CN108084107B - Method for photocatalytic synthesis of azotetrazole non-metal salt - Google Patents
Method for photocatalytic synthesis of azotetrazole non-metal salt Download PDFInfo
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Abstract
The invention discloses a method for photocatalytic synthesis of azotetrazole nonmetallic salt. It is selected from TiO2、Fe2O3、BiVO4Taking a performance stabilizing material in an alkaline solution as a photocatalyst, taking 5-aminotetrazole alkali solution as a reaction solution, and controlling the reaction time to be 5-100 h through a direct photocatalysis or photoelectrocatalysis way under the illumination condition to synthesize azotetrazole sodium or potassium salt; then, sodium or potassium azotetrazole salt is respectively subjected to ion exchange reaction with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate in water to generate azotetrazole guanidine salt or ammonium salt; finally, the azotetrazole diguanide, azotetrazole triaminoguanidine, azotetrazole ammonium and the like are obtained through filtration and separation. The method has the characteristics of environmental protection.
Description
Technical Field
The invention relates to synthesis of organic compounds, in particular to a method for synthesizing azotetrazole nonmetallic salt.
Background
The azotetrazole nonmetallic salt (such as azotetrazole ammonium salt and azotetrazole guanidine salt) has high nitrogen content, can release huge energy in the combustion process, and is often used as an energetic material in the military and civil fields. In the process of synthesizing azotetrazole non-metal salt, the most key step is that 5-aminotetrazole is generated through coupling reactionAn azotetrazole group. At present, KMnO is often utilized in the traditional method for synthesizing azotetrazole nonmetallic salt compound4As the oxidizing agent, 5-aminotetrazole is promoted to generate coupling reaction in an alkaline solution containing sodium or potassium ions to generate azotetrazole sodium or azotetrazole potassium. Then, based on the azotetrazole sodium or potassium salt, the azotetrazole sodium or potassium salt and guanidine nitrate, triaminoguanidine nitrate, ammonium nitrate and other inorganic salts are subjected to simple ion exchange reaction to synthesize corresponding azotetrazole guanidine salt and azotetrazole ammonium salt compounds. It should be noted that, in the process of synthesizing azotetrazole sodium and azotetrazole potassium by the traditional method, the reaction temperature needs to be maintained at about 60 ℃ to obtain higher yield. In addition, an excess of KMnO is often required to achieve high yields4MnO is formed during the reaction2The byproducts, which need to be filtered and removed for a plurality of times, can be well treated. In summary, the traditional method for synthesizing the azotetrazole nonmetallic salt compound has the problems of complex operation and environmental pollution in the reaction process.
Disclosure of Invention
Aiming at the limitations of the current method and technology for synthesizing azotetrazole nonmetallic salt, the invention provides a method for synthesizing azotetrazole nonmetallic salt through photocatalysis, so as to realize the purpose of green synthesis of azotetrazole nonmetallic salt at normal temperature.
The main principle and basis of the invention are as follows: under the excitation of sunlight, the semiconductor photocatalyst can generate abundant photogenerated holes in the valence band, and the semiconductor photocatalyst has strong oxidizing property. Replacement of KMnO by semiconductor photogenerated holes4The dehydrogenation coupling reaction among the 5-amino tetrazole is driven, and the synthesis process is environment-friendly.
The general technical scheme of the invention is as follows: a method for photocatalytic synthesis of azotetrazole nonmetallic salt is realized by 3 main steps of photocatalytic synthesis of azotetrazole sodium or potassium salt, ion exchange reaction of azotetrazole sodium or potassium salt and corresponding inorganic salt, separation and purification of products and the like, and comprises the following specific steps:
A. photocatalytic synthesis of sodium or potassium azotetrazole salts: promoting the 5-aminotetrazole to generate coupling reaction to generate azotetrazole sodium or potassium salt in 5-aminotetrazole alkaline solution through direct photocatalysis or photoelectrocatalysis;
B. the azotetrazole sodium or potassium salt and the corresponding inorganic salt have ion exchange reaction: dissolving and mixing the synthesized azotetrazole sodium or potassium salt with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate in water respectively to enable the two salts to generate ion displacement reaction to synthesize corresponding azotetrazole guanidine salt or ammonium salt;
C. and (3) separating and purifying products: and crystallizing the corresponding product of the reacted solution, and then filtering to obtain products such as azotetrazole biguanide salt, azotetrazole triaminoguanidine salt, azotetrazole ammonium salt and the like.
In the method, the semiconductor material with stable performance in alkaline solution is selected as the photocatalyst, which means TiO2、Fe2O3、BiVO4Semiconductor powder and thin film material; the 5-aminotetrazole alkaline solution is used as a reaction solution, namely 5-aminotetrazole is dissolved in a solution containing NaOH, KOH and Na2CO3、K2CO3、NaHCO3、KHCO3In the solution of (1); wherein the concentration range of the 5-aminotetrazole in the solution is as follows: 0.01-8 mol/L; the molar concentration ratio of the two substances in the solution is as follows: 5-aminotetrazole: base (NaOH, KOH, Na2CO3, K2CO3, NaHCO3, KHCO3) = 1: 3; under the illumination condition, the reaction condition is controlled by direct photocatalysis or photoelectrocatalysis, and the azotetrazole sodium or potassium salt is synthesized by controlling the reaction condition, namely the azotetrazole sodium or potassium salt is synthesized by a xenon lamp with a full spectrum range or the optical power of the azotetrazole sodium or potassium salt is more than 30 mW/cm2Adding TiO into 5-amino tetrazole alkali solution under natural sunlight irradiation2、Fe2O3、BiVO4Powder is subjected to direct photocatalytic synthesis reaction, or TiO is used2、Fe2O3、BiVO4Carrying out photoelectrocatalysis synthesis reaction on the thin film electrode; controlling the reaction time to be 5-100 h, and synthesizing to obtain azotetrazole sodium or potassium salt; the method for synthesizing azotetrazole sodium or potassium salt by controlling reaction conditions through direct photocatalysis or photoelectrocatalysis under the illumination condition refers to adding TiO into 5-aminotetrazole alkali solution2、Fe2O3、BiVO4When the powder is used for direct photocatalytic synthesis reaction, the continuous flow rate is 0.1-1.5 m3The air per hour enables the photocatalyst powder to be suspended in the solution for fully reacting; using TiO2、Fe2O3、BiVO4When the film electrode is subjected to photoelectrocatalysis synthesis, the platinum wire electrode is a cathode; applying a bias voltage of 0 to 1V to the semiconductor thin film photo-anode; under the illumination condition, the reaction condition is controlled through direct photocatalysis or photoelectrocatalysis, and the azotetrazole sodium or potassium salt is synthesized, namely a high-concentration azotetrazole sodium or potassium salt solution is obtained after the photocatalysis reaction at room temperature; crystallizing the azotetrazole sodium or potassium salt at the temperature of 2-10 ℃, and filtering and separating to obtain the azotetrazole sodium or potassium salt; the azotetrazole sodium or potassium salt respectively performs ion exchange reaction with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate under certain conditions to generate azotetrazole guanidine salt or ammonium salt, wherein the azotetrazole sodium or potassium salt respectively performs ion exchange reaction with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate according to the mass ratio of 1: 2, dissolving in distilled water, performing ion exchange reaction at 50-90 ℃, and performing corresponding product crystallization on the solution after reaction at 2-10 ℃; the filtration and separation to obtain azotetrazole diguanide, azotetrazole triaminoguanidine and azotetrazole ammonium refers to obtaining azotetrazole diguanide salt, azotetrazole triaminoguanidine salt and azotetrazole ammonium salt with the purity of more than 99%.
The method for photo-catalytically synthesizing azotetrazole nonmetallic salt compound does not need to add KMnO4As an oxidant, the strong oxidizing property of a photogenerated hole in a valence band of a semiconductor photocatalyst is mainly utilized to promote the coupling reaction of 5-aminotetrazole in an alkaline solution, so as to synthesize azotetrazole sodium or potassium salt at room temperature, and further synthesize azotetrazole nonmetallic salt compounds such as azotetrazole guanidine salt and azotetrazole ammonium salt. In the whole synthesis process, sunlight is absorbed by the semiconductor photocatalyst to drive reaction, and the method has the characteristics of environmental protection.
Description of the drawings: the invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a schematic diagram of the photocatalytic synthesis of azotetrazolium salt according to the present invention; FIG. 2 shows the sodium salt of azotetrazole obtained in example 113C and1h nuclear magnetic spectrogram and physical photograph; FIG. 3 is a NMR spectrum of triaminoguanidine azotetrazole prepared in example 2; FIG. 4 is a nuclear magnetic spectrum of a biguanidinium azotetrazole salt obtained in example 3; FIG. 5 is an infrared spectrum of the azobisguanidine azotetrazole salt prepared by the present invention; FIG. 6 is an infrared spectrum of triaminoguanidine azotetrazole prepared by the present invention.
Detailed Description
Embodiments of the present invention are further illustrated by the following specific examples:
A. photocatalytic synthesis of sodium or potassium azotetrazole salts: selection of TiO2、Fe2O3、BiVO4Taking a semiconductor material with stable performance in an alkaline solution as a photocatalyst, and carrying out synthesis reaction by direct photocatalysis or photoelectrocatalysis; dissolving 5-aminotetrazole in solution containing NaOH, KOH and Na2CO3、K2CO3、NaHCO3、KHCO3Preparing 0.01-8 mol/L5-amino tetrazole alkali solution as a reaction solution in alkaline solution of the substances; xenon lamp with full spectral range, or with light power greater than 30 mW/cm2Natural sunlight is used as a reaction light source. Carrying out photocatalytic reaction for 5-100 h under the condition of illumination to obtain a high-concentration azotetrazole sodium or potassium salt solution, carrying out azotetrazole sodium or potassium salt crystallization at the temperature of 2-10 ℃, and filtering and separating to obtain azotetrazole sodium or potassium salt;
B. the azotetrazole sodium or potassium salt and the corresponding inorganic salt have ion exchange reaction: respectively mixing the prepared azotetrazole sodium or potassium salt with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate according to the mass ratio of 1: 2 in proportion, dissolving the two salts in distilled water, and fully performing ion exchange reaction at the temperature of between 50 and 90 ℃ to synthesize corresponding azotetrazole guanidine salt or ammonium salt;
C. and (3) separating and purifying products: and crystallizing the corresponding product from the reacted solution at 2-10 ℃. Then, the resulting mixture was subjected to a filtration separation procedure to obtain azotetrazole biguanide salt, azotetrazole triaminoguanidine salt, and azotetrazole ammonium salt.
Example 1: 12 g of NaOH was dissolved in 200 mL of water to prepare a 1.5 mol/L NaOH solution, and 8.5 g of 5-aminotetrazole was dissolved in the NaOH solution to prepare a 0.5 mol/L5-aminotetrazole base solution. Then, the 5-aminotetrazole alkali solution is transferred to a quartz reactor, and Fe having a particle size of 10 to 500 nm is charged therein2O3(Hematite) powder 1.0 g, continuously fed in at a flow rate of 0.5 m3Air of/h to make Fe2O3The powder was suspended in the solution. Then, at 100 mW/cm2The photocatalytic synthesis reaction is carried out for 25 hours under the irradiation of sunlight. After the reaction, the solvent was gradually evaporated from the reaction solution at 70 ℃ to 70 mL, the remaining solution was cooled and crystallized at 3 ℃ and then filtered and isolated at room temperature to obtain 11.6 g of solid azotetrazole sodium pentahydrate at 77% yield. The resulting sodium azotetrazole pentahydrate was dissolved in water, 6.2 g of ammonium nitrate was added to the sodium azotetrazole solution, and the reaction solution was heated to 70 ℃ and incubated for 30 min. Then, the reacted solution was cooled and crystallized at 5 ℃ to obtain 6.5 g of azotetrazole ammonium salt as a solid by filtration, and the yield was 84%.
Example 2 weigh 8.3 g K2CO3Dissolved in 100 mL of water to prepare 0.6 mol/L K2CO3The solution was then weighed out and 1.7 g of 5-aminotetrazole was dissolved in the K2CO3In the solution, a 0.2 mol/L solution of 5-aminotetrazole base was prepared. With BiVO4The film is a photo-anode, the platinum wire electrode is a cathode, the 5-amino tetrazole alkaline solution is used as electrolyte, and the photoelectrocatalysis synthesis reaction is performed in a quartz electrolytic cell. At 200 mW/cm2Under the illumination of a full-spectrum xenon lamp, BiVO is performed through a direct-current power supply4The thin film electrode was biased at 0V for 20 hours of the photoelectrocatalytic synthesis reaction. After the reaction, the solvent was gradually evaporated to 30 mL at 75 ℃ and the potassium azotetrazole salt solution was cooled and crystallized at 5 ℃ and then filtered and isolated at room temperature to obtain 2.0 g of potassium azotetrazole solid in a reaction yield of 81%. Dissolving the obtained azotetrazole potassium in water, and adding triamino2.7 g of guanidine nitrate, and the reaction solution was heated to 80 ℃ and kept warm for 20 min. Subsequently, the reacted solution was cooled and crystallized at 4 ℃ and isolated by filtration to obtain 2.6 g of triaminoguanidinium azotetrazole salt as a solid in 86% yield.
Example 3 16.8 g of KOH was dissolved in 100 mL of water to prepare a 3.0 mol/L KOH solution, and 8.5 g of 5-aminotetrazole was dissolved in the KOH solution to prepare a 1 mol/L5-aminotetrazole base solution. Then, the 5-aminotetrazole alkali solution is transferred to a quartz reactor, and anatase TiO with the particle size of 10-200 nm is put into the quartz reactor20.5 g of powder, continuously feeding in a flow of 0.2 m3Air to TiO2The powder was suspended in the solution. Next, under xenon lamp irradiation with a full spectral range (200 mW/cm)2) The reaction was carried out for 50 h. After the reaction, the solvent was gradually evaporated at 70 ℃ to 35 mL, the remaining solution was crystallized from the potassium azotetrazole salt at 5 ℃ and filtered and washed to obtain 8.3 g of potassium azotetrazole with a reaction yield of 69%. The obtained potassium azotetrazole was dissolved in water, 8.4 g of guanidine nitrate was added thereto, and the reaction solution was heated to 65 ℃ and kept warm for 40 min. Subsequently, the reacted solution was cooled and crystallized at 8 ℃ and separated by filtration to obtain 8.0 g of azobisguanidine azotetrazole salt as a solid in a reaction yield of 82%.
EXAMPLE 4 weighing 25.2 g NaHCO3Dissolving in 100 mL of water to prepare 3.0 mol/L NaHCO3The solution was then weighed out and 8.5 g of 5-aminotetrazole dissolved in NaHCO3In the solution, 1 mol/L of 5-aminotetrazole alkali solution was prepared. With Fe2O3The film is a photo-anode, the platinum wire electrode is a cathode, the 5-amino tetrazole alkaline solution is used as electrolyte, and the photoelectrocatalysis synthesis reaction is performed in a quartz electrolytic cell. At 150 mW/cm2Under the illumination of a full-spectrum xenon lamp, Fe is generated by a direct-current power supply2O3The thin film electrode is applied with a bias voltage of 0.5V to carry out the photoelectrocatalysis synthesis reaction for 18 h. After the reaction, the solvent is gradually evaporated to 35 mL under the condition of 60 ℃, the residual solution is placed under the condition of 8 ℃ for azotetrazole sodium salt crystallization, and the azotetrazole sodium pentahydrate is obtained after filtration and washingHydrate 10.7 g, reaction yield 71%. The resulting sodium azotetrazole was dissolved in water, 8.7 g of guanidine nitrate was added thereto, and the reaction solution was heated to 80 ℃ and kept warm for 35 min. Then, the reacted solution was cooled and crystallized at 7 ℃ to obtain 8.8g of azobisguanidium azotetrazole salt as a solid, which was isolated by filtration at 87% yield.
EXAMPLE 5 63.6 g Na were weighed2CO3Dissolved in 500 mL of water to prepare 1.2 mol/L Na2CO3The solution was then weighed out and 17.0 g of 5-aminotetrazole dissolved in NaHCO3In the solution, a 0.4 mol/L solution of 5-aminotetrazole base was prepared. Then, the 5-aminotetrazole alkali solution is transferred to a quartz reactor, and BiVO having a particle diameter of 10 to 200 nm is charged therein41.5 g of powder, with a continuous flow of 1.0 m3BiVO by air/h4The powder was suspended in the solution. Then, at 150 mW/cm2The photocatalytic synthesis reaction is carried out for 40 hours under the irradiation of sunlight. After the reaction, the solvent was gradually evaporated from the reaction solution at 80 ℃ to 150 mL, the remaining solution was cooled and crystallized at 4 ℃ and then separated by suction filtration at room temperature to obtain 21.9 g of solid sodium azotetrazole pentahydrate in 73% yield. The resulting sodium azotetrazole pentahydrate was dissolved in water, and 24.4 g of guanidine triaminonitrate was added to the sodium azotetrazole solution, and the reaction solution was heated to 90 ℃ and incubated for 50 min. Subsequently, the reacted solution was cooled and crystallized at 7 ℃ to obtain 23.2 g of azotetrazole ammonium salt as a solid by filtration, and the yield was 85%.
The nonmetallic azotetrazole salt is prepared according to the above-mentioned embodiments and the above-mentioned treatment method. The embodiments of the present invention can be implemented, and the present invention is not limited to these embodiments.
Claims (1)
1. A method for photocatalytic synthesis of azotetrazole nonmetallic salt is characterized in that: the method comprises the following steps of carrying out photocatalytic synthesis on azotetrazole sodium or potassium salt, carrying out ion exchange reaction on the azotetrazole sodium or potassium salt and corresponding inorganic salt, and separating and purifying a product, wherein the method comprises the following 3 main steps:
A. photocatalytic synthesis of sodium or potassium azotetrazole salts: selection of TiO2、Fe2O3、BiVO4The powder or its film material is used as photocatalyst, and 5-aminotetrazole is dissolved in solution containing NaOH, KOH and Na2CO3、K2CO3、NaHCO3Or KHCO3As a reaction solution in the alkaline solution; wherein the concentration range of the 5-aminotetrazole in the reaction solution is as follows: 0.01-8 mol/L; the molar concentration ratio of the two substances in the solution is as follows: 5-aminotetrazole: base = 1: 3; then, in a xenon lamp with a full spectrum range or an optical power of more than 30 mW/cm2By adding TiO into 5-aminotetrazole alkali solution under natural sunlight irradiation2、Fe2O3、BiVO4Powder is subjected to direct photocatalytic synthesis reaction, or TiO is used2、Fe2O3、BiVO4Carrying out photoelectrocatalysis synthesis reaction on the thin film electrode; controlling the reaction time to be 5-100 h, and synthesizing to obtain azotetrazole sodium or potassium salt; wherein TiO is added to a 5-aminotetrazole alkali solution2、Fe2O3、BiVO4When the powder is used for direct photocatalytic synthesis reaction, the continuous flow rate is 0.1-1.5 m3The air per hour enables the photocatalyst powder to be suspended in the solution for fully reacting; and use of TiO2、Fe2O3、BiVO4When the film electrode is subjected to photoelectrocatalysis synthesis, the platinum wire electrode is a cathode; applying a bias voltage of 0 to 1V on the photo-anodes of the several semiconductor thin films; obtaining high-concentration azotetrazole sodium or potassium salt solution after the photocatalytic reaction at room temperature; crystallizing the azotetrazole sodium or potassium salt at the temperature of 2-10 ℃, and filtering and separating to obtain the azotetrazole sodium or potassium salt;
B. the azotetrazole sodium or potassium salt and the corresponding inorganic salt have ion exchange reaction: respectively mixing the azotetrazole sodium or potassium salt synthesized in the last step with guanidine nitrate, triaminoguanidine nitrate and ammonium nitrate according to the mass ratio of 1: 2, dissolving in distilled water, performing ion exchange reaction at 50-90 ℃, and performing corresponding product crystallization on the solution after reaction at 2-10 ℃;
C. and (3) separating and purifying products: crystallizing the reacted solution, and filtering to separate azotetrazole biguanide salt, azotetrazole triaminoguanidine salt and azotetrazole ammonium salt with purity over 99%.
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