A cyclic process for preparing intercalated zirconium phosphate based on solvent extraction system

Abstract

The invention discloses a circulation process for preparing intercalated zirconium phosphate based on a solvent extraction system. The invention relates to the technical field of zirconium phosphate preparation. The method comprises: S1, mixing an aqueous phase feed liquid containing zirconium ions with an organic phase extraction solvent, and separating the phases; S2, mixing the organic phase with a stripping aqueous phase feed liquid containing phosphate, and separating the phases; S3, performing solid-liquid separation on the aqueous phase suspension to obtain intercalated zirconium phosphate; S4, adding zirconium ions to the residual aqueous phase to obtain A; adding an ionic liquid extractant and a diluent to the stripping organic phase to obtain B; adding phosphate ions to the aqueous phase to obtain C; S5, then using A, B and C as the above-mentioned aqueous phase feed liquid, organic phase extraction solvent, stripping aqueous phase feed liquid, and so on, and reciprocating steps S1-S3 to prepare intercalated zirconium phosphate. By utilizing the phase interface reaction of the extraction system, while generating zirconium phosphate, an ionic liquid intercalation agent is introduced into the interlayer gap thereof, effectively preventing the stacking of zirconium phosphate sheets. The circulation process has a high recycling rate for raw materials.

Description

Technical Field

[0001] The invention relates to the technical field of zirconium phosphate preparation, and in particular to a circulation process for preparing intercalated zirconium phosphate based on a solvent extraction system. Background Art

[0002] Zirconium phosphate is a two-dimensional layered material with special physical and chemical properties. There are a large number of proton acid sites between the zirconium phosphate layers, which have a strong solid acid catalytic dehydrogenation effect under high-temperature combustion conditions, which can promote the cross-linking of organic polymers into carbon and generate a graphite-like carbon layer structure. At the same time, its own two-dimensional structure has a sheet barrier effect, which can synergize with the graphite-like carbon layer to further prevent heat and mass transfer between the gas phase and the condensed phase, thereby exerting excellent flame retardant properties.

[0003] The basic principle of zirconium phosphate synthesis is to use phosphate to react with zirconium ions to produce precipitation. Traditional synthesis methods include reflux method, thermal hydrolysis method, etc. On the one hand, due to the extremely low solubility of zirconium phosphate precipitation, the precipitation reaction occurs extremely quickly; on the other hand, due to the large number of active hydroxyl groups on the surface of two-dimensional zirconium phosphate, multiple layers of synthetic zirconium phosphate are often stacked on each other, resulting in a larger particle size of the product. When directly added as a flame retardant, it has poor compatibility with the organic polymer interface and is difficult to disperse evenly.

[0004] In order to improve the interfacial compatibility between zirconium phosphate and polymer, the commonly used chemical means is to use the intercalation method to disperse the multilayer zirconium phosphate support layer and then modify the surface of the intercalated zirconium phosphate. For example, in order to realize the composite modification of zirconium phosphate by graphitized carbon nitride, Chinese patent application CN110591156A needs to pre-intercalate zirconium phosphate with small molecule amine first, and ultrasonically treat it for 6-12 hours; then, it is necessary to use surfactant as intercalation agent, and further ultrasonically treat it for 6-12 hours under heating conditions of 30-100°C to obtain the intercalated zirconium phosphate suspension. For another example, in order to realize the modification of zirconium phosphate loaded with organic phosphorus, Chinese patent application CN116376115A needs to first use highly carcinogenic substances such as tetrahydrofuran as solvents and amines as pre-intercalation agents, and treat them under the combined action of stirring and ultrasound for 2-4 hours; then, add quaternary ammonium salt intercalation agents, heat and stir for 4-6 hours, and then prepare the intercalated zirconium phosphate suspension. In the above patents, due to the strong interlayer interaction of zirconium phosphate and the narrow interlayer spacing (about 0.7nm), the intercalation process generally takes a long time, which seriously affects the production efficiency. At the same time, the intercalation agent and pre-intercalation agent used are expensive, and the actual utilization rate of the intercalation reaction is low. A large amount of remaining reagents are not recycled, which greatly increases the preparation cost of intercalated zirconium phosphate.

[0005] Therefore, it is necessary to optimize the preparation process of zirconium phosphate and prepare intercalated zirconium phosphate with a small number of layers and a large interlayer spacing in a short time; at the same time, the unreacted reagents can be recycled and reused to reduce the preparation cost of intercalated zirconium phosphate, which has important research significance for the application or subsequent modification of zirconium phosphate flame retardants. Summary of the invention

[0006] The purpose of the present invention is to address the above-mentioned shortcomings of the prior art and propose a cyclic process technology for preparing intercalated zirconium phosphate, which is time-saving, efficient, material-saving and environmentally friendly. The intercalated zirconium phosphate prepared has a small crystal particle size, a small number of layers, a large interlayer spacing, strong interface compatibility with polymers, and wide applicability for surface modification.

[0007] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system of the present invention comprises the following steps:

[0008] S1, mixing and stirring the aqueous phase liquid containing zirconium ions with an organic phase extraction solvent to extract the zirconium ions into the organic phase, standing, and phase separation to obtain a raffinate aqueous phase and an organic phase loaded with zirconium ions; the organic phase extraction solvent includes an ionic liquid extractant and a diluent;

[0009] S2, mixing the loaded organic phase obtained in step S1 with the stripping aqueous phase feed liquid containing phosphate, standing, and phase separation to obtain the stripping organic phase and the aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0010] S3, performing solid-liquid separation on the aqueous suspension containing intercalated zirconium phosphate obtained in step S2 to obtain an aqueous phase and a solid phase, washing and drying the solid phase to obtain intercalated zirconium phosphate;

[0011] S4, adding zirconium ions to the raffinate aqueous phase in step S1 to obtain a circulating aqueous phase feed liquid A; adding an ionic liquid extractant and a diluent to the stripping organic phase in step S2 to obtain a circulating organic phase extraction solvent B; adding phosphate ions to the aqueous phase obtained in step S3 to obtain a circulating stripping aqueous phase feed liquid C;

[0012] S5, then use the circulating aqueous phase feed liquid A, circulating organic phase extraction solvent B and circulating stripping aqueous phase feed liquid C in step S4 as the aqueous phase feed liquid, organic phase extraction solvent and stripping aqueous phase feed liquid in steps S1-S3, and repeat steps S1-S3 to obtain intercalated zirconium phosphate;

[0013] Steps S1-S5 are repeated in this way to prepare intercalated zirconium phosphate.

[0014] Furthermore, the intercalated zirconium phosphate is α-zirconium phosphate or γ-zirconium phosphate.

[0015] Furthermore, in step S1, the aqueous phase feed liquid further contains an auxiliary agent I, and in step S4, the auxiliary agent I needs to be added to the raffinate aqueous phase; and\or,

[0016] The auxiliary agent I includes any one or more of acids and salts; and\or,

[0017] The acid is selected from any one or more of inorganic acids or small molecule organic acids; and\or,

[0018] The acid is selected from at least one of acid, perhalic acid, hypohalous acid, nitric acid, sulfuric acid, boric acid, fluoroboric acid, thiocyanic acid, hydrocyanic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, cinnamic acid or citric acid; and\or,

[0019] The salt is selected from any one or more of alkali metal salts, alkaline earth metal salts or ammonium salts; and\or,

[0020] The concentration of the acid and / or salt is 0.01 mol / L to 12 mol / L; and / or,

[0021] The concentration of the acid and / or salt is 0.1 mol / L to 5 mol / L; and / or,

[0022] The concentration of the zirconium ion is 0.0001 mol / L to 1.65 mol / L; and\or,

[0023] The concentration of the zirconium ions is 0.1 mol / L to 1.2 mol / L.

[0024] Furthermore, the ionic liquid extractant is a molecule having

[0025] An organic extractant of structure, wherein the element A is any one of nitrogen, phosphorus, arsenic, antimony and bismuth of the main group V of the periodic table; B is any one of inorganic acid ions, organic acid ions or hydroxide ions; n is the valence of the selected acid ion B; X1, X2, X3 and X4 are independently selected from any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted aryl; and\or,

[0026] The diluent is any one or more of alkanes, aromatic hydrocarbons, esters, ketones, ethers, alcohols, alcohol ethers, aldehydes or amines; and\or,

[0027] The volume ratio of the ionic liquid extractant to the diluent is 1:50 to 50:1; and\or,

[0028] The volume ratio of the ionic liquid extractant to the diluent is 1:20 to 20:1.

[0029] Furthermore, in step S1, the volume ratio of the aqueous phase feed liquid to the organic phase extraction solvent is 1:50 to 50:1; and\or,

[0030] The volume ratio of the aqueous phase feed liquid to the organic phase extraction solvent is 1:20 to 20:1; and\or,

[0031] In step S1, the aqueous phase feed liquid and the organic phase extraction solvent are mixed and stirred at a speed of 10 rpm to 1000 rpm; and\or,

[0032] The mixing speed of the aqueous phase feed liquid and the organic phase extraction solvent is 60 rpm to 600 rpm; and\or,

[0033] The mixing and stirring time is 1 min to 60 min.

[0034] Further, in step S2, the phosphate radical is selected from any one or more of phosphoric acid, pyrophosphate, polyphosphate, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate and polyphosphate; and\or,

[0035] The phosphate concentration is 0.0001 mol / L to 12 mol / L; and\or,

[0036] The phosphate concentration is 0.05 mol / L to 5 mol / L.

[0037] Furthermore, the stripping aqueous phase feed liquid in step S2 also includes auxiliary agent II, and in step S4, auxiliary agent II is also required to be added to the aqueous phase obtained in step S3; and\or,

[0038] The auxiliary agent II includes any one or more of small molecule organic matter, inorganic acid or salt; and\or,

[0039] The small molecule organic compound is selected from any one or more of amines, alcohols, alcoholamines, esters, and carboxylic acids; and\or,

[0040] The amine is selected from any one or more of methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, p-aniline or bistrifluoromethanesulfonyl imide; and\or,

[0041] The alcohol is selected from any one or more of methanol, ethanol, ethylene glycol, and isopropanol; and\or,

[0042] The alcoholamine is selected from any one or more of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanol, N,N-dibutylethanolamine or N,N-dipropylethanolamine; and\or,

[0043] 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,

[0044] The carboxylic acid is selected from any one or more of formic acid, acetic acid, oxalic acid, propionic acid or lactic acid; and\or, the inorganic acid is selected from any one or more of halogen acid, perhalogen acid, hypohalogen acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, fluoroboric acid; and\or,

[0045] The salt is selected from any one or more of alkali metal salts, alkaline earth metal salts and ammonium salts.

[0046] Further, in step S2, the molar ratio of the phosphate to the auxiliary agent II is 100:1 to 1:50; and\or,

[0047] The molar ratio of the phosphate radical to the auxiliary agent II is 10:1 to 1:10.

[0048] Further, in step S2, the volume ratio of the loaded organic phase to the stripping aqueous phase is 100:1 to 1:50; and\or, the volume ratio of the loaded organic phase to the stripping aqueous phase is 20:1 to 1:20; and\or,

[0049] In step S2, the loading organic phase and the stripping water phase are mixed and stirred at a speed of 10 rpm to 1000 rpm; and\or,

[0050] The loading organic phase and the stripping water phase are mixed and stirred at a speed of 10 rpm to 300 rpm; and\or,

[0051] The mixing and stirring time is 1 min to 60 min.

[0052] Further, in step S3, the washing step is washing with acetone 1 to 5 times, washing with ethanol 1 to 5 times, and washing with water 1 to 5 times; and\or,

[0053] In step S3, the drying temperature is 30-80°C and the time is 1-12 hours.

[0054] The principle of the present invention is:

[0055] 1) The ionic liquid extractant can extract zirconium ions and auxiliary agent I into the organic phase in the form of an extractant. In the organic phase, the structure and properties of the zirconium-containing extractant are relatively stable. When the loaded organic phase is reversely extracted, the zirconium ions in the extractant pass through the interface of the two phases and migrate to the stripping water phase. The mass transfer process is slow. At the interface of the two phases, the contact reaction rate of zirconium ions and phosphate ions in the stripping water phase is greatly reduced, effectively avoiding the agglomeration of zirconium phosphate crystal particles.

[0056] 2) At the interface between the two phases, the ionic liquid in the organic phase extraction solvent can also be used as an intercalation agent, and the acids and salts in the aqueous phase feed liquid can be used as auxiliary agent I. Auxiliary agent I not only helps to improve the extraction efficiency and complex stability of zirconium ions by the organic phase extraction solvent, but also can be used as an auxiliary intercalation agent in the process of zirconium phosphate generation; small molecular organic matter, inorganic salts, inorganic acids, etc. in the stripping aqueous phase feed liquid can be used as auxiliary agent II, and auxiliary agent II is mainly used as an auxiliary intercalation agent for zirconium phosphate. The intercalation agent and the auxiliary intercalation agent quickly enter the gap between the zirconium phosphate sheets, effectively preventing the stacking of the zirconium phosphate sheets, so that the number of intercalated zirconium phosphate sheets prepared is small and the interlayer spacing is large.

[0057] 3) During the formation of intercalated zirconium phosphate, the actual consumption rate of the ionic liquid, additive I and additive II is low and the surplus is large. After being recovered by liquid-liquid separation or solid-liquid separation operation, they can be recycled with a little addition and supplementation.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] 1) The complex stability and interfacial mass transfer process of the extraction system are utilized to fully slow down the contact reaction rate between zirconium ions and phosphate ions, thereby effectively reducing the crystal particle size of zirconium phosphate.

[0060] 2) By utilizing the interfacial reaction of the extraction system, while generating zirconium phosphate, ionic liquid intercalants and auxiliary intercalants are introduced into the interlayer gaps, effectively preventing the stacking of zirconium phosphate sheets. The prepared intercalated phosphate sheets have a small number of layers, strong interface compatibility, and wide applicability of surface modification.

[0061] 3) In the extraction system, the formation reaction of zirconium phosphate and the intercalation reaction proceed simultaneously, which greatly shortens the preparation time of intercalated zirconium phosphate and improves the synthesis efficiency.

[0062] 4) The process technology route described in the present invention can realize the efficient recovery and recycling of the reagents not involved in the reaction during the preparation of the intercalated zirconium phosphate, significantly improve the utilization rate of raw materials, and reduce the preparation cost of the intercalated zirconium phosphate. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 This is a schematic diagram of the cyclic process for preparing intercalated zirconium phosphate according to the present invention;

[0064] Figure 2 This is a transmission electron microscope (TEM) photograph of the intercalated zirconium phosphate prepared in Example 4. DETAILED DESCRIPTION

[0065] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0066] Example 1

[0067] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0068] 1) preparing an aqueous phase feed liquid containing 0.5 mol / L zirconium ion, 3 mol / L sulfuric acid, and 0.6 mol / L potassium sulfate, dissolving the extractant heptyltriethylammonium chloride and the diluent n-hexane in a volume ratio of 1:5 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:3, setting the stirring speed to 100 r / min, and the stirring time to 12 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0069] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 5:2, setting the stirring speed to 120 r / min, the stirring time to 20 min, standing, and phase separation to obtain a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate, respectively;

[0070] 3) filtering the aqueous suspension containing intercalated zirconium phosphate obtained in step 2) to obtain a solid phase and an aqueous phase, washing the solid phase with acetone twice, ethanol twice, and water twice, and drying at 60° C. for 6 hours to obtain an intercalated zirconium phosphate flame retardant;

[0071] 4) adding zirconium ions, sulfuric acid and potassium sulfate to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding an extractant, heptyltriethylammonium chloride, and a diluent, n-hexane, to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding ammonium phosphate, phosphoric acid, ethylenediamine and potassium chloride to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0072] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0073] Example 2

[0074] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0075] 1) preparing an aqueous phase feed liquid containing 1 mol / L zirconium ions, 2 mol / L perchloric acid, and 0.6 mol / L sodium iodide, dissolving the extractant dodecyltrimethylammonium nitrate and the diluent isoamyl alcohol in a volume ratio of 1:10 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 10:1, setting the stirring speed to 150 r / min, and the stirring time to 20 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0076] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase at a volume ratio of 10:1, setting the stirring speed to 100 r / min, the stirring time to 30 min, standing, and phase separation to obtain a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate, respectively;

[0077] 3) filtering the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), washing the solid phase with acetone once, ethanol once, and water twice, and drying at 80° C. for 3 h to obtain an intercalated zirconium phosphate flame retardant;

[0078] 4) adding zirconium ions, perchloric acid, and sodium iodide to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding an extractant, dodecyltrimethylammonium nitrate, and a diluent, isoamyl alcohol to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding phosphoric acid, methylamine, ethylenediamine, and ammonium chloride to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0079] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0080] Example 3

[0081] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0082] 1) preparing an aqueous phase feed liquid containing 0.75 mol / L zirconium ion, 3 mol / L sodium fluoroborate, and 2.2 mol / L sulfuric acid, dissolving the extractant dodecyl dimethyl benzyl ammonium fluoride and the diluent xylene in a volume ratio of 1:3 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 9:1, setting the stirring speed to 300 r / min, and the stirring time to 10 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0083] 2) preparing a stripping aqueous phase feed liquid 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 3:2, setting the stirring speed to 200 r / min, the stirring time to 30 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate, respectively;

[0084] 3) filtering the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), washing the solid phase with acetone once, ethanol twice, and water three times, and drying at 70° C. for 3 h to obtain an intercalated zirconium phosphate flame retardant;

[0085] 4) adding zirconium ions, sodium fluoroborate and sulfuric acid to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding an extractant, dodecyldimethylbenzylammonium fluoride, and a diluent, xylene, to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding potassium pyrophosphate, methylamine, ethylene glycol, ethyl acetate and formic acid to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0086] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0087] Example 4

[0088] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0089] 1) preparing an aqueous phase feed liquid containing 0.9 mol / L zirconium ions, 3.5 mol / L sodium thiocyanate, and 4 mol / L hydrochloric acid, dissolving the extractant dihexyldimethylammonium iodate and the diluent amyl acetate in a volume ratio of 2:9 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:1, setting the stirring speed to 200 r / min, and the stirring time to 20 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0090] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase at a volume ratio of 20:1, setting the stirring speed to 150 r / min, the stirring time to 30 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0091] 3) filtering the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), washing the solid phase with acetone once, ethanol once, and water three times, and drying at 75° C. for 3 h to obtain an intercalated zirconium phosphate flame retardant;

[0092] 4) adding zirconium ions, sodium thiocyanate and hydrochloric acid to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding an extractant dihexyldimethylammonium iodate and a diluent amyl acetate to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding potassium hydrogen phosphate, aniline, diethanolamine, acetic acid and hydrochloric acid to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0093] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0094] Figure 2 This is a transmission electron microscope (TEM) photograph of the intercalated zirconium phosphate prepared in Example 4. Figure 2 As shown, the size of zirconium phosphate is between 150nm-230nm.

[0095] Example 5

[0096] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0097] 1) preparing an aqueous phase feed liquid containing 1.0 mol / L zirconium ions, 3 mol / L hydrocyanic acid, and 1.2 mol / L lithium bromide, dissolving the extractant tetrabutylammonium hydroxide and the diluent petroleum ether in a volume ratio of 1:15 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:12, setting the stirring speed to 450 r / min, and the stirring time to 8 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0098] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 1:3, setting the stirring speed to 60 r / min, the stirring time to 12 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0099] 3) Filter the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), wash the solid phase with acetone twice, ethanol once, and water twice, and dry at 80° C. for 1.5 h to obtain an intercalated zirconium phosphate flame retardant.

[0100] 4) adding zirconium ions, hydrocyanic acid and lithium bromide to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding tetrabutylammonium hydroxide as an extractant and petroleum ether as a diluent to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding ammonium dihydrogen phosphate, p-aniline, triethanolamine and sulfuric acid to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0101] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0102] Example 6

[0103] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0104] 1) preparing an aqueous phase feed liquid containing 0.25 mol / L zirconium ion, 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, dissolving the extractant tetrabutylammonium sulfonate and the diluents ethanol and isoamyl alcohol in a volume ratio of 2:2:10 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 5:2, setting the stirring speed to 150 r / min, and the stirring time to 18 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0105] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 1:2, setting the stirring speed to 600 r / min, the stirring time to 20 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0106] 3) Filter the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), wash the solid phase with acetone twice, ethanol four times, and water twice, and dry it at 45° C. for 4 hours to obtain an intercalated zirconium phosphate flame retardant.

[0107] 4) adding zirconium ions, sulfuric acid, lactic acid, lithium chloride and magnesium sulfate to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding tetrabutylammonium sulfonate as an extractant and ethanol and isoamyl alcohol as diluents to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding potassium pyrophosphate, phosphoric acid, methylamine, N,N-dimethylethanol, sulfuric acid and lithium sulfate to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0108] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0109] Example 7

[0110] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0111] 1) preparing an aqueous phase feed liquid containing 0.005 mol / L zirconium ion, 1.2 mol / L sodium bromide, 5 mol / L potassium iodide, 0.1 mol / L aluminum sulfate, and 0.6 mol / L hydrochloric acid, dissolving the extractant didodecyl dimethyl ammonium bromide and tetramethyl ammonium fluoride and the diluent ethylene glycol tert-butyl ether in a volume ratio of 4:1:20 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:1, setting the stirring speed to 300 r / min, and the stirring time to 10 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0112] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 1:6, setting the stirring speed to 350 r / min, the stirring time to 30 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0113] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed with acetone once, ethanol four times, and water three times in sequence, and dried at 55° C. for 1.5 h to obtain an intercalated zirconium phosphate flame retardant.

[0114] 4) adding zirconium ions, sodium bromide, potassium iodide, aluminum sulfate, and hydrochloric acid to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding extractants didodecyldimethylammonium bromide and tetramethylammonium fluoride and diluent ethylene glycol tert-butyl ether to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding potassium hydrogen phosphate, polyphosphoric acid, ethanolamine, N,N-dimethylethanol, ammonium acetate, and hydroboric acid to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0115] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0116] Example 8

[0117] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0118] 1) preparing an aqueous phase feed liquid 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, dissolving the extractant tetradecyl trihexyl phosphonium chloride and tetraethyl ammonium bromide and the diluent hexyl acetate in a volume ratio of 2:1:10 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:4, setting the stirring speed to 220 r / min, and the stirring time to 13 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0119] 2) preparing a stripping aqueous phase 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 3:10, setting the stirring speed to 120 r / min, the stirring time to 10 min, standing, phase separation, and obtaining a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate respectively;

[0120] 3) Filter the aqueous suspension containing intercalated zirconium phosphate obtained in step 2), wash the solid phase with acetone once, ethanol three times, and water three times, and dry at 55° C. for 1.5 h to obtain an intercalated zirconium phosphate flame retardant.

[0121] 4) adding zirconium ions, ammonium thiocyanate, potassium iodide, ammonium sulfate and hydrochloric acid to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding an extractant of tetradecyltrihexylphosphonium chloride and tetraethylammonium bromide and a diluent of hexyl acetate to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding phosphoric acid, sulfuric acid, calcium dihydrogen phosphate, diethanolamine, methylamine and sodium fluoroborate to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0122] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0123] Example 9

[0124] A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system comprises the following steps:

[0125] 1) preparing an aqueous phase feed liquid 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, dissolving the extractant tetraoctyl arsenic bromide and the diluent propylene glycol butyl ether in a volume ratio of 1:4 to prepare an organic phase extraction solvent, mixing the aqueous phase feed liquid and the organic phase extraction solvent in a volume ratio of 1:2, setting the stirring speed to 280 r / min, and the stirring time to 15 min, so that the zirconium ions are extracted into the organic phase, standing, and phase separation, respectively obtaining a raffinate aqueous phase and an extracted organic phase loaded with zirconium ions;

[0126] 2) preparing a stripping aqueous phase feed 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, mixing the loaded organic phase obtained in step 1) with the stripping aqueous phase in a volume ratio of 1:10, setting the stirring speed to 300 r / min, the stirring time to 10 min, standing, and phase separation to obtain a stripping organic phase and an aqueous phase suspension containing intercalated zirconium phosphate, respectively;

[0127] 3) The aqueous suspension containing intercalated zirconium phosphate obtained in step 2) is filtered, and the solid phase is washed with acetone once, ethanol twice, and water three times in sequence, and dried at 60° C. for 1.5 h to obtain an intercalated zirconium phosphate flame retardant.

[0128] 4) adding zirconium ions, potassium bis(trifluoromethanesulfonyl)imide, ammonium sulfate and nitric acid to the raffinate aqueous phase in step 1) to obtain a circulating aqueous phase feed liquid A; adding tetraoctyl arsenic bromide as an extractant and propylene glycol butyl ether as a diluent to the stripping organic phase in step 2) to obtain a circulating organic phase extraction solvent B; adding ammonium polyphosphate, sulfuric acid, magnesium hydrogen phosphate and ethylenediamine to the aqueous phase obtained in step 3) to obtain a circulating stripping aqueous phase feed liquid C;

[0129] 5) Then, the circulating aqueous phase feed liquid A, the circulating organic phase extraction solvent B and the circulating stripping aqueous phase feed liquid C in step 4) are used as the aqueous phase feed liquid, the organic phase extraction solvent and the stripping aqueous phase feed liquid in steps 1) to 3), and steps S1 to S3 are repeated to obtain intercalated zirconium phosphate.

[0130] For matters not mentioned above, the prior art applies.

[0131] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art to which the present invention belongs may make various modifications or supplements to the specific embodiments described or replace them in a similar manner, but they will not deviate from the direction of the present invention or exceed the scope defined by the attached claims. Those skilled in the art should understand that any modification, equivalent substitution, improvement, etc. made to the above embodiments based on the technical essence of the present invention shall be included in the protection scope of the present invention.

Claims

1. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system, characterized in that: The following steps are involved: S1, mixing and stirring the aqueous phase liquid containing zirconium ions with an organic phase extraction solvent to extract the zirconium ions into the organic phase, standing, and phase separation to obtain a raffinate aqueous phase and an organic phase loaded with zirconium ions; the organic phase extraction solvent includes an ionic liquid extractant and a diluent; S2, mixing the loaded organic phase obtained in step S1 with the stripping aqueous phase feed liquid containing phosphate, standing, and phase separation to obtain the stripping organic phase and the aqueous phase suspension containing intercalated zirconium phosphate respectively; S3, performing solid-liquid separation on the aqueous suspension containing intercalated zirconium phosphate obtained in step S2 to obtain an aqueous phase and a solid phase, washing and drying the solid phase to obtain intercalated zirconium phosphate; S4, adding zirconium ions to the raffinate aqueous phase in step S1 to obtain a circulating aqueous phase feed liquid A; adding an ionic liquid extractant and a diluent to the stripping organic phase in step S2 to obtain a circulating organic phase extraction solvent B; adding phosphate ions to the aqueous phase obtained in step S3 to obtain a circulating stripping aqueous phase feed liquid C; S5, then use the circulating aqueous phase feed liquid A, circulating organic phase extraction solvent B and circulating stripping aqueous phase feed liquid C in step S4 as the aqueous phase feed liquid, organic phase extraction solvent and stripping aqueous phase feed liquid in steps S1-S3, and repeat steps S1-S3 to obtain intercalated zirconium phosphate; Steps S1-S5 are repeated in this way to prepare intercalated zirconium phosphate; Ionic liquid extractants are molecules with An organic extractant of structure, wherein the element A is any one of nitrogen, phosphorus and arsenic of the main group V of the periodic table; B is any one of inorganic acid radical ions, organic acid radical ions or hydroxide ions; n is the valence of the selected acid radical ion B; X1, X2, X3 and X4 are independently selected from any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted aryl; The diluent is any one or more of alkanes, aromatic hydrocarbons, esters, ketones, ethers, alcohols, alcohol ethers, aldehydes or amines.

2. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: The intercalated zirconium phosphate is α-zirconium phosphate or γ-zirconium phosphate.

3. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: In step S1, the aqueous phase feed liquid further contains an auxiliary agent I, and in step S4, the auxiliary agent I needs to be added to the raffinate aqueous phase; and\or, The auxiliary agent I includes any one or more of acids and salts; and\or, The acid is 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 acid, perhalic acid, hypohalous acid, nitric acid, sulfuric acid, boric acid, fluoroboric acid, thiocyanic acid, hydrocyanic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, cinnamic acid or citric acid; and\or, The salt is selected from any one or more of alkali metal salts, alkaline earth metal salts or ammonium salts; and\or, The concentration of the acid and / or salt is 0.01 mol / L to 12 mol / L; and / or, The concentration of the acid and / or salt is 0.1 mol / L to 5 mol / L; and / or, The concentration of the zirconium ion is 0.0001 mol / L to 1.65 mol / L; and\or, The concentration of the zirconium ions is 0.1 mol / L to 1.2 mol / L.

4. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed 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. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: In step S1, the volume ratio of the aqueous phase feed liquid to the organic phase extraction solvent is 1:50 to 50:1; and\or, The volume ratio of the aqueous phase feed liquid to the organic phase extraction solvent is 1:20 to 20:1; and\or, In step S1, the aqueous phase feed liquid and the organic phase extraction solvent are mixed and stirred at a speed of 10 rpm to 1000 rpm; and\or, The aqueous phase feed liquid 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 1min~60min.

6. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: In step S2, the phosphate radical 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~5 mol / L.

7. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: The stripping aqueous phase feed liquid in step S2 also includes auxiliary agent II, and in step S4, auxiliary agent II is also added to the aqueous phase obtained in step S3; and\or, The auxiliary agent II includes any one or more of small molecule organic matter, inorganic acid or salt; and\or, The small molecule organic compound is selected from any one or more of amines, alcohols, alcoholamines, esters, and carboxylic acids; and\or, The amine is selected from any one or more of methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, p-aniline or bistrifluoromethanesulfonyl imide; and\or, The alcohol is selected from any one or more of methanol, ethanol, ethylene glycol, and isopropanol; and\or, The alcoholamine is 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 acid is selected from any one or more of formic acid, acetic acid, oxalic acid, propionic acid or lactic acid; and\or, the inorganic acid is selected from any one or more of halogen acid, perhalogen acid, hypohalogen acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, fluoroboric acid; and\or, The salt is selected from any one or more of alkali metal salts, alkaline earth metal salts and ammonium salts.

8. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: In step S2, the molar ratio of the phosphate to the auxiliary agent II is 100:1 to 1:50; and\or, The molar ratio of the phosphate radical to the auxiliary agent II is 10:1 to 1:

10.

9. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system as claimed in claim 1, characterized in that: In step S2, the volume ratio of the loaded organic phase to the stripping aqueous phase is 100:1 to 1:50; and\or, the volume ratio of the loaded organic phase to the stripping aqueous phase is 20:1 to 1:20; and\or, In step S2, the loaded organic phase and the stripping water phase are mixed and stirred at a speed of 10 rpm to 1000 rpm; and\or, The loading organic phase and the stripping water phase are mixed and stirred at a speed of 10 rpm to 300 rpm; and\or, The mixing time is 1min~60min.

10. A cyclic process for preparing intercalated zirconium phosphate based on a solvent extraction system according to claim 1, characterized in that: In step S3, the washing step is washing with acetone 1 to 5 times, washing with ethanol 1 to 5 times, and washing with water 1 to 5 times; and\or, In step S3, the drying temperature is 30-80°C and the drying time is 1-12 hours.

Images