A method for preparing sodium hexanitroate

Abstract

This application provides a method for preparing sodium hexanitrobenzene, belonging to the field of electronic chemical technology. The method involves mixing and reacting an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a co-solvent, and an organic diluent. The aqueous phase is separated to prepare the organic phase. Through two-phase reaction and ion exchange, the Co... 2+ With NO2 ‑ The formed complex anion [Co(NO2)3] ‑ Or [Co(NO2)4] 2‑ Extraction is performed into the organic phase to improve raw material utilization. Then, under acidic conditions, the organic phase, oxidant, and sodium nitrite aqueous solution 2 are mixed to carry out an oxidation reaction, oxidizing the complex anion to generate [Co(NO2)4]. ‑ Through ion exchange, [Co(NO2)4] ‑ Sodium hexanitrobenzene is prepared by transferring it to an aqueous phase, separating the aqueous phase, and crystallizing it. At the same time, adjusting the process parameters can significantly improve the yield and purity of sodium hexanitrobenzene.

Description

Technical Field

[0001] This application relates to the field of electronic chemicals technology, and in particular to a method for preparing sodium hexanitrobenzene. Background Technology

[0002] Sodium hexanitrocobaltate (Na3[Co(NO2)6]), also known as sodium cobalt nitrite or sodium hexanitrocobalt(III)ate, is an orange to yellowish-brown crystal or powder. It is named for its anionic ligand [Co(NO2)6]. 3- With S6 symmetry, sodium hexanitrobenzene possesses certain ion-binding capacity, redox activity, and structural tunability, and has broad application prospects in fields such as analytical chemistry, emergency medicine, and materials science.

[0003] Traditional methods for preparing sodium hexanitrocobaltate include simplified solution method, air oxidation method and hydrogen peroxide oxidation method, which have drawbacks such as low yield and purity, high consumption of raw materials such as sodium nitrite and large amount of high-salt wastewater generated. Summary of the Invention

[0004] Therefore, the main objective of this application is to provide a method for preparing sodium hexanitrocobaltate to improve the yield and purity of sodium hexanitrocobaltate.

[0005] The first aspect of this application provides a method for preparing sodium hexanitrobenzene, comprising the following steps:

[0006] Sodium nitrite aqueous solution 1, divalent cobalt salt, oil-soluble quaternary ammonium salt extractant, co-solvent and organic diluent are mixed and reacted for 10-50 min, the aqueous phase is separated and the organic phase is prepared;

[0007] Under acidic conditions, an organic phase, an oxidant, and an aqueous solution of sodium nitrite 2 are mixed to carry out an oxidation reaction, the aqueous phase is separated, and the aqueous phase is crystallized to prepare sodium hexanitrobenzene.

[0008] The mass ratio of the sodium nitrite aqueous solution 1 to the divalent cobalt salt is (5.0~25.0):1;

[0009] The concentration of the sodium nitrite aqueous solution 1 is 5.0~10.0 mol / L;

[0010] The oil-soluble quaternary ammonium salt extractant has the structural formula R3CH3NCl; wherein R is octyl and / or decyl;

[0011] The concentration of the sodium nitrite aqueous solution 2 is 1.0~5.0 mol / L;

[0012] The mass ratio of the organic phase to the sodium nitrite aqueous solution 2 is 1:(0.3~1);

[0013] The mass ratio of the sodium nitrite aqueous solution 2 to the oxidant is 1:(0.2~0.8);

[0014] Crystallization treatment conditions include vacuum concentration crystallization or solvent crystallization;

[0015] The conditions for vacuum concentration and crystallization include a concentration temperature of 50℃~70℃.

[0016] In some embodiments, the mass ratio of sodium nitrite aqueous solution 1, oil-soluble quaternary ammonium salt extractant, co-solvent, and organic diluent is 1:(0.1~0.4):(0.02~0.08):(0.1~0.4).

[0017] In some embodiments, the oil-soluble quaternary ammonium salt extractant includes brands Aliquat 336 and / or N263.

[0018] In some embodiments, the divalent cobalt salt includes one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, and cobalt acetate tetrahydrate;

[0019] The co-solvent includes isopropanol;

[0020] The organic diluent includes sulfonated kerosene.

[0021] In some implementations, the temperature of the mixing reaction is 20-70°C.

[0022] In some embodiments, the oxidant includes benzoquinone oxidants.

[0023] In some embodiments, the benzoquinone oxidant includes one or more of ortho-benzoquinone, p-benzoquinone, and 1,4-naphthoquinone.

[0024] In some implementations, acidic conditions include providing an acidic environment using hydrochloric acid.

[0025] In some embodiments, the step of mixing the organic phase, oxidant, and sodium nitrite aqueous solution 2 under acidic conditions to carry out the oxidation reaction includes:

[0026] An oxidation reaction is carried out by mixing hydrochloric acid aqueous solution, organic phase, oxidant and sodium nitrite aqueous solution 2;

[0027] The hydrochloric acid aqueous solution contains 30-38% hydrochloric acid by mass.

[0028] In some embodiments, the mass ratio of the sodium nitrite aqueous solution 2, the oxidant, and the hydrochloric acid is 1:(0.2~0.8):(0.1~0.8).

[0029] In some embodiments, the oxidation reaction conditions include: a reaction temperature of 20-70°C and a reaction time of 50-300 min.

[0030] In some embodiments, the conditions for vacuum concentration crystallization include a vacuum pressure of -0.04 to -0.08 MPa.

[0031] In some embodiments, the crystallization process is carried out under solvent crystallization conditions, which include mixing ethanol and an aqueous phase, aging the mixture, and then crystallizing.

[0032] In some embodiments, the volume ratio of aqueous phase to ethanol is 1:(3~10).

[0033] In some implementations, the aging conditions include an aging time of 30 to 50 minutes.

[0034] In some embodiments, washing and drying are also included after the crystallization process.

[0035] In some embodiments, the solvents used for washing include diethyl ether and / or ethanol;

[0036] In some implementations, drying includes vacuum drying.

[0037] In some embodiments, the vacuum drying conditions include: vacuum pressure of -0.5 to -0.8 MPa, drying temperature of 20 to 70°C, and drying time of 1 to 4 hours.

[0038] Compared with traditional technologies, this application has at least the following beneficial effects:

[0039] This application involves mixing and reacting an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a cosolvent, and an organic diluent. The aqueous phase is then separated to prepare the organic phase. Through a two-phase reaction and ion exchange, the Co... 2+ With NO2 - The formed complex anion [Co(NO2)3] - Or [Co(NO2)4] 2- Extraction is performed into the organic phase to improve raw material utilization. Then, under acidic conditions, the organic phase, oxidant, and sodium nitrite aqueous solution 2 are mixed to carry out an oxidation reaction, oxidizing the complex anion to generate [Co(NO2)4]. - Through ion exchange, [Co(NO2)4] - Sodium hexanitrocobaltate is prepared by transferring it to an aqueous phase, separating the aqueous phase, and crystallizing it. At the same time, adjusting the process parameters can significantly improve the yield and purity of sodium hexanitrocobaltate. Attached Figure Description

[0040] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0041] Figure 1 SEM image of sodium hexanitrobenzene prepared in Example 1;

[0042] Figure 2 XRD patterns of sodium hexanitrocobaltate and sodium hexanitrocobaltate standard prepared in Example 1. Detailed Implementation

[0043] The present application will be further described in detail below with reference to the embodiments and examples. These embodiments and examples are only for illustrating the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. In addition, numerous specific details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0045] To address the issues of low yield and low purity in current methods for preparing sodium hexanitrobenzene, this application involves mixing and reacting an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a co-solvent, and an organic diluent. The aqueous phase is then separated to prepare the organic phase. Through a two-phase reaction and ion exchange, the Co... 2+ With NO2 - The formed complex anion [Co(NO2)3] - Or [Co(NO2)4] 2- Extraction is performed into the organic phase to improve raw material utilization. Then, under acidic conditions, the organic phase, oxidant, and sodium nitrite aqueous solution 2 are mixed to carry out an oxidation reaction, oxidizing the complex anion to generate [Co(NO2)4]. -Through ion exchange, [Co(NO2)4] - Sodium hexanitrocobaltate is prepared by transferring it to an aqueous phase, separating the aqueous phase, and crystallizing it. At the same time, adjusting the process parameters can significantly improve the yield and purity of sodium hexanitrocobaltate.

[0046] The first aspect of this application provides a method for preparing sodium hexanitrobenzene, comprising the following steps:

[0047] Sodium nitrite aqueous solution 1, divalent cobalt salt, oil-soluble quaternary ammonium salt extractant, co-solvent and organic diluent are mixed and reacted for 10-50 min, the aqueous phase is separated and the organic phase is prepared;

[0048] Under acidic conditions, an organic phase, an oxidant, and an aqueous solution of sodium nitrite 2 are mixed to carry out an oxidation reaction, the aqueous phase is separated, and the aqueous phase is crystallized to prepare sodium hexanitrobenzene.

[0049] The mass ratio of the sodium nitrite aqueous solution 1 to the divalent cobalt salt is (5.0~25.0):1;

[0050] The concentration of the sodium nitrite aqueous solution 1 is 5.0~10.0 mol / L;

[0051] The oil-soluble quaternary ammonium salt extractant has the structural formula R3CH3NCl; wherein R is octyl and / or decyl;

[0052] The concentration of the sodium nitrite aqueous solution 2 is 1.0~5.0 mol / L;

[0053] The mass ratio of the organic phase to the sodium nitrite aqueous solution 2 is 1:(0.3~1);

[0054] The mass ratio of the sodium nitrite aqueous solution 2 to the oxidant is 1:(0.2~0.8);

[0055] Crystallization treatment conditions include vacuum concentration crystallization or solvent crystallization;

[0056] The conditions for vacuum concentration and crystallization include a concentration temperature of 50℃~70℃.

[0057] This application involves mixing and reacting an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a cosolvent, and an organic diluent. The aqueous phase is then separated to prepare the organic phase. Through a two-phase reaction and ion exchange, the Co... 2+ With NO2 - The formed complex anion [Co(NO2)3] - Or [Co(NO2)4] 2-Extraction is performed into the organic phase to improve raw material utilization. Then, under acidic conditions, the organic phase, oxidant, and sodium nitrite aqueous solution 2 are mixed to carry out an oxidation reaction, oxidizing the complex anion to generate [Co(NO2)4]. - Through ion exchange, [Co(NO2)4] - Sodium hexanitrocobaltate is prepared by transferring it to an aqueous phase, separating the aqueous phase, and crystallizing it. At the same time, adjusting the process parameters can significantly improve the yield and purity of sodium hexanitrocobaltate.

[0058] In some embodiments, the concentration of the sodium nitrite aqueous solution 1 is 5.0~10.0 mol / L, which can be 5.0 mol / L, 6.0 mol / L, 7.0 mol / L, 8.0 mol / L, 9.0 mol / L or 10.0 mol / L.

[0059] In some embodiments, the mass ratio of the sodium nitrite aqueous solution 1 to the divalent cobalt salt is (5.0~25.0):1, which can be 5.0:1, 6.25:1, 10:1, 15:1, 20:1 or 25:1.

[0060] In some embodiments, the mass ratio of sodium nitrite aqueous solution 1, oil-soluble quaternary ammonium salt extractant, co-solvent, and organic diluent is 1:(0.1~0.4):(0.02~0.08):(0.1~0.4), which can be 1:0.1:0.02:0.1, 1:0.3:0.05:0.3, 1:0.2:0.06:0.2, 1:0.4:0.08:0.4, or 1:0.3:0.07:0.3.

[0061] In some embodiments, the oil-soluble quaternary ammonium salt extractant includes brands Aliquat 336 and / or N263.

[0062] In some embodiments, the divalent cobalt salt includes one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, and cobalt acetate tetrahydrate;

[0063] The co-solvent includes isopropanol;

[0064] The organic diluent includes sulfonated kerosene.

[0065] In some embodiments, an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a co-solvent, and an organic diluent are mixed and reacted for 30-50 minutes.

[0066] In some embodiments, an aqueous solution of sodium nitrite, a divalent cobalt salt, an oil-soluble quaternary ammonium salt extractant, a co-solvent, and an organic diluent are mixed and reacted for 30-40 minutes.

[0067] In some embodiments, the temperature of the mixing reaction is 20-70°C, which can be 20°C, 30°C, 40°C, 50°C, 60°C or 70°C.

[0068] In some embodiments, the oxidant includes benzoquinone oxidants.

[0069] In some embodiments, the benzoquinone oxidant includes one or more of ortho-benzoquinone, p-benzoquinone, and 1,4-naphthoquinone.

[0070] In some implementations, acidic conditions include providing an acidic environment using hydrochloric acid.

[0071] In some embodiments, the step of mixing the organic phase, oxidant, and sodium nitrite aqueous solution 2 under acidic conditions to carry out the oxidation reaction includes:

[0072] An oxidation reaction is carried out by mixing hydrochloric acid aqueous solution, organic phase, oxidant and sodium nitrite aqueous solution 2;

[0073] The hydrochloric acid aqueous solution contains 30-38% hydrochloric acid by mass.

[0074] In some embodiments, the concentration of the sodium nitrite aqueous solution 2 is 1.0~5.0 mol / L, which can be 1.0 mol / L, 2.0 mol / L, 3.0 mol / L, 4.0 mol / L or 5.0 mol / L.

[0075] In some embodiments, the mass ratio of the organic phase to the sodium nitrite aqueous solution 2 is 1:(0.3~1), which can be 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.

[0076] In some embodiments, the mass ratio of the sodium nitrite aqueous solution 2 to the oxidant is 1:(0.2~0.8), which can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7 or 1:0.8.

[0077] In some embodiments, the mass ratio of the sodium nitrite aqueous solution 2, the oxidant and the hydrochloric acid is 1:(0.2~0.8):(0.1~0.8), which can be 1:0.4:0.5, 1:0.3:0.6 or 1:0.4:0.1.

[0078] In some embodiments, the conditions for the oxidation reaction include: a reaction temperature of 20~70°C, which can be 20°C, 30°C, 40°C, 50°C, 60°C or 70°C; and a reaction time of 50~300 min, which can be 50 min, 60 min, 70 min, 80 min, 100 min, 150 min, 200 min, 250 min or 300 min.

[0079] In some embodiments, the conditions for vacuum concentration crystallization include a vacuum pressure of -0.04 to -0.08 MPa, which can be -0.04 MPa, -0.05 MPa, -0.06 MPa, -0.07 MPa, or -0.08 MPa.

[0080] In some embodiments, the conditions for vacuum concentration crystallization include a concentration temperature of 50°C to 70°C, which can be 50°C, 60°C, or 70°C.

[0081] In some embodiments, the crystallization process is carried out under solvent crystallization conditions, which include mixing ethanol and an aqueous phase, aging the mixture, and then crystallizing.

[0082] In some embodiments, solvent crystallization includes: mixing ethanol and an aqueous phase in a co-current manner, aging the mixture, and then crystallizing.

[0083] In some embodiments, the volume ratio of the aqueous phase to ethanol is 1:(3~10), which can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0084] In some implementations, the aging conditions include an aging time of 30 to 50 minutes, which can be 30 minutes, 40 minutes, or 50 minutes.

[0085] In some embodiments, washing and drying are also included after the crystallization process.

[0086] In some embodiments, the solvents used for washing include diethyl ether and / or ethanol;

[0087] In some implementations, drying includes vacuum drying.

[0088] In some embodiments, the vacuum drying conditions include: a vacuum pressure of -0.5 to -0.8 MPa, which can be -0.5 MPa, -0.6 MPa, -0.7 MPa or -0.8 MPa; a drying temperature of 20 to 70°C, which can be 20°C, 30°C, 40°C, 50°C, 60°C or 70°C; and a drying time of 1 to 4 hours, which can be 1 hour, 2 hours, 3 hours or 4 hours.

[0089] In some embodiments, after mixing the organic phase, oxidant, and sodium nitrite aqueous solution 2 under acidic conditions to carry out an oxidation reaction, extraction, and separation of the aqueous phase, the method further includes a step of separating the organic phase and recovering the oil-soluble quaternary ammonium salt extractant. This step of separating the organic phase and recovering the oil-soluble quaternary ammonium salt extractant includes:

[0090] Separate the organic phase, mix the organic phase with soluble sodium salt and water, extract and separate the aqueous phase, and recover the oil phase containing oil-soluble quaternary ammonium salt extractant;

[0091] The soluble sodium salt includes sodium carbonate and / or sodium bicarbonate;

[0092] The mass ratio of the organic phase, the soluble sodium salt, and the water is (0.3~0.6):(0.2-1):1;

[0093] The conditions for mixing the organic phase with soluble sodium salt and water include: a mixing time of 20 to 60 minutes, which can be 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes; and a mixing temperature of 10 to 40 degrees Celsius, which can be 10 degrees Celsius, 20 degrees Celsius, 30 degrees Celsius or 40 degrees Celsius.

[0094] This application achieves the recycling and reuse of raw materials by separating the organic phase and recovering the oil phase containing oil-soluble quaternary ammonium salt extractants.

[0095] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0096] Example 1

[0097] 3000g of 6.0mol / L sodium nitrite aqueous solution, 600g of cobalt nitrate hexahydrate, 900g of quaternary ammonium salt N263, 150g of isopropanol and 800g of sulfonated kerosene were mixed and reacted at 40℃ for 30min, allowed to stand for 20min, and the aqueous phase was separated to obtain 3400g of organic phase.

[0098] The obtained organic phase, 800 g of 5.0 mol / L sodium nitrite aqueous solution 2, 300 g of o-benzoquinone and 400 g of hydrochloric acid were mixed and subjected to an oxidation reaction at 30 °C for 100 min. After the reaction was completed, the mixture was allowed to stand for 30 min to separate the aqueous phase and organic phase 1. The aqueous phase was concentrated under reduced pressure at -0.05 MPa and 70 °C, and then cooled to crystallize, yielding a crystalline wet product. The crystalline wet product was washed with diethyl ether and dried at 70 °C for 4 h to obtain sodium hexanitrobenzene, with a yield of 92.2%.

[0099] Organic phase 1: 5000g of pure water and 1000g of sodium carbonate were mixed and reacted at 20°C for 20 minutes. After extraction and separation, an organic phase containing the extractant was obtained (895g of extractant and 3410g of organic phase).

[0100] The prepared sodium hexanitrocobaltate was subjected to SEM scanning and XRD analysis, and the results are as follows: Figure 1 and Figure 2 As shown, the prepared sodium hexanitrocobaltate was compared with the standard XRD pattern of sodium hexanitrocobaltate, confirming that the product obtained in this example is sodium hexanitrocobaltate.

[0101] The sodium hexanitrocobaltate prepared above was analyzed by atomic emission spectrometry (ICP), and the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm. Chemical analysis showed that the nitrate content was 15 ppm, and the product purity was 99.8%.

[0102] Example 2

[0103] 10,000 g of 1.0 mol / L sodium nitrite aqueous solution, 400 g of cobalt acetate tetrahydrate, 1800 g of quaternary ammonium salt Aliquat336, 600 g of isopropanol and 2000 g of sulfonated kerosene were mixed and reacted at 70 °C for 30 min, allowed to stand for 25 min, and the aqueous phase was separated to obtain 5200 g of organic phase.

[0104] The obtained organic phase, 4200 g of 1.0 mol / L sodium nitrite aqueous solution, 1200 g of p-benzoquinone and 2500 g of hydrochloric acid were mixed and subjected to an oxidation reaction at 50 °C for 80 min. After the reaction was completed, the mixture was allowed to stand for 20 min to separate the aqueous phase and organic phase 1. The aqueous phase was mixed with 8 times its volume of ethanol in a co-current flow and aged for 40 min to obtain a crystalline wet product. The crystalline wet product was washed with diethyl ether and dried at 50 °C for 4 h to obtain sodium hexanitrobenzene with a yield of 90.4%.

[0105] Organic phase 1: 9000g of pure water and 3000g of sodium bicarbonate were mixed and reacted at 40°C for 20 minutes. After extraction and separation, an organic phase containing the extractant was obtained (1795g of extractant and 5160g of organic phase).

[0106] The sodium hexanitrocobaltate prepared above was analyzed by atomic emission spectrometry (ICP), and the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm. Chemical analysis showed that the nitrate content was 20 ppm, and the product purity was 99.6%.

[0107] Example 3

[0108] 5000g of 3.0mol / L sodium nitrite aqueous solution, 800g of cobalt chloride hexahydrate, 2000g of quaternary ammonium salt Aliquat336, 400g of isopropanol and 2000g of sulfonated kerosene were mixed and reacted at 60℃ for 40min, allowed to stand for 30min, and the aqueous phase was separated to obtain 6150g of organic phase.

[0109] The obtained organic phase, 4000 g of 3.0 mol / L sodium nitrite aqueous solution, 1500 g of o-benzoquinone, and 2100 g of hydrochloric acid were subjected to an oxidation reaction at 60 °C for 80 min. After the reaction was completed, the mixture was allowed to stand for 15 min to separate the aqueous phase and organic phase 1. The aqueous phase was mixed with 8 times its volume of ethanol in a co-current flow and aged for 40 min to obtain a crystalline wet product. The crystalline wet product was washed with diethyl ether and dried at 70 °C for 2 h to obtain sodium hexanitrobenzene with a yield of 91.6%.

[0110] Organic phase 1: 8000g of pure water and 2000g of sodium carbonate were mixed and reacted at 30°C for 50 minutes. After extraction and separation, an organic phase containing the extractant was obtained (1990g of extractant and 6170g of organic phase).

[0111] The sodium hexanitrobenzene prepared above was analyzed by atomic emission spectrometry (ICP), and the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm. Chemical analysis showed that the nitrate content was 20 ppm, and the product purity was 99.8%.

[0112] Example 4

[0113] 3000g of 4.0mol / L sodium nitrite aqueous solution, 200g of cobalt chloride hexahydrate, 900g of quaternary ammonium salt N263, 200g of isopropanol and 900g of sulfonated kerosene were mixed and reacted at 60℃ for 30min, allowed to stand for 40min, and the aqueous phase was separated to obtain 2500g of organic phase.

[0114] The obtained organic phase, 1000 g of 3.0 mol / L sodium nitrite aqueous solution, 450 g of o-benzoquinone and 120 g of hydrochloric acid were mixed and subjected to an oxidation reaction at 30 °C for 70 min. After the reaction was completed, the mixture was allowed to stand for 30 min to separate the aqueous phase and organic phase 1. The aqueous phase was concentrated under reduced pressure at -0.05 MPa and 70 °C, and then cooled to crystallize, yielding a crystalline wet product. The crystalline wet product was washed with diethyl ether and dried at 70 °C for 2 h to obtain sodium hexanitrobenzene, with a yield of 92.0%.

[0115] Organic phase 1: 6000g of pure water and 1500g of sodium carbonate were mixed and reacted at 20°C for 60 minutes. After extraction and separation, an organic phase containing the extractant was obtained (895g of extractant and 2520g of organic phase).

[0116] The sodium hexanitrocobaltate prepared above was analyzed by atomic emission spectrometry (ICP), and the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm. Chemical analysis showed that the nitrate content was 25 ppm, and the product purity was 99.8%.

[0117] Comparative Example 1

[0118] The preparation methods of sodium hexanitrocobaltate in Comparative Example 1 and Example 1 are basically the same, except that "quaternary ammonium salt N263" is replaced with "tetrabutylammonium chloride", and sodium hexanitrocobaltate is prepared according to the method of Example 1.

[0119] The yield of prepared sodium hexanitrobenzene was 74.6%. ICP-based atomic emission spectrometry analysis showed that the contents of impurities—magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead—were all less than 10 ppm. Chemical analysis revealed a nitrate content of 340 ppm, and the product purity was 96.7%.

[0120] Compared with Example 1, Comparative Example 1, which used hydrophilic tetrabutylammonium chloride as the extractant, showed lower yield and purity of sodium hexanitrobenzene. The yield decreased from 92.2% to 74.6%, and the purity decreased from 99.8% to 96.7%. This indicates that most of the Co... 2+ The difficulty in entering the extractant also results in excessive sodium nitrite residue during back-extraction, significantly reducing the yield and purity of sodium hexanitrocobaltate, while also reducing the utilization rate of raw materials.

[0121] Comparative Example 2

[0122] The preparation method of sodium hexanitrocobaltate in Comparative Example 2 is basically the same as that in Example 1, except that "3000g of 6.0mol / L sodium nitrite aqueous solution 1" is replaced with "1000g of 6.0mol / L sodium nitrite aqueous solution 1", and sodium hexanitrocobaltate is prepared according to the method in Example 1.

[0123] The yield of prepared sodium hexanitrobenzene was 69.6%. ICP-based atomic emission spectrometry analysis showed that the contents of impurities—magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead—were all less than 10 ppm. Chemical analysis revealed a nitrate content of 790 ppm, and the product purity was 90.3%.

[0124] Compared with Example 1, Comparative Example 2 reduced the amount of sodium nitrite aqueous solution 1, resulting in lower yield and purity of sodium hexanitrocobaltate. The yield decreased from 92.2% to 69.6%, and the purity decreased from 99.8% to 90.3%. This indicates that most of the Co... 2+ Ions have difficulty entering oil-soluble quaternary ammonium salt extractants, which also results in excessive sodium nitrite residue during back-extraction, significantly reducing the yield and purity of sodium hexanitrocobaltate, and also reducing the utilization rate of raw materials.

[0125] Comparative Example 3

[0126] The preparation method of sodium hexanitrocobaltate in Comparative Example 3 is basically the same as that in Example 1, except that: 3000g of 6.0mol / L sodium nitrite aqueous solution, 600g of cobalt nitrate hexahydrate, 900g of quaternary ammonium salt N263, 150g of isopropanol and 800g of sulfonated kerosene are mixed at 40°C for 5min; sodium hexanitrocobaltate is prepared according to the method of Example 1.

[0127] The yield of prepared sodium hexanitrobenzene was 79.2%. ICP-based atomic emission spectrometry analysis showed that the contents of impurities—magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead—were all less than 10 ppm. Chemical analysis revealed a nitrate content of 260 ppm, and the product purity was 95.4%.

[0128] Compared with Example 1, Comparative Example 3 shortened the extraction time, significantly reduced the yield and purity of sodium hexanitrobenzene, with the yield decreasing from 92.2% to 79.2% and the purity decreasing from 99.8% to 95.4%, while also reducing the utilization rate of raw materials.

[0129] Comparative Example 4

[0130] The preparation method of sodium hexanitrocobaltate in Comparative Example 4 is basically the same as that in Example 1, except that "800g of 5.0mol / L sodium nitrite aqueous solution 2" is replaced with "350g of 5.0mol / L sodium nitrite aqueous solution 2"; sodium hexanitrocobaltate is prepared according to the method in Example 1.

[0131] The yield of prepared sodium hexanitrobenzene was 59.1%. ICP-based atomic emission spectrometry analysis showed that the contents of impurities—magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead—were all less than 10 ppm. Chemical analysis revealed a nitrate content of 20 ppm, and the product purity was 99.1%.

[0132] Compared with Example 1, Comparative Example 4 reduced the amount of sodium nitrite aqueous solution 2, which significantly reduced the yield and purity of sodium hexanitrocobaltate. The yield decreased from 92.2% to 59.1%, and the purity decreased from 99.8% to 99.1%.

[0133] Comparative Example 5

[0134] The preparation method of sodium hexanitrocobaltate in Comparative Example 5 is basically the same as that in Example 1, except that "300g o-benzoquinone" is replaced with "100g o-benzoquinone", and sodium hexanitrocobaltate is prepared according to the method in Example 1.

[0135] The yield of prepared sodium hexanitrobenzene was 61.0%. ICP analysis showed that the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm, and the product purity was 96.3%.

[0136] Compared with Example 1, Comparative Example 5 reduced the amount of o-benzoquinone, resulting in a significant decrease in the yield and purity of sodium hexanitrocobaltate. The yield decreased from 92.2% to 61%, and the purity decreased from 99.8% to 96.3%. This indicates that most of the Co... 2+ If oxidation does not occur and the sodium nitrite does not enter the aqueous phase, it will also result in excessive sodium nitrite residue in the back-extraction solution and low raw material utilization.

[0137] Comparative Example 6

[0138] The preparation method of sodium hexanitrocobaltate in Comparative Example 6 is basically the same as that in Example 1, except that the temperature of vacuum concentration "70°C" is replaced with "90°C", and sodium hexanitrocobaltate is prepared according to the method in Example 1.

[0139] The yield of prepared sodium hexanitrobenzene was 86.0%. ICP analysis showed that the contents of impurities magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium, and lead were all less than 10 ppm, and the product purity was 91.3%.

[0140] Compared with Example 1, Comparative Example 6, by increasing the vacuum concentration temperature, significantly reduced the yield and purity of sodium hexanitrocobaltate. The yield decreased from 92.2% to 86%, and the purity decreased from 99.8% to 91.3%. This indicates that excessively high vacuum concentration temperatures caused some sodium hexanitrocobaltate to decompose, significantly reducing its yield and purity.

[0141] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0142] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A process for the preparation of sodium hexanitroate, characterized in that, Includes the following steps: Sodium nitrite aqueous solution 1, divalent cobalt salt, oil-soluble quaternary ammonium salt extractant, co-solvent and organic diluent are mixed and reacted for 10-50 min, the aqueous phase is separated and the organic phase is prepared; Under acidic conditions, an organic phase, an oxidant, and an aqueous solution of sodium nitrite 2 are mixed to carry out an oxidation reaction, the aqueous phase is separated, and the aqueous phase is crystallized to prepare sodium hexanitrobenzene. The mass ratio of the sodium nitrite aqueous solution 1 to the divalent cobalt salt is (5.0~25.0):1; The concentration of the sodium nitrite aqueous solution 1 is 5.0~6.0 mol / L; The oil-soluble quaternary ammonium salt extractant has the structural formula R3CH3NCl; wherein R is octyl and / or decyl; The mass ratio of sodium nitrite aqueous solution, oil-soluble quaternary ammonium salt extractant, co-solvent, and organic diluent is 1:(0.1~0.4):(0.02~0.08):(0.1~0.4). The concentration of the sodium nitrite aqueous solution 2 is 1.0~5.0 mol / L; The mass ratio of the organic phase to the sodium nitrite aqueous solution 2 is 1:(0.3~1); The mass ratio of the sodium nitrite aqueous solution 2 to the oxidant is 1:(0.2~0.8); The oxidant is a benzoquinone oxidant; Crystallization treatment conditions include vacuum concentration crystallization or solvent crystallization; The conditions for vacuum concentration and crystallization include a concentration temperature of 50℃~70℃.

2. The process for the preparation of sodium hexanitroate cobalt according to claim 1, characterized in that, The oil-soluble quaternary ammonium salt extractants include brands Aliquat 336 and / or N263.

3. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The divalent cobalt salt includes one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, and cobalt acetate tetrahydrate. The co-solvent includes isopropanol; The organic diluent includes sulfonated kerosene.

4. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The temperature for the mixed reaction is 20-70℃.

5. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The benzoquinone oxidizing agents are one or more of ortho-benzoquinone, para-benzoquinone, and 1,4-naphthoquinone.

6. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, Acidic conditions include: using hydrochloric acid to provide an acidic environment.

7. The method for preparing sodium hexanitrocobaltate according to claim 6, characterized in that, Under acidic conditions, the steps for carrying out the oxidation reaction by mixing the organic phase, oxidant, and sodium nitrite aqueous solution 2 include: An oxidation reaction is carried out by mixing hydrochloric acid aqueous solution, organic phase, oxidant and sodium nitrite aqueous solution 2; The hydrochloric acid aqueous solution contains 30-38% hydrochloric acid by mass.

8. The method for preparing sodium hexanitrocobaltate according to claim 7, characterized in that, The mass ratio of the sodium nitrite aqueous solution 2, the oxidant, and the hydrochloric acid is 1:(0.2~0.8):(0.1~0.8).

9. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The conditions for the oxidation reaction include: a reaction temperature of 20~70℃ and a reaction time of 50~300min.

10. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The conditions for vacuum concentration and crystallization include: vacuum pressure -0.04 to -0.08 MPa.

11. The method for preparing sodium hexanitrocobaltate according to claim 1, characterized in that, The crystallization process is solvent crystallization, which involves mixing ethanol and water, aging the mixture, and then crystallizing.

12. The method for preparing sodium hexanitrocobaltate according to claim 11, characterized in that, The volume ratio of aqueous phase to ethanol is 1:(3~10).

13. The method for preparing sodium hexanitrocobaltate according to claim 11, characterized in that, The aging conditions include an aging time of 30-50 minutes.

14. The method for preparing sodium hexanitrocobaltate according to claim 11, characterized in that, After the crystallization process, the process also includes washing and drying.

15. The method for preparing sodium hexanitrocobaltate according to claim 14, characterized in that, The solvents used for washing include ether and / or ethanol.

16. The method for preparing sodium hexanitrocobaltate according to claim 14, characterized in that, Drying includes vacuum drying.

17. The method for preparing sodium hexanitrocobaltate according to claim 16, characterized in that, The conditions for vacuum drying include: vacuum pressure of -0.5 to -0.8 MPa, drying temperature of 20 to 70°C, and drying time of 1 to 4 hours.

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