, thermally treated, thus reliably destroying the micropollutants.
- the suspension with the precipitant and the activated carbon is added to the waste water in the settling tank and/or in the inlet to the settling tank by means of a dosing device.
- a dosing device Earlier addition to the biological purification stage and/or its feed is also being considered.
- the temporal and spatial coupling is as close as possible realized.
- the addition of a product that can be dosed in liquid reduces the micropollutants contained in the pre-clarified water at the same time as a precipitation step, preferably phosphate precipitation, by means of metal salts, in particular by more than 30%, preferably by more than 50%.
- This stabilized suspension can, for example, be added from IBCs with commercially available dosing devices, in particular dosing pumps, at a suitable point, e.g.
- a suitable tracer compound for evaluating the adsorptive separation is benzotriazole, which is reduced by at least 20%, also by more than 40%, even by more than 70% compared to the feed concentration.
- the adsorptively bound micropollutants accumulate in the sewage sludge and can be thermally treated with it, for example, and thus destroyed. Carbamazepine could also be used as a tracer compound.
- the method according to the invention and the common source of addition according to the invention can also be used in applications other than the field of sewage treatment plants, for example in the local treatment of drinking water, but also for the purification of problematic wastewater from industry (dyeing, electroplating, food processing, etc.) , i.e. places where unwanted micropollutants are removed/reduced according to the polluter-pays principle.
- an amount of 0.005% to 0.2% of the amount of liquid to be treated converted during this time is added from this suspension, depending on the load on the liquid per unit of time, in particular at the comparatively higher loads, definitely more, preferably up to 0.5%, even up to 1% or 2%, and with comparatively low loads also less, for example from 0.002%.
- the suspension contains the fourth substance with a metal ion concentration in moles per mass, based on the suspension, of more than 0.5 mol/kg, preferably more than 1 mol/kg, more preferably more than 1.2 mol/kg , in particular more than 1.5 mol/kg and/or less than 3.3 mol/kg, preferably less than 3 mol/kg, more preferably less than 2.7 mol/kg, in particular less than 2.5 mol/kg contains.
- the lower limit of 0.5 mol/kg could also be raised to 0.65 mol/kg or to 0.8 mol/kg. In further embodiments, upper limits of 2 mol/kg, 1.6 mol/kg and even 1.3 mol/kg are also considered.
- the suspension contains the third component, calculated as powdered activated carbon (dry) with a mass, based on the fourth substance, per amount of metal ions of more than 11 g/mol, preferably more than 16 g/mol, more preferably more than 22 g/mol, in particular more than 27 g/mol and/or less than 220 g/mol, preferably less than 165 g/mol, more preferably less than 110 g/mol, in particular less than 83 g/mol.
- dry powdered activated carbon
- the suspension contains the third component calculated as powdered activated carbon (dry) in a percentage by weight of the suspension of more than 2%, preferably more than 3%, more preferably more than 4%, in particular more than 5% and/or less than 40%, preferably less than 30%, more preferably less than 20%, in particular less than 15%.
- a ratio of more than 7%, more preferably more than 8.5%, also more than 10% and in particular more than 11.5% is even more preferred in this regard.
- the ß value of the suspension based on an aqueous reference solution of 11.2° dH and 10 mg PO4-P/L and a final value of 1 mg PO4-P/L, is less than 2.5, preferably less than 2.0, in particular less than 1.5. It is assumed that not less than 0.5, also not less than 0.6, in particular not less than 0.7, is obtained for this.
- ßFäii [Fe/56+AI/27]/[Bd,p,fäii/31] (where Fe is the iron content, AI is the aluminum content of the precipitating agent) usually given in the technical literature and Bd.p.Fäii is the chemically precipitated phosphorus), ß-value to be calculated from values obtained in a real plant for various reasons (possibly additional sulfide precipitation; polymeric structure of the metal salt; consumption of active ingredients for other, plant-related reactions; other, e.g. biological phosphate binding) is difficult to compare, according to the invention for the ß-value of a suspension according to the invention the determination of the values to be taken as a basis is decisive as follows:
- the initial concentration of 10 mg PO4-P/L is adjusted by completely dissolving the corresponding amount of Na2HPC>4.
- the suspension contains a/the fifth substance, in particular finely divided S1O2, in a weight percentage of more than 4%, preferably more than 6%, more preferably more than 8%, in particular more than 10% and/or or less than 25%, preferably less than 22%, more preferably less than 20%, especially less than 18%.
- This ratio can also be at least 11.6%.
- the weight percentage of the third material is greater than that of the fifth material.
- the weight percentage of the third substance can also be lower than that of the fifth substance.
- the total weight proportion of the third and fifth substances, based on the suspension is preferably 15% or higher, more preferably 17.5% or higher, in particular 20% or higher, even 22% or higher.
- the function of the S1O2 also has a positive effect on the fact that there is no significant segregation or settling of the activated carbon in the suspension. As a result, a substantially uniform separating effect can be achieved over the entire contents of the container.
- the S1O2 could, for example, contain SiO2 in the form of amorphous silicic acid, but it could also be contained elsewhere.
- the separation efficiency for methylene blue of the third substance in mg methylene blue per g of the third substance is greater than 20, preferably greater than 35, more preferably greater than 50, in particular greater than 90, preferably even greater than 120, in particular greater than 140, and/or the separation efficiency for methylene blue in the suspension in mg of methylene blue per 10 mL of the suspension is greater than 25, preferably greater than 50, more preferably more than 80, in particular more than 120.
- the separation efficiency for methylene blue of the third substance in mg methylene blue per g of the third substance is less than 600, also less than 450, and also can be less than 300, and/or the separation efficiency for methylene blue in the suspension in mg of methylene blue per 10 mL of the suspension can be less than 2000, also less than 1200, and also less than 800 or even 600.
- the suspension contains no more than 2%, preferably no more than 1%, in particular no more than 0.5% or even 0.2% of a particularly long-chain thickener based in particular on polysaccharides, preferably no gum arabic or xanthan gum based thickeners in higher than these proportions. Furthermore, the suspension preferably contains no further organic chemicals and/or no surfactants.
- the suspension is provided or it contributes to the provision of the suspension by treating an aluminum and/or iron-containing raw material, preferably an iron and/or aluminum-containing phyllosilicate, particularly preferably kaolin, by treatment with concentrated acid, in particular Hydrochloric acid or sulfuric acid or a combination thereof, to form a suspension containing aluminum salt solution and S1O2, and the third substance is added to this suspension in powder form.
- the fifth substance/SiOa produced in this way has thereby received a surface activation which has a favorable effect on the suspension.
- other metal salts can also be present or added for the fourth substance and/or additional/different SiO 2 can be added for the fifth substance.
- the majority of the fourth substance and/or the majority of the fifth substance originates from the suspension thus obtained from the raw material/layered silicate.
- a basicity of the fourth substance measured as in [0017] DE 10 2012 019 709 A1, which is included by reference in this regard, of not more than 20%, even less than 15%, even less than 10%.
- the invention prefers suspensions with a basicity of less than 20%, preferably less than 15%, especially less than 10%.
- kaolin or metakaolin with a particle size of 95% ⁇ 63 ⁇ m (sieve residue (DIN sieve)), particularly preferably 95% ⁇ 20 ⁇ m (particle size distribution (Sedigraph 5100)) is exhaustively broken down in concentrated hydrochloric acid at elevated temperatures and under pressure . After cooling the reaction mixture, a suspension containing aluminum chloride and SiO 2 is obtained.
- the kaolin or metakaolin has a particle size distribution of 95% less than 63 ⁇ m, preferably less than 45pm, more preferably less than 32pm, especially less than 20pm.
- This treatment and grain size distribution is also considered to be beneficial for other starting materials/layered silicates. For example, bentonite or montmorillonite is also considered.
- bentonite or montmorillonite is also considered.
- the inventors of the present invention have recognized that when using this starting material, a suitable quantitative ratio of fifth substance to fourth substance and at the same time a suitable fine grain size of the fifth substance can be achieved without the need for further admixing.
- the molar ratio of the amount of substance of the fifth substance to the amount of metal ions of the fourth substance is generally greater than 0.2 mol/mol, preferably 0.35 mol/mol, more preferably 0.5, regardless of the type of production mol/mol, in particular less than 0.67 mol/mol and/or a value of less than 2.0 mol/mol, preferably less than 1.6 mol/mol, more particularly preferably less than 1.3 mol/mol.
- the amount of substance of the fifth substance relates to the constitutional repeating unit, in the preferred case calculated as SiC, for example. It is preferably provided that, in addition to possibly a grinding process for the layered silicate, no subsequent grinding process is carried out for the fifth substance and in particular for the third substance.
- a suspension 1 is added to a tank 3 containing micropollutants and phosphate-containing waste water 2, embodied in this example by a tank for the third cleaning stage of a sewage treatment plant, in particular according to the following examples.
- Example 1 Commercially available PAG (Donau PAG activis) with activated carbon (AK)
- Donau PAC activis were mixed with a hydrochloric acid treated Carbopal MB4 40 pm in different concentrations (2%, 5%, 10%).
- the adsorption properties of the metal salt-activated carbon suspension product were compared with that of a pure activated carbon-water mixture with regard to the separation efficiency of methylene blue.
- the mixtures showed both a good flocculation effect and an appreciable methylene blue adsorption (133-154 mg methylene blue/g carbon). Under laboratory conditions, the flocculation effect is comparable to commercially available polyaluminum chlorides (PAC) or iron chlorides (FeCh) without AK. The mixtures also proved to be stable for (but only) a few days ( ⁇ 1 week) at 20°C. However, there was no clumping or similar effects. After the suspension had been stirred up, a dosable suspension was obtained again for a short time without impairing the effect.
- PAC polyaluminum chlorides
- FeCh iron chlorides
- First 14953 kg of 34% HCl are placed in an industrial, enamelled stirred tank reactor, as used for PAG production and with a total volume of 18200 L. 6249 kg of kaolin containing 47% SiO2, 35% Al2O3 and having a particle size distribution of 97.4% ⁇ 25 ⁇ m are suspended with stirring. The mixture is heated until the self-reaction starts at approx. 130 °C. It is then kept at >160° C. for >2 h. The product is cooled to ⁇ 60 °C and stored in suitable containers.
Abstract
L'invention concerne un procédé pour modifier la concentration d'au moins une deuxième substance organique dans un liquide constitué principalement d'eau et contenant une première substance notamment phosphatée par adsorption de particules de la deuxième substance sur une troisième substance qui est ajoutée au liquide, qui se compose principalement de carbone en pourcentage en poids et présente une surface interne de plus de 100 m2/g sous un effet favorisant un mouvement de la troisième substance adsorbante avec une composante de direction de mouvement dans la direction de la gravité par un produit d'une précipitation de la première substance avec une quatrième substance qui est ajoutée au liquide et qui contient un sel métallique contenant du fer ou de l'aluminium ou en est constituée, procédé dans lequel l'ajout de la quatrième substance et l'ajout de la troisième substance, qui est déjà prétraitée d'une manière à contrecarrer son mouvement dans le liquide avec une composante de mouvement contraire à la direction de la gravité avant cet ajout, ont lieu à proximité l'un de l'autre dans le temps et l'espace.
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DE102020006846.4A DE102020006846A1 (de) | 2020-11-06 | 2020-11-06 | Verfahren zur Behandlung einer Flüssigkeit und Zugabequelle dafür |
PCT/EP2021/079376 WO2022096289A1 (fr) | 2020-11-06 | 2021-10-22 | Procédé de traitement de liquide et source d'ajout pour celui-ci |
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EP4240698A1 true EP4240698A1 (fr) | 2023-09-13 |
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DE3636993C1 (de) | 1986-10-30 | 1988-03-31 | Preussag Ag Bauwesen | Verfahren zur chemisch-physikalischen Aufbereitung von Abwasser |
DE4206646C2 (de) | 1992-03-03 | 1994-06-01 | Uwe Kromozinski | Verfahren zur Reinigung von Abwasser und Adsorptionsmittel |
DE10210786A1 (de) | 2002-03-12 | 2003-10-02 | Bayer Ag | Mischungen aus Adsorbermaterialien |
DE102012019709A1 (de) | 2012-10-08 | 2014-04-10 | Daniel Pacik | Mittel zur Aufbereitung von wässrigen Medien und dessen Verwendung |
CN104310553B (zh) * | 2014-10-31 | 2016-06-29 | 武汉钢铁(集团)公司 | 高炉除尘灰的资源化利用方法 |
CN108975420A (zh) * | 2017-06-05 | 2018-12-11 | 艺康美国股份有限公司 | 化学需氧量(cod)去除粉末混合物 |
DE102018111145A1 (de) | 2018-05-09 | 2019-11-14 | Huber Se | Verfahren zur Rückgewinnung von Phosphor aus Abwasser |
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