RU2035994C1 - Aluminosilicate sorbent and method for its production - Google Patents

Abstract

FIELD: production of sorbents. SUBSTANCE: sorbent contains aluminosilicate ion exchange minerals and foreign minerals, their quantities are 70-98 and 2-30 mass % respectively; exchange capacity of proposed sorbent being 1.2-2.1 mg equiv/g. Proposed sorbent is prepared by enrichment of natural zeolite-containing raw materials. Said method involves crushing, gravitation, magnetic separation and classification. The latter process is carried out by sizing two fractions: coarse fraction containing particles more than 0.1-3 mm in size and fine fraction containing particles being less than 0.1-3 mm in size. Chemical enrichment of fine fraction takes place by its treatment with aqueous solutions of acids, alkali or salts or by their consequently treatment by these reagents. Concentration of mentioned above reagent is 1-10 mass %. EFFECT: decreases content of toxic impurities, increases exchange capacity of sorbent. 4 cl, 2 tbl

Description

 The invention relates to aluminosilicate sorbents for multi-use, containing natural ion-exchange aluminosilicate minerals (zeolites, clay minerals) in amounts significantly exceeding their content in the original mineral raw materials, having a high exchange capacity and freed from harmful impurities.

 Known sorbents based on natural zeolites and methods of enrichment of aluminosilicate natural sorbents in order to increase the content of ion-exchange minerals and chemical modification to obtain monocationic forms [1-3] These methods relate to the enrichment of poor mineral raw materials with a content of useful components of less than 50 wt.

 Using magnetic separation methods, it is possible to increase the zeolite content in the concentrate in comparison with the original rock by 3-5 wt. Gravity methods (concentration table, cyclones, sluices) achieved enrichment of 5-7% compared with the original rock. Flotation enrichment methods are also not very effective in the enrichment of aluminosilicate sorbents and pollute the grain surface with harmful flotation reagents. In addition, enrichment methods and ion-exchange modification methods do not allow to get rid of the main part of normalized toxic elements (heavy metals, etc.) that are constantly present in natural mineral raw materials.

 The disadvantage of enriched aluminosilicate natural sorbents obtained earlier is the low content of ion-exchange minerals (less than 70 wt.), High (up to 10 wt.) The content of impurity nonaluminosilicate minerals (sulfides, hydroxides of iron and manganese, phosphates, carbonates and metallic iron), as well as toxic chemical elements (As, Cd, Hg, Pb, etc.).

 The objective of the invention is to obtain an environmentally friendly aluminosilicate sorbent with a high content of aluminosilicate ion-exchange minerals (zeolites, clay minerals) and a low content of impurity minerals (quartz, feldspars, mica, sulfides and metal oxides) and toxic elements (Fe, Mn, Pb, Zn, Cu, Cd, As, Hg, etc.) in comparison with natural zeolite raw materials. In addition, the task is set to buildup (increase exchange capacity and kinetic indicators) and refine (reduce the concentration of abrasive minerals and toxic elements, bleach), natural raw materials. All this ensures the production of aluminosilicate sorbent suitable for use in such new areas as the production of detergents, veterinary and medical pharmacological preparations, perfumes and food products.

 For this, an aluminosilicate sorbent containing a natural ion-exchange aluminosilicate mineral, as an ion-exchange mineral, contains a zeolite from the range of clinoptilolite or mordenite, or phillipsite, or chabazite, or a mixture thereof, or a mixture of zeolite with montmorillonite and impurity minerals such as quartz, feldspar, mica ingredients, wt.

Natural aluminosilicate ion exchanger 70-98
Impurity minerals 2-30 has an exchange capacity of 1.2-2.1 mEq / g and a particle size distribution of less than 0.1-3 mm.

In the method of producing aluminosilicate sorbent, including crushing, grinding, classification, magnetic and gravitational enrichment in one or several stages in air or aqueous medium, two classes of particle size of the following particle size distribution are distinguished in classification, mm: Large class more than 0.1-3 Small class less than 0.1-3
In this case, the large class is used to obtain other products or to the dump, and the small class is used for further enrichment or grinding to the required particle size distribution. Selective grinding and classification can increase the content of zeolite in the sorbent by 10-30 wt. The sequence of application of the methods of selective grinding and classification and methods of gravitational and magnetic enrichment can be different.

 After mechanical enrichment, the sorbent can be subjected to additional chemical treatment with aqueous solutions of acids or alkalis, or salts, or sequential treatment with these reagents with a concentration of 1-10 wt. allowing to reduce the content of toxic components in the sorbent by 30-80 wt. and increase the exchange capacity of the sorbent by 0.1-0.5 mEq / g Chemical treatment can also significantly improve the kinetic characteristics of the proposed sorbent.

 The essence of the method for producing the sorbent consists in the selective grinding of zeolite and clay minerals and their concentration in the small class with air or wet classification, as well as in chemical buildup and refinement of the natural sorbent. Obtained by the proposed method, the sorbent is characterized by a significant improvement in technological parameters compared with untreated natural raw materials.

 PRI me R 1. Zeolite-bearing rock with a clinoptilolite content of 68 wt. crushed to a particle size of 1 mm, subjected to dry magnetic separation and air classification by particle size class 0.2 mm Moreover, due to the classification, enrichment of 14 wt. and due to magnetic separation, by 2 wt.

 The enriched product was subjected to treatment with a 1% hydrochloric acid solution and transferred to the Ca form with a 5% calcium hydroxide solution. The exchange capacity of the sorbent increased by 0.3 mEq / g, and the degree of purification from toxic elements was 50 wt.

 Aluminosilicate sorbent contains 84 wt. clinoptilolite and has an exchange capacity of 1.6 mEq / g.

 PRI me R 2. Zeolite-bentonite rock with a content of ion-exchange aluminosilicate minerals 71 wt. crushed to a particle size of 1 mm, it was classified on a hydrocyclone according to the size class in a discharge of a 0.1 mm hydrocyclone. Moreover, due to wet classification, enrichment of 20 wt.

 The enriched product was treated with a 3% aqueous solution of oxalic acid and converted to the Na form by treatment with a 5% aqueous solution of sodium hydroxide. Due to chemical treatment, the exchange capacity of the sorbent increased by 0.4 mEq / g, and the degree of purification from heavy metals and other toxic elements was 80 wt.

 Aluminosilicate sorbent contains 91 wt. clinoptilolite and montmorillonite and has an exchange capacity of 1.8 mEq / g.

 PRI me R 3. Zeolite rock with a content of 68 wt. mixtures of clinoptilolite and mordenite, crushed to a particle size of 3 mm, subjected to magnetic separation, stage grinding and classification according to the particle size class of 0.5 mm Moreover, due to selective crushing and classification, enrichment of the concentrate with zeolite for 12 wt. The concentrate was not subjected to chemical treatment.

 Aluminosilicate sorbent contains 80 wt. clinoptilolite and mordenite and has an exchange capacity of 1.4 mEq / g.

 PRI me R 4. Zeolite rock with a mordenite content of 60 wt. crushed to a particle size of 3 mm, subjected to staged crushing and classification according to the particle size class 1 mm and dry magnetic separation. In this case, enrichment of the concentrate with mordenite by 11 wt.

 The concentrate was chemically treated with a 10% aqueous hydrochloric acid solution to obtain the hydrogen form of mordenite.

 Aluminosilicate sorbent contains 71 wt. mordenite and has an exchange capacity of 1.2 mEq / g.

 PRI me R 5. Zeolite-containing rock with a concentration of phillipsite 45 wt. crushed to a particle size of 3 mm, subjected to staged refinement and classification according to the class of particle size of 2 mm and dry magnetic separation. As a result of selective crushing and classification, enrichment of 9 wt.

 The concentrate was chemically treated with a 10% aqueous solution of potassium chloride in order to obtain a potassium form of the sorbent.

 Aluminosilicate sorbent contains 70 wt. phillipsitis and has an exchange capacity of 1.5 mEq / g.

 PRI me R 6. Ore picking concentrate containing 70 wt. Chabazite, crushed to a particle size of 5 mm, is subjected to magnetic separation and classification according to a particle size class of 3 mm. Due to magnetic separation and classification, enrichment of 28 wt. and obtained a monomineral fraction of chabazite containing only 2 wt. impurity minerals (quartz).

 Chemical treatment of the concentrate was not carried out.

 Aluminosilicate sorbent contains 98 wt. chabazite and has an exchange capacity of 2.1 mEq / g.

 The results of the examples are summarized in tables 1 and 2, illustrating the composition and method of producing aluminosilicate sorbent from various types of natural mineral raw materials.

Claims (3)

 1. Aluminosilicate natural sorbent containing ion-exchange and impurity minerals, characterized in that as an ion-exchange mineral it contains zeolites from the range of clinoptilolite, or mordenite, or phillipsite, or chabazite, or a mixture thereof, or a mixture of zeolites with montmorillonite and impurity minerals such as quartz , feldspars, mica in the following ratio of ingredients, wt. Aluminosilicate ion-exchange minerals 70 98
Impurity Minerals 2 30
has an exchange capacity of 1.2 to 2.1 mEq / g and a particle size distribution of less than 0.1 3 mm.  2. A method of producing aluminosilicate sorbent, including crushing, grinding, classification, gravitational and magnetic enrichment in air or aqueous medium, characterized in that during classification there are two classes of particle size with the following particle size distribution, mm: large class more than 0.1 3, small class less than 0.1 3.  3. The method according to claim 2, characterized in that the sorbent of particle size classes less than 0.1 3 mm is additionally subjected to chemical treatment with aqueous solutions of acids, or alkalis, or salts or sequential treatment with these reagents with a concentration of solutions of 1 to 10 wt.

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