CN111330548A - A kind of preparation method of adsorption resin composite aluminum-based lithium adsorbent - Google Patents

Abstract

The invention discloses a preparation method of an adsorption resin composite aluminum-based lithium adsorbent. 10-20 parts of an adsorption resin with a pore size of ≥50 nm and a specific surface area of ≥300 m2/g, 6-15 parts of aluminum chloride salt, 1-5 parts of an adsorption resin 1-10 mol/L lye solution was added into 10-30 parts of solvent while stirring, the addition of lye solution was stopped when the pH value of the solution was 4.5-7.0, the reaction was completed, then filtered and dried to obtain the adsorption resin composite Aluminum-based lithium adsorbent; no binder is added in the preparation process, and the dispersibility is good. The macroporous adsorbent resin has the characteristics of large pore size, large specific surface area, and large adsorption capacity, which is beneficial to the industrialization of brine extraction lithium adsorbent.

Description

A kind of preparation method of adsorption resin composite aluminum-based lithium adsorbent

technical field

The invention belongs to the technical field of chemical industry, and relates to a preparation method of an adsorption resin composite aluminum-based lithium adsorbent.

Background technique

Lithium (Li) is one of the important rare metals closely related to the national economy and people's lives. Its metals and compounds are widely used in glass, ceramics, chemicals, medicine and other fields. Especially since the 21st century, with the rapid development of science and technology, metal Lithium and its compounds have been widely used in high-energy batteries, aerospace, nuclear fusion power generation and ultra-light and high-strength lithium alloys, resulting in an increasing demand for them, which has become an irreplaceable energy metal in the 21st century.

my country is a country with large lithium resources in salt lake brine. Salt lake lithium resources account for more than 80% of national lithium resources and about 1/3 of the world's salt lake lithium resources. It is initially estimated that the prospective reserves of lithium salts are tens of millions of tons, mainly distributed in western my country. In Qinghai and Tibet, the lithium resources in Qinghai are mainly sulfate type, concentrated in the Qaidam Basin and the northern side of the carbonate type lithium resource belt in northern Tibet; the lithium resources in Tibet are mainly carbonate type, concentrated in the Zabuye Salt Lake in the west of northern Tibet and Bangor-Dujali Lake in the east. Among them, the Qaidam Basin in Qinghai and the Zabuye Salt Lake in Tibet have large reserves of lithium resources and are of high grade. They are important lithium resources in the world, and they are also important resource bases for the development of lithium salt industry in my country in the future. The salt lake in the Qaidam Basin is located in the plateau area with arid climate and consists of 18 main salt lakes. The brine of the salt lake contains rich mineral resources such as Li, B, K, Mg, Na, Br, etc. Among them, the one with higher lithium content is Yiliping Lake, Dongtai Jiner Lake, Chaerhan Lake and Dachaidan Lake Tibet Zabuye Salt Lake, located in the southern part of the northern Tibetan Plateau, is one of the four deposits in the world with lithium reserves exceeding one million tons, with an altitude of more than 4Km. A closed basin salt lake with no outflow, the brine has a high salinity, the total salt content reaches more than 33%, and is rich in Na, K, Br, I, Li, B and other elements;

The composition of salt lake brine is complex, usually Na, K, Mg, Li, Ca, B and other ions coexist, and the composition of salt lake brine is also very different with different regions, resulting in the current use of major salt lakes. The production process is not the same, which objectively hinders the development of lithium resources in salt lake brine. In addition, Li ⁺ in salt lake brine is often accompanied by a large number of alkali metal and alkaline earth metal ions. Due to their similar chemical properties due to the diagonal relationship, the existence of these ions is not conducive to the separation and extraction of lithium, especially the existence of a large amount of ^Mg The separation and extraction of ⁺ is more difficult. Most of the lithium resources in salt lake brine in my country have the characteristics of high magnesium-lithium ratio. Compared with other lithium resources in foreign salt lakes, the development of lithium resources in salt lake brine in my country is more difficult. Therefore, how to solve the world problem of separation of magnesium and lithium will determine the success or failure of the development of lithium resources in salt lake brine in my country.

According to the literature, to obtain LiCl·2Al(OH) ₃ ·nH ₂ O or its analogues, there are mainly four methods: mechanochemical synthesis method, soaking method, acidification conversion method and precipitation method.

The patent application 201710235736 of Qinghai Salt Lake Industry Co., Ltd. discloses a preparation method and lithium sorbent, which are prepared and reacted first to generate LiCl 2.2～2.8Al(OH) ₃ 2.7～3.9H ₂ O, and then solidified Liquid separation, drying, grinding and pulverization to form powder, adding binder and liquid chlorine to realize mixed granulation, and finally sieving to obtain lithium adsorbent.

The patent application 201710274742 of BYD Co., Ltd. discloses a supported lithium adsorbent and its preparation method. The supported lithium adsorbent comprises: a support body and a porous microstructure formed by solidifying the lithium adsorbent powder and the adhesive in the pores of the support body. Patent Application No. 201711031854 discloses lithium sorbent composite particles and a preparation method thereof, including an active lithium sorbent and a binder, wherein at least part of the particles of the active lithium sorbent are between particles and/or the particles of the active lithium sorbent are connected to each other. Pores are formed between the binders, the porosity of the lithium adsorbent composite particles is 1%-45%, the adsorption and desorption speed is fast, the adsorption and desorption amount is large and stable.

The patent application of East China University of Science and Technology 201811331549 Lithium adsorbent or its precursor powder, various polymers, pore-forming agents and organic solvents are mixed under the conditions of normal pressure and temperature of 10-190 ° C, and stirred for 1-120 min to obtain uniform mixture; drop the above-mentioned uniform mixture into the solution, or extrude the above-mentioned uniform mixture to be crushed, and obtain granular lithium adsorbent after washing.

The aforementioned preparation methods are inseparable, resulting in the disadvantages of small specific surface area and small adsorption capacity of the final lithium adsorbent;

US patent US4221767 discloses a MWA-1-OH resin resin with LiCl·2Al(OH) ₃ ·nH ₂ O, the principle of which is to use ionic bonding to load aluminum salts on the skeleton, because the specific surface area of the skeleton itself is less than 50㎡/g, the prepared lithium adsorbent has a small specific surface area and a small loading of adsorbent groups.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method of an adsorption resin composite aluminum-based lithium adsorbent, the preparation process is free of binder, and utilizes the characteristics of a large specific surface area of the adsorption resin to solve the problem that the lithium adsorbent prepared by the traditional method has a small specific surface area and a large adsorption capacity. low problem.

For achieving the above object, the technical scheme adopted in the present invention is:

A preparation method of an adsorption resin composite aluminum-based lithium adsorbent, in terms of parts by mass, weigh 10-20 parts of an adsorption resin with a pore size of ≥50 nm and a specific surface area of ≥300 m2/g, 6-15 parts of aluminum chloride salt, Add 1-5 parts of lithium salt into 10-30 parts of solvent, control the reaction temperature to be 40-80 ℃, add 1-10 mol/L alkali solution while stirring, control the feeding time to be 15-60 min, and the pH value of the solution is 4.5 At -7.0, the addition of alkaline solution was stopped, the reaction was completed, and then filtered and dried to obtain an adsorption resin composite aluminum-based lithium adsorbent.

Further, the adsorption resin has a particle size of 0.315-1.25 mm and an adsorption resin with a water content of 40-80%.

Further, the cross-linking degree of the adsorption resin is 40-80% or the adsorption resin is an ultra-high cross-linking resin.

Further, the aluminum chloride salt is ALCl 3 ·6H ₂ O or ALCl 3 ; the lithium salt is one or more of lithium chloride, lithium carbonate, lithium hydroxide and lithium sulfate.

Further, the solvent is one or more of water, methanol, ethanol and methylal; the lye is one or more of lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution and ammonia water variety.

Further, the adsorption resin is prepared from skeleton material, cross-linking agent, extractant and porogen with a mass of 40-150% of the skeleton material; the skeleton material is styrene, acrylonitrile, methyl acrylate, allylamine, One or more of phenolic.

Further, the porogen is a non-good solvent, a high molecular polymer or a linear polymer.

Further, the non-good solvent is liquid paraffin, solvent oil, solid paraffin, one or more of n-heptane, alkane, fatty acid, ethylene glycol and propylene glycol; the high molecular polymer is polystyrene, polyacrylic acid One or more of methyl ester, polyvinyl acetate and polyvinyl chloride.

Further, the cross-linking agent is divinylbenzene, ethylene glycol dimethacrylate, allyl tripolyisocyanate, allyl itaconic acid, ethylene polyamine, hydroquinone, isophthalic acid one or more of the phenols.

Further, the extractant is one of toluene, methylal, methanol, ethanol, methyl acetate, dimethylamide, and xylene.

The preparation method of the adsorption resin composite aluminum-based lithium adsorbent of the invention has the advantages of no binder added in the preparation process, good dispersibility, large pore size of the macroporous adsorption resin, large specific surface area, and large adsorption capacity of the obtained lithium adsorbent, which is beneficial to brine extraction. Industrialization of lithium sorbents.

Detailed ways

The present invention will be described in further detail below with reference to specific embodiments, but it is not intended to limit the present invention.

Example 1

Styrene is selected as the skeleton material, polystyrene with a mass of 40% of the skeleton material is used as a porogen, divinylbenzene is used as a cross-linking agent, and toluene is used as an extractant, and a suspension polymerization method is used to prepare a cross-linking degree of 40% and a particle size It is an adsorption resin of 0.315mm, the average pore size of the obtained resin is 50nm, the specific surface area is 350㎡/g, and the water content is 40%;

Using a large pore size adsorption resin matrix with a pore size of ≥50nm and a specific surface area of 350㎡/g, an adsorption resin composite aluminum-based lithium adsorbent was prepared: Weigh 10g of adsorption resin, 6g of _ALCl3 6H2O, 1g of lithium chloride, Put it into a glass-lined reaction vessel of 10 g methanol, control the reaction temperature to 40 ° C, start stirring, add 1 mol/L lithium hydroxide solution, control the feeding time to be 15 min, and control the pH value to be 4.5 as the reaction end point. After the reaction is completed, Then suction filtration, and the methanol is dried to obtain the adsorption resin composite aluminum-based lithium adsorbent-1; 5 grams of samples are taken and put into 200 ml of brine mother liquor for adsorption experiments, and the comprehensive calculation shows that the adsorption capacity is 2.8 mg/g;

Example 2:

Acrylonitrile was used as the skeleton material, liquid paraffin with a mass of 150% of the skeleton material was used as the porogen, divinylbenzene was used as the cross-linking agent, and toluene was used as the extractant. 1.25mm adsorption resin, the average pore size of the obtained resin is 100nm, the specific surface area is 480㎡/g, and the water content is 80%;

Using a large pore size adsorption resin matrix with a pore size of 100 nm and a specific surface area of 480 m2/g, an adsorption resin composite aluminum-based lithium adsorbent was prepared: weigh 20 g of adsorption resin, 15 g of ALCl3 6H ₂ O, 5 g of lithium chloride, Add it into a steel-lined tetrafluoro reaction vessel with 30 g of water, control the water temperature to be 80 ° C, start stirring, add 10 mol/L sodium hydroxide solution, control the dripping time to be 60 min, and control the pH value to be 7.0 as the end of the reaction, then Vacuum filtration and filtration, and dry naturally to obtain adsorption resin composite aluminum-based lithium adsorbent-2; take 5 grams of brine mother liquor into 200ml to carry out adsorption experiments, and the comprehensive calculation shows that the adsorption capacity is 4.1mg/g;

Example 3:

Methyl acrylate is selected as skeleton material, n-heptane with 100% skeleton material quality is used as porogen, allyl tripolyisocyanate is used as cross-linking agent, methyl acetate is used as extractant, and suspension polymerization method is used to prepare cross-linking agent. The adsorption resin with a linkage degree of 50% and a particle size of 1.0 mm is obtained with an average pore size of 100 nm, a specific surface area of 320 m2/g, and an adsorption resin with a water content of 70%;

Using a large-pore adsorption resin matrix with a pore size of 100 nm and a specific surface area of 320 m2/g, an adsorption resin composite aluminum-based lithium adsorbent was prepared: weigh 20 g of adsorption resin, 15 g of ALCl3 6H ₂ O, 5 g of lithium chloride, add Into the steel-lined tetrafluoro reaction vessel of 20g ethanol, control the ethanol temperature to be 60 ℃, start stirring, add 10mol/L sodium hydroxide solution, control the dripping time to be 30min, control the pH value to be 6.0 as the reaction end point, then vacuum Suction filtration, vacuum drying, to obtain adsorption resin composite aluminum-based lithium adsorbent-3; take 5 grams of brine mother liquor into 200ml to carry out adsorption experiments, and the comprehensive calculation shows that the adsorption capacity is 3.4mg/g;

Example 4:

Methyl acrylate was used as the skeleton material, n-heptane with 100% of the skeleton material mass was used as the porogen, allyl triisocyanate was used as the crosslinking agent, and xylene was used as the extractant, and the spray granulation method was used to prepare the crosslinking agent. The adsorption resin with a linkage degree of 60% and a particle size of 0.8mm has an average pore size of 90nm, a specific surface area of 310㎡/g, and a water content of 60%;

Use a large pore size adsorption resin matrix with a pore size of 90nm to prepare an adsorption resin composite aluminum-based lithium adsorbent: weigh 15g of adsorption resin, 10g of anhydrous ALCl3, 5g of lithium carbonate, and add them to 20g of methylal. In the reaction vessel, control the methylal temperature to be 20°C, start stirring, add 5mol/L sodium hydroxide solution, control the dropwise addition time to be 40min, and control the pH value to be 5.0 as the reaction end point, then vacuum filtration and vacuum drying , to obtain the adsorption resin composite aluminum-based lithium adsorbent-4; take 5 grams of brine mother liquor into 200ml to carry out the adsorption experiment, and the comprehensive calculation obtains the adsorption amount to be 3.9mg/g;

Example 5:

Phenolic aldehyde is selected as the skeleton material, ethylene glycol with 100% of the skeleton material mass is used as the porogen, resorcinol is used as the crosslinking agent, and methylal is used as the extractant, and a reversed-phase suspension polymerization method is used to prepare ultra-high cross-linked, The adsorption resin with a particle size of 0.8mm has an average pore size of 80nm, a specific surface area of 610㎡/g, and a water content of 65%;

Using a large pore size adsorption resin matrix with a pore size of 80nm and a specific surface area of 610㎡/g, the adsorption resin composite aluminum-based lithium adsorbent was prepared: Weigh 15g of adsorption resin, 10g of anhydrous ALCl3, 5g of lithium carbonate, and added to 20g of methyl alcohol. In the glass-lined reaction vessel of acetal, control the reaction temperature to be 20°C, start stirring, add 5mol/L lithium hydroxide solution, control the dripping time to be 30min, and control the pH value to be 5.0 as the end of the reaction, then vacuum filtration , vacuum drying to obtain adsorption resin composite aluminum-based lithium adsorbent-5; take 5 grams of brine mother liquor into 200ml to carry out adsorption experiments, and comprehensively calculate the adsorption amount to be 3.6mg/g.

Example 6:

Allylamine is used as the skeleton material, polyvinyl chloride with 100% of the skeleton material mass is used as the porogen, ethylene glycol dimethacrylate is used as the crosslinking agent, and dimethyl amide is used as the extractant, and the reversed-phase suspension polymerization method is adopted, An adsorption resin with a cross-linking degree of 80% and a particle size of 1.25 mm was prepared. The average pore diameter of the obtained resin was 80 nm, the specific surface area was 610 m2/g, and the water content was 80%;

Using a large pore size adsorption resin matrix with a pore size of 80nm and a specific surface area of 610㎡/g, an adsorption resin composite aluminum-based lithium adsorbent was prepared: Weigh 15g of adsorption resin, 10g of anhydrous ALCl3, 3g of lithium hydroxide, and added to 20g In the glass-lined reaction vessel of methanol, control the reaction temperature to be 20°C, start stirring, add 5mol/L potassium hydroxide solution and ammonia water, control the dripping time to be 30min, and control the pH value to be 5.0 as the reaction end point, then vacuum filtration Filtration and vacuum drying to obtain adsorption resin composite aluminum-based lithium adsorbent-6.

Example 7:

Allylamine and styrene are selected as skeleton materials, alkanes and fatty acids with 100% mass of skeleton materials are porogens, hydroquinone is used as cross-linking agent, methanol is used as extractant, and reversed-phase suspension polymerization is used to prepare cross-linking degree. 80% adsorption resin with a particle size of 1.25mm, the obtained resin has an average pore size of 80nm, a specific surface area of 610㎡/g, and a water content of 80%; the extractant can also be ethanol. The cross-linking agent can also be one or more of allyl itaconic acid, ethylene polyamine, and ethylene polyamine. The porogen can also be one or more of mineral spirits, solid paraffin, and propylene glycol; or one or more of polymethyl acrylate, polyvinyl acetate, and polyvinyl acetate.

Using a large pore size adsorption resin matrix with a pore size of 80nm and a specific surface area of 610㎡/g, an adsorption resin composite aluminum-based lithium adsorbent was prepared: Weigh 10g of adsorption resin, 8g of anhydrous ALCl3, 5g of lithium sulfate, and added to 20g of water In the glass-lined reaction vessel, control the reaction temperature to be 20°C, start stirring, add 5mol/L potassium hydroxide solution and ammonia water, control the dripping time to be 30min, and control the pH value to be 6.0 as the reaction end point, then vacuum filtration , and vacuum drying to obtain adsorption resin composite aluminum-based lithium adsorbent-7.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: Modifications or equivalent substitutions are made to the specific embodiments, and any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention shall all be included in the scope of the present claims.

Claims (10)

1. A preparation method of an adsorption resin composite aluminum lithium adsorbent is characterized by comprising the following steps: weighing 10-20 parts by mass of adsorption resin with the pore diameter of more than or equal to 50nm and the specific surface area of more than or equal to 300 square meters per gram, 6-15 parts of aluminum chloride salt and 1-5 parts of lithium salt, adding the mixture into 10-30 parts of solvent, controlling the reaction temperature to be 40-80 ℃, adding 1-10mol/L alkali liquor while stirring, controlling the feeding time to be 15-60min, stopping adding the alkali liquor when the pH value of the solution is 4.5-7.0, finishing the reaction, and then filtering and drying to obtain the adsorption resin composite aluminum lithium adsorbent.

2. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 1, wherein: the particle size of the adsorption resin is 0.315-1.25mm, and the water content of the adsorption resin is 40-80%.

3. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 1, wherein: the crosslinking degree of the adsorption resin is 40-80% or the adsorption resin is ultrahigh crosslinking resin.

4. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 1, wherein: the aluminum chloride salt is ALCl3 & 6H₂O or ALCl 3; the lithium salt is one or more of lithium chloride, lithium carbonate, lithium hydroxide and lithium sulfate.

5. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 1, wherein: the solvent is one or more of water, methanol, ethanol, dichloroethane and methylal; the alkali liquor is one or more of lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution and ammonia water.

6. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to any one of claims 1 to 5, wherein: the adsorption resin is prepared from a framework material, a cross-linking agent, an extracting agent and a pore-foaming agent accounting for 40-150% of the mass of the framework material; the framework material is one or more of styrene, acrylonitrile, methyl acrylate, allylamine and phenolic aldehyde.

7. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 6, wherein: the pore-foaming agent is a poor solvent, a high molecular polymer or a linear high molecular.

8. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 6, wherein: the poor solvent is one or more of liquid paraffin, solvent oil, solid paraffin, n-heptane, alkane, fatty acid, ethylene glycol and propylene glycol; the high molecular polymer is one or more of polystyrene, polymethyl acrylate, polyvinyl acetate and polyvinyl chloride.

9. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 6, wherein: the cross-linking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl isocyanurate, allyl itaconate, ethylene polyamine, hydroquinone and resorcinol.

10. The method for preparing the adsorbent resin composite aluminum-based lithium adsorbent according to claim 6, wherein: the extractant is one of toluene, methylal, methanol, ethanol, methyl acetate, dimethyl amide and xylene.