A method for preparing intercalated zirconium phosphate using a solvent extraction system

Abstract

This invention discloses a method for preparing intercalated zirconium phosphate using a solvent extraction system. This invention relates to the field of zirconium phosphate preparation technology. The method includes the following steps: S1, mixing and stirring an aqueous solution containing zirconium ions with an organic extraction solvent to obtain a zirconium-loaded organic phase; S2, mixing and stirring the organic phase obtained in step S1 with a back-extraction aqueous solution containing phosphate ions; S3, performing solid-liquid separation on the aqueous suspension, washing and drying the solid phase to obtain intercalated zirconium phosphate. Utilizing the complexation stability and interfacial mass transfer process of the extraction system, the contact reaction rate between zirconium ions and phosphate ions is sufficiently slowed, effectively reducing the crystal particle size of the zirconium phosphate flame retardant. By utilizing the interfacial reaction of the extraction system, ionic liquids and auxiliary intercalating agents are introduced into the interlayer gaps of zirconium phosphate during its generation, effectively preventing the stacking of zirconium phosphate layers, resulting in a flame retardant with fewer layers and a larger interlayer spacing.

Description

Technical Field

[0001] This invention relates to the field of zirconium phosphate preparation technology, and in particular to a method for preparing intercalated zirconium phosphate using a solvent extraction system. Background Technology

[0002] Zirconium phosphate is a two-dimensional layered structure material with unique physicochemical properties. The interlayers of zirconium phosphate contain numerous proton acid sites, exhibiting strong solid acid-catalyzed dehydrogenation under high-temperature combustion conditions. This promotes the cross-linking of organic polymers into carbon, generating a graphite-like carbon layer structure. Simultaneously, its two-dimensional structure possesses a layered barrier effect, which synergistically works with the graphite-like carbon layer to further prevent heat and mass transfer between the gas and condensed phases, thus exhibiting excellent flame-retardant properties.

[0003] The basic principle of zirconium phosphate synthesis is the precipitation reaction between phosphate and zirconium ions. Traditional synthesis methods include reflux and hot water hydrolysis. However, due to the extremely low solubility of zirconium phosphate precipitate, the precipitation reaction occurs very rapidly. Furthermore, because the surface of two-dimensional zirconium phosphate contains a large number of active hydroxyl groups, the multiple layers of synthesized zirconium phosphate often stack and overlap, resulting in large product particle sizes. When directly added as a flame retardant, it exhibits poor interfacial compatibility with organic polymers, making uniform dispersion difficult.

[0004] To improve the interfacial compatibility between zirconium phosphate and polymers, a common chemical approach is intercalation, which involves dispersing multiple layers of zirconium phosphate and then modifying the surface of the zirconium phosphate. However, due to the strong interlayer forces and narrow interlayer spacing (approximately 0.7 nm) of zirconium phosphate, the chemical intercalation method is time-consuming, severely impacting production efficiency. For example, Chinese patent application CN110591156A, to achieve composite modification of zirconium phosphate with graphitized carbon nitride, requires first using a small molecule amine as a pre-intercalating agent and ultrasonically treating it for 6-12 hours; then, a surfactant is used as an intercalating agent, and the mixture is further ultrasonically treated at 30-100°C for 6-12 hours to obtain an intercalated zirconium phosphate suspension. For example, Chinese patent application CN116376115A requires that to achieve organophosphorus modification of zirconium phosphate, it is necessary to first use highly carcinogenic substances such as tetrahydrofuran as solvents and amines as pre-intercalating agents, and treat them for 2-4 hours under the combined action of stirring and ultrasound; then, quaternary ammonium salt intercalating agents are added, and the mixture is heated and stirred for 4-6 hours to prepare an intercalated zirconium phosphate suspension for subsequent modification.

[0005] Therefore, optimizing the synthesis method of zirconium phosphate and preparing intercalated zirconium phosphate with fewer lamellae and larger interlayer spacing in a short time is of great research significance for the application or subsequent modification of zirconium phosphate flame retardants. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of the prior art by proposing a time-saving, efficient, and environmentally friendly method for preparing intercalated zirconium phosphate using a solvent extraction system. The method yields intercalated zirconium phosphate with small crystal particle size, few lamellae, large interlayer spacing, strong interfacial compatibility with polymers, and wide applicability for surface modification.

[0007] The present invention provides a method for preparing intercalated zirconium phosphate using a solvent extraction system, comprising the following steps:

[0008] S1. Mix and stir the aqueous solution containing zirconium ions with the organic phase extraction solvent to extract the zirconium ions into the organic phase. Let it stand, separate the phases, and obtain the raffinate aqueous phase and the zirconium-loaded organic phase, respectively.

[0009] S2. The loaded organic phase obtained in step S1 is mixed and stirred with the back-extraction aqueous solution containing phosphate, allowed to stand, and separated into phases to obtain the back-extraction organic phase and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0010] S3. The aqueous suspension containing intercalated zirconium phosphate obtained in step S2 is subjected to solid-liquid separation. The solid phase is washed and dried to obtain intercalated zirconium phosphate.

[0011] In step S1, the organic phase extraction solvent includes an ionic liquid extractant and a diluent.

[0012] Furthermore, the intercalated zirconium phosphate is α-zirconium phosphate or γ-zirconium phosphate.

[0013] Furthermore, in step S1, the aqueous phase feed solution also contains additive I; and / or,

[0014] The auxiliary agent I includes any one or more of acids and salts; and / or,

[0015] The acids are selected from any one or more of inorganic acids or small molecule organic acids; and / or,

[0016] The acid is selected from at least one of the following: acid, perhalic acid, hypohalic acid, nitric acid, sulfuric acid, boric acid, fluoroboric acid, thiocyanate, hydrocyanic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, cinnamic acid, or citric acid; and / or,

[0017] The salts are selected from any one or more of alkali metal salts, alkaline earth metal salts, or ammonium salts; and / or,

[0018] The concentration of the acids and / or salts is 0.01 mol / L to 12 mol / L; and / or,

[0019] The concentration of the acids and / or salts is 0.1 mol / L to 5 mol / L; and / or,

[0020] The concentration of zirconium ions is 0.0001 mol / L to 1.65 mol / L; and / or,

[0021] The concentration of zirconium ions is 0.1 mol / L to 1.2 mol / L.

[0022] Furthermore, the ionic liquid extractant has molecules with

[0023] An organic extractant with the following structure: A is any one of nitrogen, phosphorus, arsenic, antimony, and bismuth, all elements in Group V of the periodic table; B is any one of inorganic acid radicals, organic acid radicals, or hydroxide ions; n is the valence of the selected acid radical B; X1, X2, X3, and X4 are independently selected from any one of substituted or unsubstituted straight-chain or branched alkyl groups, or substituted or unsubstituted aryl groups; and / or,

[0024] The diluent is any one or more of alkanes, aromatics, esters, ketones, ethers, alcohols, alcohol ethers, aldehydes, or amines; and / or,

[0025] The volume ratio of the ionic liquid extractant to the diluent is 1:50 to 50:1; and / or,

[0026] The volume ratio of the ionic liquid extractant to the diluent is 1:20 to 20:1.

[0027] Furthermore, in step S1, the volume ratio of the aqueous phase feed solution to the organic phase extraction solvent is 1:50 to 50:1; and / or,

[0028] The volume ratio of the aqueous phase feed solution to the organic phase extraction solvent is 1:20 to 20:1; and / or,

[0029] In step S1, the aqueous phase feed solution and the organic phase extraction solvent are mixed and stirred at a speed of 10 rpm to 1000 rpm; and / or,

[0030] The aqueous phase feed solution and the organic phase extraction solvent are mixed and stirred at a speed of 60 rpm to 600 rpm; and / or,

[0031] The mixing time is 1 min to 60 min.

[0032] Furthermore, in step S2, the phosphate group is selected from any one or more of phosphoric acid, pyrophosphate, polyphosphate, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, and polyphosphate; and / or,

[0033] The phosphate concentration is 0.0001 mol / L to 12 mol / L; and / or,

[0034] The phosphate concentration is 0.05 mol / L to 5 mol / L.

[0035] Furthermore, the back-extraction aqueous phase feed solution in step S2 also includes auxiliary agent II; and / or,

[0036] The auxiliary agent II includes any one or more of small molecule organic compounds, inorganic acids, or salts; and / or,

[0037] The small molecule organic compound is selected from any one or more of amines, alcohols, alkanolamines, esters, and carboxylic acids; and / or,

[0038] The amine is selected from any one or more of methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, p-aniline, or bis(trifluoromethanesulfonyl)imide; and / or,

[0039] The alcohols are selected from any one or more of methanol, ethanol, ethylene glycol, and isopropanol; and / or,

[0040] The alkanolamines are selected from any one or more of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanol, N,N-dibutylethanolamine, or N,N-dipropylethanolamine; and / or,

[0041] The esters are selected from any one or more of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate; and / or,

[0042] The carboxylic acids are selected from any one or more of formic acid, acetic acid, oxalic acid, propionic acid, or lactic acid; and / or, the inorganic acids are selected from any one or more of halogen acids, perhalogen acids, hypohalogen acids, nitric acid, sulfuric acid, phosphoric acid, boric acid, and fluoroboric acid; and / or,

[0043] The salts are selected from any one or more of alkali metal salts, alkaline earth metal salts, and ammonium salts.

[0044] Furthermore, in step S2, the molar ratio of phosphate to adjuvant II is 100:1 to 1:50; and / or,

[0045] The molar ratio of phosphate to adjuvant II is 10:1 to 1:10.

[0046] Further, in step S2, the volume ratio of the supported organic phase to the back-extraction aqueous phase is 100:1 to 1:50; and / or, the volume ratio of the supported organic phase to the back-extraction aqueous phase is 20:1 to 1:20; and / or,

[0047] In step S2, the mixing speed of the supported organic phase and the back-extraction aqueous phase is 10 rpm to 1000 rpm; and / or,

[0048] The mixing speed of the supported organic phase and the back-extracted aqueous phase is 10 rpm to 300 rpm; and / or,

[0049] The mixing time is 1 min to 60 min.

[0050] Furthermore, in step S3, the washing step includes washing with acetone 1-5 times, washing with ethanol 1-5 times, and washing with water 1-5 times; and / or,

[0051] In step S3, the drying temperature is 30-80℃ and the time is 1-12h.

[0052] The principle of this invention is as follows:

[0053] 1) Ionic liquid extractants can extract zirconium ions and complex anions into the organic phase in the form of a complex. In the organic phase, this zirconium-containing complex exhibits relatively stable structure and properties. During back-extraction of the supported organic phase, the migration and mass transfer of zirconium ions across the two-phase interface into the back-extraction aqueous phase is slow. At the two-phase interface, the reaction rate between zirconium ions and phosphate ions in the back-extraction aqueous phase is significantly reduced, effectively preventing the agglomeration of zirconium phosphate crystal particles.

[0054] 2) At the two-phase interface, the ionic liquid in the organic phase extraction solvent can also be used as an intercalating agent, and the acids and salts in the aqueous phase feed solution can be used as auxiliary agent I. Auxiliary agent I not only helps to improve the extraction efficiency and complexation stability of zirconium ions by the organic phase extraction solvent, but also can be used as an auxiliary intercalating agent in the zirconium phosphate generation process. The small molecule organic matter, inorganic salts, inorganic acids, etc. in the back-extraction aqueous phase feed solution can be used as auxiliary agent II. Auxiliary agent II is mainly used as an auxiliary intercalating agent for zirconium phosphate. The intercalating agent and auxiliary intercalating agent quickly enter the interlayer gap of zirconium phosphate, effectively preventing the stacking of zirconium phosphate layers, thereby making the prepared intercalated zirconium phosphate flame retardant have fewer layers and larger interlayer spacing.

[0055] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0056] 1) By utilizing the complexation stability of the extraction system and the mass transfer process at the phase interface, the contact reaction rate between zirconium ions and phosphate ions is significantly slowed down, effectively reducing the crystal particle size of zirconium phosphate flame retardant.

[0057] 2) By utilizing the phase interface reaction of the extraction system, ionic liquid intercalating agents and auxiliary intercalating agents are introduced into the interlayer gaps of zirconium phosphate while generating zirconium phosphate, which effectively prevents the stacking of zirconium phosphate layers. The prepared intercalated phosphate layers have a small number of layers, strong interfacial compatibility, and wide applicability for surface modification.

[0058] 3) In the extraction system, the formation reaction of zirconium phosphate and the intercalation reaction are carried out simultaneously, which greatly shortens the preparation time of intercalated zirconium phosphate flame retardant and has high synthesis efficiency. Attached Figure Description

[0059] Figure 1 This is a transmission electron microscope (TEM) image of the intercalated zirconium phosphate prepared in Example 4. Detailed Implementation

[0060] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings. However, the present invention is not limited to these embodiments.

[0061] Example 1

[0062] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0063] 1) Prepare an aqueous solution containing 0.5 mol / L zirconium ions, 3 mol / L sulfuric acid, and 0.6 mol / L potassium sulfate. Prepare an organic phase extraction solvent by mixing heptyltriethylammonium chloride as the extractant and n-hexane as the diluent at a volume ratio of 1:5. Mix the aqueous solution with the organic phase extraction solvent at a volume ratio of 1:3 and stir. Set the stirring speed to 100 r / min and the stirring time to 12 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0064] 2) Prepare an aqueous back-extraction solution containing 0.05 mol / L ammonium phosphate, 0.005 mol / L phosphoric acid, 0.005 mol / L ethylenediamine, and 0.05 mol / L potassium chloride. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 5:2. Set the stirring speed to 120 r / min and the stirring time to 20 min. Let it stand and separate the phases to obtain the organic back-extraction solution and the aqueous suspension containing intercalated zirconium phosphate.

[0065] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed twice with acetone, twice with ethanol, and twice with water in sequence. It is then dried at 60°C for 6 hours to obtain the intercalated zirconium phosphate flame retardant.

[0066] Example 2

[0067] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0068] 1) Prepare an aqueous solution containing 1 mol / L zirconium ions, 2 mol / L perchloric acid, and 0.6 mol / L sodium iodide. Prepare an organic phase extraction solvent by mixing dodecyltrimethylammonium nitrate as the extractant and isoamyl alcohol as the diluent at a volume ratio of 1:10. Mix the aqueous solution with the organic phase extraction solvent at a volume ratio of 10:1 and stir. Set the stirring speed to 150 r / min and the stirring time to 20 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0069] 2) Prepare an aqueous back-extraction solution containing 0.1 mol / L phosphoric acid, 0.01 mol / L methylamine, 0.005 mol / L ethylenediamine, and 0.05 mol / L ammonium chloride. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 10:1. Set the stirring speed to 100 r / min and the stirring time to 30 min. Let it stand and separate the phases to obtain the organic back-extraction phase and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0070] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, once with ethanol, and twice with water. It is then dried at 80°C for 3 hours to obtain the intercalated zirconium phosphate flame retardant.

[0071] Example 3

[0072] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0073] 1) Prepare an aqueous solution containing 0.75 mol / L zirconium ions, 3 mol / L sodium fluoroborate, and 2.2 mol / L sulfuric acid. Prepare an organic phase extraction solvent by mixing dodecyl dimethyl benzyl ammonium fluoride extractant and xylene diluent at a volume ratio of 1:3. Mix the aqueous solution and the organic phase extraction solvent at a volume ratio of 9:1 and stir. Set the stirring speed to 300 r / min and the stirring time to 10 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0074] 2) Prepare an aqueous back-extraction solution containing 0.1 mol / L potassium pyrophosphate, 0.005 mol / L methylamine, 0.01 mol / L ethylene glycol, 0.5 mol / L ethyl acetate, and 0.5 mol / L formic acid. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 3:2. Set the stirring speed to 200 r / min and the stirring time to 30 min. Let it stand, separate the phases, and obtain the organic back-extraction solution and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0075] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, twice with ethanol, and three times with water. It is then dried at 70°C for 3 hours to obtain the intercalated zirconium phosphate flame retardant.

[0076] Example 4

[0077] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0078] 1) Prepare an aqueous solution containing 0.9 mol / L zirconium ions, 3.5 mol / L sodium thiocyanate, and 4 mol / L hydrochloric acid. Prepare an organic phase extraction solvent by mixing dihexyldimethyliodate ammonium extractant and amyl acetate diluent at a volume ratio of 2:9. Mix the aqueous solution and the organic phase extraction solvent at a volume ratio of 1:1 and stir at a stirring speed of 200 r / min for 20 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0079] 2) Prepare an aqueous back-extraction solution containing 1.2 mol / L potassium hydrogen phosphate, 0.005 mol / L aniline, 0.015 mol / L diethanolamine, 1.5 mol / L acetic acid, and 2.5 mol / L hydrochloric acid. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 20:1. Set the stirring speed to 150 r / min and the stirring time to 30 min. Let it stand, separate the phases, and obtain the organic back-extraction solution and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0080] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, once with ethanol, and three times with water. It is then dried at 75°C for 3 hours to obtain the intercalated zirconium phosphate flame retardant.

[0081] Figure 1 The image shown is a transmission electron microscope (TEM) image of the intercalated zirconium phosphate prepared in Example 4, such as... Figure 1 As shown, the size of zirconium phosphate is between 150nm and 230nm.

[0082] Example 5

[0083] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0084] 1) Prepare an aqueous feed solution containing 1.0 mol / L zirconium ions, 3 mol / L hydrogen cyanide, and 1.2 mol / L lithium bromide. Prepare an organic phase extraction solvent by mixing tetrabutylammonium hydroxide extractant and petroleum ether diluent at a volume ratio of 1:15. Mix the aqueous feed solution and the organic phase extraction solvent at a volume ratio of 1:12 and stir. Set the stirring speed to 450 r / min and the stirring time to 8 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0085] 2) Prepare an aqueous back-extraction solution containing 1.2 mol / L ammonium dihydrogen phosphate, 0.015 mol / L p-aniline, 0.02 mol / L triethanolamine, and 1.5 mol / L sulfuric acid. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 1:3. Set the stirring speed to 60 r / min and the stirring time to 12 min. Let it stand and separate the phases to obtain the organic back-extraction phase and the aqueous suspension containing intercalated zirconium phosphate.

[0086] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed twice with acetone, once with ethanol, and twice with water in sequence. It is then dried at 80°C for 1.5 h to obtain the intercalated zirconium phosphate flame retardant.

[0087] Example 6

[0088] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0089] 1) Prepare an aqueous solution containing 0.25 mol / L zirconium ions, 2.2 mol / L sulfuric acid, 0.1 mol / L lactic acid, 0.15 mol / L lithium chloride, and 0.1 mol / L magnesium sulfate. Prepare an organic phase extraction solvent by mixing the extractant tetrabutylammonium sulfonate and the diluents ethanol and isoamyl alcohol at a volume ratio of 2:2:10. Mix the aqueous solution with the organic phase extraction solvent at a volume ratio of 5:2 and stir. Set the stirring speed to 150 r / min and the stirring time to 18 min to extract zirconium ions into the organic phase. After standing, separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0090] 2) Prepare an aqueous back-extraction solution containing 0.2 mol / L potassium pyrophosphate, 0.2 mol / L phosphoric acid, 0.05 mol / L methylamine, 0.02 mol / L N,N-dimethylethanol, 3.5 mol / L sulfuric acid, and 0.05 mol / L lithium sulfate. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 1:2. Set the stirring speed to 600 r / min and the stirring time to 20 min. Let it stand and separate the phases to obtain the organic back-extraction solution and the aqueous suspension containing intercalated zirconium phosphate.

[0091] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) was filtered, and the solid phase was washed twice with acetone, four times with ethanol, and twice with water. It was then dried at 45°C for 4 hours to obtain the intercalated zirconium phosphate flame retardant.

[0092] Example 7

[0093] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0094] 1) Prepare an aqueous solution containing 0.005 mol / L zirconium ions, 1.2 mol / L sodium bromide, 5 mol / L potassium iodide, 0.1 mol / L aluminum sulfate, and 0.6 mol / L hydrochloric acid. Prepare an organic phase extraction solvent by mixing the extractants didodecyl dimethyl ammonium bromide and tetramethyl ammonium fluoride with the diluent ethylene glycol tert-butyl ether at a volume ratio of 4:1:20. Mix the aqueous solution with the organic phase extraction solvent at a volume ratio of 1:1 and stir at a stirring speed of 300 r / min for 10 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0095] 2) Prepare an aqueous back-extraction solution containing 0.2 mol / L potassium hydrogen phosphate, 0.05 mol / L polyphosphoric acid, 0.001 mol / L ethanolamine, 0.001 mol / L N,N-dimethylethanol, 0.05 mol / L ammonium acetate, and 0.5 mol / L hydroboric acid. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 1:6. Set the stirring speed to 350 r / min and the stirring time to 30 min. Let it stand and separate the phases to obtain the organic back-extraction solution and the aqueous suspension containing intercalated zirconium phosphate.

[0096] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, four times with ethanol, and three times with water. It is then dried at 55°C for 1.5 hours to obtain the intercalated zirconium phosphate flame retardant.

[0097] Example 8

[0098] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0099] 1) Prepare an aqueous solution containing 1.25 mol / L zirconium ions, 3.5 mol / L ammonium thiocyanate, 0.2 mol / L potassium iodide, 0.3 mol / L ammonium sulfate, and 3.5 mol / L hydrochloric acid. Prepare an organic phase extraction solvent by mixing tetradecyltrihexylphosphonium chloride and tetraethylammonium bromide extractants with hexyl acetate at a volume ratio of 2:1:10. Mix the aqueous solution with the organic phase extraction solvent at a volume ratio of 1:4 and stir at a stirring speed of 220 r / min for 13 min to extract zirconium ions into the organic phase. Allow the mixture to stand and separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0100] 2) Prepare an aqueous back-extraction feed solution containing 1.2 mol / L phosphoric acid, 1.0 mol / L sulfuric acid, 0.05 mol / L calcium dihydrogen phosphate, 0.0055 mol / L diethanolamine, 0.001 mol / L methylamine, and 0.05 mol / L sodium fluoroborate. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction phase at a volume ratio of 3:10. Set the stirring speed to 120 r / min and the stirring time to 10 min. Let it stand, separate the phases, and obtain the organic back-extraction phase and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0101] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, three times with ethanol, and three times with water in sequence. It is then dried at 55°C for 1.5 hours to obtain the intercalated zirconium phosphate flame retardant.

[0102] Example 9

[0103] A method for preparing intercalated zirconium phosphate using a solvent extraction system includes the following steps:

[0104] 1) Prepare an aqueous solution containing 1.05 mol / L zirconium ions, 2.5 mol / L potassium bis(trifluoromethanesulfonyl)imide, 0.3 mol / L ammonium sulfate, and 2.5 mol / L nitric acid. Prepare an organic phase extraction solvent by mixing the extractant tetraoctylarsine bromide and the diluent propylene glycol butyl ether at a volume ratio of 1:4. Mix the aqueous solution and the organic phase extraction solvent at a volume ratio of 1:2 and stir. Set the stirring speed to 280 r / min and the stirring time to 15 min to extract zirconium ions into the organic phase. After standing, separate the phases to obtain the raffinate aqueous phase and the zirconium-loaded organic phase.

[0105] 2) Prepare an aqueous back-extraction solution containing 0.1 mol / L ammonium polyphosphate, 0.5 mol / L sulfuric acid, 0.02 mol / L magnesium hydrogen phosphate, and 0.001 mol / L ethylenediamine. Mix the loaded organic phase obtained in step 1) with the aqueous back-extraction solution at a volume ratio of 1:10. Set the stirring speed to 300 r / min and the stirring time to 10 min. Let it stand, separate the phases, and obtain the aqueous back-extraction organic phase and the aqueous suspension containing intercalated zirconium phosphate, respectively.

[0106] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed once with acetone, twice with ethanol, and three times with water. It is then dried at 60°C for 1.5 hours to obtain the intercalated zirconium phosphate flame retardant.

[0107] For any points not covered above, existing technologies shall apply.

[0108] Although specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, without departing from the direction of the invention or exceeding the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc., made to the above embodiments based on the technical essence of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing intercalated zirconium phosphate using a solvent extraction system, characterized in that: Includes the following steps: S1. Mix and stir the aqueous solution containing zirconium ions with the organic phase extraction solvent to extract the zirconium ions into the organic phase. Let it stand, separate the phases, and obtain the raffinate aqueous phase and the zirconium-loaded organic phase, respectively. S2. The loaded organic phase obtained in step S1 is mixed and stirred with the back-extraction aqueous solution containing phosphate, allowed to stand, and separated into phases to obtain the back-extraction organic phase and the aqueous suspension containing intercalated zirconium phosphate, respectively. S3. The aqueous suspension containing intercalated zirconium phosphate obtained in step S2 is subjected to solid-liquid separation. The solid phase is washed and dried to obtain intercalated zirconium phosphate. In step S1, the organic phase extraction solvent includes an ionic liquid extractant and a diluent; The ionic liquid extractant has molecules with An organic extractant with the following structure: A is any one of nitrogen, phosphorus, arsenic, antimony, and bismuth, all elements in Group V of the periodic table; B is any one of inorganic acid radicals, organic acid radicals, or hydroxide ions; n is the valence of the selected acid radical B; X1, X2, X3, and X4 are independently selected from any one of substituted or unsubstituted straight-chain or branched alkyl groups, or substituted or unsubstituted aryl groups; and / or, The diluent is any one or more of alkanes, aromatics, esters, ketones, ethers, alcohols, alcohol ethers, aldehydes, or amines.

2. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: The intercalated zirconium phosphate is α-zirconium phosphate or γ-zirconium phosphate.

3. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S1, the aqueous phase feed solution also contains additive I; and / or, The auxiliary agent I includes any one or more of acids and salts; and / or, The acids are selected from any one or more of inorganic acids or small molecule organic acids; and / or, The acid is selected from at least one of the following: acid, perhalic acid, hypohalic acid, nitric acid, sulfuric acid, boric acid, fluoroboric acid, thiocyanate, hydrocyanic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, cinnamic acid, or citric acid; and / or, The salts are selected from any one or more of alkali metal salts, alkaline earth metal salts, or ammonium salts; and / or, The concentration of the acids and / or salts is 0.01 mol / L to 12 mol / L; and / or, The concentration of the acids and / or salts is 0.1 mol / L to 5 mol / L; and / or, The concentration of zirconium ions is 0.0001 mol / L to 1.65 mol / L; and / or, The concentration of zirconium ions is 0.1 mol / L to 1.2 mol / L.

4. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: The volume ratio of the ionic liquid extractant to the diluent is 1:50 to 50:1; and / or, The volume ratio of the ionic liquid extractant to the diluent is 1:20 to 20:

1.

5. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S1, the volume ratio of the aqueous phase feed solution to the organic phase extraction solvent is 1:50 to 50:1; and / or, The volume ratio of the aqueous phase feed solution to the organic phase extraction solvent is 1:20 to 20:1; and / or, In step S1, the stirring speed for mixing the aqueous phase feed solution and the organic phase extraction solvent is 10 rpm to 1000 rpm. and / or, The aqueous phase feed solution and the organic phase extraction solvent are mixed and stirred at a speed of 60 rpm to 600 rpm; and / or, The mixing time is 1 min to 60 min.

6. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S2, the phosphate group is selected from any one or more of phosphoric acid, pyrophosphate, polyphosphate, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, and polyphosphate; and / or, The phosphate concentration is 0.0001 mol / L to 12 mol / L; and / or, The phosphate concentration is 0.05 mol / L to 5 mol / L.

7. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: The back-extraction aqueous feed solution in step S2 further includes auxiliary agent II; and / or, The auxiliary agent II includes any one or more of small molecule organic compounds, inorganic acids, or salts; and / or, The small molecule organic compound is selected from any one or more of amines, alcohols, alkanolamines, esters, and carboxylic acids; and / or, The amine is selected from any one or more of methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, p-aniline, or bis(trifluoromethanesulfonyl)imide; and / or, The alcohols are selected from any one or more of methanol, ethanol, ethylene glycol, and isopropanol; and / or, The alkanolamines are selected from any one or more of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanol, N,N-dibutylethanolamine, or N,N-dipropylethanolamine; and / or, The esters are selected from any one or more of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate; and / or, The carboxylic acids are selected from any one or more of formic acid, acetic acid, oxalic acid, propionic acid, or lactic acid; and / or, the inorganic acids are selected from any one or more of halogen acids, perhalogen acids, hypohalogen acids, nitric acid, sulfuric acid, phosphoric acid, boric acid, and fluoroboric acid; and / or, The salts are selected from any one or more of alkali metal salts, alkaline earth metal salts, and ammonium salts.

8. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S2, the molar ratio of phosphate to adjuvant II is 100:1 to 1:50; and / or, The molar ratio of phosphate to adjuvant II is 10:1 to 1:

10.

9. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S2, the volume ratio of the supported organic phase to the back-extraction aqueous phase is 100:1 to 1:50; and / or, the volume ratio of the supported organic phase to the back-extraction aqueous phase is 20:1 to 1:20; and / or, In step S2, the mixing speed of the supported organic phase and the back-extraction aqueous phase is 10 rpm to 1000 rpm; and / or, The mixing speed of the supported organic phase and the back-extracted aqueous phase is 10 rpm to 300 rpm; and / or, The mixing time is 1 min to 60 min.

10. The method for preparing intercalated zirconium phosphate using a solvent extraction system as described in claim 1, characterized in that: In step S3, the washing step includes washing with acetone 1-5 times, washing with ethanol 1-5 times, and washing with water 1-5 times; and / or, In step S3, the drying temperature is 30-80℃ and the time is 1-12h.

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