CN106119886B - A method of pressurization electrolytic cell and intensified electrolysis - Google Patents
A method of pressurization electrolytic cell and intensified electrolysis Download PDFInfo
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- CN106119886B CN106119886B CN201610466368.6A CN201610466368A CN106119886B CN 106119886 B CN106119886 B CN 106119886B CN 201610466368 A CN201610466368 A CN 201610466368A CN 106119886 B CN106119886 B CN 106119886B
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B9/05—Pressure cells
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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
- 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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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of methods of pressurization electrolytic cell and intensified electrolysis, which includes: reactive tank；The electrode being placed in reactive tank, including cathode and anode；Electrolyte membrane separates cathode and anode；Pressurizing device, including gas supply device and/or heating device.The pressurization electrolytic cell can pressurize under conditions of room temperature, pass through the process that can strengthen the transmitting of the mass transport process of electrode interface, the especially element sulphur in mineral, strengthen mineral purification of pressurizeing；The conductive capability for reinforcing electrolyte, to be effectively reduced the energy consumption of electrolytic hydrogen production；It can reinforce the precipitation and transmitting of active oxygen in electrolyte using oxygen pressing, to improve electrolyte anode oxidation process, and then improve cathode hydrogen evolution efficiency.The pressurization electrolytic cell is particularly suitable for the electrolysis of heterogeneous system, can be realized the reinforcing of cathode hydrogen production process, while increasing the quantity and reaction rate of anode active oxygen.
Description
Technical field
The invention belongs to electrolysis tech fields, are related to the method for a kind of pressurize electrolytic cell and intensified electrolysis.
Background technique
At present industrially prepare hydrogen method specifically include that water electrolysis method, water-gas method, electrolysis saturated common salt water law,
Natural gas synthetic method etc., it is current application relatively one of wide, the method for production technology comparative maturity, electricity that wherein electrolysis water, which prepares hydrogen,
Solution water hydrogen manufacturing is the current commercial technology for obtaining high-purity hydrogen, is applied in fuel pressurization electrolytic cell field and aerospace neck
Domain.The energy consumption of electrolytic hydrogen production most ideally should be 2.69kWh/Nm3, however the total energy consumption of hydrogen producing technology is 6.7- at present
7.3kWh/Nm3Even and the water electrolysis hydrogen producing technological synthesis efficiency of comercial operation is relatively low, only 50-55%.Therefore
Energy consumption height is the bottleneck in water electrolysis hydrogen producing technology commercialization process.
In the 1970s, carbon material, such as graphite is added in water electrolysis process anode in the researchs such as Coughlin R.W. discovery
Or liberation of hydrogen efficiency can be improved in coal, reduces tank voltage, this method mainly leads to water electrolysis process Anodic using the addition of coal
Oxygen evolution reaction part replaced the cell reaction of anode, and reduces the sulfur content in coal by mineral, finally makes water power
Hydrogen production efficiency is solved close to 100%.It can thus be appreciated that water electrolysis hydrogen producing efficiency not only can be improved in the electrolytic hydrogen production of mineral, but also can
The desulfurization that mineral realize mineral is purified, and mineral electrolytic desulfurization hydrogen manufacturing integrated technique has following advantages: 1) reaction condition
It is relatively mild；2) compared with other desulfurization technologies, environmental pollution is small；3) anode desulfurization carries out simultaneously with cathode hydrogen manufacturing.Although mine
There are the above advantages for object electrolytic desulfurization hydrogen integrated technique, but high energy consumption, low is constantly subjected to during its integration
The restriction of current efficiency.
In order to reduce water electrolysis hydrogen producing energy consumption, a variety of methods are had studied both at home and abroad, such as prepare efficient hydrogen evolution electrode material such as
The catalytic electrolysis such as platinumiridio and titanium-diamond alloy；Efficiently pressurization electrolytic cell such as gas-diffusion electrode pressurization electrolytic cell, fluidisation
Electrode pressurization electrolytic cell etc. increases the contact area of electrode and electrolyte；Outfield intensifying such as ultrasonic wave, super gravity field etc., by strong
Change the disengaging rate of anode and cathode bubble；Change electrolysis system and mineral, acid are such as added, alkali etc. reduces the resistance of electrolysis system, realizes
The raising of liberation of hydrogen current efficiency.The essence of these methods is exactly to improve the biography during water electrolysis hydrogen producing and electrolytic desulfurization
Matter and electrochemical reaction reduce energy consumption of reaction and improve current efficiency.
By further investigation discovery electrolysis system at normal temperatures and pressures tank voltage it is higher and pressurize electrolyte bath resistance
Greatly, and under alkaline system various active oxygen can be generated in water electrolysis process, such as the HO of the anode and O of cathode2 -, they
Oxidability is strong compared to common oxide isolation ability, the rate constant of oxidation reaction is big, oxidation rate is unrestricted.So
How HO. and O improved2 -Output and rate are the key that improve mineral electrolysis high-efficient purification.Research shows that the production of active oxygen
Necessary not only for efficient catalytic electrode, it is also necessary to which active oxygen presoma is transmitted from electrolysis main body to electrode surface, can just be mentioned in this way
The efficiency that highly reactive form of oxygen is formed.Therefore only have while strengthening active oxygen presoma (HO, O2 -) mass transfer and reaction i.e. strengthen it
Transmitting and receiving and losing electrons ability could inherently improve active oxygen (HO, O2 -) production quantity and generating rate.However it is ultrasonic
Although the methods of wave, hypergravity and Gas Stirring enhance transmitting of the active oxygen presoma from electrolyte to electrode, but these
Method can not meet the dual function for strengthening active oxygen presoma and receiving and losing electrons simultaneously, can not also increase active oxygen presoma
Quantity.
In June, 2009 China Shipbuilding Industry Corporation's July 1st eight Research Institute gone out 6-600/1.8 type water electrolysis
Hydrogen producing amount reaches 600m to device for producing hydrogen per hour3, operating pressure 1.8MPa.Specific energy consumption 4.4kWh, in recent years, China's water
Electrolytic hydrogen production technology is greatly developed, however the energy consumption of hydrogen manufacturing is still larger [gas separation, 2009,04:50-52.].
Denmark in 2013 there is scholar to study and produced high temperature and pressure is lauched under alkaline system electrolysis unit and
Electrolysis water obtains 98.7% current efficiency under 240 DEG C, 370MPa and 1.481V tank voltage.[J.Power Sources,
2013,229,22-31.].The hot spot studied both at home and abroad for the research for the electrolysis system that pressurizes focuses on alkaline system pressure (hydraulic) water more
Electrolytic hydrogen production gas, electrolysis system is mostly homogeneous, however the heterophasic system of mineral pressurization electrolysis is not reported but, heterogeneous
I.e. comprising electrolyte (liquid phase) and being different from by the electrolytic process occurred in the pressurized systems of electrolysis object mineral (solid phase) above
The presence of the electrolysis system for the even phase system being previously mentioned, pressure can not only promote the liberation of hydrogen process of cathode, for the oxygen of anode
Change process can also have an immense impact on, for example increase active oxygen in the generation rate and yield of anode and then promote mineral
Purification process.In addition to this research shows that cathode can generate the extremely strong O of activity under alkaline system2, and the presence of pressure is especially
The increase of oxygen partial pressure, which can strengthen its production quantity and formation speed, can further strengthen the purification process of mineral.More than being based on
Analysis presses electrolysis installation compared to traditional even addition, and non-even phase pressurized equipment has the characteristics that following and advantage:
1, by improving the pressure of electrolysis system, multiphase mass transfer, including active oxygen presoma (HO, O can be strengthened2 -) and
Yin-yang the two poles of the earth form active oxygen (HO, O2 -) transmitting.
2, by improving the pressure of electrolysis system, heterogeneous reaction, including active oxygen oxygen (HO, O can be strengthened2 -) and mine
Composition granule is respectively in the reaction at yin-yang the two poles of the earth.
3, by improving the pressure of electrolysis system, the generation quantity of multiphase particle can be strengthened and generating speed, including work
Property oxygen presoma (HO, O2 -) and the formation of yin-yang the two poles of the earth active oxygen (HO, O2 -) generation quantity.
4, by improving electrolysis system pressure, strengthen the decomposition of mineral grain and non-homogeneous particle, improve heterogeneous materials
Granule density in the electrolytic solution increases the contact probability of heterogeneous materials and electrode.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of pressurization electrolytic cell and intensified electrolysis
Method, the pressurization electrolytic cell can cause the equilibrium constant of water to increase by pressurization, and the solvability of water increases, especially oxygen
The solubility of gas increases；Pressure increases oxygen in water diffusion coefficient, the enhancing of electrolyte conductive capability；Pressurization can promote
The decomposition of mineral, and then increase the effective concentration of organic matter in electrolyte, the mass transfer ability of electrolyte can also be improved, increase is led
Electrically；In addition, pressure process promotes the precipitation of active oxygen, so that mineral grain is easier that oxidation reaction occurs in electrode surface.
Therefore, the pressurization electrolytic cell is particularly suitable for the process of mineral electrolysis, strengthens the mass transfer ability of mineral grain and electrolyte, and
Active oxygen is precipitated and transmitting, to improve mineral electrolytic anodization process, and then improves cathode hydrogen evolution efficiency.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of pressurization electrolytic cell, the pressurization electrolytic cell includes:
Reactive tank, including groove body and slot cover, groove body and slot cover are tightly connected, and sealable cathode connection is arranged in slot cover
Hole, positive connecting hole and air inlet；
The electrode being placed in reactive tank, including cathode and anode, cathode pass through the cathode phase of cathode connecting hole and power supply
Even, anode is connected by anode connecting hole with the anode of power supply；
Electrolyte membrane is set in reactive tank, and cathode and anode are separated；
Pressurizing device, for improving the pressure in reactive tank, including gas supply device and/or heating device, gas is supplied
It is connected to by air inlet with reactive tank to the gas outlet of device, the heating device is used for supply response slot heat and/or evaporation
Vapor pressurizes to reactive tank.
Pressurization electrolytic cell provided by the invention realizes pressurization during water electrolysis and mineral are electrolysed.The pressurization
Pressurization can be realized in electrolytic cell at normal temperature, can input oxygen simultaneously in pressure process, due to being acted on while oxygen and pressure,
In electrolytic process, active oxygen species content is significantly improved, and then electrolytic efficiency significantly improves, such as solid mineral substance electrolytic desulfurization
In, the desulfurization degree under 0.1MPa is 40%, be can be improved using desulfurization degree of the pressurization electrolytic cell provided by the invention at 1.7MPa
To 95%.
Pressurization electrolytic cell provided by the invention can by gas supply device to pressurization electrolytic cell pressurization and/or directly to
The spontaneous steam pressure of electrolyte heating.Meanwhile the pressure change in electrolytic process is detected by pressure gauge, heating temperature is according to work
The requirement of skill can be adjusted arbitrarily.When temperature reaches 100 DEG C, the pressure in slot increases as the temperature rises, the liter of pressure
Height causes the equilibrium constant of water to increase, and the solvability of water increases and diffusion coefficient increases, the conductive capability of electrolyte also with
Increase.
The gas supply device includes oxygen feedway.Oxygen can promote the electrolytic efficiency of pressurization electrolytic cell.
Preferably, the gas supply device includes pressure gas cylinder.
Gas in the gas supply device supply response slot can be oxygen or the gaseous mixture of oxygen and other gases.Institute
Stating gas supply device and heating device can cooperate and provide reactive tank corresponding pressure, and supply oxygen appropriate and heat
Amount, is in the liquid in reactive tank under the conditions of certain temperature.
The pressurization electrolytic cell further includes reference electrode, and the reference electrode passes through the sealable ginseng being arranged on reactive tank
It is placed in reactive tank than electrode ports, the cathode, anode and reference electrode are connected with electrochemical workstation.
The setting of the reference electrode can be used for detecting the electrode potential in reactive tank.
Preferably, the reference electrode is solid state reference electrode or silver chloride electrode.
Preferably, the cathode, anode and reference electrode distribution triangular in shape.
Preferably, the cathode, anode and reference electrode pass through conductive rod respectively and are connected with power supply, the conductive rod surface
It is enclosed with pressure-resistant insulation sleeve.The material of the pressure resistance insulation sleeve is unrestricted, as long as can be under the condition of high voltage in reactive tank
Insulation.Preferably high-temperature silica gel.
Preferably, the conductive rod is connect with slot cover by bolt seal.
Preferably, the surface coating polytetrafluoroethylene (PTFE) for being bolted place.
Described conductive rod one end is connected with electrode, and the other end is connected with conducting wire, and the conducting wire is connected with power supply.
Conductive rod is connect with electrode surface will apply as a connector because to be inserted into liquid in reactive tank
The heat-resisting material of one layer of insulation, and to be connect with extraneous power supply so the junction with slot cover needs sealing just to can guarantee in this way
The stabilization of pressure.
The pressurization electrolytic cell further includes the agitating device for electrolyte in stirred tank.The agitating device is used for
Stirring electrolyte keeps the transmitting of its solute rapider.
Preferably, the agitating device includes motor and blender, and the blender is placed by sealable stirring port
In reactive tank.
The pressurization electrolytic cell further includes thermocouple and pressure measuring instruments, and the thermocouple is by being arranged on reactive tank
Sealable temperature survey mouth and pressure measurement mouth are placed in reactive tank.
Preferably, the pressure measuring instruments is pressure gauge.
The material of the groove body and slot cover is metal, and the pressure of 15MPa can be born at 30 DEG C.
Preferably, the groove body inner wall surface insulation.
Preferably, the groove body inner wall surface is polytetrafluoroethylene (PTFE).
Preferably, it is tightly connected between the groove body and slot cover by teflin ring.
In order to adapt to the electrolysis system of high pressure and alkaline system in reactive tank, the material of the cathode and anode be nickel, copper,
In titanium, lead, tin, cerium or its oxide any one or at least two combination, it is however preferred to have stronger pressure-resistant corrosion-resistant
Ability and the relatively high electrode material of current efficiency, such as the oxide of nickel and/or the oxide of tin.It is typical but non-limiting
Combination such as: nickel and copper, titanium, lead and tin, nickel, copper and cerium, the oxide of nickel, copper and copper, titanium, lead, tin and cerium oxide, nickel
Oxide, titanyl compound, the oxide of tin and lead oxide.The oxide of the nickel such as nickel oxide NiO, the oxidation of copper
Object such as copper oxide CuO, titanyl compound such as titanium dioxide TiO2, the oxide of lead such as brown lead oxide PbO2, the oxide of tin is such as
Stannic oxide SnO2, the oxide of cerium such as ceria CeO2。
Preferably, the material of the cathode and anode is SnO2(stannic oxide), CeO2(ceria) or PbO2(dioxy
Change lead) in any one or at least two combination.Typical but non-limiting combination such as SnO2With CeO2, SnO2With PbO2,
SnO2、CeO2With PbO2。
Preferably, the cathode is coated with silica gel back to the side of anode, and the anode is carried on the back anticathode side and is coated with
Silica gel.
Preferably, the cathode is identical with the structure of anode.
The electrolyte membrane is ion Membrane cover, and the ion Membrane cover wraps up cathode and/or anode wherein, realizes electrode
Separation.
Preferably, the material of the ion die sleeve is cationic membrane.
Preferably, the width of the diaphragm ion Membrane cover is greater than the width of electrode, is highly higher than the liquid level of electrolyte,
Thickness is greater than the diameter of conductive rod.
The heating device includes electric furnace, and the electric furnace includes resistance wire furnace core, and the electric furnace is by slot
Body surrounds wherein.
Preferably, the heating device further includes the controller for controlling electric furnace temperature.
Preferably, the oxygen feedway includes pressure gas cylinder.
Preferably, the sealable cathode connecting hole, positive connecting hole, air inlet, stirring port, temperature survey mouth and pressure
The surface of power measuring mouth is coated with polytetrafluoroethylene (PTFE) and/or is provided with teflin ring.
An object of the present invention, which also resides in, provides a kind of method of intensified electrolysis, the method are as follows: is pressurizeed by supply
Cell gas and/or thermogenetic vapor is added to realize the pressurization of pressurization electrolytic cell, be electrolysed, pressure when electrolysis is
0.1-5MPa, such as 0.3MPa, 0.6MPa, 1MPa, 1.8MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or
4.8MPa etc., preferably 1.5-2.0MPa；Electrolysis uses alkaline electrolyte, and the concentration of alkaline matter therein is 0.1-2mol/L,
Such as 0.2mol/L, 0.5mol/L, 0.7mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L or 1.8mol/L, preferably 0.5-
1.5mol/L。
Pressurization can be realized the increase of active specy in electrolytic process, to improve electrolytic efficiency.
The electrolysis is solid mineral electrolytic desulfurization, water electrolysis hydrogen producing or wastewater electrolytic degradation COD.
Compared with prior art, the invention has the benefit that
1, pressurization electrolytic cell provided by the invention can pressurize under conditions of room temperature, and three in the pressurization electrolytic cell
Electrode distribution triangular in shape can be used for electrochemical property test.
2, pressurization electrolytic cell provided by the invention can strengthen the mass transport process of electrode interface, especially mineral by pressurization
In element sulphur transmitting, strengthen mineral purification process, under 50 DEG C, the aqueous slkali of oxygen pressure 2MPa, 0.5mol/L, energy
Enough obtain 95% or more desulfurization degree；
3, pressurization electrolytic cell provided by the invention can reinforce the conductive capability of electrolyte, and the hydrogen generated by pressurization
Gas is compression hydrogen, to reduce 1/4 than conventional electrolysis hydrogen manufacturing energy consumption.
4, pressurization electrolytic cell provided by the invention can reinforce the precipitation and transmitting of active oxygen in electrolyte by pressurization, from
And improve electrolyte anode oxidation process, and then improve cathode hydrogen evolution efficiency (pressurization improves 50% than normal pressure electrolytic efficiency).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of pressurization electrolytic cell and its auxiliary equipment that embodiment 2 provides.
Fig. 2 a is the structural schematic diagram for the pressurization electrolyte bath that embodiment 2 provides.
Fig. 2 b is the structural schematic diagram of the electrode that embodiment 2 provides and conductive rod.
Fig. 2 c is the structural schematic diagram for the cationic Membrane cover that embodiment 2 provides.
Fig. 3 is the Cyclic voltamogram curve graph of embodiment 3,4,5 and 6.
Fig. 4 is the anodic polarization curves figure of embodiment 3,4,5 and 6.
Fig. 5 is the cathodic polarization curve figure of embodiment 3,4,5 and 6.
Fig. 6 is temperature-oxygen evolution potential curve graph of embodiment 3,4,5 and 6.
Fig. 7 is temperature-hydrogen-evolution overpotential curve graph of embodiment 3,4,5 and 6.
Fig. 8 is temperature-desulfuration efficiency figure of embodiment 7,8,9 and 10.
Fig. 9 is temperature-desulfuration efficiency figure under the pressurization of embodiment 11,12,13 and 14.
Figure 10 is pressure-desulfuration efficiency figure of embodiment 7,11,15,16 and 17.
Wherein, 1, sealing bolt；2, conductive rod；3, pressure-resistant insulation sleeve；4, pressure-resistant electrode；5 heat-resistant pressure-resistant silica gel；6, thermoelectricity
It is even；7, cathode；8, polytetrafluoro sealing ring；9, agitating device；10, reference electrode；11, electric furnace；12, anode；13, it is corrosion-resistant
Pressure-resistant inner wall；14, motor；15, pressure gas cylinder；16, electrolysis power；17, pressure gas cylinder pressure gauge；18, pressure gauge；
19, controller；B indicates length；H indicates height；D indicates width.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1:
A kind of pressurization electrolytic cell, the pressurization electrolytic cell include:
Reactive tank, including groove body and slot cover, groove body and slot cover are tightly connected, and sealable cathode connection is arranged in slot cover
Hole, positive connecting hole and air inlet；
The electrode being placed in reactive tank, including cathode 7 and anode 12, cathode 7 pass through the negative of cathode connecting hole and power supply
Extremely it is connected, anode 12 is connected by 12 connecting hole of anode with the anode of power supply；
Electrolyte membrane is set in reactive tank, and cathode 7 and anode 12 are separated；
Pressurizing device, for improving the pressure in reactive tank, including gas supply device and/or heating device, gas is supplied
It is connected to by air inlet with reactive tank to the gas outlet of device, heating device is steamed for supply response slot heat and/or evaporation water
Gas pressurizes to reactive tank.
Embodiment 2:
A kind of pressurization electrolytic cell, as shown in Figure 1.The pressurization electrolytic cell includes:
Reactive tank, including groove body and slot cover, groove body and slot cover are tightly connected, and sealable cathode connection is arranged in slot cover
Hole, positive connecting hole and air inlet；
The electrode being placed in reactive tank, the anode 12 being arranged including cathode 7 and corresponding thereto, cathode 7 pass through cathode and connect
It connects hole to be connected with the cathode of power supply, anode 12 is connected by 12 connecting hole of anode with the anode of power supply；
Ion Membrane cover is wrapped on cathode 7；
Heating device, including electric furnace 11, the reactive tank are placed in electric furnace 11, the furnace of the electric furnace 11
Core is resistance wire furnace core, and the heating device surrounds the groove body of reactive tank wherein；
The gas outlet of pressure gas cylinder 15, pressure gas cylinder 15 is connected to by air inlet with reactive tank, the high pressure
Gas bomb 15 is used for supply response slot oxygen or improves the pressure in reactive tank simultaneously.
The pressurization electrolytic cell further includes agitating device 9, thermocouple 6, pressure gauge 18 and reference electrode 10, the stirring dress
Setting 9 includes motor 14 and stirring rod, and the stirring rod, thermocouple 6 and reference electrode 10 are all set in reactive tank, and and slot
Lid is tightly connected, and agitating device 9 is connect with motor 14, can be rotated along axis and is used for agitating solution；The pressure gauge 18 and motor
14 are set to outside reactive tank.
The reactive tank includes internal cathode 7, anode 12,10 three of reference electrode distribution triangular in shape, electrode with lead
2 lower end of torch connection upper end is connect with slot cover by bolt seal, and electrolyte, cathode 7 and anode 12 are placed in pressurization electrolytic cell
In, electrolyte submerges cathode 7 and anode 12, and the anode and cathode of DC power supply pass through conductive rod 2 and cathode 7, anode 12 respectively
It is connected, DC power supply is placed in outside pressurization electrolytic cell.
The material of the reactive tank is metal, and the groove body wall is coated with insulating materials.
The structure of the electrode is as shown in Figure 2 b, and the electrode includes electrode slice and conductive rod 2,2 surface of conductive rod
It is coated with pressure-resistant insulation sleeve 3 (material is high-temperature silica gel), the electrode slice side is coated with silica gel.Described 2 one end of conductive rod with
Electrode slice is connected, and the other end is connected by conducting wire with power supply, is wherein connected between conductive rod 2 and slot cover by bolt seal.Spiral shell
Bolt junction is coated with polytetrafluoroethylene (PTFE).
The structure of the ion Membrane cover is as shown in Figure 2 c, and the width d of the cation Membrane cover is greater than the width of electrode, height
H is higher than the liquid level of electrolyte, and thickness b is greater than the diameter of conductive rod 2.
The working principle of the pressurization electrolytic cell hydrogen manufacturing are as follows: anode 12 is passing through conductive rod 2 and conducting wire and DC power supply just
Extremely it is connected, thus it is positively charged on anode 12, oxidation reaction occurs thereon；Cathode 7 passes through conductive rod 2 and conducting wire and DC power supply
Cathode be connected, so negatively charged on cathode 7, reduction reaction occurs thereon.Stirring rod is rotated according to the speed of setting, in slot
Solution also rotate with it, with the effect of heating device, the temperature in reactive tank is gradually increased, when the temperature in slot is more than
At 100 DEG C, the pressure in slot increases as the temperature rises, and the pressure value in slot can be monitored in real time in external pressure gauge 18
Variation；Pressure gas cylinder supplies oxygen into reactive tank while pressurization.The increase of pressure and oxygen divide in the solution
Increase cause the solubility of solution in slot to increase, the contents of the active oxygen species in electrolyte improves, and the electric conductivity of solution mentions
High and greatly reduce the energy consumption that cathode 7 reacts hydrogen manufacturing, hydrogen production efficiency significantly improves.
Embodiment 3:
With pressurization electrolytic tank electrolysis water-coal-slurry as described in example 2, specific steps are as follows: weigh 40g sodium hydroxide, be dissolved in 1L
In distilled water, 20g coal is added thereto after its dissolution, after stirring, is poured into pressurization electrolytic cell, it is molten in the electrolytic cell that pressurizes
The temperature of liquid is maintained at 100 DEG C, pressure 0.1MPa, is not passed through oxygen, and agitating device revolving speed 200r/min handles 120min.
Embodiment 4:
The embodiment 4 is 140 DEG C except temperature, and pressure is outside 0.4MPa, remaining is same as Example 3.
Embodiment 5:
The embodiment 5 is 180 DEG C except temperature, and pressure is outside 0.9MPa, remaining is same as Example 3.
Embodiment 6:
The embodiment 6 is 220 DEG C except temperature, and pressure is outside 2.1MPa, remaining is same as Example 3.
Embodiment 7:
The embodiment 7 is 50 DEG C except temperature, changes 20g coal into 20g bauxite slurry, with outside oxygen pressing, remaining and reality
It is identical to apply example 3.
Embodiment 8:
The embodiment 8 is same as Example 7, uniquely the difference lies in that temperature is changed to 30 DEG C.
Embodiment 9:
The embodiment 9 is same as Example 7, uniquely the difference lies in that temperature is changed to 40 DEG C.
Embodiment 10:
The embodiment 10 is same as Example 7, uniquely the difference lies in that temperature is changed to 60 DEG C.
Embodiment 11:
The embodiment 11 is same as Example 7, uniquely the difference lies in that pressure is changed to 2MPa.
Embodiment 12:
The embodiment 12 is same as Example 8, uniquely the difference lies in that pressure is changed to 2MPa.
Embodiment 13:
The embodiment 13 is same as Example 9, uniquely the difference lies in that pressure is changed to 2MPa.
Embodiment 14:
The embodiment 14 is same as in Example 10, uniquely the difference lies in that pressure is changed to 2MPa.
Embodiment 15:
The embodiment 15 is same as Example 7, uniquely the difference lies in that pressure is changed to 1MPa.
Embodiment 16:
The embodiment 16 is same as Example 7, uniquely the difference lies in that pressure is changed to 1.5MPa.
Embodiment 17:
The embodiment 17 is same as Example 7, uniquely the difference lies in that pressure is changed to 1.7MPa.
Performance test:
Cyclic voltammetry curve, anodic polarization curves, cathodic polarization curve, when m- oxygen evolution potential, when m- hydrogen-evolution overpotential, when
The test method of m- potential windows.
Electro-chemical test is carried out to embodiment 3,4,5 and 6, test result is as shown in Fig. 3,4,5,6 and 7.By Fig. 3,4,
5, known to 6 and 7: as the increase liberation of hydrogen and oxygen evolution potential of temperature and pressure are changed, liberation of hydrogen and oxygen evolution potential are with temperature
Spend the increase of pressure and increase, but due to the increased amplitude of hydrogen-evolution overpotential be greater than oxygen evolution potential thus overall potential under
Drop.It follows that pressurization can promote the decomposition of coal, and then increase the effective concentration of organic matter in electrolyte, can also improve
The mass transfer ability of electrolyte increases electric conductivity；In addition, pressure process promotes the precipitation of active oxygen, so that coal particle is easier
Oxidation reaction occurs for electrode surface.Therefore using pressurization coal slurry electrolytic process, strengthen the mass transfer ability of coal particle and electrolyte, and
Oxide group is precipitated and transmitting, to improve coal slurry electrolytic anodization process.
Electrolytic desulfurization procedural test to embodiment 7,8,9 and 10, result are as shown in Figure 8.To embodiment 11,12,13
With 14 electrolytic desulfurization procedural test, result is as shown in Figure 9.By Fig. 8 and Fig. 9 it is found that in atmospheric conditions in a certain range
The interior increase with solution temperature, the desulfurization effect of bauxite increased.The desulfurization effect phase of bauxite under an increased pressure
Temperature each under normal pressure increased and temperature desulfurization effect at 60 DEG C is not the higher pressurization of best illustration temperature
The desulfurization effect of electrolysis unit is not better.
The electrolytic desulfurization process of comparative example 7,11,12,13 and 14 it is found that with oxygen pressure increase, bauxite
Desulfurization effect obviously increased.Illustrate that the increase of pressure promotes the generation for dissolving active oxygen in ore pulp and then enhances mine
The desulfurization effect of slurry.
The electrolytic desulfurization process of testing example 7,11,15,16 and 17, the results are shown in Figure 10, as can be seen from the figure
Desulfuration efficiency significantly improves explanation and is pressurized with the generation conducive to active oxygen and then promotes active oxygen mineral with the increase of pressure
Reaction enhance desulfurization effect, best desulfurization effect 95.69% is obtained when pressure reaches 1.7Mpa and is obtained with electrochemistry experiment
The notional result obtained is consistent.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (28)
1. a kind of pressurization electrolytic cell, which is characterized in that the pressurization electrolytic cell includes:
Reactive tank, including groove body and slot cover, groove body and slot cover are tightly connected, and sealable cathode connecting hole, just is arranged in slot cover
Pole connecting hole and air inlet；
The electrode being placed in reactive tank, including cathode and anode, cathode are connected by cathode connecting hole with the cathode of power supply, sun
Pole is connected by anode connecting hole with the anode of power supply；
Electrolyte membrane is set in reactive tank, and cathode and anode are separated；
Pressurizing device, for improving the pressure in reactive tank, including gas supply device and heating device, gas supply device
Gas outlet is connected to by air inlet with reactive tank, and the heating device is produced for supply response slot heat and/or evaporation electrolyte
Unboiled water steam pressurizes to reactive tank；
The gas supply device includes oxygen feedway；
The electrolyte membrane is ion Membrane cover, and the ion Membrane cover wraps up cathode and/or anode wherein；The ion Membrane cover
Material is cationic membrane；The width of the ion Membrane cover is greater than the width of electrode, is highly higher than the liquid level of electrolyte, thickness
Greater than the diameter of conductive rod.
2. pressurization electrolytic cell according to claim 1, which is characterized in that the gas supply device includes high pressure gas steel
Bottle.
3. pressurization electrolytic cell according to claim 1, which is characterized in that the pressurization electrolytic cell further includes reference electrode,
The reference electrode is placed in reactive tank by the sealable reference electrode mouth being arranged on reactive tank, the cathode, anode
It is connected with electrochemical workstation with reference electrode.
4. pressurization electrolytic cell according to claim 3, which is characterized in that the reference electrode is solid state reference electrode.
5. pressurization electrolytic cell according to claim 4, which is characterized in that the solid state reference electrode is silver chloride electrode.
6. pressurization electrolytic cell according to claim 3, which is characterized in that the cathode, anode and reference electrode are in triangle
Shape distribution.
7. pressurization electrolytic cell according to claim 3, which is characterized in that the cathode, anode and reference electrode lead to respectively
It crosses conductive rod to be connected with power supply, the conductive rod is coated with pressure-resistant insulation sleeve.
8. pressurization electrolytic cell according to claim 7, which is characterized in that the material of the pressure resistance insulation sleeve is high temperature silicon
Glue.
9. pressurization electrolytic cell according to claim 7, which is characterized in that the conductive rod and slot cover are connected by bolt seal
It connects.
10. pressurization electrolytic cell according to claim 9, which is characterized in that the surface coating poly- four for being bolted place
Vinyl fluoride.
11. pressurization electrolytic cell according to claim 1, which is characterized in that the pressurization electrolytic cell further includes for stirring
The agitating device of electrolyte in reactive tank.
12. pressurization electrolytic cell according to claim 11, which is characterized in that the agitating device includes motor and stirring
Bar, the stirring rod are placed in reactive tank by sealable stirring port.
13. pressurization electrolytic cell according to claim 1, which is characterized in that the pressurization electrolytic cell further include thermocouple and
Pressure measuring instruments, the thermocouple are placed in reactive tank by the sealable temperature survey mouth being arranged on reactive tank.
14. pressurization electrolytic cell according to claim 13, which is characterized in that the pressure measuring instruments is pressure gauge.
15. pressurization electrolytic cell according to claim 1, which is characterized in that the material of the groove body and slot cover is metal,
Its pressure that 15MPa can be born at 30 DEG C.
16. pressurization electrolytic cell according to claim 1, which is characterized in that the groove body inner wall surface insulation.
17. pressurization electrolytic cell according to claim 1, which is characterized in that the groove body inner wall surface is polytetrafluoroethylene (PTFE).
18. pressurization electrolytic cell according to claim 1, which is characterized in that pass through polytetrafluoro between the groove body and slot cover
Ethylene sealing ring is tightly connected.
19. pressurization electrolytic cell according to claim 1, which is characterized in that the material of the cathode and anode be nickel, copper,
In titanium, lead, tin, cerium or its oxide any one or at least two combination.
20. pressurization electrolytic cell according to claim 1, which is characterized in that the material of the cathode and anode is nickel
The oxide of oxide and/or tin.
21. pressurization electrolytic cell according to claim 1, which is characterized in that the material of the cathode and anode is titanium dioxide
In tin, ceria or brown lead oxide any one or at least two combination.
22. pressurization electrolytic cell according to claim 1, which is characterized in that the side of the cathode back to anode is coated with
Silica gel, the anode carry on the back anticathode side and are coated with silica gel.
23. pressurization electrolytic cell according to claim 1, which is characterized in that the cathode is identical with the structure of anode.
24. pressurization electrolytic cell according to claim 1, which is characterized in that the heating device includes electric furnace, described
Electric furnace includes resistance wire furnace core, and the electric furnace surrounds the groove body of the reactive tank wherein.
25. pressurization electrolytic cell according to claim 1, which is characterized in that the heating device further includes for controlling electricity
The controller of furnace temp.
26. utilizing the method for pressurization electrolytic cell intensified electrolysis described in one of claim 1-25, which is characterized in that the method
Are as follows: by supply pressurization cell gas and/or thermogenetic vapor is added to realize the pressurization of pressurization electrolytic cell, is electrolysed,
Pressure when electrolysis is 0.1-5MPa；Electrolysis uses alkaline electrolyte, and the concentration of alkaline electrolyte neutral and alkali substance is 0.1-
2mol/L。
27. utilizing the method for the electrolytic cell intensified electrolysis that pressurizes described in claim 26, which is characterized in that pressure when electrolysis is
1.5-2.0MPa；The concentration of alkaline electrolyte neutral and alkali substance is 0.5-1.5mol/L.
28. according to the method for claim 26, which is characterized in that the electrolysis is solid mineral electrolytic desulfurization, water electrolysis
Hydrogen manufacturing or wastewater electrolytic degradation COD.
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| CN110346402A (en) * | 2019-06-20 | 2019-10-18 | 浙江大学 | The forceful electric power electrode assembly used under Elevated Gravity |
| CN113430536B (en) * | 2021-07-16 | 2022-04-08 | 阳光电源股份有限公司 | Water electrolysis hydrogen production system |
| CN113652712A (en) * | 2021-09-24 | 2021-11-16 | 南通安思卓新能源有限公司 | Efficient nickel-based self-assembly oxygen evolution electrode |
| CN114032569B (en) * | 2021-11-18 | 2023-07-04 | 四川华能氢能科技有限公司 | High-efficiency electrolytic structure device |
| CN114016062B (en) * | 2021-12-15 | 2022-07-26 | 江苏高瓴水务科技有限公司 | Intelligent electrolytic tank convenient for hydrogen production by water electrolysis |
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| CN1922342A (en) * | 2004-02-18 | 2007-02-28 | 株式会社荏原制作所 | Method and apparatus for producing hydrogen |
| CN101213325A (en) * | 2006-01-20 | 2008-07-02 | 东洋炭素株式会社 | Electrolytic apparatus for producing fluorine or nitrogen trifluoride |
| CN102317505A (en) * | 2008-10-27 | 2012-01-11 | 卡萨尔化学股份有限公司 | High pressure electrolyser |
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| CN1922342A (en) * | 2004-02-18 | 2007-02-28 | 株式会社荏原制作所 | Method and apparatus for producing hydrogen |
| CN101213325A (en) * | 2006-01-20 | 2008-07-02 | 东洋炭素株式会社 | Electrolytic apparatus for producing fluorine or nitrogen trifluoride |
| CN102317505A (en) * | 2008-10-27 | 2012-01-11 | 卡萨尔化学股份有限公司 | High pressure electrolyser |
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