CN110093621B - Hydrogen-free continuous electrochemical oxidation IO3-Transformation to IO4-Method (2) - Google Patents
Hydrogen-free continuous electrochemical oxidation IO3-Transformation to IO4-Method (2) Download PDFInfo
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- CN110093621B CN110093621B CN201910335633.0A CN201910335633A CN110093621B CN 110093621 B CN110093621 B CN 110093621B CN 201910335633 A CN201910335633 A CN 201910335633A CN 110093621 B CN110093621 B CN 110093621B
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Abstract
The invention relates to the field of preparation of periodate by electrochemical synthesis, in particular to a hydrogen-free continuous electrochemical oxidation IO3 ‑Transformation to IO4 ‑The method comprises the steps of using a diaphragm type plate-and-frame electrolytic cell as an electrolytic device, using a metal oxide coating electrode or a graphite electrode as an anode, using an air electrode as a cathode, using a homogeneous cation diaphragm as a diaphragm material, and using MIO3Solution and H2SO4The mixed solution of the solution is used as anolyte and H2SO4Using solution as catholyte, and adopting constant current continuous electrolysis method to electrolyze IO3 ‑Conversion to IO4 ‑And M is Na or K. The method adopts the air electrode as the cathode, avoids the generation of hydrogen and the overflow of sulfuric acid mist, and reduces the voltage of the tank, thereby saving the power consumption; continuous electrolysis can be realized, and the current efficiency is high and the energy consumption is low; meanwhile, the method avoids the discharge of a large amount of waste water by a chlorine oxidation method, and is particularly suitable for recycling periodate in the oxidation reaction of the vicinal diol in industry.
Description
Technical Field
The invention relates to the field of preparation of periodate by electrochemical synthesis, in particular to a hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The method of (1).
Background
Periodate is a selective, mild chemical oxidant, and is effectively suitable for the oxidation of compounds in which a carbonyl group or a hydroxyl group is adjacent to a second carbonyl group or a hydroxyl group, such as α -diol, α -ketone, α -diketone and α -ketoaldehyde, etc., and a selective and sensitive detection method for periodate, in molecular biology, environmental monitoring, food, etcThe method also has good application in the fields of science and clinical diagnosis; recently proposed photoactivated periodate salts (UV/IO)4 -) The method is used as a novel advanced oxidation technology, shows higher capability of removing water-containing organic compounds in some researches, and has wide application prospect in the aspect of dye decoloration.
At present, strong oxidizing chemical reagents such as chlorine and sodium hypochlorite are mainly used for oxidizing iodate to generate periodate. Chlorine and sodium hypochlorite oxidation iodate all need go on in strong alkaline medium, need consume a large amount of raw materials, and economic cost is higher, still can produce a large amount of sodium chloride accessory substances simultaneously, has caused the emission of a large amount of stostes and high concentration sodium chloride solution, and the polluted environment has increased the degree of difficulty of safety ring protects production. Chlorine is a yellow-green toxic gas with strong pungent smell, and has strict requirements on use conditions, storage equipment and the like, so that the sodium periodate prepared by using a chlorine oxidation method has strict requirements on safety production, complex and complicated method, difficult control on operation and low safety degree.
The electrochemical oxidation method converts iodate into periodate, and separates the anode and cathode of the electrolytic cell by using a diaphragm, IO3 -Oxidation reaction in the anode region to produce IO4 -Due to the barrier action of the diaphragm, IO4 -Is difficult to enter the cathode area to be reduced to obtain periodate. However, the cell voltage of the diaphragm electrolysis method is high, a large amount of hydrogen can be separated out from the cathode, sulfuric acid is brought out to form acid mist, the environmental pollution is serious, and meanwhile, the explosion limit of hydrogen is low, and the danger of hydrogen explosion is easy to occur. The invention adopts the air electrode as the cathode, and oxygen in the air and hydrogen ions in the solution are directly reduced into water, thereby fundamentally avoiding the generation of hydrogen, avoiding the overflow of sulfuric acid mist, simultaneously greatly reducing the tank voltage, reducing the power consumption, having low production cost, simple process, high conversion rate and easy industrialized production.
Disclosure of Invention
The invention aims to solve the problems that the prior electrochemical oxidation method converts iodate into periodate, has serious environmental pollution and is easy to generate hydrogenThe shortage of explosion hazard, and provides a hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The method avoids the generation of hydrogen, improves the safety, has higher conversion rate and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The method is based on a diaphragm type plate frame electrolytic cell, and the method comprises the following steps: in diaphragm plate and frame cells, with MIO3Solution and H2SO4The mixed solution of the solution is used as anolyte and H2SO4Using solution as catholyte, metal oxide coating electrode or graphite electrode as anode, air electrode as cathode, and constant current continuous electrolysis3 -Conversion to IO4 -And M is Na or K.
Preferably, the anode of the diaphragm type plate-and-frame electrolytic cell is a mesh or plate-shaped titanium-based metal oxide coating electrode, and the metal oxide coating is PbO2、SnO2、IrO2/Ta2O5Or RuO2/TiO2。
Preferably, the current collector of the air electrode is a titanium mesh, a copper alloy or a nickel mesh, the catalyst layer in the air electrode takes porous carbon as a carrier, and the catalyst of the catalyst layer is MnO2Or MnO2And IrO2The catalytic layer is made of MnO with the mass fraction of 5-25%2IrO with mass fraction of 0-0.1%2The balance of porous carbon, and the total of the raw materials is 100%.
Preferably, the constant current continuous electrolysis method comprises the steps of continuously dripping the anolyte into the anode chamber of the electrolytic cell, discharging the anolyte after electrolysis from the bottom of the anode chamber of the electrolytic cell, wherein V is 0.187 × I ×η/C, V is the flow rate, η is the set current efficiency, and C is MIO3I is the electrolysis current; the catholyte does not disappear theoreticallyAnd water can be continuously added dropwise to keep the liquid level and the anode liquid level equal.
Preferably, the composition of the anolyte is 0.1-1.0 mol/L of MIO3The solution is mixed with 0-1.5 mol/L H2SO4The mixed solution of the solution, wherein the catholyte is H of 0-1.5 mol/L2SO4And (3) solution.
Preferably, the diaphragm of the diaphragm plate-and-frame electrolytic cell is a homogeneous cation exchange membrane.
The method comprises at least one diaphragm type plate frame electrolytic cell, and further comprises a cathode chamber electrolyte distribution pipe and an anode chamber electrolyte distribution pipe, wherein catholyte and anolyte respectively enter the cathode chamber and the anode chamber from the cathode chamber and the anode chamber electrolyte distribution pipe, the bottoms of the cathode chamber and the anode chamber are respectively connected with a cathode chamber electrolyte outflow collecting pipe and an anode chamber electrolyte outflow collecting pipe, and electrolyzed catholyte and anolyte respectively flow into the cathode chamber electrolyte outflow collecting pipe and the anode chamber electrolyte outflow collecting pipe.
The invention has the beneficial effects that:
the invention relates to a hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The method comprises the steps of using a diaphragm type plate frame groove as an electrolyzer, using a metal oxide coating electrode or a graphite electrode as an anode, using an air electrode as a cathode, using a homogeneous phase cation diaphragm as a diaphragm material, and using Na (K) IO3And H2SO4The mixed solution of (A) is used as an anolyte, and H is used2SO4Using solution as catholyte, and adopting constant current continuous electrolysis method to electrolyze IO3 -Conversion to IO4 -. The method adopts the air electrode as the cathode, avoids the generation of hydrogen and the overflow of sulfuric acid mist, and reduces the voltage of the tank, thereby saving the power consumption; continuous electrolysis can be realized, and the current efficiency is high and the energy consumption is low; meanwhile, the method avoids the discharge of a large amount of waste water by a chlorine oxidation method, and is particularly suitable for recycling periodate in the oxidation reaction of the vicinal diol.
Drawings
FIG. 1 shows a hydrogen-free continuous electrochemical oxidation IO of the present invention3 -Transformation to IO4 -A process diagram of the method of (1);
FIG. 2 is a schematic view of a diaphragm plate and frame electrolyzer of the invention and an air electrode;
FIG. 3 is a schematic view of the air electrode of the diaphragm plate frame electrolytic cell of the present invention.
In the figure: 1-electrolytic cell (insulating material, PP, PVC, etc.), 2-cathode chamber electrolyte distribution pipe, 3-anode chamber electrolyte distribution pipe, 4-anode chamber electrolyte outflow collecting pipe, 5-cathode chamber electrolyte outflow collecting pipe, 6-anode, 7-homogeneous cation diaphragm, 8-air electrode cathode, 9-current collector, 10-air electrode catalyst layer, 11-air electrode porous layer and 12-air electrode fixing frame.
Detailed Description
The technical solution of the present invention is further illustrated by the following embodiments in conjunction with the accompanying drawings.
Example 1:
referring to FIGS. 1 to 3, FIG. 1 shows a hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The process of the method is shown in the schematic diagram, the electrolytic tank 1 in figure 2 is a diaphragm plate frame electrolytic tank made of polypropylene material, and the anode is reticular titanium-based PbO2The cathode of the coated electrode is an air electrode, the figure 3 is a schematic diagram of the air electrode, the current collector of the air electrode is a titanium mesh, the carrier of the catalyst layer 10 is porous carbon, and the catalyst is 24 wt% MnO2+0.1wt％IrO2The area of the electrode is 50cm × 50cm, the cathode and the anode are separated by a polyphenylsulfonic acid homogeneous cation diaphragm 7, the distance between the diaphragm and the cathode and the anode is 2cm, the area of the membrane is 60cm × 60cm, the anolyte is 0.5mol/L NaIO3And 1.0mol/L H2SO4The catholyte is 0.5mol/LH2SO4The anolyte is continuously dripped into the upper part of the liquid level of the anode chamber of the electrolytic cell from an anode chamber electrolyte distribution pipe 3 at the flow rate of 2.0L/h, and an electrolysis product in the anode chamber overflows from the bottom of the anode of the electrolytic cell to an anode chamber electrolyte collecting pipe 4 at the flow rate of 2.0L/h; the catholyte is slowly dripped into the upper part of the liquid level of the cathode chamber of the electrolytic bath from the cathode distribution pipe 2 to keep the liquid level and the anode chamber balancedAnd controlling the overflow flow of the electrolysis products in the cathode chamber to be 0. Stable constant current continuous electrolysis with a current density of 225A/m2。
Titrating by using a sodium thiosulfate standard solution in the presence of a masking agent sodium molybdate and a demasking agent oxalic acid, and sequentially determining IO in an electrolysis product3 -And IO4 -The current efficiency was calculated to be 92.5%.
Examples 2 to 10:
the method of the embodiments 2 to 10 is the same as that of the embodiment 1, wherein the anode electrodes different from those of the embodiment 1 are selected for the embodiments 2, 3 and 4, the other process parameters are the same as those of the embodiment 1, the air electrode catalyst layer different from that of the embodiment 1 is selected for the embodiments 5, 6, 7, 8, 9 and 10, the other process parameters are the same as those of the embodiment 1, the reticular titanium-based SnO2 coating electrode is selected for the embodiment 2, and the reticular titanium-based IrO is selected for the embodiment 32/Ta2O5The coating electrode is an anode, and example 4 selects reticular titanium-based RuO2/TiO2The coated electrode was an anode, and the catalyst layer of the air electrode of example 5 was made of (6 wt% MnO)2+0.1wt％IrO2) Catalyst layer of air electrode of example 6 selected as (12 wt% MnO)2+0.1wt％IrO2) Catalyst layer of air electrode of example 7 selected as (18 wt% MnO)2+0.1wt％IrO2) Catalyst layer of air electrode of example 8 selected as (24 wt% MnO)2+0.01wt％IrO2) Catalyst layer of air electrode of example 9 selected as (24 wt% MnO)2+0.05wt％IrO2) Catalyst layer of air electrode of example 10 selected as (24 wt% MnO)2+0.08wt％ IrO2) C, discussing the electrooxidation of different electrode materials to form IO4 -The results of the experiment are shown in Table 1.
Table 1: electrooxidation of dissimilar electrode materials to IO4 -Experimental results of (2)
The results show that PbO2the/Ti electrode is a more effective anode material, catalyzing small amount of IrO in the air cathode2Affecting the current efficiency of the anode, a more suitable cathode catalyst is (24 wt% MnO)2+ 0.08-0.1wt％IrO2)/C。
Examples 11 to 16:
the electrolyte composition and the constant current control method were adjusted according to the method of example 1, and the current and flow rate were set according to the relationship of V0.187 × I ×η/C, where V is the flow rate (mL/h), η is the set current efficiency (%), η is set to 95%, and C is MIO3The amount concentration (mol/L) of the substance(s) in (A) and I is an electrolysis current (A). The electrolyte composition, flow rate and current density were optimized, other parameters of the electrolytic material were the same as those of example 1, and the electrode area was 0.25m2Discussing the formation of IO by electro-oxidation of different anolyte components4 -The results are shown in Table 2.
Table 2: electrooxidation of different anolyte components to IO4 -Experimental results of (2)
The results in Table 2 show that the anolyte needs to be added with sulfuric acid component, and the current and the flow rate are controlled according to the relation that V is 0.187 × I ×η/C and are 50-500A/m2Current efficiency exceeding 90% can be obtained within the range; wherein the more optimized conditions are: anolyte is 0.5mol/L NaIO3+ 1.0mol/L H2SO4The catholyte is 0.5mol/LH2SO4The current density of the solution is controlled within the range of 100-300A/m2。
Examples 17 to 20:
referring to FIG. 1, an anode compartment electrolyte distribution tube is prepared according to the method of example 1The electrolyte in the electrolyte is replaced by sodium periodate to oxidize sorbitol to generate L-xylose for some enterprises, mother liquor after products are separated, the main component of the mother liquor is sodium iodate solution, and the electrolyte distribution pipe in the cathode chamber is 0.5mol/LH2SO4Solution, stable constant current continuous electrolysis, current density of 225A/m2Carrying out multi-batch mother liquor electrolysis, the process parameters are the same as example 1, discussing the electro-oxidation generation IO of different mother liquor batches of the enterprise4 -The results of the experiment are shown in Table 3.
Table 3: electrooxidation of mother liquor to IO in different batches4 -Experimental results of (2)
| Examples | Mother liquor batch | Cell voltage/V | Current efficiency/%) |
| 17 | 1 | 3.02 | 91.6 |
| 18 | 2 | 3.02 | 91.0 |
| 19 | 5 | 3.14 | 88.4 |
| 20 | 10 | 3.17 | 85.6 |
The results in Table 3 show that the method is applied to recycling of L-xylose mother liquor generated by oxidizing sorbitol, the current efficiency exceeds 85 percent, and the method is a method for synthesizing sodium periodate by electrooxidation of sodium iodate and has industrial application prospect.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (4)
1. Hydrogen-free continuous electrochemical oxidation IO3 -Transformation to IO4 -The method is characterized in that based on a diaphragm type plate frame electrolytic cell, the method comprises the following steps: in diaphragm plate and frame cells, with MIO3Solution and H2SO4The mixed solution of the solution is used as anolyte and H2SO4Using solution as catholyte, metal oxide coating electrode or graphite electrode as anode, air electrode as cathode, and constant current continuous electrolysis3 -Conversion to IO4 -M is Na or K, the anode of the diaphragm type plate frame electrolytic cell is a net-shaped or plate-shaped titanium-based metal oxide coating electrode, and the metal oxide coating is PbO2、SnO2、IrO2/Ta2O5Or RuO2/TiO2The current collector of the air electrode is a titanium net, a copper alloy or a nickel net, a catalyst layer in the air electrode takes porous carbon as a carrier, the raw materials of the catalyst layer are MnO2 with the mass fraction of 5-25%, IrO2 with the mass fraction of 0-0.1%, and the balance is porous carbon, the total sum of the raw materials is 100%, and the constant-current continuous electrolysis method comprises the following steps: continuously dripping the anolyte into the anode chamber of the electrolytic bath,the electrolyzed anolyte flows out from the bottom of the anode chamber of the electrolytic cell, the dropping speed and the flowing speed of the anolyte are both V =0.187 × I ×η/C, wherein V is the flow speed, η is the set current efficiency, and C is MIO3I is the electrolysis current.
2. The hydrogen-free continuous electrochemical oxidation IO of claim 13 -Transformation to IO4 -The method is characterized in that the current density of the constant-current continuous electrolysis is 50-500A/m2。
3. The hydrogen-free continuous electrochemical oxidation IO of claim 13 -Transformation to IO4 -The method is characterized in that the composition of the anolyte is 0.1-1.0 mol/L of MIO3The solution is mixed with 0-1.5 mol/L H2SO4The mixed solution of the solution, wherein the catholyte is H of 0-1.5 mol/L2SO4And (3) solution.
4. The hydrogen-free continuous electrochemical oxidation IO of claim 13 -Transformation to IO4 -The method is characterized in that the diaphragm of the diaphragm type plate-and-frame electrolytic cell is a homogeneous cation exchange membrane.
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| BE632859A (en) * | 1962-05-28 | |||
| JPS5623286A (en) * | 1979-08-01 | 1981-03-05 | Japan Carlit Co Ltd:The | Electrolytic producing apparatus of periodic acid or periodate |
| JPS61221388A (en) * | 1985-03-27 | 1986-10-01 | Japan Carlit Co Ltd:The | Electrolytic cell for producing periodate |
| GB9125680D0 (en) * | 1991-12-03 | 1992-01-29 | Ici Plc | Electrochemical cell |
| CN1266312C (en) * | 2002-06-17 | 2006-07-26 | 重庆大学 | Air electrode catalyst and its preparing process |
| CN108878942A (en) * | 2018-07-05 | 2018-11-23 | 浙江工业大学 | A kind of internal circulation gas-lift type microbial fuel cell unit and its application |
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