CN111017955A - Ammonia production method and system based on chemical chain reaction - Google Patents
Ammonia production method and system based on chemical chain reaction Download PDFInfo
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- CN111017955A CN111017955A CN201911339839.7A CN201911339839A CN111017955A CN 111017955 A CN111017955 A CN 111017955A CN 201911339839 A CN201911339839 A CN 201911339839A CN 111017955 A CN111017955 A CN 111017955A
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
Abstract
The invention relates to an ammonia production method and system based on chemical chain reaction. In the ammonia preparation method, solid metal and nitrogen gas are subjected to nitridation reaction to generate a nitrogen carrier; the nitrogen carrier and hydrogen gas are subjected to ammoniation reaction to generate ammonia gas and regenerated solid metal. The ammonia production system comprises a nitriding fluidized bed and an ammoniation fluidized bed; the nitriding fluidized bed is used for carrying out nitriding reaction on solid metal and nitrogen in the nitriding fluidized bed to generate a nitrogen carrier; the ammoniation fluidized bed is used for carrying out ammoniation reaction on the nitrogen carrier and the hydrogen generated by the ammoniation fluidized bed to generate ammonia gas and regenerated solid metal. Compared with the Hubbo method, the ammonia preparation method and the system have the advantages of low energy consumption, low cost, high ammonia preparation efficiency, simple operation and the like, and are efficient and economic.
Description
Technical Field
The invention relates to an ammonia production method and system based on chemical chain reaction.
Background
Ammonia is an important chemical product with wide application, and has wide application in the fields of chemical fertilizers, refrigeration, denitration and the like. The combustion reaction of ammonia is: 4NH3+3O2＝2N2+6H2O generates nitrogen and water which have no pollution to the environment, ammonia can be used as a new clean energy,and realizing carbon emission reduction.
At present, there are many technologies related to ammonia production, including ammonia production from natural gas, ammonia production from coal (coke), ammonia production from nitrogen hydrogenation, etc., and the principle is to convert extracted hydrogen and nitrogen into ammonia gas by the habo method under the condition of high-temperature and high-pressure catalyst.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a simple ammonia production method and system based on chemical chain reaction.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides an ammonia preparation method based on chemical chain reaction, which comprises the following steps: s1, carrying out nitridation reaction on the solid metal and nitrogen in a nitridation fluidized bed to generate a nitrogen carrier; and S2, carrying nitrogen and hydrogen to carry out ammoniation reaction in an ammoniation fluidized bed to generate ammonia and regenerated solid metal.
According to the invention, in step S1: the solid metal and nitrogen are subjected to nitridation reaction at the temperature of 100-600 ℃ and under normal pressure; in step S2: the generated nitrogen carrier and hydrogen gas are subjected to amination reaction at 100-500 ℃ and normal pressure.
According to the invention, the solid metal is Li, the Li and nitrogen carry out nitridation reaction under the conditions that the volume ratio is 6:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Li3N，Li3Carrying out amination reaction on N and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 300 ℃ to generate ammonia gas and Li; or the solid metal is Mg, the nitriding reaction is carried out on the Mg and the nitrogen under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Mg3N2，Mg3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia gas and Mg; or the solid metal is Zn, the Zn and the nitrogen gas are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Zn3N2，Zn3N2Carrying out amination reaction with hydrogen at the volume ratio of 1:3 and at the temperature of less than or equal to 400 ℃ to generate ammonia gas and Zn; or the solid metal is Mn, the Mn and the nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 400 ℃, and the generated nitrogen carrier is Mn3N2，Mn3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia and Mn; or the solid metal is Fe, the Fe and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 8:1 and the temperature is less than or equal to 100 ℃, and the generated nitrogen carrier is Fe2N and Fe4N，Fe2N and Fe4Carrying out amination reaction on the N whole and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 100 ℃ to generate ammonia gas and Fe; or the solid metal is Mo, the Mo and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 2:1 and the temperature is less than or equal to 150 ℃, the generated nitrogen carrier is MoN, and the MoN and hydrogen are subjected to amination reaction under the conditions that the volume ratio is 2:3 and the temperature is less than or equal to 125 ℃ to generate ammonia gas and Mo.
According to the invention, step S1 further comprises: unreacted nitrogen in the nitriding fluidized bed carries nitrogen carriers to leave the nitriding fluidized bed, then the nitrogen and the nitrogen carriers are separated through a first solid-gas separator, the separated nitrogen is sent back to the nitriding fluidized bed, and the separated nitrogen carriers are sent to an ammoniation fluidized bed; step S2 further includes: the mixed gas containing the generated ammonia gas and the unreacted hydrogen gas in the ammoniation fluidized bed carries the regenerated solid metal to leave the ammoniation fluidized bed, then the regenerated solid metal and the mixed gas are separated through a second solid-gas separator, the separated regenerated solid metal is sent into the nitriding fluidized bed, the separated mixed gas enables the hydrogen gas and the gaseous or liquid ammonia to be respectively discharged through a separating device, and the discharged hydrogen gas is sent back to the ammoniation fluidized bed.
The invention provides an ammonia preparation system of an ammonia preparation method based on chemical chain reaction, which comprises a nitriding fluidized bed, a first solid-gas separator, an ammoniation fluidized bed, a second solid-gas separator and a separation device, wherein the nitriding fluidized bed is arranged on the top of the first solid-gas separator; the nitriding fluidized bed is used for carrying out nitriding reaction on solid metal and nitrogen in the nitriding fluidized bed to generate a nitrogen carrier, and unreacted nitrogen and the nitrogen carrier can be discharged together; the first solid-gas separator is communicated with the nitriding fluidized bed to receive unreacted nitrogen and nitrogen carriers discharged by the nitriding fluidized bed and separate the nitrogen and the nitrogen carriers; the ammoniation fluidized bed is communicated with the first solid-gas separator to receive the nitrogen carrier separated by the first solid-gas separator, and the ammoniation fluidized bed is used for carrying out ammoniation reaction on the nitrogen carrier and hydrogen gas therein to generate ammonia gas and regenerated solid metal, and discharging the generated ammonia gas, unreacted hydrogen gas and regenerated solid metal together; the second solid-gas separator is communicated with the ammoniation fluidized bed to receive the ammonia gas, the unreacted hydrogen gas and the regenerated solid metal which are discharged from the ammoniation fluidized bed, and separate the regenerated solid metal and the mixed gas comprising the ammonia gas and the hydrogen gas; the separation device is communicated with the second solid-gas separator to receive the mixed gas and separate out hydrogen and gaseous or liquid ammonia.
According to the invention, the first solid-gas separator comprises a first solid-gas separator gas outlet which is communicated with the nitriding fluidized bed so as to send the separated nitrogen back to the nitriding fluidized bed; the second solid-gas separator is communicated with the nitriding fluidized bed so as to send the regenerated solid metal into the nitriding fluidized bed; the separation device is communicated with the ammoniation fluidized bed so as to send the separated hydrogen back to the ammoniation fluidized bed.
According to the invention, the nitriding fluidized bed comprises a nitriding fluidized bed body, a nitrogen inlet, a nitriding fluidized bed outlet, a nitriding fluidized bed feed inlet, a nitriding fluidized bed return port and a nitriding fluidized bed return port, wherein the nitrogen inlet, the nitriding fluidized bed outlet, the nitriding fluidized bed feed inlet, the nitriding fluidized bed return port and the nitriding fluidized bed return port are all communicated with the interior of the nitriding fluidized bed body; the first solid-gas separator also comprises a first solid-gas separator inlet and a first solid-gas separator solid outlet, the first solid-gas separator inlet is communicated with the outlet of the nitriding fluidized bed, and the first solid-gas separator gas outlet is communicated with the gas return port of the nitriding fluidized bed; the ammonification fluidized bed comprises an ammonification fluidized bed body, a hydrogen inlet, an ammonification fluidized bed outlet, an ammonification fluidized bed feed inlet and an ammonification fluidized bed return gas port, wherein the hydrogen inlet, the ammonification fluidized bed outlet, the ammonification fluidized bed feed inlet and the ammonification fluidized bed return gas port are all communicated with the inside of the ammonification fluidized bed body; the second solid-gas separator comprises a second solid-gas separator inlet, a second solid-gas separator gas outlet and a second solid-gas separator solid outlet, the second solid-gas separator inlet is communicated with the ammoniation fluidized bed outlet, and the second solid-gas separator solid outlet is communicated with the nitriding fluidized bed material return port; the separation device comprises a separation device inlet, a first separation device outlet and a second separation device outlet, the separation device inlet is communicated with the gas outlet of the second solid-gas separator, the first separation device outlet is communicated with the gas return port of the ammoniation fluidized bed, and the second separation device outlet is used for discharging gaseous or liquid ammonia.
(III) advantageous effects
The invention has the beneficial effects that:
the basic principle of the ammonia preparation method is that solid metal firstly reacts with nitrogen to generate nitrogen carrier, and then reacts with hydrogen to generate ammonia gas through ammoniation reaction. Compared with the Hubbo method, the method has the advantages of low energy consumption, low cost, high ammonia production efficiency, simple operation and the like, can obtain high-purity ammonia gas or liquid ammonia, and is an efficient and economic ammonia production method.
The ammonia production system has simple structure, can obtain high-purity ammonia gas or liquid ammonia, has low investment and energy consumption, and is an efficient and economic ammonia production system based on chemical chain reaction.
Drawings
FIG. 1 is a schematic diagram of an ammonia system based on a chemical looping reaction provided in the following detailed description.
[ reference numerals ]
1: nitriding the fluidized bed; 11: an outlet of the nitriding fluidized bed; 12: a feeding hole of a nitriding fluidized bed; 13: nitriding the fluidized bed body; 14: a gas return port of the nitriding fluidized bed; 15: a nitrogen inlet; 16: a material returning port of the nitriding fluidized bed;
2: a first solid-gas separator; 21: a solid outlet of the first solid-gas separator; 22: a gas outlet of the first solid-gas separator; 23: a first solid-gas separator inlet;
3: an ammoniation fluidized bed; 31: an outlet of the ammoniation fluidized bed; 32: an ammoniation fluidized bed gas return port; 33: ammoniating the fluidized bed body; 34: a hydrogen inlet; 35: a feed inlet of an ammoniation fluidized bed;
4: a second solid-gas separator; 41: an inlet of a second solid-gas separator; 42: a solid outlet of the second solid-gas separator; 43: a gas outlet of the second solid-gas separator;
5: a separation device; 51: a separation device inlet; 52: a separation device first outlet; 53: a second outlet of the separation device.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings. Where directional terms such as "top," "bottom," "upper," "lower," etc., are used herein, reference is made to the orientation shown in fig. 1.
Example one
Referring to fig. 1, the present example provides an ammonia production system based on a chemical looping reaction. The ammonia production system based on the chemical chain reaction comprises a nitridation reactor 1, a first solid-gas separator 2, an ammoniation reactor 3, a second solid-gas separator 4 and a separation device 5.
The nitriding reactor 1 is used for nitriding solid metal and nitrogen gas in the nitriding reactor to generate nitrogen carrier (solid), and unreacted nitrogen gas and the nitrogen carrier can be discharged together.
Specifically, the nitriding fluidized bed 1 comprises a nitriding fluidized bed body 13, a nitrogen inlet 15, a nitriding fluidized bed outlet 11, a nitriding fluidized bed feed inlet 12, a nitriding fluidized bed gas return port 14 and a nitriding fluidized bed material return port 16. Solid metal and nitrogen are supplied to the interior of the nitriding fluidized bed body 13 to carry out nitriding reaction in the nitriding fluidized bed body, and a nitrogen carrier is generated. The nitrogen inlet 15, the outlet 11 of the nitriding fluidized bed, the feeding port 12 of the nitriding fluidized bed, the gas return port 14 of the nitriding fluidized bed and the material return port 16 of the nitriding fluidized bed are communicated with the inside of the bed body 13 of the nitriding fluidized bed. The nitrogen inlet 15 is arranged at the bottom of the bed body 13 of the nitriding fluidized bed and is used for allowing nitrogen to enter the interior of the bed body 13 of the nitriding fluidized bed. The feeding port 12 of the nitriding fluidized bed is positioned at the upper part of the side wall of the bed body 13 of the nitriding fluidized bed, so that nitrogen carriers which are added at first and are newly supplied enter the interior of the bed body 13 of the nitriding fluidized bed. The outlet 11 of the nitriding fluidized bed is arranged at the top of the bed body 13 of the nitriding fluidized bed, so that unreacted nitrogen and generated nitrogen carriers can be discharged out of the nitriding fluidized bed 1. The air return port 14 of the nitriding fluidized bed is arranged at the bottom of the bed body 13 of the nitriding fluidized bed, and is used for discharging unreacted nitrogen out of the nitriding fluidized bed 1 and then entering the interior of the bed body 13 of the nitriding fluidized bed for recycling. The nitriding fluidized bed material returning port 16 is arranged at the lower part of the side wall of the nitriding fluidized bed body 13, and is used for returning the regenerated nitrogen carrier in the subsequent process steps to the interior of the nitriding fluidized bed body 13 for cyclic utilization.
The first solid-gas separator 2 communicates with the nitriding fluidized bed 1 to receive the unreacted nitrogen gas and the nitrogen carrier discharged from the nitriding fluidized bed 1 and separate the nitrogen gas and the nitrogen carrier.
Specifically, the first solid-gas separator 2 is located above the nitriding fluidized bed 1. The first solid-gas separator 2 comprises a first solid-gas separator inlet 23, a first solid-gas separator gas outlet 22 and a first solid-gas separator solids outlet 21. The first solid-gas separator inlet 23 communicates with the outlet 11 of the nitriding fluidized bed to receive unreacted nitrogen and nitrogen carrier in the nitriding fluidized bed 1. The first solid-gas separator 2 is used for separating nitrogen gas and nitrogen carrier. And a gas outlet 22 of the first solid-gas separator is communicated with the gas return port 14 of the nitriding fluidized bed and is used for returning the separated nitrogen to the nitriding fluidized bed 1 for recycling. The solid outlet 21 of the first solid-gas separator is used for discharging the separated nitrogen carrier.
The ammoniation fluidized bed 3 is communicated with the first solid-gas separator 2 to receive the nitrogen carrier separated by the first solid-gas separator 2, and the ammoniation reactor 3 is used for ammoniation reaction of the nitrogen carrier and hydrogen generated by the ammoniation reactor to generate ammonia gas and regenerated solid metal, and the generated ammonia gas, unreacted hydrogen gas and regenerated solid metal are discharged together. Wherein the regenerated solid metal is identical to the solid metal previously participating in the reaction in the nitriding reactor 1.
Specifically, the ammoniation fluidized bed 3 comprises an ammoniation fluidized bed body 33, a hydrogen inlet 34, an ammoniation fluidized bed outlet 31, an ammoniation fluidized bed feed inlet 35 and an ammoniation fluidized bed return gas inlet 32. The nitrogen-carrying body and the hydrogen gas are supplied to the interior of the bed body 33 of the ammoniation fluidized bed for ammoniation reaction to generate ammonia gas and regenerated solid metal. The hydrogen inlet 34, the ammoniation fluidized bed outlet 31, the nitrogenation fluidized bed feed inlet 12 and the ammoniation fluidized bed return port 32 are all communicated with the inside of the ammoniation fluidized bed body 33. The hydrogen inlet 34 is disposed at the bottom of the ammoniated fluidized bed body 33 and is used for injecting hydrogen into the ammoniated fluidized bed body 33. The feeding port 32 of the ammoniation fluidized bed is arranged at the lower part of the side wall of the bed body 33 of the ammoniation fluidized bed, is lower than the solid outlet 21 of the first solid-gas separator and is communicated with the solid outlet 21 of the first solid-gas separator so as to receive the nitrogen carrier separated by the first solid-gas separator 2. An ammoniated fluidized bed outlet 31 is provided at the top of the bed 33 of the ammoniated fluidized bed for carrying the regenerated solid metal out of the ammoniated fluidized bed 3 with a mixture comprising the generated ammonia gas and unreacted hydrogen gas. The return port 32 of the ammoniation fluidized bed is arranged at the lower part of the side wall of the bed body 33 of the ammoniation fluidized bed and is used for receiving unreacted hydrogen and returning the hydrogen to the nitriding fluidized bed 1 for recycling.
The second solid-gas separator 4 is in communication with the ammoniation fluidized bed 3 to receive the ammonia gas, unreacted hydrogen gas and regenerated solid metal discharged from the ammoniation fluidized bed 3 and to separate the regenerated solid metal and a mixture gas including the ammonia gas and the hydrogen gas.
In particular, the second solid-gas separator 4 is located above the ammoniated fluidizer. The second solid-gas separator 4 comprises a second solid-gas separator inlet 41, a second solid-gas separator gas outlet 43 and a second solid-gas separator solids outlet 42. The second solid gas separator inlet 41 is in communication with the ammoniated fluidized bed outlet 31 to receive ammonia gas, unreacted hydrogen gas and regenerated solid metal exiting the ammoniated fluidized bed 3. The second solid-gas separator 4 is used for separating the regenerated solid metal and the mixed gas (including ammonia gas and hydrogen gas). The solid outlet 42 of the second solid-gas separator is higher than the return port 16 of the nitriding fluidized bed and is communicated with the return port 16 of the nitriding fluidized bed so as to return the regenerated solid metal to the nitriding fluidized bed 1 for recycling. The gas outlet 43 of the second solid-gas separator is used for discharging the mixed gas.
The separation device 5 is communicated with the second solid-gas separator 4 to receive the mixed gas and separate out hydrogen and gaseous or liquid ammonia.
In particular, the separation device 5 is located laterally to the second solid-gas separator 4. The separating device 5 comprises a separating device inlet 51, a separating device first outlet 52 and a separating device second outlet 53. The separator inlet 51 communicates with the second solid-gas separator gas outlet 43 to receive the above-mentioned mixture gas. The separation device 5 is used to separate hydrogen and ammonia (gaseous or liquid). The first outlet 52 of the separation device is in communication with the return gas port 32 of the ammoniation fluidized bed to send separated nitrogen back to the nitriding fluidized bed 1. The second outlet 53 of the separation device is used to discharge ammonia (gaseous or liquid) to the subsequent collection device. Preferably, the separation device 5 is a pressure device to separate ammonia gas into high-purity liquid ammonia from hydrogen gas. Of course, the invention is not limited to other well-established ammonia-hydrogen separation devices, such as condensing devices, for separating the mixed hydrogen and ammonia gases.
The communication mentioned in the embodiment is preferably communicated by adopting a pipeline.
In conclusion, the ammonia production system based on the chemical chain reaction has a simple structure, can obtain high-purity ammonia gas or liquid ammonia, has low investment and energy consumption, and is an efficient and economic ammonia production system based on the chemical chain reaction. And the nitrogen, the hydrogen and the oxygen carrier are recycled, so that the cost is further reduced.
Example two
The embodiment provides an ammonia production method based on chemical chain reaction, which is implemented by using the ammonia production system based on chemical chain reaction in the first embodiment, and the method comprises the following steps:
s1, carrying out a nitridation reaction on the solid metal and nitrogen in the nitridation fluidized bed 1 to generate a nitrogen carrier;
s2, carrying nitrogen and hydrogen gas to generate ammonia gas and regenerated solid metal in the ammonification reaction in the ammonification fluidized bed 3.
Specifically, in step S1:
solid metal is filled into the nitriding fluidized bed 1 from a feeding hole 12 of the nitriding fluidized bed, and the feeding hole 12 of the nitriding fluidized bed is closed after the feeding is finished. Nitrogen, either pure nitrogen produced by means of chemical looping or the like or nitrogen obtained by air separation, is fed into the bed 13 of the nitriding fluidized bed through a nitrogen inlet 15. The nitrogen gas moves upwards in the nitriding fluidized bed 1, and the solid metal and the nitrogen gas in the nitriding fluidized bed 1 are subjected to nitriding reaction at the temperature of 100-600 ℃ and under normal pressure to generate the nitrogen carrier. Wherein, the solid metal refers to a metal simple substance, and the nitriding reaction is expressed by the following chemical equation:
Mex+(y/2)N2(g)→MexNywherein Me represents a metal element, and x and y are selected according to the selected specific metal.
For example, the solid metal is Li, the volume ratio of Li to nitrogen is 6:1, and the temperature is less than or equal to 300 ℃, the generated solid nitride-carried nitrogen carrier is Li3N；
For example, the solid metal is Mg, the nitriding reaction of Mg and nitrogen occurs under the conditions that the volume ratio of Mg to nitrogen is 3:1 and the temperature is less than or equal to 300 ℃, and the generated solid nitride nitrogen carrier is Mg3N2；
For example, the solid metal is Zn, the Zn and nitrogen gas are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 300 ℃, and the generated solid nitride nitrogen carrier is Zn3N2；
For example, the solid metal is Mn, the Mn and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 400 ℃, and the generated solid nitride nitrogen carrier is Mn3N2；
For example, the solid metal is Fe, the Fe and nitrogen gas are subjected to nitridation reaction under the conditions that the volume ratio is 8:1 and the temperature is less than or equal to 100 ℃, and the generated solid nitride carrier nitrogen is Fe2N and Fe4N；
For example, the solid metal is Mo, the Mo and nitrogen carry out nitridation reaction under the conditions that the volume ratio is 2:1 and the temperature is less than or equal to 150 ℃, and the generated solid nitride carrier nitrogen is MoN.
After the reaction is stable, unreacted nitrogen in the nitriding fluidized bed 1 carries nitrogen carriers to move upwards to leave the nitriding fluidized bed 1 from the outlet 11 of the nitriding fluidized bed, the nitrogen carriers enter the first solid-gas separator 2 through the inlet 23 of the first solid-gas separator, then the nitrogen and the nitrogen carriers are separated through the first solid-gas separator 2, the separated nitrogen is sent back to the inside of the nitriding fluidized bed body 13 through the gas outlet 22 of the first solid-gas separator and the gas return port 14 of the nitriding fluidized bed, and the separated nitrogen carriers are sent to the inside of the ammonification fluidized bed body 33 through the solid outlet 21 of the first solid-gas separator and the feed port 35 of the ammonification fluidized bed.
The gas flow can be tested by respectively arranging venturi flow meters on a pipeline connected with the nitrogen inlet 15 and a pipeline between the outlet 11 of the nitriding fluidized bed and the inlet 23 of the first solid-gas separator, and when the measured values of the two gas flow meters are similar or equivalent, the reaction can be considered to be stable.
Specifically, in step S2:
hydrogen is introduced into the bed body 33 of the ammoniation fluidized bed from a hydrogen inlet 34, and the hydrogen can be obtained by chemical looping hydrogen production, fossil fuel hydrogen production and the like. The hydrogen gas moves upwards in the ammonification fluidized bed body 33, and the nitrogen-carrying body and the hydrogen gas in the ammonification fluidized bed body 33 carry out ammonification reaction at the temperature of 100 ℃ and 500 ℃ and under normal pressure to generate ammonia gas and regenerated solid metal. The above-described amination reaction is represented by the following chemical equation:
MexNy+(3y/2)H2(g)→xMe+yNH3(g)。
the solid nitride carrier is Li3In the case of N, Li3Carrying out amination reaction on N and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 300 ℃ to generate ammonia gas and Li;
the solid nitride carrier being Mg3N2In the case of (2), Mg3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia gas and Mg;
the solid nitride carrier is Zn3N2In the case of (1), Zn3N2Carrying out amination reaction with hydrogen at the volume ratio of 1:3 and at the temperature of less than or equal to 400 ℃ to generate ammonia gas and Zn;
the solid nitride carrier is Mn3N2In the case of (2), Mn3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia and Mn;
the solid nitride carrier is Fe2N and Fe4In the case of N, Fe2N and Fe4Carrying out amination reaction on the N whole and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 100 ℃ to generate ammonia gas and Fe;
under the condition that the solid nitride carrier is MoN, the MoN and hydrogen are subjected to amination reaction at the volume ratio of 2:3 and the temperature of less than or equal to 125 ℃ to generate ammonia gas and Mo.
The mixed gas (including the generated ammonia gas and the unreacted hydrogen gas) in the ammoniation fluidized bed 3 moves upwards to carry the regenerated solid metal to leave the ammoniation fluidized bed 3 from an outlet 31 of the ammoniation fluidized bed, enters a second solid-gas separator 4 through an inlet 41 of the second solid-gas separator, then the regenerated solid metal and the mixed gas are separated by the second solid-gas separator 4, the separated regenerated solid metal is sent into the nitriding fluidized bed 1 through a solid outlet 42 of the second solid-gas separator, the separated mixed gas enters a separating device 5 through a gas outlet 43 of the second solid-gas separator and an inlet 51 of the separating device, and the hydrogen gas and the gaseous or liquid ammonia are formed through the separating device 5. The hydrogen is discharged from the first outlet 52 of the separation device and then enters the bed body 33 of the ammoniation fluidized bed through the gas return port of the ammoniation fluidized bed 3, and the discharged hydrogen is sent back to the ammoniation fluidized bed 3 for recycling. While gaseous or liquid ammonia is discharged from the second outlet 53 of the separation device to a subsequent collection device. When the separation device 5 is a pressure device, liquid ammonia is discharged from the second outlet 53 of the separation device.
In summary, the present embodiment is a novel method for producing ammonia by using chemical chains, and the basic principle is that the nitrogen carrier reacts with nitrogen to form nitride, and then reacts with hydrogen to form ammonia through ammonification. Compared with the Hubbo method, the method has the advantages of low energy consumption, low cost, high ammonia production efficiency, simple operation and the like, can obtain high-purity ammonia gas or liquid ammonia, and is an efficient and economic ammonia production method. And the nitrogen, the hydrogen and the oxygen carrier are recycled, so that the cost is further reduced.
Of course, the ammonia production method of the present invention is not limited to the ammonia production system based on the chemical looping reaction of the present invention, and can be applied to any ammonia production system capable of realizing the corresponding steps.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (7)
1. A method for preparing ammonia based on chemical chain reaction is characterized by comprising the following steps:
s1, carrying out nitridation reaction on the solid metal and nitrogen in the nitridation fluidized bed (1) to generate a nitrogen carrier;
s2, the nitrogen carrier and hydrogen are subjected to an ammoniation reaction in an ammoniation fluidized bed (3) to generate ammonia gas and regenerated solid metal.
2. The ammonia production method based on chemical looping reaction according to claim 1,
in step S1:
the solid metal and nitrogen are subjected to nitridation reaction at the temperature of 100-600 ℃ and under normal pressure;
in step S2:
the generated nitrogen carrier and hydrogen gas are subjected to amination reaction at 100-500 ℃ and normal pressure.
3. The ammonia production method based on chemical looping reaction according to claim 2,
the solid metal is Li, the Li and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 6:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Li3N，Li3Carrying out amination reaction on N and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 300 ℃ to generate ammonia gas and Li; or
The solid metal is Mg, the nitriding reaction is carried out on the Mg and nitrogen under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Mg3N2，Mg3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia gas and Mg; or
The solid metal is Zn, the Zn and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 300 ℃, and the generated nitrogen carrier is Zn3N2，Zn3N2Carrying out amination reaction with hydrogen at the volume ratio of 1:3 and at the temperature of less than or equal to 400 ℃ to generate ammonia gas and Zn; or
The solid metal is Mn, the Mn and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 3:1 and the temperature is less than or equal to 400 ℃, and the generated nitrogen carrier is Mn3N2，Mn3N2Carrying out an ammoniation reaction with hydrogen at a volume ratio of 1:3 and at a temperature of less than or equal to 500 ℃ to generate ammonia and Mn; or
The solid metal is Fe, the Fe and nitrogen are subjected to nitridation reaction under the conditions that the volume ratio is 8:1 and the temperature is less than or equal to 100 ℃, and the generated nitrogen carrier is Fe2N and Fe4N，Fe2N and Fe4Carrying out amination reaction on the N whole and hydrogen at the volume ratio of 2:3 and at the temperature of less than or equal to 100 ℃ to generate ammonia gas and Fe; or
The solid metal is Mo, the Mo and nitrogen are subjected to nitridation reaction at the temperature of less than or equal to 150 ℃ in the volume ratio of 2:1, the generated nitrogen carrier is MoN, and the MoN and hydrogen are subjected to amination reaction at the volume ratio of 2:3 at the temperature of less than or equal to 125 ℃ to generate ammonia gas and Mo.
4. The ammonia production method based on chemical looping reaction according to claim 1,
step S1 further includes:
unreacted nitrogen in the nitriding fluidized bed (1) carries the nitrogen carrier to leave the nitriding fluidized bed (1), then the nitrogen and the nitrogen carrier are separated through a first solid-gas separator (2), the separated nitrogen is sent back to the nitriding fluidized bed (1), and the separated nitrogen carrier is sent to the ammoniation fluidized bed (3);
step S2 further includes:
the mixed gas containing generated ammonia gas and unreacted hydrogen gas in the ammoniation fluidized bed (3) carries regenerated solid metal to leave the ammoniation fluidized bed (3), then the regenerated solid metal and the mixed gas are separated through a second solid-gas separator (4), the separated regenerated solid metal is sent into the nitriding fluidized bed (1), the separated mixed gas enables the hydrogen gas and gaseous or liquid ammonia to be respectively discharged through a separating device (5), and the discharged hydrogen gas is sent back to the ammoniation fluidized bed (3).
5. An ammonia production system for the ammonia production method based on the chemical looping reaction according to any one of claims 1 to 4, characterized by comprising a nitriding fluidized bed (1), a first solid-gas separator (2), an ammoniation fluidized bed (3), a second solid-gas separator (4) and a separation device (5);
the nitriding fluidized bed (1) is used for carrying out nitriding reaction on solid metal and nitrogen in the nitriding fluidized bed to generate a nitrogen carrier, and unreacted nitrogen and the nitrogen carrier can be discharged together;
the first solid-gas separator (2) is communicated with the nitriding fluidized bed (1) to receive unreacted nitrogen and the nitrogen carrier discharged from the nitriding fluidized bed (1) and separate the nitrogen and the nitrogen carrier;
the ammoniation fluidized bed (3) is communicated with the first solid-gas separator (2) to receive the nitrogen carrier separated by the first solid-gas separator (2), and the ammoniation fluidized bed (3) is used for carrying out ammoniation reaction on the nitrogen carrier and hydrogen gas therein to generate ammonia gas and regenerated solid metal, and discharging the generated ammonia gas, unreacted hydrogen gas and regenerated solid metal together;
the second solid-gas separator (4) is communicated with the ammoniation fluidized bed (3) to receive the ammonia gas, the unreacted hydrogen gas and the regenerated solid metal which are discharged out of the ammoniation fluidized bed (3), and separate the regenerated solid metal and a mixed gas comprising the ammonia gas and the hydrogen gas;
the separation device (5) is communicated with the second solid-gas separator (4) to receive the mixed gas and separate hydrogen and gaseous or liquid ammonia.
6. The ammonia production system of claim 5,
the first solid-gas separator (2) comprises a first solid-gas separator gas outlet (22), and the first solid-gas separator gas outlet (22) is communicated with the nitriding fluidized bed (1) so as to send separated nitrogen back to the nitriding fluidized bed (1);
the second solid-gas separator (4) is communicated with the nitriding fluidized bed (1) so as to feed the regenerated solid metal into the nitriding fluidized bed (1);
the separation device (5) is communicated with the ammoniation fluidized bed (3) to send the separated hydrogen back to the ammoniation fluidized bed (3).
7. The ammonia production system of claim 6,
the nitriding fluidized bed (1) comprises a nitriding fluidized bed body (13), a nitrogen inlet (15), a nitriding fluidized bed outlet (11), a nitriding fluidized bed feed inlet (12), a nitriding fluidized bed return gas port (14) and a nitriding fluidized bed return gas port (16), wherein the nitrogen inlet (15), the nitriding fluidized bed outlet (11), the nitriding fluidized bed feed inlet (12), the nitriding fluidized bed return gas port (14) and the nitriding fluidized bed return gas port (16) are communicated with the inside of the nitriding fluidized bed body (13), the nitrogen inlet (15) is arranged at the bottom of the nitriding fluidized bed body (13), the nitriding fluidized bed outlet (11) is arranged at the top of the nitriding fluidized bed body (13), the nitriding fluidized bed feed inlet (12) is arranged at the upper part of the side wall of the nitriding fluidized bed body (13), the nitriding fluidized bed return gas port (14) is arranged at the bottom of the nitriding fluidized bed body (13), the nitriding fluidized bed material returning port (16) is arranged at the lower part of the side wall of the nitriding fluidized bed body (13);
the first solid-gas separator (2) further comprises a first solid-gas separator inlet (23) and a first solid-gas separator solid outlet (21), the first solid-gas separator inlet (23) is communicated with the nitriding fluidized bed outlet (11), and the first solid-gas separator gas outlet (22) is communicated with the nitriding fluidized bed gas return port (14);
the ammoniation fluidized bed (3) comprises an ammoniation fluidized bed body (33), a hydrogen inlet (34), an ammoniation fluidized bed outlet (31), an ammoniation fluidized bed feed inlet (35) and an ammoniation fluidized bed return port (32), the hydrogen inlet (34), the ammoniated fluidized bed outlet (31), the ammoniated fluidized bed feed inlet (35) and the ammoniated fluidized bed return air port (32) are all communicated with the inside of the ammoniated fluidized bed body (33), the hydrogen inlet (34) is arranged at the bottom of the ammoniation fluidized bed body (33), the outlet (31) of the ammoniation fluidized bed is arranged at the top of the bed body (33) of the ammoniation fluidized bed, the feed inlet (35) and the return air port (32) of the ammoniation fluidized bed are arranged at the lower part of the side wall of the bed body (33) of the ammoniation fluidized bed, the feed inlet (12) of the nitriding fluidized bed is communicated with the solid outlet (21) of the first solid-gas separator;
the second solid-gas separator (4) comprises a second solid-gas separator inlet (41), a second solid-gas separator gas outlet (43) and a second solid-gas separator solid outlet (42), the second solid-gas separator inlet (41) is communicated with the ammoniated fluidized bed outlet (31), and the second solid-gas separator solid outlet (42) is communicated with the nitriding fluidized bed return port (16);
the separation device (5) comprises a separation device inlet (51), a separation device first outlet (52) and a separation device second outlet (53), the separation device inlet (51) is communicated with the second solid-gas separator gas outlet (43), the separation device first outlet (52) is communicated with the ammoniated fluidized bed return gas port (32), and the separation device second outlet (53) is used for discharging gaseous or liquid ammonia.
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