CN102583278A - Process for producing nitric acid by dielectric barrier discharge nitrogen fixation - Google Patents
Process for producing nitric acid by dielectric barrier discharge nitrogen fixation Download PDFInfo
- Publication number
- CN102583278A CN102583278A CN201210015353XA CN201210015353A CN102583278A CN 102583278 A CN102583278 A CN 102583278A CN 201210015353X A CN201210015353X A CN 201210015353XA CN 201210015353 A CN201210015353 A CN 201210015353A CN 102583278 A CN102583278 A CN 102583278A
- Authority
- CN
- China
- Prior art keywords
- nitric acid
- stainless steel
- nitrogen
- dielectric barrier
- tooth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a process for producing nitric acid by dielectric barrier discharge nitrogen fixation, comprising a tooth-shaped stainless steel cylinder, wherein an insulation tube is sheathed outside the tooth-shaped stainless steel cylinder, a gap between the tooth-shaped stainless steel cylinder and the insulation tube is 3-30mm, a stainless steel wire mesh is wound outside the insulation tube, the tooth-shaped stainless steel cylinder is connected with a shell, the stainless steel wire mesh is connected with a high voltage wiring terminal, and a power supply inputs high voltage alternating current to a reactor by virtue of the high voltage wiring terminal. Gas enters by virtue of a gas inlet of the reactor and is ionized through alternating current high voltage discharge to generate nitrogen plasma, the nitrogen plasma enters into a secondary reactor from an exposure hole at the bottom to be reacted with water, and nitric acid solution is obtained. In the invention, air is exposed into a dielectric barrier reactor, nitrogen is promoted to be ionized in a discharge process to form the nitrogen plasma, a liquid phase plasma chemical reaction is induced, the nitric acid is generated, one-step conversion of nitrogen to nitric acid is realized, the problem that a nitrogen source is utilized in the manner that ammonia is firstly synthesized and then is converted into the nitric acid in the prior art is solved, and a technological process is simple.
Description
Technical field
The present invention relates to a kind of novel medium barrier discharge plasma device, be specifically related to a kind of gas phase ac high-voltage discharge nitrogen ionization is formed nitrogen plasma, become the preparation method of nitric acid again with the water reaction conversion.
Background technology
The process that the nitrogen of free state in the air is converted into nitrogenous compound that can passive plant utilization is called fixed nitrogen.Fixed nitrogen can be divided into natural fixed nitrogen and artificial fixed nitrogen.Natural fixed nitrogen comprises thunder and lightning fixed nitrogen, two kinds of principal modes of vinelandii biological nitrogen fixation.French chemist in 1901 is reined in the summer special case and is studied hydrogen and the nitrogen directly reaction of synthetic ammonia under high pressure at first, has started the precedent of high pressure synthetic ammonia.Physicist, chemical industry expert Haber and his student of Germany worked out a kind of HTHP catalysis method synthetic ammonia afterwards.National investigation of pollution sources data in 1985, the average wastewater discharge of large-scale ammonia plant ton ammonolysis product is 11.1 tons, and medium-sized factory is 217.24 tons, and small-sized factory is 249.4 tons.Kind of waste water is complicated, and environmental pollution is serious.The ammonia production process also can produce sulfide, carbon monoxide, carbonic acid gas and various dusty gas.In addition, exposed high temperature service and pipeline pollute also particularly serious to the thermal radiation that surrounding environment causes.Along with the growth and the Agricultural Development of world population, human more and more big to the requirement of nitrogenous fertilizer, and industrial synthetic ammonia needs under high-temperature and high-pressure conditions, to carry out, and causes severe energy waste.In addition, though about the research of biological nitrogen fixation certain achievement has been arranged, great majority research still is in theory stage, fails to be applied in the actual agriculture prodn.Most of farm crop still need nitrogenous fertilizer to solve to the demand of nitrogen, also depend on chemical industry to a certain extent.Therefore the technique for fixing of research nitrogen has very important significance under the normal temperature and pressure conditions.
There is form in the 4th kind of material that plasma body is known as except that solid-state, liquid state and gaseous state, by the conducting fluid that electronics, ion, radical and neutral particle are formed, and the whole electroneutral that keeps.Plasma body has the particular chemical reactive behavior, shows the specific performance different with other states of matter, is referred to as the 4th attitude of material.Producing plasma body has multiple mode, and common have dielectric barrier discharge and photoglow under the normal atmosphere, corona discharge, direct current glow discharge, dense ionization geseous discharge, a thermal ionization discharge etc.This technology of plasma body synthetic ammonia had report very early.The people such as KazuoSugiyama of Japanese Saitama university in 1986 have introduced under the normal temperature photoglow and have used MgO, CaO, A1
2O
3, WO
3, NaCl, SiO
2-A1
2O
3Deng the research of catalyzer synthetic ammonia, but not concrete concentration of setting forth synthetic ammonia in the literary composition.The people such as Shigeyuki Thnaka of Tokyo Aoyama Gakuin university have introduced and have utilized radio frequency and microwave plasma, with N
2, H
2Dissociate, excite, under the katalysis of iron wire coil, combine to generate NH
3Research.Yet the report that utilizes the direct nitric acid synthesis of certain technology is bright it is arranged.Utilize discharge plasma technique to realize nitric acid production through nitrogen fixation in the water, as main basic raw material, reaction process need not to be aided with high temperature, high pressure catalyzer, is a kind of green fixed nitrogen new technology of potentialization with empty G&W in this process utilization.At present, less about this technological systematic study, the fixed nitrogen transformation efficiency awaits further raising.
In this seminar early-stage Study, discharged 21 minutes, the concentration of nitric acid is respectively 1.36 and 1.53 mmol L-1, and the productive rate of nitric acid is 1.99 * 10-9mol J-1 and 2.24 * 10-9mol J-1 under the unit intake.
Summary of the invention
The objective of the invention is to overcome the above problem that prior art exists, the device that a kind of technology is simple, can airborne nitrogen be fixed as nitric acid in water is provided, to make things convenient for the utilization of nitrogen.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention realizes through following technical scheme:
Dielectric barrier discharge is nitrogen system nitric acid fixedly; Comprise the stainless steel column of profile of tooth, the stainless steel column overcoat of said profile of tooth has an insulation tube, and the gap between stainless steel column of said profile of tooth and the said insulation tube is 3-30mm; One deck Stainless Steel Cloth that twine said insulation tube outside; The stainless steel column of the said profile of tooth ground connection that links to each other with shell, said Stainless Steel Cloth links to each other with high tension terminal, and power supply is imported High Level AC Voltage through said high tension terminal to reactor drum.
Preferably, said insulation tube is a quartz glass tube.
Preferably, said insulation tube is an alundum tube.
Preferably, said insulation tube is a vitrified pipe.
Dielectric barrier discharge is nitrogen system nitric acid fixedly, and gas is crossed the reactor drum inlet mouth and got into, and produces nitrogen plasma through ac high-voltage discharge ionization, and solarization air cap gets into secondary reactor and water reaction from the bottom, obtains salpeter solution
Further, the alternating voltage peak of said discharge power supply input reactor is greater than 10kV, and frequency is higher than 9kHz, exchanges intake and is higher than 110W.
Further, ionization of air and the reaction of liquid phase fixed nitrogen are accomplished in two zones respectively, and said gas is air.
The invention has the beneficial effects as follows:
The present invention is by exposing to the sun with air in the dielectric impedance reactor; Impel nitrogen ionization in discharge process to form nitrogen plasma; Bring out the liquid phase plasma chemical reaction; Generate nitric acid; Realized the step conversion of nitrogen to nitric acid; Solved first synthetic ammonia in the prior art, be converted into the problem that nitric acid utilizes nitrogenous source again, technical process is simple;
Because the present invention obtains nitric acid through a step, need not supplementary meanss such as catalyzer, high temperature, high pressure; With empty G&W is raw material, is the energy with the electric energy, avoids the use of primary energy source;
The nitrogen plasma that the solarization air cap of device of the present invention through the bottom exposes to the sun and produce after the nitrogen ionization fully contacts it with water, improve nitrogen-fixing efficiency.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, understands technique means of the present invention in order can more to know, and can implement according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. specify as after.Embodiment of the present invention is provided by following examples and accompanying drawing thereof in detail.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is dielectric impedance reactor structure figure;
Fig. 2 is the structure drawing of device of the embodiment of the invention one, two;
Fig. 3 is liquid phase HNO when exposing to the sun air among the embodiment one
2, HNO
3The concentration change synoptic diagram;
Fig. 4 is liquid phase HNO when exposing to the sun air among the embodiment two
2, HNO
3The concentration change synoptic diagram;
Fig. 5 is the structure drawing of device of the embodiment of the invention three;
Fig. 6 is liquid phase HNO when exposing to the sun air and oxygen mixture among the embodiment three
2, NO
3The concentration change synoptic diagram;
Fig. 7 is a dielectric impedance reactor drum insulation tube annexation synoptic diagram.
Label declaration among the figure: 1, inlet mouth, 2, the air outlet, 3, high tension terminal, a, the stainless steel column of profile of tooth (negative electrode), b, insulation tube, c, Stainless Steel Cloth (anode).
Embodiment
Below with reference to accompanying drawing and combine embodiment, specify the present invention.
Embodiment one: with reference to Fig. 1, shown in Figure 7; A kind of dielectric impedance reactor drum, said negative electrode are the stainless steel column a of profile of tooth, and overcoat one insulation tube b is the block media medium; Anode is one deck Stainless Steel Cloth c that twine insulation tube outside, the stainless steel column of the profile of tooth ground connection that links to each other with shell.High tension terminal 3 links to each other with Stainless Steel Cloth; Power supply is imported High Level AC Voltage through high tension terminal to reactor drum; Gas is crossed reactor drum inlet mouth 1 and is got into, and produces plasma body through ac high-voltage discharge ionization, and solarization air cap gets into secondary reactor generation liquid-phase chemical reaction from the bottom.
Referring to shown in Figure 2, adopt the device of present embodiment to carry out fixed nitrogen in the water, expose to the sun with air to total system, in the quadrate secondary reactor drum, add 1 mmol/L H
2O
2Solution is regulated high-voltage power voltage, and the dielectric barrier discharge reaction takes place the input AC high pressure, produces plasma body, the NO that different time records
2 -, NO
3 -The concentration change situation as shown in Figure 3.
In the device of present embodiment, the power supply output parameter is: PV, 15.64 kV; Frequency, 5-20 kHz.
Input reactor power is 118.78 W; Aeration flow: 160 L h-1 (air); Reactor drum water sample volume: 400 mL (being 1 mmol/L H2O2 solution).
Visible from Fig. 3, it is 0.072 mmol L-1 that nitrous acid content rises to peak concentration earlier, drops to after 12 minutes to be lower than detection limit.Nitric acid is liquid phase fixed nitrogen final product, discharges 1 hour, and concentration of nitric acid reaches 11.128 mmol L-1.The productive rate of nitric acid (output that refers to nitric acid under the unit energy) is 1.04 * 10-8 mol J-1, i.e. 2.36 g/kWh.
Embodiment two: Fig. 1 stops reactor drum for a kind of novel medium, and said negative electrode is the stainless steel column a of profile of tooth, and overcoat one insulation tube b is the block media medium, and anode is one deck Stainless Steel Cloth c that twine insulation tube outside, the stainless steel column of the profile of tooth ground connection that links to each other with shell.High tension terminal 3 links to each other with Stainless Steel Cloth; Power supply is imported High Level AC Voltage through high tension terminal to reactor drum; Gas is crossed reactor drum inlet mouth 1 and is got into, and produces plasma body through ac high-voltage discharge ionization, and solarization air cap gets into secondary reactor generation liquid-phase chemical reaction from the bottom.
Referring to shown in Figure 2, adopt the device of present embodiment to carry out fixed nitrogen in the water, expose to the sun with air to total system, in the quadrate secondary reactor drum, add 1mmol/L H
2O
2Solution is regulated high-voltage power supply, and the dielectric barrier discharge reaction takes place the input AC high pressure, produces plasma body, the HNO that different time records
2, HNO
3The concentration change situation as shown in Figure 4.
In the device of present embodiment, the power supply output parameter is: PV, 15.64kV; Frequency, 5-20kHz.
Input reactor power is 118.78 W; Aeration flow: 160 L h
-1(air); Reactor drum water sample volume: 800 mL (are 1mmol/L H
2O
2Solution).
Visible from Fig. 4, nitrous acid content reaches peak concentration when rising to 6 minutes earlier be 0.118 mmol L
-1, drop to after 18 minutes and be lower than detection limit.Nitric acid content continues to rise, and discharges 1 hour, and concentration of nitric acid reaches 5.484 mmol L-1.Nitric acid is liquid phase fixed nitrogen final product, and productive rate (output that refers to nitric acid under the unit energy) is 1.03 * 10
-8Mol J
-1, i.e. 2.33 g/kWh.
Embodiment three: referring to shown in Figure 5, adopt the device of present embodiment to carry out fixed nitrogen in the water, exposing to the sun with air and oxygen to total system is a certain proportion of gas mixture; In synthetic glass and core secondary reactor, add water; Regulate high-voltage power supply, the dielectric barrier discharge reaction takes place in the input AC high pressure; Produce plasma body, the HNO that different time records
2, HNO
3The concentration change situation as shown in Figure 6.
In the device of present embodiment, the power supply output parameter is: PV, 16 kV; Frequency, 10.56 kHz.
Input reactor power is 155.54 W; Aeration flow: 105 L h-1 (air) and 135 L h-1 (oxygen); Reactor drum water sample TV: 2L.
Visible from Fig. 6, initial reaction stage, the HNO that liquid phase generates
2, HNO
3In rising trend and the concentration of concentration and the two proportion in solution are approaching, but after reaction 140 minutes, HNO
2Concentration no longer continues to rise, and about 3.25 mmol L-1, fluctuates HNO
3Concentration surpasses HNO
2, react 4 hours HNO
3Concentration reaches 7.16 mmol L-1.Liquid phase fixed nitrogen product is main with nitric acid, accounts for 70%.The productive rate of nitric acid (output that refers to nitric acid under the unit energy) is 6.39 * 10-9 mol J-1, i.e. 1.45 g/kWh.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the fixing nitrogen system nitric acid of dielectric barrier discharge; It is characterized in that: comprise the stainless steel column of profile of tooth (a); The outer insulation tube (b) that is with of the stainless steel column of said profile of tooth (a); Gap between stainless steel column of said profile of tooth (a) and the said insulation tube (b) is 3-30mm, one deck Stainless Steel Cloth (c) that twine said insulation tube (b) outside, the stainless steel column of said profile of tooth (a) ground connection that links to each other with shell; Said Stainless Steel Cloth (c) links to each other with high tension terminal (3), and power supply is imported High Level AC Voltage through said high tension terminal (3) to reactor drum.
2. dielectric barrier discharge according to claim 1 is nitrogen system nitric acid fixedly, it is characterized in that: said insulation tube (b) is a quartz glass tube.
3. dielectric barrier discharge according to claim 1 is nitrogen system nitric acid fixedly, it is characterized in that: said insulation tube (b) is an alundum tube.
4. dielectric barrier discharge according to claim 1 is nitrogen system nitric acid fixedly, it is characterized in that: said insulation tube (b) is a vitrified pipe.
5. the fixing nitrogen system nitric acid of dielectric barrier discharge, it is characterized in that: gas is crossed reactor drum inlet mouth (1) and is got into, and produces nitrogen plasma through ac high-voltage discharge ionization, and solarization air cap gets into secondary reactor and water reaction, acquisition salpeter solution from the bottom.
6. dielectric barrier discharge according to claim 5 is nitrogen system nitric acid fixedly, it is characterized in that: the alternating voltage peak of said discharge power supply input reactor is greater than 10kV, and frequency is higher than 9kHz, exchanges intake and is higher than 110W.
7. dielectric barrier discharge according to claim 5 is nitrogen system nitric acid fixedly, it is characterized in that: ionization of air and the reaction of liquid phase fixed nitrogen are accomplished in two zones respectively, and said gas is air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210015353XA CN102583278A (en) | 2012-01-18 | 2012-01-18 | Process for producing nitric acid by dielectric barrier discharge nitrogen fixation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210015353XA CN102583278A (en) | 2012-01-18 | 2012-01-18 | Process for producing nitric acid by dielectric barrier discharge nitrogen fixation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102583278A true CN102583278A (en) | 2012-07-18 |
Family
ID=46472644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210015353XA Pending CN102583278A (en) | 2012-01-18 | 2012-01-18 | Process for producing nitric acid by dielectric barrier discharge nitrogen fixation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102583278A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291283A (en) * | 2014-09-11 | 2015-01-21 | 中山大学 | Method for preparing nitrogen-containing liquid fertilizer by using microplasmas |
| CN104291282A (en) * | 2014-09-11 | 2015-01-21 | 中山大学 | Method for preparing nitrogen-containing liquid fertilizer by adopting non-thermal arc plasma |
| CN110327749A (en) * | 2019-07-18 | 2019-10-15 | 重庆工商大学 | A kind of method of low-temperature plasma degradation dimethylbenzene and synchronous fixed nitrogen |
| CN111058051A (en) * | 2019-12-31 | 2020-04-24 | 中国科学院长春应用化学研究所 | Normal-temperature normal-pressure electrochemical nitrogen fertilizer production system |
| CN111389326A (en) * | 2020-03-24 | 2020-07-10 | 四川大学 | Nitrogen fixation device and method based on liquid film-dielectric barrier discharge low-temperature plasma |
| CN113545190A (en) * | 2021-07-26 | 2021-10-26 | 南京工业大学 | Low-temperature plasma soil nitrogen fixation device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287040A (en) * | 1979-05-08 | 1981-09-01 | G.D. Societa Per Azioni | Production of nitric oxides |
| US4705670A (en) * | 1985-09-03 | 1987-11-10 | Hare Louis R O | Multiple oxidation nitrogen fixation |
| CN2755072Y (en) * | 2004-11-25 | 2006-02-01 | 吕丹 | Ionized discharger for nitrogen fixation |
| EP1630133A1 (en) * | 2004-08-27 | 2006-03-01 | Innovative Ozone Services Inc. | Method and arrangement for producing nitrogen oxides |
-
2012
- 2012-01-18 CN CN201210015353XA patent/CN102583278A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287040A (en) * | 1979-05-08 | 1981-09-01 | G.D. Societa Per Azioni | Production of nitric oxides |
| US4705670A (en) * | 1985-09-03 | 1987-11-10 | Hare Louis R O | Multiple oxidation nitrogen fixation |
| EP1630133A1 (en) * | 2004-08-27 | 2006-03-01 | Innovative Ozone Services Inc. | Method and arrangement for producing nitrogen oxides |
| CN2755072Y (en) * | 2004-11-25 | 2006-02-01 | 吕丹 | Ionized discharger for nitrogen fixation |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291283A (en) * | 2014-09-11 | 2015-01-21 | 中山大学 | Method for preparing nitrogen-containing liquid fertilizer by using microplasmas |
| CN104291282A (en) * | 2014-09-11 | 2015-01-21 | 中山大学 | Method for preparing nitrogen-containing liquid fertilizer by adopting non-thermal arc plasma |
| CN110327749A (en) * | 2019-07-18 | 2019-10-15 | 重庆工商大学 | A kind of method of low-temperature plasma degradation dimethylbenzene and synchronous fixed nitrogen |
| CN111058051A (en) * | 2019-12-31 | 2020-04-24 | 中国科学院长春应用化学研究所 | Normal-temperature normal-pressure electrochemical nitrogen fertilizer production system |
| CN111389326A (en) * | 2020-03-24 | 2020-07-10 | 四川大学 | Nitrogen fixation device and method based on liquid film-dielectric barrier discharge low-temperature plasma |
| CN113545190A (en) * | 2021-07-26 | 2021-10-26 | 南京工业大学 | Low-temperature plasma soil nitrogen fixation device |
| CN113545190B (en) * | 2021-07-26 | 2023-02-24 | 南京工业大学 | Low-temperature plasma soil nitrogen fixation device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102583278A (en) | Process for producing nitric acid by dielectric barrier discharge nitrogen fixation | |
| Patil et al. | Plasma N2-fixation: 1900–2014 | |
| CN108990248B (en) | Plasma generating device and application thereof | |
| CN110372006B (en) | Method and device for preparing ammonia by using dielectric barrier discharge low-temperature plasma in cooperation with catalyst | |
| CN109200970A (en) | Low-temperature plasma dual field assists device and the application of gas phase reaction synthesis compound | |
| Wong et al. | Microplasma‐discharge‐based nitrogen fixation driven by triboelectric nanogenerator toward self‐powered mechano‐nitrogenous fertilizer supplier | |
| CN107207248B (en) | Energy storage transportation resources and energy carrier system | |
| CN105967455A (en) | Refuse leachate self-powered denitration apparatus and method | |
| CN104761431A (en) | Method for preparing methanol by converting coal mine gas under synergistic action of plasma and catalyst | |
| CN207227171U (en) | Small-sized dielectric barrier discharge water treatment device | |
| CN209250931U (en) | A kind of plasma producing apparatus | |
| CN107528077A (en) | The energy is produced from pollutant | |
| WO2019193605A1 (en) | A process for production of nitric acid | |
| CN216678196U (en) | Distributed nitrogen fixation system | |
| CN102826511B (en) | Method and device for preparing active calcium hydride | |
| CN206472362U (en) | Equipment occurs for comb and low temperature plasma | |
| CN201997244U (en) | High-energy low-temperature plasma purifying device | |
| CN214031729U (en) | Low-temperature plasma-assisted catalytic waste gas-fuel reforming hydrogen production device | |
| CN204385149U (en) | A kind of coke(oven)gas cold shock formula methanation reaction device | |
| CN104261413B (en) | Plasma deoxidization in low termprature producing trichlorosilane by using silicon tetrachloride method and device thereof | |
| CN202808347U (en) | Device for preparing active calcium hydride | |
| CN108862322A (en) | A kind of preparation method of lime nitrogen | |
| CN106542964A (en) | Using carbon dioxide and the method and catalyst of water photocatalysis synthesizing methanol | |
| CN102515453B (en) | High-concentration anaerobic digestion treating device for urban sludge and use method | |
| CN208210407U (en) | Plasma discharge plate and plasma reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120718 |
|
| WD01 | Invention patent application deemed withdrawn after publication |