CN1048293C - Alkaline hydrogen peroxide generator of adding non-ionic catalyst to cathode water solution - Google Patents
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- CN1048293C CN1048293C CN94107429A CN94107429A CN1048293C CN 1048293 C CN1048293 C CN 1048293C CN 94107429 A CN94107429 A CN 94107429A CN 94107429 A CN94107429 A CN 94107429A CN 1048293 C CN1048293 C CN 1048293C
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Abstract
The present invention belongs to the field of the preparation of inorganic compounds by electrochemical methods, which relates to a basic hydrogen peroxide generator in which a nonionic catalyst is added to a cathode aqueous solution. The nonionic compounds are not repulsed by a cathode, the satisfactory working index can be obtained under the condition of low concentration (5*10<-5>M), and therefore, the trouble of recovering the catalyst is also avoided. The catalyst can be precipitated from the solution after being used, and the pollution to water discharge caused by soluble organic compounds is avoided. The generator directly uses low pressure air (0.05MPa), has the advantages of low equipment cost and running cost, and is easy to realize industrialized application.
Description
The present invention relates to a kind of production method of alkaline hydrogen peroxide water solution.Belong to the electrochemical method technical field.
This century the fifties, after the industrialization of anthracene ester legal system hydrogen peroxide, because the decline of price, the Application Areas of hydrogen peroxide is enlarged day by day, thereafter people are in order to seek more economical production method, carried out number of research projects, one of method that wherein is hopeful most to drop into industrial application is the method for oxygen in cathodic reduction.The advantage of this method is: for the enterprise that needs alkaline hydrogen peroxide water solution in a large number provides rig-site utilization equipment, factory is by setting up alkaline hydrogen peroxide water solution generator, replace and buy the commodity hydrogen peroxide, can save the taking of concentrated expense, packing charge, transport charge, standing loss, current assets of hydrogen peroxide, significantly reduce the actual usage charges of hydrogen peroxide.
Since oxygen in water or in the buck solution degree all very little, if plan to develop hydrogen peroxide generator with industrial application value, must seek the mass transfer velocity that improves oxygen and prevent the method that side reaction produces, to guarantee when improving current density, increase throughput, keeping very high current efficiency.
In order to solve above-mentioned technical key issue, a lot of patented technologies have appearred, belong to different types of technological line.
United States Patent (USP) 4067787 provides a kind of technology that adds 2,7 anthraquinone disulfonic acid sodium catalyst 0.44mol/l at cathode water solution.
Its working conditions is:
Effective working area 0.36dm of test electrode
2,
Anode material-platinum,
Cathode material-vitreous carbon,
Between the anode negative electrode, be separated with cationic exchange membrane,
Contain NaOH 20g/l and catalyzer 0.44mol/l (181g/l) in the aqueous solution that negative electrode enters,
The oxygen that negative electrode enters: 8 l/h,
At the anode round-robin be: HNO
30.1mol/l.
The working index of electrode is:
Bath voltage: 4.2V,
Current density: 5A/dm
2,
The concentration of hydrogen peroxide in catholyte: 2.76g/l,
Current efficiency: 93%.
Its major defect is: because the higher 0.44mol/l of catalyst concn that adds in cathode water solution, be mixed with a large amount of catalyzer in the hydrogen peroxide that negative electrode is produced, so the hydrogen peroxide that is produced can't directly use at the scene, the step that must remove catalyzer below the process:
1, adds slaked lime in the hydrogen peroxide that negative electrode produces, make hydrogen peroxide change CaO into
28H
2O precipitation is separated out, and left NaOH and catalyst mixture in the aqueous solution sent negative electrode again back to and used;
2, with CaO
28H
2O is placed in the encloses container, adds CO
2Make it to generate CaCo
3↓+H
2O
2, then CaCO
3Precipitate and separate is gone out, and will obtain H
2O
2
The Chinese patent 87103988 of inventor's development provides a kind of " producing electrolyzer and method for making thereof that alkaline hydrogen peroxide is used ", the method that this patent adds catalyzer is to use the negative electrode that contains naphtoquinone compounds, its method for making is: earlier 2,6 anthraquinone disulfonic acid sodium water solutions (negatively charged ion) of 0.5% concentration and dodecyl benzyl dimethyl ammonium chloride (positively charged ion) aqueous solution; Again cathode carbon felt is placed in this mixing solutions, in the hole of carbon felt, generates a large amount of needle-like crystals through diel.This acicular catalyzer and the cathode carbon felt that is full of electronics have a large amount of point of contact, when the ketone group of plane of crystal is reduced to hydroxyl, have increased wetting ability, and needle is absorbed on the carbon cathode through dissolving gradually again, finishes catalytic process.
The main performance index of this patent is:
The throughput 338 gram H of unit cathode area
2O
2(100%)/m
2H
The direct current consumption 4.55KWh/kgH of unit output
2O
2(100%)
Its main drawback is: the negative electrode that contains naphtoquinone compounds is too short work-ing life, through about one month continuous operation, acicular catalyzer has consumed because of dissolving gradually, must be to containing the negative electrode regeneration of naphtoquinone compounds, its regeneration way is earlier through washing and centrifuge dripping, be placed on drying in the hot-air oven again, contain naphtoquinone compounds then once again and handle, so the carbon felt porosity after the regeneration is not as new product, acicular catalyzer crystal recoverable amount significantly reduces, again life-span time spent shorter, especially the carbon felt is dried in air, easily oxidation of surface, resistance raises, cause the carbon felt to be scrapped at last, therefore regenerated hell to pay, and the expense height.
The object of the present invention is to provide a kind of production method of alkaline hydrogen peroxide water solution, in the cathode water solution of alkaline hydrogen peroxide generator, add the nonionic naphthoquinone derivatives that anionic compound and-ium compound reaction with quinones generate temporary dissolubility and make catalyzer, in concentration 10
-4-10
-5Under the condition of mol/l, keep higher current efficiency and improve throughput, make the alkaline hydrogen peroxide water solution that does not contain catalyzer, reach the purpose that the hydrogen peroxide of production can rig-site utilization.
The object of the present invention is achieved like this: a kind of production method of alkaline hydrogen peroxide water solution, it is characterized in that: the alkaline hydrogen peroxide generator that this production method is used be configured to the two ends rubber seal, negative electrode is stainless steel plate and graphitized carbon felt, anode is stainless steel plate and plastic support network, the centre is provided with cation exchange membrane, alkaline hydrogen peroxide generator is separated into cathode compartment and anolyte compartment, end at cathode compartment is provided with air-in and two soft water inlets, the other end is provided with the outlet of alkaline hydrogen peroxide water solution, be provided with the inlet of circulation buck at an end of anolyte compartment, the other end is provided with the outlet of circulation buck; Its technical process is for importing the anionic compound of quinones and the-ium compound aqueous solution respectively by above-mentioned two soft water inlet, these two kinds of compounds react when meeting, generate the non-ionic type naphthoquinone derivatives catalyzer of temporary dissolubility, this catalyst concentration is 10
-4-10
-5Mol/l, the airborne oxygen catalytic reduction that will import cathode compartment at the catalyzer of this temporary dissolubility of cathode compartment is HOO
-Ion and HO
-Ion, the positively charged ion in anolyte compartment's round-robin buck passes above-mentioned cation exchange membrane and enters cathode compartment and HOO simultaneously
-Ion and HO
-Ion combination generates alkaline hydrogen peroxide water solution, draws from the outlet that is positioned at the cathode compartment the other end, and wherein contained temporary dissolubility catalyzer crystallization is gradually separated out, and makes the not alkaline hydrogen peroxide water solution of residual catalyst.
This quinones anionic compound is a sodium anthraquinone sulfonate, or anthraquinone disulphonate, or alkyl naphthoquinones sodium sulfonate; This is-ium compound to be stearyl dimethyl benzyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.
Characteristics of the present invention are: catalyzer of the present invention is under the very little condition of concentration (for example 10
-4-10
-5Mol/l) anionic compound of quinones and-ium compound reaction generate the non-ionic type naphthoquinone derivatives of temporary dissolubility, they form the time that insolubles needs a few hours through overbunching, and cathode water solution is counted from the under meter metering, end to generating outside the alkaline hydrogen peroxide solution discharge producer, total has only the several minutes time, therefore it is very sufficient utilizing the time of the non-ionic catalyst of this temporary dissolubility, catalytic efficiency is higher, reach higher current efficiency and throughput, and make equipment simple with operation is very easy.
Further specify below in conjunction with preferred embodiment and accompanying drawing:
Fig. 1 is an alkaline hydrogen peroxide generator structural representation of the present invention.Fig. 2 is the test-results graphic representation of the embodiment of the invention 1.
Embodiment 1 catalyzer effect test of the present invention.Test 1: in cathode water solution, do not add the test of catalyzer.Test conditions: the effective working area of test electrode: 1.05dm
2, anode material: stainless steel plate, cathode material: graphitized carbon felt, thick 7mm, weight 800g/m
2, between the anode negative electrode, be separated with cation membrane, what enter negative electrode is that soft water and air (air pressure 0.02Mpa, 24 liters/hour of flows) buck are in anode circulation (1.7 liters/hour of NaOH concentration 120-140 grams per liter internal circulating loads).Test-results sees Table 1, and wherein bath voltage selects three kinds of changing value I, II, III tables one not to add the test-results of catalyzer in cathode water solution
Test 2: the test that adds catalyzer of the present invention in cathode water solution: alkaline hydrogen peroxide generator structure of the present invention as shown in Figure 1.Among the figure: 1 for soft water inlet (containing the quinones anionic compound) 2 be alkaline H for soft water inlet (containing organic cation compound) 3 for gas inlet 4
2O
2Aqueous solution outlet 5 is that negative electrode stainless steel plate 8 is that graphitized carbon felt 9 is rubber pad test electrode together test 1 for anode stainless steel plate 11 for plastic support network 12 for cation membrane 10 for circulation buck inlet 6 for circulation buck+oxygen outlet 7.The catalyzer of the present invention that adds in cathode water solution is: add 1 * 10 in 50% water
-4Add 1 * 10 in 2-sodium anthraquinone sulfonate 50% water of mol/l
-4The dodecyl benzyl dimethyl ammonium chloride of mol/l, the concentration that both react the nonionic naphthoquinone derivatives that forms temporary dissolubility is 5 * 10
-5Mol/l, its chemical equation that forms temporary dissolubility catalyzer is as follows:
Test-results sees Table two, and wherein bath voltage selects two kinds of changing value IV and V that the data of table one and table two gained are mapped as shown in Figure 2, and among the figure: single line is a catalyst-free in the negative electrode water,
I | II | III | |
Bath voltage (V) | 1.82 | 2.01 | 2.21 |
Electric current (A) | 3.1 | 4.6 | 6.7 |
Current density A/m 2 | 299 | 444 | 646 |
Anode buck temperature out (℃) | 27 | 30 | 34 |
Cathode product flow (l/h) | 0.105 | 0.105 | 0.105 |
Concentration of hydrogen peroxide (g/l) | 17.15 | 18.80 | 23.25 |
Naoh concentration (g/l) | 36.74 | 55.80 | 76.52 |
Working index | |||
Alkali compares NaOH/H 2O 2 | 2.14 | 2.93 | 3.29 |
Current efficiency (%) | 91.5 | 67.5 | 57.5 |
Direct current consumption kWh/kgH 2O 2(100%) | 3.13 | 4.69 | 6.07 |
Throughput kgH 2O 2(100%)/m 2·h | 0.171 | 0.188 | 0.232 |
Two-wire is to add temporary dissolubility non-ionic type naphthoquinone derivatives catalyzer of the present invention in the negative electrode water.
Table two adds the test-results of catalyzer of the present invention in cathode water solution
IV | V | |
Bath voltage (V) | 2.07 | 2.48 |
Electric current (A) | 6.4 | 10.7 |
Current density A/m 2 | 618 | 1019 |
Air pressure (MPa) | 0.02 | 0.025 |
Air flow quantity (l/h) | 21 | 51 |
Anode buck temperature out (℃) | 34 | 42 |
Cathode product flow (l/h) | 0.11 | 0.175 |
Concentration of hydrogen peroxide (g/l) | 34.87 | 38.42 |
Naoh concentration (g/l) | 80.33 | 82.72 |
Working index | ||
Alkali compares NaOH/H 2O 2 | 2.3 | 2.15 |
Current efficiency (%) | 94.7% | 99% |
Direct current consumption kWh/kgH 2O 2(100%) | 3.45 | 3.95 |
Throughput kgH 2O 2(100%)/m 2·h | 0.382 | 0.64 |
Consult Fig. 2 and table one and table two:
Shown in single line among table one and Fig. 2, when the raising bath voltage was brought up to 2.21V by 1.82V, it increased current density 299 → 646A/m in the test that does not add catalyzer in the cathode water solution
2, causing that current efficiency descends 91.5 → 57.5%, alkali is than the 2.14 → 3.29NaOH/H that raises
2O
2, and throughput increases little 1.171 → 0.232kgH
2O
2/ m
2H, the direct current consumption of therefore producing hydrogen peroxide obviously increases by 3.13 → 6.07kWh/kgH
2O
2Its reason an aforesaid quadrielectron reduction pair reaction occurred and has caused.
The test that adds catalyzer of the present invention in cathode water solution is shown in the two-wire among table two and Fig. 2, when improving bath voltage 2.07 → 2.48V, 618 → 1019A/m when increasing substantially current density
2, throughput significantly improves 0.382 → 0.64kgH
2O
2/ m
2H, current efficiency has kept very high level 94.7 → 99%, and the alkali ratio remains at 2.3 → 2.15NaOH/H about theoretical value
2O
2
Above-mentioned simultaneous test illustrates catalyzer of the present invention when improving bath voltage and increasing substantially current density, and the ability of producing hydrogen peroxide can be multiplied, and current efficiency remains on more than 94%, and the alkali ratio remains on theoretical value (2.3-2.15NaOH/H
2O
2).It is the effect that catalyzer of the present invention has alkaline hydrogen peroxide generator to improve significantly current efficiency and increases yields of hydrogen peroxide and improve the quality.The analysis of causes is as follows:
When (1) not having catalyzer, shown in single line among table 1 and Fig. 2, the oxygen in the experiment is in the reduction of negative electrode
Reaction is:
Analyze from equilibrium electrode potential: HO
2 -Further be reduced to OH
-Current potential be E
0=0.89V is than generating HO
2 -It is positive many that the ionic current potential is wanted, in case visible O
2Molecule is O at the Ka band electroreduction
2 -After, be not easy to rest on HO
2 -Ionic intermediateness and will further be reduced to OH
-But because HO
2 -Be subjected to the repulsion of negative electrode, make HO
2 -Be reduced to OH
-Electropotential obviously shift to losing side.This is can produce HO when bath voltage is very low
2 -Reason.When improving bath voltage in order to improve current density, the negative electrode negative potential goes beyond the limit, at this moment HO
2 -Further be reduced to OH
-Quadrielectron reduction reaction obviously occur, this is to cause in table one test afterwards that current efficiency descends, alkali is than the reason that rises in the hydrogen peroxide of generation.
When (2) in cathode water solution, adding catalyzer of the present invention, because catalyst replaced oxygen in the reaction of cathodic reduction is:
Wherein to represent the reduction potential of derivative group naphthoquinone derivatives catalyzer be 0.15V to X, and O
2→ O
2 -Reduction potential be-0.56V, therefore make reduction potential move 0.71V after adding catalyzer of the present invention to pros, this is very favorable factor, when its result improves bath voltage at hydrogen peroxide generator, when current density surpasses 1000A/m
2, still keep high current efficiency.Illustrate to add that the mechanism of reduction reaction has become behind the catalyzer of the present invention, improved O
2Mass transfer process and limited the generation of pair reaction.
(3) non-ionic catalyst used in the present invention owing to not repelled by negative electrode, under the minimum situation of concentration, has reached satisfied working index by improving operating frequency.Particularly importantly: do not have the trouble that must reclaim catalyzer, develop into rig-site utilization equipment so have ready conditions.
(4) by quinones anionic compound and-ium compound, under lower concentration 10
-4~10
-5Mol/l generates the temporary dissolubility non-ionic compound of molecular state when initial reaction, this moment, dispersity was the highest, after finishing catalysis by negative electrode, to assemble after a few hours for crystalline solid and separate out from solution, these characteristics are very important, and it makes environment avoid the pollution of solubilised state naphthoquinone derivatives.In other words this " dissolubility temporarily " is a rare advantage, because if utilize the means of organic synthesis, develop water-soluble quinones non-ionic derivate and use as catalyzer, then must manage it is removed away from solution, just can prevent to cause environmental pollution, that will increase cost greatly.
Using 2-sodium anthraquinone sulfonate and dodecyl benzyl dimethyl ammonium chloride in the embodiments of the invention is the most cheap chemical as catalyzer; but be not only to be that these two kinds of chemical can form quinones non-ionic derivate catalyzer; use other quinones anionic compound instead and use other-ium compound non-ionic type naphthoquinone derivatives catalyzer of making instead, all belong to protection scope of the present invention.
Embodiment 2
Catalyzer of the present invention can also make with other quinones anionic compound and-ium compound reaction, have same effect, concrete effect sees Table three: (catalyst concn is with test 2) table three: other quinones anionic compounds and-ium compound effect
The hydrogen peroxide generator that adds non-ionic type naphthoquinone derivatives catalyzer of the present invention in cathode water solution has the following advantages:
I | II | |
The quinones anionic compound | 2,7 anthraquinone disulphonates | The methyl naphthoquinone sodium sulfonate |
-ium compound | Stearyl dimethyl benzyl ammonium chloride | Dodecyl benzyl dimethyl ammonium chloride |
Bath voltage (V) | 2.07 | 2.11 |
Electric current A) | 6.5 | 5.2 |
Current density (A/m 2) | 627 | 495 |
Air pressure (Mpa) | 0.02 | 0.02 |
Air flow quantity (l/h) | 27 | 27 |
Anode buck temperature out ℃ | 30 | 30 |
Negative electrode produces hydrogen peroxide flow (l/h) | 0.09 | 0.07 |
Concentration of hydrogen peroxide (g/l) | 44.52 | 44.88 |
Naoh concentration (g/l) | 94.7 | 106.54 |
Working index | ||
The alkali ratio | 2.13 | 2.37 |
Current efficiency % | 97.2 | 88.8 |
Direct current consumption kwh/KgH 2O 2(100%) | 3.36 | 3.74 |
Throughput KgH 2O 2(100%)m 2·h | 0.4 | 0.28 |
1. catalyzer of the present invention makes alkaline hydrogen peroxide generator significantly increase the output of hydrogen peroxide.
2. because catalyst concn of the present invention is 10
-4~10
-5Mol/l makes the hydrogen peroxide of generation not contain excess catalyst, and purity is higher, can on-the-spotly use, and exempts the trouble of removing catalyzer.
3. needn't use huge carbon element of surface-area and water repellent agent to do negative electrode, the life problems that lost efficacy so do not exist negative electrode to be soaked into by buck.
4. used negative electrode does not need regular chemical treatment, and catalyst system therefor does not need to do recovery.
5. directly use low pressure 0.05MPa air, the simple cost of equipment is low.Installation and easy to operate, working cost is low.
Claims (3)
1, a kind of production method of alkaline hydrogen peroxide water solution, it is characterized in that: the two ends that are configured to of the alkaline hydrogen peroxide generator that this production method is used seal with rubber pad (12), negative electrode is stainless steel plate (7) and graphitized carbon felt (8), anode is stainless steel plate (10) and plastic support network (11), the centre is provided with cation exchange membrane (9) alkaline hydrogen peroxide generator is separated into cathode compartment and anolyte compartment, end at cathode compartment is provided with air-in (3) and two soft water inlets (1), (2), the other end is provided with the outlet (4) of alkaline hydrogen peroxide water solution, be provided with the inlet (5) of circulation buck at an end of anolyte compartment, the other end is provided with the outlet (6) of circulation buck; Its technical process is for importing the anionic compound of quinones and the-ium compound aqueous solution respectively by above-mentioned two soft water inlets (1), (2), these two kinds of compounds react when meeting, generate the non-ionic type naphthoquinone derivatives catalyzer of temporary dissolubility, this catalyst concentration is 10
-4-10
-5Mol/l, the airborne oxygen catalytic reduction that will import cathode compartment at the catalyzer of this temporary dissolubility of cathode compartment is HOO
-Ion and HO
-Ion, the positively charged ion in anolyte compartment's round-robin buck passes above-mentioned cation exchange membrane and enters cathode compartment and HOO simultaneously
-Ion and HO
-Ion combination generates alkaline hydrogen peroxide water solution, draws from the outlet (4) that is positioned at the cathode compartment the other end, and wherein contained temporary dissolubility catalyzer crystallization is gradually separated out, and makes the not alkaline hydrogen peroxide water solution of residual catalyst.
2, the production method of alkaline hydrogen peroxide water solution as claimed in claim 1 is characterized in that: this quinones anionic compound is a sodium anthraquinone sulfonate, or anthraquinone disulphonate, or alkyl naphthoquinones sodium sulfonate.
3, the production method of alkaline hydrogen peroxide water solution as claimed in claim 1 is characterized in that: this is-ium compound to be stearyl dimethyl benzyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.
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CN104372371B (en) * | 2014-09-24 | 2017-10-17 | 南开大学 | A kind of hydrogen peroxide generator and the method for the processing of organic waste water power Fenton |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4067787A (en) * | 1974-11-13 | 1978-01-10 | Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung | Method of making hydrogen peroxide |
US4533443A (en) * | 1983-10-19 | 1985-08-06 | Massachusetts Institute Of Technology | Production of hydrogen peroxide |
US4572774A (en) * | 1983-10-19 | 1986-02-25 | Massachusetts Institute Of Technology | Apparatus for production of hydrogen peroxide |
CN1006468B (en) * | 1987-06-04 | 1990-01-17 | 中国人民解放军88352部队 | Air electrode for producing basic hydrogen peroxide and its manufacturing method |
-
1994
- 1994-07-21 CN CN94107429A patent/CN1048293C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4067787A (en) * | 1974-11-13 | 1978-01-10 | Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung | Method of making hydrogen peroxide |
US4533443A (en) * | 1983-10-19 | 1985-08-06 | Massachusetts Institute Of Technology | Production of hydrogen peroxide |
US4572774A (en) * | 1983-10-19 | 1986-02-25 | Massachusetts Institute Of Technology | Apparatus for production of hydrogen peroxide |
CN1006468B (en) * | 1987-06-04 | 1990-01-17 | 中国人民解放军88352部队 | Air electrode for producing basic hydrogen peroxide and its manufacturing method |
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