阅读说明：本技术 利用水蒸气使六氨氯化镁的脱氨的方法 (Process for deamination of magnesium chloride hexammoniate using water vapour ) 是由 姜永要 王伟 郑锐 于 2021-08-03 设计创作，主要内容包括：本发明提供一种利用水蒸气使六氨氯化镁的脱氨的方法,通过利用水蒸气通过六氨氯化镁发生置换反应置换出六氨氯化镁MgCl2·6NH3中的NH3生成MgCl2·6H2O,氨气以氨水形式收集,操作简单,能耗较低,同时脱氨过程中大量氨被回收,实现了资源循环利用。(The invention provides a method for deamination of magnesium chloride hexammoniate by using water vapor, wherein the water vapor is used for replacing NH3 in MgCl 2.6 NH3 to generate MgCl 2.6H 2O through the replacement reaction of magnesium chloride hexammoniate, ammonia gas is collected in the form of ammonia water, the operation is simple, the energy consumption is low, and meanwhile, a large amount of ammonia is recovered in the deamination process, so that the cyclic utilization of resources is realized.)

1. A method for deaminating magnesium chloride hexammoniate using steam, comprising: the method comprises the following steps:

the method comprises the following steps: the method comprises the following steps of (1) crushing a sample of magnesium hexammoniate, adding the crushed magnesium hexammoniate into a material high-level tank (2) of a reactor (1), and adding magnesium hexammoniate powder onto an automatic adjusting and punching partition plate (3) in the reactor (1) by opening a ball valve of the material high-level tank (2);

step two: starting the heating reactor (1), and controlling the temperature of the reactor to be 110-120 ℃;

step three: starting a steam generator (4) connected with a reactor (1), controlling the temperature of steam at an outlet of the steam generator to be 110-130 ℃, starting a peristaltic pump (5) connected with the steam generator (4), controlling the speed to be 5-100g/min according to the feeding amount, pumping the steam into the reactor (1) to react with magnesium hexammoniate powder, reacting the steam with the magnesium hexammoniate powder to generate magnesium chloride and ammonia gas, recovering the ammonia gas by an ammonia water recovery device connected with the reactor (1), changing the ammonia gas into the ammonia water by the ammonia water recovery device which is connected with a water inlet pipe, carrying out online concentration detection on the concentration of the recovered ammonia water, continuously detecting the concentration of the ammonia water for 30min without change, and finishing the reaction.

2. The method of deaminating magnesium chloride hexammoniate according to claim 1, wherein said deaminating step comprises the steps of: the first step also comprises the following steps of detecting the ammonia content: preparing 0.1mol/L magnesium chloride hexammoniate solution from magnesium chloride hexammoniate powder, taking methyl red as an indicator, dripping the magnesium chloride hexammoniate solution by 0.1mol/L sodium hydroxide standard liquid, and detecting the ammonia content in the magnesium chloride hexammoniate solution; and after the ammonia content is detected, analyzing the ammonia content of the sample magnesium chloride hexammoniate by a thermogravimetric analysis method, and further verifying whether the components of the sample magnesium chloride hexammoniate are the same as those detected by a titration method.

3. The method of deaminating magnesium chloride hexammoniate according to claim 2, wherein said deaminating step comprises the steps of: and quantitatively adding acid to dissolve the magnesium hexammoniate powder in the process of preparing the solution.

4. The method of deaminating magnesium chloride hexammoniate according to claim 1, wherein said deaminating step comprises the steps of: and in the third step, the outlet of the water vapor generator (4) is connected with a connecting pipeline of the reactor (1) and is heated by a heating belt, the temperature is controlled to be 120-130 ℃, and the water entering the reactor (1) is ensured to be water vapor.

5. The method of deaminating magnesium chloride hexammoniate according to claim 1, wherein said deaminating step comprises the steps of: the ammonia water recovery device comprises a primary ammonia water recovery device (6), the primary ammonia water recovery device is connected with a secondary ammonia water recovery device (8) through a secondary air outlet pipe (7), and ammonia water concentration testers are arranged in the primary ammonia water recovery device and the secondary ammonia water recovery device; the top of the reactor (1) is connected with a primary ammonia water recovery device through a first air outlet pipe (9).

6. The method of deaminating magnesium chloride hexammoniate according to claim 5, wherein said deaminating step comprises the steps of: and the part of the second outlet pipe (7) in the secondary ammonia water recovery device (8) and the part of the first outlet pipe (9) in the primary ammonia water recovery device (6) are perforated.

7. The method of deaminating magnesium chloride hexammoniate according to claim 5, wherein said deaminating step comprises the steps of: a steam outlet pipe (10) connected with a steam generator (4) is arranged below the automatic adjusting punching partition plate (3) in the reactor (1), and the steam is positioned below the magnesium hexaamlodipine powder and reacts with the magnesium hexaamlodipine powder.

8. The method of deaminating magnesium chloride hexammoniate according to claim 1, wherein said deaminating step comprises the steps of: and after the reaction of the reactor (1) is finished, detecting the residual solid components in a fixed storage tank (11) at the bottom of the reactor (1).

Technical Field

The invention relates to the field of magnesium chloride hexammoniate, in particular to a method for deaminating magnesium chloride hexammoniate by using water vapor.

Background

The magnesium chloride hexammoniate is a complex formed by ammonia and anhydrous magnesium chloride, has a molecular formula of MgCl 2.6NH 3, has reversible ammonia absorption and desorption characteristics, and is an excellent hydrogen storage material. Magnesium chloride hexammoniate (MgCl2 · 6NH3) is an important intermediate in complex decomposition methods, and its synthesis process is classified into different synthetic route methods such as a high boiling point solvent system method, a water-ammonia system method, a low boiling point solvent system method, and a magnesium silicide synthesis method. The synthetic route of magnesium silicide is actually the byproduct of the reaction of magnesium silicide and ammonium chloride in liquid ammonia to prepare monosilane (SiH4), and compared with the former 3 methods, the method has the characteristics of short process route, high yield of magnesium chloride hexammoniate, low production cost and the like, and simultaneously, the main product of the method is monosilane, which is a very important high-purity silane gas in modern microelectronics and new energy industries, and the monosilane is widely applied to microelectronics and photoelectronic industries, is used for manufacturing solar cells, flat panel displays, glass and steel coatings, and is the only intermediate product for producing granular high-purity silicon on a large scale in the world to date. The method has the advantages of high silane yield, easily obtained reaction raw materials, simple operation, easily achieved temperature and pressure process conditions and the like, a large amount of byproduct magnesium chloride hexammoniate (MgCl2 & 6NH3) is generated and accumulated, ammonia in the accumulated magnesium chloride hexammoniate can be continuously volatilized to pollute the environment, the law enforcement strength and public opinion supervision attention of environmental protection departments are further improved, and the byproduct magnesium chloride hexammoniate needs to be timely treated in order to reduce environmental pollution.

Ammonia gas and magnesium chloride can be obtained by deaminating magnesium chloride hexammoniate (MgCl 2.6NH 3), the ammonia gas of a gas product can be recycled, and the magnesium chloride of a solid product can be used for preparing high-purity anhydrous magnesium chloride, so that the aims of fully utilizing resources and safely discharging wastes in the conversion process are fulfilled.

The classical technology of the deamination of magnesium chloride hexammoniate is high-temperature calcination deamination, the related reports on the method of the high-temperature deamination of magnesium chloride hexammoniate are less, patents CN101462746A and CN1135743A only refer to the concept of pyrolysis of magnesium chloride hexammoniate, the temperature of 290 ℃ is theoretically required, the actual situation is not the case, and the temperature required by complete deamination is up to 500-; although patent CN102336422A provides a pyrolysis method and device, the method also needs to provide a temperature as high as 500-600 ℃ to ensure rapid deamination, and has the disadvantages of excessive energy consumption, excessive cost and low economic benefit. Therefore, the development of a novel and efficient deamination method is of great significance.

Disclosure of Invention

In order to solve the problems, the invention provides a method for deaminating magnesium chloride hexammoniate by using water vapor, wherein the water vapor is used for replacing NH3 in MgCl 2.6 NH3 to generate MgCl 2.6H 2O through the replacement reaction of magnesium chloride hexammoniate, ammonia gas is collected in the form of ammonia water, the operation is simple, the energy consumption is low, and meanwhile, a large amount of ammonia is recovered in the deamination process, so that the cyclic utilization of resources is realized.

The invention aims to provide a method for deaminating magnesium chloride hexammoniate by using water vapor, which comprises the following steps of:

the method comprises the following steps: adding a crushed sample of magnesium hexaamlodipine into a material high-level tank of a reactor, and adding magnesium hexaamlodipine powder onto an automatic adjusting perforated partition plate in the reactor by opening a ball valve of the material high-level tank;

step two: starting the heating reactor, and controlling the temperature of the reactor to be 110-120 ℃;

step three: starting a steam generator connected with a reactor, controlling the temperature of steam at an outlet of the steam generator to be 110-130 ℃, starting a peristaltic pump connected with the steam generator, controlling the speed to be 5-100g/min according to the feeding amount, pumping the steam into the reactor to react with magnesium hexammoniate, reacting the steam with the magnesium hexammoniate to generate magnesium chloride and ammonia gas, recovering the ammonia gas by an ammonia water recovery device connected with the reactor, changing the ammonia gas into ammonia water by the ammonia water recovery device, carrying out online concentration detection on the concentration of the recovered ammonia water, continuously detecting the concentration of the ammonia water for 30min without change, and finishing the reaction.

The further improvement lies in that: the first step also comprises the following steps of detecting the ammonia content: preparing 0.1mol/L magnesium chloride hexammoniate solution from magnesium chloride hexammoniate powder, taking methyl red as an indicator, dripping the magnesium chloride hexammoniate solution by 0.1mol/L sodium hydroxide standard liquid, and detecting the ammonia content in the magnesium chloride hexammoniate solution; and after the ammonia content is detected, analyzing the ammonia content of the sample magnesium chloride hexammoniate by a thermogravimetric analysis method, and further verifying whether the components of the sample magnesium chloride hexammoniate are the same as those detected by a titration method.

The further improvement lies in that: and quantitatively adding acid to dissolve the magnesium hexammoniate powder in the process of preparing the solution.

The further improvement lies in that: and in the third step, the outlet of the water vapor generator is connected with a connecting pipeline of the reactor and is heated by a heating belt, the temperature is controlled to be 120-130 ℃, and the water entering the reactor is ensured to be water vapor.

The further improvement lies in that: the ammonia water recovery device comprises a primary ammonia water recovery device, the primary ammonia water recovery device is connected with a secondary ammonia water recovery device through a secondary air outlet pipe, and ammonia water concentration testers are arranged in the primary ammonia water recovery device and the secondary ammonia water recovery device; the top of the reactor is connected with a primary ammonia water recovery device through an air outlet pipe;

the further improvement lies in that: and the part of the air outlet pipe, which is positioned in the secondary ammonia water recovery device, and the part of the air outlet pipe, which is positioned in the primary ammonia water recovery device, are perforated.

The further improvement lies in that: and a steam outlet pipe connected with a steam generator is arranged below the automatic adjusting punching partition plate in the reactor, and the steam is positioned below the magnesium hexaamlodipine powder and reacts with the magnesium hexaamlodipine powder.

The further improvement lies in that: and after the reaction of the reactor is finished, detecting the residual solid components in a fixed storage tank at the bottom of the reactor.

The reaction principle of the invention is as follows:

MgCl2 & 6NH3+6H2O (water vapor) × MgCl2 & 6H2O +6NH3 ×, and ammonia gas is prepared into ammonia water.

The invention has the beneficial effects that: according to the invention, the ammonia content of magnesium chloride hexammoniate is detected firstly, so that the ammonia water amount obtained in the whole reaction can be known approximately, the reaction end point can be well assisted and judged, and the deamination efficiency can be inspected; then, water vapor is used for reaction at the lower part and magnesium chloride hexammoniate is used for reaction at the upper part, so that the reaction effect is better and more thorough; NH3 in magnesium chloride hexammoniate MgCl 2.6 NH3 is replaced by magnesium chloride hexammoniate through a displacement reaction to generate MgCl 2.6H 2O, ammonia gas is regenerated into ammonia water for collection, the operation is simple, the energy consumption is low, and meanwhile, a large amount of ammonia is recovered in the deamination process, so that the resource recycling is realized;

the magnesium chloride hexammoniate has poor solubility, so that the magnesium chloride hexammoniate is quantitatively dissolved by adding acid in the process of preparing the solution, and the solution is conveniently prepared; the ammonia water recovery device comprises a primary ammonia water recovery device and a secondary ammonia water recovery device, so that ammonia water is recovered more thoroughly; detecting the residual solid components in the fixed storage tank after the reaction is finished, and judging whether the residual solid components are magnesium chloride; the outlet of the steam generator is connected with a connecting pipeline of the reactor and is heated by a heating belt to ensure that the steam reaction is carried out; the part of the gas outlet pipe in the secondary ammonia water recovery device and the part of the gas outlet pipe in the primary ammonia water recovery device are both perforated, so that the ammonia gas is discharged more quickly and uniformly.

Drawings

FIG. 1 is a schematic diagram of an apparatus for the reaction of the present invention.

FIG. 2 is a schematic diagram of thermogravimetric analysis of magnesium chloride hexammoniate in accordance with an embodiment.

In fig. 1: 1-reactor, 2-material high-level tank, 3-automatic adjusting perforated partition board, 4-steam generator, 5-peristaltic pump, 6-primary ammonia water recovery device, 7-outlet pipe two, 8-secondary ammonia water recovery device, 9-outlet pipe one, 10-steam outlet pipe, 11-solid storage tank, 12-ball valve one, 13-ball valve two, 14-water tank, 15-ammonia water concentration tester, 16-water inlet pipe, 17-water outlet pipe, 18-automatic outlet pipe, and 19-thermometer.

Detailed Description

In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.

Weighing 9.85g (0.5mol) of a magnesium chloride hexammoniate sample, preparing a 0.1mol/L magnesium chloride hexammoniate solution, using methyl red as an indicator, using 0.1mol/L sodium hydroxide standard solution to measure the ammonia content of the magnesium chloride hexammoniate solution to be 51.3%, judging that the sample is magnesium chloride hexammoniate with 6NH3 (MgCl 2.6NH 3), analyzing the ammonia content of the magnesium chloride hexammoniate sample by a thermogravimetry method, further verifying the components of the magnesium chloride hexammoniate sample, and obtaining a result consistent with a titration method as shown in figure 2, wherein the sample is magnesium chloride hexammoniate with 6NH3 (MgCl 2.6NH 3).

As shown in figure 1, the reaction device comprises a reactor 1, the top of the reactor 1 is connected with a material high-level tank 2 through a ball valve I12, the middle part in the reactor 1 is provided with an automatic adjusting perforated partition plate 3, and the bottom of the reactor 1 is connected with a solid storage tank 11 through a ball valve II 13;

the bottom in the reactor 1 is provided with a left steam outlet pipe 10 and a right steam outlet pipe 10, the steam outlet pipes 10 are connected with a steam generator 4 through pipelines, heating belts are wound outside the pipelines for heating, the steam generator 4 is connected with a peristaltic pump 5, and the peristaltic pump 5 is connected with a water tank 14;

the top of the reactor 1 is connected with a primary ammonia water recovery device 6 through a first air outlet pipe 9, and the primary ammonia water recovery device 6 is connected with a secondary ammonia water recovery device 8 through a second air outlet pipe 7, so that ammonia water is recovered more thoroughly; an ammonia water concentration tester 15 is arranged in both the ammonia water concentration tester and is used for detecting the ammonia water concentration; the part of the second outlet pipe 7 in the secondary ammonia water recovery device 8 and the part of the first outlet pipe 9 in the primary ammonia water recovery device 6 are both perforated, so that the ammonia gas is discharged more quickly and uniformly.

The primary ammonia water recovery device 6 and the secondary ammonia water recovery device 8 are both provided with a water inlet pipe 16 and a water outlet pipe 17, and the top of the secondary ammonia water recovery device 8 is provided with an automatic air outlet pipe 18.

The reactor 1 is also provided with a thermometer 19.

Example one

S1: weighing 5Kg of magnesium chloride hexammoniate sample, crushing and uniformly putting into a reactor 1, and connecting a device as shown in figure 1;

s2: the connecting pipe of the water vapor generator 4 is inserted into the water tank 14 through the peristaltic pump 5;

s3: heating the reactor 1, and controlling the temperature of the reactor to be 120 ℃;

s4: starting the water vapor generator 4, controlling the temperature of the water vapor outlet to be 120 ℃ by heating, winding a heating belt on the pipeline of the water vapor generator 4 and the water vapor outlet pipe 10 for heating, controlling the temperature to be 120 ℃, and ensuring that the water entering the reactor 1 is water vapor;

s5: starting a peristaltic pump 5, controlling the speed to be 40g/min, carrying out a water vapor deamination reaction, receiving ammonia gas by using water, introducing water into a primary ammonia water recovery device 6 and a secondary ammonia water recovery device 8 to recover the ammonia gas to obtain ammonia water, and detecting the concentration of the ammonia water on line by using an ammonia water concentration tester 15;

s6: detecting the ammonia water concentration continuously for 30min without change on line, and finishing the water vapor replacement reaction;

s7: after the reaction, the solid state in the solid storage tank 11 was white crystals, and the ammonia content was 0.6% by titration.

Example two

S1: weighing 8Kg of magnesium chloride hexammoniate sample, crushing and uniformly putting into a reactor 1, and connecting the device as shown in figure 1;

s2: the connecting pipe of the water vapor generator 4 is inserted into the water tank 14 through the peristaltic pump 5;

s3: heating the reactor 1, and controlling the temperature of the reactor to be 120 ℃;

s4: starting the water vapor generator 4, controlling the temperature of the water vapor outlet to be 120 ℃ by heating, winding a heating belt on the pipeline of the water vapor generator 4 and the water vapor outlet pipe 10 for heating, controlling the temperature to be 120 ℃, and ensuring that the water entering the reactor 1 is water vapor;

s5: starting a peristaltic pump 5, controlling the speed to be 60g/min, carrying out a water vapor deamination reaction, receiving ammonia gas by using water, introducing water to a primary ammonia water recovery device 6 and a secondary ammonia water recovery device 8 to recover the ammonia gas to obtain ammonia water, and detecting the concentration of the ammonia water on line by using an ammonia water concentration tester 15;

s6: detecting the ammonia water concentration continuously for 30min without change on line, and finishing the water vapor replacement reaction;

s7: after the reaction, the solid state in the solid storage tank 11 was white crystals, and the ammonia content was 0.5% by titration.

Example three

S1: weighing 10kg of magnesium chloride hexammoniate sample, crushing, uniformly putting into a reactor 1, and connecting a device as shown in figure 1;

s2: the connecting pipe of the water vapor generator 4 is inserted into the water tank 14 through the peristaltic pump 5;

s3: heating the reactor 1, and controlling the temperature of the reactor to be 120 ℃;

s4: starting the water vapor generator 4, controlling the temperature of the water vapor outlet to be 120 ℃ by heating, winding a heating belt on the pipeline of the water vapor generator 4 and the water vapor outlet pipe 10 for heating, controlling the temperature to be 120 ℃, and ensuring that the water entering the reactor 1 is water vapor;

s5: starting a peristaltic pump 5, controlling the speed to be 80g/min, carrying out a water vapor deamination reaction, receiving ammonia gas by using water, introducing water into a primary ammonia water recovery device 6 and a secondary ammonia water recovery device 8 to recover the ammonia gas to obtain ammonia water, and detecting the concentration of the ammonia water on line by using an ammonia water concentration tester 15;

s6: detecting the ammonia water concentration continuously for 30min without change on line, and finishing the water vapor replacement reaction;

s7: after the reaction, the solid state in the solid storage tank 11 was white crystals, and the ammonia content was 0.6% by titration.

It can be seen that the above examples illustrate that by first detecting the ammonia content of magnesium chloride hexammoniate, it is convenient to understand approximately the amount of ammonia water obtained by the entire reaction; then, water vapor is used for reaction at the lower part and magnesium chloride hexammoniate is used for reaction at the upper part, so that the reaction effect is better and more thorough; NH3 in magnesium chloride hexammoniate MgCl 2.6 NH3 is replaced by magnesium chloride hexammoniate through a displacement reaction to generate MgCl 2.6H 2O, ammonia gas is regenerated into ammonia water for collection, the operation is simple, the energy consumption is low, a large amount of ammonia is recovered in the deamination process, and the cyclic utilization of resources is realized.