CN115094445A - Method for preparing ammonia gas by reducing algae slurry by fluidized bed electrochemical technology - Google Patents
Method for preparing ammonia gas by reducing algae slurry by fluidized bed electrochemical technology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The application discloses a method for preparing ammonia by reducing algae slurry by utilizing a fluidized bed electrochemical technology, which comprises the steps of establishing a particle electrode fluidized bed electrochemical reaction system, wherein the particle electrode fluidized bed electrochemical reaction system comprises an anode chamber, a cathode chamber, a proton membrane, a constant current power supply, an anode electrode, a cathode electrode, a manganese-based particle electrode, an inverted trapezoidal horn mouth, an anode chamber gas outlet, a cathode chamber liquid inlet, an oxygen storage tank, an algae slurry pool, a peristaltic pump, a compressor, a separator, an ammonia storage tank and a liquid distributor; stirring the crushed water-containing blue algae and deionized water, and adding a dispersing agent to form algae slurry; deionized water is added into the anode chamber, algae slurry and a particle electrode are added into the cathode chamber, after a constant current power supply is switched on, a peristaltic pump is started, and the combination of nitrogen-containing groups, free electrons and hydrogen ions of algae biomass is catalyzed through the coupling of an interface electric field and the particle electrode to generate ammonia, so that the cathode chamber realizes the fluidization circulation of the algae slurry in a target fluidization state.
Description
Technical Field
The invention belongs to the field of electrochemical ammonia production, and particularly relates to a method for preparing ammonia by reducing algae slurry by using a fluidized bed electrochemical technology.
Background
As a second-place commercial chemical in the current generation, ammonia is not only a basic raw material for grain and industrial production, but also an important energy carrier for a zero-carbon economic system due to the outstanding advantages of hydrogen and carbon richness, high energy density, easiness in storage and transportation and the like. In the century hot tide of carbon peaking, carbon neutralization, the economic production and safe utilization of ammonia is becoming a focus of global attention. The haber-Bosch method has high inherent efficiency in ammonia production, contributes more than 90% of the ammonia synthesis amount in the world, renovates the nitrogen ecology cycle supply mode, and faces increasingly severe energy consumption and carbon emission problems under the era principle of global carbon emission reduction. The haber method consumes a large amount of fossil fuels, is used for reforming to prepare hydrogen, provides driving energy for reaction, and maintains harsh reaction conditions of high temperature (400-600 ℃) and high pressure (20-40 MPa), thereby consuming 3% of the total energy of the world and generating carbon emission of over 4.5 million tons every year. Based on renewable energy, the method for preparing ammonia in green with low energy consumption and mild reaction conditions is explored.
The electrocatalytic nitrogen reduction ammonia production is carried out by adopting renewable electric energy such as solar energy, wind energy and the like to drive reaction, electrolytic water replaces methane reforming to serve as a hydrogen source, the energy of the system is changed by regulating and controlling an interface electric field, the high-temperature and high-pressure reaction condition is avoided, the contradiction limitation between ammonia nitrogen conversion kinetics and thermodynamics can be broken, the advantages are highlighted in the aspects of raw material selection, energy supply, production regulation and control and the like, the electrocatalytic nitrogen reduction ammonia production has industrial development potential for replacing the Haber method to produce ammonia, and the electrocatalytic nitrogen reduction ammonia production method is a research hotspot in the field of current green ammonia synthesis. However, N 2 The non-polar linear molecule is a non-polar linear molecule consisting of nitrogen triple bonds (N ≡ N), has large first ionization energy and stable chemical property, has large energy band gap (10.82 eV) between the highest occupied orbit and the lowest empty orbit, has negative electron affinity (-1.9 eV) and high ionization potential (15.8 eV), blocks electron gain and loss, and increases the difficulty of activated fracture of nitrogen molecules. Aiming at the technical bottleneck that nitrogen is not easy to activate and adsorb, the existing research is usually carried out through the design modification of a catalytic material and the cooperative optimization of an electrocatalysis system so as to reduce the dissociation energy barrier of nitrogen and increase the ammonia production rate of electrocatalysis synthesis ammonia. ElectrocatalysisThe ammonia production by nitrogen reduction has achieved stage progress with good results, but still faces a plurality of challenges, the solubility and mass transfer diffusion rate of nitrogen are low, the adsorption and activation difficulty of an inert nitrogen triple bond is large, and a hydrogen evolution competition reaction exists, so that the ammonia production rate is only mu g ∙ cm -2 ∙h -1 In order of magnitude, the Faraday efficiency is generally lower than 10%, and far from reaching the basic standard of commercialization. Therefore, the steps of enhancing the dissolution, mass transfer and activation of nitrogen are key scientific problems to be solved urgently in the electrochemical catalytic synthesis of ammonia.
The algae biomass used as the third generation biofuel rich in hydrogen has the outstanding advantages of large storage amount, high growth rate, strong environmental adaptability, neutral carbon and the like, can efficiently adsorb nitrogen and phosphorus elements in a eutrophic water system, has the body nitrogen content of 5-10 wt.%, is not suitable for direct combustion use, but has excellent ammonia nitrogen recovery potential. An emerging ammonia production technology based on catalytic cracking of algae is originally disclosed as Zhengrong, and the nutrient value of algae nitrogen is expected to be preserved at a mild pyrolysis temperature and in a reducing atmosphere, so that internal organic nitrogen is preserved as NH 3 The form is that the main body escapes. The nitrogen-rich algae biomass cracking process of preparing ammonia includes using self-source nitrogen as ammonia synthesizing nitrogen source, replacing partial hydrogen source with hydrogen-rich active component for supply, and introducing water vapor and H 2 Under the mixed atmosphere, the desorption of amino groups of amide, pyrrole and pyridine is accelerated by a ZSM-5 molecular sieve and a Zr-based or perovskite catalyst, and the nitrogen-containing pyrolysis gasification semi-product is promoted to be directionally converted into NH 3 . However, the reaction temperature contradiction exists in the thermal cracking of algae to prepare ammonia, the ammoniation efficiency has a larger promotion space, and the high temperature can promote the gaseous transformation of stable nitrogen species, but can also make the product NH 3 Further decomposed into N 2 And H 2 Low temperature pyrolysis cannot completely crack nitrogen-containing heterocycles, so that about 47% of the self-derived nitrogen remains in the nitrogen-containing groups of the coke, such as graphite nitrogen, pyridine nitrogen, pyrrole nitrogen, nitrogen oxide, and the like. In addition, the algae has extremely high water content (>90 wt.%) to make it dry and dehydrate, and the energy consumption for internal aqueous phase transformation is very large, and the economic prospect of directly adopting thermochemical conversion to prepare ammonia is questionable.
In conclusion, the existing technical route for preparing ammonia by electrocatalytic nitrogen reduction has two technical problems,one is N 2 The solubility and the mass transfer diffusion rate of the catalyst are low, the adsorption and activation difficulty of the inert nitrogen triple bond N [ identical to ] N is high, and hydrogen evolution competition reaction exists, so that the reaction rate of preparing ammonia by electro-catalytic nitrogen reduction is low, and the ammonia production efficiency is low; secondly, the temperature range of the ammonia preparation by algae thermochemical cracking is limited, and the high temperature can cause the product NH 3 Further decomposed into N 2 And H 2 And the low-temperature pyrolysis can not completely crack the nitrogen-containing heterocycle, so that the ammonia production efficiency is low, and meanwhile, the economic prospect of the algae is questioned due to the extremely high water content.
Aiming at the problems, the application adopts algae self-source nitrogen (nitrogen-containing organic matters) to replace N in the conventional electrocatalytic nitrogen reduction ammonia production 2 As an ammonia source, the method for preparing ammonia by reducing the algae slurry by using the fluidized bed electrochemical technology is provided, the speed control steps of mass transfer and activation of nitrogen in the electrochemical catalytic synthesis of ammonia can be avoided, and a brand new thought is provided for a green sustainable ammonia preparation process.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems of slow reaction rate, low ammonia production efficiency and the like of preparing ammonia by electro-catalytic nitrogen reduction in the prior art, the application provides a method for preparing ammonia by reducing algae slurry by utilizing a fluidized bed electrochemical technology.
The technical scheme is as follows:
in order to solve the technical problems, the application provides a method for preparing ammonia by reducing algae slurry by using a fluidized bed electrochemical technology, which is characterized by comprising the following steps of:
s1 establishing a fluidized bed electrochemical reaction system: the method is characterized in that a three-dimensional particle electrode fluidized bed is adopted as an electrochemical reactor and comprises an anode chamber, a cathode chamber, a proton membrane, a constant current power supply, an anode electrode, a cathode electrode, an inverted trapezoidal bell mouth, an anode chamber gas outlet, a cathode chamber liquid inlet, an oxygen storage tank, an algae slurry tank, a peristaltic pump, a compressor, a separator, an ammonia storage tank, a liquid distributor and a manganese-based particle electrode; wherein, the bottom of the anode chamber is inserted with an anode electrode, and the upper part of the anode chamber is provided with an anode chamber gas outlet; the anode chamber and the cathode chamber are separated by a proton membrane; the bottom of the cathode chamber is inserted with a cathode electrode, the liquid distributor is arranged on the inner side of the bottom surface of the cathode chamber, the manganese-based particle electrodes are dispersed in the cathode chamber, the upper part of the cathode chamber is an inverted-trapezoid horn mouth, a cathode chamber gas outlet and a cathode chamber liquid outlet are arranged on one side of the inverted-trapezoid horn mouth, the cathode chamber gas outlet is arranged above the cathode chamber liquid outlet, and a cathode chamber liquid inlet is arranged on the bottom surface of the cathode chamber; the cathode of the constant current power supply is connected with the cathode electrode, and the anode of the constant current power supply is connected with the anode electrode; the gas outlet of the anode chamber is connected with the oxygen inlet of the oxygen storage tank; the gas outlet of the cathode chamber is connected with the inlet of a compressor, the outlet of the compressor is connected with the inlet of a separator, and the ammonia gas outlet of the separator is connected with the gas inlet of an ammonia storage tank; the liquid outlet of the cathode chamber is connected with the inlet of the algae slurry pool, the outlet of the algae slurry pool is connected with the inlet of the peristaltic pump, and the outlet of the peristaltic pump is connected with the liquid inlet of the cathode chamber;
s2 preparation of algae slurry: smashing original blue algae to the particle size of less than 0.5mm by a blender, stirring the smashed water-containing blue algae and deionized water, adding a dispersing agent, and continuing stirring to form algae slurry;
s3 preparation of ammonia gas: adding deionized water into the anode chamber, adding the deionized water to 2/3 of the height of the anode chamber, adding algae slurry and a manganese-based particle electrode into the cathode chamber, wherein the adding quality of the manganese-based particle electrode takes the expansion height of the bed layer in a target fluid state as an index, switching on a constant current power supply, and then starting a peristaltic pump to enable the cathode chamber to realize the fluidization circulation of the algae slurry in a target fluidization state, wherein the peristaltic pump realizes power supply by an external power supply; after the anode is electrified, the anode electrode in the anode chamber can electrolyze the deionized water to generate protons (hydrogen ions) and byproduct oxygen, wherein the protons (hydrogen ions) enter the cathode chamber through the proton membrane, and the byproduct oxygen is discharged out of the anode chamber through the gas outlet of the anode chamber and is collected through the oxygen inlet of the oxygen storage tank; the reaction process that the organic matter of algae slurry is hydrogenated and reduced into ammonia occurs in the cathode chamber, the generated ammonia gas and other mixed gas enter the compressor through the gas outlet of the cathode chamber to realize pressurization, the pressurized mixed gas is input into the separator, the separator separates the mixed gas into pure ammonia gas and other gas, and the ammonia gas enters the ammonia storage tank to realize storage.
Further, in step S1, the proton membrane is a Nafion-117 proton exchange membrane, the anode electrode is a titanium metal mesh, and the cathode electrode is a graphite rod; the manganese-based granular electrode is prepared by an immersion method, namely Mn (NO) 3 ) 2 ·4H 2 O solution and KNO 3 The solution is immersion liquid to Al 2 O 3 Impregnating the granules with KNO 3 Mass ratio of solution less than 20 wt.%, Al 2 O 3 The grain diameter of the particles is between 0.2 and 0.45mm, after dipping, drying and calcining for 6 hours at 950 ℃ under the air atmosphere, and after screening, the carrier Al with the grain diameter range of 0.2 to 0.45mm is obtained 2 O 3 Supported manganese-based particle electrode, wherein Al 2 O 3 Mass fraction about 40 wt.%, Mn 2 O 3 Is about 60 wt.%.
Further, in the step S2, the dispersant is naphthalene sulfonate, the addition amount is 0.5-1.5 wt.% of the mass of the water-containing cyanobacteria, the mass of the cyanobacteria accounts for 40-70 wt.% of the mass of the slurry (cyanobacteria + deionized water), and the cyanobacteria slurry is a pseudoplastic fluid.
Further, after the power is turned on in step S3, the anode electrode in the anode chamber electrolyzes the deionized water to generate protons (hydrogen ions) and oxygen as a byproduct, which has the following reaction formula:
2H 2 O→4H + +O 2 +e - 。
further, the protons (hydrogen ions) generated by the electrolysis in step S3 enter the cathode chamber through the proton membrane, and participate in the reductive amination reaction of the nitrogen-containing groups of the algae with hydrogen to obtain electrons, and the reaction formula is as follows:
nitrogen-containing group + H + +e - → organic matter + NH 3 。
Further, the manganese-based particle electrode described in step S3 is subjected to high-frequency fluidization and collision to enhance charge transfer from the cathode electrode to the nitrogen-containing organic matter of the algae, and to guide charge to transfer to the nitrogen-containing groups of the algae, thereby catalyzing dissociation of the nitrogen-containing groups of the algae; the target fluidization state is a bubbling fluidization state, and the fluidization speed is 0.1-0.4 m/s.
Further, the reductive amination reaction of the algae with the nitrogen-containing group through hydrogenation to obtain electronsTwo reaction paths of organic nitrogen and inorganic nitrogen are distinguished; wherein the inorganic nitrogen is predominantly NO 3 - Root and NH 4 + The roots with electrons and protons (hydrogen ions), while the reaction pathways for organic nitrogen are primarily algal amino acid nitrogen and protein nitrogen, including and not limited to glutamic acid C 5 H 9 NO 4 Leucine C 6 H 13 NO 2 Aspartic acid C 4 H 7 NO 4 Glycine C 2 H 5 NO 2 Phenylalanine C 9 H 11 NO 2 The series of reaction processes of hydrolysis, peptide bond fracture and dimerization cyclization are realized through interface electric field driving and manganese-based particle electrode catalysis.
Has the advantages that:
1. the technical advantages of electro-catalytic nitrogen reduction for ammonia production, biomass ammonia nitrogen recovery and a fluidized bed electrochemical reactor are combined, and the resource utilization of gas, liquid and solid multi-phase products of algae can be effectively realized;
2. greatly improving the product selectivity and ammonia production rate of the electro-catalytic synthesis ammonia;
3. renewable energy sources such as solar energy, wind energy and the like can be used as external power sources to provide electric drive, and a distributed ammonia synthesis system which is low in carbon emission, simple and convenient to operate and accurate to prepare as required is effectively formed.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for producing ammonia by electrochemical reduction of algae in a fluidized bed with granular electrodes according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the granular electrode fluidized bed catalytic reduction of algae for ammonia production, wherein a is an algae ammonia nitrogen conversion reaction path in an interfacial electric field, and b is a granular electrode nitrogen-carrying-ammonification mechanism.
Description of the drawings reference numbers: 1-anode chamber, 2-cathode chamber, 3-proton membrane, 4-constant current power supply, 5-anode electrode, 6-cathode electrode, 7-inverted trapezoidal bell mouth, 8-anode chamber gas outlet, 9-cathode chamber gas outlet, 10-cathode chamber liquid outlet, 11-cathode chamber liquid inlet, 12-oxygen storage tank, 13-algae slurry tank, 14-peristaltic pump, 15-compressor, 16-separator, 17-ammonia storage tank, 18-liquid distributor and 19-manganese-based particle electrode.
Detailed Description
The following examples will give the skilled person a more complete understanding of the present invention, but do not limit the invention in any way.
Example 1
As shown in fig. 1, a fluidized bed electrochemical reaction system required by the present application is first established:
s1, a three-dimensional particle electrode fluidized bed is adopted as an electrochemical reactor, and the three-dimensional particle electrode fluidized bed comprises an anode chamber 1, a cathode chamber 2, a proton membrane 3, a constant current power supply 4, an anode electrode 5, a cathode electrode 6, an inverted trapezoidal bell mouth 7, an anode chamber gas outlet 8, a cathode chamber gas outlet 9, a cathode chamber liquid outlet 10, a cathode chamber liquid inlet 11, an oxygen storage tank 12, an algae slurry tank 13, a peristaltic pump 14, a compressor 15, a separator 16, an ammonia storage tank 17, a liquid distributor 18 and a manganese-based particle electrode 19; wherein, the bottom of the anode chamber 1 is inserted with an anode electrode 5, and the upper part of the anode chamber 1 is provided with an anode chamber gas outlet 8; the anode chamber 1 and the cathode chamber 2 are separated by a proton membrane 3; a cathode electrode 6 is inserted into the bottom of the cathode chamber 2, a liquid distributor 18 covers the inner side of the bottom surface of the cathode chamber 2, manganese-based particle electrodes 19 are dispersed in the cathode chamber 2, the upper part of the cathode chamber 2 is an inverted trapezoidal horn-shaped opening 7, a cathode chamber gas outlet 9 and a cathode chamber liquid outlet 10 are arranged on one side of the inverted trapezoidal horn-shaped opening 7, the cathode chamber gas outlet 9 is arranged above the cathode chamber liquid outlet 10, and a cathode chamber liquid inlet 11 is arranged on the outer side of the bottom surface of the cathode chamber 2; the cathode of the constant current source 4 is connected with the cathode electrode 6, and the anode of the constant current source 4 is connected with the anode electrode 5; the gas outlet 8 of the anode chamber is connected with the oxygen inlet of the oxygen storage tank 12; the gas outlet 9 of the cathode chamber is connected with the inlet of a compressor 15, the outlet of the compressor 15 is connected with the inlet of a separator 16, and the ammonia gas outlet of the separator 16 is connected with the gas inlet of an ammonia storage tank 17; a liquid outlet 10 of the cathode chamber is connected with an inlet of an algae slurry pool 13, an outlet of the algae slurry pool 13 is connected with an inlet of a peristaltic pump 14, and an outlet of the peristaltic pump 14 is connected with a liquid inlet 11 of the cathode chamber; wherein the anode electrode 5 is titanium metal mesh, the cathode electrode 6 is graphite rod, and Mn (NO) is used as the anode electrode 3 ) 2 ·4H 2 O solution and KNO 3 The solution is immersion liquid to Al 2 O 3 The particles are impregnated with KNO 3 The mass ratio of the solution is less than 20 wt.%; drying and calcining at 950 ℃ for 6 hours after impregnation until the manganese-based granular electrode 19 with the grain size range of 0.2-0.45mm is obtained after screening, and the carrier Al 2 O 3 Supported manganese-based particle electrode, wherein Al 2 O 3 Mass fraction about 40 wt.%, Mn 2 O 3 About 60 wt.%;
s2 preparation of algae slurry: smashing original blue-green algae to the particle size of less than 0.5mm by a blender, stirring the smashed water-containing blue-green algae and deionized water, adding naphthalenesulfonate serving as a dispersant, and continuously stirring to form pseudoplastic fluid of algae slurry;
s3 preparation of ammonia gas: adding deionized water into the anode chamber 1, filling the deionized water to 2/3 of the volume of the anode chamber, adding algae slurry and a manganese-based particle electrode 19 into the cathode chamber 2, switching on a constant current power supply 4, and then starting a peristaltic pump 14 to enable the cathode chamber 2 to realize fluidization circulation of the algae slurry in a target fluidization state, wherein the peristaltic pump 14 is powered by an external power supply of 220V; after being electrified, the anode electrode 5 in the anode chamber 1 can electrolyze the deionized water to generate hydrogen ions and byproduct oxygen, wherein the hydrogen ions enter the cathode chamber 2 through the proton membrane 3, and the byproduct oxygen is discharged out of the anode chamber 1 through the anode chamber gas outlet 8 and collected through the oxygen inlet of the oxygen storage tank 12; the reaction process of reducing organic hydrogen of algae slurry into ammonia in the cathode chamber 2 is carried out, the generated ammonia gas and other mixed gas enter the compressor 15 through the cathode chamber gas outlet 9 to realize pressurization, the pressurized mixed gas is input into the separator 16, the separator 16 separates the mixed gas into pure ammonia gas and other gas, and the ammonia gas enters the ammonia storage tank 17 to be stored.
Claims (7)
1. A method for preparing ammonia by reducing algae slurry by fluidized bed electrochemical technology is characterized in that: the method comprises the following steps:
s1 establishing a fluidized bed electrochemical reaction system: the method is characterized in that a three-dimensional particle electrode fluidized bed is adopted as an electrochemical reactor and comprises an anode chamber (1), a cathode chamber (2), a proton membrane (3), a constant current power supply (4), an anode electrode (5), a cathode electrode (6), an inverted trapezoidal horn mouth (7), an anode chamber gas outlet (8), a cathode chamber gas outlet (9), a cathode chamber liquid outlet (10), a cathode chamber liquid inlet (11), an oxygen storage tank (12), an algae slurry tank (13), a peristaltic pump (14), a compressor (15), a separator (16), an ammonia storage tank (17), a liquid distributor (18) and a manganese-based particle electrode (19); wherein, the bottom of the anode chamber (1) is inserted with an anode electrode (5), and the upper part of the anode chamber (1) is provided with an anode chamber gas outlet (8); the anode chamber (1) and the cathode chamber (2) are separated by a proton membrane (3); a cathode electrode (6) is inserted into the bottom of the cathode chamber (2), a liquid distributor (18) is arranged on the inner side of the bottom surface of the cathode chamber (2), a manganese-based particle electrode (19) is dispersed inside the cathode chamber (2), an inverted trapezoidal horn mouth (7) is arranged at the upper part of the cathode chamber (2), a cathode chamber gas outlet (9) and a cathode chamber liquid outlet (10) are arranged on one side of the inverted trapezoidal horn mouth (7), the cathode chamber gas outlet (9) is arranged above the cathode chamber liquid outlet (10), and a cathode chamber liquid inlet (11) is arranged on the outer side of the bottom surface of the cathode chamber (2); the cathode of the constant current power supply (4) is connected with the cathode electrode (6), and the anode of the constant current power supply (4) is connected with the anode electrode (5); the gas outlet (8) of the anode chamber is connected with the oxygen inlet of the oxygen storage tank (12); a gas outlet (9) of the cathode chamber is connected with an inlet of a compressor (15), an outlet of the compressor (15) is connected with an inlet of a separator (16), and an ammonia gas outlet of the separator (16) is connected with a gas inlet of an ammonia storage tank (17); a liquid outlet (10) of the cathode chamber is connected with an inlet of an algae slurry pool (13), an outlet of the algae slurry pool (13) is connected with an inlet of a peristaltic pump (14), and an outlet of the peristaltic pump (14) is connected with a liquid inlet (11) of the cathode chamber;
s2 preparation of algae slurry: smashing original blue algae to the particle size of less than 0.5mm by a blender, stirring the smashed water-containing blue algae and deionized water, adding a dispersing agent, and continuing stirring to form algae slurry;
s3 preparation of ammonia gas: deionized water is added into the anode chamber (1), the amount of the deionized water is added to 2/3 of the height of the anode chamber (1), algae slurry and a manganese-based particle electrode (19) are added into the cathode chamber (2), the adding quality of the manganese-based particle electrode (19) takes the expansion height of a bed layer in a target fluid state as an index, after a constant current power supply (4) is switched on, a peristaltic pump (14) is started, so that the cathode chamber (2) realizes the fluidization circulation of the algae slurry in the target fluidization state, wherein the peristaltic pump (14) realizes power supply by an external power supply; after electrification, an anode electrode (5) in the anode chamber (1) electrolyzes deionized water to generate protons (hydrogen ions) and byproduct oxygen, wherein the protons (hydrogen ions) enter the cathode chamber (2) through a proton membrane (3), and the byproduct oxygen is discharged out of the anode chamber (1) through an anode chamber gas outlet (8) and collected through an oxygen inlet of an oxygen storage tank (12); the reaction process of hydrogenation reduction of algae slurry organic matters into ammonia occurs in the cathode chamber (2), the generated ammonia gas and other mixed gas enter the compressor (15) through the cathode chamber gas outlet (9) to realize pressurization, the pressurized mixed gas is input into the separator (16), then the separator (16) separates the mixed gas into pure ammonia gas and other gas, and the ammonia gas enters the ammonia storage tank (17) to realize storage.
2. The method for preparing ammonia gas by reducing algae slurry by the fluidized bed electrochemical technology according to claim 1, wherein the method comprises the following steps: step S1, the proton membrane (3) is a Nafion-117 proton exchange membrane, the anode electrode (5) is a titanium metal mesh, and the cathode electrode (6) is a graphite rod; the manganese-based granular electrode (19) is produced by an immersion method, namely by Mn (NO) 3 ) 2 ·4H 2 O solution and KNO 3 The solution is immersion liquid to Al 2 O 3 Impregnating the granules with KNO 3 Mass ratio of solution less than 20 wt.%, Al 2 O 3 The grain diameter of the particles is between 0.2 and 0.45mm, after the particles are soaked, the particles are dried and calcined for 6 hours at the high temperature of 950 ℃ in the air atmosphere, and after the particles are screened, the carrier Al with the grain diameter range of 0.2 to 0.45mm is obtained 2 O 3 Supported manganese-based particle electrode, wherein Al 2 O 3 Mass fraction about 40 wt.%, Mn 2 O 3 Is about 60 wt.%.
3. The method for preparing ammonia gas by reducing algae slurry through the fluidized bed electrochemical technology as claimed in claim 1, wherein: step S2, the dispersant is naphthalene sulfonate, the addition amount is 0.5-1.5 wt% of the mass of the water-containing blue algae, the mass of the blue algae accounts for 40-70 wt% of the mass of the slurry (blue algae + deionized water), and the algae slurry is pseudoplastic fluid.
4. The method for preparing ammonia gas by reducing algae slurry by the fluidized bed electrochemical technology according to claim 1, wherein the method comprises the following steps: after the energization in step S3, the anode electrode (5) in the anode chamber (1) can electrolyze deionized water to generate protons (hydrogen ions) and oxygen as a byproduct, and the reaction formula is as follows:
2H 2 O→4H + +O 2 +e - 。
5. the method for preparing ammonia gas by reducing algae slurry by the fluidized bed electrochemical technology according to claim 1, wherein the method comprises the following steps: the protons (hydrogen ions) generated by the electrolysis in the step S3 enter the cathode chamber (2) through the proton membrane (3) and participate in the reduction ammoniation reaction of the electrons obtained by the hydrogenation of the nitrogen-containing groups of the algae, and the reaction formula is as follows:
nitrogen-containing group + H + +e - → organic + NH 3 。
6. The method for preparing ammonia gas by reducing algae slurry through the fluidized bed electrochemical technology as claimed in claim 1, wherein: the manganese-based particle electrode (19) in the step S3 is used for strengthening the charge transfer from the cathode electrode to the algae nitrogen-containing organic matter, guiding the charge to transfer to the algae nitrogen-containing groups and catalyzing the dissociation of the algae nitrogen-containing groups through high-frequency secondary fluidization collision; the target fluidization state is a bubbling fluidization state, and the fluidization speed is 0.1-0.4 m/s.
7. The method for preparing ammonia gas by reducing algae slurry by fluidized bed electrochemical technology according to claim 5, wherein: the reductive amination reaction for obtaining electrons by the hydrogenation of the nitrogen-containing groups of the algae is divided into two reactions of organic nitrogen and inorganic nitrogenA route; wherein the inorganic nitrogen is predominantly NO 3 - Root and NH 4 + The roots with electrons and protons (hydrogen ions), while the reaction pathways for organic nitrogen are primarily algal amino acid nitrogen and protein nitrogen, including and not limited to glutamic acid C 5 H 9 NO 4 Leucine C 6 H 13 NO 2 Aspartic acid C 4 H 7 NO 4 Glycine C 2 H 5 NO 2 Phenylalanine C 9 H 11 NO 2 The series of reaction processes of hydrolysis, peptide bond fracture and dimerization cyclization are realized through interface electric field driving and manganese-based particle electrode (19) catalysis.
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