CN116102035A - Method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal - Google Patents
Method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal Download PDFInfo
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- CN116102035A CN116102035A CN202211434005.6A CN202211434005A CN116102035A CN 116102035 A CN116102035 A CN 116102035A CN 202211434005 A CN202211434005 A CN 202211434005A CN 116102035 A CN116102035 A CN 116102035A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 114
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 57
- 239000011777 magnesium Substances 0.000 claims abstract description 57
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 54
- -1 magnesium nitride Chemical class 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 26
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001404 mediated effect Effects 0.000 abstract description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 230000008901 benefit Effects 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal, which specifically comprises the following steps: reacting magnesium metal with nitrogen at high temperature to generate magnesium nitride, adding the magnesium nitride into water to generate magnesium hydroxide precipitate and ammonia gas, introducing hydrogen chloride gas into the magnesium hydroxide solution to obtain magnesium chloride solution, further heating and dehydrating to obtain anhydrous magnesium chloride, electrolyzing the anhydrous magnesium chloride to obtain chlorine gas and magnesium metal, and igniting the chlorine gas in hydrogen generated by water electrolysis to obtain the hydrogen chloride gas; thus forming a complete cycle. Compared with the circulation process of synthesizing ammonia mediated by metal lithium, the overpotential of magnesium ion reduction to metal magnesium is lower than that of lithium ion reduction to metal lithium, so that the electric energy required for electrolyzing magnesium chloride is lower than that of lithium chloride, the cost of the electric energy required for electrolyzing the magnesium chloride is lower, and only some reaction heat energy is required to be additionally provided. The metal magnesium mediated ammonia synthesis system is more suitable for being used as a supplement for consuming redundant electric energy and heat energy in various chemical industry, and has better application prospect.
Description
Technical Field
The invention relates to a method for synthesizing ammonia, in particular to a method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal.
Background
Nitrogen is an essential component of life forms and modern industrial society on earth. Ammonia (NH) 3 ) Is considered to be the most common chemical in modern times and is widely used in the chemical industry, while NH 3 Easy to store and transport, and plays an important role in future hydrogen economy. Currently, the only ammonia synthesis technology on an industrial scale was developed by the german chemist haber and bosch in the beginning of the 20 th centuryGas phase N 2 And H 2 The synthesis ammonia process is used as raw material. The Haber process has the problems of harsh conditions, high requirements on equipment, high energy consumption (2% of energy supply is consumed worldwide each year), low conversion rate and the like, and is not in line with the requirements of economic and social development. Especially when meeting the demand of small-scale synthetic ammonia, the Haber method synthetic ammonia device not only needs to put in huge construction cost in the early stage, but also has lower economic benefit compared with smaller scale.
Electrochemical synthesis of ammonia has been demonstrated in recent years to be feasible under mild conditions, as compared to the haber process, and is a potential ammonia replacement technique. However, the prior art has some technical difficulties to break through, so that the performances of ammonia production rate, faraday efficiency and the like are not high, and the commercial production gap is large.
Therefore, a metal-mediated ammonia synthesis strategy is proposed at present, taking magnesium metal as an example, magnesium metal reacts with nitrogen to obtain magnesium nitride, then magnesium hydroxide and ammonia are obtained after the magnesium hydroxide reacts with water continuously, magnesium hydroxide is electrolyzed after the magnesium hydroxide reacts to obtain magnesium metal, the metal is recycled, and the electric energy is the largest consumption in the recycling. The reduction potential of magnesium metal is lower than that of lithium metal. Therefore, the theoretical consumption of electric energy to reduce magnesium salts to metallic magnesium is less under the same conditions. In addition, magnesium metal requires less cost during storage and transportation than lithium metal.
Disclosure of Invention
The invention at least solves the existing problems of the industrial Haber method for synthesizing ammonia, and has the advantage of a certain technical cost compared with the method of synthesizing ammonia by participation of metallic lithium in circulation. The invention aims to provide a method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal.
The invention provides a method for synthesizing ammonia by taking magnesium metal as key medium and circularly participating in nitrogen fixation, which comprises the following steps: reacting magnesium metal with nitrogen at high temperature to generate magnesium nitride, adding magnesium nitride into water to generate magnesium hydroxide precipitate and ammonia gas, introducing hydrogen chloride gas into the magnesium hydroxide solution to obtain magnesium chloride solution, further heating and dehydrating to obtain anhydrous magnesium chloride, heating the anhydrous magnesium chloride to a molten state (700 ℃), electrolyzing to obtain chlorine gas and magnesium metal, and igniting the chlorine gas in hydrogen generated by water electrolysis to obtain hydrogen chloride gas; thus forming a complete cycle.
In the invention, the magnesium metal is used as a main carrier for nitrogen fixation, can be regenerated in the circulation process, and has no obvious consumption process except for some unavoidable loss.
In the invention, only nitrogen and water are used as chemical raw materials in the ammonia synthesis process, and electric energy is used as driving force for pushing circulation.
In the invention, magnesium metal is used as a key medium, and magnesium metal is obtained by electrolytic melting of magnesium chloride to realize the cyclic regeneration process.
In the invention, except nitrogen and water, the other raw materials participating in the circulation process of synthetic ammonia can realize the regeneration of percentage, and besides the unavoidable loss, the circulation efficiency of metal magnesium and chlorine can be close to 100 percent.
The invention has the advantage that the redundant electric energy and heat energy in the chemical industry can be utilized to realize small-scale synthesis of ammonia. The electric energy and the heat energy which are difficult to store are converted into high-energy-ratio and stable chemical energy.
The invention has the advantage that the redundant electric energy and heat energy in the chemical industry can be utilized to realize small-scale synthesis of ammonia. The electric energy and the heat energy which are difficult to store are converted into high-energy-ratio and stable chemical energy.
Compared with the industrial Haber method, the metal magnesium mediated synthesis ammonia system has lower requirement on a reaction device and is more beneficial to controlling the cost in the design of the device for synthesizing ammonia on a small scale.
Compared to the metal lithium mediated recycle process of synthetic ammonia, the overpotential for magnesium ion reduction to metal magnesium is lower than lithium ion reduction to metal lithium, and thus less power is required to electrolyze magnesium chloride than to electrolyze lithium chloride. Meanwhile, the cost of the metal magnesium in storage and transportation is lower than that of the metal lithium, better economic benefit can be realized in the small-scale ammonia synthesis process, the input cost of the infrastructure is obviously reduced, and the metal magnesium is more suitable for being used as a supplement for consuming redundant electric energy and heat energy in various chemical industry and has better flexibility.
The aim of the invention is achieved by the following scheme:
a method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal, which comprises the following steps:
(1) Heating and igniting metal magnesium in high-purity nitrogen to obtain magnesium nitride powder; generating solid magnesium nitride, collecting the generated magnesium nitride in nitrogen atmosphere, and preparing for the next reaction;
(2) Adding magnesium nitride powder into water, generating ammonia gas and magnesium hydroxide precipitate at normal temperature, collecting ammonia in a gaseous form, gradually increasing the temperature of the solution along with the reaction of magnesium nitride and water, and discharging ammonia in the residual dissolved solution;
(3) Introducing hydrogen chloride gas into the solution with the magnesium hydroxide precipitate until the magnesium hydroxide precipitate disappears, completely generating magnesium chloride, and further heating and concentrating to separate the magnesium chloride from the solution to obtain anhydrous magnesium chloride;
(4) Heating anhydrous magnesium chloride and anhydrous chloride salt to a molten state (700 ℃), electrifying to electrolyze, obtaining chlorine gas at an anode and obtaining magnesium metal at a cathode;
(5) The electrolysis of water generates hydrogen and oxygen, and the hydrogen and the chlorine are mixed and ignited to obtain hydrogen chloride gas;
the magnesium metal and hydrogen chloride are regenerated in the cycle, and the entire cycle is closed.
The heating ignition temperature of the metal magnesium and the high-purity nitrogen in the step (1) is 400-1000 ℃, preferably more than 700 ℃, so that the generation rate of magnesium nitride can be obviously improved;
the dosage ratio of the magnesium nitride to the water in the step (2) is 0.2-10 g: 50-2000 mL;
the reaction of magnesium nitride and water in the step (2) can be carried out at room temperature, the generated gas is ammonia only, and the gas generated by the reaction is collected to obtain high-purity ammonia; the reaction of magnesium nitride with water to produce ammonia and magnesium hydroxide is an exothermic reaction, and as the reaction proceeds, the system temperature gradually increases, and the reaction rate further increases. If the temperature is increased, the reaction speed can be further increased;
in the step (2), magnesium nitride reacts with water to generate magnesium hydroxide precipitate, a certain amount of hydrogen chloride gas is introduced into the water after separation, ammonium chloride is obtained after reaction, and finally ammonium chloride solid is obtained after dehydration;
the heating in the step (3) means heating at a temperature of 100-180 ℃ to obtain anhydrous magnesium chloride, and the preferable temperature is 150 ℃;
the anhydrous chloride in the step (4) is at least one of potassium chloride, sodium chloride, calcium chloride and other chlorides, so that the conductivity of the solution can be improved; in addition, the sodium chloride is added to promote the wetting angle between the electrolyte and the electrodes and promote the metal magnesium to collect on the electrodes; the calcium chloride can increase the density of the electrolyte, so that the reduced magnesium floats on the surface of the electrolyte more easily and is easy to collect;
the anhydrous chloride salt in step (4) is preferably anhydrous calcium chloride; the molar ratio of the anhydrous magnesium chloride to the anhydrous calcium chloride is 1: (0.2-1.2);
in the process for producing hydrogen chloride gas in the step (5), the molar ratio of hydrogen to chlorine is (1.2 to 2): 1, preferably 1.5:1.
compared with the prior art, the invention has the following advantages:
in the invention, the magnesium metal is used as the nitrogen fixation carrier, and the nitrogen fixation process of magnesium nitride is obtained by igniting in nitrogen, so that compared with the high-temperature and high-pressure conditions required by the Haber method, the reaction requirement and the efficiency of the nitrogen fixation of the magnesium metal have obvious advantages.
In the present invention, the nitrogen required for synthesizing ammonia gas is derived from nitrogen gas, and protons are derived from water.
In the invention, magnesium nitride directly reacts with water to generate ammonia and magnesium hydroxide precipitate, and magnesium hydroxide and ammonia can be separated and purified through simple precipitation separation and dehydration processes, thus greatly reducing the cost of product separation and purification.
In the invention, chlorine gas participates in the process of magnesium metal reduction (magnesium chloride is obtained by electrolysis and fusion) and synthesis of hydrogen chloride gas.
In the present invention, the metalMethod for synthesizing ammonia by magnesium circulation nitrogen fixation, and realizing faster Mg 2+ →Mg→Mg 3 N 2 →NH 3 The rate of the synthesis of ammonia depends on the rate of the electrolytic magnesium chloride and magnesium nitride synthesis.
In the present invention, in addition to nitrogen and water as main consumables, the theoretical conversion of the product involved in this cycle (magnesium- > magnesium nitride- > magnesium hydroxide- > magnesium chloride, magnesium chloride- > chlorine- > hydrogen chloride) at the time of conversion to the next product is close to 100%. Therefore, the circulation process has great application prospect.
Drawings
FIG. 1 is a schematic diagram of a method for synthesizing ammonia by circulating nitrogen with magnesium metal according to an embodiment of the invention.
Detailed Description
Specific embodiments of the present invention are further described below with reference to examples, but the embodiments and protection of the present invention are not limited to the examples provided below. It should be understood that if an existing process is involved in the industry and the laboratory is not able to fully simulate the conditions required for the process, the process should be implemented in accordance with industry standards in practice. Furthermore, the particular embodiments described below, unless otherwise indicated, are readily apparent to those skilled in the art from the teachings herein. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
(1) In this embodiment, the reaction of magnesium metal and nitrogen gas in a tube furnace produces magnesium nitride, which comprises the following steps:
1) A small amount of magnesium metal (0.5 g) was taken and charged into a tube furnace.
2) Continuously introducing 50ml/min of hydrogen into the tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and maintaining for 30min to ensure that magnesium oxide on the surface is reduced into magnesium metal.
3) At the same temperature, the hydrogen was replaced with nitrogen. After 2 hours of reaction, a yellowish green powder was obtained in a tube furnace.
The result shows that the magnesium nitride is successfully synthesized, and the conversion rate of the metal magnesium is more than 90 percent.
(2) In this example, magnesium nitride was added to water to form magnesium hydroxide and ammonia.
In this example, the reaction of lithium nitride with ammonium chloride was carried out in a fume hood. The method comprises the following steps:
1) An appropriate amount of magnesium nitride (0.5 g) was added to 50mL of the aqueous solution.
2) The magnesium nitride reacts vigorously in water, and the rise in solution temperature is clearly perceived.
3) After the reaction, white precipitate was observed in water, and the generated gas was absorbed by a 0.1mol/L hydrochloric acid solution, and the concentration of ammonia in the hydrochloric acid solution was measured by an indophenol blue color development method.
The results show that magnesium nitride reacts well with water, and the conversion rate of magnesium nitride is close to 100%.
(3) In this example, the magnesium hydroxide precipitate was added with hydrogen chloride to form a magnesium chloride solution.
1) An appropriate amount of magnesium hydroxide (0.5 g) was added to a 0.1mol/L hydrochloric acid solution (50 mL) to simulate the passage of hydrogen chloride into water.
2) The magnesium hydroxide was rapidly dissolved in the hydrochloric acid solution, and the complete disappearance of the white precipitate was observed in about 2 minutes.
The results show that magnesium hydroxide is completely converted into magnesium chloride, and the conversion rate of magnesium hydroxide is close to 100%.
Further concentrating at 150deg.C to separate magnesium chloride from the solution to obtain anhydrous magnesium chloride.
(4) In this example, molten calcium chloride and magnesium chloride mixture was electrolyzed to produce chlorine gas and magnesium metal.
The electrolysis process in the examples was carried out in a fume hood, with the following specific steps:
1) Proper amounts of anhydrous calcium chloride (5 g) and anhydrous magnesium chloride (15 g) are weighed and put into a crucible, and are heated to a molten state by an alcohol lamp under the protection of argon atmosphere.
2) And inserting a graphite rod into the crucible, electrifying to electrolyze, wherein obvious bubbles are generated at the anode, and floating molten metal is arranged on the surface of the molten liquid after a period of time.
3) Gradually cooling the liquid in the crucible, and pouring out the surface molten metal after the calcium chloride and magnesium chloride eutectic liquid is solidified, so as to obtain the magnesium metal.
The results show that magnesium metal and chlorine gas were successfully obtained by electrolysis of molten magnesium chloride salt.
(5) In this example, electrolysis of water produces hydrogen and oxygen. The method comprises the following specific steps:
1) In an H-cell, both the cathode and anode were tested using platinum sheets.
2) And electrifying to electrolyze, wherein obvious bubbles are generated at the cathode and the anode.
The results indicate that hydrogen is generated at the cathode and oxygen is generated at the anode. In addition, the partial reactions, such as the industrial technologies of magnesium metal production by an electrolytic cell, hydrogen chloride industry, hydrogen production by water electrolysis and the like, are very mature, so that the actual industrial production conditions should be based in the implementation process.
Hydrogen and chlorine were mixed in a molar ratio of 1.5:1, mixing and igniting to obtain hydrogen chloride gas;
the magnesium metal and hydrogen chloride are regenerated in the cycle, and the entire cycle is closed.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing ammonia by medium circulation nitrogen fixation based on magnesium metal is characterized in that: heating and igniting metal magnesium and nitrogen to react to generate magnesium nitride, adding the magnesium nitride into water to generate magnesium hydroxide precipitate and ammonia gas, introducing hydrogen chloride gas into the magnesium hydroxide solution to obtain magnesium chloride solution, further heating and dehydrating to obtain anhydrous magnesium chloride, heating the anhydrous magnesium chloride to a molten state, electrolyzing to obtain chlorine gas and metal magnesium, and igniting the chlorine gas in hydrogen generated by water electrolysis to obtain hydrogen chloride gas; thus forming a complete cycle.
2. The method for synthesizing ammonia by circulating nitrogen based on a medium of metal magnesium according to claim 1, which is characterized by comprising the following steps:
(1) Heating and igniting metal magnesium in nitrogen to obtain magnesium nitride powder; generating solid magnesium nitride, collecting the generated magnesium nitride in nitrogen atmosphere, and preparing for the next reaction;
(2) Adding magnesium nitride powder into water, generating ammonia gas and magnesium hydroxide precipitate at normal temperature, collecting ammonia in a gaseous form, gradually increasing the temperature of the solution along with the reaction of magnesium nitride and water, and discharging ammonia in the residual dissolved solution;
(3) Introducing hydrogen chloride gas into the solution with the magnesium hydroxide precipitate until the magnesium hydroxide precipitate disappears, completely generating magnesium chloride, and further heating and concentrating to separate the magnesium chloride from the solution to obtain anhydrous magnesium chloride;
(4) Heating anhydrous magnesium chloride and anhydrous chloride salt to a molten state, electrifying to electrolyze, obtaining chlorine at an anode and obtaining magnesium metal at a cathode;
(5) The electrolysis of water generates hydrogen and oxygen, and the hydrogen and the chlorine are mixed and ignited to obtain hydrogen chloride gas;
the magnesium metal and hydrogen chloride are regenerated in the cycle, and the entire cycle is closed.
3. The method for synthesizing ammonia by circulating nitrogen-fixing through medium based on metal magnesium according to claim 1 or 2, wherein the method comprises the following steps: the heating ignition temperature of the magnesium metal and the nitrogen is 400-1000 ℃.
4. The method for synthesizing ammonia by circulating nitrogen-fixing through medium based on metal magnesium according to claim 1 or 2, wherein the method comprises the following steps: the heating ignition temperature of the magnesium metal and the nitrogen is 700-1000 ℃.
5. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 2, wherein the method comprises the following steps: the dosage ratio of the magnesium nitride to the water in the step (2) is 0.2-10 g: 50-2000 mL.
6. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 2, wherein the method comprises the following steps: the heating in the step (3) means heating at a temperature of 100-180 ℃ to obtain anhydrous magnesium chloride.
7. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 6, wherein the method comprises the following steps: the heating in the step (3) means heating at a temperature of 150 ℃ to obtain anhydrous magnesium chloride.
8. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 2, wherein the method comprises the following steps: the anhydrous chloride in the step (4) is at least one of potassium chloride, sodium chloride and calcium chloride.
9. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 2, wherein the method comprises the following steps: the anhydrous chloride salt in the step (4) is anhydrous calcium chloride; the molar ratio of the anhydrous magnesium chloride to the anhydrous calcium chloride is 1: (0.2-1.2).
10. The method for synthesizing ammonia by circulating nitrogen-fixing medium based on magnesium metal according to claim 2, wherein the method comprises the following steps: in the step (5), the molar ratio of the hydrogen to the chlorine is (1.2-2): 1.
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| CN110877894A (en) * | 2018-09-06 | 2020-03-13 | 氢储(上海)能源科技有限公司 | Hydrogen storage and discharge method and system based on magnesium-based hydrogen storage material |
| CN114604831A (en) * | 2022-04-13 | 2022-06-10 | 清华大学 | Method for synthesizing ammonia by circularly fixing nitrogen with metal lithium |
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| CN110877894A (en) * | 2018-09-06 | 2020-03-13 | 氢储(上海)能源科技有限公司 | Hydrogen storage and discharge method and system based on magnesium-based hydrogen storage material |
| CN114604831A (en) * | 2022-04-13 | 2022-06-10 | 清华大学 | Method for synthesizing ammonia by circularly fixing nitrogen with metal lithium |
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| Title |
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| 陈闽: "《做有趣老师，教有趣化学》", 31 December 2020, 中国海洋大学出版社, pages: 60 * |
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