FR2558841A1 - Composite material which has ion exchanger and/or chelating properties, process for obtaining it and applications - Google Patents

Abstract

The composite material comprises a copolymer of a phenolic monomer and of an aldehyde monomer. It is characterised in that the copolymer is a resin which has chelating and/or ion exchanger properties and in that the resin coats a plant- or protein-based cellulose support. Application to the recovery of metals in effluents and to the production of vitamin B12.

Description

COMPOSITE MATERIAL HAVING PROPERTIES
ION AND / OR CHELATING EXCHANGERS,
ITS PROCESS FOR OBTAINING AND APPLICATIONS.

 The present invention relates to the field of manufacture and applications of chelating and / or ion exchange resins.

 It relates more particularly to the obtaining of new materials allowing the recovery of metal ions and the applications thereof.

 Work on chelating resins dates back approximately to 1959. Among the main resins which have been proposed to date, mention may be made of copolymers obtained by condensation of formaldehyde (formaldehyde) with one phenol or several phenols. The latter monomer is most often constituted by 8-hydroxyquinoline.

 Thus it can be noted that, despite the numerous studies to introduce hydroxy-quinolines, none has, at present, found an industrial outlet. In addition, the few resins on the market find their application mainly in the analytical field and little or not in the purely industrial field such as wastewater treatment, this being, for the moment, reserved mainly for ion exchange resins.

 The work of F. VERNON and K.M. NYO (Anal. Chim.

1977, 93, 203-210) have shown that the method of manufacture has a great importance on the characteristics, in particular, on the capacities of the resins. Their work constitutes an optimization of the operating conditions.

They have tried, by increasing the water retention, to improve both the capacity and the kinetics of exchange, but these properties are hardly compatible with good mechanical properties, the resins tending to appear, then, in the form of gel. Reference may also be made to the publication "Report of Investigation, 1978, 8315, Bureau of Mines, Tungsten recovery from searles lake brines" concerning the same type of resins.

 It is also necessary to underline the price, rather high, of the resins used, which also constitutes an obstacle for the intensive industrial use of these chelating or ion exchange resins. There was therefore a need, for the manufacture under advantageous economic conditions, of a chelating or ion exchange resin, less costly in energy and in raw materials. This observation has also led to the elimination of the processes using grinding of the resins for the production of beads, this grinding step also involving great energy expenditure.

 The invention provides a solution to the above problems and relates to a new composite material, comprising a copolymer of phenolic monomer-hydroxylated monomer, characterized in that said copolymer is a resin having chelating and / or ion exchange properties and that it is coated around a cellulosic, vegetable or protein carrier.

The copolymer used in the context of the present invention may preferably be chosen from the following resins
- 8-hydroxy quinoline, ethylenediamine, resorcinol, formaldehyde;
- 8-hydroxy quinoline, resorcinol, formaldehyde;
- phenol, formaldehyde;
- 8-hydroxy quinoline, phenol, formaldehyde;
- 5-hydroxy quinoline, resorcinol, formaldehyde;
- salicylic acid, resorcinol, formaldehyde;
- 5-hydroxy-8-hydroxy quinoline, resorcinol, formaldehyde.

 The support, around which the resin is coated, may consist of wood, in a divided state, such as shavings, or possibly sawdust. It can also be cellulosic fibers, more particularly, vegetable fibers, such as cotton fibers or other plants. It can also be animal hair.

 When the support is wood, it can also be in massive form.

 For certain applications, the composite material according to the invention can comprise metal cations fixed in the chelating and / or ion exchange resin.

The method for manufacturing the composite material according to the invention comprises the following steps
a) preparation of a prepolymer, by mixing, in the presence of an appropriate solvent, with a phenolic monomer and an aldehyde monomer;
b) mixing the prepolymer thus obtained in the presence of a vegetable or protein cellulosic support;
c) polymerization of the prepolymer.

 The phenolic monomer preferably consists of a hydroxy-quinoline or UQ mixture of two or more hydroxy-quinolines such as in particular by 8-hydroxyquinoline, or 5-hydroxyquinoline. This monomer can also consist of salicylic acid.

 More generally, the phenolic monomer can consist of a substituted or unsubstituted phenol.

 It will be noted that the support containing compounds, at least in part of aromatic nature, having reaction sites having a suitable electronic density, the applicants assume, without wishing to be bound to a given theory, that the bond between the support and the copolymer is insured under remarkable conditions. In fact, the crosslinking of the copolymer continues with the support itself.

 Finally, the aldehyde monomer can consist, for example, of formaldehyde.

 The copolymer can also comprise other monomers such as, for example, ethylene diamine.

 The chelating and / or ion exchange properties of the composite materials according to the invention make it possible to recover metal ions from industrial effluents.

Among these metals, mention may be made of Zn, Ni, Cu, Pb,
Sn, Va, Cr and Co.

 In the context of the present invention, preferably soda water is used as the solvent for the prepolymer.

 The copolymerization reaction, and more particularly, the condensation reaction, is therefore carried out, as indicated above, in the presence of the chosen support.

 It should be noted that, under certain conditions, it should also be possible to use, as a support, natural fibers, provided however that an appropriate treatment is carried out beforehand, such as, for example, treatment with hydrochloric acid. .

 As already mentioned, any natural fiber or cellulosic or proteinaceous mixture can be used. These may in particular be by-products from the food industry or plant treatment.

 When the support consists of wood, it can be in the solid state or in the form of shavings or sawdust. It is quite certain that the use of a support, in divided form, makes it possible to obtain a larger apparent surface for the chelating and / or ion exchange resin and therefore allows better metal extraction results.

 The fundamental applications of the composite materials according to the invention relate to the extraction of metals, in particular in industrial effluents, with a view firstly to the recovery of said metals, when this is economically advantageous, and secondly, to allow '' Avoid pollution and comply with the standards and regulations in force.

 A second application of these composite materials is linked to the nature of the metals which it is possible to absorb.

 Mention will in particular be made of the case of copper, which can be fixed by the resins, which makes it possible to obtain materials having anti-fungal or anti-algae properties, copper itself. Copper is cited here by way of example, but it goes without saying that any other metal or compound containing metal, could be considered, depending on the chemical, physical, biological, bactericidal, bacteriostatic or other properties which it possesses and which it could therefore confer on the composite material of the invention.

 These properties make it possible to envisage applications within the framework of the conservation of textiles (tarpaulins, bags on the ground, tent cloths ...) the conservation of ropes, leathers, glues, the fungistatization of packaging papers, the production of fungicidal paints and the manufacture of wood protection products.

 It is also possible to envisage making, from the materials according to the invention, laminates for making boats, the composite material in which the copper ions have been fixed, making the structure of the boat hull benefit from its anti-algae properties.

 It is also possible to envisage fixing tin ions in the composite material, and still by chelation, in order to produce flame retardant coatings.

 Insofar as the chelating resins can fix the cobalt ion, it is also possible to envisage applying the composite materials according to the invention to the industrial recovery of vitamin B12 since this vitamin is produced in organic waste, for example, poultry droppings.

 It goes without saying that this enumeration of application is in no way limiting, and that insofar as it is possible to fix such or such metal ion, the recovery of organic or mineral molecules containing these ions could be envisaged.

 The following examples are intended to illustrate the invention without in any way limiting its scope.

EXAMPLE I
Manufacture of hydroxy quinoline based resins.

 2N sodium hydroxide (20 ml) and 2.074 g of hydroxy quinoline are introduced into a reactor. It is left for a quarter of an hour with stirring.

 Then introduced 3.45 g of formalin at 37.2% with stirring, checking that the temperature does not rise above 45 OC.

 The mixture is brought to 45 ° C. and left at this temperature for 1 hour.

 The mixture is cooled to 25 ° C. and then the resorcinol (1.57 g) is introduced with stirring.

 It is left to react for 5 min. then the last part of 37.2% formalin is introduced, that is to say 3.115 g.

The formalin is introduced slowly enough so that the temperature does not exceed 50 OC, the rate of temperature rise must remain below 3 OC / min.

It is left to react at 50 ° C., following the viscosity of the product during the condensation. When the viscosity reaches 3.5 Pa.s at 4 Pa @ s, it is rapidly cooled
A sufficient quantity of water is then introduced to bring the viscosity of the mixture down to 0.66 Pa.s.

This amount is of the order of 0 to 45 g of water per 100 g of mixture.

 To proceed with the coating of wood shavings, 100 g of wood shavings are introduced into a mixer, then slowly stirring the prepolymer.

 The amount of prepolymer to be intruduced is a function of the amount of water added at the end of its preparation. This quantity can correspond approximately, for C-O g of chips, to approximately 86 g of active material 3 or approximately 500 g of prepolymer).

 The shavings are brought to the oven for 12 h at 60 C.

 Then washed with plenty of water, then with diluted soda.

EXAMPLE II
Manufacture of salicylic acid resins.

 20 ml of 2N sodium hydroxide are introduced into a reactor, then 1.97 g of salicylic acid with stirring. Agitation is maintained for a quarter of an hour.

 Then introduced 3.45 g of formalin, 37.2%, slowly, with stirring.

 It is heated between GO and 65 C for 3 h 30 min.

 After cooling to 25 ° C., 1.57 g of resorcinol are introduced, and the mixture is left stirring for 5 min.

 The second part of the formalin is then introduced, that is to say 3.45 g while monitoring the temperature, the temperature not to rise above 50 C.

 The mixture is maintained at this temperature for a time sufficient to reach a viscosity of 2.5 Pa.s.

 It cools quickly.

 The coating is then carried out on wood shavings as described in Example I.

EXAMPLE III
Manufacture of a 5-hydroxy-quinoline-8-hydroxy-quinoline-phenol-formaldehyde resin.

 A crude mixture of 5-hydroxyquinoline and 8-hydroxyquinoline (2.74 g) is introduced into a reactor. Then 20 ml of 2N sodium hydroxide are added.

 3.115 g of 37.2% formalin is added and the mixture is heated for 1 hour at a temperature of the order of 45 to 50 ° C.

 1.311 g of phenol are then introduced and the mixture is left stirring for 5 min. Then poured 3.45 g of formalin and heated to 50 OC for 1 h.

 Let cool.

 To carry out the coating and grafting on the wood, the total quantity of the reactor is poured onto 12.5 g of wood chips.

 When the shavings have been properly impregnated, put in the oven overnight at 60 ° C., then wash with N / 10 soda, and rinse with water until a neutral pH is obtained.

EXAMPLE IV
The resin described in Example II was used to remove the metal content in water leaving a wastewater settling tank.

 200 liters of water were treated (pH 4.5 to 5) ...

 The water leaving the decanter contained 17 mg / l of zinc, 4 mg / l of iron and 0.33 ml / l of chromium.

 These waters were treated at a rate equivalent to 3600 l of water per 24 h.

 It was found, in all the samples, contents lower than 0.4 mg / l for zinc, 0.6 mg / l for iron and 0.1 mg / l for chromium, that is to say a total of 1, 1 mg / l for all metals combined, which was significantly lower than the legal requirements, i.e. is mg / i.

 It will be specified that in the present description, the expression phenolic monomer or aldehyde monomer also denotes a mixture of two or more phenolic monomers or aldehyde monomers.

Claims (10)

 1. Composite material comprising a copolymer of a phenolic monomer and an aldehyde monomer, characterized in that said copolymer is a resin having chelating or ion-exchange properties and in that this coats a cellulosic, vegetable support or protein.  2. Material according to claim 1, characterized in that said copolymer is chosen from the following resins  - 8-hydroxyquinoline, ethylenediamine, resorcinol, formaldehyde  - 8-hydroxyquinoline, resorcinol, formaldehyde  - phenol, formaldehyde  - 8-hydroxy quinoline, phenol, formaldehyde  - 5-hydroxyquinoline, resorcinol, formaldehyde  - salicylic acid, resorcinol, formaldehyde  - 5-hydroxy-8-hydroxy quinoline, resorcinol, formaldehyde  3. Material according to one of claims 1 or 2, characterized in that the support consists of chips or sawdust or vegetable fibers, such as cotton fibers, or animal hair.  Material according to any one of claims 1 to 3, characterized in that it comprises metal cations.  5. Method for obtaining a composite material according to any one of claims 1 to 3, characterized in that it comprises the following steps  a) preparation of a prepolymer, by mixing, in the presence of an appropriate solvent, of a phenolic monomer, then with an aldehyde monomer;  b) mixture of the prepolymer thus obtained in the presence of a cellulose, vegetable or protein carrier,  c) polymerization of the prepolymer.  6. Method according to claim 5, characterized in that the phenolic monomer consists of one or more hydroxy-quinolines such as in particular 8-hydroxy-quinoline, 5-hydroxy-quinoline or with salicylic acid .  7. Method according to one of claims 5 to 6, characterized in that the phenolic monomer consists of a substituted or unsubstituted phenol.  8. Process according to any one of claims 5 to 6, characterized in that the aldehyde monomer is formaldehyde.  9. Method according to any one of reien dications 5 to 8, characterized in that other monomers such as: ethylene diamine are introduced into the copolymer.  10. Application of a material according to any one of claims X to 3 å the recovery of metal ions, such as in particular Zn, Ni, Cu, Pb, Sn, Va, Cr and Co.  11. Application of a material according to any one of claims 1 to 3 2 recovering vitamin B12.  12. Application of a material according to claim 4 for the protection of fibers against mold in which the chelate metal ion is Cu and the support is a fiber such as cotton.