WO2009132688A1

WO2009132688A1 - Method for treating water containing unwanted elements

Info

Publication number: WO2009132688A1
Application number: PCT/EP2008/055150
Authority: WO
Inventors: Jean-Pierre Bas
Original assignee: S.A. Spadel N.V., Societe De Services,De Participations, De Direction Et D'elaboration
Priority date: 2008-04-28
Filing date: 2008-04-28
Publication date: 2009-11-05

Abstract

The invention relates to a method for treating water in order to remove undesired metals by passing said water on a bed of a filtering material having at least one portion that comprises an active layer of manganese oxides, wherein a solid material containing manganese compounds partially soluble in the treated water is provided upstream from the bed of filtering material, thus triggering a re-deposition of a layer of active oxides further downstream in the filter.

Description

Water treatment process containing undesirable elements

The present invention relates to a water treatment method which makes it possible to remove concentrations of unstable elements (iron and manganese) or undesirable or even toxic (arsenic, and other trace metals) in water intended for human consumption. The process can be applied to industrial water to remove heavy metals before discharge into the external environment.

A traditional physico-chemical process of demanganization / de-ironing (more generally of heavy metals elimination) of water consists in chemically oxidizing these metals with potassium permanganate, chlorine or ozone manganese, then filtering the water on a granular material (such as sand). This material is coated with precipitates of manganese oxide (essentially bioxide) to form what is called a "green sand". Such a "green sand" can also be prepared by first depositing a film of hydrated manganese dioxide on the surface of a granular material.

An example of implementation of this principle is described in RU 2275335 relates to an application of this principle. This principle is also referred to in WO 02/38511 and WO 03/095372. However, this document relates more particularly to a water treatment process for the removal of unwanted metals without the addition of strong oxidant, with a filter material of simplified preparation. The essential feature of the method according to WO 02838511 and WO 03/095372 is to pass the treated water through a filter bed comprising manganese dioxide grains having a hardness greater than 6 on the Mohs scale. This process does not cause or very little loss of filter material.

Reference is made to the same principle of "green sand" ("manganese sand") in the documents EP 1 095 911 and JP 10-137772. However, these documents relate more particularly to a water treatment process allowing the removal of iron or manganese, with a filter material whose particularity is to be implemented in a fluidized bed with tight control of the pH of reaction.

The objective of the present invention is to provide an alternative method for the treatment of water, particularly respectful of the quality of the water obtained, and simple and reliable as to its industrial implementation.

For this purpose, the invention provides a water treatment process for removing undesirable metals by passing said waters over a bed of filter material at least a portion of which comprises a layer of manganese oxides, which method has the particularity that a solid material (a material in the form of solid particles), comprising manganese compounds partially soluble in the treated water, is disposed / introduced into the stream of treated water, upstream of the bed of material filtering, inducing re-deposition (precipitation) of a layer of active oxides further downstream in the bed of filter material.

The term manganese compounds as used herein should be understood in a broad sense, which may include pure or mixed oxides, hydroxides, oxyhydroxides and / or carbonates of manganese and / or iron and manganese.

The term partially soluble compounds in treated water as used herein should be understood as minerals susceptible to dissolution by the water to be treated, releasing manganese (and / or iron) ions. . The term active oxides as used herein should be understood as neo-formed oxides with a highly imperfect structure involving / forming "nanotubes" capable of capturing cations and anions. According to preferred embodiments of the invention, the material comprising manganese compounds that are partially soluble in the treated water is placed on the surface of the bed of filtering material or in a compartment located upstream of the bed of filter material, before and after / or during the passage of the water to be treated on said bed of filter material. It can also be introduced into the bed by an alluvialization process consisting of introducing a suspension of partially soluble manganese compounds under pressure at the inlet of the bed of filtering materials.

It is obvious that the thickness of the bed of filter material must be sufficient to allow re-deposition (precipitation) of a layer of active oxides in the bed of filter materials. Under commercial conditions this thickness is generally between 60 cm and 1.5 m, for treated water flow rates between 1 and 10 m / h.

According to other preferred features of the invention, the oxidation-reduction potential and / or the pH of the water to be treated are adjusted before passing over the manganese compound (s) and the bed of filter material.

In particular, the redox potential is preferably adjusted to a value between 0.150 and 0.400 V, ideally between about 0.200 and about 0.300 V, and / or the pH is preferably adjusted between 5.5 and 7.5, ideally between 6, 0 and 7.0.

The essential aspect of the process according to the invention lies in the use of a treatment mineral ("doping agent"), in the form of solid, upstream of the filter bed, comprising manganese compounds in relatively soluble form, for treating (removing) undesirable cations and / or anions from water, even if it contains little iron and / or manganese, and this, thanks to a doping effect of the filter bed.

In the capture of the undesirable elements (Fe, Mn, As, Ni, ...) one can note a neoformation of oxides and hydroxides of manganese under the appropriate conditions of pH and oxidation.

These precipitates are obtained in two stages: rapid adsorption on the crystalline defects of the initial filtering material (sand)

- Slower light oxidation under conditions of low redox potential.

They become the new sensors for their own cations (Mn) but also, following the same steps, for many cations and anions.

The water, if it is naturally rich in manganese, provides the quantity necessary for the regeneration of the badly formed sensors and the process is therefore autogenerated (continuous formation of oxides) and self-regenerated (initialization of the sensor sites).

For an insufficient natural presence of Mn, soluble minerals are added which supply the water with the Mn necessary for the neoformation lower in the filter of the oxidized mineral sensors. The added mineral then acts as a dopant. Most doping media have a complex mineralogy of oxides, hydroxides, oxyhydroxides, or even carbonates.

The dissolution of the doping mineral causes its progressive disappearance and thus the stop of the neoformation of the badly formed sensors, if it is not replaced. In a first phase, the adsorption occurs on the hydrated surface of a grain of filter material (quartz) forming an initial crust of malformed Mn hydroxides.

As soon as a deposit of hydroxide or Mn oxide has occurred, it is this mineral that becomes the adsorbent and the process accelerates.

It should be noted that the traces of the Mn oxyhydroxide already formed in the water can serve as an initiator by depositing on the sand grains of the filter.

The mineralogy of oxyhydroxide deposits is very complex, especially since the subsequent slow evolution by oxidation changes the mineralogical composition of the initial deposit.

An evolution of manganese oxyhydroxides can be observed for example: turbo-birnesite (malformed) → birnesite (better crystallized) → pyrolusite The principle of the process according to the invention is thus to add a manganese compound which dissolves in the water to be treated. The dissolution can be natural because of the original aggressiveness of the water or induced by acidification (with carbon dioxide). A second step is to pass over a granular filter where the dissolved manganese precipitates in the form of amorphous or poorly crystallized compounds capable of adsorption removing unwanted elements. The material "manganese compound" used may come from:

other water treatment filters which are naturally loaded with oxides in view of the significant concentration naturally present in the water they treat,

- quarry materials with a strong manganiferous component

- synthetic materials.

These are relatively well crystallized Mn oxides / oxyhydroxides / carbonates whose crystalline structure has few vacancies capable of adsorbing but of sufficient solubility to provide with water the complement of Mn. This contribution then gives rise to the neoformation of oxyhydroxides less well crystallized lower in the filter.

It is these neoformés which adsorb the undesirable ions of the water (Fe, Mn ₁ As, F, ...) The typical example of this operation is the progressive dissolution of a Nsutite (γ-MnO ₂ ) with neoformation more low in the filter of a poorly crystallized birnesite (called turbo-birnésite) high adsorption.

Particularly useful materials for the implementation of the method according to the invention are, for example, oxyhydroxides type manganese oxide of Mn, type manganese oxides Y-MnO ₂ type manganese oxides Nsutite, and manganese oxides as obtained from an electrolysis of a manganese salt (such as, for example, the manganese dioxide of the CIR 189 type marketed by ERACHEM, obtained by electrolysis of a manganese sulphate). Manganese carbonates are also suitable for applications where the composition of the water can be changed.

The material used is in granular form optionally mixed with silica sand or a pH-correcting substrate

(calcium carbonate and or magnesium)

The material used dissolves in a first step to precipitate in a second form of specific compounds in relation to the composition of the treated water. The material, as it dissolves, must be regularly renewed by continuous recharge or siltation to continue its action.

The filter where the precipitation and retention of undesirable elements occur, should be backwashed whenever necessary, to remove excess material The second step of co-precipitation may be accompanied by adjustment of the reaction conditions of either oxygenation (increase of the redox potential) or reduction of acidity (degassing, filtration materials producing alkalinity). The process is particularly suitable for acidic waters with a low alkaline reserve.

In the case of drinking water, the process is particularly suitable for the treatment of water containing little iron or manganese, but with concentrations higher than standards, which requires intervention. The quantities are insufficient to obtain, without the dopant, the formation of unstable oxides necessary for the retention of the troublesome species. The process is then used to meet the standards of potability.

In the case of industrial water, there may be only toxic metals to be removed. The method can be used to meet rejection standards.

The use of the only introduction of manganese oxides as a sensor / initiator may prove to be insufficient insofar as the water to be treated is outside the range of stability of the oxide sensors. It is then necessary to combine several techniques. In the case of drinking water, degassing can be provided to reduce the concentration of free carbon dioxide and the use of oxygen to raise the oxidation-reduction potential. In the case of industrial waters, chemical adjustments of the pH can be provided once the dissolution of the dopant has been obtained. It is thus ensured that, in the precipitation phase, the oxidation zone to be reformed remains in the stability range. Filtration speeds must generally be reduced to maximize the use of oxide formation techniques. Other features of the invention will appear on reading the examples which follow, given purely by way of illustration and not limitation.

Example 1: Treatment of a drinking water

The sequence of operations can (in the most complex case) be composed of the following steps: pH adjustment by degassing aeration / oxygenation - filtration on granular material mixed with the doping material pH adjustment by degassing

In general, the acidity of a drinking water is related to its concentration of free carbon dioxide. The passage of water through a stripping column in the air or in a vacuum column will remove a large part of this gas and raise the pH by 0.5 unit. The air / water ratio in the case of stripping or the intensity of the vacuum in the second case must be tested because it is necessary to maintain a residual aggressiveness to obtain the dissolution of the dopant. Aeration / oxygenation This operation is justified if the previous step is absent or carried out in a vacuum column which also removes oxygen. In difficult cases, the air can be replaced by pure oxygen especially in the first two or three months of the start of a new installation. The goal is to achieve aeration saturation and concentrations up to 30 mg / l in the case of oxygenation. The oxidizing gas is introduced using Venturi system optionally on a circulation loop fed from the outlet of the next step (filter) and which returns the oxygenated water at the head of the latter. Filtration on granular materials The basic granular material may be silica sand on which a volume of oxides of 10 to 20% is superimposed. Filtration speeds are slow from 3 to 5 m / h. The thickness of the sand bed is at least 60 cm with a granulometry of 0.4 to 0.8 mm. The backwash required to remove dopant residues and excess precipitation is at 20m / h. The regular addition of dopant is done by opening a manhole disposed in the upper part of the filter.

EXAMPLE 2 Treatment of an Industrial Water The sequence of operations can (in the most complex case) be composed of the following steps: adjustment of the pH dissolution of the dopant readjustment of the pH - aeration / oxygenation filtration on granular materials Adjustment of the pH

Here the goal is rather to temporarily acidify the water if its aggressiveness is insufficient. Carbon dioxide is used because it can be more easily removed once the dissolution of the dopant obtained. It is necessary to reach concentrations of the order of 100 mg / l. It can be injected by venturi with recirculation loop as indicated above for oxygenation. Dissolution of the dopant The pH-adjusted water passes into a reservoir of identical design to a filter filled with the doping material possibly mixed with sand. The sand / dopant ratio is a function of the concentration to be obtained in dissolved manganese. The regular addition of dopant is done by opening a manhole disposed in the upper part of the filter. PH adjustment It is a question of putting the system back under the conditions of precipitation of the oxides. This can be achieved by degassing or stripping but as we are in the industrial field, chemical reagents can also be used. Ventilation / oxygenation

This operation is identical to that described for drinking water. Filtration on granular materials

The basic granular material may be sand mixed with a manganese oxide which will act as a co-precipitation catalyst.

This oxide facilitates the start of the reaction but after a few months, the process must maintain itself thanks to the dissolution obtained in the second stage. Filtration speeds are slow from 3 to 5 m / h. The thickness of the sand bed is at least 60 cm with a granulometry of 0.4 to 0.8 mm. The backwash required to remove residual dopant and excess precipitation is at 20m / h

Claims

A method of treating water with a view to removing undesirable metals by passing said water over a bed of filter material at least a portion of which comprises a layer of manganese oxides, characterized in that a solid material, comprising manganese compounds partially soluble in the treated water, is disposed in the treated water flow, upstream of the bed of filter material, inducing re-deposition of a layer of active oxides further downstream in the bed filter material.

2. Method according to claim 1, characterized in that the material comprising manganese compounds is disposed on the surface of the bed of filter material or in a compartment located upstream of the bed of filter material, before and / or during the passage of treated water on said bed of filter material.

3. Method according to either of claims 1 and 2, characterized in that the oxidation-reduction potential and / or the pH of the treated water is / are adjusted (s) prior to passage over the oxide (s) ( s) of manganese and the bed of filter material.

4. Method according to claim 3, characterized in that the oxidation-reduction potential is adjusted to a value between 0.150 and 0.400 V, preferably between about 0.200 and about 0.300 V.

5. Method according to either of claims 3 and 4, characterized in that the pH is adjusted between 5.5 and 7.5, preferably between 6.0 and 7.0.

6. Process according to either of the preceding claims, characterized in that the material comprising manganese compounds is chosen from materials comprising carbonates and / or oxides of manganese (oxyhydroxide type).

Min).

7. Process according to claim 6, characterized in that the material comprising manganese compounds is chosen from materials comprising γ-MnO ₂ type manganese oxides, Nsutite type manganese oxides and / or manganese oxides. obtained by electrolysis of manganese salts.