阅读说明：本技术 一种吸附镓专用螯合树脂及制备方法 (Special chelate resin for adsorbing gallium and preparation method thereof ) 是由 陈宋辉 于 2020-03-03 设计创作，主要内容包括：本发明公开了一种吸附镓专用螯合树脂,吸附镓专用螯合树脂各组分及其百分比含量如下：明胶：20%~30%；氯化钙水溶液：3%~5%；聚合稀释剂：20%~25%；盐酸羧胺：5%~7%；无水碳酸钠：2%~4%；亲水反应剂：余量,本发明还提供了一种吸附镓专用螯合树脂制备方法,聚合稀释剂以及亲水反应剂的加入,大大提高了螯合树脂表面的微孔数量以及与拜耳母液的接触程度,使得螯合树脂能够充分地与拜耳母液进行吸附反应,大大提高了螯合树脂对拜尔母液镓的吸附量,具有良好吸附提取能力。(The invention discloses a special chelate resin for adsorbing gallium, which comprises the following components in percentage by weight: gelatin: 20% -30%; calcium chloride aqueous solution: 3% -5%; polymerization diluent: 20% -25%; and (3) carboxyl amine hydrochloride: 5% -7%; anhydrous sodium carbonate: 2% -4%; hydrophilic reactant: and in addition, the invention also provides a preparation method of the special chelating resin for adsorbing gallium, and the addition of the polymerization diluent and the hydrophilic reactant greatly improves the number of micropores on the surface of the chelating resin and the contact degree with the Bayer mother liquor, so that the chelating resin can fully perform adsorption reaction with the Bayer mother liquor, the adsorption capacity of the chelating resin on the gallium in the Bayer mother liquor is greatly improved, and the chelating resin has good adsorption and extraction capacity.)

1. The special chelating resin for adsorbing gallium is characterized in that: the special chelating resin for absorbing gallium comprises the following components in percentage by weight:

gelatin: 20% -30%;

calcium chloride aqueous solution: 3% -5%;

polymerization diluent: 20% -25%;

and (3) carboxyl amine hydrochloride: 5% -7%;

anhydrous sodium carbonate: 2% -4%;

hydrophilic reactant: and (4) the balance.

2. The chelating resin special for adsorbing gallium as described in claim 1, wherein: the concentration of the calcium chloride aqueous solution is 50-70 ppm.

3. The chelating resin special for adsorbing gallium as described in claim 1, wherein: the polymerization diluent comprises acrylonitrile, divinyl benzene, an oil phase diluent and benzoyl peroxide, and the percentage of each component is 1:1.5:0.8: 1.2.

4. The chelating resin special for adsorbing gallium as described in claim 1, wherein: the oil phase diluent comprises cyclohexanone and xylene, and the mixing ratio of the cyclohexanone to the xylene is 2: 1.

5. The chelating resin special for adsorbing gallium as described in claim 1, wherein: the percentage concentration of the benzoyl peroxide is 1% -3%.

6. The chelating resin special for adsorbing gallium as described in claim 1, wherein: the hydrophilic reactant adopts ethanol.

7. A preparation method of special chelate resin for adsorbing gallium is characterized by comprising the following steps: the method comprises the following steps:

s100, dissolving a suspension medium: mixing and heating the calcium chloride solution and the gelatin and continuously stirring until the gelatin is completely dissolved;

s200, polymerization reaction production: adding the polymerization diluent into the gelatin mixed solution according to the proportion, mixing, stirring and heating, and gradually heating for polymerization;

s300, intermediate substance extraction: sieving a 20-50-mesh polymer, repeatedly washing with hot water and cold water, filtering, and air-drying for later use;

s400, preparation and production of finished products: adding a hydrophilic reactant into the polymer, dissolving the hydroxylamine hydrochloride and the anhydrous sodium carbonate into the polymer, swelling the polymer at the constant temperature of 30-35 ℃ for 1h, heating the polymer to 70-80 ℃ for reaction for 6-8 h, washing the synthesized resin with cold water, performing suction filtration, and storing the resin in a wet state.

Technical Field

The invention relates to the technical field of metal extraction, in particular to a special chelating resin for adsorbing gallium and a preparation method thereof.

Background

Due to the low concentration of gallium in the earth's crust. The content of the active ingredients in the earth crust is 0.0015 percent of the total amount. It is widespread, but not present in the pure metallic state, but in the form of langasite (CuGaS 2), but rare and economically unimportant. Gallium is a by-product of industrial processing of sphalerite, pyrite, bauxite, germanite.

In nature, the trace amount of the zinc oxide is usually dispersed in bauxite, sphalerite and other ores. Is prepared by extracting from bauxite. When the zinc ore is burned at high temperature, gallium volatilizes in the form of a compound and condenses in the flue, and the gallium often coexists with indium and thallium. The crude gallium can be prepared by electrolysis and washing, and the high-purity gallium can be obtained by refining.

More than 90% of the primary gallium in the world is extracted in the process of producing the alumina, so that the method is a comprehensive utilization of mineral resources, the added value of the mineral resources is increased by extracting the metal gallium, the quality of the alumina is improved, and the pollution of waste red mud is reduced, thereby being very in line with the principle that the current low-carbon economy obtains the maximum utilization value at the minimum natural resource cost. The content of gallium in other metal deposits is extremely low, and can only reach hundreds of grams per ton after certain enrichment, so that the extraction of gallium is very difficult, and on the other hand, due to the concomitant relation, the yield of gallium is difficult to be greatly pulled due to the rising price of gallium, so that the annual yield of primary gallium is extremely low, the annual yield of the gallium is less than 300 tons in the whole world and is half of the yield of primary indium, and if the condition cannot be improved, the gallium will be seriously short in the future 20-30 years.

The existing method for extracting gallium from bauxite is mostly carried out by adopting a method of adsorption extraction of chelating resin in Bayer mother liquor. However, in the use process of the existing special chelating resin for absorbing gallium, the contact reaction between the chelating resin and Bayer mother liquor is insufficient, so that the chelating resin has weak adsorption capacity and certain defects.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides the special chelating resin for adsorbing gallium and the preparation method thereof, which can improve the number of micropores on the surface of the chelating resin and the contact degree with Bayer mother liquor, so that the chelating resin can fully perform adsorption reaction with the Bayer mother liquor, and the adsorption quantity of the chelating resin to the gallium in the Bayer mother liquor is improved.

In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:

the special chelate resin for adsorbing gallium comprises the following components in percentage by weight:

gelatin: 20% -30%;

calcium chloride aqueous solution: 3% -5%;

polymerization diluent: 20% -25%;

and (3) carboxyl amine hydrochloride: 5% -7%;

anhydrous sodium carbonate: 2% -4%;

hydrophilic reactant: and (4) the balance.

Preferably, in the chelating resin special for absorbing gallium, the concentration of the calcium chloride aqueous solution is 50-70 ppm.

Preferably, in the chelating resin special for absorbing gallium, the polymerization diluent comprises acrylonitrile, divinylbenzene, an oil phase diluent and benzoyl peroxide, and the percentage of each component is 1:1.5:0.8: 1.2.

Preferably, in the above chelating resin special for absorbing gallium, the oil phase diluent comprises cyclohexanone and xylene, and the mixing ratio of the cyclohexanone to the xylene is 2: 1.

Preferably, in the special chelating resin for absorbing gallium, the percentage concentration of benzoyl peroxide is 1% -3%.

Preferably, in the chelating resin special for absorbing gallium, the hydrophilic reactant is ethanol.

A preparation method of special chelating resin for adsorbing gallium comprises the following steps:

s100, dissolving a suspension medium: mixing and heating the calcium chloride solution and the gelatin and continuously stirring until the gelatin is completely dissolved;

s200, polymerization reaction production: adding the polymerization diluent into the gelatin mixed solution according to the proportion, mixing, stirring and heating, and gradually heating for polymerization;

s300, intermediate substance extraction: sieving a 20-50-mesh polymer, repeatedly washing with hot water and cold water, filtering, and air-drying for later use;

s400, preparation and production of finished products: adding a hydrophilic reactant into the polymer, dissolving the hydroxylamine hydrochloride and the anhydrous sodium carbonate into the polymer, swelling the polymer at the constant temperature of 30-35 ℃ for 1h, heating the polymer to 70-80 ℃ for reaction for 6-8 h, washing the synthesized resin with cold water, performing suction filtration, and storing the resin in a wet state.

The invention has the beneficial effects that:

the invention has reasonable design, and the addition of the polymeric diluent and the hydrophilic reactant greatly improves the number of micropores on the surface of the chelate resin and the contact degree with the Bayer mother liquor, so that the chelate resin can fully perform adsorption reaction with the Bayer mother liquor, greatly improves the adsorption capacity of the chelate resin to the gallium in the Bayer mother liquor, and has good adsorption and extraction capacity.

Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a flow chart of the preparation method of the chelating resin special for absorbing gallium of the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment is a chelating resin special for absorbing gallium, which comprises the following components in percentage by weight: gelatin: 20% -30%; calcium chloride aqueous solution: 3% -5%;

polymerization diluent: 20% -25%; and (3) carboxyl amine hydrochloride: 5% -7%; anhydrous sodium carbonate: 2% -4%; hydrophilic reactant: and (4) the balance. The concentration of the calcium chloride aqueous solution is 50-70 ppm, the polymerization diluent comprises acrylonitrile, divinylbenzene, an oil phase diluent and benzoyl peroxide, the percentage of each component is 1:1.5:0.8:1.2, the oil phase diluent comprises cyclohexanone and xylene, the mixing ratio of the cyclohexanone to the xylene is 2:1, the percentage concentration of the benzoyl peroxide is 1% -3%, and the hydrophilic reactant adopts ethanol.

Referring to fig. 1, the present invention also provides a method for preparing chelating resin special for adsorbing gallium, comprising the following steps:

s100, dissolving a suspension medium: mixing and heating the calcium chloride solution and the gelatin and continuously stirring until the gelatin is completely dissolved;

s200, polymerization reaction production: adding the polymerization diluent into the gelatin mixed solution according to the proportion, mixing, stirring and heating, and gradually heating for polymerization;

s300, intermediate substance extraction: sieving a 20-50-mesh polymer, repeatedly washing with hot water and cold water, filtering, and air-drying for later use;

s400, preparation and production of finished products: adding a hydrophilic reactant into the polymer, dissolving the hydroxylamine hydrochloride and the anhydrous sodium carbonate into the polymer, swelling the polymer at the constant temperature of 30-35 ℃ for 1h, heating the polymer to 70-80 ℃ for reaction for 6-8 h, washing the synthesized resin with cold water, performing suction filtration, and storing the resin in a wet state.

The invention has reasonable design, and the addition of the polymeric diluent and the hydrophilic reactant greatly improves the number of micropores on the surface of the chelate resin and the contact degree with the Bayer mother liquor, so that the chelate resin can fully perform adsorption reaction with the Bayer mother liquor, greatly improves the adsorption capacity of the chelate resin to the gallium in the Bayer mother liquor, and has good adsorption and extraction capacity.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.