CN109830731A - A kind of electricity-generating method and its device based on acid-base neutralization reaction - Google Patents
A kind of electricity-generating method and its device based on acid-base neutralization reaction Download PDFInfo
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Abstract
The present invention provides a kind of electricity-generating method and its device based on acid-base neutralization reaction, which is that discarded soda acid resource is also utilized while converting electric energy for the chemical energy of acid-base reaction using traditional acid-base neutralization reaction.It include cation-exchange membrane and acid bath and lye pond in power generator provided by the invention, wherein the concentration of acid solution is 0.001-12mol/L, and the concentration of alkaline solution is 0.001-12mol/L.H in acid solution+By the rate of cation-exchange membrane much larger than rate of the cation by cation-exchange membrane in the alkaline solution, H+Interior electric current is formd with migration rate difference cationic in alkaline solution；While electronics is then transmitted to the cathode electrode in lye pond through external circuit on the anode electrode of acid bath side, forms extrinsic current, realizes conversion of the chemical energy to electric energy.In addition, being somebody's turn to do the electricity-generating method based on acid-base neutralization reaction has the advantages that generating efficiency is high, efficiently uses discarded acid & alkali liquid, added value is increased for the processing of industrial waste acid salkali waste.
Description
Technical field
It the present invention relates to the use of technical field of power generation.More particularly, to a kind of power generation side based on acid-base neutralization reaction
Method and its device.
Background technique
With economic fast development, demand of the mankind to the energy is also increasing, and wherein electric power energy performance is especially prominent
Out.From daily life, work or even the development of enterprise all be unable to do without electric power support, and the conventional electric power generation mode in China with
In the majority using fossil fuel thermal power generation, although novel electric power energy development has great progress but compared with social demand, still
So have differences.Conventional electric power generation mode brings very big influence to environment while solving social demand, such as environmental pollution, noise
Pollution etc..In addition, increasingly depleted fossil fuel makes the energy shortage problem of facing mankind sternness.Therefore, energy benefit is promoted
With efficiency, reinforce heat recovery, seeks the economy of energy and environmental protection coordinated development is inevitable problem.
Soda acid can be used as cleaning agent, raw material, catalyst and be applied to industrial production as important chemical products.It is refining
Oil product manufacture, Essential Chemistry manufacture, steel calendering processing, Treatment of Metal Surface and heat treatment process, electronic components fabrication and
Various spent acid, spent lye can be generated in other nonspecific industry production, sale and use processes.Industrial waste acid salkali waste not only produces
Amount is big, and has the hazard properties such as corrosivity, toxicity and reactivity, big to environmental hazard, it is improper conduct oneself well set will cause it is serious
Resource waste and pollution.In view of factors such as investment, operating cost and disposition scales, more universal spent acid salkali waste is applied at present
Disposing technique mainly has neutralisation, spray roasting, ion-exchange and chemical transformation etc..Wherein neutralisation is most general at present
All over the spent acid salkali waste processing method of application.Therefore it provides a kind of power generator and electricity-generating method based on acid-base neutralization reaction come
It realizes the processing of spent acid salkali waste, and increases added value for the processing of industrial waste acid salkali waste.
Summary of the invention
The purpose of the present invention is to provide a kind of power generator based on acid-base neutralization reaction of function admirable.
Second object of the present invention is to provide a kind of electricity-generating method based on acid-base neutralization reaction.
To reach the first purpose of this invention, the present invention is adopted the following technical solutions:
A kind of power generator based on acid-base neutralization reaction, described device include: electrode and cation-exchange membrane, the sun
Amberplex two sides are respectively acid bath and lye pond；The concentration of acid solution is 0.001-12mol/L in the acid bath；
The concentration of the lye pond neutral and alkali solution is 0.001-12mol/L.
Further, for example, the concentration of the acid solution can also be but be not limited to 0.005-11mol/L, 0.01-
10mol/L, 0.05-9mol/L, 0.1-8mol/L, 0.5-7mol/L or 1-6mol/L etc.；The concentration of the alkaline solution may be used also
Think but is not limited to 0.005-11mol/L, 0.01-10mol/L, 0.05-9 mol/L, 0.1-8mol/L, 0.5-7mol/L or 1-
6mol/L etc..
It should be noted that the acid solution in the present invention refers in the presence of largely free H+Solution, alkaline solution is
Refer to there is largely free OH-Solution.When acid solution concentration is in 0.001-12mol/L, alkaline solution concentration is in 0.001-
When 12mol/L, in solution there are enough free H+It is migrated into alkaline solution and OH by cation-exchange membrane-In generation
And reaction, drive the progress of power generation process.In the specific implementation process, H in the acid solution+Pass through cation-exchange membrane
The rate H that is greater than in the alkaline solution cation by the rate of cation-exchange membrane, in acid solution+By sun from
Cation forms interior electric current by the difference of the rate of cation-exchange membrane in the rate and alkaline solution of proton exchange.
Preferably, the H in the acid solution+Concentration is equal with the cation concn in the alkaline solution.
Preferably, the cation-exchange membrane with a thickness of 0.01-200 μm.
Further, for example, the thickness of the cation-exchange membrane can also be but be not limited to 0.01-180 μm, 0.1-
150 μm, 1-120 μm, 10-100 μm, 20-90 μm, 40-80 μm or 50-70 μm etc..
Preferably, the cation-exchange membrane is selected from transition metal carbon/nitride film, Nafion membrane, poly (ether sulfone) film, polyethers
One of ether ketone film, sulfonated polyether sulfone film, sulfonated polyether-ether-ketone film, CSE cation-exchange membrane etc..
In the power generator provided by the invention based on acid-base neutralization reaction, the two sides of cation-exchange membrane are respectively at acid
Property solution and alkaline solution be in contact, need it with acid-alkali-corrosive-resisting, and the performance that the permission cation of selectivity passes through
It is not influenced by acid-base property.
Transition metal carbon/nitride film, that is, MXene film, the film are stratiform two-dimensional structure, have excellent electric conductivity, H+
The resistance being subject in transition process is very small.The thickness of the film is usually 0.01-30 μm, and the interlamellar spacing in film is 0.1-
0.5nm。
MXene film can be by commercially available acquisition, can also be by from Mn+1AXnA layers are etched selectively to out in phase and
It is prepared, wherein M is transition metal, is selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Cr or Mo；A is IIIA or IVA race member
Element；X be C and or N；N=1,2 or 3, i.e. Mn+1AXnFor M2AX, M3AX2Or M4AX3.During the preparation process, it generally selects containing fluorine
The etching liquid of ion, such as the mixture of hydrofluoric acid, ammonium acid fluoride, hydrochloric acid and lithium fluoride, after a certain period of time, selective is clear for etching
Except Mn+1AXnIn A atom, and carbide lamella and or nitride layer surface produce the functions such as end oxygen, hydroxyl and fluorine
Group T, forms Mn+1XnTx；PH is washed to as neutrality；The ultrasonic stripping means assisted using intercalator, by the multilayer after etching
MXene removing prepares certain thickness two-dimentional cation selective MXene film at few layer, finally by the method for suction filtration.
Preferably, the acid solution be selected from hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid, oxalic acid, carbonic acid,
One of hypochlorous acid etc. is a variety of；The alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, barium hydroxide, ammonia
One of water etc. is a variety of.In an acidic solution, the cation that solute generates after ionizing in a solvent is entirely H+；In alkali
In property solution, the anion that solute generates after ionizing in a solvent is entirely OH-.H in power generator, in acid solution+
The rate and alkaline solution by cation-exchange membrane in cation by the difference of the rate of cation-exchange membrane, formed in electricity
Stream, and move to the H in lye pond+With the OH in lye pond-Neutralization reaction occurs.This process realizes spent acid and salkali waste
It neutralizes, converts electric energy for chemical energy, increase added value for the processing of industrial waste acid salkali waste.
Preferably, the electrode in titanium-based iridium coating layer electrode, titanium-based ruthenium coating electrode, silver/silver chloride electrode one
Kind.
In the present invention, the working environment of electrode is acid and alkalinity, and there are a large amount of H for surrounding them+Or OH-, therefore
It when selecting electrode, needs to consider the corrosion resistance and stability of electrode, avoids due to electrode surface erosion and size change
Caused extrinsic current potential declines problem.It is the electrode size stabilization of ti-based coating electrode provided by the invention, long working life, resistance to
Corrosivity is high, and current density is high, overpotential is small, can avoid deformed short circuit problem；In addition, silver/silver chloride electrode has
High stability and reversibility, even if in an acidic solution, electrode surface can also be protected well, and potential is stablized,
It is good to reappear performance.Above-mentioned electrode is all suitable for the power generator based on acid-base neutralization reaction.
In conjunction with power generation process, the H of acid bath side+The rate in lye pond is migrated into much larger than lye by cation-exchange membrane
Cation transport enters the rate of acid bath, a large amount of H in pond+Migration form interior electric current, and with the OH in lye pond-It neutralizes
Reaction, further promotes H+Migration to lye pond side.And remaining a large amount of anion in the acid solution of acid bath side,
The anode surface of acid bath side is assembled, and anode electrode and anion occur oxidation reaction and lose electronics, and electronics passes through external circuit stream
To the cathode surface of lye pond side, cathode electrode obtains electronics and reduction reaction occurs.
The second aspect of the invention is to provide a kind of electricity-generating method using above-mentioned power generator.
In the specific implementation process, the power generation process the following steps are included:
1) acid solution and alkaline solution are introduced into acid bath and lye pond respectively, the H in acid solution+Pass through cation
Cation forms interior electric current by the difference of the rate of cation-exchange membrane in the rate and alkaline solution of exchange membrane；Move to lye
H in pond+With the OH in lye pond-Neutralization reaction occurs；
2) electron-transport on the anode electrode of acid bath side forms external circuit, realizes to the cathode electrode of lye pond side
The power generation of acid-base neutralization reaction driving.
In conjunction with above-mentioned power generator and electricity-generating method, power generation process provided by the invention be can be described as: in the present invention,
Acid solution and alkaline solution are introduced into acid bath and lye pond respectively, the H in acid solution+Cation is passed through by acid bath side
The rate that exchange membrane migrates into lye pond side migrates into acid bath by cation-exchange membrane much larger than cation in alkaline solution
The rate of side, therefore form interior electric current.H+OH in final and lye pond-Neutralization reaction: H occurs++OH-→H2O, neutralization reaction
Also accelerate hydrogen ion (H+) migration；Oxidation reaction occurs for the anode electrode of acid bath side, and the electronics lost is passed by external circuit
Cathode electrode is transported to, extrinsic current is formed, realizes the power generation of acid-base neutralization reaction driving.This power generation process realizes spent acid and gives up
The effective use of alkali, and generating efficiency is high.
Beneficial effects of the present invention are as follows:
The present invention provides a kind of electricity-generating method and its device based on acid-base neutralization reaction, which is to utilize tradition
Acid-base neutralization reaction, also utilize waste resource while converting electric energy for the chemical energy that spent acid salkali waste reacts.The present invention
It include cation-exchange membrane and acid bath and lye pond, H in acid solution in the power generator of offer+It is exchanged by cation
For the rate of film much larger than cation in the alkaline solution by the rate of cation-exchange membrane, migration rate difference forms interior electricity
Stream；While electronics is then transmitted to the cathode electrode in lye pond through external circuit on the anode electrode of acid bath side, forms extrinsic current, it is real
Conversion of the chemical energy to electric energy is showed.In addition, should be had based on electricity-generating method of acid-base neutralization reaction, generating efficiency was high, effective benefit
The advantages of with discarded acid & alkali liquid, increases added value for the processing of industrial waste acid salkali waste.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the electron scanning micrograph of 1 middle-jiao yang, function of the spleen and stomach ion exchange MXene film of embodiment, and wherein a is surface topography,
B is cross-section morphology.
Fig. 2 is the schematic diagram based on acid-base neutralization reaction power generator used by embodiment 1.
Fig. 3 show the current density (figure a) that the electricity-generating method in embodiment 1 obtains, generated output density (figure b) with it is outer
Sensitivity figure.
Fig. 4 be the obtained current density of electricity-generating method (figure a) in embodiment 2, generated output density (figure b) with it is outer
Sensitivity figure.
Fig. 5 be the obtained current density of electricity-generating method (figure a) in embodiment 3, generated output density (figure b) with it is outer
Sensitivity figure.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Next several specific embodiments are enumerated to illustrate the power generator and process of acid-base neutralization driving.
Embodiment 1
Fig. 2 is the power generator based on acid-base neutralization reaction based on cation exchange MXene film that the present invention utilizes, should
Device is mainly made of cation exchange MXene film and electrode, acid bath and lye pond.
The device middle-jiao yang, function of the spleen and stomach ion exchange MXene film is Ti3C2TxMXene film, with a thickness of 13 μm, interlamellar spacing 0.3nm；Electricity
Extremely sheet silver/silver chloride electrode；Acid solution is hydrochloric acid, and alkaline solution is potassium hydroxide solution, and wherein hydrochloric acid solution is dense
Degree is 0.01mol/L, and the concentration of potassium hydroxide solution is 0.01 mol/L.
Power generation process: hydrochloric acid solution and potassium hydroxide dope are introduced into acid bath and lye pond respectively, in hydrochloric acid solution
Hydrogen ion is much larger than potassium ion by lye pond by the rate that cation exchange MXene film migrates into lye pond side by acid bath side
The rate that MXene film migrates into acid bath side, a large amount of hydrogen ions electric current into the migration in lye pond formation are exchanged by cation；
Move to the hydrogen ion (H in lye pond+) and lye pond in hydroxyl (OH-) neutralization reaction: H occurs++OH-→H2O accelerates
Hydrogen ion (H+) migration；The cathode that electronics is then transmitted to lye pond through external circuit on the anode electrode of acid bath side simultaneously is electric
Pole forms external circuit, realizes conversion of the chemical energy to electric energy.
The relationship of generated output, current density and external resistance is as shown in Figure 3 in above-mentioned power generation process, it is found that when outer
When boundary's resistance is 20000 Ω, output power density 0.30W/m2。
Embodiment 2
Power generator and power generation process are identical with embodiment 1, only change the following parameter in power generator:
Cation-exchange membrane is business in the device117 film of perfluorinated membranes, thickness are about 184.5 μm, electricity
Extremely sheet silver/silver chloride electrode；Acid solution is hydrochloric acid, and alkaline solution is potassium hydroxide, and wherein the concentration of hydrochloric acid solution is
0.1mol/L, the concentration of potassium hydroxide solution are 0.1mol/L.
The relationship of generated output, current density and external resistance is as shown in figure 4, the results show that when outer in above-mentioned power generation process
When boundary's resistance is 2000 Ω, the output power of the power generator is 7.60W/m2。
Embodiment 3
Power generator and power generation process are identical with embodiment 1, only change the following parameter in power generator:
Cation-exchange membrane is the CSE cation-exchange membrane of ASTOM company in the device, and thickness is about 112.55 μm,
Electrode is sheet silver/silver chloride electrode electrode；Acid solution is hydrochloric acid, alkaline solution is sodium hydroxide, wherein hydrochloric acid solution
Concentration is 1mol/L, and the concentration of sodium hydroxide solution is 1mol/L.
The relationship of generated output, current density and external resistance is as shown in Figure 5 in above-mentioned power generation process.The results show that when outer
When boundary's resistance is 220k Ω, the output power of the power generator is 0.285W/m2。
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (9)
1. a kind of power generator based on acid-base neutralization reaction, which is characterized in that described device includes electrode and cation exchange
Film, the cation-exchange membrane two sides are respectively acid bath and lye pond；The concentration of acid solution is in the acid bath
0.001-12mol/L；The concentration of the lye pond neutral and alkali solution is 0.001-12mol/L.
2. power generator according to claim 1, which is characterized in that the H in the acid solution+Concentration and the alkalinity
Cation concn in solution is equal.
3. power generator according to claim 1, which is characterized in that the cation-exchange membrane with a thickness of 0.01-200
μm。
4. power generator according to claim 1, which is characterized in that the cation-exchange membrane be selected from transition metal carbon/
Nitride film, Nafion membrane, poly (ether sulfone) film, polyether-ether-ketone film, sulfonated polyether sulfone film, sulfonated polyether-ether-ketone film, CSE cation are handed over
Change one of film.
5. power generator according to claim 1, which is characterized in that the acid solution be selected from hydrochloric acid, sulfuric acid, nitric acid,
One of perchloric acid, hydroiodic acid, hydrobromic acid, oxalic acid, carbonic acid, hypochlorous acid are a variety of；The alkaline solution is selected from sodium hydroxide
One of solution, potassium hydroxide solution, barium hydroxide, ammonium hydroxide are a variety of.
6. power generator according to claim 1, which is characterized in that the electrode is selected from titanium-based iridium coating layer electrode, titanium-based
One of ruthenium coating electrode, silver/silver chloride electrode.
7. power generator according to claim 1, which is characterized in that the electrode of the acid bath side is anode, the alkali
The electrode of liquid pool side is cathode.
8. a kind of electricity-generating method based on acid-base neutralization reaction, which is characterized in that the electricity-generating method is to utilize claim 1-7
What any power generator carried out.
9. electricity-generating method according to claim 8, which is characterized in that the power generation process the following steps are included:
1) acid solution and alkaline solution are introduced into acid bath and lye pond respectively, the H in acid solution+It is exchanged by cation
Cation forms interior electric current by the difference of the rate of cation-exchange membrane in the rate and alkaline solution of film；It moves in lye pond
H+With the OH in lye pond-Neutralization reaction occurs, further promotes the H in acid solution+Migration；
2) electron-transport on the anode electrode of acid bath side forms extrinsic current, realizes soda acid to the cathode electrode of lye pond side
The power generation of neutralization reaction driving.
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