Process and apparatus for the preparation of methylamine hydroiodide

Abstract

The application provides a preparation method and device of methylamine hydroiodide. The preparation method of the methylamine hydroiodide comprises the following steps: mixing hydrogen iodide gas and methylamine gas to obtain methylamine hydroiodide. Through direct reaction of the hydrogen iodide gas and the methylamine gas, the solid methylamine hydroiodide is obtained, no other impurities are generated in the reaction process, the obtained methylamine hydroiodide has high purity, no additional purification is needed, the process is simple, and cost is saved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of raw material preparation of perovskite solar cells, in particular to a preparation method and device of methylamine hydroiodide. BACKGROUND

[0002] Perovskite solar cells have the advantages of simple process and low cost, and can realize cheap photovoltaic power generation, which is very suitable for commercial production. Methylamine hydroiodide (CH6IN) as a preferred raw material for preparing perovskite solar cells plays an important role in the crystalline quality of perovskite and the photoelectric conversion efficiency of solar cells.

[0003] The traditional preparation process of methylamine hydroiodide is to mix hydroiodic acid aqueous solution and methylamine solution, and remove the solvent by rotary evaporation after the reaction is completed. The traditional preparation process has the following problems: the water solution will produce iodine impurities when exposed to light or air during storage, and needs to be purified before use; the methylamine hydroiodide prepared by liquid phase reaction contains iodine and other reducing agents, which needs a complicated purification process, thereby increasing the preparation cost of methylamine hydroiodide. SUMMARY

[0004] The purpose of the present application is to provide a preparation method and device of methylamine hydroiodide to solve the technical problems of the prior art that the hydroiodic acid aqueous solution needs to be purified before use and the obtained methylamine hydroiodide has low purity and a complicated purification process.

[0005] To solve the above technical problems, the technical solutions of the present application are as follows:

[0006] The present application provides a preparation method of methylamine hydroiodide, comprising the following steps: mixing hydrogen iodide gas and methylamine gas to obtain methylamine hydroiodide.

[0007] Preferably, the molar ratio of the hydrogen iodide gas to the methylamine gas is 1:(1-3).

[0008] Preferably, after mixing the hydrogen iodide gas and the methylamine gas, the reaction temperature is-40-0℃ and the reaction pressure is 100-500 kilopascals.

[0009] Preferably, the hydrogen iodide gas is obtained by the following steps: uniformly mixing solid red phosphorus and solid iodine, adding water to obtain hydrogen iodide gas.

[0010] Further preferably, the solid red phosphorus, solid iodine and water are in a ratio of (1-3):1:(3-10).

[0011] Further preferably, the reaction temperature of the solid red phosphorus, solid iodine and water is 30-90℃.

[0012] Preferably, the method for preparing methylamine hydroiodide further comprises a step of removing water vapor in the hydrogen iodide gas.

[0013] The present application also provides a device for preparing methylamine hydroiodide, comprising:

[0014] a hydrogen iodide gas generating unit adapted to provide hydrogen iodide gas;

[0015] a methylamine gas storage unit adapted to provide methylamine gas;

[0016] a methylamine hydroiodide generating unit connected with the hydrogen iodide gas generating unit and the methylamine gas storage unit respectively, and adapted to provide a space for mixing reaction of hydrogen iodide gas and methylamine gas.

[0017] Preferably, a water removal unit is further arranged between the hydrogen iodide gas generating unit and the methylamine hydroiodide generating unit.

[0018] The hydrogen iodide gas generating unit comprises a water storage unit and a gas generating unit.

[0019] The water storage unit is connected with the gas generating unit and adapted to add water to the gas generating unit.

[0020] The gas generating unit is adapted to provide a space for mixing reaction of solid red phosphorus, solid iodine and water.

[0021] Preferably, the methylamine hydroiodide generating unit is further connected with a tail gas treatment unit.

[0022] The above-mentioned scheme of the present application at least has the following beneficial effects:

[0023] (1) The method for preparing methylamine hydroiodide comprises the following steps: mixing hydrogen iodide gas and methylamine gas to obtain methylamine hydroiodide. Solid methylamine hydroiodide is obtained by direct reaction of hydrogen iodide gas and methylamine gas. No other impurities are generated during the reaction, the obtained methylamine hydroiodide has high purity, does not need additional purification, the process is simple, and cost is saved.

[0024] (2) The method for preparing methylamine hydroiodide adopts hydrogen iodide gas obtained by the following steps: uniformly mixing solid red phosphorus and solid iodine, adding water to obtain hydrogen iodide gas. By directly preparing hydrogen iodide gas, high-purity raw materials for preparing methylamine hydroiodide are obtained, and the technical problems that hydrogen iodide acid solution is easily decomposed into iodine under air and light in the traditional preparation method and needs to be purified before use are solved.

[0025] (3) The preparation device of the methylamine hydroiodide of the present application, comprising: a hydrogen iodide gas generating part, a methylamine gas storage part, a methylamine hydroiodide generating part, the hydrogen iodide gas generating part is suitable for providing hydrogen iodide gas; the methylamine gas storage part is suitable for providing methylamine gas; the methylamine hydroiodide generating part is connected with the hydrogen iodide gas generating part and the methylamine gas storage part respectively, and is suitable for providing the space of the mixed reaction of hydrogen iodide gas and methylamine gas. The preparation device of the methylamine hydroiodide can realize the continuous production of the methylamine hydroiodide, greatly improving the production efficiency and yield. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 is a structural schematic diagram of the preparation device of the methylamine hydroiodide of the present application.

[0027] 1, hydrogen iodide gas generating part; 11, water storage unit; 12, gas generating unit; 13, feeding port; 14, discharge port; 2, methylamine gas storage part; 3, methylamine hydroiodide generating part; 31, discharge port; 4, water removal part; 5, tail gas treatment part. DETAILED DESCRIPTION

[0028] Exemplary embodiments of the present disclosure will be described in greater detail below with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that the present disclosure can be more thoroughly understood and the scope of the present disclosure can be accurately conveyed to those skilled in the art.

[0029] Example 1

[0030] The preparation method of the methylamine hydroiodide of the present embodiment comprises the following steps:

[0031] (1) Mix solid red phosphorus and solid iodine element uniformly, add water to obtain hydrogen iodide gas. The molar ratio of the solid red phosphorus, the solid iodine element and the water is 3:3:10; the reaction temperature of the solid red phosphorus, the solid iodine element and the water is 60°C, the reaction pressure is normal pressure, and the suitable reaction time of the reaction product is 30 min.

[0032] The chemical reaction equation involved in this process is: 2P+3I2+6H2O=6HI+2H3PO3.

[0033] (2) The hydrogen iodide gas obtained in step (1) is removed by drying agent phosphorus pentoxide to remove water vapor introduced by the above reaction to obtain dry hydrogen iodide gas.

[0034] (3) mixing the dry hydrogen iodide gas obtained in step (2) and the methylamine gas to obtain methylamine hydroiodide. The molar ratio of the hydrogen iodide gas to the methylamine gas is 1:2; the reaction temperature is -20℃, the reaction pressure is 200 kiloPascal, and the suitable reaction time for obtaining the reaction product is 30 min.

[0035] The chemical reaction equation involved in this process is: HI + CH3NH2 = CH3NH3I.

[0036] Example 2

[0037] The preparation method of the methylamine hydroiodide of the present example comprises the following steps:

[0038] (1) mixing solid red phosphorus and solid iodine element uniformly, adding water to obtain hydrogen iodide gas. The molar ratio of the solid red phosphorus, the solid iodine element and the water is 1:1:10; the reaction temperature of the solid red phosphorus, the solid iodine element and the water is 30℃, the reaction pressure is normal pressure, and the suitable reaction time for obtaining the reaction product is 30 min.

[0039] The chemical reaction equation involved in this process is: 2P + 3I2 + 6H2O = 6HI + 2H3PO3.

[0040] (2) removing the water vapor introduced by the above reaction from the hydrogen iodide gas obtained in step (1) by using the drying agent phosphorus pentoxide to obtain dry hydrogen iodide gas.

[0041] (3) mixing the dry hydrogen iodide gas obtained in step (2) and the methylamine gas to obtain methylamine hydroiodide. The molar ratio of the hydrogen iodide gas to the methylamine gas is 1:1; the reaction temperature is -40℃, the reaction pressure is 100 kiloPascal, and the suitable reaction time for obtaining the reaction product is 30 min.

[0042] The chemical reaction equation involved in this process is: HI + CH3NH2 = CH3NH3I.

[0043] Example 3

[0044] The preparation method of the methylamine hydroiodide of the present example comprises the following steps:

[0045] (1) mixing solid red phosphorus and solid iodine element uniformly, adding water to obtain hydrogen iodide gas. The molar ratio of the solid red phosphorus, the solid iodine element and the water is 3:1:3; the reaction temperature of the solid red phosphorus, the solid iodine element and the water is 90℃, the reaction pressure is normal pressure, and the suitable reaction time for obtaining the reaction product is 30 min.

[0046] The chemical reaction equation involved in this process is: 2P + 3I2 + 6H2O = 6HI + 2H3PO3.

[0047] (2) Pass the hydrogen iodide gas obtained in step (1) through the desiccant phosphorus pentoxide to remove the water vapor introduced by the above reaction, and obtain dry hydrogen iodide gas.

[0048] (3) The dry hydrogen iodide gas obtained in step (2) and methylamine gas are mixed to obtain methylamine hydroiodate. The molar ratio of hydrogen iodide gas to methylamine gas is 1:3; the reaction temperature is 0°C, the reaction pressure is 500 kPa, and the suitable reaction time to obtain the reaction product is 30 min.

[0049] The chemical reaction equation involved in this process is: HI + CH3NH2 = CH3NH3I.

[0050] Example 4

[0051] This embodiment provides an apparatus for preparing methylamine hydroiodate, which can be used to implement the preparation methods of methylamine hydroiodate in Examples 1-3, such as... Figure 1 As shown, it includes: a hydrogen iodide gas generating unit 1, a methylamine gas storage unit 2, and a methylamine hydroiodate generating unit 3.

[0052] The system comprises a hydrogen iodide gas generating unit 1, adapted to provide hydrogen iodide gas; a methylamine gas storage unit 2, adapted to provide methylamine gas; and a methylamine hydroiodate generating unit 3, which is connected to both the hydrogen iodide gas generating unit 1 and the methylamine gas storage unit 2, and is adapted to provide space for the mixing and reaction of hydrogen iodide gas and methylamine gas. In a preferred embodiment, the hydrogen iodide gas generating unit 1 includes a water storage unit 11 and a gas generating unit 12; the water storage unit 11 is adapted to add water to the gas generating unit, for example, it can be a water tank; the gas generating unit 12 is adapted to provide space for the mixing and reaction of solid red phosphorus, solid iodine, and water, for example, it can be a sealed container. The methylamine gas storage unit 2 and the methylamine hydroiodate generating unit 3 can be sealed containers.

[0053] The hydrogen iodide gas generating unit 1 further includes a feeding port 13 and a discharging port 14. The feeding port 13 is adapted to add solid red phosphorus and solid iodine to the gas generating unit, and the discharging port 14 is adapted to remove the reaction residue from the gas generating unit.

[0054] The methylamine hydroiodide generating section 3 is provided with a discharge port 31, which is suitable for collecting methylamine hydroiodide after production is completed.

[0055] A dehydration section 4 is also provided between the hydrogen iodide gas generating section 1 and the methylamine hydroiodate generating section 3. Since the hydrogen iodide gas generating reaction is an exothermic reaction, the hydrogen iodide gas may contain water vapor. The dehydration section 4 is suitable for removing the water vapor. For example, it can be a drying oven containing phosphorus pentoxide.

[0056] The methylamine hydroiodide generating part 3 is also connected with a tail gas treatment part 5, which is suitable for collecting the uncompletely reflected hydrogen iodide gas and methylamine gas. For example, it can be a sealed water tank filled with water. Both the hydrogen iodide gas and the methylamine gas have the characteristic of being easily soluble in water. The excess gas can be introduced into the water through a pipeline to absorb the tail gas. In addition, a pipeline can be additionally arranged on the top of the sealed water tank for balancing the pressure inside and outside the water tank.

[0057] The hydrogen iodide gas generating part 1, the methylamine gas storage part 2, the methylamine hydroiodide generating part 3, the water removal part 4 and the tail gas treatment part 5 are connected by pipelines, and the gas flows in the direction of the arrow in the figure. Figure 1

[0058] The specific operation mode of the methylamine hydroiodide preparation device described in the embodiment is as follows:

[0059] The solid red phosphorus and the solid iodine are uniformly mixed, and the hydrogen iodide gas generating part 1 is filled with the mixture through the feeding port 13. The water storage unit 11 is opened, and water is added to the hydrogen iodide gas generating part 1. The reaction condition is observed, and after the hydrogen iodide gas is generated, the methylamine gas storage part 2 is opened, and the methylamine gas is introduced into the methylamine hydroiodide generating part 3. The reaction condition is observed, and when the product accumulates to a certain extent, the water storage unit 11 and the methylamine gas storage part 2 are closed, the discharge port 31 is opened, and the methylamine hydroiodide is collected; the discharge port 14 is opened, and the remaining reaction material of the hydrogen iodide gas generating part 1 is collected.

[0060] Comparative Example

[0061] The preparation method of the methylamine hydroiodide in the comparative example comprises the following steps:

[0062] (1) Purification of hydroiodic acid

[0063] The hydroiodic acid is taken and extracted with a tributyl phosphate chloroform solution to remove free iodine, so as to obtain the purified hydroiodic acid; wherein the purified hydroiodic acid is a water solution with a mass concentration of 57wt%.

[0064] (2) Synthesis of methylamine hydroiodide

[0065] The hydroiodic acid obtained in step (1) is added to a 40wt% methylamine methanol solution in an ice water bath and stirred for 2 hours. After the reaction is completed, the solvent water and methanol are distilled off under reduced pressure to obtain a yellow crude product of methylamine hydroiodide.

[0066] (3) Purification of methylamine hydroiodide

[0067] The yellow crude product of methylamine hydroiodide obtained in step (2) is recrystallized with ethanol, washed with diethyl ether for three times, filtered, vacuum dried to obtain the methylamine hydroiodide.​

[0068] Effect verification example

[0069] (1) The methylamine hydroiodide prepared in Example 1-3 and the comparative example was taken, and the purity was determined by high performance liquid chromatography, and the following data was obtained:

[0070] No. Example 1 Example 2 Example 3 Comparative Example Purity (%) 99.0 98.5 98.6 97.0

[0071] (2) The methylamine hydroiodide prepared in Example 1-3 and the comparative example was taken as raw material, and the remaining conditions were kept the same, and a perovskite solar cell was prepared, and the open circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency of the perovskite solar cell were determined. The following data was obtained:

[0072] No. Example 1 Example 2 Example 3 Comparative Example Open-circuit voltage (V) 0.96 0.95 0.95 0.95 Short circuit current (mA-cm -2 ) 23.76 23.54 23.41 23.24 Fill factor 0.76 0.75 0.72 0.72 Photoelectric conversion efficiency (%) 17.34 16.77 16.01 15.90

[0073] According to the comparison between Example 1-3 and the comparative example, it can be seen that the purity of the methylamine hydroiodide prepared by the preparation method of the methylamine hydroiodide according to the application is significantly improved. The perovskite solar cell prepared by using the methylamine hydroiodide prepared by the preparation method of the methylamine hydroiodide according to the application as raw material has significantly improved performance.

[0074] The above is the preferred embodiment of the application. It should be pointed out that for ordinary skilled in the art, without departing from the principles of the application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. A process for the preparation of methylamine hydroiodide, characterized in that, It comprises the following steps: Mixing dry hydrogen iodide gas and methylamine gas to obtain methylamine hydroiodide; The molar ratio of the dry hydrogen iodide gas to the methylamine gas is 1:2; After mixing the dry hydrogen iodide gas and the methylamine gas, the reaction temperature is-20℃ and the reaction pressure is 200 kiloPascal; The dry hydrogen iodide gas is obtained by the following steps: Mixing solid red phosphorus and solid iodine to obtain hydrogen iodide gas; Removing water vapor in the hydrogen iodide gas to obtain dry hydrogen iodide gas; The molar ratio of the solid red phosphorus, the solid iodine and the water is 3:3:10; The reaction temperature of the solid red phosphorus, the solid iodine and the water is 60℃.

2. A device for the preparation of methylamine hydroiodide, characterized in that It comprises: A hydrogen iodide gas generating part (1) adapted to provide hydrogen iodide gas; The hydrogen iodide gas generating part comprises a water storage unit (11) and a gas generating unit (12); The water storage unit (11) is connected with the gas generating unit (12) and is adapted to add water to the gas generating unit; The gas generating unit (11) is adapted to provide a mixing reaction space for solid red phosphorus, solid iodine and water; the molar ratio of the solid red phosphorus, the solid iodine and the water is 3:3:10; and the reaction temperature of the solid red phosphorus, the solid iodine and the water is 60℃; A methylamine gas storage part (2) adapted to provide methylamine gas; A methylamine hydroiodide generating part (3) connected with the hydrogen iodide gas generating part (1) and the methylamine gas storage part (2) and adapted to provide a mixing reaction space for hydrogen iodide gas and methylamine gas; the molar ratio of the hydrogen iodide gas to the methylamine gas is 1:2; and after mixing the hydrogen iodide gas and the methylamine gas, the reaction temperature is-20℃ and the reaction pressure is 200 kiloPascal; A water removal part (4) is further arranged between the hydrogen iodide gas generating part (1) and the methylamine hydroiodide generating part (3).

3. The apparatus for preparing methylamine hydroiodide according to claim 2, characterized by The methylamine hydroiodide generating part (3) is further connected with a tail gas treatment part (5).

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