CN106119886A - A kind of method of pressurize electrolysis bath and intensified electrolysis - Google Patents

A kind of method of pressurize electrolysis bath and intensified electrolysis Download PDF

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Publication number
CN106119886A
CN106119886A CN201610466368.6A CN201610466368A CN106119886A CN 106119886 A CN106119886 A CN 106119886A CN 201610466368 A CN201610466368 A CN 201610466368A CN 106119886 A CN106119886 A CN 106119886A
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pressurization
electrolysis
anode
electrolysis bath
pressure
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CN106119886B (en
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公旭中
王志
周玉健
王东
王明涌
孙丽媛
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Institute of Process Engineering of CAS
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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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The method that the invention provides a kind of pressurize electrolysis bath and intensified electrolysis, this pressurization electrolysis bath includes: reactive tank；The electrode being positioned in reactive tank, including negative electrode and anode；Electrolyte membrane, separates negative electrode and anode；Pressue device, including gas supply device and/or heater.This pressurization electrolysis bath can pressurize under conditions of room temperature, can be strengthened the transmission of the mass transport process of electrode interface, the especially element sulphur in mineral, the process of strengthening mineral purification by pressurization；Add the conductive capability of strong electrolyte, thus be effectively reduced the energy consumption of electrolytic hydrogen production；Utilize oxygen pressing can strengthen precipitation and the transmission of active oxygen in electrolyte, thus improve electrolyte anode oxidation process, and then improve cathode hydrogen evolution efficiency.This pressurization electrolysis bath is particularly suited for the electrolysis of heterogeneous system, it is possible to realize the strengthening of negative electrode hydrogen production process, increases quantity and the reaction rate of anode active oxygen simultaneously.

Description

A kind of method of pressurize electrolysis bath and intensified electrolysis
Technical field
The invention belongs to electrolysis tech field, the method relating to a kind of pressurize electrolysis bath and intensified electrolysis.
Background technology
The most industrial method preparing hydrogen specifically include that water electrolysis method, water gas method, electrolysis saturated common salt water law, Natural gas synthetic method etc., wherein electrolysis water prepare hydrogen be that at present application is relatively wide, one of the method for production technology comparative maturity, electricity Solve the commercial technology that water hydrogen manufacturing is currently acquired high-purity hydrogen, apply at fuel pressurization electrolysis bath field and Aero-Space neck Territory.Electrolytic hydrogen production energy consumption the most ideally should be 2.69kWh/Nm3, but the total energy consumption of hydrogen producing technology is 6.7-at present 7.3kWh/Nm3, and even commercial off-the-shelf water electrolysis hydrogen producing technological synthesis efficiency is relatively low, only 50-55%.Therefore Energy consumption height is the bottleneck in water electrolysis hydrogen producing technology commercialization process.
20 century 70s, Coughlin R.W. etc. studies and finds to add material with carbon element, such as graphite at water electrolysis process anode Or coal can improve liberation of hydrogen efficiency, reducing tank voltage, the method causes water electrolysis process Anodic mainly by the addition of coal Oxygen evolution reaction part is replaced in the cell reaction of anode by mineral, and the sulfur content in coal is reduced, and finally makes water power Solve hydrogen production efficiency close to 100%.It can thus be appreciated that the electrolytic hydrogen production of mineral is possible not only to improve water electrolysis hydrogen producing efficiency, and can Purify mineral and realize the desulfurization of mineral, and mineral electrolytic desulfurization hydrogen manufacturing integrated technique possesses advantages below: 1) reaction condition Relatively mild；2) compared with other desulfurization technology, environmental pollution is little；3) anode desulfurization is carried out with negative electrode hydrogen manufacturing simultaneously.Although ore deposit There is above advantage in thing electrolytic desulfurization hydrogen integrated technique, but is constantly subjected to high energy consumption, low during its integration The restriction of current efficiency.
In order to reduce water electrolysis hydrogen producing energy consumption, have studied multiple way both at home and abroad, as prepared efficient hydrogen evolution electrode material such as The catalytic electrolysis such as platinumiridio and titanium-diamond alloy；Efficiently pressurization electrolysis bath such as gas-diffusion electrode pressurization electrolysis bath, fluidisation Electrode pressurization electrolysis bath etc. increases the contact area of electrode and electrolyte；Outfield intensifying such as ultrasound wave, super gravity field etc., by by force Change the disengaging speed of anode and cathode bubble；Changing electrolysis system and such as add mineral, acid, alkali etc. reduces the resistance of electrolysis system, it is achieved The raising of liberation of hydrogen current efficiency.The essence of these methods is contemplated 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.
Find that electrolysis system tank voltage at normal temperatures and pressures is higher and the resistance of the electrolyte bath that pressurizes by further investigation Greatly, and water electrolysis process can produce under alkaline system various active oxygen, such as the HO and the O of negative electrode of anode2 -, they Oxidability is strong compared to common oxide isolation ability, the speed constant of oxidation reaction is big, oxidation rate is unrestricted.So How to improve HO and O2 -Volume of production and speed are to improve the key of mineral electrolysis high-efficient purification.Research shows the production of active oxygen Necessary not only for efficient catalytic electrode, in addition it is also necessary to active oxygen presoma is transmitted to electrode surface by being electrolysed main body, the most just can carry The efficiency that highly reactive form of oxygen is formed.Therefore strengthen active oxygen presoma (HO, O the most simultaneously2 -) mass transfer and reaction i.e. strengthen it Transmission and receiving and losing electrons ability could inherently improve active oxygen (HO, O2 -) growing amount and generating rate.But it is ultrasonic Although the methods such as ripple, hypergravity and Gas Stirring enhance active oxygen presoma by electrolyte to the transmission of electrode, but these Method cannot meet strengthening active oxygen presoma and the dual-use function of receiving and losing electrons simultaneously, also cannot increase active oxygen presoma Quantity.
China Shipbuilding Industry Corporation's in June, the 2009 Research Institute July 1st eight has gone out 6-600/1.8 type water electrolysis Device for producing hydrogen hydrogen producing amount per hour reaches 600m3, operating pressure is 1.8MPa.Specific energy consumption 4.4kWh, in recent years, China's water Electrolytic hydrogen production technology is greatly developed, but the energy consumption of hydrogen manufacturing the biggest [gas separates, 2009,04:50-52.].
Denmark in 2013 have scholar's research the electrolysis unit having produced water under High Temperature High Pressure under alkaline system and 240 DEG C, be electrolysed water under 370MPa and 1.481V tank voltage and obtain the current efficiency of 98.7%.[J.Power Sources, 2013,229,22-31.].Focus pressurization electrolysis system being studied to research both at home and abroad focuses on alkaline system pressure (hydraulic) water more Electrolytic hydrogen production gas, electrolysis system mostly is homogeneous, but the heterophasic system for mineral pressurization electrolysis is not the most reported, heterogeneous I.e. comprise electrolyte (liquid phase) and be different from above by the electrolytic process occurred in the pressurized systems of electrolysis object mineral (solid phase) The electrolysis system of the even phase system being previously mentioned, the existence of pressure can not only promote the liberation of hydrogen process of negative electrode, for the oxygen of anode Change process also is able to have an immense impact on, and such as increases active oxygen at the generations speed of anode and generation amount and then promotion mineral Purification process.In addition research shows that under alkaline system, negative electrode can produce the O that activity is extremely strong2 -, and the existence of pressure is particularly The increase of oxygen partial pressure can strengthen its growing amount and formation speed can strengthen the purification process of mineral further.More than based on Analyzing, compare traditional even addition pressure electrolysis installation, non-even phase pressurized equipment has following feature and an advantage:
1, by improving the pressure of electrolysis system, multiphase mass transfer can be strengthened, including active oxygen presoma (HO, O2 -) and Negative and positive the two poles of the earth form active oxygen (HO, O2 -) transmission.
2, by improving the pressure of electrolysis system, heterogeneous reaction can be strengthened, including active oxygen oxygen (HO, O2 -) and ore deposit Composition granule is respectively in the reaction at negative and positive the two poles of the earth.
3, by improving the pressure of electrolysis system, the generation quantity of heterogeneous particle can be strengthened and produce speed, including living Property oxygen presoma (HO, O2 -) and the formation of negative and positive the two poles of the earth active oxygen (HO, O2 -) generation quantity.
4, by improving electrolysis system pressure, strengthening mineral grain and the decomposition of 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
The deficiency existed for prior art, it is an object of the invention to provide a kind of pressurize electrolysis bath and intensified electrolysis Method, described pressurization electrolysis bath can cause the equilibrium constant of water to increase by pressurization, and the solvability of water increases, especially oxygen The dissolubility of gas increases；Pressure makes oxygen in water diffusion coefficient increase, and electrolyte conductive capability strengthens；Pressurization can promote The decomposition of mineral, and then increase organic valid density in electrolyte, it is also possible to improving the mass transfer ability of electrolyte, increase is led Electrically；It addition, pressure process promotes the precipitation of active oxygen so that mineral grain is easier in electrode surface generation oxidation reaction. Therefore, described pressurization electrolysis bath is particularly suited for the process of mineral electrolysis, strengthens mineral grain and the mass transfer ability of electrolyte, and Active oxygen separates out and transmission, thus improves mineral electrolytic anodization process, and then improves cathode hydrogen evolution efficiency.
For reaching this purpose, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of pressurization electrolysis bath, and described pressurization electrolysis bath includes:
Reactive tank, including cell body and groove lid, cell body is tightly connected with groove lid, groove lid arranges sealable negative pole and connects Hole, positive pole connecting hole and air inlet；
The electrode being positioned in reactive tank, including negative electrode and anode, negative electrode is by the negative pole phase of negative pole connecting hole with power supply Even, anode is connected with the positive pole of power supply by anode connecting hole；
Electrolyte membrane, is arranged in reactive tank, negative electrode and anode is separated；
Pressue device, for improving the pressure in reactive tank, including gas supply device and/or heater, gas supplies Being connected with reactive tank by air inlet to the gas outlet of device, described heater is used for supply response groove heat and/or evaporation Reactive tank is pressurizeed by steam.
The pressurization electrolysis bath that the present invention provides, realizes pressurization during water electrolysis and mineral are electrolysed.Described pressurization Electrolysis bath can realize pressurization at normal temperatures, can be simultaneously entered oxygen in pressure process, owing to acting on while oxygen and pressure, In electrolytic process, active oxygen species content significantly improves, and then electrolytic efficiency significantly improves, such as solid mineral material electrolytic desulfurization In, the desulfurization degree under 0.1MPa is 40%, and the pressurization electrolysis bath desulfurization degree under 1.7MPa using the present invention to provide can improve To 95%.
The present invention provide pressurization electrolysis bath can by gas supply device to pressurization electrolysis bath pressurize and/or directly to The electrolyte spontaneous steam pressure of intensification., being changed by the pressure in Pressure gauge detection electrolytic process, heating-up temperature is according to work meanwhile The requirement of skill can arbitrarily regulate.When temperature reaches 100 DEG C, the pressure in groove increases along with the rising of temperature, 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.
Described gas supply device includes oxygen feedway.Oxygen can promote the electrolytic efficiency of pressurization electrolysis bath.
Preferably, described gas supply device includes pressure gas cylinder.
Gas in described gas supply device supply response groove can be the gaseous mixture of oxygen or oxygen and other gas.Institute State gas supply device and heater can cooperate and provide the corresponding pressure of reactive tank, and supply suitable oxygen and heat Amount, makes the liquid in reactive tank be under certain temperature conditions.
Described pressurization electrolysis bath also includes reference electrode, and described reference electrode is by the sealable ginseng arranged on reactive tank Being positioned in reactive tank than electrode ports, described negative electrode, anode are all connected with electrochemical workstation with reference electrode.
The setting of described reference electrode can be used for detecting the electrode potential in reactive tank.
Preferably, described reference electrode is solid state reference electrode or silver chloride electrode.
Preferably, described negative electrode, anode and reference electrode distribution triangular in shape.
Preferably, described negative electrode, anode are connected with power supply by contact rod respectively with reference electrode, described contact rod surface It is enclosed with pressure insulation sleeve.The material of described pressure insulation sleeve is unrestricted, as long as can be under the condition of high voltage in reactive tank Insulate.It is preferably high-temperature silica gel.
Preferably, described contact rod is connected by bolt seal with groove lid.
Preferably, the surface-coated politef of described bolt junction.
Described contact rod one end is connected with electrode, and the other end is connected with wire, and described wire is connected with power supply.
Contact rod is connected so surface to be coated with electrode because of in liquid to be inserted as a connector in reactive tank The material that one layer of insulation is heat-resisting, and to be connected so needing to seal such guarantee with the junction of groove lid with extraneous power supply Stablizing of pressure.
Described pressurization electrolysis bath also includes the agitating device of electrolyte in stirred tank.Described agitating device is used for Stirring electrolyte makes it solute transfer rapider.
Preferably, described agitating device includes that motor and agitator, described agitator are placed by sealable stirring port In reactive tank.
Described pressurization electrolysis bath also includes thermocouple and pressure measuring instruments, and described thermocouple is by setting on reactive tank Sealable temperature survey mouth and pressure measxurement mouth are positioned in reactive tank.
Preferably, described pressure measuring instruments is Pressure gauge.
The material of described cell body and groove lid is metal, and it can bear the pressure of 15MPa at 30 DEG C.
Preferably, described cell body inner wall surface insulation.
Preferably, described cell body inner wall surface is politef.
Preferably, it is tightly connected by teflin ring between described cell body and groove lid.
For adjustment reaction groove inner high voltage and the electrolysis system of alkaline system, the material of described negative electrode and anode be nickel, copper, Any one or the combination of at least two in titanium, lead, stannum, cerium or its oxide, it is however preferred to have stronger pressure-resistant corrosion-resistant Ability and the of a relatively high electrode material of current efficiency, such as oxide and/or the oxide of stannum of nickel.Typical case but non-limiting Combination such as: nickel and copper, titanium, lead and stannum, nickel, copper and cerium, the oxide of nickel, copper and copper, the oxide of titanium, lead, stannum and cerium, nickel Oxide, titanyl compound, the oxide of oxide and lead of stannum.The oxide of described nickel such as nickel oxide NiO, the oxidation of copper Thing such as copper oxide CuO, titanyl compound such as titanium dioxide TiO2, the oxide of lead such as Lead oxide brown PbO2, the oxide of stannum is such as Tin ash SnO2, the oxide of cerium such as ceria CeO2。
Preferably, the material of described negative electrode and anode is SnO2(tin ash), CeO2(ceria) or PbO2(dioxy Change lead) in any one or the combination of at least two.Typical but non-limiting combination such as SnO2With CeO2, SnO2With PbO2, SnO2、CeO2With PbO2。
Preferably, described negative electrode is coated with silica gel back to the side of anode, and described anode is carried on the back anticathode side and is coated with Silica gel.
Preferably, described negative electrode is identical with the structure of anode.
Described electrolyte membrane is ion Membrane cover, and negative electrode and/or anode are wrapped up wherein by described ion Membrane cover, it is achieved electrode Separate.
Preferably, the material of described ion die sleeve is cationic membrane.
Preferably, the width of described barrier film ion Membrane cover is higher than the liquid level of electrolyte more than the width of electrode, height, Thickness is more than the diameter of contact rod.
Described heater includes that electric furnace, described electric furnace include resistance wire combustion chamber, and described electric furnace is by groove Body surrounds wherein.
Preferably, described heater also includes the controller for controlling electric furnace temperature.
Preferably, described oxygen feedway includes pressure gas cylinder.
Preferably, described sealable negative pole connecting hole, positive pole connecting hole, air inlet, stirring port, temperature survey mouth and pressure Power is measured the surface of mouth and is coated with politef and/or is provided with teflin ring.
An object of the present invention also resides in a kind of method providing intensified electrolysis, and described method is: pressurizeed by supply Cell gas and/or add thermogenetic steam realize pressurization electrolysis bath pressurization, be electrolysed, pressure during 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 etc., preferably 0.5- 1.5mol/L。
Pressurization is capable of the increase of active specy in electrolytic process, thus improves electrolytic efficiency.
Described electrolysis is solid mineral electrolytic desulfurization, water electrolysis hydrogen producing or wastewater electrolytic degraded COD.
Compared with prior art, the invention have the benefit that
1, the pressurization electrolysis bath that the present invention provides can pressurize under conditions of room temperature, and in described pressurization electrolysis bath three Electrode distribution triangular in shape may be used for electrochemical property test.
2, the pressurization electrolysis bath that the present invention provides can strengthen the mass transport process of electrode interface, especially mineral by pressurization In element sulphur transmission, strengthening mineral purify process, at 50 DEG C, under the aqueous slkali of oxygen pressure 2MPa, 0.5mol/L, energy Enough obtain the desulfurization degree of more than 95%；
3, the pressurization electrolysis bath that the present invention provides can add the conductive capability of strong electrolyte, and the hydrogen generated by pressurization Gas is compression hydrogen, thus reduces 1/4 than conventional electrolysis hydrogen manufacturing energy consumption.
4, the pressurization electrolysis bath that the present invention provides can strengthen precipitation and the transmission of active oxygen in electrolyte by pressurization, from And improve electrolyte anode oxidation process, and then improve cathode hydrogen evolution efficiency (add pressure ratio normal-pressure electric solution efficiency and improve 50%).
Accompanying drawing explanation
Fig. 1 is pressurize electrolysis bath and the structural representation of auxiliary equipment thereof that embodiment 2 provides.
The structural representation of the pressurization electrolyte bath that Fig. 2 a provides for embodiment 2.
Fig. 2 b is the electrode structural representation with contact rod of embodiment 2 offer.
Fig. 2 c is the structural representation of the cation Membrane cover that embodiment 2 provides.
Fig. 3 is the Cyclic voltamogram curve chart 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 the temperature-oxygen evolution potential curve chart of embodiment 3,4,5 and 6.
Fig. 7 is the temperature-hydrogen-evolution overpotential curve chart of embodiment 3,4,5 and 6.
Fig. 8 is the temperature-desulfuration efficiency figure of embodiment 7,8,9 and 10.
Fig. 9 is the temperature the adding pressure-desulfuration efficiency figure of embodiment 11,12,13 and 14.
Figure 10 is the pressure-desulfuration efficiency figure of embodiment 7,11,15,16 and 17.
Wherein, 1, sealing bolt；2, contact rod；3, pressure insulation sleeve；4, pressure electrode；5 heat-resistant pressure-resistant silica gel；6, thermoelectricity Even；7, negative electrode；8, polytetrafluoro sealing ring；9, agitating device；10, reference electrode；11, electric furnace；12, anode；13, corrosion-resistant Pressure inwall；14, motor；15, pressure gas cylinder；16, electrolysis power；17, pressure gas cylinder Pressure gauge；18, Pressure gauge； 19, controller；B represents length；H represents height；D represents width.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Embodiment 1:
A kind of pressurization electrolysis bath, described pressurization electrolysis bath includes:
Reactive tank, including cell body and groove lid, cell body is tightly connected with groove lid, groove lid arranges sealable negative pole and connects Hole, positive pole connecting hole and air inlet；
The electrode being positioned in reactive tank, including negative electrode 7 and anode 12, negative electrode 7 is negative by negative pole connecting hole and power supply The most connected, anode 12 is connected with the positive pole of power supply by anode 12 connecting hole；
Electrolyte membrane, is arranged in reactive tank, negative electrode 7 and anode 12 is separated；
Pressue device, for improving the pressure in reactive tank, including gas supply device and/or heater, gas supplies Being connected with reactive tank by air inlet to the gas outlet of device, heater steams for supply response groove heat and/or evaporation water Reactive tank is pressurizeed by gas.
Embodiment 2:
A kind of pressurization electrolysis bath, as shown in Figure 1.Described pressurization electrolysis bath includes:
Reactive tank, including cell body and groove lid, cell body is tightly connected with groove lid, groove lid arranges sealable negative pole and connects Hole, positive pole connecting hole and air inlet；
The electrode being positioned in reactive tank, including negative electrode 7 and the anode 12 that arranges corresponding thereto, negative electrode 7 is by negative pole even Connecing hole to be connected with the negative pole of power supply, anode 12 is connected with the positive pole of power supply by anode 12 connecting hole；
Ion Membrane cover, is wrapped on negative electrode 7；
Heater, including electric furnace 11, described reactive tank is placed in electric furnace 11, the stove of described electric furnace 11 Core is resistance wire combustion chamber, and the cell body of reactive tank is surrounded wherein by described heater；
Pressure gas cylinder 15, the gas outlet of pressure gas cylinder 15 is connected with reactive tank by air inlet, described high pressure Gas bomb 15 is for supply response groove oxygen or improves the pressure in reactive tank simultaneously.
Described pressurization electrolysis bath also includes agitating device 9, thermocouple 6, Pressure gauge 18 and reference electrode 10, described stirring dress Putting 9 and include motor 14 and stirring rod, described stirring rod, thermocouple 6 and reference electrode 10 may be contained within reactive tank, and and groove Lid is tightly connected, and agitating device 9 is connected with motor 14, it is possible to rotate for agitating solution along axle；Described Pressure gauge 18 and motor 14 are arranged at outside reactive tank.
Described reactive tank include inside negative electrode 7, anode 12, reference electrode 10 three distribution triangular in shape, electrode with lead Connection upper end, torch 2 lower end is connected by bolt seal with groove lid, and electrolyte, negative electrode 7 and anode 12 are placed in the electrolysis bath that pressurizes In, electrolyte submergence negative electrode 7 and anode 12, the positive pole of DC source and negative pole are respectively by contact rod 2 and negative electrode 7, anode 12 Being connected, DC source is placed in outside pressurization electrolysis bath.
The material of described reactive tank is metal, and described cell body wall scribbles insulant.
As shown in Figure 2 b, described electrode includes electrode slice and contact rod 2, described contact rod 2 surface to the structure of described electrode Being coated with pressure insulation sleeve 3 (material is high-temperature silica gel), described electrode slice side is coated with silica gel.Described contact rod 2 one end with Electrode slice is connected, and the other end is connected with power supply by wire, is wherein connected by bolt seal between contact rod 2 with groove lid.Spiral shell Bolt junction is coated with politef.
As shown in Figure 2 c, the width d of described cation Membrane cover is more than the width of electrode, highly for the structure of described ion Membrane cover H is higher than the liquid level of electrolyte, and thickness b is more than the diameter of contact rod 2.
The operation principle of described pressurization electrolysis bath hydrogen manufacturing is: anode 12 with DC source is just passing through contact rod 2 and wire The most connected, thus positively charged on anode 12, it occurs oxidation reaction；Negative electrode 7 is by contact rod 2 and wire and DC source Negative pole be connected, so electronegative on negative electrode 7, it occurs reduction reaction.Stirring rod rotates according to the speed set, in groove Solution also concomitant rotation, along with the effect of heater, the temperature in reactive tank is gradually increased, when the temperature in groove exceedes When 100 DEG C, the pressure in groove increases along with the rising of temperature, and external Pressure gauge 18 can monitor the force value in groove in real time Change；While pressurization, pressure gas cylinder supplies oxygen in reactive tank.The increase of pressure and oxygen dividing potential drop in the solution Increase cause the dissolubility of solution in groove to increase, the content of the active oxygen species in electrolyte improves, and the electric conductivity of solution carries High and greatly reduce negative electrode 7 and react the energy consumption of hydrogen manufacturing, hydrogen production efficiency significantly improves.
Embodiment 3:
By the pressurization electrolytic tank electrolysis water-coal-slurry described in embodiment 2, concretely comprise the following steps: weigh 40g sodium hydroxide, be dissolved in 1L In distilled water, after it dissolves, it is added thereto to 20g coal, after stirring, is poured in pressurization electrolysis bath, molten in pressurization electrolysis bath The temperature of liquid is maintained at 100 DEG C, pressure 0.1MPa, is not passed through oxygen, agitating device rotating speed 200r/min, processes 120min.
Embodiment 4:
Described embodiment 4 is 140 DEG C except temperature, and pressure is that outside 0.4MPa, remaining is same as in Example 3.
Embodiment 5:
Described embodiment 5 is 180 DEG C except temperature, and pressure is that outside 0.9MPa, remaining is same as in Example 3.
Embodiment 6:
Described embodiment 6 is 220 DEG C except temperature, and pressure is that outside 2.1MPa, remaining is same as in Example 3.
Embodiment 7:
Described embodiment 7 is 50 DEG C except temperature, changes 20g coal into 20g bauxite slurry, and with outside oxygen pressing, remaining is with real Execute example 3 identical.
Embodiment 8:
Described embodiment 8 is same as in Example 7, and unique difference is, temperature changes into 30 DEG C.
Embodiment 9:
Described embodiment 9 is same as in Example 7, and unique difference is, temperature changes into 40 DEG C.
Embodiment 10:
Described embodiment 10 is same as in Example 7, and unique difference is, temperature changes into 60 DEG C.
Embodiment 11:
Described embodiment 11 is same as in Example 7, and unique difference is, changes pressure into 2MPa.
Embodiment 12:
Described embodiment 12 is the same as in Example 8, and unique difference is, changes pressure into 2MPa.
Embodiment 13:
Described embodiment 13 is the same as in Example 9, and unique difference is, changes pressure into 2MPa.
Embodiment 14:
Described embodiment 14 is same as in Example 10, and unique difference is, changes pressure into 2MPa.
Embodiment 15:
Described embodiment 15 is same as in Example 7, and unique difference is, changes pressure into 1MPa.
Embodiment 16:
Described embodiment 16 is same as in Example 7, and unique difference is, changes pressure into 1.5MPa.
Embodiment 17:
Described embodiment 17 is same as in Example 7, and unique difference is, changes pressure into 1.7MPa.
Performance test:
Cyclic voltammetry curve, anodic polarization curves, cathodic polarization curve, time m-oxygen evolution potential, time m-hydrogen-evolution overpotential, time The method of testing of m-potential windows.
Embodiment 3,4,5 and 6 is carried out electro-chemical test, and its test result is as shown in Fig. 3,4,5,6 and 7.By Fig. 3,4, 5,6 and 7 understand: along with increase liberation of hydrogen and the oxygen evolution potential of temperature and pressure there occurs that change, liberation of hydrogen and oxygen evolution potential are along with temperature The degree increase of pressure and increase, but the amplitude increased due to hydrogen-evolution overpotential more than oxygen evolution potential thus overall electromotive force under Fall.It follows that pressurization can promote the decomposition of coal, and then increase organic valid density in electrolyte, it is also possible to improve The mass transfer ability of electrolyte, increases electric conductivity；It addition, pressure process promotes the precipitation of active oxygen so that coal particle is easier to Electrode surface generation oxidation reaction.Therefore use pressurization coal slurry electrolytic process, strengthen coal particle and the mass transfer ability of electrolyte, and Oxide group separates out and transmission, thus improves coal slurry electrolytic anodization process.(and then improve cathode hydrogen evolution efficiency.)
Electrolytic desulfurization procedural test to embodiment 7,8,9 and 10, its result is as shown in Figure 8.To embodiment 11,12,13 With the electrolytic desulfurization procedural test of 14, its result is as shown in Figure 9.From Fig. 8 and Fig. 9, in atmospheric conditions in certain limit Interior along with the increase of solution temperature, the desulfurized effect of bauxite increased.The desulfurized effect phase of bauxite under an increased pressure Each temperature under normal pressure all be increased and temperature desulfurized effect when 60 DEG C is not the highest pressurization of best illustration temperature The desulfurized effect of electrolysis unit is not the best.
The electrolytic desulfurization process of comparative example 7,11,12,13 and 14 understands, along with the increase of oxygen pressure, bauxite Desulfurized effect substantially increased.Illustrate that the increase of pressure promotes ore pulp dissolves the generation of active oxygen and then enhances ore deposit The desulfurized effect of slurry.
The electrolytic desulfurization process of testing example 7,11,15,16 and 17, result as shown in Figure 10, as can be seen from the figure It is pressurized with the generation of beneficially active oxygen along with the increase desulfuration efficiency of pressure significantly improves explanation and then promotes active oxygen mineral Reaction enhance desulfurized effect, obtain optimal desulfurized effect 95.69% when pressure reaches 1.7Mpa and obtain with electrochemistry experiment The notional result obtained is consistent.
Applicant states, the foregoing is only the detailed description of the invention of the present invention, but protection scope of the present invention not office Being limited to this, person of ordinary skill in the field is it will be clearly understood that any those skilled in the art of belonging to take off in the present invention In the technical scope of dew, the change that can readily occur in or replacement, within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a pressurization electrolysis bath, it is characterised in that described pressurization electrolysis bath includes:
Reactive tank, including cell body and groove lid, cell body is tightly connected with groove lid, and groove lid arranges sealable negative pole connecting hole, just Pole connecting hole and air inlet；
The electrode being positioned in reactive tank, including negative electrode and anode, negative electrode is connected with the negative pole of power supply by negative pole connecting hole, sun Pole is connected with the positive pole of power supply by anode connecting hole；
Electrolyte membrane, is arranged in reactive tank, negative electrode and anode is separated；
Pressue device, for improving the pressure in reactive tank, including gas supply device and/or heater, gas supply dress The gas outlet put is connected with reactive tank by air inlet, and described heater steams for supply response groove heat and/or evaporation water Reactive tank is pressurizeed by gas.
Pressurization electrolysis bath the most according to claim 1, it is characterised in that described gas supply device includes oxygen supply dress Put；
Preferably, described gas supply device includes pressure gas cylinder；
Preferably, described pressurization electrolysis bath also includes reference electrode, and described reference electrode is salable by arrange on reactive tank Reference electrode mouth be positioned in reactive tank, described negative electrode, anode are all connected with electrochemical workstation with reference electrode；
Preferably, described reference electrode is solid state reference electrode or silver chloride electrode；
Preferably, described negative electrode, anode and reference electrode distribution triangular in shape；
Preferably, described negative electrode, anode are connected with power supply by contact rod respectively with reference electrode, and described contact rod surface is wrapped up There is pressure insulation sleeve；
Preferably, the material of described pressure insulation sleeve is high-temperature silica gel；
Preferably, described contact rod is connected by bolt seal with groove lid；
Preferably, the surface-coated politef of described bolt junction.
Pressurization electrolysis bath the most according to claim 1 and 2, it is characterised in that described pressurization electrolysis bath also includes for stirring Mix the agitating device of electrolyte in reactive tank；
Preferably, described agitating device includes that motor and puddler, described puddler are positioned over instead by sealable stirring port Answer in groove.
4. according to the pressurization electrolysis bath one of claim 1-3 Suo Shu, it is characterised in that described pressurization electrolysis bath also includes thermoelectricity Even summation pressure measuring instruments, described thermocouple is put by sealable temperature survey mouth and the pressure measxurement mouth arranged on reactive tank It is placed in reactive tank；
Preferably, described pressure measuring instruments is Pressure gauge.
5. according to the pressurization electrolysis bath one of claim 1-4 Suo Shu, it is characterised in that the material of described cell body and groove lid is Metal, it can bear the pressure of 15MPa at 30 DEG C；
Preferably, described cell body inner wall surface insulation；
Preferably, described cell body inner wall surface is politef；
Preferably, it is tightly connected by teflin ring between described cell body and groove lid.
6. according to the pressurization electrolysis bath one of claim 1-5 Suo Shu, it is characterised in that the material of described negative electrode and anode is Any one or the oxide of the combination of at least two, preferably nickel in nickel, copper, titanium, lead, stannum, cerium or its oxide and/or The oxide of stannum；
Preferably, during the material of described negative electrode and anode is tin ash, ceria or Lead oxide brown any one or extremely The combination of few two kinds；
Preferably, described negative electrode is coated with silica gel back to the side of anode, and described anode is carried on the back anticathode side and is coated with silica gel；
Preferably, described negative electrode is identical with the structure of anode.
7. according to the pressurization electrolysis bath one of claim 1-6 Suo Shu, it is characterised in that described electrolyte membrane is ion Membrane cover, Negative electrode and/or anode are wrapped up wherein by described ion Membrane cover；
Preferably, the material of described ion die sleeve is cationic membrane；
Preferably, the width of described barrier film ion Membrane cover is more than the width of electrode, and height is higher than the liquid level of electrolyte, thickness Diameter more than contact rod.
8. according to the pressurization electrolysis bath one of claim 1-7 Suo Shu, it is characterised in that described heater includes electrical heating Stove, described electric furnace includes resistance wire combustion chamber, and the cell body of described reactive tank is surrounded wherein by described electric furnace；
Preferably, described heater also includes the controller for controlling electric furnace temperature.
9. the method utilizing the described pressurization electrolysis bath intensified electrolysis of one of claim 1-8, it is characterised in that described method For: by supplying pressurization cell gas and/or adding the pressurization of thermogenetic steam realization pressurization electrolysis bath, it is electrolysed, Pressure during electrolysis is 0.1-5MPa, preferably 1.5-2.0MPa；Electrolysis uses alkaline electrolyte, alkaline electrolyte neutral and alkali material Concentration be 0.1-2mol/L, preferably 0.5-1.5mol/L.
Method the most according to claim 9, it is characterised in that described electrolysis is solid mineral electrolytic desulfurization, water electrolysis system Hydrogen or wastewater electrolytic degraded COD.
CN201610466368.6A 2016-06-23 2016-06-23 A method of pressurization electrolytic cell and intensified electrolysis Expired - Fee Related CN106119886B (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN110346402A (en) * 2019-06-20 2019-10-18 浙江大学 The forceful electric power electrode assembly used under Elevated Gravity
CN113430536A (en) * 2021-07-16 2021-09-24 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
CN114016062A (en) * 2021-12-15 2022-02-08 江苏高瓴水务科技有限公司 Intelligent electrolytic tank convenient for hydrogen production by water electrolysis
CN114032569A (en) * 2021-11-18 2022-02-11 四川华能氢能科技有限公司 Efficient electrolysis constructional device

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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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110346402A (en) * 2019-06-20 2019-10-18 浙江大学 The forceful electric power electrode assembly used under Elevated Gravity
CN113430536A (en) * 2021-07-16 2021-09-24 阳光电源股份有限公司 Water electrolysis hydrogen production system
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
CN114032569A (en) * 2021-11-18 2022-02-11 四川华能氢能科技有限公司 Efficient electrolysis constructional device
CN114016062A (en) * 2021-12-15 2022-02-08 江苏高瓴水务科技有限公司 Intelligent electrolytic tank convenient for hydrogen production by water electrolysis
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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