KR102316889B1 - Manufaturing method of zeolite using lithium residue - Google Patents

Abstract

The present disclosure includes the steps of preparing a lithium by-product; adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product; adjusting the molar ratio of silicon to aluminum (Si/Al ratio) included in the washed lithium by-product; uniformly mixing an alkali powder with the lithium by-product whose molar ratio of silicon to aluminum is adjusted; forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; mixing a solution with the heat-treated raw material; And it relates to a zeolite manufacturing method comprising a; crystallizing the heat-treated raw material mixed with the solution.

Description

Zeolite manufacturing method using lithium by-product {MANUFATURING METHOD OF ZEOLITE USING LITHIUM RESIDUE}

The present disclosure relates to a zeolite manufacturing method using a lithium by-product, and more particularly, to a zeolite obtained by using a lithium by-product generated during a process of recovering lithium from lithium ore.

Zeolite (Zeolite, M[(Al ₂ O ₃ )x (SiO ₂ )y]zH ₂ O) is a material used as a catalyst for laundry detergent, heavy metal removal in wastewater, and harmful substances in exhaust gas. This is because the unique applied mineralogical properties of zeolite, namely, cation exchange capacity (CEC), adsorption and molecular sieve properties, catalytic properties, dehydration and resorption properties, etc., have been applied to related industries. It is being utilized and applied due to the fact that it has utility value.

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

In recent years, as the application range of zeolite has been greatly expanded, more diversity is required in the pore structure and properties of zeolite, and research to synthesize a zeolite having a new pore structure and applied mineralogical properties has been conducted, and it is in the spotlight in industrial applications. About 150 kinds of synthetic zeolites, including ZSM-5, which are being received, have been developed.

Zeolite synthesis is usually prepared by a hydrothermal process, so-called “hydrogel process”, under temperature conditions ranging from room temperature to 200°C. In general, zeolites do not require special pressure conditions in the production process and are relatively easily synthesized at low temperatures.

Synthetic zeolite has various pore properties as well as excellent performance and efficacy, but when applied in practice, it has some disadvantages in terms of price compared to cheaper natural zeolite.

Therefore, efforts are currently underway to find a cheaper synthetic method (Cost effective method) capable of homogeneously synthesizing zeolite having excellent properties.

As a cheaper synthesis method, cheaper natural materials such as sodium silicate, sodium aluminate, silica gel, which are reagent-type materials that have been mainly used as raw materials for zeolite synthesis, Methods using a silicate mineral having a composition suitable for synthesis as a raw material are being considered. Studies on the synthesis of zeolite using natural minerals have mainly been made on clay, kaolin, kaolin, and volcanic vitreous rocks.

In addition, research on using various by-products generated in large quantities in industrial processes as raw materials for zeolite synthesis instead of natural minerals with insufficient natural resources is also in progress.

_{Currently, reagent grade sodium silicate (Na 2} SiO ₃ ), sodium aluminate (NaAlO ₂ ), aluminum hydroxide (Aluminium hydroxide, Al(OH) ₃ ) that are generally used as raw materials for zeolite synthesis ), etc., because most of them show a purity of 98% or higher, the quality of the zeolite produced using these raw materials is also manufactured with very high purity.

However, when zeolite is manufactured using natural minerals (clay, kaolin, kaolin, etc.), which are very cheap raw materials compared to reagent-grade raw materials, or by-products generated from industrial processes instead of natural minerals that lack natural resources, they are present in natural minerals or by-products generated by industrial processes. Various impure minerals and impurities are introduced into the final product, zeolite, and have a problem of lowering the quality.

Therefore, there is a need for a method for removing or reducing impurities in raw materials in order to manufacture zeolite of excellent quality using inexpensive raw materials such as natural minerals or by-products generated from industrial processes.

The present disclosure is to provide a high-quality zeolite and a method for manufacturing the same by extracting lithium from lithium ore and using the residual lithium by-product.

A method for producing a zeolite according to an embodiment of the present disclosure includes the steps of preparing a lithium by-product; adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product; adjusting the molar ratio of silicon to aluminum (Si/Al ratio) included in the washed lithium by-product; uniformly mixing an alkali powder with the lithium by-product whose molar ratio of silicon to aluminum is adjusted; forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; mixing a solution with the heat-treated raw material; and crystallizing the heat-treated raw material in which the solution is mixed.

In the step of uniformly mixing the alkali powder with the lithium by-product of which the molar ratio of silicon to aluminum is adjusted; in the alkali powder/lithium by-product weight ratio may be 1.0 or more.

Forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; In, the heat treatment may be performed at a temperature of 500° C. or higher.

Forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; In, the heat treatment time may be 30 minutes or more,

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

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

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

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

The step of mixing the solution with the heat-treated raw material; may be a step such that the OH- ion molar concentration of the solution including the heat-treated raw material is 1.0 to 6.0M concentration.

In the step of mixing the solution with the heat-treated raw material; the solution may be distilled water.

In the step of mixing a solution with the heat-treated raw material; in the solution, the solution may be an alkali solution for supplying OH- ions to the solution containing the heat-treated raw material.

Crystallizing the heat-treated raw material in which the solution is mixed; may have a crystallization temperature of 60 to 100 °C.

Crystallizing the heat-treated raw material in which the solution is mixed; crystallization time may be 12 hours or more.

forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; Thereafter, the method may further include pulverizing the heat-treated raw material into a powder.

crystallizing the heat-treated raw material in which the solution is mixed; thereafter, filtering the crystals; and washing and drying the filtered crystals.

The zeolite produced by the zeolite manufacturing method of the embodiment of the present disclosure may be composed of only one or more crystal phases selected from the group consisting of P-type zeolite, A-type zeolite, and X-type zeolite.

According to one embodiment of the present disclosure, it is possible to obtain a synthetic zeolite having excellent quality from a lithium by-product generated in a large amount in a process for recovering lithium from lithium ore.

In addition, according to an embodiment of the present disclosure, a high value-added lithium by-product is possible by manufacturing a zeolite that can be used as a gas adsorbent, a laundry detergent, a heavy metal treatment in wastewater, a catalyst for removing harmful gases, etc. from the lithium by-product.

In addition, according to one embodiment of the present disclosure, it is possible to contribute to the construction of a resource recycling society by suggesting a method for recycling a large amount of lithium by-products to be landfilled.

Terms such as first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only 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 the purpose of referring to specific embodiments only, and is not intended to limit the invention. As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite. The meaning of "comprising," as used herein, specifies a particular characteristic, region, integer, step, operation, element and/or component, and includes the presence or absence of another characteristic, region, integer, step, operation, 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 the other part, or the other part may be involved in between. In contrast, when a part refers to being "directly above" another part, the other part is not interposed therebetween.

In addition, unless otherwise specified, % means weight %, and 1 ppm is 0.0001 weight %.

Although not defined otherwise, all terms including technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Commonly used terms defined in the dictionary are additionally interpreted as having a meaning consistent with the related technical literature and the presently disclosed content, and unless defined, they are not interpreted in an ideal or very formal meaning.

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

The present disclosure relates to a process for recovering lithium from lithium ore, which is concentrated to about 6% by flotation of lithium ore containing about 1.5% _{of Li 2 O, in particular, lithium ore heat treatment, grinding, sulfuric acid roasting, water leaching, and} An object of the present invention is to provide a method for improving the quality of synthetic zeolite from lithium by-products generated in large amounts in a series of solid-liquid separation processes.

Lithium ore is mainly composed of spodumene (Spodumene, LiAl ₂ SiO ₆ ) minerals, and the residue remaining after recovering Li by roasting sulfate and water leaching, that is, the lithium by-product is Al ₂ O _{3 ·} 4SiO ₂ , Mica (mica, (K,Ca,Na) ₂ (Fe,Mg,Al,Mn,Fe,Ti) _{4~ 6} (Si,Al) ₈ (OH,F)) and quartz that occupies 90% of the earth's crust, that is, crystalline quartz (SiO ₂ ) is a material containing about 10%.

Since zeolite is a material in which an alumina component and a silica component are composed of a network structure, various types of zeolite can be manufactured through appropriate crystallization reaction using lithium by-products composed of the same alumina component and silica component as the zeolite component. judge that there will be

Therefore, the present disclosure discloses that in the process of recovering lithium from lithium ore, in particular, the sum of both silica and alumina components generated in large amounts in a series of ore heat treatment, pulverization, sulfuric acid roasting, water leaching, and solid-liquid separation is 90% or more When manufacturing synthetic zeolite that is used as laundry detergent, adsorbent, heavy metal treatment agent in wastewater, catalyst for removing harmful substances in exhaust gas, etc. using lithium by-product in the form of an aluminosilicate compound, mica or quartz present in lithium by-product due to a stable crystalline phase of quartz (SiO _2), that is, a strong alkali solution conditions under very stable, with only a small section has got the dissolution characteristics that are pre-processed major impurity the crystalline SiO ₂ to lower the quality of the final product zeolite zeolite An object of the present invention is to provide a method for improving the quality of zeolite by excluding the incorporation of impurities in the product.

Hereinafter, we will look at each step in detail.

A zeolite manufacturing method according to an embodiment of the present disclosure includes the steps of preparing a lithium by-product; adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product; adjusting the molar ratio of silicon to aluminum (Si/Al ratio) included in the washed lithium by-product; uniformly mixing an alkali powder with the lithium by-product whose molar ratio of silicon to aluminum is adjusted; forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; mixing a solution with the heat-treated raw material; and crystallizing the heat-treated raw material in which the solution is mixed.

Preparing the lithium by-product; heat-treating the lithium-containing ore; pulverizing the heat-treated lithium-containing ore; precipitating the lithium component in the pulverized lithium-containing ore as lithium sulfate; leaching the lithium sulfate into water; and obtaining a lithium residue by solid-liquid separation.

In the step of uniformly mixing the alkali powder with the lithium by-product of which the molar ratio of silicon to aluminum is adjusted; in the alkali powder/lithium by-product weight ratio may be 1.0 or more. _{The SiO 2} crystal phase disappeared in the mixed and heat-treated raw material prepared under the conditions of alkali powder/lithium by-product weight ratio of 1.0 or more, and the final product prepared through a crystallization reaction using a sample in which the _{SiO 2 crystal phase disappeared is a P-type zeolite} , only P-type + X-type zeolites can be produced.

However, when the alkali powder/lithium by-product weight ratio is less than 1.0, the SiO ₂ crystal phase exists as it is in the same state as the raw material lithium by-product, and the final product produced through the crystallization reaction using a sample in which the _{SiO 2 crystal phase is mixed is an ion} It can be produced as a material in which _{various zeolite crystalline phases and SiO 2} crystalline phases are mixed, such as pyroxene and hydroxysodalite, which have low exchange capacity and low industrial applicability, as well as haseok, P-type zeolite, and X-type zeolite, adversely affecting the quality of zeolite. There is a problem affecting

Therefore, in the step of preparing a uniform mixture by mixing the lithium by-product and the alkali powder, the SiO ₂ crystal phase present in the lithium by-product reacts sufficiently with the added alkali powder by adjusting the weight ratio of the alkali powder/lithium by-product to 1.0 or more and heat treatment. It is possible to improve the quality of synthetic zeolite by allowing soluble substance forms (sodium silicate, sodium aluminate, sodium aluminium silicate) to be produced and this sample to form a zeolite single phase through the subsequent crystallization process.

Any of the alkali powders may be used as long as they provide the components necessary for zeolite formation. For example, NaOH supplying Na is preferable, and KOH may also be used. In addition, the alkali used can be uniformly mixed with the lithium by-product, and it is more preferable to use a powder form with high reactivity.

Forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; In, the heat treatment may be performed at a temperature of 500° C. or higher. Specifically, it may be in the range of 500 to 800 °C, more specifically in the range of 550 to 600 °C.

In the step of heat-treating the lithium by-product mixed with the alkali powder to form a raw material; in, the heat treatment time may be 30 minutes or more. Specifically, the time may range from 30 minutes to 3 hours, more specifically from 1 hour to 2 hours.

When the heat treatment temperature is less than 500 ° C and the heat treatment time is less than 30 minutes, the SiO ₂ crystal phase present in the lithium by-product reacts with the added alkali powder and the activation energy (Ea) required for transition to a new crystal phase is insufficient, which is a soluble form material. This is because the transition reaction to sodium silicate, sodium aluminate, sodium aluminum silicate, or the like does not proceed sufficiently. As for the heat treatment temperature and heat treatment time, it is sufficient to supply only the activation energy required for the complete transition of the reactant to a new product, and it is preferable to use as low energy as possible within the range of conditions that can supply the activation energy. If the heat treatment temperature is excessively high or the heat treatment time is excessively long, not only is it disadvantageous in terms of energy use, but also, after heat treatment, lithium by-product and alkali, a low-melting compound, react to form a very strong bond. This is because another grinding energy is required in the refinement process of raw materials for

The step of washing the lithium by-product to adjust the lithium by-product to pH 6 to 8 may be a step of removing the conjugate base of the acid from the lithium by-product. The conjugate base of the acid may be a sulfate group (SO ₄ ^2- ) resulting from sulfuric acid roasting during lithium water leaching.

The reason that lithium by-products are acidic is that, when roasting with sulfuric acid in the lithium ore pretreatment process, excess sulfuric acid is used, so the sulfuric acid remaining unreacted during water leaching is dissolved and contained in the lithium by-products. Therefore, if the acidic lithium by-product containing the remaining sulfuric acid group (SO ₄ ^2- ) is used as a raw material for zeolite production without washing with water, the residual sulfate ion will consume the alkali component added for reaction with the lithium by-product raw material first. As a result, not only the addition of an excess of alkali is required, but also the added alkali component and the remaining sulfate group (SO ₄ ^2- ) ions react to form the salt (Na ₂ SO ₄ ). As a result, insoluble quartz It is not preferable because it interferes with the formation of a soluble mineral phase (SiO ₂ +NaOH→Na ₂ SiO _{3 ) formed by reaction with an alkali and added alkali.} Therefore, in order to use the acidic lithium by-product generated in the lithium recovery process as a raw material for manufacturing synthetic zeolite, the acidic lithium by-product is washed with sufficient water _{to remove sulfate group (SO 4} ^2- ) ions to form a neutral lithium by-product. Manufacturing must be preceded.

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

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

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

When the molar ratio of Si and Al components in the lithium by-product raw material is less than 0.75 and under the condition that exceeds 3.0, the final product is hydroxysodalite (HS, hydroxysodalite, Na ₈ (AlSiO ₆ ) ₄ (OH) ₂ ) or Since a zeolite form with low industrial applicability such as Analcime (NaAlSi ₂ O ₆ H ₂ O) is mixed and produced, it is impossible to prepare a single crystalline phase of zeolite. However, in the case of preparing the reaction by adjusting the molar ratio (Si/Al molar ratio) of Si and Al components in the lithium by-product raw material to be in the range of 0.75 to 3.0, the final product is zeolite P type, zeolite A type, or zeolite X type depending on the molar ratio conditions. It can be prepared in a single crystal phase. Therefore, in the step of adjusting the component ratio suitable for zeolite formation, it is necessary to adjust the molar ratio of Si and Al components in the lithium residue raw material to within the range of 0.75 to 3.0 by supplementing the alumina and silica components.

The step of mixing the solution with the heat-treated raw material; may be a step such that the OH- ion molar concentration of the solution including the heat-treated raw material is 1.0 to 6.0M concentration. The adjusting of the OH- ion molar concentration of the solution including the heat-treated raw material may include controlling the alkali concentration on a solution basis including the amount of alkali powder added to the raw material.

In the step of mixing the solution with the heat-treated raw material; the solution may be distilled water. In the step of mixing a solution with the heat-treated raw material; In, the solution may be an alkali solution for supplying OH- ions to the heat-treated raw material.

In the final product prepared under the condition that the OH- concentration of the solution containing the raw material is 1.0M or less, in addition to the zeolite crystal phase, hydroxysodalite or bantamite is mixed and produced, so it is impossible to prepare a single crystal phase of zeolite. In addition, the final product prepared under the condition that the OH- concentration of the solution containing the raw material is 6.0M or higher is produced as a zeolite crystal, but hydroxy sodalite, which lacks industrial applicability due to low ion exchange capacity, is produced as a single phase. there may be However, when the OH- concentration of the solution containing the raw material is in the range of 1.0M to 6.0M, the final product is produced as a single phase of P-type and A-type zeolite having very good crystallinity.

Crystallizing the heat-treated raw material in which the solution is mixed; may have a crystallization temperature of 60 to 100 °C. Specifically, the crystallization temperature may be in the range of 70 to 100 °C, more specifically 90 to 95 °C. When the crystallization temperature is 60 ° C or less, the final product belongs to the zeolite crystal, but the ion-exchange capacity is low to produce a magnolia with low industrial applicability. Hydroxy sodalite is mixed and produced.

Crystallizing the heat-treated raw material in which the solution is mixed; crystallization time may be 12 hours or more. Even if the reaction is performed by setting the crystallization time to 12 hours or less, the final product has low ion exchange capacity, which is undesirable because it is produced as gaolite with low industrial applicability.

forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; Thereafter, the method may further include pulverizing the heat-treated raw material into a powder.

crystallizing the heat-treated raw material in which the solution is mixed; thereafter, filtering the crystals; and washing and drying the filtered crystals.

In the step of separating the zeolite crystals by solid-liquid separation after crystallization, sufficiently washing the separated zeolite crystals with water and drying to recover the final product, the excess NaOH remaining in the zeolite product is removed by sufficient water washing to remove the pH of the product It is necessary to adjust to the neutral region (pH 6~9). This is because Na ions remaining in the zeolite product due to insufficient water washing act as a cause of deterioration of the quality and various performances of the zeolite. Therefore, in the step of recovering the final product prepared by crystallization, it is preferable to adjust the pH of the product to a neutral region by removing the excess NaOH remaining in the zeolite by a sufficient water washing process.

The zeolite prepared according to one embodiment of the present disclosure may be composed of only one or more crystal phases selected from the group consisting of P-type zeolite, A-type zeolite, and X-type zeolite. Specifically, the zeolite prepared according to one embodiment of the present disclosure may be made of only a single P-type zeolite crystal phase.

lithium by-product

In a series of processes to recover 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 at the Li +} ion site of the ore by the sulfuric acid roasting process. ^{H +} ions dissociated from sulfuric acid are ion-exchanged, and the ion-exchanged Li ⁺ ions combine with the dissociated SO ₄ ^2- ions, and the precipitation reaction proceeds to precipitate as lithium sulfate (Li ₂ SO ₄ ).

Lithium by-product can be prepared by leaching the precipitated lithium sulfate (Li ₂ SO ₄ ) using water and then separating the solid-liquid. Lithium sulfate (Li ₂ SO ₄ ) is dissolved in water and leached, whereas aluminosilicate (Al ₂ O ₃ 4SiO ₂ , AlSi ₂ O ₆ ) is not dissolved in water and remains in the form of a solid compound to form a lithium by-product. can do.

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, K _{2 O,} It is a crystalline phase composed of aluminosilicate (Al ₂ O ₃ 4SiO ₂ , AlSi ₂ O ₆ ), silica (SiO ₂ ), and albite, and has an average particle size of about 25 μm.

The main mineral phase of lithium by-products, the aluminosilicate compound mineral phase (aluminosilicate, Albite), which shows about 93% content, is composed of silica and alumina, which are the main components of zeolite, so it can be sufficiently used as a raw material for synthetic zeolite. is judged However, in the lithium by-product, in addition to the aluminosilicate compound, which is the main component of zeolite, about 7% of _{quartzite (SiO 2 ), a mineralogically very stable form caused by mica or quartz in lithium ore, is contained.} If it is not removed, it will act as a factor that deteriorates the quality of the final product, zeolite.

_{The origin of the SiO 2} mineral phase mixed in the lithium by-product is because the mother rock containing the lithium component is mainly a mica type ore, and since the silica component, which accounts for more than 90% of the crustal components, is contained in the lithium ore, lithium component extraction It will coexist in the lithium by-product remaining later. The SiO ₂ mineral phase is mineralogically very stable, insoluble in a strong acid solution, and is known as a material exhibiting properties of dissolving only a very small amount even under a strong alkaline solution condition.

The present disclosure provides _{the quality of zeolite by excluding the incorporation of impure minerals into the final product, zeolite, by transferring the mineralogically very stable SiO 2} mineral phase to a chemically soluble form through pre-treatment so that it can be utilized as a silica source, which is a component of zeolite. is to improve

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

Example

(1) Preparation of lithium by-products

Lithium ore having a lithium oxide (Li2O) content of about 1.5% was removed by flotation, etc. to remove feldspar and mica, and then concentrated to about 6% lithium oxide (Li2O) content.

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

After roasting the sulfuric acid, 5 times the weight of water was added, stirred, water leached for 1 hour, and the lithium by-product was recovered by separating the solid and liquid using a filter press.

The components and contents of the lithium by-product recovered from the filter press are shown in Tables 1 and 2 below, the results of XRD analysis are shown in Table 3, and the measurement results of the particle size distribution are shown in FIG. 2, respectively.

XRF analysis (wt%) 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 no analysis 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 (wt%) 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 condensed, and the moisture content was about 39% and the pH was about 3.1, which is slightly acidic.

(2) pH control of lithium by-products

[Invention 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 solid-liquid ratio (water/lithium by-product, weight ratio) was adjusted to 5/1, and 500 rpm After stirring for 3 hours, the series of filtration and drying operations were repeated 3 times and washed 3 times to prepare a lithium by-product having a pH of 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 4 below.

[Comparative Example 1] Water washing was performed under the same conditions as in Inventive Example 1 except that the water 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] Water washing was performed under the same conditions as in Invention Example 1 except that the water 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) Amount of washing water (Kg) Wash (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 shown in Table 5 below.

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

However, in Comparative Example 1 and Comparative Example 2, the pH of the lithium by-product prepared by performing water washing only once or twice was 3.23 and 3.84, respectively. Through this, it was found that the washed lithium by-products of Comparative Examples 1 and ² showed weak acidity because _{sulfate ions (SO 4 2- ) caused by excess sulfuric acid used during sulfuric acid roasting remained.}

As a result of checking the presence or absence of changes in the components and contents of the lithium by-products prepared according to the number of times of washing in Table 5, it was confirmed that there was almost no change according to the number of times of washing.

Therefore, in order to use the process-generated lithium by-product as a raw material for manufacturing zeolite, it is necessary _{to minimize the sulfuric acid group (SO 4} ^2- ) present in the lithium by-product through a sufficient water washing process to adjust the pH of the lithium by-product to a neutral region. very important.

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

[Invention Examples 2 to 8]

The lithium by-product washed with water according to Inventive Example 1 had a component composition ratio of 12.6 mol% Al and 31.4 mol% Si. _{NaAlO 2} or Na ₂ SiO ₃ was added to 50 g of the neutral lithium by-product to adjust the Si/Al component molar ratio in the lithium by-product to be 0.75, 1.0, 1.5, 2.0, 2.25, 2.5, 3.0.

A sample obtained by adjusting the weight ratio of alkali powder/lithium by-product to 1.25 by adding 62.5 g of NaOH alkali powder to 50 g of the component-adjusted lithium by-product was uniformly mixed using a tumbler mixer to form a raw material. Thereafter, the homogeneous raw material was put into an alumina crucible, and the raw material was heat-treated by furnace cooling after maintaining it at 550 °C for 1.5 hours in a muffle furnace at a temperature increase rate of 10 °C/min.

After the heat-treated raw material was put into a 2L glass reactor, 1560 ml of distilled water was added (alkali 62.5g/distilled water 1560ml=1.0M NaOH solution) to prepare a 1.0M solution in alkali concentration of the reaction solution. It was heated to 90° C. while stirring at 500 rpm, and maintained for 24 hours to crystallize. The crystallized sample was repeatedly washed with water until the pH reached 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product. The heat-treated raw material obtained after heat-treating the lithium by-product and alkali powder and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 6 below.

[Comparative Examples 3 to 4]

Zeolites were synthesized in the same manner as in Inventive Examples 2 to 8, except that the Si/Al molar ratio was set to 0.5 and 3.5, and the results are shown in Table 6, respectively.

division residue
Si/Al (molar ratio) Alkali powder/lithium by-product
(weight ratio) heat treatment temperature/
heat treatment time alkali
Solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 2 0.75 1.25 550℃
1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-X+Z-A 3 1.0 1.25 550℃
1.5h 1.0 90 24 “ Z-X 4 1.5 1.25 550℃1.5h 1.0 90 24 “ Z-P 5 2.0 1.25 550℃1.5h 1.0 90 24 “ Z-P 6 2.25 1.25 550℃1.5h 1.0 90 24 “ Z-P 7 2.5 1.25 550℃1.5h 1.0 90 24 “ Z-P 8 3.0 1.25 550℃1.5h 1.0 90 24 “ Z-P comparative example 3 0.5 1.25 550℃
1.5h 1.0 90 24 “ Defense Stone + Z-A 4 3.5 1.25 550℃
1.5h 1.0 90 24 “ Z-P+H.S

* 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 hydroxysodalite.

As shown in [Invention Examples 2 to 8] of Table 5, an alumina component or a silica component was added and supplied to adjust the Si/Al component molar ratio to 0.75 to 3.0, and the alkali powder/lithium by-product weight ratio was adjusted to 1.25 to 550 in ℃ sample heat-treated produced for 1.5 hours, Na ₂ SiO _3, bangbiseok (analcime), nepheline (nepheline), etc. have been created as a new material, a quartz (quartz, SiO ₂₎ was present in the lithium-product mineral is reacted with an alkali Soluble Na ₂ SiO _{3 It} can be confirmed that the transition. The final product prepared by crystallization using the heat treatment sample could be prepared as zeolite P-type and zeolite X-type with good crystallinity. In addition, even in the case of using the lithium by-product raw material ratio (Si/Al=2.25) without adjusting the Si/Al component ratio as it is (Invention Example 6), a zeolite P-type single phase could be produced.

However, as shown in Comparative Examples (3~4), the final product prepared using a solution in which the Al content was relatively high by adjusting the Si/Al component molar ratio to 0.5 excessively low was mixed with zeolite other than A-type zeolite. , when the Si/Al component molar ratio is excessively high to 3.5 and the Si content is adjusted to a relatively very high component ratio, it can be confirmed that hydroxy sodalite is mixed in addition to the zeolite P type. have.

Therefore, if the neutral lithium by-product raw material ratio (Si/Al=2.25) is used as it is or the Si/Al component molar ratio is adjusted within the range of 0.75 to 3.0 through component adjustment, the quartz present in the lithium by-product raw material is soluble in the final product It can be confirmed that a single crystal phase of zeolite with good crystallinity is generated by transitioning to _{Na 2} SiO ₃ , which is a component, and contributing to zeolite production.

(4) Alkali powder content control

[Inventive Examples 9 to 11]

The lithium by-product washed with water according to Inventive Example 1 had a component composition ratio of 12.6 mol% Al and 31.4 mol% Si. This neutral lithium by-product was used as it was without any component adjustment.

A raw material was prepared by adding 50, 62.5, and 75 g of alkali powder to 50 g of lithium by-product, respectively, adjusting the weight ratio of alkali powder/lithium by-product to 1.0, 1.25, and 1.50, respectively. This raw material was uniformly mixed using a tumbler mixer, the uniformly mixed raw material was put into an alumina crucible, respectively, and the temperature was raised at 10 °C/min in a muffle furnace and maintained at 550 °C for 1.5 hours. After furnace cooling, heat-treated raw materials were prepared. After the heat-treated raw material was put into a 2L glass reactor, 1250ml, 1560ml, and 1850ml of distilled water were added to prepare a 1.0M solution of the alkali concentration of the reaction solution, and the temperature was raised to 90°C while stirring at 500rpm, and maintained for 24 hours. and crystallized.

The crystallization-finished sample was repeatedly washed with water until pH was 9, and the water-washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

The sample obtained after heat-treating the lithium by-product and the alkali mixture and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 7 below.

[Comparative Examples 5 to 7]

15 g, 25 g, and 37.5 g of alkali powder were added to 50 g of lithium by-product, respectively, and the weight ratio of alkali powder/lithium by-product was adjusted to 0.3, 0.5, and 0.75, respectively, and after the heat treatment sample was put into a 2L glass reactor, each additional 25 g NaOH/1L distilled water , an additional 15 g NaOH/1L, an additional 2.5 g NaOH/1L were added to prepare an alkali concentration of 1.0M, and the same method as in the Inventive Example was carried out, and a sample obtained after heat-treating a lithium by-product and an alkali mixture and the crystal phase of the final product prepared by crystallization was analyzed by XRD, and the results are shown in Table 7 below.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) Heat treatment temperature/heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 9 2.25 1.0 550℃
1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 10 2.25 1.25 550℃
1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 11 2.25 1.50 550℃1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P comparative example 5 2.25 0.3 550℃
1.5h 1.0 90 24 stele
Tetrasodium Trialuminosilicate
Ha Seok
Quartz (SiO ₂ ) Defense Stone + ZP
+quartz 6 2.25 0.5 550℃
1.5h 1.0 90 24 Na ₂ SiO ₃
stele
HS
Ha Seok
Quartz (SiO ₂ ) Z-P+HS
+quartz 7 2.25 0.75 550℃1.5h 1.0 90 24 Na ₂ SiO ₃
stele
HS
Ha Seok
Quartz (SiO ₂ ) Z-P+HS
+quartz

* In the above table, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 9 to 11 of Table 7, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the weight ratio of the alkali powder to the lithium by-product was set to 1.0 or more. The heat-treated sample is _{produced as a compound of Na 2} SiO ₃ , bantamite, and oxite, and it can be confirmed that _{the quartz (SiO 2} ) mineral phase present in the raw material lithium by-product reacts with the added alkali _{to convert to soluble Na 2} SiO _{3 .} It can be seen that the final product prepared by crystallizing the raw materials of this invention example is produced as a zeolite P-type single phase with good crystallinity, respectively.

However, as shown in Comparative Examples 5 to 7, when the ratio of the alkali powder to the lithium by-product was adjusted to less than 1.0, it can be confirmed that, in addition to the P-type zeolite, banisterite or HS (hydrosisodalite) is mixed and produced. .

Therefore, in the case of preparing a lithium by-product-alkali mixture by adding alkali powder to the lithium by-product raw material, when crystallizing by adjusting the weight ratio of the alkali powder to the lithium by-product raw material to 1.0 or more, the final product zeolite does not contain quartz. It can be confirmed that a single crystal phase of zeolite with very good crystallinity is produced.

(5) Control of heat treatment temperature

[Inventive Examples 12 to 16]

After adding 62.5 g of alkali powder to 50 g of lithium by-product, the alkali powder/lithium by-product weight ratio was adjusted to 1.25, and then uniformly mixed using a tumbler mixer, and the uniformly mixed raw material was put into an alumina crucible, muffle furnace) at a temperature increase rate of 10°C/min and maintained at 500°C, 550°C, 600°C, 700°C, and 800°C for 1.5 hours, respectively, and then furnace-cooled to prepare heat-treated raw materials. After the heat-treated raw material was put into a 2L glass reactor, 1560 ml of distilled water was added without adding NaOH to prepare a 1.0M solution in alkali concentration of the reaction solution, and the temperature was raised to 90° C. while stirring at 500 rpm, and maintained for 24 hours to crystallize. did.

After the crystallization was completed, the sample was repeatedly washed with water until pH was 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

The sample obtained after heat-treating the lithium by-product and the alkali mixture and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 8, respectively.

[Comparative Examples 8 to 10]

It was carried out in the same manner as in the above invention example, except that the raw material in which the lithium by-product and the alkali powder were uniformly mixed was heat-treated at 300°C, 400°C, and 450°C for 1.5 hours, respectively, and the lithium by-product and the alkali mixture were heat-treated Then, the obtained raw material and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 8, respectively.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) heat treatment temperature
heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 12 2.25 1.25 500℃
1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 13 2.25 1.25 550℃
1.5h 1.0 90 24 “ Z-P 14 2.25 1.25 600℃1.5h 1.0 90 24 “ Z-P 15 2.25 1.25 700℃1.5h 1.0 90 24 “ Z-P 16 2.25 1.25 800℃1.5h 1.0 90 24 “ Z-P comparative example 8 2.25 1.25 300℃
1.5h 1.0 90 24 stele
Ha Seok
quartz Defense Stone + ZP
+ Quartz 9 2.25 1.25 400℃
1.5h 1.0 90 24 stele
Ha Seok
quartz Z-P+HS
+ Quartz 10 2.25 1.25 450℃1.5h 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok
quartz Z-P+HS
+ Quartz

* In the table above, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 12 to 16 of Table 8, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the ratio of the alkali powder to the lithium by-product was 1.25. Samples prepared by heat treatment for 1.5 hours under conditions in the range of 500 ° C to 800 ° C, respectively, were produced as Na ₂ SiO ₃ , banisterite, and halite compounds, and the quartz (SiO ₂ ) mineral phase present in the raw lithium byproduct reacted with added alkali Soluble Na ₂ SiO _{3 It} can be confirmed that the transition.

The final product prepared by crystallizing this sample was produced as a zeolite P-type single phase with good crystallinity, respectively.

However, as shown in Comparative Examples 8 to 10, in the case of a raw material prepared by heat treatment at a heat treatment temperature of less than 500 ° C., Na ₂ SiO ₃ , and exists in the form of minerals such as magnolia, haite, and quartz, and this raw material is In the final product produced by crystallization using the P-type zeolite, pyrethrum, HS (hydroxysodalite), quartz, etc. are mixed, resulting in lowering the quality of the zeolite.

Therefore, when a uniform mixture of lithium by-product-alkali powder is heat-treated, the alkali powder added at a heat treatment temperature of 500° C. or higher and the quartz (SiO ₂ ) crystal phase present in the lithium by-product, which is the raw material, are supplied with sufficient activation energy and are soluble Phosphorus Na ₂ SiO ₃ It is desirable to allow the transition reaction to proceed to the material.

(6) Control of heat treatment time

[Inventive Examples 17 to 21]

After adding 62.5 g of alkali powder to 50 g of the lithium by-product of Invention Example 1 to adjust the alkali powder/lithium by-product weight ratio to 1.25, the mixture was uniformly mixed using a tumbler mixer, and the uniformly mixed raw material was put into an alumina crucible. , in a muffle furnace at a temperature increase rate of 10°C/min, maintained at 550°C for 30 minutes, 1 hour, 1.5 hours, 2 hours, and 3 hours, and then furnace-cooled to prepare a heat-treated raw material. After inputting the heat-treated raw material into a 2L glass reactor, 1560 ml of distilled water was added without additional NaOH input to prepare a 1.0M solution in alkali concentration of the reaction solution, and the temperature was raised to 90° C. while stirring at 500 rpm, and maintained for 24 hours to crystallize. did.

After the crystallization was completed, the sample was repeatedly washed with water until pH was 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

The sample obtained after heat-treating the lithium by-product and the alkali mixture and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 9, respectively.

[Comparative Examples 11 to 12]

It was carried out in the same manner as in the invention example, except that the raw material in which the lithium by-product and the alkali powder were uniformly mixed was heat-treated at 550° C. for 10 minutes and 20 minutes, respectively, and the lithium by-product and the alkali mixture were heat-treated. The sample and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 9, respectively.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) Heat treatment temperature/heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 17 2.25 1.25 550℃
30 min. 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 18 2.25 1.25 550℃
1.0h 1.0 90 24 “ Z-P 19 2.25 1.25 550℃1.5h 1.0 90 24 “ Z-P 20 2.25 1.25 550℃2.0h 1.0 90 24 “ Z-P 21 2.25 1.25 550℃3.0h 1.0 90 24 “ Z-P comparative example 11 2.25 1.25 300℃
10 min. 1.0 90 24 stele
Ha Seok
quartz Defense Stone + ZP
+quartz 12 2.25 1.25 400℃
20 min. 1.0 90 24 stele
Ha Seok
quartz Z-P+HS
+quartz

* In the table above, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 17 to 21 of Table 9, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the ratio of alkali powder to lithium by-product was 1.25. Samples prepared by heat treatment at 550° C. for 30 minutes to 3 hours, respectively, were produced as Na ₂ SiO ₃ , bantamite, and pyrite, and the quartz (SiO ₂ ) mineral phase present in the raw material lithium by-product reacted with added alkali to form soluble It can be confirmed that the _{Na 2} SiO _{3 material has been transferred.} The final products prepared by crystallizing this sample were each produced as a zeolite P-type single phase with good crystallinity.

However, as shown in Comparative Examples (11 to 12), in the case of a sample prepared by heat treatment under the condition of a heat treatment time of less than 30 minutes, Na ₂ SiO ₃ , and exists in the form of minerals such as magnolia, haite, and quartz, and this sample is In the final product produced by crystallization using P-type zeolite, pyrethrum, HS (hydroxysodalite), quartz, etc. are mixed, resulting in lowering the quality of the zeolite.

_{Therefore, in the case of heat treatment of a uniform mixture of lithium by-product-alkali powder, the quartz (SiO 2} ) crystal phase present in the lithium by-product, which is the raw material, and the alkali powder added by setting the heat treatment time to 30 minutes or more at the heat treatment temperature of 500° C. or higher It is preferable to receive sufficient activation energy so that the transition reaction to be converted into _{a soluble Na 2} SiO _{3 material can proceed.}

(7) Control of crystallization temperature

[Inventive Examples 22 to 26]

The neutral lithium by-product prepared under the conditions of [Invention Example 1] is a raw material in which the component composition ratio is Al 12.6 mol% and Si 28.41 mol%, and the Si/Al ratio is 2.25.

50 g of neutral lithium by-product was used as a raw material without adjusting the composition of the lithium by-product raw material. After adding 62.5 g of alkali powder to 50 g of lithium by-product, the alkali powder/lithium by-product weight ratio was adjusted to 1.25, and then uniformly mixed using a tumbler mixer, and the uniformly mixed raw material was put into an alumina crucible, muffle furnace) at a heating rate of 10°C/min and maintained at 550°C for 1.5 hours, followed by furnace cooling to prepare a heat-treated raw material. After the heat-treated raw material was put into a 2L glass reactor, 1560 ml of distilled water was added without adding NaOH to prepare a 1.0M solution with an alkali concentration of the reaction solution, and stirred at 500 rpm at 60°C, 70°C, 80°C, 90°C, The temperature was raised to 100 °C, respectively, and maintained for 24 hours to crystallize.

After the crystallization was completed, the sample was repeatedly washed with water until pH was 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

The sample obtained after heat-treating the lithium byproduct and the alkali mixture and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 10, respectively.

[Comparative Examples 13 to 14]

It was carried out in the same manner as in the invention example, except that the raw material, which was heat-treated by maintaining the sample of a homogeneous mixture of lithium by-product and alkali powder at 550 ° C. for 1.5 hours, was crystallized at a crystallization temperature of 50 ° C. and 110 ° C. The samples obtained after the alkali mixture was heat-treated and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 10, respectively.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) heat treatment temperature
heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 22 2.25 1.25 550℃
1.5h. 1.0 60 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 23 2.25 1.25 550℃
1.5h 1.0 70 24 “ Z-P 24 2.25 1.25 550℃1.5h 1.0 80 24 “ Z-P 25 2.25 1.25 550℃1.5h 1.0 90 24 “ Z-P 26 2.25 1.25 550℃1.5h 1.0 100 24 “ Z-P comparative example 13 2.25 1.25 550℃
1.5h 1.0 50 24 stele
Ha Seok
quartz stele 14 2.25 1.25 550℃
1.5h 1.0 110 24 stele
Ha Seok
quartz Defense Stone + Z-P

* In the table above, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 22 to 26 of Table 10, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the ratio of alkali powder to lithium by-product was 1.25. Samples prepared by heat treatment at 550° C. for 1.5 hours each were produced as Na ₂ SiO ₃ , banisterite, and pyrite, and the quartz (SiO ₂ ) mineral phase present in the raw lithium by-product reacted with the added alkali powder to form soluble Na ₂ It can be confirmed that the transition to the _{SiO 3 material.} The final product prepared by crystallizing this sample at a crystallization temperature of 60°C to 100°C, respectively, was produced as a zeolite P-type single phase with good crystallinity.

However, as shown in Comparative Examples 13 to 14, the final product prepared by crystallizing the crystallization treatment temperature at 50° C. and 110° C., respectively, was produced as a single phase of garolite or a product in which P-type zeolite and garterite were mixed.

Therefore, it can be seen that when a zeolite crystal is prepared by crystallizing a sample prepared by heat-treating a mixture of lithium by-product and alkali powder, it is preferable to prepare the crystallization temperature by adjusting the crystallization temperature within the range of 60 to 100°C.

(8) Crystallization alkali solution concentration control

[Inventive Examples 27 to 32]

The neutral lithium by-product prepared under the conditions of Invention Example 1 is a raw material in which the component composition ratio is Al 12.6 mol% and Si 28.41 mol%, and the Si/Al ratio is 2.25.

50 g of neutral lithium by-product was used as a raw material without adjusting the composition of the lithium by-product raw material. After adding 62.5 g of alkali powder to 50 g of this lithium by-product, the alkali powder/lithium by-product weight ratio was adjusted to 1.25, and then uniformly mixed using a tumbler mixer, and the uniformly mixed raw material was put into an alumina crucible, (Muffle furnace) at a heating rate of 10°C/min, maintained at 550°C for 1.5 hours, and then furnace-cooled to prepare a heat-treated raw material. After the heat-treated raw material is put into a 2L glass reactor, additional alkali is added to prepare the alkali concentration of the reaction solution into 1.0M, 2.0M, 3.0M, 4.0M, 5.0M, and 6.0M solutions, respectively, while stirring at 500rpm The temperature was raised to 90 °C, respectively, and was maintained for 24 hours to crystallize.

After the crystallization was completed, the sample was repeatedly washed with water until pH was 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

The sample obtained after heat-treating the lithium by-product and the alkali mixture and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 11, respectively.

[Comparative Examples 15 to 16]

After the heat-treated raw material was put into a 2L glass reactor, additional alkali was added, and the alkali concentration of the reaction solution was prepared and treated with 0.5M and 7.0M solutions, respectively, in the same manner as in the invention example, and lithium After heat treatment of the by-product and alkali mixture, the sample obtained and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 11, respectively.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) heat treatment temperature
heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 27 2.25 1.25 550℃
1.5h. 1.0 90 24 Na ₂ SiO ₃
stele
Ha Seok Z-P 28 2.25 1.25 550℃
1.5h 2.0 90 24 “ Z-P 29 2.25 1.25 550℃1.5h 3.0 90 24 “ Z-P 30 2.25 1.25 550℃1.5h 4.0 90 24 “ Z-P 31 2.25 1.25 550℃1.5h 5.0 90 24 “ Z-P 32 2.25 1.25 550℃1.5h 6.0 90 24 “ Z-P comparative example 15 2.25 1.25 550℃
1.5h 0.5 90 24 “ Z-P+H.S+Gatestone 16 2.25 1.25 550℃
1.5h 0.7 90 24 “ H.S.

* In the table above, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 27 to 32 of Table 11, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the weight ratio of the alkali powder to the lithium by-product was 1.25. Samples prepared by heat treatment at 550° C. for 1.5 hours each were produced as Na ₂ SiO ₃ , bantamite, and pyrite, and the quartz (SiO ₂ ) mineral phase present in the raw lithium by-product reacted with the added alkali powder to form soluble Na ₂ It can be confirmed that the transition to the _{SiO 3 material.} After adjusting the alkali concentration of the reaction solution to 1.0~6.0M concentration by adding additional alkali to this sample, the final product prepared by crystallizing each at a crystallization temperature of 90°C for 24 hours is a zeolite P-type single phase with good crystallinity, respectively. was created

However, as shown in Comparative Examples 15 to 16, when the alkali concentration of the reaction solution was adjusted to a concentration of 0.5 M and crystallized, it can be confirmed that H.S (hydroxysodalite) and banister are mixed in addition to zeolite P type. On the other hand, when the alkali concentration is adjusted to 7.0M and crystallized, it can be confirmed that H.S (hydroxysodalite) is produced as a single phase.

Therefore, when a zeolite crystal is prepared by crystallizing a raw material prepared by heat-treating a mixture of lithium by-product and alkali powder, when the mixture is mixed with an alkali solution to crystallize into zeolite, the alkali concentration of the mixed solution is in the range of 1.0 to 6.0M It can be seen that it is preferable to adjust the reaction within

(9) crystallization time control

[Inventive Examples 33 to 35]

The neutral lithium by-product of Invention Example 1 is a raw material in which the component composition ratio is Al 12.6 mol% and Si 28.41 mol%, and the Si/Al ratio is 2.25. 50 g of this neutral lithium by-product was used as a raw material as it was, without any component adjustment.

After adding 62.5 g of alkali powder to 50 g of lithium by-product to adjust the weight ratio of alkali powder/lithium by-product to 1.25, uniformly mixing using a tumbler mixer, and putting the uniformly mixed raw material into an alumina crucible, with a muffle furnace ( muffle furnace) at a heating rate of 10°C/min and maintained at 550°C for 1.5 hours, followed by furnace cooling to prepare a heat-treated raw material. After putting the heat-treated raw material into a 2L glass reactor, 1560 ml of distilled water was added without adding NaOH to prepare a 1.0M solution of alkali concentration of the reaction solution, and the temperature was raised to 90° C. while stirring at 500 rpm for 12 hours, 24 hours, 48 hours crystallized while holding each for an hour.

After the crystallization was completed, the sample was repeatedly washed with water until pH was 9, and the washed sample was filtered and dried sufficiently at 105° C. to prepare a final product.

After heat treatment of the lithium by-product and alkali mixture, the obtained raw material and the crystal phase of the final product prepared by crystallization were analyzed by XRD, and the results are shown in Table 12, respectively.

[Comparative Examples 17 to 19]

Except for crystallizing the heat-treated sample at a crystallization temperature of 90° C. for 1 hour, 3 hours, and 6 hours, respectively, the raw material obtained by uniformly mixing lithium by-product and alkali powder was maintained at 550° C. for 1.5 hours. It was carried out in the same way as honor, and the results are shown in Table 12, respectively.

division residue
Si/Al (molar ratio) Alkali/Lithium By-product
(weight ratio) heat treatment temperature
heat treatment time Alkaline solution concentration (M) crystallization
Temperature (℃) crystallization
time (hr.) after heat treatment
crystalline phase after crystallization
crystalline phase invention example 33 2.25 1.25 550℃
1.5h. 1.0 90 12 Na ₂ SiO ₃
stele
Ha Seok Z-P 34 2.25 1.25 550℃
1.5h 1.0 90 24 “ Z-P 35 2.25 1.25 550℃1.5h 1.0 90 48 “ Z-P comparative example 17 2.25 1.25 550℃
1.5h 1.0 90 One stele
Ha Seok
quartz stele 18 2.25 1.25 550℃
1.5h 1.0 90 3 stele
Ha Seok
quartz stele 19 2.25 1.25 550℃1.5h 1.0 90 6 stele
Ha Seok
quartz stele

* In the table above, Z-A, Z-X and Z-P mean A-type zeolite, X-type zeolite, and P-type zeolite, respectively. H.S means hydroxysodalite.

As shown in Invention Examples 33 to 35 of Table 12, the lithium by-product component ratio (Si/Al=2.25) was used as it is without arbitrarily adjusting the Si/Al component ratio, and the ratio of the alkali powder to the lithium by-product was 1.25. The raw materials prepared by heat treatment at 550° C. for 1.5 hours each were produced as Na ₂ SiO ₃ , banisterite, and pyrite, and the quartz (SiO ₂ ) mineral phase present in the raw lithium by-product reacted with the added alkali powder to form soluble Na ₂ SiO _{3 It} can be confirmed that the material has been transferred. The final products prepared by crystallizing this sample at a crystallization temperature of 90° C. under conditions in the range of 12 hours or more were each produced as a zeolite P-type single phase with good crystallinity.

However, as shown in Comparative Examples 17 to 19, the final products prepared by crystallizing each crystallization treatment time under the condition of less than 12 hours were produced as a single phase of garite.

Therefore, when producing zeolite crystals by crystallizing a sample prepared by heat-treating a mixture of lithium by-product and alkali powder, it is preferable to prepare the crystallization temperature by adjusting the crystallization treatment time to 12 hours or more within the range of 60 to 100 ° C. it can be seen that

The present invention is not limited to the embodiments, but may be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains may develop other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that this may be practiced. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (16)

preparing a lithium by-product;
adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product with water three or more times;
adjusting the molar ratio of silicon to aluminum (Si/Al ratio) included in the washed lithium by-product;
uniformly mixing an alkali powder with the lithium by-product whose molar ratio of silicon to aluminum is adjusted;
forming a raw material by heat-treating the lithium by-product mixed with the alkali powder;
mixing a solution with the heat-treated raw material; and
Including; crystallizing the heat-treated raw material in which the solution is mixed;
In the step of uniformly mixing the alkali powder with the lithium by-product with the molar ratio of silicon to aluminum adjusted;
The alkali powder/lithium by-product weight ratio is 1.0 or more,
A method for manufacturing zeolite. delete According to claim 1,
In the step of heat-treating the lithium by-product mixed with the alkali powder to form a raw material;
Heat treatment is a zeolite manufacturing method, wherein the temperature is 500 ° C. or higher. According to claim 1,
In the step of heat-treating the lithium by-product mixed with the alkali powder to form a raw material;
The heat treatment time is 30 minutes or more, zeolite manufacturing method. According to claim 1,
adjusting the lithium by-product to pH 6 to 8 by washing the lithium by-product;
The step of removing the conjugate base of the acid from the lithium by-product, zeolite manufacturing method. According to claim 1,
Adjusting the molar ratio of silicon to aluminum (Si/Al ratio) contained in the washed lithium by-product;
The step of adjusting the molar ratio of silicon to aluminum (Si/Al ratio) contained in the lithium by-product to 0.75 to 3.0 by adding an alumina supplementary material or silica supplementary material to the lithium byproduct. 7. The method of claim 6,
wherein the alumina supplemental material comprises at least one of alumina hydrate (Al(OH) ₃ ) and sodium aluminate (NaAlO ₂ ). 7. The method of claim 6,
wherein the silica supplemental material is sodium silicate (Na ₂ OSiO ₂ ). According to claim 1,
Mixing the solution with the heat-treated raw material;
The step of allowing the OH- ion molar concentration of the solution containing the heat-treated raw material to be 1.0 to 6.0M, the zeolite manufacturing method. 10. The method of claim 9,
In the step of mixing the solution to the heat-treated raw material;
The solution is distilled water, zeolite manufacturing method. 10. The method of claim 9,
In the step of mixing a solution with the heat-treated raw material;
The solution is an alkaline solution for supplying OH- ions to a solution containing the heat-treated raw material, the method for producing zeolite. According to claim 1,
Crystallizing the heat-treated raw material in which the solution is mixed;
The crystallization temperature is 60 to 100 ℃, zeolite manufacturing method. According to claim 1,
Crystallizing the heat-treated raw material in which the solution is mixed;
A method for producing a zeolite, wherein the crystallization time is 12 hours or more. According to claim 1,
forming a raw material by heat-treating the lithium by-product mixed with the alkali powder; Since the,
Further comprising the step of pulverizing the heat-treated raw material to pulverize, zeolite manufacturing method. According to claim 1,
crystallizing the heat-treated raw material in which the solution is mixed; Since the,
filtering the crystals; and
A method for producing zeolite further comprising; washing the filtered crystals with water and drying the crystals. 16. The zeolite prepared according to any one of claims 1 and 3 to 15, wherein the zeolite consists only of one or more crystal phases selected from the group consisting of P-type zeolite, A-type zeolite, and X-type zeolite.