KR20200133467A - Manufaturing method of zeolite using lithium residue - Google Patents

Abstract

Washing the lithium by-product from the lithium by-product to adjust the lithium by-product to pH 6 to 8; First adjusting the molar ratio of silicon to aluminum contained in the washed lithium by-product (Si/Al ratio); Adjusting the mixing ratio of the lithium by-product and the alkali material in which the molar ratio is adjusted (weight of lithium by-product/OH ^{-number of} moles of ions); Preparing a hydrogel form by adding an alkali substance to the lithium by-product having the molar ratio adjusted at the mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions); A first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal; Introducing a zeolite manufacturing method comprising a.

Description

Method of manufacturing zeolite using lithium by-product {MANUFATURING METHOD OF ZEOLITE USING LITHIUM RESIDUE}

The present disclosure relates to a method of manufacturing a zeolite using lithium by-products, and more specifically, to a zeolite obtained by using a lithium by-product generated during a process of recovering lithium from lithium ore, and a manufacturing method thereof with high cost efficiency.

Zeolite (M[(Al ₂ O ₃ ) _x (SiO ₂ ) _y ]zH ₂ O) is a material used as a laundry detergent, a catalyst for removing heavy metals in wastewater, and for removing harmful substances from exhaust gas. This is because the unique applied mineralogical properties of zeolites, ie, cation exchange properties (CEC), adsorption and molecular sieve properties, catalyst properties, dehydration and resorption properties, etc. It is being used and applied because of its utility value.

In the study of zeolite synthesis, in 1949, the A-type zeolite was first synthesized by Union Carbide's research team for industrial application, and as the excellent applied mineralogical properties of the A-type synthetic zeolite became known, interest in the synthesis of zeolite increased. The study was followed. In the 1960s, the successful application of petrochemical processes in the United States and the emergence of new synthetic zeolites with excellent efficacy such as X-type and Y-type zeolites led to full-scale research on zeolites.

In recent years, as the application range of zeolite has been greatly expanded, more diversity in the pore structure and characteristics of zeolite is required, and research to synthesize zeolite with new pore structure and applied mineralogical properties has been progressed, leading to the spotlight in industrial applications. A number of synthetic zeolites of about 150 types, including ZSM-5, have been developed.

Zeolite synthesis is usually produced by a hydrothermal process called “Hydrogel Process” under a temperature range of 200℃ to room temperature. In general, zeolites do not require special pressure conditions during formation and are relatively easily synthesized at low temperatures.

Synthetic zeolite not only has various pore characteristics, but also has excellent performance and efficacy, but when actually applied, it has some difficulties in terms of price compared to cheaper natural zeolites.

Therefore, efforts are currently being made to find a cheaper synthesis method capable of homogeneously synthesizing zeolite having excellent properties. In this way, a method of using as a raw material a natural material cheaper than a reagent-type material (sodium silicate, sodium aluminate, silica gel, etc.), which was used as a raw material for the synthesis of zeolite, that is, a silicate mineral having a composition suitable for the synthesis of zeolite as a raw material. Has become. Studies on the synthesis of zeolites using natural minerals have mainly been conducted on clay, kaolin, kaolin, and volcanic vitreous rocks.

In addition, researches on using various by-products generated in large quantities in industrial processes as raw materials for zeolite synthesis are ongoing, instead of natural minerals that lack resources.

To provide a method for producing a zeolite with high cost-efficiency and good crystallinity from lithium by-products including aluminosilicate compounds composed of alumina and silica, which are generated in large quantities in a series of processes for recovering lithium from lithium ore. do.

Zeolite production method according to an embodiment of the present invention comprises the steps of adjusting the lithium by-product to pH 6 to 8 by washing with water; First adjusting the molar ratio (Si/Al ratio) of silicon to aluminum contained in the washed lithium by-product; Preparing a hydrogel form by adding an alkali substance to the lithium by-product whose molar ratio is first adjusted; And a first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal. In the step of preparing a hydrogel form by adding an alkali material to the lithium by-product whose molar ratio is adjusted, the mixing ratio of the lithium by-product to the alkali material, (weight of lithium by-product / OH ^{-number of} moles of ions) is 100 g/mol Below.

The step of adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product with water may be a step of removing a conjugate base of an acid from the lithium by-product.

The step of adjusting the molar ratio of silicon to aluminum (Si/Al) contained in the washed lithium by-product includes adding an alumina supplementing material or a silica supplementing material to the lithium by-product to add silicon to aluminum contained in the lithium by-product. It may be a step of adjusting the molar ratio (Si/Al) to 0.75 to 3.0.

The alumina supplement material may include one or more of alumina hydrate (Al(OH) ₃ ) and sodium aluminate (NaAlO ₂ ).

The silica supplement material may be sodium silicate (Na ₂ OSiO ₂ ).

In the step of preparing a hydrogel form by adding an alkali material to the lithium by-product whose molar ratio is adjusted, the alkali material may have an OH ^- ion molar concentration of 1.0 to 6.0 M.

The alkaline substance may be sodium hydroxide (NaOH).

In the first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a first crystal, the first crystallization step may have a first crystallization temperature of 60 to 100°C.

In the first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal, the first crystallization step may have a first crystallization time of 12 hours or more.

In the first crystallization step of crystallizing the hydrogel-type lithium by-product to produce crystals, the stirring blade is at least one from the group consisting of a propeller type, a turbine blade type, and a plate type, the agitator blade diameter is 7 cm, and the blade is 2 In a stirrer having a reactor volume of 2 L (diameter 13 cm, height 20 cm), the first crystallization stirring speed may be 300 to 600 rpm.

Filtering the primary crystal after the first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a crystal; And washing and drying the filtered primary crystal with water.

The lithium by-product is based on the total 100% by weight, alumina (Al ₂ O ₃ ): 20 to 30% by weight, silica (SiO ₂ ): 60 to 70% by weight, iron oxide (Fe ₂ O ₃ ), calcium oxide (CaO) , Sodium oxide (Na ₂ O) and potassium oxide (K ₂ O), at least one: 10% by weight or less may be included.

Separating the first crystal of zeolite and the filtrate generated by solid-liquid separation after the first crystallization step of crystallizing the lithium by-product in the form of hydrogel to prepare a crystal; Secondly adjusting the molar ratio of silicon to aluminum (Si/Al) contained in the separated filtrate; And a second crystallization step of crystallizing the filtrate whose molar ratio is adjusted to prepare crystals.

Secondly adjusting the molar ratio of silicon to aluminum (Si/Al) contained in the separated filtrate comprises adding an alumina supplementing material or a silica supplementing material to the lithium by-product, It may be a step of adjusting the molar ratio of silicon (Si/Al) to 0.75 to 3.0.

The alumina supplement material may include one or more of alumina hydrate (Al(OH) ₃ ) and sodium aluminate (NaAlO ₂ ).

The silica supplement material may be sodium silicate (Na ₂ OSiO ₂ ).

In the second crystallization step of crystallizing the filtrate having the second molar ratio adjusted to produce crystals, the second crystallization step may have a second crystallization temperature of 60 to 100°C.

In the second crystallization step of crystallizing the filtrate whose molar ratio is adjusted to prepare crystals, the second crystallization step may have a second crystallization time of more than 2 hours.

Filtering the secondary crystal after the secondary crystallization step of crystallizing the filtrate whose molar ratio is adjusted to prepare crystals; And washing and drying the filtered secondary crystals with water.

The zeolite according to an embodiment of the present invention may consist of only one paper-shaped crystal phase selected from the group consisting of P-type zeolite, A-type zeolite, and X-type zeolite.

In the present invention, it is possible to produce a zeolite having high crystallinity and high cost efficiency from lithium by-products generated in large amounts in the process of recovering lithium from lithium ore.

The zeolite thus prepared can be used as a gas adsorbent, laundry detergent, heavy metal treatment in wastewater, and a catalyst for removing harmful gases.

In addition, not only can zeolite crystals be prepared by primary crystallization of lithium by-products, but also impurities content, whiteness, etc. through secondary crystallization using unreacted residual Si components in the filtrate recovered through solid-liquid separation after primary crystallization. Secondary products with higher quality than tea products can be recovered, and the product recovery rate compared to input raw materials can be improved while minimizing the loss of raw materials.

1 is a view showing the particle size distribution of lithium residues generated in a solid-liquid separation process after water leaching in a zeolite manufacturing method according to an embodiment of the present invention.

Terms such as first, second and third are used to describe various parts, components, regions, layers, and/or sections, but are not limited thereto. These terms are only used to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.

The terminology used herein is for referring only to specific embodiments and is not intended to limit the present invention. Singular forms as used herein also include plural forms unless the phrases clearly indicate the opposite. As used in the specification, the meaning of “comprising” specifies a specific characteristic, region, integer, step, action, element and/or component, and the presence of another characteristic, region, integer, step, action, element and/or component It does not exclude additions.

When a part is referred to as being "on" or "on" another part, it may be directly on or on another part, or other parts may be involved in between. In contrast, when a part is referred to as being “directly above” another part, no other part is intervened.

Although not defined differently, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

Terms defined in a commonly used dictionary are additionally interpreted as having a meaning consistent with the related technical literature and the presently disclosed content, and are not interpreted in an ideal or very formal meaning unless defined.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Lithium by-product

In a series of processes for recovering lithium from lithium ore, Spodumene (Li ₂ O Al ₂ O ₃ 4SiO ₂ , LiAl ₂ Si ₂ O ₆ ), the main mineral phase of lithium ore, is placed in the Li ⁺ ion site of the ore by sulfuric acid roasting process. It is ion-exchanged with H ⁺ ions dissociated from sulfuric acid, and the ion-exchanged Li ⁺ ions are bonded to the dissociated SO ₄ ^2- ions, and a precipitation reaction proceeds to precipitate lithium sulfate (Li ₂ SO ₄ ).

The precipitated lithium sulfate (Li ₂ SO ₄ ) can be leached using water and then solid-liquid separated to prepare a lithium by-product. Lithium sulfate (Li ₂ SO ₄ ) is dissolved in water and leached, whereas aluminosilicates (Al ₂ O ₃ 4SiO ₂ , AlSi ₂ O ₆ ) are not dissolved in water and remain in the form of solid compounds, forming lithium by-products. can do.

The lithium by-product contains about 26% by weight of Al ₂ O ₃ , about 66% by weight of SiO ₂ , 1.6% by weight of Fe ₂ O ₃ , and 0.1 to 0.4% by weight of alkali metals such as CaO, Na ₂ O, and K ₂ O, As a crystal phase composed of aluminosilicate (Al ₂ O ₃ 4SiO ₂ , AlSi ₂ O ₆ ), silica (SiO ₂ ), and albite, it has an average particle size of about 25 μm.

Since lithium by-products having such physical and chemical properties are composed of silica and alumina, which are major constituents of zeolite, they can be sufficiently used as raw materials for synthetic zeolites.

Step of washing lithium by-product

Lithium by-products from the process of recovering lithium from lithium ore are acidic. The reason that lithium by-products are acidic is that sulfuric acid, which remained unreacted during water leaching, is dissolved and included in lithium by-products and remains because excess sulfuric acid is used when roasting with sulfuric acid in the pretreatment of lithium ore.

When acidic lithium by-products including sulfuric acid group (SO ₄ ^2- ) are used as a raw material for zeolite production without washing with water, residual sulfate group ions first consume the alkali component added for the dissolution reaction of the lithium by-product raw material. Due to this, not only an excessive amount of alkali needs to be added, but also the added alkali component and the remaining sulfuric acid group (SO ₄ ^2- ) ions react to form forget-me-not, and as a result, the hydrogel formation reaction is hindered. Therefore, it is not preferable to use an acidic lithium by-product having a pH of less than 6 for zeolite production without washing with water. In addition, in the case of washing with an alkali other than water, the pH may exceed 8, but even in this case, since sulfate ions and alkali react in the solution to generate forgetfulness or impurity ions accordingly, it is not preferable.

Therefore, in order to use the acidic lithium by-product generated from the process as a raw material for producing synthetic zeolite, the acidic lithium by-product is removed through a sufficient washing process to remove the sulfuric acid group (SO ₄ ^2- ) ions to pH 6 to 8, specifically Preparation with lithium by-products of pH 6.08 to 7.0 must be preceded.

Accordingly, the acidic lithium by-product washing process of the present invention is performed by repeating a series of steps of completely drying the recovered lithium by-product in a dryer, and adding distilled water to the completely dried lithium by-product, stirring, filtering, and drying the pH 6 to 8, specifically May be to obtain a lithium by-product of pH 6.08 to 7.0.

Control of the first molar ratio of silicon to aluminum (Si/Al)

In the step of first adjusting a lithium by-product of pH 6 to 8 prepared through a sufficient washing process to a constitutional molar ratio suitable for zeolite formation, the molar ratio of Si and Al components in the lithium by-product (Si /Al molar ratio) is preferably in the range of 0.75 to 3.0. Specifically, it is preferable to adjust the component so that it is in the range of 1.5 to 2.5, and more specifically, it is preferable to adjust the component so that it is 2.25.

When the Si and Al molar ratio in the lithium by-product raw material is 0.75 or less or 3.0 or more, the final product is hydroxysodalite (Hydroxysodalite, Na ₈ (AlSiO ₆ ) ₄ (OH) ₂ ) or analsim (Analcime, NaAlSi) in addition to the zeolite crystal phase. ₂ O ₆ H ₂ O), a zeolite form with low industrial applicability is mixed and produced. However, in the case of manufacturing by reacting by adjusting the molar ratio of Si and Al components (Si/Al molar ratio) in the lithium by-product raw material to the range of 0.75 to 3.0, the final product is zeolite P type, zeolite A type, zeolite X type according to the molar ratio condition. It can be produced as a single crystal phase.

Accordingly, the step of first adjusting the molar ratio of Si and Al components in the lithium by-product raw material of the present invention to a constitutional molar ratio suitable for zeolite formation is to introduce Si and Al components in the lithium residue raw material by adding an alumina supplementing material or a silica supplementing material to the lithium by-product. It may be a step of adjusting the molar ratio of (Si/Al molar ratio) to within the range of 0.75 to 3.0.

In the present invention, the alumina supplement material used to supplement the alumina component may include alumina hydrate (Al(OH) ₃ ), sodium aluminate (NaAlO ₂ ), etc., and used to supplement the silica component. As a silica component supplemental material, sodium silicate (Na ₂ OSiO ₂ ) may be used, respectively.

Addition of alkaline substances to lithium by-products

The mixing ratio of the lithium by-product and the alkali solution adjusted to the molar ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is preferably adjusted to a range of 100 g/mol or less. Specifically, the mixing ratio of the lithium by-product and the alkali solution adjusted to the molar ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is preferably adjusted in the range of 25 g/mol to 100 g/mol. Specifically, the mixing ratio is preferably adjusted to 50 g/mol to 90 g/mol, more specifically 60 g/mol to 80 g/mol.

The final product prepared under the condition that the mixing ratio of the lithium by-product and the alkali solution (weight of lithium by-product/OH ^{-number of} moles of ions) is more than 100 g/mol is produced by mixing Analcime in P-type zeolite or analsim ( Analcime) produced as a single phase. In other words, when the solid lithium by-product, which is a raw material, is excessively increased above the proper mixing ratio compared to the alkali solution as a dissolving agent, not only the dissolution reaction ability of the alkali solution decreases, but also the amount of Na supply from the alkaline solution required for zeolite formation becomes insufficient. This is because the product, Analcime, precipitates as crystals. If the mixing ratio is less than 25 g/mol, manufacturing cost efficiency is lowered, which is not preferable.

Accordingly, the step of adjusting the mixing ratio of the lithium by-product and the alkali solution of the present invention (weight of lithium by-product/OH ^{-number of} moles of ions) is a step of adjusting the mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) to a range of 100 g/mol or less. Can be

In the step of preparing a hydrogel by adding and dissolving alkali to the lithium by-product raw material with the molar ratio adjusted at the mixing ratio, the OH ^- ion molar concentration of the added alkali solution is preferably 1.0M to 6.0M. Do. Specifically, the alkali solution to be added may be NaOH. Specifically, the OH ^- ion molar concentration may be 1.5 to 5.0M, more specifically 2.5 to 3.5M.

In addition to the zeolite crystal phase, the final product prepared under the condition that the added OH ^- ion molar concentration is 1.0M or less contains SOD or analcime (Analcime, NaAlSi ₂ O ₆ H ₂ O), making it impossible to prepare a single crystal phase of zeolite. do. In addition, the final product prepared under the condition of OH ^- ion molar concentration of 6.0M or higher is a zeolite crystal, but the SOD is produced in a single phase, which is insufficient in industrial applicability due to low ion exchange ability.

However, when an alkali solution having an OH ^- ion molar concentration of 1.0M to 6.0M is used, the final product is obtained as a single phase of P-type and A-type zeolite having very good crystallinity.

Thus, in the present invention, the alkali material used to prepare a hydrogel by dissolving and reacting by adding it to a lithium by-product raw material may have an OH ^- ion molar concentration of 1.0M to 6.0M.

Zeolite primary crystallization

In the first crystallization step for preparing zeolite crystals from a hydrogel produced by mixing an alkali solution with a lithium by-product, the first crystallization temperature is in the range of 60 to 100°C, more preferably in the range of 90 to 95°C. When the primary crystallization temperature is less than 60℃, the final product belongs to the zeolite crystal, but it produces an analcime with low industrial applicability due to low ion exchange capacity, and when the primary crystallization temperature is 100℃ or higher. In addition to the zeolite crystal phase, hydroxy sodalite is additionally incorporated to form.

In addition, in the first crystallization step for preparing zeolite crystals from a hydrogel produced by mixing an alkali solution with a lithium by-product, the first crystallization time is preferably adjusted to 12 hours or more. Specifically, the first crystallization time is 12 to 48 hours. Even when the reaction is performed by setting the first crystallization time to less than 12 hours, the final product is not preferable because it is generated as an analcime. It is not preferable in terms of manufacturing cost to react by setting the first crystallization time to more than 48 hours.

In addition, in the first crystallization step for preparing zeolite crystals from a hydrogel produced by mixing an alkali solution with a lithium by-product, the stirring blade is at least one from the group consisting of a propeller type, a turbine blade type, and a plate type, and a stirrer In a stirrer having a blade diameter of 7 cm, blades of 2 to 4, and a reactor volume of 2 L (diameter 13 cm, height 20 cm), the primary crystallization stirring speed is preferably performed at 300 to 600 rpm. When the primary crystallization stirring speed is less than 300 rpm, the final product is generated as an anal shim, and in the case of more than 600 rpm, it is not preferable because it is produced as a mixed crystal phase of the anal shim and SOD.

However, the hydrogel is at least one in the group consisting of a propeller type, a turbine blade type, and a plate type, and the condition of the first crystallization temperature range of 60 to 100°C, the first crystallization time condition of 12 hours or more, and the stirring blade are In the case of reaction with a stirrer with a diameter of 7 cm, 2 to 4 blades, and a reactor volume of 2 L (diameter 13 cm, height 20 cm) under the conditions of a stirring speed of 300 to 600 rpm, the final product is a single zeolite with good crystallinity. It can be produced in a crystalline phase.

Accordingly, in the first crystallization step of preparing the zeolite crystal of the present invention, the temperature is in the range of 60 to 100°C, the crystallization time is at least 12 hours, and the stirring blade is at least one from the group consisting of a propeller type, a turbine blade type, and a plate type, The stirrer blade diameter is 7 cm, the blade is 2 to 4, the reactor volume may be a step of a stirring speed of 300 to 600 rpm in a stirrer having a volume of 2L (diameter 13cm, height 20cm).

Recovery of primary zeolite crystals

After the first zeolite crystallization step, the first zeolite crystal and the filtrate generated by solid-liquid separation are separated.

The separated primary crystals of zeolite are sufficiently washed with water, dried, and the final primary product is recovered.At this stage, excess NaOH is removed by sufficient water washing to adjust the pH of the primary product to 7-9. It is necessary to give. This is because Na ions remaining in the primary product due to insufficient washing with water act as a cause of deteriorating the quality and performance of zeolite.

Therefore, the present invention is after the step of preparing zeolite primary crystals, filtering the primary crystals, and adjusting the pH of the product to 7 to 9 by sufficiently washing the filtered primary crystals to remove excess NaOH. It may include.

Zeolite secondary crystallization

In order to recover the zeolite secondary crystals from the filtrate separated by solid-liquid separation after the zeolite primary crystallization step, the step of secondly adjusting the molar ratio of silicon to aluminum (Si/Al) contained in the separated filtrate; And a second crystallization step of crystallizing the filtrate in which the molar ratio is adjusted to prepare crystals.

In the second controlling of the molar ratio of silicon to aluminum (Si/Al) contained in the separated filtrate, it is preferable to adjust the molar ratio to 0.75 to 3.0. The reason is the same as in the first molar ratio control step, when the molar ratio of Si and Al components in the lithium by-product raw material is 0.75 or less or 3.0 or more, in addition to the zeolite crystal phase, hydroxysodalite (Na ₈ (AlSiO _{6 )) in} the final product This is because zeolite forms with low industrial applicability such as) ₄ (OH) ₂ ) or Analcime (NaAlSi ₂ O ₆ H ₂ O) are mixed and produced.

In the second crystallization step for preparing zeolite crystals from the filtrate in which the molar ratio is secondarily adjusted, the second crystallization temperature is in the range of 60 to 100°C, more preferably in the range of 90 to 95°C, and the second crystallization It is preferable to adjust the time to more than 2 hours and carry out. Specifically, the secondary crystallization time is more than 2 hours and less than 24 hours.

The reason for the limitation of the secondary crystallization temperature is the same as the reason for the limitation of the primary crystallization temperature. When the secondary crystallization temperature is 60℃ or less, an analcime is generated, and when the secondary crystallization temperature is 100℃ or more, hide This is because oxy sodalite is mixed and produced.

In the case of reaction by setting the secondary crystallization time to 2 hours or less, the final product is not preferable because analsim and SOD are mixed and generated. The primary crystallization reaction is a heterogeneous reaction of a solid-liquid reaction, in which a solid lithium by-product is dissolved in alkali over a long period of time, and then zeolite crystals are formed by an interionic condensation reaction, whereas the secondary crystallization reaction is a homogeneous reaction between liquids. As one reaction, since it is a reaction in which zeolite is generated by ion precipitation and condensation reaction by alkali, the reaction is completed relatively very quickly, so that the secondary crystallization reaction time is shortened compared to the primary crystallization time of 12 hours or longer. When the secondary crystallization time is exceeded 24 hours, it is not preferable in terms of manufacturing cost, so it is preferable to set the reaction time to 24 hours or less.

Accordingly, the second crystallization step of preparing the zeolite crystal of the present invention may be a step in which the temperature is in the range of 60 to 100°C and the crystallization time is more than 2 hours.

Recovery of secondary crystals of zeolite

After the zeolite secondary crystallization step, the zeolite secondary crystals generated by solid-liquid separation and the filtrate are separated.

The separated zeolite secondary crystals are sufficiently washed with water and dried to recover the final secondary product.At this stage, excess NaOH is removed by sufficient water washing to adjust the pH of the secondary product to 7-9. It is necessary to give. This is because Na ions remaining in the secondary product due to insufficient water washing act as a cause of deteriorating the quality and performance of zeolite.

Accordingly, the present invention is to adjust the pH of the product to the 7 to 9 range by removing excess NaOH by sufficiently washing the second crystal after the step of preparing the zeolite secondary crystal, filtering the secondary crystal, and sufficiently washing the filtered secondary crystal. It may include steps.

Example

(1) Preparation of lithium by-products

Lithium ore with a lithium oxide (Li ₂ O) content of about 1.5% was removed from feldspar and mica by flotation ore, and concentrated to a lithium oxide (Li ₂ O) content of about 6%.

Thereafter, heat treatment was performed at 1000°C to convert to β-spodumene, followed by pulverization treatment to adjust the particle size to improve reactivity in the subsequent process. 95% sulfuric acid was added 3 times by weight ratio to β-spodumene whose particle size was adjusted, mixed, and then roasted with sulfuric acid for 1 hour at 250°C.

After roasting with sulfuric acid, 5 times the weight of water was added and stirred for 1 hour, followed by water leaching for 1 hour, and solid-liquid separation using a filter press to recover lithium by-products.

Components and contents of lithium by-products recovered from the filter press are shown in Tables 1 and 2 below, XRD analysis results are shown in Table 3, and particle size distribution measurements are shown in Fig. 2, respectively.

XRF analysis (% by weight) ingredient Li ₂ O Al ₂ O ₃ SiO ₂ CaO Na ₂ O K ₂ O P ₂ O ₅ Fe ₂ O ₃ CoO MnO Cr ₂ O ₃ MgO CuO NiO TiO ₂ content Not analyzed 25.8 66.2 0.4 0.1 0.5 0.1 1.6 - 0.1 0.03 0.1 - 0.01 0.04

ICP analysis (% by weight) ingredient Li Al Si Ca Na K P Fe Co Mn Cr Mg Cu Ni content 0.51 12.59 28.41 0.32 0.40 0.60 0.063 1.11 <0.005 0.11 0.023 0.21 <0.005 0.01

division Ingredient ratio Aluminosilicate (AlSi ₂ O ₆ ) 83.7% Quartz (SiO ₂ ) 6.7% Albite (Na(AlSi ₃ O ₈ ) 9.6%

The lithium by-product recovered from the filter press was in a state in which very fine particles were aggregated, the moisture content was about 39%, and the pH was about 3.1, which was slightly acidic.

(2) pH control of lithium by-products

[Inventive Example 1] The prepared lithium by-product was sufficiently dried in a dryer, and 15 kg of distilled water was added to 3 kg of the completely dried lithium by-product, and the high-liquid ratio (water/lithium by-product, weight ratio) was adjusted to 5/1 conditions, and 500 rpm After stirring for 3 hours, the operation of filtering and drying was repeated 3 times and washed with water 3 times to prepare lithium by-products of pH 6 to 8.

The pH of the washed lithium by-product was measured according to the pH measurement standard of the waste process test method, and the results are shown in Table 3 below.

[Comparative Example 1] Washing was performed under the same conditions as Inventive Example 1, except that the washing operation was performed only once, and the pH of the washed lithium by-product was measured, and the results are shown in Table 4 below.

[Comparative Example 2] Washing was performed under the same conditions as Inventive Example 1, except that the washing operation was performed only twice, and the pH of the washed lithium by-product was measured, and the results are shown in Table 4 below.

division High cost
(Residue/water, weight ratio) Residual amount (Kg) Washing water volume (Kg) Water (times) By-product final pH Invention Example 1 1/5 3 15 3rd time 6.08 Comparative Example 1 1/5 3 15 1 time 3.23 Comparative Example 2 1/5 3 15 Episode 2 3.84

In addition, the components and contents of the samples prepared by washing the lithium residue with water once, twice, and three times were analyzed by ICP, and are shown in Table 5 below.

As shown in Table 4, in Inventive Example 1, the final pH of the lithium by-product prepared by repeating three times of stirring, filtering, and drying under the conditions of 1/5 of a high-liquid ratio (lithium by-product/water weight ratio) was 6.08. , It was found that the pH reached 6.08, which is a neutral region, compared to the pH 3.13 of the first recovered process-generated lithium by-product after water leaching. This is because excess unreacted sulfuric acid solution remaining in the lithium by-product was removed by repeated washing with water.

However, in the case of Comparative Example 1 and Comparative Example 2, the pH of the lithium by-product prepared by performing only one or two washing times was 3.23 and 3.84, respectively. Through this, it was found that the washed lithium by-products of Comparative Examples 1 and 2 remained weakly acidic due to the remaining sulfate ions (SO ₄ ^2- ) caused by an excess of sulfuric acid used during sulfuric acid roasting.

Therefore, by sufficiently washing the acidic lithium by-product with water to remove the conjugate base of the acid used during roasting from the lithium by-product, preferably the sulfate ion (SO ₄ ^2- ), the pH of the lithium by-product is in the range of 6 to 8, more specifically It can be formed in the range of 6.08 to 7.0.

As shown in Table 5, as a result of confirming the presence or absence of changes in the components and contents of lithium by-products prepared according to the number of washings with water, it was confirmed that there was little change depending on the number of washings with water. Therefore, in order to use the process-generated lithium by-product as a raw material for zeolite production, the pH of the lithium by-product is adjusted to 6 to 8 by minimizing the sulfate ions (SO ₄ ^2- ) present in the lithium by-product through sufficient water washing. You can see that it is very important.

(3) Primary control of the molar ratio of silicon to aluminum (Si/Al)

[Inventive Example 2] The aluminum (Al) component of the lithium by-product washed with water according to Inventive Example 1 was 12.6 mol, and the silicon (Si) component was 31.4 mol. Sodium aluminate (NaAlO ₂ ) was added as an alumina supplement to 40 g of lithium by-products in the pH range of 6 to 8 to adjust the molar ratio of Si/Al in the lithium by-product to 0.75.

After introducing the component-adjusted lithium by-product into a 2L glass reactor, 1000ml of a 2.5M NaOH solution (addition: 50g/2.5M NaOH 1L) was added and stirred at 500 rpm for 1 to 5 minutes to make the lithium residue raw material homogeneous. A slurry in a dispersed hydrogel state was prepared.

The prepared hydrogel was heated to 90° C., stirred at 500 rpm, and maintained for 24 hours to crystallize. After crystallization, the sample was filtered to separate solid-liquid, and washed repeatedly until the pH reached 9, and the sample after washing was filtered and sufficiently dried at 105°C to prepare a final product. The crystal phase and crystallinity of the final product were analyzed by XRD, and the results are shown in Table 6 below.

[Inventive Example 3] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 1.0, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Inventive Example 4] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 1.5, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Inventive Example 5] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 2.0, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Inventive Example 6] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 2.25, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Inventive Example 7] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 2.5, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Inventive Example 8] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 3.0, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Comparative Example 3] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 0.5, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

[Comparative Example 4] Except that the molar ratio of Si/Al in the lithium by-product was adjusted to 3.5, it was carried out under the same conditions as Inventive Example 2, and the results are shown in Table 6 below.

division Si/Al molar ratio NaOH
Concentration (M) Amount of alkali added
(OH ^- mol/g by product) crystallization
Temperature(℃) crystallization
Time(hr) Formation crystal phase/crystallinity Ratio of crystalline phase and amorphous phase (wt%) Invention Example 2 0.75 2.5 30 90 24 Z-X + Z-A/Good Z: 3%, A: 97% Invention Example 3 1.0 2.5 30 90 24 Z-X/Good 100% Invention Example 4 1.5 2.5 30 90 24 Z-P/Good 100% Inventive Example 5 2.0 2.5 30 90 24 Z-P/Good 100% Inventive Example 6 2.25 2.5 30 90 24 Z-P/Good 100% Invention Example 7 2.5 2.5 30 90 24 Z-P/Good 100% Inventive Example 8 3.0 2.5 30 90 24 Z-P/Good 100% Comparative Example 3 0.5 2.5 30 90 24 Anal Sim + Z-A Anal Sim:15%, A:85% 4 in comparison 3.5 2.5 30 90 24 Z-P + H.S H.S:25%,P;75%

* In Table 6, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxide sodalite.

As shown in Table 6, in the case of Inventive Examples 2 to 8 in which the Si/Al molar ratio was first adjusted to 0.75 to 3.0 by adding and supplying insufficient alumina components, the final products were zeolite A type and zeolite X having good crystallinity. And zeolite P-type. In addition, a zeolite P-type single phase could be produced even when the molar ratio of the lithium by-product raw material (Si/Al=2.25) was used without adjusting the Si/Al molar ratio (Invention Example 6).

On the other hand, in the case of Comparative Example 3 having a relatively high Al content by first adjusting the Si/Al molar ratio to 0.5, the final product was produced by mixing an anal shim other than zeolite A type, and the Si/Al molar ratio was adjusted to 3.5 In the case of Comparative Example 4 having a relatively high Si content, it was confirmed that hydroxysodalite was mixed in addition to zeolite P-type to be produced.

Therefore, if the molar ratio of the lithium by-product material at pH 6 to 8 (Si/Al=2.25) is used as it is or the Si/Al component molar ratio is first adjusted within the range of 0.75 to 3.0 through component adjustment, zeolite single phase with good crystallinity You can see that you can get

(4) Mixing ratio of lithium by-product/alkali solution (weight of lithium by-product/OH ^- Number of moles of ions)

[Inventive Example 9] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 25 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of NaOH 1M is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 25 g/mol.

[Inventive Example 10] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 50 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of 1.0 M NaOH solution was added to each. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of 1M NaOH is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 50 g/mol.

[Inventive Example 11] A final product was prepared under the same conditions as Inventive Example 6, except that 60 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of 1M NaOH is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 60 g/mol.

[Inventive Example 12] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 70 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of 1M NaOH is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 70 g/mol.

[Inventive Example 13] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 80 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, the OH ^- ion molar concentration of NaOH 1M is 1M, so the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 80 g/mol.

[Inventive Example 14] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 90 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of NaOH 1M is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 90 g/mol.

[Inventive Example 15] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 100 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of NaOH 1M is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 100 g/mol.

[Comparative Example 5] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 150 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of a 1.0 M NaOH solution was added to each of them. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of NaOH 1M is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 150 g/mol.

[Comparative Example 6] A final product was prepared by carrying out the same conditions as Inventive Example 6, except that 200 g of lithium by-products were added to a 2L glass reactor and then 1000 mL of 1.0 M NaOH solution was added to each. The crystal phase and crystallinity were analyzed by XRD, and the results are shown in Table 7. At this time, since the OH ^- ion molar concentration of 1M NaOH is 1M, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) is 200 g/mol.

division Si/Al (molar ratio) Lithium by-product weight (g) NaOH concentration (M) Lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) (g/mol) Crystallization temperature (℃) Crystallization time
(hr) Produce crystal phase/
Crystallinity Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 9 2.25 25 1.0 25 90 24 Z-P/Good 100% Inventive Example 10 2.25 50 1.0 50 90 24 Z-P/Good 100% Invention Example 11 2.25 60 1.0 60 90 24 Z-P/Good 100% Inventive Example 12 2.25 70 1.0 70 90 24 Z-P/Good 100% Inventive Example 13 2.25 80 1.0 80 90 24 Z-P/Good 100% Inventive Example 14 2.25 90 1.0 90 90 24 Z-P/Good 100% Inventive Example 15 2.25 100 1.0 100 90 24 Z-P/Good 100% Comparative Example 5 2.25 150 1.0 150 90 24 Anal Sim+Z-P Anal Sim: 43%P:53% Comparative Example 6 2.25 200 1.0 200 90 24 Anal Sim 100%

* In Table 7, Z-P means a P-type zeolite.

As shown in Table 7, a lithium by-product having an unadjusted lithium by-product raw material molar ratio (Si/Al=2.25) was used, and the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) was 100 g/ It was confirmed that the final products of Inventive Examples 9 to 15 prepared by adjusting to mol or less were produced as a single phase of zeolite P type having good crystallinity.

On the other hand, in the case of Comparative Examples 5 and 6 in which the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) was adjusted to more than 100 g/mol, in addition to the P-type zeolite, an anal shim was mixed, or It was confirmed that it was generated as a single phase.

Therefore, it was confirmed that a zeolite having good crystallinity can be prepared by adjusting the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) to 100 g/mol or less to crystallize. Specifically, the lithium by-product/alkali solution mixing ratio (weight of lithium by-product/OH ^{-number of} moles of ions) adjusted to the molar ratio is preferably adjusted in the range of 25 g/mol to 100 g/mol.

(5) Adjusting the concentration of alkaline substances

[Inventive Example 16] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 1.0M, that is, OH ^- ion molar concentration of 1.0M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 17] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 1.5M, that is, OH ^- ion molar concentration of 1.5M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 18] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 2.0M, that is, OH ^- ion molar concentration of 2.0M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 19] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkali substance was adjusted to 2.5M, that is, OH ^- ion molar concentration of 2.5M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 20] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 3.0M, that is, OH ^- ion molar concentration of 3.0M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 21] It was carried out under the same conditions as Inventive Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 3.5M, that is, OH ^- ion molar concentration of 3.5M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 22] It was carried out under the same conditions as Inventive Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 4.0M, that is, OH ^- ion molar concentration of 4.0M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 23] Except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 5.0M, that is, OH ^- ion molar concentration of 5.0M, it was carried out under the same conditions as Inventive Example 10, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Inventive Example 24] It was carried out under the same conditions as Inventive Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 6.0M, that is, OH ^- ion molar concentration of 6.0M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Comparative Example 7] It was carried out under the same conditions as Invention Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 0.5M, that is, OH ^- ion molar concentration of 0.5M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Comparative Example 8] It was carried out under the same conditions as Invention Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 7.0M, that is, OH ^- ion molar concentration of 7.0M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

[Comparative Example 9] It was carried out under the same conditions as Inventive Example 10, except that the concentration of the sodium hydroxide (NaOH) solution added as an alkaline substance was adjusted to 10.0M, that is, OH ^- ion molar concentration of 10.0M, and the final product The crystal phase and crystallinity were analyzed by XRD and are shown in Table 8 below.

division Si/Al (molar ratio) OH ^- concentration (M) Crystallization temperature (℃) Crystallization time
(hr) Produced crystal phase/crystalline Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 16 2.25 1.0 90 24 Z-P/Good 100% Inventive Example 17 2.25 1.5 90 24 Z-P/Good 100% Inventive Example 18 2.25 2.0 90 24 Z-P+Z-A/Good P:93%,A:7% Inventive Example 19 2.25 2.5 90 24 Z-P+Z-A/Good P:72%, A:28% Inventive Example 20 2.25 3.0 90 24 Z-A/Good 100% Inventive Example 21 2.25 3.5 90 24 Z-A/Good 100% Inventive Example 22 2.25 4.0 90 24 Z-A+Z-X/Good A:97.4%,X:2.6% Inventive Example 23 2.25 5.0 90 24 Z-A+Z-X/Good A:98.1%,X:1.9% Inventive Example 24 2.25 6.0 90 24 Z-A+Z-X/Good A:98.3,X:1.7% Comparative Example 7 2.25 0.5 90 24 Anal Sim + SOD Anal Sim: 89%, SOD: 11% Comparative Example 8 2.25 7.0 90 24 SOD 100% Comparative Example 9 2.25 10.0 90 24 SOD 100%

* In Table 8, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively.

As shown in Table 8, a lithium by-product with a Si/Al molar ratio of 2.25 was used by adjusting the components, and the concentration of the sodium hydroxide (NaOH) solution added as an alkali material was 1.0 to 6.0 M, that is, OH ^- ion molar concentration In the case of Inventive Examples 16 to 24 adjusted to 1.0 to 6.0 M, the final product was prepared from zeolite A type, zeolite X type, zeolite P type, zeolite P+A type, and zeolite A+X type. Could

On the other hand, in the case of Comparative Example 7 prepared using a sodium hydroxide (NaOH) solution concentration of less than 1.0M 0.5M, that is, OH ^- ion molar concentration of 0.5M, although it is a zeolite crystal, its ion exchange capacity is small, making it industrially applicable. In the case of Comparative Examples 8 and 9 using a sodium hydroxide (NaOH) solution concentration of 7.0M or more, that is, an OH ^- ion molar concentration of 7.0M or more, a low analsim and SOD mixed phase is generated. I could confirm that.

Therefore, in the case of proceeding the dissolution reaction of lithium by-products by addition of an alkali solution, it was confirmed that a single crystal phase of zeolite with good crystallinity can be prepared by crystallizing the OH ^- ion molar concentration using a solution within the range of 1.0M to 6.0M. Could

(6) control of the primary crystallization temperature

[Inventive Example 25] Except that the primary crystallization temperature was adjusted to 60° C., and carried out under the same conditions as Inventive Example 16, the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Inventive Example 26] Except that the first crystallization temperature was adjusted to 70°C, and carried out under the same conditions as Inventive Example 16, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Inventive Example 27] Except that the first crystallization temperature was adjusted to 80°C, and carried out under the same conditions as Inventive Example 16, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Inventive Example 28] Except that the first crystallization temperature was adjusted to 90°C, and carried out under the same conditions as Inventive Example 16, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Inventive Example 29] Except that the first crystallization temperature was adjusted to 100°C, and carried out under the same conditions as Inventive Example 16, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Comparative Example 10] It was carried out under the same conditions as Inventive Example 16, except that the first crystallization temperature was adjusted to 50°C, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Comparative Example 11] Except that the first crystallization temperature was adjusted to 110 ℃ carried out under the same conditions as in Inventive Example 16, and the crystal phase and crystallinity of the prepared final product was analyzed by XRD, and the results are as follows. It is shown in Table 9.

[Comparative Example 12] Except that the primary crystallization temperature was adjusted to 120 °C and carried out under the same conditions as Inventive Example 16, the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 9.

division Residue
Si/Al (molar ratio) Alkaline solution concentration (M) Weight of lithium by-product/OH ^{-number of} moles of ions (g/mol) Crystallization temperature (℃) Crystallization time
(hr.) Produced crystal phase/crystalline Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 25 2.25 1.0 50 60 24 Z-P/Good 100% Inventive Example 26 2.25 1.0 50 70 24 Z-P/Good 100% Inventive Example 27 2.25 1.0 50 80 24 Z-P/Good 100% Inventive Example 28 2.25 1.0 50 90 24 Z-P/Good 100% Inventive Example 29 2.25 1.0 50 100 24 Z-P/Good 100% Comparative Example 10 2.25 1.0 50 50 24 Anal Sim 100% Comparative Example 11 2.25 1.0 50 110 24 Z-P+H.S P:94%, H.S:6% Comparative Example 12 2.25 1.0 50 120 24 Z-P+H.S P:89%, H.S:11%

* In Table 9, Z-P means each P-type zeolite. H.S means hydroxy sodalite.

As shown in Table 9, a hydrogel prepared using a lithium by-product raw material composition molar ratio (Si/Al molar ratio = 2.25) as it is, and a sodium hydroxide (NaOH) solution having a concentration of 1.0M is used as a primary crystallization temperature. The final products of Inventive Examples 25 to 29 prepared by crystallization in the range of 60 to 100°C could be prepared as a single phase of zeolite P type having good crystallinity.

However, in the case of Comparative Example 10 in which the crystallization temperature was adjusted to 60°C or less, the final product produced was an analsim single phase, and Comparative Examples 11 and 12 in which the primary crystallization temperature was adjusted to 110°C and 120°C, respectively. In addition to the P-type zeolite, it was confirmed that hydroxysodalite was mixed and produced as a final product.

Accordingly, it was confirmed that a zeolite crystal phase having good crystallinity can be prepared by adjusting the primary crystallization temperature to 60 to 100°C.

(7) Control of the first crystallization time

[Inventive Example 30] The first crystallization time was carried out under the same conditions as Inventive Example 28, except that the first crystallization time was performed for 12 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

[Inventive Example 31] The first crystallization time was carried out under the same conditions as Inventive Example 28, except that the first crystallization time was performed for 24 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

[Inventive Example 32] The first crystallization time was carried out under the same conditions as Invention Example 28, except that the first crystallization time was performed for 48 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

[Comparative Example 13] The first crystallization time was carried out under the same conditions as Inventive Example 28, except that the first crystallization time was performed for 1 hour, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

[Comparative Example 14] The first crystallization time was carried out under the same conditions as Inventive Example 28, except that the first crystallization time was performed for 3 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

[Comparative Example 15] The first crystallization time was carried out under the same conditions as Inventive Example 28, except that the first crystallization time was performed for 6 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 10.

division Residue
Si/Al (molar ratio) Alkaline solution concentration (M) Weight of lithium by-product/OH ^{-number of} moles of ions (g/mol) Crystallization temperature (℃) Crystallization time
(hr.) Produce crystal phase/
Crystallinity Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 30 2.25 1.0 50 90 12 Z-P/Good 100% Inventive Example 31 2.25 1.0 50 90 24 Z-P/Good 100% Inventive Example 32 2.25 1.0 50 90 48 Z-P/Good 100% Comparative Example 13 2.25 1.0 50 90 One Anal Sim 100% Comparative Example 14 2.25 1.0 50 90 3 Anal Sim 100% Comparative Example 15 2.25 1.0 50 90 6 Anal Sim 100%

* In Table 10, Z-P means P-type zeolite.

As shown in Table 10, a lithium by-product raw material composition molar ratio (Si/Al molar ratio=2.25) was used as it was, and a sodium hydroxide (NaOH) solution having a concentration of 1.0M, the crystallization temperature was set to 90° C. for 12 hours or more 1 It was confirmed that the final products of Inventive Examples 30 to 32 prepared by secondary crystallization were prepared as zeolite P-type with good crystallinity.

However, as shown in Comparative Examples 13 to 15, when the first crystallization time is 12 hours or less, that is, when the first crystallization time is 1, 3, and 6 hours, respectively, the final product is produced only as an analsim single phase. Could be confirmed.

Therefore, it was confirmed that a zeolite crystal phase having good crystallinity can be prepared by adjusting the first crystallization time to a range of 12 hours or more.

(8) Adjustment of the first crystallization stirring speed

[Inventive Example 33] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm) except for the first crystallization at a stirring speed of 300 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

[Inventive Example 34] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm), except for the primary crystallization at a stirring speed of 400 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

[Inventive Example 35] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm) except for the primary crystallization at a stirring speed of 500 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

[Inventive Example 36] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm) except for the first crystallization at a stirring speed of 600 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

[Comparative Example 16] A final primary product was prepared in the same manner as in Invention Example 31, except that the primary crystallization was performed without stirring (stirring speed 0 rpm), and the crystal phase and crystallinity of the final primary product ( Crystallinity) was analyzed by XRD, and the results are shown in Table 11 below.

[Comparative Example 17] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm) except for the first crystallization at a stirring speed of 200 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

[Comparative Example 18] The stirring blade is two plate-shaped, the blade diameter is 7cm, the width is 1.5cm, the reactor volume is 2L (diameter 13cm, height 20cm) except for the first crystallization at a stirring speed of 700 rpm in a stirrer Then, a final primary product was prepared in the same manner as in Inventive Example 31, and the crystal phase and crystallinity of the produced final primary product were analyzed by XRD, and the results are shown in Table 11 below.

division Si/Al (molar ratio) Alkaline solution concentration (M) Stirring speed (rpm) Crystallization temperature (℃) Crystallization time
(hr.) Produced crystal phase/crystalline Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 33 2.25 1.0 300 90 24 Z-P/Good 100% Inventive Example 34 2.25 1.0 400 90 24 Z-P/Good 100% Inventive Example 35 2.25 1.0 500 90 24 Z-P/Good 100% Inventive Example 36 2.25 1.0 600 90 24 Z-P/Good 100% Comparative Example 16 2.25 1.0 Stop (0rpm) 90 24 Anal Sim 100% Comparative Example 17 2.25 1.0 200 90 24 Anal Sim 100% Comparative Example 18 2.25 1.0 700 90 24 Anal Sim+SOD+Z-P Anal Sim:87%, SOD:7%,P:6%

* In Table 11, Z-P means P-type zeolite.

As shown in Table 11, the lithium by-product raw material composition molar ratio (Si/Al molar ratio=2.25) was used as it was, and a sodium hydroxide (NaOH) solution having a concentration of 1.0M, the crystallization temperature was 90°C, and the crystallization time was Inventive Example 33 in which the stirring blade was two plate-shaped, the blade diameter was 7 cm, and the width was 1.5 cm, and the stirring speed was 300 to 600 rpm in a stirrer with a reactor volume of 2 L (diameter 13 cm, height 20 cm). It was confirmed that the final products of to 36 were prepared as zeolite P-type having good crystallinity.

However, as shown in Comparative Examples 16 to 18, when not agitated, when the stirring speed is set to 200 rpm, or 700 rpm, the final product is produced as an analsim single phase or a mixture of analsim, SOD and zeolite P type. Could be confirmed.

Therefore, in the first crystallization, the stirring blade was two plate-shaped, the blade diameter was 7 cm, and the width was 1.5 cm, and the stirring speed was adjusted in the range of 300 to 600 rpm in a stirrer with a reactor volume of 2 L (diameter 13 cm, height 20 cm). When prepared, it was confirmed that a zeolite crystal phase having good crystallinity could be produced.

(9) Filtrate separation after first crystallization

Inventive Examples 16, 20, 23, and 24 using the alkali concentrations of 1.0M, 3.0M, 5.0M, and 6.0M were first crystallized with zeolite, followed by solid-liquid separation, and the zeolite primary crystal was recovered as a primary product and separated. The content of the main components of the filtrate was analyzed and shown in Table 12 below.

division Ingredients in the filtrate after primary crystallization Alkali concentration Si (ppm) Al (ppm) Na(NaOH)
(ppm) Inventive Example 16 1 mol 5140 15 18400 (0.78mol) Inventive Example 20 3 mol 8240 139 65100 (2.83mol) Inventive Example 23 5 mol 9720 165 111600 (4.8mol) Inventive Example 24 6 mol 8860 273 150800 (6.56mol) Comparative Example 8 7mol 8780 280 172000 (7.23mol) Comparative Example 9 10mol 8900 482 205600 (8.93mol)

(10) Secondary control of the ratio of silicon to aluminum (Si/Al)

According to the analysis of the filtrate component in Table 12, Al is mostly consumed in the first crystallization reaction and remains in the filtrate as a small amount of up to 300 ppm is unreacted, whereas the Si component is unreacted to at least 5000 ppm and filtered. It can be confirmed that it remains in the liquid.

[Inventive Example 37] After the first crystallization of Inventive Example 16, the Si/Al ratio in the separated filtrate was adjusted to 2.25, the temperature was raised to 90° C., stirred at 500 rpm, and maintained for 24 hours for secondary crystallization. After secondary crystallization, the sample was filtered to separate solid-liquid, and then washed repeatedly until pH reached 9, and the sample after washing was filtered and dried sufficiently at 105°C to prepare a final secondary product. The crystal phase and crystallinity of the final secondary product were analyzed by XRD, and the results are shown in Table 13 below.

[Inventive Example 38] A final secondary product was prepared in the same manner as Inventive Example 37, except that the Si/Al ratio in the filtrate separated after the first crystallization of Inventive Example 20 was adjusted to 2.25, The crystal phase and crystallinity of the secondary product were analyzed by XRD, and the results are shown in Table 13 below.

[Inventive Example 39] A final secondary product was prepared in the same manner as Inventive Example 37, except that the Si/Al ratio in the filtrate separated after the first crystallization of Inventive Example 23 was adjusted to 2.25, The crystal phase and crystallinity of the secondary product were analyzed by XRD, and the results are shown in Table 13 below.

[Inventive Example 40] A final secondary product was prepared in the same manner as Invention Example 37, except that the Si/Al ratio in the filtrate separated after the first crystallization of Inventive Example 24 was adjusted to 2.25, The crystal phase and crystallinity of the secondary product were analyzed by XRD, and the results are shown in Table 13 below.

[Comparative Example 19] A final secondary product was prepared by the same method as Inventive Example 37, except that the Si/Al ratio in the filtrate separated after the first crystallization of Comparative Example 8 was adjusted to 2.25, The crystal phase and crystallinity of the secondary product were analyzed by XRD, and the results are shown in Table 13 below.

[Comparative Example 20] A final secondary product was prepared by the same method as Invention Example 37, except that the Si/Al ratio in the filtrate separated after the first crystallization of Comparative Example 9 was adjusted to 2.25, The crystal phase and crystallinity of the secondary product were analyzed by XRD, and the results are shown in Table 13 below.

division Si/Al (molar ratio) NaOH solution concentration (M) added during the first crystallization Crystallization temperature (℃) Crystallization time
(hr.) Generated crystal phase/crystallinity/color Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 37 2.25 1.0 90 24 Z-P/good/white 100% Inventive Example 38 2.25 3.0 90 24 Z-A +Z-X/good/white A:98.5%X:1.5% Inventive Example 39 2.25 5.0 90 24 Z-A+Z-X/good/white A:98.0%X:2.0% Inventive Example 40 2.25 6.0 90 24 Z-A+Z-X/good/white A:98.3%X:1.7% Comparative Example 19 2.25 7.0 90 24 SOD 100% Comparative Example 20 2.25 10.0 90 24 SOD 100%

* In Table 13, Z-P, Z-A, and Z-X refer to P-type, A-type, and X-type zeolites, respectively.

As shown in Table 13 above, the final secondary products of Inventive Examples 37 to 40 prepared by secondary crystallization after adding insufficient Al component to the separated filtrate after primary crystallization to adjust the Si/Al molar ratio to 2.25, It was confirmed that the zeolite P-type single phase or A+X type was prepared with good crystallinity.

However, as shown in Comparative Examples 19 and 20, after primary crystallization using an alkali solution of 7.0M and 10.0M concentration, an insufficient Al component was added to the separated filtrate, and the Si/Al molar ratio was adjusted to 2.25. In the case of crystallization, it was confirmed that the final product was produced as a single phase SOD.

In addition, as impurities remaining in lithium by-products, in particular, Fe, Mica, and Quartz (SiO ₂ ) components, which are coloring components, are mostly included in zeolite produced by primary crystallization, and the primary crystallization product has a bright yellow color, so the whiteness is somewhat. Although inferior, it was confirmed that most of the impurities were removed in the filtrate separated after the first crystallization, and the final secondary product manufactured using this was recovered as a white powder having very excellent whiteness.

Therefore, zeolite having good crystallinity and excellent whiteness by adjusting the Si/Al molar ratio of the filtrate separated by solid-liquid separation after primary crystallization using an alkali solution 1.0M to 6.0M, that is, OH ^- ion 1.0 to 6.0M It was confirmed that a crystal phase could be prepared.

(10) control of the secondary crystallization time

[Inventive Example 41] The second crystallization time was carried out under the same conditions as Inventive Example 37, except that the second crystallization time was performed for 3 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Inventive Example 42] The second crystallization time was carried out under the same conditions as Inventive Example 37, except that the second crystallization time was performed for 6 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Inventive Example 43] The second crystallization time was carried out under the same conditions as Inventive Example 37, except that the second crystallization time was performed for 12 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Inventive Example 44] Except that the second crystallization time was performed for 24 hours, it was carried out under the same conditions as Inventive Example 37, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Comparative Example 21] The second crystallization time was carried out under the same conditions as Inventive Example 37 except for 0.5 hour, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Comparative Example 22] The second crystallization time was carried out under the same conditions as Inventive Example 37, except that the second crystallization time was performed for 1 hour, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

[Comparative Example 23] The second crystallization time was carried out under the same conditions as Inventive Example 37, except that the second crystallization time was performed for 2 hours, and the crystal phase and crystallinity of the prepared final product were analyzed by XRD, and the results are as follows. It is shown in Table 14.

division Si/Al (molar ratio) NaOH solution concentration (M) added during the first crystallization Crystallization temperature (℃) Crystallization time
(hr.) Generated crystal phase/crystallinity/color Ratio of crystalline phase and amorphous phase (wt%) Inventive Example 41 2.25 1.0 90 3 Z-P/good/white 100% Inventive Example 42 2.25 1.0 90 6 Z-P/good/white 100% Inventive Example 43 2.25 1.0 90 12 Z-P/good/white 100% Inventive Example 44 2.25 1.0 90 24 Z-P/good/white 100% Comparative Example 21 2.25 1.0 90 0.5 Anal Sim 100% Comparative Example 22 2.25 1.0 90 One Anal Sim 100% Comparative Example 23 2.25 1.0 90 2 Anal Sim+Z-P P: 92% Anal Sim: 8%

* In Table 14, Z-P means P-type zeolite.

As shown in Table 14 above, after the first crystallization was performed, the Si/Al molar ratio was adjusted to 2.25 by adding an insufficient Al component to the separated filtrate. It was confirmed that the final secondary products of Inventive Examples 41 to 44 were made of P-type zeolite having good crystallinity.

However, as shown in Comparative Examples 21 to 23, when the secondary crystallization time is 2 hours or less, that is, when the crystallization time is 0.1, 1, and 2 hours, respectively, the final product is an analsim single phase or analsim and zeolite. It was confirmed that it was produced as a P-type mixed phase.

Therefore, it was confirmed that a zeolite crystal phase having good crystallinity could be prepared by adjusting the secondary crystallization time to a range of more than 2 hours.

The present invention is not limited to the above embodiments and/or embodiments, but may be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains change the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented in other specific forms without doing so. Therefore, it should be understood that the embodiments and/or embodiments described above are illustrative and non-limiting in all respects.

Claims (20)

Washing the lithium by-product with water to adjust the lithium by-product to pH 6 to 8;
First adjusting the molar ratio of silicon to aluminum contained in the washed lithium by-product (Si/Al ratio);
Preparing a hydrogel form by adding an alkali substance to the lithium by-product whose molar ratio is first adjusted; And
A first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal;
Including,
In the step of preparing a hydrogel form by adding an alkali substance to the lithium by-product having the molar ratio adjusted,
The mixing ratio of lithium by-products to alkaline substances (weight of lithium by-products/OH ^{-number of} moles of ions) is 100 g/mol or less. The method of claim 1,
The step of adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product with water,
The step of removing the conjugate base of the acid from the lithium by-product, zeolite production method. The method of claim 1,
Adjusting the molar ratio of silicon to aluminum (Si/Al ratio) contained in the washed lithium by-product,
In the step of adjusting the molar ratio of silicon to aluminum (Si/Al ratio) of 0.75 to 3.0 by adding an alumina supplementing material or a silica supplementing material to the lithium by-product, zeolite manufacturing method. The method of claim 3,
The alumina supplement material comprises at least one of alumina hydrate (Al(OH) ₃ ) and sodium aluminate (NaAlO ₂ ), zeolite production method. The method of claim 3,
The silica supplement material is sodium silicate (Na ₂ OSiO ₂ ), zeolite production method. The method of claim 1,
In the step of preparing a hydrogel form by adding an alkali substance to the lithium by-product having the molar ratio adjusted,
The alkaline material is OH ^- ion molar concentration of 1.0 to 6.0M, zeolite production method. The method of claim 1,
The alkaline substance is sodium hydroxide (NaOH), zeolite production method. The method of claim 1,
In the first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal,
In the first crystallization step, the first crystallization temperature is 60 to 100 °C, a zeolite production method. The method of claim 1,
In the first crystallization step of crystallizing the lithium by-product in the form of a hydrogel to prepare a primary crystal,
In the first crystallization step, the first crystallization time is 12 hours or more. The method of claim 1,
In the first crystallization step of crystallizing the lithium by-product in the form of hydrogel to prepare a crystal,
The first crystallization stirring speed is 300 to 600 rpm, zeolite production method. The method of claim 1,
After the first crystallization step of crystallizing the lithium by-product in the form of the hydrogel to prepare a crystal,
Filtering the primary crystal; And
The zeolite production method further comprising; washing and drying the filtered primary crystal. The method of claim 1,
The lithium by-product is based on the total 100% by weight, alumina (Al ₂ O ₃ ): 20 to 30% by weight, silica (SIO ₂ ): 60 to 70% by weight, iron oxide (Fe ₂ O ₃ ), calcium oxide (CaO) , Sodium oxide (Na ₂ O) and potassium oxide (K ₂ O) in one or more: 10% by weight or less containing, zeolite production method. The method of claim 1,
After the first crystallization step of crystallizing the lithium by-product in the form of the hydrogel to prepare a crystal,
Separating the primary crystals of zeolite and the filtrate produced by solid-liquid separation;
Secondly adjusting the molar ratio of silicon to aluminum (Si/Al ratio) contained in the separated filtrate; And
Further comprising a second crystallization step of crystallizing the filtrate whose molar ratio is adjusted to prepare crystals. The method of claim 13,
Secondly adjusting the molar ratio of silicon to aluminum (Si/Al ratio) contained in the separated filtrate,
In the step of adjusting the molar ratio of silicon to aluminum (Si/Al ratio) of 0.75 to 3.0 by adding an alumina supplementing material or a silica supplementing material to the lithium by-product, zeolite manufacturing method. The method of claim 14,
The alumina supplement material comprises at least one of alumina hydrate (Al(OH) ₃ ) and sodium aluminate (NaAlO ₂ ), zeolite production method. The method of claim 14,
The silica supplement material is sodium silicate (Na ₂ OSiO ₂ ), zeolite production method. The method of claim 13,
In the second crystallization step of crystallizing the filtrate whose molar ratio is secondarily adjusted to prepare crystals,
The second crystallization step is a second crystallization temperature of 60 to 100 ℃, zeolite production method. The method of claim 13,
In the second crystallization step of crystallizing the filtrate with the molar ratio adjusted to prepare crystals,
In the second crystallization step, the second crystallization time is more than 2 hours, zeolite production method. The method of claim 13,
After the second crystallization step of crystallizing the filtrate with the molar ratio adjusted to prepare crystals,
Filtering the secondary crystals; And
The zeolite production method further comprising; washing and drying the filtered secondary crystals with water. The method according to any one of claims 1 to 19,
The zeolite produced by the zeolite production method is composed of only one paper-shaped crystal phase selected from the group consisting of P-type zeolite, A-type zeolite, and X-type zeolite.

Images