CN1281791C - Preparation method of oxygenated cathode and anode containing quinine used for production of alkaline hydrogen peroxide - Google Patents
Preparation method of oxygenated cathode and anode containing quinine used for production of alkaline hydrogen peroxide Download PDFInfo
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- CN1281791C CN1281791C CN 200410013514 CN200410013514A CN1281791C CN 1281791 C CN1281791 C CN 1281791C CN 200410013514 CN200410013514 CN 200410013514 CN 200410013514 A CN200410013514 A CN 200410013514A CN 1281791 C CN1281791 C CN 1281791C
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Abstract
The present invention relates to a chinone containing oxygenating cathode used for producing alkali hydrogen peroxide and a preparation method of the cathode, and relates to the chinone containing oxygenating cathode used for producing the alkali hydrogen peroxide and the preparation technology of the chinone containing oxygenating cathode. A ventilation hole (11) is arranged on the pipe wall of an oxygenating pipe (7) of the present invention, and at least one oxygenating pipe (7) is fixed in graphite felt (2). The method comprises: the graphite felt is taken and placed in a nitric acid solution whose concentration is 10% to be soaked for 2 hours; after being taken out, the graphite felt is washed by distilled water and is soaked by a sodium hydroxide solution whose concentration is 4% for 2 hours; after being taken out and washed by the distilled water, the graphite felt is naturally aired and is immersed in a saturated ethanol solution of 2-ethyl anthraquinone for 10 to 24 hours; finally, the oxygenating pipe (7) whose pipe wall is provided with the ventilation hole (11) is inserted into the graphite felt (2). The chinone containing oxygenating cathode of the present invention has the advantages of simple structure, low energy consumption and convenient and safe operation, and the preparation method of the cathode has the advantages of simple and convenient process flow, reliable quality of the cathode and no environmental pollution.
Description
Technical field: the present invention relates to a kind of containing the quinone oxygenated cathode and containing the preparation technology of quinone oxygenated cathode of alkaline hydrogen peroxide that be used to produce.
Background technology: industrial mass production hydrogen peroxide has following three kinds of methods: 1. heated oxide barium in the oxygen, dissolve barium peroxide with acid subsequently, thereby obtain hydrogen peroxide; 2. sulfuric acid or its salt are carried out electrolytic anodization,,, and obtain hydrogen peroxide then with its hydrolysis so that it is transformed into persulphate; 3. organism (the being generally anthraquinone) catalyzed oxidation that circulates is then with its reduction.Though people know other method, promptly produce hydrogen peroxide for some time, yet this method just just is being used for producing superoxol industrial recently with the cathodic reduction method of oxygen.The labour intensity of above-listed first kind of commercial run is big, and the required energy consumption height of second method is now seldom used.Variously anthraquinonely the solution that contains 70～90% (weight) hydrogen peroxide can be produced usually, therefore transportation and carrying cost can be reduced; Yet have a bit very important; promptly because the complicacy of these methods; the anthraquinone technological line requires the practicality of hydrogen source and the extensive use of the nonaqueous phase solvent of catalyst recirculation is provided; higher relatively capital and working cost have been caused; therefore these methods only help the scale operation of commerciality, batch production, are inapplicable to small-scale or situ production hydrogen peroxide.Since the sixties in last century, a lot of impressive progresses have been obtained in the research aspect the electroreduction oxygen production alkaline hydrogen peroxide, but up to now also less than the precedent that formally comes into operation with technical scale, trace it to its cause is exactly that these methods have run into all difficulties in dropping into industrial production, for example: 1, with the graphite granule be the method (for example US3969201) of cathode material, make this method reach industrial available working index, must use pure oxygen and require and work under elevated pressures, it is difficult that such working conditions causes electrode to maximize; 2, be cathode material with the carbon felt, " Development of Trickled-Bed Electrolyzer for On-SiteElectrochemical Production of Hydrogen Peroxide " (Joumal of theElectrochemical Society as Yamada etc., 1999,146 (7): 2487～2591), for making this method drop into industrial production, at the electrode outside need with the saturated repeatedly a large amount of round-robin cathode solution of oxygen, so complicated operation, running cost costliness; 3, be raw material with carbon black, gac or graphite, add the hydrophobic substance of tetrafluoroethylene class, make membranaceous oxygen reduction electrode (as US4384931, US4357217) on the net at metallic nickel.Also obtained working index preferably with this method, but still exist electrode and soaked into by buck and the shortcoming that lost efficacy, and every plate electrode all need be provided with wind box, make its structure complicated, especially when dropping into industrial application, to make hundreds of large size diaphragm, these diaphragm-operated Gas permeability uniformities are difficult for, so when maximizing, also meet difficulty.4, make cathode material (as US4067787) with graphite or glass charcoal, this patent is to reach industrial feasible working index, the catalyzer that in cathode solution, adds suitable concentration, as 2, the 7-anthraquinone disulphonate, the alternation that utilizes the oxidation state of catalyzer and go back ortho states is finished the preparation of alkaline hydrogen peroxide, and its working index is more satisfactory, but shortcoming is that (alkaline hydrogen peroxide) is mixed with a large amount of catalyzer in cathode product, needs a series of separation formalities to separate catalyzer and hydrogen peroxide.5, use contains the quinone air cathode, rely on the quinones substance that contains in the negative electrode carbon core to carry out the redox alternation response, the reaction process of anthraquinone preparing hydrogen peroxide transferred to carry out (as CN87103988) on the electrode, do not separate though this method does not need to carry out product afterwards, need to adopt low-pressure air under the condition of sealing, to move.
Summary of the invention: for solving the problem that prior art exists, the invention provides a kind of preparation method who contains quinone oxygenated cathode and negative electrode who is used to produce alkaline hydrogen peroxide, the quinone oxygenated cathode that contains of the present invention has simple in structure, it is low to produce the alkaline hydrogen peroxide energy consumption, easy to operate, safety, it is easy that the preparation method of negative electrode has technical process, negative electrode reliable in quality, characteristics free from environmental pollution.The quinone oxygenated cathode 12 that contains that is used to produce alkaline hydrogen peroxide of the present invention is made up of graphite felt 2, oxygenation pipe 7, has ventilating pit 11 on the tube wall of oxygenation pipe 7, at least one oxygenation pipe 7 of graphite felt 2 internal fixing.Described graphite felt 2 constitutes skeleton by low-density carbon-carbon composite, contains quinones substance in porous carbon-carbon composite.The preparation method who contains the quinone oxygenated cathode is: get graphite felt, putting into concentration and be 10% salpeter solution soaked 2 hours, take out the back distilled water flushing, be that 4% sodium hydroxide solution soaked 2 hours with concentration again, taking-up is dried after with distilled water flushing naturally, immersed then in the ethanolic soln of saturated 2-ethyl-anthraquinone 10-24 hour, drip after taking out and go redundant solution, again with drying naturally behind the distilled water flush away unnecessary alcohol solution, make in the graphite felt to form water-fast quinones substance crystallization, the oxygenation pipe 7 that has ventilating pit 11 on the tube wall is inserted in the graphite felt 2 get final product at last.The material of described oxygenation pipe 7 is tetrafluoroethylene.The present invention use be fixed with the anthraquinone catalyzer on the electrode contain the quinone oxygenated cathode, directly rely on negative electrode that electronics is provided, and in porous cathode, send into simultaneously oxygen, just can utilize quinones substance on electrode, to generate hydrogen peroxide through hocketing of redox reaction, not needing to carry out product separates, usedly contain the stable performance of quinone oxygenated cathode, do not need regular chemical treatment.The present invention has improved the aeration structure that contains quinone oxygenation electrode, interted the oxygenation pipe of some amount in negative electrode inside, can make oxygen from the whole negative electrode of negative electrode internal divergence, can make the negative electrode oxygenation abundant like this, there is not the dead angle, can be under the situation of direct normal pressure oxygen preparation alkaline hydrogen peroxide and obtain satisfied index, do not exist electrode soaked into by buck and the shortcoming that lost efficacy.Directly use normal pressure oxygen, the simple cost of equipment is low, installation and easy to operate.Use present device to produce alkaline hydrogen peroxide, reacted 1 hour, promptly can obtain the product that concentration is 10～20g/L, contain quinone oxygenated cathode operational conditions and effect stability, be subjected to the restriction of oxygenation less, can amplify operation, and do not need hydrogen peroxide is purified.Gained alkaline hydrogen peroxide solution of the present invention, the concentration that reaches bleached pulp and papermaking (contains 1%-2%H
2O
2), can be directly used in pulp and paper industry.The quinone oxygenated cathode that contains of the present invention has simple in structurely, produces low, easy to operate, the safety of alkaline hydrogen peroxide energy consumption, and it is easy that the preparation method of negative electrode has technical process, negative electrode reliable in quality, advantage free from environmental pollution.
Description of drawings: Fig. 1 is the structural representation that the present invention contains the quinone oxygenated cathode, and Fig. 2 uses to contain the fundamental diagram that the quinone oxygenated cathode is produced alkaline hydrogen peroxide.
Embodiment: being used to of (see figure 1) present embodiment produces the quinone oxygenated cathode 12 that contains of alkaline hydrogen peroxide and is made up of graphite felt 2, oxygenation pipe 7, have ventilating pit 11 on the tube wall of oxygenation pipe 7, three oxygenation pipes 7 are fixed in the graphite felt 2, and the oxygen inlet 8 of oxygenation pipe 7 is towards the below.Described graphite felt 2 constitutes skeleton by low-density carbon-carbon composite, contains quinones substance in porous carbon-carbon composite.The preparation method who contains the quinone oxygenated cathode is: get graphite felt, putting into concentration and be 10% salpeter solution soaked 2 hours, take out the back distilled water flushing, be that 4% sodium hydroxide solution soaked 2 hours with concentration again, taking-up is dried after with distilled water flushing naturally, immersed then in the ethanolic soln of saturated 2-ethyl-anthraquinone 10-24 hour, drip after taking out and go redundant solution, again with drying naturally behind the distilled water flush away unnecessary alcohol solution, make in the graphite felt to form water-fast quinones substance crystallization, the oxygenation pipe 7 that has ventilating pit 11 on the tube wall is inserted in the graphite felt 2 get final product at last.The material of described oxygenation pipe 7 is tetrafluoroethylene.
Principle of work: contain the fundamental diagram that the quinone oxygenated cathode prepares alkaline hydrogen peroxide and described in detail with provided by the present invention.Fig. 2 shows the device that the unit electrolytic bath that utilizes a plurality of acyclic types to arrange is produced hydrogen peroxide, be provided with two anolyte compartments 5 and two cathode compartments 6 in this electrolyzer 1, containing quinone oxygenated cathode 12 is made up of anthraquinone-modified graphite felt 2 and oxygenation pipe 7, anode 4 is DSA anodes, and cationic exchange membrane 3 is arranged between negative electrode and anode; At negative electrode, oxygen enters from oxygen inlet 8, be diffused into whole negative electrode, and the circulation buck enters anode from buck inlet 9, overflows from relief outlet 10, after the energising, sodium ion is swum to negative electrode by barrier film from anode, oxygen carries out two electronic reduction reactions containing on the quinone oxygenated cathode, generate alkaline hydrogen peroxide water solution, that is the sodium peroxide aqueous solution.In containing on the quinone oxygenated cathode of the present invention's preparation, when two electronic reduction reactions prepare hydrogen peroxide, have following two processes to carry out simultaneously:
(1) airborne
(2)
That is to say, contain the quinone oxygenated cathode except directly oxygen and water being reduced to HO
2 -+ OH
-Also the reaction process of anthraquinone preparation hydrogen peroxide is transferred on the electrode simultaneously and carried out outward.The concentration that electrochemistry oxygen cathodic reduction produces hydrogen peroxide is not suitable for it is concentrated and makes high hydrogen peroxide product and sell generally all below 5% (weight), because of its cost too high.But rare alkaline hydrogen peroxide solution is specially adapted to the bleaching industry of wood pulp.Except the bleaching of wood pulp, the basic solution of hydrogen peroxide also is fit to do other bleaching application and chemical bleaching operation, and in this class bleaching operation, the hydrogen peroxide of the electrochemical production of lower concentration does not need further to concentrate promptly can use.The hydrogen peroxide that utilizes the present invention to produce can be used for the production of Chemicals, can produce the superoxide of series, as organo-peroxides such as calcium peroxide, SPC-D, sodium peroxide, Sodium peroxoborate, Textone and benzoyl peroxides etc.Also can be used for disinfection sanitizer, deodovization agent of food, pharmaceutical sector etc.
Test 1: the effective working area of test electrode: 60cm
2, anode material: DSA electrode, cathode material: contain the quinone oxygenated cathode, thick 8mm, weight 1200g/m
2This moment is interspersed side by side 2 oxygenation pipes (oxygenation bore 3mm) on negative electrode, between the anode negative electrode, be separated with cation membrane, the cathode compartment volume: cathode compartment 5cm length * 1.5cm is wide * 13cm height (sulculus), that enter negative electrode is buck and oxygen (NaOH concentration 40g/L, oxygen is condition of normal pressure), move 1 hour, operational conditions and result are as shown in table 1:
The effect that table 1 changes voltage compares
| Voltage (V) | 1.2 | 1.4 | 1.6 | 1.8 | 2.0 | 2.2 |
| Electric current (A) | 0.42 | 0.65 | 0.81 | 1.09 | 1.15 | 1.39 |
| Current density (A/m 2) | 70 | 108 | 135 | 182 | 192 | 232 |
| H 2O 2Concentration (g/L) | 6.38 | 7.62 | 8.42 | 10.02 | 9.12 | 7.07 |
| Current efficiency (%) | 59.9 | 46.2 | 41.0 | 36.2 | 31.3 | 20.0 |
| Direct current consumption kWh/kgH 2O 2(100％) | 3.16 | 4.78 | 6.16 | 7.83 | 10.09 | 17.30 |
As can be seen from Table 1, current density raises along with the rising of voltage, and when voltage is 1.8V, current density is 182A/m
2The time, H
2O
2Concentration reach and be 10.02g/L to the maximum, current efficiency is 36.2%, direct current consumption is 7.83kWh/kgH
2O
2(100%).
Test electrode material, barrier film, operational conditions are with test 1, the effective working area of test electrode: 120cm
2, on negative electrode, interting 4 oxygenation pipes this moment side by side, the cathode compartment volume: 10cm length * 1.5cm is wide * the 13cm height, operational conditions and result are as shown in table 2:
The effect that table 2 changes voltage compares
| Voltage (V) | 1.8 | 2.0 | 2.2 |
| Electric current (A) | 1.2 | 2.2 | 2.9 |
| Current density (A/m 2) | 100 | 183 | 242 |
| H 2O 2Concentration (g/L) | 7.09 | 10.07 | 6.11 |
| Current efficiency (%) | 46.6 | 36.1 | 16.6 |
| Direct current consumption kWh/kgH 2O 2(100％) | 5.47 | 8.74 | 20.88 |
As can be seen from Table 2, current density raises along with the rising of voltage, H
2O
2Concentration also raise along with the rising of current density, when voltage is 2.0V, current density is 183A/m
2The time, H
2O
2Concentration reach and be 10.07g/L to the maximum, current efficiency is 36.1%, direct current consumption is 8.74kWh/kgH
2O
2(100%).
Use the result of vat and sulculus operation to be more or less the same H
2O
2Concentration be 10g/L, use contain quinone oxygenated cathode operational conditions and effect more stable, be subjected to the restriction of oxygenation less, can amplify operation, and not need hydrogen peroxide is purified.Gained alkaline hydrogen peroxide solution of the present invention, the concentration that reaches bleached pulp and papermaking (contains 1%-2%H
2O
2), can be directly used in pulp and paper industry.
Claims (4)
- What 1, be used to produce alkaline hydrogen peroxide contains the quinone oxygenated cathode, it is characterized in that containing quinone oxygenated cathode (12) is made up of graphite felt (2), oxygenation pipe (7), have ventilating pit (11) on the tube wall of oxygenation pipe (7), at least one oxygenation pipe (7) of graphite felt (2) internal fixing, described graphite felt (2) constitutes skeleton by low-density carbon-carbon composite, contains quinones substance in porous carbon-carbon composite.
- 2, according to claim 1 be used to produce alkaline hydrogen peroxide contain the quinone oxygenated cathode, the oxygen inlet (8) that it is characterized in that oxygenation pipe (7) is towards the below.
- 3, the preparation method who contains the quinone oxygenated cathode, it is characterized in that getting graphite felt, putting into concentration and be 10% salpeter solution soaked 2 hours, take out the back distilled water flushing, be that 4% sodium hydroxide solution soaked 2 hours with concentration again, taking-up is dried after with distilled water flushing naturally, immersed then in the ethanolic soln of saturated 2-ethyl-anthraquinone 10-24 hour, drip after taking out and go redundant solution, again with drying naturally behind the distilled water flush away unnecessary alcohol solution, make in the graphite felt to form water-fast quinones substance crystallization, the oxygenation pipe (7) that has ventilating pit (11) on the tube wall is inserted in the graphite felt (2) get final product at last.
- 4, the preparation method who contains the quinone oxygenated cathode according to claim 3 is characterized in that the material of described oxygenation pipe (7) is a tetrafluoroethylene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013514 CN1281791C (en) | 2004-01-14 | 2004-01-14 | Preparation method of oxygenated cathode and anode containing quinine used for production of alkaline hydrogen peroxide |
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|---|---|---|---|
| CN 200410013514 CN1281791C (en) | 2004-01-14 | 2004-01-14 | Preparation method of oxygenated cathode and anode containing quinine used for production of alkaline hydrogen peroxide |
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|---|---|
| CN1557994A CN1557994A (en) | 2004-12-29 |
| CN1281791C true CN1281791C (en) | 2006-10-25 |
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