CN104630811A - Novel electrolysis ammonia production device - Google Patents
Novel electrolysis ammonia production device Download PDFInfo
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- CN104630811A CN104630811A CN201510080411.0A CN201510080411A CN104630811A CN 104630811 A CN104630811 A CN 104630811A CN 201510080411 A CN201510080411 A CN 201510080411A CN 104630811 A CN104630811 A CN 104630811A
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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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- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention provides a novel electrolysis ammonia production device. The novel electrolysis ammonia production device comprises a reaction container, wherein an iron-nickel alloy foam electrode and a platinum electrode which are taken as a cathode and an anode are arranged in the reaction container. In an operation process, vanadium hydroxide, magnesium sulphate, sodium hydroxide and purified water are added into the reaction container to obtain vanadium hydroxide aqueous solution; then the air is compressed, the compressed air is introduced into the reaction container by virtue of an air flow meter, the iron-nickel alloy foam electrode in the reaction container is electrified, and electrolysis reaction is carried out; and nitrogen can be reduced into ammonia by virtue of the cathode in the reaction container, a byproduct oxygen is produced at the anode, mixed gas of ammonia gas and nitrogen can be obtained, and pure ammonia gas can be obtained by separating the mixed gas by virtue of a separator. The novel electrolysis ammonia production device has the advantages that the used electrolysis raw materials are available, and electrochemical reaction can be carried out only by utilizing the air and a catalyst; besides, the novel electrolysis ammonia production device is simple in structure and low in manufacturing cost and especially can utilize solar energy and wind energy to generate electricity and produce ammonia, and no pollutant is produced, so that the novel electrolysis ammonia production device is a green ammonia synthesis device worthy of being widely popularized.
Description
Technical field
The present invention relates to a kind of ammonia generating apparatus, particularly a kind of Novel electrolytic ammonia-preparing device.
Background technology
Ammonia is one of maximum Chemicals of output, traditional industry synthetic ammonia technology be fritz Haber (Fritz Haber) invention in 1905, be therefore also referred to as aber process synthetic ammonia.Aber process synthetic ammonia needs the high pressure of 20 ~ 50MPa and the high temperature of 500 DEG C, and makes catalyzer with iron, and hydrogen and nitrogen synthetic ammonia under catalyzer, high temperature, high pressure, transformation efficiency is 10%-15%.
Electrochemical method synthetic ammonia breaches the thermodynamical restriction of traditional Harber ammonia synthesis, and reaction is carried out at ambient pressure, reduces the requirement to equipment.Electrochemical method is similar to the efficiency of existing synthetic method, is a kind of desirable normal temperature and pressure synthetic ammonia method.Electrochemical method synthetic ammonia can make some thermodynamics cells with non-spontaneous reactions (as N
2+ 3H
2o=2NH
3+ 1.5O
2, K298=10
-120) occur under the promotion of electric energy, thus expand the research field of ammonia synthesis mode; Also the thermodynamics spontaneous reaction (as Haber-Bosch ammonia synthesis reaction) by equilibrium-limited can be made not to be subject to or the less restriction by thermodynamic(al)equilibrium.Such as, the electrochemical method synthetic ammonia carried out under high temperature (570 DEG C), normal pressure, the transformation efficiency of hydrogen close to 100%, can have the possibility realizing normal temperature and pressure synthetic ammonia.To the further investigation of electrochemical synthesis ammonia, current efficiency and transformation efficiency can be increased substantially, and make the cost of electrochemical synthesis ammonia mainly focus on simple power consumption, so then electrochemical method synthetic ammonia remote districts that are sufficient at electric energy or that can effectively convert solar energy into electrical energy are expected to occupy a tiny space.Particularly in future, when the synthetic ammonia feedstock such as oil, coal price may be caused significantly to raise up due to energy dilemma, Haber-Bosch ammonia cost will be caused to be doubled and redoubled, this becomes a kind of useful selection by making electrochemical method synthetic ammonia.Meanwhile, electrochemical process ammonia synthesis unit is simple, the miniaturization be put on automobile as movable equipment, for automobile provides ammonia fuel of can being tried one's best.
Summary of the invention
The object of the present invention is to provide a kind of Novel electrolytic ammonia-preparing device, to realize electrolysis ammonia, high efficiency ammonia processed can be carried out simultaneously.
Another object of the present invention is to provide a kind of Novel electrolytic ammonia-preparing device, to realize with the method ammonia of smaller size smaller, less resource, the fuel making automobile uses.
For achieving the above object, the invention provides a kind of Novel electrolytic ammonia-preparing device, comprise reaction vessel, the first compressor, separator, the second compressor, air compressor, ammonia tank and direct supply;
Metallic cathode and metal anode is provided with in described reaction vessel, described reaction vessel top is provided with add water valve and venting port, described venting port is connected with the entrance of the first compressor, the described outlet of the first compressor is connected with the entrance of separator, first outlet of described separator is connected with the second compressor, second outlet of described separator communicates with extraneous air, and the outlet of described second compressor is connected with ammonia tank;
When adopting this device electrolysis ammonia, described reaction vessel is built with the vanadium hydroxide aqueous solution, the negative pole of described direct supply is connected with described metallic cathode simultaneously, the positive pole of described direct supply is connected with described metal anode, air compressor will be fed through described metallic cathode place after air compressing, electrolysis produces the mixed gas of ammonia and nitrogen, described mixed gas enters separator by ammonia and nitrogen separation after the first compressor compresses, nitrogen after separation is through the second outlet emptying, and the ammonia after separation inputs described ammonia tank after entering the second compressor compresses;
Also dividing plate is provided with between described metallic cathode and metal anode.
Preferably, also comprise air flowmeter, air flowmeter is connected with described air compressor, and described air compressor is fed through described metallic cathode place by after air compressing after described air flowmeter measuring flow.
Preferably, also agitator is provided with in described reaction vessel.
Preferably, also comprise supply unit, described supply unit is that described agitator is powered.
Preferably, described metallic cathode is iron-nickel alloy foam electrode; Described metal anode is platinum electrode.
Preferably, described reaction vessel top is also provided with reducing valve.
Preferably, described reaction vessel top is also provided with oxygen emptying valve, and the oxygen produced during electrolysis ammonia is exported by described oxygen emptying valve.
Preferably, also comprise engine, described oxygen emptying valve is connected with described engine, and the oxygen produced during electrolysis ammonia exports described engine to by described oxygen emptying valve.
Preferably, being also provided with thermostatic regulator in described reaction vessel, is 60 DEG C ~ 110 DEG C for regulating the temperature in reaction vessel.Normally carry out to keep electrolysis.
In working process of the present invention, in reaction vessel, add vanadium hydroxide, magnesium sulfate, sodium hydroxide, and add pure water by filler, obtain vanadium hydroxide mixed aqueous solution.After switching on power, air compressor is by after air pressurized, and make it enter into iron-nickel alloy foam electrode surface, agitator works simultaneously and makes dissolution homogeneity in container, iron-nickel alloy foam negative electrode then in vessel reactor can make nitrogen reduction ammonification, and negative pole then has by product oxygen to produce.The by product oxygen emptying produced in container, isolates pure ammonia by the ammonia of generation through separator, and enters in ammonia tank through air compressor.
The total reaction equation of the electrolytic process in reaction vessel of the present invention is 2N
2+ 6H
2o=4NH
3+ 3O
2.This reaction process is containing catalyst V (OH)
2, magnesium ion, sodium ion the aqueous solution in the electrochemical reaction of carrying out, its concrete reaction principle is as follows:
V (OH)
2under magnesium ion and hydroxide ion existent condition, when temperature is greater than 70 DEG C, nitrogen reduction ammonification can be made on negative electrode:
12V(OH)
2+2N
2+12H
2O→12V(OH)
3+NH
3
By the electrochemical reduction on negative electrode, V(OH)
2, can regenerate:
12V(OH)
3+12e
-→12V(OH)
2+12OH
-
Anode then has by product oxygen produce:
12OH
-→3O
2+6H
2O+12e
-
The electrochemical method of the green ammonia of this preparation being using value is larger.
Novel electrolytic ammonia-preparing device provided by the invention by arranging platinum electrode and iron-nickel alloy foam electrode respectively as the anode of electrolytic reaction and negative electrode in reaction vessel, and in container, add vanadium hydroxide as catalyzer, when passing into air, electrolytic reaction is carried out in energising, can obtain ammonia.The reaction conditions of this electrolytic reaction is easy to reach, and realize easily, and utilize air to carry out, cost is lower.This device, in the process of electrolysis ammonia, only produces ammonia, oxygen and nitrogen, pollution-free, and only needs power supply to get final product work, especially can utilize sun power, wind power generation ammonia, and contamination-free produces, and is a kind of green ammonia-preparing device being applicable to extensively promoting.
Accompanying drawing explanation
Fig. 1 is the structural representation of the Novel electrolytic ammonia-preparing device of the embodiment of the present invention one;
Fig. 2 is the structural representation of the Novel electrolytic ammonia-preparing device of a preferred embodiment of the present invention.
Label declaration: 1-reaction vessel; 2-agitator; 3-iron-nickel alloy foam electrode; 4-platinum electrode; 5-adds water valve; 6-pressure loading valve; 7-oxygen emptying valve; 8-air flowmeter; 9-air compressor; 10-supply unit; 11-compressor; 12-separator; 13-compressor; 14-ammonia tank; 15-engine.
Embodiment
For better the present invention being described, hereby with a preferred embodiment, and accompanying drawing is coordinated to elaborate to the present invention, specific as follows:
Embodiment one:
As shown in Figure 1, Novel electrolytic ammonia-preparing device provided by the invention, comprises reaction vessel 1, first compressor 11, separator 12, second compressor 13, ammonia tank 14 and direct supply 10.
Wherein, in reaction vessel 1, be provided with agitator 2, iron-nickel alloy foam electrode 3 and platinum electrode 4, between iron-nickel alloy foam electrode 3 and platinum electrode 4, be also provided with dividing plate 15.The top of reaction vessel 1 is provided with the valve 5 that adds water, reducing valve 6, oxygen emptying valve 7 and venting port.The negative pole of direct supply 10 is connected with iron-nickel alloy foam electrode 3, and the positive pole of direct supply 10 is connected with platinum electrode 4.
The venting port of reaction vessel 1 is connected with the entrance of the first compressor 11, and the outlet of the first compressor 11 is connected with the entrance of separator 12.Separator 12 has two outlets, and wherein, the first outlet of separator 12 is connected with the second compressor 13, and the second outlet of separator 12 communicates with outside air.The outlet of the second compressor 13 is connected with ammonia tank 14.
The iron-nickel alloy foam electrode 3 of reaction vessel 1 is also connected with an air flowmeter 8, and air flowmeter 8 is connected with air compressor 9.Air compressor 9 is for being fed through iron-nickel alloy foam electrode 3 place by after air compressing through air flowmeter 8.
When the device adopting the present embodiment to provide carries out electrolysis ammonia, in reaction vessel 1, add vanadium hydroxide, and add pure water by the valve 5 that adds water, obtain vanadium hydroxide solution.After switching on power, air compressor 9 is by after air pressurized, and the flow ensureing air is measured by air flowmeter 8, it is made to enter in reaction vessel 1, agitator 2 starts the solution in stirring reaction container 1 simultaneously, make dissolution homogeneity in container, then the negative electrode (i.e. iron-nickel alloy foam electrode 3) in reaction vessel 1 can make nitrogen reduction ammonification, and anode (i.e. platinum electrode) place then has by product oxygen to produce.The by product oxygen produced in container is entered in air by oxygen emptying valve 7.And the mixed gas of the ammonia produced in container and nitrogen by venting port enter the first compressor 11 carry out first time pressurization, pressurization after input separator 12, by separator 12, mixed gas is separated into pure ammonia and nitrogen.Wherein, the ammonia after separation enters the second compressor 13 through the first outlet of separator 12 and carries out second time pressurization, and second time is sent in ammonia tank 14 again and stored after becoming liquefied ammonia after pressurizeing.And the nitrogen after being separated directly exports in outside air through the second outlet of separator 12.
In the process of electrolysis ammonia, owing to entering negative electrode iron-nickel alloy foam place as the air of raw material, thus, export in exhaust ports in the gas of the first compressor and be also mixed with from the oxygen in air, this part oxygen, after separator separating treatment, is together discharged in extraneous air with nitrogen.
Wherein, cathode compartment and anolyte compartment can separate by dividing plate 15, the oxygen natural separation that the ammonia that negative electrode is generated and anode generate, and being convenient to classification and exporting.Preferably, this device also comprises supply unit and thermostatic regulator, and supply unit is used for powering for agitator 2, and thermostatic regulator is positioned at reaction vessel, for regulating the solution temperature in reaction vessel, makes electrolytic reaction temperature-stable.
In other preferred embodiments, as shown in Figure 2, this device can also comprise an engine 15, now, oxygen emptying valve 7 is connected with engine 15, and the oxygen produced in the process of electrolysis ammonia exports engine 15 place to, for engine 15 by oxygen emptying valve 7.
When the device adopting above-described embodiment to provide carries out electrolysis ammonia, temperature of reaction is 70 DEG C.Containing catalyst V (OH)
2, magnesium sulfate, sodium hydroxide the aqueous solution of 2000 milliliters in pass into the air that flow is per minute 10 liters, anode metal platinum, negative electrode adopt iron nickel foam alloy, adopt voltage 30V, electric current 18A, in the reaction process of 60 minutes, the ammonia of 28 grams can be obtained.
Certainly, the present invention is not limited with above-described embodiment, and the chemical substance in solution can adjust according to the structure of said apparatus by those skilled in the art, and whole process can also be optimized further, and current efficiency is further enhanced.Such as, when air velocity is accelerated, correspondingly improve strength of current, the speed of electrolytic reaction can be improved.Wherein, temperature of reaction can be at 60 DEG C---the arbitrary temperature between 110 DEG C.In addition, metallic cathode and metal anode can also replace with the metallic substance that can be applicable to apparatus of the present invention of other types as negative electrode or anode.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art is in the technical scope that the present invention discloses; the distortion do the present invention or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (9)
1. a Novel electrolytic ammonia-preparing device, is characterized in that, comprises reaction vessel, the first compressor, separator, the second compressor, air compressor, ammonia tank and direct supply;
Metallic cathode and metal anode is provided with in described reaction vessel, described reaction vessel top is provided with add water valve and venting port, described venting port is connected with the entrance of the first compressor, the described outlet of the first compressor is connected with the entrance of separator, first outlet of described separator is connected with the second compressor, second outlet of described separator communicates with extraneous air, and the outlet of described second compressor is connected with ammonia tank;
When adopting this device electrolysis ammonia, described reaction vessel is built with the vanadium hydroxide aqueous solution, the negative pole of described direct supply is connected with described metallic cathode simultaneously, the positive pole of described direct supply is connected with described metal anode, air compressor will be fed through described metallic cathode place after air compressing, electrolysis produces the mixed gas of ammonia and nitrogen, described mixed gas enters separator by ammonia and nitrogen separation after the first compressor compresses, nitrogen after separation is through the second outlet emptying, and the ammonia after separation inputs described ammonia tank after entering the second compressor compresses;
Also dividing plate is provided with between described metallic cathode and metal anode.
2. Novel electrolytic ammonia-preparing device according to claim 1, it is characterized in that, also comprise air flowmeter, air flowmeter is connected with described air compressor, and described air compressor is fed through described metallic cathode place by after air compressing after described air flowmeter measuring flow.
3. Novel electrolytic ammonia-preparing device according to claim 1 and 2, is characterized in that, is also provided with agitator in described reaction vessel.
4. Novel electrolytic ammonia-preparing device according to claim 3, is characterized in that, also comprise supply unit, and described supply unit is that described agitator is powered.
5. Novel electrolytic ammonia-preparing device according to claim 1 and 2, is characterized in that, described metallic cathode is iron-nickel alloy foam electrode; Described metal anode is platinum electrode.
6. Novel electrolytic ammonia-preparing device according to claim 1 and 2, is characterized in that, described reaction vessel top is also provided with reducing valve.
7. Novel electrolytic ammonia-preparing device according to claim 1 and 2, is characterized in that, described reaction vessel top is also provided with oxygen emptying valve, and the oxygen produced during electrolysis ammonia is by the emptying of described oxygen emptying valve.
8. Novel electrolytic ammonia-preparing device according to claim 7, is characterized in that, also comprise engine, and described oxygen emptying valve is connected with described engine, and the oxygen produced during electrolysis ammonia exports described engine to by described oxygen emptying valve.
9. Novel electrolytic ammonia-preparing device according to claim 1, is characterized in that, is also provided with thermostatic regulator in described reaction vessel, is 60 DEG C ~ 110 DEG C normally carries out to keep electrolysis for regulating the temperature in reaction vessel.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105540609A (en) * | 2015-12-30 | 2016-05-04 | 中国石油大学(北京) | Carbon-footprint-free ammonia synthesis device and method, and application thereof |
CN106480469A (en) * | 2016-07-14 | 2017-03-08 | 张国权 | The manufacture method of small-sized ammonia machine processed |
CN107810291A (en) * | 2015-06-17 | 2018-03-16 | 西门子股份公司 | For synthesizing the electrochemical cell and technique of ammonia |
CN109477229A (en) * | 2016-07-28 | 2019-03-15 | 西门子股份公司 | Generate the electrochemical method of ammonia |
CN109913885A (en) * | 2019-03-11 | 2019-06-21 | 刘志刚 | A kind of renewable ammonia (green ammonia) synthesis technology and apparatus system |
CN110284144A (en) * | 2019-06-29 | 2019-09-27 | 华南理工大学 | A kind of organic electrolyte and the preparation method and application thereof of electro-catalysis synthesis ammonia |
CN115094445A (en) * | 2022-05-17 | 2022-09-23 | 南京师范大学 | Method for preparing ammonia gas by reducing algae slurry by fluidized bed electrochemical technology |
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CN103866343A (en) * | 2014-03-25 | 2014-06-18 | 内蒙古科技大学 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107810291A (en) * | 2015-06-17 | 2018-03-16 | 西门子股份公司 | For synthesizing the electrochemical cell and technique of ammonia |
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CN107810291B (en) * | 2015-06-17 | 2020-03-27 | 西门子股份公司 | Electrochemical cell and process for ammonia synthesis |
CN105540609A (en) * | 2015-12-30 | 2016-05-04 | 中国石油大学(北京) | Carbon-footprint-free ammonia synthesis device and method, and application thereof |
CN106480469A (en) * | 2016-07-14 | 2017-03-08 | 张国权 | The manufacture method of small-sized ammonia machine processed |
CN109477229A (en) * | 2016-07-28 | 2019-03-15 | 西门子股份公司 | Generate the electrochemical method of ammonia |
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CN109913885A (en) * | 2019-03-11 | 2019-06-21 | 刘志刚 | A kind of renewable ammonia (green ammonia) synthesis technology and apparatus system |
CN110284144A (en) * | 2019-06-29 | 2019-09-27 | 华南理工大学 | A kind of organic electrolyte and the preparation method and application thereof of electro-catalysis synthesis ammonia |
CN115094445A (en) * | 2022-05-17 | 2022-09-23 | 南京师范大学 | Method for preparing ammonia gas by reducing algae slurry by fluidized bed electrochemical technology |
CN115094445B (en) * | 2022-05-17 | 2023-11-21 | 南京师范大学 | Method for preparing ammonia gas by reducing algae slurry through fluidized bed electrochemical technology |
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