CN105420752B - A kind of filled type oriented flow electrochemical reactor - Google Patents
A kind of filled type oriented flow electrochemical reactor Download PDFInfo
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- CN105420752B CN105420752B CN201510757864.2A CN201510757864A CN105420752B CN 105420752 B CN105420752 B CN 105420752B CN 201510757864 A CN201510757864 A CN 201510757864A CN 105420752 B CN105420752 B CN 105420752B
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 230000008676 import Effects 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims description 26
- 238000011010 flushing procedure Methods 0.000 claims description 18
- 230000005611 electricity Effects 0.000 claims description 9
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- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011335 coal coke Substances 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 55
- 238000010276 construction Methods 0.000 abstract description 7
- 230000009466 transformation Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 36
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 26
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 17
- 239000000376 reactant Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000001360 synchronised effect Effects 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000010092 rubber production Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920013674 Lumarith Polymers 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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Classifications
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of filled type oriented flow electrochemical reactor, solves the problems such as low existing reaction transformation efficiency of existing electrochemical reactor, high energy consumption, complicated, operating cost is high, bad adaptability.Technical scheme includes cylinder, the cylinder both ends are respectively import connection short tube and outlet connection short tube, at least one reaction member is provided with the cylinder, the reaction member is made up of two poles to opposite and mutually insulated electrode chamber, respectively cathode chamber and anode chamber, the import of the cylinder connect two electrode chambers of the short tube successively through the reaction member and connected with outlet connection short tube.Simple in construction, cost of investment and operating cost of the invention are low, transformation efficiency is high, suitable for a variety of property electrolyte.
Description
Technical field
The present invention relates to a kind of electrolysis reactor, specifically a kind of filled type oriented flow electrochemical reactor.
Background technology
Traditional electrochemical reactor is different by structure, can be divided into box, filter-press type or plate and frame, special construction formula three
Class；It is different by its working method, batch (-type), plunger streaming can be divided into, continuously stir box three class.The three-diemsnional electrode of special construction
Reactor and plunger streaming electrode reactor typically need to prevent product enters opposite electrode region from reversible reaction occurs
The barrier film of special construction is used, there is fine reversible reaction for being electrochemically transformed between this reactant and product
System, using the conversion ratio that power consumption can be saved after barrier film, improves reactant.But due to the presence of separation membrane, both cause to react
Complicated, the increase reactor cost of manufacture of device, also hinders the mixing diffusion effect of reactant, reduces unit volume electricity
Solve the service efficiency of reactor.Well may be used especially for having comprising electrochemical conversion between some reactants and product
Inverse property, while the very low reaction system of invertibity is electrochemically transformed between some reactants and product, using such reactor,
Due to the segmentation of barrier film, its conversion ratio highest also will be less than 50%.
If adiponitrile is the intermediate that manufactures nylon66 fiber, while but also as the auxiliary agent and herbicide of rubber production.Second two
In the electrosynthesis glyoxal of nitrile, traditional method is using the propylene of petroleum industry as raw material, in the presence of catalyst first in two steps
It is processed as acrylonitrile solution：
Then, by electrolysis, dintrile is generated in cathode surface hydrogenation dimerization：
2CH2=CHCN+2H2O+2e→NO(CH2)4CN+2OH- (1-2)
Analysis O occurs for anode2Reaction：
Overall reaction is：
In traditional electrolysis process, the flow direction as the acrylonitrile solution of electrolyte is parallel with electrode surface, i.e., anti-
Liquid is answered to flow to the other end by one end of pole plate in the region that minus plate and positive plate surround.To prevent cathodic region material from entering
In anolyte, using cation-exchange membrane as barrier film；, need to be by OH to avoid the generation of negative electrode side reaction-Negative electrode is removed as early as possible
Area, existing equipment are difficult to；Because acrylonitrile reduction potential is very negative, it is also necessary to using the high material of hydrogen-evolution overpotential as cloudy
Pole, prevent liberation of hydrogen.
Therefore there is following subject matter in existing electrolysis reactor：
(1) it is directed to have between reactant and product and is electrochemically transformed reversible reaction system, existing electricity well
Solution device can cause to convert repeatedly in electrolysis reactor between reactant and product, both influence transformation efficiency, waste electricity again
Consumption；
(2) existing electrolysis unit can not be provided effectively the reactant of electrode surface fast using the flowing of electrolyte itself
The larger turbulence power of speed renewal, electrochemical reaction rates are slower, and then reduce reaction conversion ratio；
(3), for the reaction system containing side reaction of complexity, existing electrolysis unit, which timely and effective can not remove, causes pair anti-
The electrochemical reaction product answered；
(4) existing electrolysis unit is complicated, and floor space is big.
The content of the invention
The invention aims to solve above-mentioned technical problem, there is provided a kind of simple in construction, cost of investment and operation into
This is low, transformation efficiency is high, the filled type oriented flow electrochemical reactor suitable for a variety of property electrolyte.
Technical scheme includes cylinder, and the cylinder both ends are respectively that import connection short tube and outlet connect short tube, the cylinder
At least one reaction member is provided with vivo, the reaction member is made up of two poles to opposite and mutually insulated electrode chamber, point
Not Wei cathode chamber and anode chamber, import two electrode chambers of the connection short tube successively through the reaction member and the outlet of the cylinder
Connect short tube connection.
The electrode chamber is made up of at least one piece of porous plate electrode with the region that corresponding cylinder surrounds, or by conduction material
Network structure made of material and corresponding cylinder composition.
The electrode chamber is made up of the porous plate electrode at both ends with the region that corresponding cylinder surrounds, and is filled out in the electrode chamber
Filled with conductive electrode material.
The electrode material is modified granular active carbon, coal coke, petroleum coke or the corrosion resistant gold of precious metal salt
Category bits or metal ball, granularity 8-20mm.
Network structure made of the conductive material can use conduct electricity very well, the lead that corrosion resistance is strong, platinum, titanium, stone
The materials such as ink are made, and preferably voidage control is in 0.7-0.9.
The porous plate electrode is AND DEWATERING FOR ORIFICE STRUCTURE, and the aperture on orifice plate is 6-10mm.
The porous plate electrode runs parallel of two neighboring electrode chamber end is set, and has gap, the gap between porous plate electrode
One end be connected by porous plate electrode with one end of the feed pathway on electrode chamber internal face, the other end of the feed pathway
Connect flushing liquor inlet tube；The other end in the gap is by one of the apocenosis passage on porous plate electrode and electrode chamber internal face
End connection, the other end connection flushing liquor outlet of the apocenosis passage.
The width in the gap is 1-10mm.
The cylinder is horizontal, is provided with gas buffer tank at the top of each electrode chamber, the gas buffer box top is provided with gas
Body outlet.
The porous plate electrode of each electrode chamber conducts with corresponding electrode chamber wall.
For problem present in background technology, inventor has carried out following improvement to existing electrolysis reactor：
The barrier film commonly used in existing electrochemical reactor is eliminated, changes electrochemical reactor cellular construction.It is described anti-
Unit is answered to be made up of two poles to opposite and mutually insulated electrode chamber, filling electrode material in electrode chamber, or electrode chamber
Network structure it can be formed made of electrolysis material；Electrolyte flows through the electrode chamber of series connection successively, on the one hand avoids in electrolyte
Reactant and product between converted repeatedly in electrolysis reactor, improve transformation efficiency, it is energy-saving, on the other hand, fill out
Electrode material or the network structure composition filled；It is uniform in electrode chamber to be also beneficial to electrolyte, thus and stir without separately setting
Device is mixed, structure is further simplified, reduces energy consumption；
Creative sets porous plate electrode at the both ends of electrode chamber, and porous plate electrode is the electrode with AND DEWATERING FOR ORIFICE STRUCTURE,
Porous plate electrode sets the space (i.e. electrode chamber) that relative closure on the one hand can be formed with corresponding cylinder, in order in electrode
Indoor filling electrode material, on the other hand, in order to be electrolysed the electricity that liquid stream can be by the perforate on porous plate electrode by a polarity
Pole room reduces resistance, liquid phase flow direction is perpendicular to porous plate electrode to another opposite polarity electrode chamber directed flow
Surface, electrolyte occur in the electrode chamber of a polarity oxidation or reduction reaction after enter back into another reversed pole to electrode
Room is reduced or oxidation reaction, avoids converting repeatedly, high conversion efficiency；By each self-corresponding porous between two neighboring electrode chamber
Plate electrode (total to have two porous plate electrodes) separates, and is further ensured that the reliability of conversion reaction, improves reaction efficiency.It is described
The aperture of porous plate electrode is 6-10mm, and crossing conference causes the electrode material of filling to be lost in, while is unfavorable for being electrolysed
Liquid it is uniform.The too small electrode material for occurring that partial hole is filled blocks, while can increase the resistance of electrolyte flow.
The porous plate electrode runs parallel of two neighboring electrode chamber end is set, and has gap between porous plate electrode, the gap is
In order to ensure that adjacent existing electrode chamber is in state of insulation.Meanwhile the setting in gap also helps fine solid particles in electrode chamber
The removing of thing, when the particulate matter and filling electrode material crushed particles that contain in electrolyte are gathered in gap, by flushing liquor
Inlet tube is passed through flushing liquor, and flushing liquor enters between adjacent two porous plate electrodes through the feed pathway on electrode chamber cylinder inboard wall face
The one end in gap, is rinsed to gap, and the discharge opeing that flushing liquor is entered on electrode chamber cylinder inboard wall face by the other end in gap is led to
Road, finally discharged by flushing liquor outlet.
The width in gap is preferably 1-10mm, and crossing conference causes the efficiency of cell reaction to decline, too small to increase reactor
Processing and installation cost.
Reactor of the present invention can be designed as needed it is vertical or horizontal, when reactor for it is horizontal when, can be in electrode
Ceiling portion sets gas buffer tank, and gas buffer tank has multiple effects, is produced for collecting in course of reaction among caused reaction
Thing such as gas, and discharge in time；It is alternatively arranged as filling the addition mouth of electrode material；When needs are passed through reactant such as into electrolyte
When gas participates in reaction, gas can be filled with into electrode chamber by gas buffer tank and/or flushing liquor inlet tube.
Reactor of the present invention can use a reaction member, and two or more multiple reactions can also be used single
Member series connection.
When being provided with least two reaction members in reactor, putting in order for electrode chamber can in two neighboring reaction member
It may be reversed with identical, those skilled in the art can need rationally to determine according to the conversion of reactant in electrolyte.
Further, during cell reaction, excessive electrochemical reaction precipitate separates out on the porous plate electrode of cathode chamber,
It can cause in electrolyte that reactant concentration is too low, influence changing effect.Meanwhile precipitate is also possible to block the electrode material of filling
The micropore of material, reduce the specific surface area of electrode, the now polarity of two electrode chambers of interchangeable, and change electrolyte in reactor
Interior flow direction, make precipitate that oxidation occur and reenter in electrolyte, to improve the self-purification capacity of reactor.
Beneficial effect：
The present invention is using being filled with cathode chamber and the anode chamber of electrode material, with reference to porous plate electrode, make liquid stream perpendicular to
Porous plate electrode flowing, when flowing through the electrode chamber filled with electrode material, particulate electrode material or network structure convection body tool
There is uniform effect, compact-sized without stirring facility, specific electrode surface is big, filler particles shape filler in electrode chamber, the work of filler
With making the passage of electrolyte flow tortuous, the stream of electrolyte when less turbulence during electrolyte flow is more than plate electrode structures
It is dynamic, to turbulence power caused by reactant when increasing liquid phase flowing, be advantageous to the renewal of electrode surface reaction solution, improve reaction and turn
Rate；Strong applicability, suitable for the reaction system containing side reaction of complexity, timely and effective it can remove the electrification for causing side reaction
Reaction product is learned, the electrolyte of the reactant containing good reversibility is applicable not only to, is also suitable simultaneously containing the anti-of good reversibility
Answer the electrolyte of thing and poorly reversible reactant.Reaction structure of the present invention is simple, floor space is small, simple to operate, operating cost
It is low, be easy to in-site installation.
Brief description of the drawings
Fig. 1 is the structure of reactor figure of embodiment 3.
Fig. 2 is the structure of reactor figure of embodiment 1.
Fig. 3 is the structure of reactor figure of embodiment 5.
B-B that Fig. 4 is Fig. 3 is cutd open to figure.
Fig. 5 is the structure of reactor figure of embodiment 2.
Wherein, 1- cylinders, 2- electrode chambers, 3- electrode materials, the porous plate electrodes of 4-, 5- baffle-boxs, 6- gas discharge outlets, 7-
Gap, 8- flushing liquors inlet tube, 9- flushing liquors outlet, 10- feed pathways, 11- apocenosis passages, 12- insulating flanges, 13- enter
Mouth connection short tube, 14- outlets connection short tube, 15- filling electrodes conveying end, 16- network structures.
Embodiment
Explanation is further explained to the present invention below in conjunction with the accompanying drawings：
Embodiment 1：
Referring to Fig. 2, the present embodiment reactor is horizontal, and one end of cylinder 1 is provided with import connection short tube 13, and the other end is provided with
Outlet connection short tube 14, cylinder 1 is interior to be provided with a reaction member, is made up of the electrode chamber 2 of two mutually insulateds, respectively negative electrode
Room and anode chamber, the electrode chamber 2 are made up of the porous plate electrode 4 at both ends with the region that corresponding cylinder 1 surrounds, the electrode chamber
Conductive electrode material 3 is filled with 2.The electrode material 3 can be modified granulated activated of precious metal salt
Charcoal, coal coke, petroleum coke or corrosion resistant metal fillings or metal ball, granularity are that (granularity of electrode material 3 is more than more 8-20mm
The aperture of orifice electrode 4).The both ends of the electrode chamber 2 are equipped with porous plate electrode 4 (aperture 6-10mm), two electrode chambers
2 porous plate electrode 4 corresponds to access negative electrode and anode terminal (not shown) respectively, and it is the moon to make two electrode chambers 2 one
Pole room one is anode chamber, in order that porous plate electrode 4 conducts with the wall of corresponding electrode chamber 2, can such as use conductive spiral shell
Porous plate electrode 4 is connected by nail with the wall of electrode chamber 2, the binding post access wall of electrode chamber 2, electric current is imported corresponding porous plate
Electrode 4.And according to the property of electrolyte, lumarith can also be coated in the wall inner surface of electrode chamber 2, avoid electrolyte rotten
Lose the wall of electrode chamber 2.In the present embodiment, left side is anode chamber, and right side is cathode chamber, in the more of two adjacent electrode chambers 2
It can be connected between orifice electrode 4 by flange 12 slow absolutely, and form 1-10mm gap 7, two porous plate electrodes 4 is kept exhausted
Edge state, the one end in the gap 7 is by porous plate electrode 4 and the feed pathway 10 on electrode chamber 2 (cathode chamber) internal face
One end connects, the other end connection flushing liquor inlet tube 8 of the feed pathway 10；The other end in the gap 7 passes through porous plate
Electrode 4 is connected with one end of the apocenosis passage 11 on electrode chamber 2 (anode chamber) internal face, and the other end of the apocenosis passage 11 connects
Connect flushing liquor outlet 9.The bottom of the electrode chamber 2 is provided with filling electrode conveying end 15 and is used to take out electrode material 3, the electricity
The top of pole room 2 is provided with baffle-box 5, and the baffle-box 2 is provided with gas discharge outlet 6.
The course of work：
Adiponitrile is the intermediate for manufacturing nylon66 fiber, while but also as the auxiliary agent and herbicide of rubber production.This implementation
Acrylonitrile solution of the electrolyte in adiponitrile production technology in example.
During using oriented flow electrochemical reactor, the electrolyte is entered by the import connection short tube 13 of reactor, is first worn
Electrode chamber 2 (anode chamber) progress (1-3) oxygen evolution reaction that one layer of porous plate electrode 4 enters left side is crossed, produces oxygen.
The porous plate electrode 4 of electrode chamber 2 on the left of electrolyte cross after peroxidization, gap 7, by the electricity on right side
The porous plate electrode 4 of the one end of pole room 2, which enters, carries out (1-2) reduction reaction in the electrode chamber 4 (cathode chamber) on right side, generate second two
Nitrile.
Reacted electrolyte cross cathode chamber is flowed out by outlet connection short tube 14 in cathode chamber, that is, completes adiponitrile
Electrosynthesis glyoxal.
In anode chamber, the oxygen of generation it is anti-can to remove electrochemistry by baffle-box 5 and gas discharge outlet 6 under suction function
Answer device.
Due to the effect of the conductive material 3 of filling in electrode chamber 2, the passage of electrolyte flow is tortuous, during electrolyte flow
Less turbulence electrolyte when being more than simple plate electrode structures flowing.On the surface of porous plate electrode 4 of cathode chamber, generation
Adiponitrile and OH-, under the direct souring of electrolyte of high turbulence, the porous surface of plate electrode 4 can be quickly left, is reduced
The generation of side reaction.
Embodiment 2
Referring to Fig. 5, the network structure 16 that the electrode chamber 2 is made of an electrically conducting material forms, and without porous plate electrode 4 and its fills out
The electrode material 3 filled, remaining structure with embodiment 1, the conductive material can use conduct electricity very well, corrosion resistance is strong
The materials such as lead, platinum, titanium, graphite are made.Electrolyte is concentration tower in flue gas wet type ammonia-complexed absorption synchronized desulfuring and denitrifying system
Concentrate.
The course of work：
The concentrate physical parameter and phase of concentration tower in flue gas wet type ammonia-complexed absorption synchronized desulfuring and denitrifying system
It is as follows to close composition：
PH value：4.0~5.0；
Ammonium sulfate concentrations：30~45%；
EDTA-Fe (II)+EDTA-Fe (III) concentration：0.05~0.1mo l/L；
Absorbing liquid temperature：50-60 DEG C or so.
The electrolyte is entered by the import connection short tube 13 of reactor, and the electrode chamber 2 (anode chamber) into left side is carried out
Oxidation reaction：
In the oxidation reaction that anode chamber occurs：
2H2O→O2+4H++4e (7)
If dissolved with hydrogen in slurries, it is also possible to following react occurs：
H2→2H++2e (8)
Fe2+EDTA→Fe3+EDTA+e (2′)
Fe2+→Fe3++e (3′)
Electrode chamber 2 and gap 7 on the left of electrolyte cross after peroxidization, into (the negative electrode of electrode chamber 2 on right side
Room) in carry out reduction reaction：
In the reduction reaction that cathode chamber occurs：
Fe2+EDTA(NO)+5H++5e→Fe2+EDTA+NH3+H2O (1)
Or：
Fe3+EDTA+e→Fe2+EDTA (2)
Fe3++e→Fe2+ (3)
Fe2++2e→Fe (4)
It is 1.5-4.5V to control the reaction member middle-jiao yang, function of the spleen and stomach pole room and the potential difference of cathode chamber.
Reacted electrolyte is flowed out by outlet connection short tube 14 in cathode chamber, that is, the regenerative process for completing electrolyte is dense
The removal of iron in contracting liquid.The electrolyte (i.e. absorbing liquid) come out from reactor realizes Fe3+EDTA is reduced into Fe2+EDTA,
The absorbability to nitrogen oxides is recovered, can recycle again, in the present embodiment, de-ironing efficiency can be more than 90%.
Embodiment 3
Referring to Fig. 1, the present embodiment reactor is vertical, basic structure horizontal identical, upper electrode room 2 with embodiment 1
For cathode chamber, lower electrode room 2 is anode chamber, unique the difference is that being not provided with baffle-box 5, gas discharge outlet 6 and filling electrode
Conveying end 15, remaining is the same as embodiment 1.
Technical process：
Electrolyte source is short by the import connection of reactor bottom with embodiment 1, electrolyte with embodiment 1, course of reaction
Pipe 13 enters reactor, from the bottom to top directed flow, sequentially pass through anode chamber, cathode chamber by reactor head outlet connection it is short
Pipe 14 flows out, and remaining is the same as embodiment 1.De-ironing efficiency is 90%.
Embodiment 4
Referring to Fig. 2, the present embodiment reactor is horizontal, and structure is the same as embodiment 1.
Technical process：
Electrolyte is used as using the absorbing liquid from absorption tower in flue gas wet type ammonia-complexed absorption synchronized desulfuring and denitrifying system
The course of work of reactor described in the present embodiment is explained as follows exemplified by progress electrolytic regeneration：
Sprayed, had been carried out using desulphurization denitration absorption tower top the absorbing liquid of sulfur dioxide and nox adsorption as
Make electrolyte and be sent into electrochemical reactor of the present invention, the physical parameter and relevant components of the electrolyte are as follows：
PH value：5.0~5.5；
Ammonium sulfate concentrations：5~15%；
EDTA-Fe (II)+EDTA-Fe (III) concentration：0.015~0.05mo l/L；
Absorbing liquid temperature：50 DEG C or so.
Electrolyte horizontally enters into electrochemical reactor by one end import connection short tube 13 of cylinder 1, and liquid phase is flowed perpendicular to more
Orifice electrode 4, electrolyte flow through anode chamber, cathode chamber, the outlet most afterwards through the cylinder other end successively through the porous plate electrode 4 of polylith
Connection short tube 14 is discharged.
Include in the oxidation reaction that anode chamber occurs：
2H2O→O2+4H++4e (7)
If dissolved with hydrogen in slurries, it is also possible to following react occurs：
H2→2H++2e (8)
Fe2+EDTA→Fe3+EDTA+e (2′)
Fe2+→Fe3++e (3′)
In the reduction reaction that cathode chamber occurs：
Fe2+EDTA(NO)+5H++5e→Fe2+EDTA+NH3+H2O (1)
Or：
Fe3+EDTA+e→Fe2+EDTA (2)
Fe3++e→Fe2+ (3)
Fe2++2e→Fe (4)
The potential difference for controlling the reaction member Anodic and negative electrode is 2.0-3.0V.
The porous plate electrode 4 of reacted electrolyte cross cathode chamber connects short tube by the outlet of the other end in cathode chamber
14 outflows, that is, complete the regenerative process of electrolyte.The electrolyte (i.e. absorbing liquid) come out from electrochemical reactor realizes Fe3+
EDTA is reduced into Fe2+EDTA, recover the absorbability to nitrogen oxides, can recycle again, it is described in the present embodiment
The regeneration rate of electrolyte is more than 80%.
Because in above-mentioned electrochemical reaction, reaction (1), (2), (3), (6), (7) and (8) is regeneration of absorption solution beneficial to anti-
Should；Reaction (4) and (5) is to be particularly disadvantageous for the reaction of slurries regeneration.Therefore, the baffle-box 5 at the top of electrode chamber can be collected instead
Oxygen caused by (7) and reaction (5 ') should be reacted, and is discharged through gas discharge outlet 6.On the other hand, when need to be into electrode chamber 2 more
When changing electrode material, line replacement can be entered to the electrode material 3 in electrode chamber 2 by baffle-box 2, or be filled through electrode conveying end
15 take out the electrode material 3 changed；
When the deficiency of reproducibility component inferior sulfate radical in absorbing liquid, in electrolytic regeneration reaction, reaction (7) and (8) is
Electrochemical reaction carries out offer charge balance, therefore can be buffered in electrolyte of the case 5 into electrode chamber 2 and be passed through hydrogen, to promote
Enter the progress of reaction (8), and decomposition voltage can be reduced.
In the present embodiment, the regeneration rate of the electrolyte is more than 80%.
Also, as needed, the present invention can also use vertical reactor structure to carry out above-mentioned technique mistake described in embodiment 2
Journey, its reaction principle and the same the present embodiment of process.
Automatically cleaning：
In the cathodic compartment, reaction (4) inevitably occurs, and in order to ensure that the iron in electrolyte is component balanced, keeps away simultaneously
Blocking of the ferro element for exempting to separate out to the porous hole of plate electrode 4, periodically exchanges the positive-negative polarity of the electrode chamber in reaction member,
Original anode chamber is set to be changed into cathode chamber, originally cathode chamber is changed into anode chamber, while makes electrolyte reverse in electrochemical reactor
Flowing, make the reoxidized automatic cleaning action for entering electrolyte into ferrous ion, playing reactor of ferro element of precipitation.
In addition, for the blocking at a small amount of porous hole of plate electrode 4 and gap 7, can be by flushing liquor by flushing liquor entrance
Pipe 8 is passed through, and the hole blocked in gap 7 to rinse and the ferro element precipitate being deposited in gap 7 are sent into through feed pathway 10,
Flushing liquor fraction is entered by the porous hole of plate electrode 4 in the electrode chamber 2 of both sides, and major part is with precipitate through apocenosis passage 11
Discharged by flushing liquor outlet 9, to ensure the normal operation of electrochemical reactor, remove the iron to get off and separated out with element Iron activiation
, can be as the quality raw materials of sintering deposit on electrode material 3.
Embodiment 5
Referring to Fig. 3, electrochemical reactor has two reaction members to be horizontal in the present embodiment, and each reaction member is equal
Be made up of two electrode chambers 2, in the present embodiment, close to import connection short tube 13 start at, the electrode chamber 2 in the first reaction member according to
Secondary is cathode chamber and anode chamber, and the setting of the electrode chamber 2 of second reaction member and first reaction member electrode chamber 2 is sequentially just
Well on the contrary, being followed successively by anode chamber, cathode chamber.Above-mentioned design method is only to enumerate, and those skilled in the art also can be according to processing
Reactant selection in electrolyte makes the setting of electrode chamber 2 order of two reaction members identical.The specific knot of each reaction member
Structure is the same as embodiment 2.
The course of work：
Electrolyte with embodiment 2,
In first reaction member, the potential difference of cathode chamber and anode chamber is 2.5-4.5V, and main purpose is driving a reaction
(1) and (6) progress, so as to realize that conversion of nitrogen oxides is ammonia.Following reduction reaction occurs in cathode chamber：
Fe2+EDTA(NO)+5H++5e→Fe2+EDTA+NH3+H2O (1)
Or：
Fe3+EDTA+e→Fe2+EDTA (2)
Fe3++e→Fe2+ (3)
Fe2++2e→Fe (4)
If oxygen cathode reaction also be present containing aerobic in solution：
O2+2H2O+4e→4OH- (5)
In the oxidation reaction that anode chamber occurs：
2H2O→O2+4H++4e (7)
If dissolved with hydrogen in slurries, it is also possible to following react occurs：
H2→2H++2e (8)
There is good invertibity due to reaction (2), (4) and (6), so it is anti-that following oxidation also occurs in anode chamber
Should：
Fe2+EDTA→Fe3+EDTA+e (2′)
Fe2+→Fe3++e (3′)
Second construction unit cathode chamber of reactor and the potential difference of anode chamber are 1.5-2.5V, and main purpose is to push away
The progress of dynamic reaction (2) and (7), so as to realize the regeneration of complexes absorption.It is low to react the invertibity of (1) and (6), reaction (2),
(3) and (5) have a good invertibity, thus into reactor second reaction member when, anode chamber is introduced into, in sun
Oxidation reaction occurs for pole room：
Fe2+EDTA→Fe3+EDTA+e (2′)
Acid medium：2H2O→O2+4H++4e (7)
In the reduction reaction that cathode chamber occurs：
Fe3+EDTA+e→Fe2+EDTA (2)
Fe3++e→Fe2+ (3)
Fe2++2e→Fe (4)
If oxygen cathode reaction also be present containing aerobic in solution：
O2+2H2O+4e→4OH- (5)
More than electrochemical reaction in, reaction (1), (2), (3), (6), (7) are the beneficial reactions of regeneration of absorption solution；Reaction
(4) and (5) are the reactions for being particularly disadvantageous for slurries regeneration.So reactor be provided with baffle-box be used for isolate reaction (7) and
React oxygen caused by (5 ').Meanwhile two reaction members are set to realize the electrochemistry needed under different decomposition voltages
Reaction.
In the present embodiment, the regeneration rate of the electrolyte is more than 80%.
The embodiment of the present invention is applied in flue gas wet type ammonia-complexed absorption synchronized desulfuring and denitrifying technique, original to replace
Iron filings regeneration step, compared with original iron filings regenerate, build an iron filings tower less, without settling system, investment save 10% with
On；Also, because most of iron is useless consumption in past iron filings reproducing unit step, even unfavorable consumption.More than 50%
Iron filings consumption be the sour corrosion of absorbing liquid caused by, this part iron also add follow-up iron removaling cost.Therefore use
For the embodiment of the present invention 1 compared with iron filings regenerate, regenerative system operating cost reduces by more than 60%.
Iron removaling is carried out without precipitation using apparatus of the present invention in flue gas wet type ammonia-complexed absorption synchronized desulfuring and denitrifying technique
Thing produces, and does not add other materials to system in electrolytic regeneration and electrolysis iron removal, does not produce any discarded object, remove
Precipitate --- iron with element Iron activiation separate out on electrode material, can be as the quality raw materials of sintering deposit.
Claims (6)
1. a kind of filled type oriented flow electrochemical reactor, including cylinder, the cylinder both ends be respectively import connection short tube and
Outlet connection short tube, it is characterised in that be provided with least one reaction member in the cylinder, the reaction member from two poles to
Opposite and mutually insulated electrode chamber composition, respectively cathode chamber and anode chamber, the import connection short tube of the cylinder pass through successively
Two electrode chambers of the reaction member with outlet connection short tube connect, the electrode chamber by both ends porous plate electrode with it is corresponding
The region composition that surrounds of cylinder, is filled with conductive electrode material, two neighboring electrode chamber end in the electrode chamber
The porous plate electrode runs parallel in portion is set, and has gap between porous plate electrode, the one end in the gap is by porous plate electrode and electricity
One end connection of feed pathway on pole room internal face, the other end connection flushing liquor inlet tube of the feed pathway；Described
The other end of gap is connected by porous plate electrode with one end of the apocenosis passage on electrode chamber internal face, the apocenosis passage it is another
One end connects flushing liquor outlet.
2. filled type oriented flow electrochemical reactor as claimed in claim 1, it is characterised in that your gold the electrode material is
Belong to salt modified granular active carbon, coal coke, petroleum coke or corrosion resistant metal fillings or metal ball, granularity 8-
20mm。
3. filled type oriented flow electrochemical reactor as claimed in claim 1, it is characterised in that the porous plate electrode is hole
Harden structure, the aperture on orifice plate is 6-10mm.
4. filled type oriented flow electrochemical reactor as claimed in claim 1, it is characterised in that the width in the gap is
1-10mm.
5. the filled type oriented flow electrochemical reactor as described in claim any one of 1-4, it is characterised in that the cylinder is
It is horizontal, gas buffer tank is provided with the top of each electrode chamber, the gas buffer box top is provided with gas discharge outlet.
6. the filled type oriented flow electrochemical reactor as described in claim any one of 1-4, it is characterised in that each electrode chamber
Porous plate electrode conducted with corresponding electrode chamber wall.
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