CN105525307A - Method and device for preparing composite oxidizing agent - Google Patents
Method and device for preparing composite oxidizing agent Download PDFInfo
- Publication number
- CN105525307A CN105525307A CN201510945875.3A CN201510945875A CN105525307A CN 105525307 A CN105525307 A CN 105525307A CN 201510945875 A CN201510945875 A CN 201510945875A CN 105525307 A CN105525307 A CN 105525307A
- Authority
- CN
- China
- Prior art keywords
- tank room
- electrode
- electrodes
- equipment
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
Abstract
The invention relates to a method and device for preparing a composite oxidizing agent. The device comprises an electrolysis chamber which further comprises a stacking type electrode sequence; all electrodes of the stacking type electrode sequence are supported through supporting pieces in a series manner, and an electrolyte channel is formed between every two adjacent electrodes; and all electrodes located between the electrodes at the two ends of the stacking type electrode sequence are full electric conduction diamond electrodes. By means of the method and device, the structure of the electrolysis chamber of a device for preparing the composite oxidizing agent and the process are optimized, so that the device for preparing the composite oxidizing agent can work under high electric current density; and the composite oxidizing agent with the high oxygen evolution potential can be obtained, and the running with high-current efficiency can be achieved.
Description
Technical field
The present invention relates to a kind of technical field of electrochemistry, especially a kind of electrochemical principle that utilizes is prepared the method for composite oxidant and prepares the equipment of this composite oxidant.
Background technology
The main component of oxygenant is the oxidizing substance with certain oxidizing potential, oxygenant common on market has liquid chlorine, hypochlorous acid, hypochlorite, ozone, dioxide peroxide, hydrogen peroxide etc., all possess certain oxidizing potential, be widely used in the fields such as sterilization, sterilization, cleaning, the oxidation also for the reduction class material be made up of sulfide, organism sewage, foul smell etc. is removed.The oxidizing potential of common oxidants is followed successively by: fluorine and superoxide 3.0v, hydroxy radical qiao 2.8v, ozone 2.1v, hydrogen peroxide 1.77v, potassium permanganate 1.7v, dioxide peroxide 1.5v, chlorine 1.4v, secondary chlorine 1.36v.Its oxidation capacity of oxygenant that current potential is higher is stronger.Wherein ozone oxidation current potential is high, possesses Strong oxdiative ability, but easily decomposes, once there is leakage can cause severe safety problem; Liquid chlorine is commonly used because cost is low, if but leak, not only gas toxicity is high, and easily explodes; Clorox performance is gentleer, but oxidisability is weak, needs higher working concentration, and easily forms secondary pollution; Dioxide peroxide extremely unstable, needs matching while using, and needs situ activation, and it is produced raw material and there is hidden peril of explosion equally.Hydrogen peroxide is with low cost, but also easily blasts in higher concentrations.In a word, existing single-oxidizer ubiquity uses, store, transit link safe, healthy, environmental issue.In addition, there is anti-medicine problem for sterilization and disinfection use for a long time.
Can produce composite oxidant by the mode of anode electrolysis an alkali metal salt or acid, be a kind of mode of production of safe green comparatively speaking, but there is the bottleneck of material and technology aspect in prior art.
Such as, the generating process adopting electrolytic chlorination sodium solution to produce based on clorox is more representative with Chinese patent application CN201010230119.The prior art have employed compound series connection titanium-based metal oxide compound (ruthenium oxide) electrode of symmetric design, can produce the solution of about 3500ppm concentration.According to the turnout parameter of 11kg/h available chlorine (FAC) disclosed in it, need 9.6m
2the electrodes of points of 8 groups series connection (efficient anode area is 4.8m
2), working current is 1500A.Can convert real work current density is only had an appointment 300A/m
2, current efficiency only has 70%.
In addition, the steady anode (DimensionStableAnode, DSA) of employing titanium base ruthenium (Ru) iridium coating layer type of the prior art, also there is a fatal problem is exactly RuO
4pollution problem and the too low problem of coating life, the ruthenium dioxide in coating can be further oxided as highly toxic RuO
4be dissolved in solution, therefore adopt the electrode of ruthenium system coating can not be used for the application relevant to food safety.And when the coated anode work of ruthenium system at higher current densities time, when high groove pressure, at 10000A/m
2under above current density, coating promptly can decompose stripping, and the life-span is generally no more than 100 hours.About the principle of DSA technology see prior art " the DSA anode of high-performance multipurpose " (plating and covering with paint, volume the 3rd phase June the 23rd in 2004, Xie Suling), can be quoted as a reference herein.
Again such as, the generating process adopting electrolysis acid to produce based on hypochlorous acid is more representative with US Patent No. 6227141.The prior art discloses and adopt platinized electrode electrolysis concentrated hydrochloric acid generate chlorine and produce the technique of the disinfecting liquid of 14ppm based on hypochlorous acid with water mixed diluting, its thinking improves to make hypochlorous acid productive rate by obtaining lower bath voltage, and obtain comparatively less energy-consumption.In embodiment 10 disclosed in it, produce 10000l/hr, the hypochlorite solution of 14ppm, the namely FAC productive rate of 140g/h, need the platinum electrode of 17 230 square centimeters, its mode of connection is equivalent to 8 groups of parallel electrolytic grooves, under every groove is operated in the electric current of 105 peaces, although working current density can reach 4565A/m2, actual current efficiency is only 12.6%.
And, although can work under higher current density, there is cost high, the problem that current efficiency is low, be only confined to small-scale Application Areas in the platinum group anode that the prior art adopts.
Because working current density and current efficiency weigh the parameter directly perceived of producer space hold and electrode usage quantity, under given FAC productive rate obtains condition, higher current density and current efficiency mean less electrode area usage quantity and less space hold.
In above-mentioned prior art, although the electrolytic sodium chloride of first section of prior art can obtain the current efficiency of 70%, current density is very low, only has 300A/m
2.And though the electrolysis hydrochloric acid of second section of prior art can work under higher current density, current efficiency is very low, only has 12.6%.
Such as similar with second section of prior art, US Patent No. 3616355 is also utilize platinized platinum for electrode, obtains noble potential oxygenant by improving bath voltage, and such as its setting chlorine ion concentration is 21000ppm, and apply the voltage of 10v, current density is 7500A/m
2, the solution containing higher proportion dissolved ozone can be obtained.Its principle is owing under high potential, effects of ion loses velocity of electrons and accelerates, thus add the free radical that some lose electronics, become hydroxy radical qiao as hydroxide ion loses electronics, such as oxyradical, chlorine radical all can of short durationly be formed, form again more stable noble potential oxide compound stable existence in water afterwards, form ozone, dioxide peroxide, the hydrated ion state of hydrogen peroxide etc.After measured, ozone can relatively hypochlorite at least 2% ratio exist, this makes unit concentration be increased in the performance of FAC blending oxidizing agent.The formation concentration of this type of noble potential oxide compound and the oxygen evolution potential of electrode closely related, oxygen evolution potential increases with the increase of current density, upper example adopts the oxygen evolution potential of platinum group anode under the current density of 7500A/m2, to be about 1.9v (see " research of platinized titanium electrode ", Guangzhou non-ferrous metal journal the 10th volume the 2nd phase, in November, 2000, Zhang Jianhua), but there is the low problem of current efficiency equally in the platinum group anode adopted.Therefore, as the oxidant mixture of noble potential efficiently will be produced, need to find a kind of new processing unit, can also run with high current efficiency in order to obtain oxygen evolution potential at higher current densities simultaneously.
Summary of the invention
The present invention proposes a kind of equipment preparing composite oxidant, comprise tank room, described tank room comprises support housing, described support housing is respectively equipped with fluid inlet and liquid outlet; Wherein, described tank room comprises stacked electrode sequence further, and it is arranged on the inside of described support housing; Described stacked electrode sequence has multiple electrode being separated setting side by side, is supported in described support housing in a series arrangement between each electrode by strut member, is provided with the electrolyte passage being communicated with described fluid inlet and liquid outlet between two adjacent described electrodes; The described electrode being positioned at the two ends of described stacked electrode sequence is respectively the first end electrodes and the second end electrodes, first and second end electrodes described is respectively equipped with the terminal stud for connecting power supply, and the described electrode between first and second end electrodes described is full conductive diamond material electrodes.
Preferably, the thickness of described full conductive diamond material electrodes is 0.5 ~ 5 millimeter.
Preferably, the spacing of any pair electrode of described tank room is between 0.5 millimeter to 10 centimetres.
Preferably, the electric conductivity of the electrolytic solution in described tank room between 10ms/cm to 500ms/cm, preferably, between 20ms/cm to 200ms/cm.
Preferably, described equipment comprises further: chemicals dosing plant; Reactor, it has dosing mouth and discharge outlet, and described reactor is connected with described chemicals dosing plant by described dosing mouth; Pump, the fluid inlet of described tank room is connected with described discharge outlet by described pump.
Preferably, described equipment comprises further: register, and described register connects tank room and described reactor respectively; Self-stip control device, it is connected with the supply unit be carried on described tank room with described tank room respectively.
Present invention also offers a kind of method utilizing aforesaid device to prepare composite oxidant, described method comprises the steps:
A, power supply is loaded into described tank room by described terminal stud, makes the current density on described full conductive diamond material electrodes reach 5000 ~ 25000A/m
2;
B, the ionogen in described chemicals dosing plant to be joined in described reactor, make electrolytic solution;
C, make described electrolytic solution enter described tank room by described pump, and enter between each electrode from the fluid inlet of described tank room, and produce composite oxidant, described composite oxidant is discharged by described liquid outlet.
Preferably, described equipment comprises register further, and described register connects described tank room and described reactor respectively and carries out temperature control to it; Wherein, the working temperature controlling described tank room is 15 ~ 35 degrees Celsius.
Preferably, the flow velocity flowing through the electrolytic solution of the electrode of described tank room by described pump control is 0.1 ~ 100 liter/min/100 square centimeters.
Preferably, described equipment also comprises self-stip control device, and described self-stip control device is provided with the cleaning interval that work period, rest period and positive and negative electrode are exchanged; Wherein, the described work period terminate after after described rest period, enter the described cleaning interval again.
The present invention is by the optimization to the Structure and energy of the tank room of the equipment for the preparation of composite oxidant, thus the equipment preparing composite oxidant of the present invention can be worked at higher current densities, the composite oxidant of oxygen evolution potential can be obtained, and can run with high current efficiency.The composite oxidant of the present invention respective outer side edges such as tank room, specified property anode and cathode material, power supply, thrust pump, register, self-stip control device of being optimized structure by employing is produced, and can produce the high-performance oxygenant for different application.The steady current density of the electrode in tank room of the prior art can not more than 1500A/m
2, too high current density easily makes electrode rapid failure.Have employed full conductive diamond material electrodes in tank room of the present invention, it can at 5000 ~ 40000A/m
2current density range under long-time stable work, can obtain commercial scale produce novel high-performance, noble potential combined oxidation agent solution.
Accompanying drawing explanation
The following drawings is only intended to schematically illustrate the present invention and explain, not delimit the scope of the invention.Wherein,
Fig. 1 display be the structural representation of the tank room of the equipment for the preparation of composite oxidant according to a specific embodiment of the present invention;
Fig. 2 display be the structural representation preparing the equipment of composite oxidant according to another specific embodiment of the present invention.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and effect, now contrast accompanying drawing and the specific embodiment of the present invention is described.Wherein, identical parts adopt identical label.
As shown in Figure 1-2, wherein, Fig. 1 display is the structural representation of the tank room of the equipment for the preparation of composite oxidant according to a specific embodiment of the present invention; Fig. 2 display be the structural representation preparing the equipment of composite oxidant according to another specific embodiment of the present invention.Visible with reference to accompanying drawing, the present invention proposes and a kind ofly prepare the equipment of composite oxidant and utilize this equipment to prepare the method for composite oxidant, wherein, as shown in Figure 1, equipment of the present invention comprises tank room 10, and tank room 10 comprises support housing 11 and stacked electrode sequence 12.Support housing 11 is respectively equipped with fluid inlet 11a and liquid outlet 11b.Stacked electrode sequence 12 is arranged on the inside of support housing 11, stacked electrode sequence 12 has multiple electrode being separated setting side by side, be supported in support housing 11 in a series arrangement by strut member 100 between each electrode, wherein said strut member 100 is by making the material of acid-alkali-corrosive-resisting.The electrode being positioned at the two ends of stacked electrode sequence 12 is respectively the first end electrodes 12a and the second end electrodes 12b, first, two end electrodes 12a, 12b is respectively equipped with the terminal stud for connecting power supply, be positioned at first, two end electrodes 12a, electrode between 12b is full conductive diamond material electrodes, it is by full conductive diamond material (FMCD, FullMaterialConductiveDiamond) make that (whole electrode is all made up of conductive diamond material, such as can adopt the electrode that the FMCD of AMTechnologies (AMT) Company makes).The electrolyte passage being communicated with fluid inlet 11a and liquid outlet 11b is provided with, as shown in the figure between two adjacent electrodes.Wherein, the steady FMCD of the preferred type of the present invention develops out on the basis of film-type conductive diamond material, and this material is already commercial, commercially can make full conductive diamond material electrodes by post-treatment, this electrode is lamellar in diagram, can tolerate up to 40000A/m
2current density even higher, the life-span can reach more than 5 years.
One of the electrolyzer of the above embodiment of the present invention and prior art is not significantly both, what the electrode in the mid-way of formation stacked electrode sequence 12 of the present invention adopted is full conductive diamond material electrodes, the reason adopting conductive diamond electrode is because diamond electrode has very high oxygen evolution potential, therefore consider to be that master produces blending oxidizing agent with oxygen evolution reaction, the standard hydrogen-evolution overpotential of diamond electrode is-1.2v, theoretic voltage across poles is more than 3.4v, just can produce a large amount of free radicals, thus composite oxidant of the present invention can be generated by chain-react further.
Know-why and the application of associated conductive diamond electrode can see prior art " application of diamond coating electrode " (scientific and technical innovation Leaders, 24th phase in 2008, Du Haoming etc.), also can see " preparation of diamond coating electrode and application in the treatment of waste water thereof " (Shanghai Communications University's master thesis, Yang little Qian, 2003).A kind of preparation method of titanium base boron-doping diamond coating electrode is disclosed in Chinese patent application CN201110182167.0, the device of the full diamond coatings of a kind of preparation based on hot wire process is disclosed in Chinese patent application CN200910029305.4, wherein all be referred to correlation technique content and the purposes of associated conductive diamond coatings material, quote as a reference herein.
Although above-mentioned prior art mentions that conductive diamond material is used as the principle and advantage of electrode, but do not use as disclosed in the above embodiment of the present invention.This is because existing conductive diamond electrode is mostly film-type conductive diamond electrode, it only has one side to possess electrolysis performance, first end electrodes 12a and the second end electrodes 12b can only be used as, if used as target series connection, right capacitance structure cannot be formed into, can not the present invention be applied to.Certainly, only target is replaced and help the problem that conductive diamond material electrodes can only solve generation composite oxidant, as the oxidant mixture of noble potential efficiently will be produced, still need to carry out further process optimization to aforesaid device, will further describe this below.
During aforesaid device work of the present invention, power supply is by load voltage on first and second end electrodes 12a, the 12b of terminal stud in tank room 10, electrolytic solution enters from the fluid inlet 11a of tank room 10 between each electrode of being connected in series and carries out electrolytic reaction, thus generation composite oxidant, the composite oxidant of generation flows out from liquid outlet 11b.
In the present embodiment, except being positioned at two ends outermost first in the electrode of stacked electrode sequence 12, two end electrodes 12a, other electrode outside 12b all adopts the full conductive diamond material electrodes (FMCD electrode) be made up of full conductive diamond material, the thickness of the FMCD electrode of preferred employing is at more than 0.5mm, such as 0.5 ~ 5 millimeter, the general common thickness of film-type diamond electrode only has 1 ~ 20um, larger current density cannot be obtained as target, in contrast, the present invention adopts the FMCD electrode of more than 0.5mm thickness can long-time stable work under the current density more than 10 times.That is, the full conductive diamond material electrodes of more than 0.5mm thickness that stacked electrode sequence 12 of the present invention adopts may operate at 5000 ~ 40000A/m
2current density range under, can obtain commercial scale produce novel high-performance, noble potential combined oxidation agent solution.
Further, except improving full conductive diamond material electrodes thickness to obtain except larger current density, producing composite oxidant in order to more effective, also needing the spacing optimizing electrode, the parameter etc. of electrolytic solution.Such as, the spacing setting of any pair electrode in preferred tank room 10 is between 0.5 millimeter to 10 centimetres.First and second end electrodes 12a, 12b can be respectively platinum plating or be coated with platinum-type metal base electrode, or FMCD material binding conductive material.
Wherein, electrolytic solution can from the seawater containing natural electrolytes, brackish water, also alkaline earth salt can manually be prepared as sodium-chlor with fresh water, sodium sulfate, sodium carbonate, one or more mixing in the solution of potassium sulfate etc. are as electrolyte solution, or one or more combination solutions of mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid etc.Adopt the specific conductivity of electrolytic solution between 10ms/cm to 500ms/cm, preferably, electrolytic conductivity from 20ms/cm to 200ms/cm between.
In addition, in a specific embodiment, as shown in Figure 1, fluid inlet 11a is positioned at the below of support housing 11, and liquid outlet 11b is positioned at the top of support housing 11, and fluid inlet 11a and liquid outlet 11b lays respectively at the left and right two ends of support housing 11.In the present embodiment, electrolytic solution is flowed evenly through between often pair of electrode in tank room 10 from bottom to top by fluid inlet 11a, and make electrolytic solution redox reaction occur more completely, fully under to the potential difference of electrode, that improves oxygenant produces efficiency.Certainly, fluid inlet 11a also can be set to two, lays respectively at the left and right two ends of the below of support housing 11; Or any one selecting in two fluid inlet 11a carries out work.
The present invention is by the optimization to the Structure and energy of the tank room of the equipment for the preparation of composite oxidant, thus the equipment preparing composite oxidant of the present invention can be worked at higher current densities, the composite oxidant of oxygen evolution potential can be obtained, and can run with high current efficiency.
Such as, the present invention adopt above-mentioned optimize structure and technique tank room after, can produce obtain change flexibly in the scope of 10 ~ 60000ppm in the concentration of the composite oxidant of FAC, preferred concentration range is between 7000 ~ 40000ppm.And be based on the solution of noble potential stability oxide compound in the composite oxidant obtained, be in electrolytical solution with chlorion, recording in mixed oxide comparatively low potential hypochlorite concentration and account for 30%, all the other are noble potential oxygenant.
The structure preparing the equipment of composite oxidant of the present invention is illustrated referring to Fig. 2, as shown in Figure 2, the equipment preparing composite oxidant of the present invention, except tank room 10, comprises chemicals dosing plant 20, reactor 30 and pump 40 (such as can be thrust pump) further.Reactor 30 has dosing mouth 31 and discharge outlet 32, and reactor 30 is connected with chemicals dosing plant 20 by dosing mouth 31; The fluid inlet 11a of tank room 10 is connected with the discharge outlet 32 of reactor 30 by pump 40.
In the present embodiment, in chemicals dosing plant 20, hold ionogen, the ionogen in chemicals dosing plant 20 is added in reactor 30, in reactor 30, add the aqueous solution by pipeline simultaneously, thus form electrolytic solution.Can manual regulation or regulate the flow of the aqueous solution by under meter, densitometer in reactor 30, make the electrolytic solution in reactor 30 meet the requirements of concentration range; Then, by pump 40, the electrolytic solution that meets the requirements of in reactor 30 is pumped in tank room 10 and carries out electrolytic reaction, after electrolysis work completes, oxygenant is discharged by liquid outlet 11b, the oxygenant reaching concentration requirement is collected, and the oxygenant not meeting concentration requirement enters in reactor 30 and recycles.
Wherein, the ionogen adopted in above-described embodiment can be alkaline earth salt (as selective chlorination sodium, sodium sulfate, sodium carbonate, one or more mixing in the solution of potassium sulfate etc.), or one or more combinations of mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid etc.Preferably, adopt alkaline earth salt as electrolyte raw material.The aqueous feed solution used in reactor 30 can be fresh water, brackish water, seawater and sewage resource.Furthermore, the concentration ratio of the electrolytic solution after the aqueous solution and ionogen fully dissolve in reactor 30 can between 0 ~ 20%.Preferably, the concentration of electrolyte ratio in reactor 30 can between 2% ~ 10%.
It is that the production capacity scope of the composite oxidant of 1% is at 1 kg/hour to 500 kgs/hour that the separate unit of tank room 10 is produced in the concentration of FAC.Preferably, the production capacity scope of optimum Energy Efficiency Ratio is from 20 kgs/hour to 200 kgs/hour.
The volume range of reactor 30 can rise to 3000 liters from 10.Preferably, the volume range of reactor 30 rises to 1000 liters from 40.In addition, design exhaust outlet can be selected in the top of reactor 30, extracts gas in tank out, make it Inner Constitution negative pressure state, thus be conducive to the spilling of gas in solution by blower fan.
Pump 40 controls electrolytic solution and can be 0.1 ~ 100 liter/min/100 square centimeters by the flow rates of the electrode of tank room 10, preferably, makes the working flow of pump 40 be 0.5 ~ 40 liter/min/100 square centimeters.
In addition, when needs equipment running hours, electrolytic solution can be added continuously in chemicals dosing plant 20, electrolytic solution can be discharged continuously from the liquid outlet 11b of the discharge outlet 32 of reactor 30 or tank room 10 simultaneously, this kind of mode some particular application applicable, such as the situation of process sea-water brackish water, now chemicals dosing plant 20 is directly drawn and is carried out electrolysis containing electrolytical seawater injecting reactor 30, simultaneously tank room 10 is with open circuit, or the combined oxidation agent solution of the disposable electrolysis low concentration of mode of half open circuit for the production of.
In one of them embodiment of the present invention, equipment of the present invention also can comprise register 50, and register 50 connects tank room 10 and reactor 30 respectively.Furthermore, register 50 can be made to be connected between the liquid outlet 11b of tank room 10 and the Link Port 33 of reactor 30, wherein, register 50 can be positioned at the outside (as shown in Figure 2) of reactor 30, and register 50 also can be made to be arranged on the inside of reactor 30.
The operating temperature range of tank room 10 can be 0 ~ 95 degree Celsius.That is, regulated by the temperature of reaction in register 50 pairs of tank rooms 10, make to react comparatively stable temperature range (such as 0 ~ 95 degree Celsius) job, preferably working temperature is 15 ~ 35 degrees Celsius.
According to production environment, described register 50 can arrange and comprise refrigeration, heat-production functions, the device that liquid warming or refrigeration directly contact, and it need adopt corrosion-resistant, and the material of acid and alkali-resistance is made.
In one of them embodiment of the present invention, equipment of the present invention also can comprise self-stip control device 60, and it is connected with the supply unit 70 be carried on tank room 10 with tank room 10 respectively.
The positive and negative electrode of the supply unit 70 of self-stip control device 60 controlled loading on tank room 10 is exchanged at specified time, and its anode and cathode is changed mutually.The self-stripping unit 6 of the equipment of the embodiment of the present invention, by adopting PLC technology hardware controls power positive cathode to exchange negative and positive the two poles of the earth with symmetrical or asymmetrical time, namely utilizes " pole " between negative and positive to complete cleaning.
Self-stip control device 60 can set work and two cycles of cleaning, enters the cleaning interval, reciprocation cycle work after the work period terminates.Work period setting range can between 10 minutes ~ 8 hours; Cleaning interval setting range can between 10 seconds to 8 hour.Preferably, the work period is set between 30 minutes to 2 hours, and the cleaning interval was set between 10 seconds to 10 minute.The arranging of the self-stip control device 60 of the present embodiment can be avoided excessively cathodization, reduces anode efficiency, the well working active of holding anode.
In addition, in each working cycle, self-stip control device 60 also can set a rest period, this design is by each work of programming Control high-precision power and stops between the cleaning interval powering to tank room 10, only make pump 40 work, this rest period is conducive to the stable of the working temperature of tank room 10, discharges the gas in solution simultaneously, in the disadvantageous situation of ventilation, rest period serves regulating effect.Generally, rest period be set as 10 second ~ 10 minutes.Preferably, rest period is set as 1 ~ 3 minute.Rest period in the present embodiment ensure that in electrolytic process and produces the fully emptying of gas, improves electrolytic efficiency.
The composite oxidant of the present invention respective outer side edges such as tank room, specified property anode and cathode material, power supply, thrust pump, register 50, self-stip control device 60 of being optimized structure by employing is produced; With all kinds of alkaline earth salt, mineral acid one or more for main electrolyte, with lake water, river, well water class fresh water, also can be seawater, brackish water, all kinds of sewage is solvent, in scopes such as specified proportion, concentration, flow, temperature, potential of hydrogen, the high-performance oxygenant for different application can be produced.
Describe the preparation method of composite oxidant of the present invention with reference to the accompanying drawings in detail, described method comprises the steps:
A, the power supply in supply unit is loaded into tank room 10 by terminal stud, makes the current density of full conductive diamond material electrodes reach 10 ~ 40000A/m
2, preferred current density is 5000 ~ 25000A/m
2.
B, the ionogen in chemicals dosing plant 20 to be joined in reactor 30, make electrolytic solution.Ionogen wherein can be one or more electrolyte powders or concentrated solution.
C, by pump 40, electrolytic solution is pumped into tank room 10, and enter between each electrode from the fluid inlet 11a of tank room 10, produce composite oxidant, composite oxidant is discharged by liquid outlet 11b.
Wherein, when the current density of full conductive diamond material electrodes is 5000 ~ 10000A/m
2time, preferably first and second end electrodes 12a, 12b are thin film type metal base material electrode, i.e. the one side metal base electrode that is surface layer film with diamond, platinum, and film thickness is 1 ~ 20 micron.When the current density of full conductive diamond material electrodes is greater than 10000A/m
2time, preferably the material of first and second end electrodes 12a, 12b is FMCD material binding conductive material (as titanium, tungsten, niobium class corrosion-resistant oxidized metal sheet or Graphene etc.).
Because too high with too low flow velocity all can affect current efficiency, preferably, electrolytic solution passes through the flow rate control of electrode at 0.5 ~ 40 liter/min/100 square centimeters, can obtain better effect.
More specifically, the preparation method of the present embodiment comprises the steps:
A, power supply is loaded into tank room 10 by described terminal stud, makes the current density preferably 5000 ~ 40000A/m of full conductive diamond material electrodes
2.
B, the ionogen in chemicals dosing plant 20 to be joined in reactor 30, make electrolytic solution.
C, by pump 40, electrolytic solution is pumped into tank room 10, and enter between each electrode from the fluid inlet 11a of tank room 10, now control pump 40, makes electrolytic solution by the flow rates of the electrode of tank room 10 at 0.1 ~ 100 liter/min/100 square centimeters.
D, control register 50, make the working temperature of tank room be 15 ~ 35 degrees Celsius.
There is electrolytic reaction and produce composite oxidant in e, electrolytic solution, obtained composite oxidant is discharged by liquid outlet 11b in tank room 10.
F, after electrode work for some time (such as 10 minutes ~ 8 hours), by self-stip control device 60, the positive and negative electrode of the power supply be carried on described tank room 10 is exchanged, carries out the self-stip program of electrode.
G, after electrode clean completes, self-stip control device 60 then makes the positive and negative electrode of the power supply be carried on tank room 10 exchange, and carries out the electrolysis work of electrode.
H, after having produced of composite oxidant, powered-down device 70, now solution has reached setting concentration, completes a collection of production.
Wherein, the potential difference scope between every anticathode of tank room 10 and anode can be 4 to 40V.Preferably, the potential difference scope between every anticathode of tank room 10 and anode is at 7 to 20V.
The interpolar operating voltage of often pair of electrode can be 3.0v ~ 100v, and preferably voltage is at 7v ~ 20v.
The output ripple voltage of supply unit 70 and ripple current are between 0.01% ~ 1%.Preferably, the output ripple of supply unit 70 of the present invention is between 0.02% ~ 0.5%.
In the present embodiment, electrolytic solution is made to flow through tank room 10 successively by pump 40, register 50, reactor 30 and pump 40, reciprocation cycle certain hour, opens high precision electro source apparatus 70 and self-stip control device 60 manually or automatically, now, power supply is loaded into tank room 10, starts to complete electrolytic reaction to solution, thus constantly increases the concentration of composite oxidant.
The present invention, by the combination of above-mentioned processing unit, controls temperature of reaction, concentration of electrolyte, current density, and voltage across poles comes and flow velocity realizes optimum process, and make high-performance composite oxidant current efficiency reach to the highest, by product is minimum, and performance is the strongest.
Equipment of the present invention is by controlling the working temperature of tank room 10 the temperature range of 15 ~ 35 degree, be applied to the current density of full conductive diamond material electrodes at more than 5000A/m2, voltage across poles (one pole) controls at 5 ~ 15v, ionogen mass concentration is 3% to 10%, liquid passes through the flow rate control of electrode at 0.5 ~ 40 liter/min/100 square centimeters electrodes, thus makes the current efficiency of the production high-performance composite oxidant of this equipment reach more than 90%.
In addition, the present invention, by the technology and equipment optimized, makes ionogen transformation efficiency to reach more than 30%, reaches as high as 90%, and this is that membrane electrode under existing low current density cannot be accomplished.Constantly prepare oxygenant by electrode by recycle pump 40, concentration can be made constantly to accumulate, the concentration up to 60000ppm can be prepared.
And, the high-performance composite oxidant that the present invention is produced by above-mentioned configuration can be controlled in 500ppm ~ 60000ppm scope in the concentration of available chlorine (FAC), containing multiple oxidizing potential in mixed oxide, two kinds and above combination in the oxygenants such as hydroxyl radical free radical, potentiometric titrations, ozone free radical, ozone, superoxide, dioxide peroxide, hypochlorous acid.
Preferably, when taking sodium-chlor as main electrolyte, be 5000ppm to 50000ppm by testing the mixed oxidization substrate concentration determined.Strength of solution weight ratio is 4% to 8%.In time taking sodium-chlor as main electrolyte, determined by test, the mixed oxidization substrate concentration of the optimum efficiency that can obtain is between 7000ppm to 20000ppm.
What the present invention produced can be scope between 10 ~ 60000ppm in the concentration of the composite oxidant of FAC, and preferred concentration range is 7000 ~ 40000ppm.
What above-mentioned preferred parameter scope measuring and calculating of the present invention obtained is greater than 90% in the current efficiency of FAC, even more than 100% theoretical value.This is because FAC to analyse chlorine system computing, and creates noble potential oxide compound in the embodiment of the present invention, part comes from oxygen evolution reaction, produces and injects all kinds of Peroxygen systems free radical, so can exceed with the theoretical value of chlorine system for calculating.For comparing aspect, to calculate based on analysing chlorine system theoretical 100 peace generation per hour 132.3 grams of FAC, at operating current efficiency 90%, under current density 10000A/m2, electrode unit area productive rate is 12kg/m2.Compare chlorine system of the analysing anode of existing employing metallic coating and platinum layer membrane electrode, efficiency increases by 16 ~ 52 times.
Therefore the present invention produces composite oxidant technique from selection, structure to parameter designing, compare existing technique and achieve quantum jump, can save the space hold of average 30 times, the productive rate of unit surface improves 30 times.
Introduce several application examples of composite oxidant of the present invention below.
application example 1:
Composite oxidant of the present invention can be used for general cleaning and sterilizing field, and cleaning and sterilizing field can use the solution after this combined oxidation dilution agent usually.Such as, after combined oxidation dilution agent of the present invention, when its working concentration is at 5 ~ 500ppm (preferably, the working concentration of the diluting soln of the composite oxidant that cleaning and sterilizing field adopts is 50 ~ 200ppm, can reach and well clean effect), diluting soln can reach the sterilization effect of 7 more than LOG, its pH value is between 3 ~ 8, the pH value of preferred diluting soln between 4.5 ~ 6.5, wherein pH value adjustment can by passing into carbonic acid gas, pH value is adjusted to optimized scope by the mode of mineral acid.
application example 2:
The oxygenant that composite oxidant of the present invention can be used for all kinds of material uses, and its usual adoptable working concentration is between 10 ~ 50000ppm.Such as, the concentration range for the composite oxidant of soil remediation can adopt 10 ~ 200ppm; The concentration range of glue is broken generally between 500 ~ 10000ppm for oil-gas mining de-plugging; For removing the concentration range of formaldehydes finishing pollution generally between 100 ~ 1000ppm; For the concentration range of deodorizing generally between 50 ~ 200ppm; For the concentration range of the residual removal of food surfaces agriculture generally between 20 ~ 200ppm.
application example 3:
Composite oxidant of the present invention can be used for farming, forestry, husbandary and fishing field, for controlling disease, eliminating virus, growth promoting effects, reducing the use of agricultural chemicals.Such as, for the concentration range of the soil disinfection of farming, forestry, husbandary and fishing, water body disinfection, seed disinfection, disease control, Prevention and cure of epidemic situation generally between 10 ~ 200ppm.
application example 4:
Composite oxidant of the present invention can be used for sewage disposal, for processing the waste water of difficult degradation, to improve its biochemical, makes it reach emission standard.Concentration is generally added between 10 ~ 200ppm such as sewage disposal; The general concentration of the composite oxidant added for the waste liquid of difficult degradation is between 2000 ~ 40000ppm.
Although it will be appreciated by those skilled in the art that the present invention is described according to the mode of multiple embodiment, not each embodiment only comprises an independently technical scheme.So describe in specification sheets be only used to clear for the purpose of; specification sheets should integrally be understood by those skilled in the art, and regards technical scheme involved in each embodiment as the mode that mutually can be combined into different embodiment to understand protection scope of the present invention.
The foregoing is only the schematic embodiment of the present invention, and be not used to limit scope of the present invention.Any those skilled in the art, the equivalent variations done under the prerequisite not departing from design of the present invention and principle, amendment and combination, all should belong to the scope of protection of the invention.
Claims (10)
1. prepare the equipment of composite oxidant for one kind, comprise tank room (10), described tank room (10) comprises support housing (11), described support housing (11) is respectively equipped with fluid inlet (11a) and liquid outlet (11b); It is characterized in that, described tank room (10) comprises stacked electrode sequence (12) further, and it is arranged on the inside of described support housing (11); Described stacked electrode sequence (12) has multiple electrode being separated setting side by side, be supported in described support housing (11) in a series arrangement by strut member (100) between each electrode, between two adjacent described electrodes, be provided with the electrolyte passage being communicated with described fluid inlet (11a) and liquid outlet (11b); The described electrode being positioned at the two ends of described stacked electrode sequence (12) is respectively the first end electrodes (12a) and the second end electrodes (12b), described first and second end electrodes (12a, 12b) is respectively equipped with the terminal stud for connecting power supply, and the described electrode be positioned between described first and second end electrodes (12a, 12b) is full conductive diamond material electrodes.
2. equipment according to claim 1, is characterized in that, the thickness of described full conductive diamond material electrodes is 0.5 ~ 5 millimeter.
3. the equipment according to claim 1-2, is characterized in that, the spacing of any pair electrode of described tank room (10) is between 0.5 millimeter to 10 centimetres.
4. the equipment according to claim 1-3, is characterized in that, the electric conductivity of the electrolytic solution in described tank room (10) between 10ms/cm to 500ms/cm, preferably, between 20ms/cm to 200ms/cm.
5. equipment according to claim 1, is characterized in that, described equipment comprises further: chemicals dosing plant (20); Reactor (30), it has dosing mouth (31) and discharge outlet (32), and described reactor (30) is connected with described chemicals dosing plant (20) by described dosing mouth (31); Pump (40), the fluid inlet (11a) of described tank room (10) is connected with described discharge outlet (32) by described pump (40).
6. equipment according to claim 5, is characterized in that, described equipment comprises further: register (50), and described register (50) connects tank room (10) and described reactor (30) respectively; Self-stip control device (60), it is connected with the supply unit (70) be carried on described tank room (10) with described tank room (10) respectively.
7. utilize the equipment described in claim 1 to prepare a method for composite oxidant, it is characterized in that, described method comprises the steps:
A, power supply is loaded into described tank room (10) by described terminal stud, makes the current density on described full conductive diamond material electrodes reach 5000 ~ 25000A/m
2;
B, the ionogen in described chemicals dosing plant to be joined in described reactor, make electrolytic solution;
C, make described electrolytic solution enter described tank room by described pump, and enter between each electrode from the fluid inlet of described tank room, and produce composite oxidant, described composite oxidant is discharged by described liquid outlet.
8. method according to claim 7, is characterized in that: described equipment comprises register further, and described register connects described tank room and described reactor respectively and carries out temperature control to it; Wherein, the working temperature controlling described tank room is 15 ~ 35 degrees Celsius.
9. method according to claim 7, is characterized in that: the flow velocity controlling to flow through the electrolytic solution of the electrode of described tank room by described pump is 0.1 ~ 100 liter/min/100 square centimeters.
10. method according to claim 7, is characterized in that: described equipment also comprises self-stip control device, and described self-stip control device is provided with the cleaning interval that work period, rest period and positive and negative electrode are exchanged; Wherein, the described work period terminate after after described rest period, enter the described cleaning interval again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945875.3A CN105525307A (en) | 2015-12-17 | 2015-12-17 | Method and device for preparing composite oxidizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945875.3A CN105525307A (en) | 2015-12-17 | 2015-12-17 | Method and device for preparing composite oxidizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105525307A true CN105525307A (en) | 2016-04-27 |
Family
ID=55767822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510945875.3A Pending CN105525307A (en) | 2015-12-17 | 2015-12-17 | Method and device for preparing composite oxidizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105525307A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158116A (en) * | 2019-05-31 | 2019-08-23 | 凯莱英医药集团（天津）股份有限公司 | Electrolysis unit and electrolysis system |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399247A (en) * | 1993-12-22 | 1995-03-21 | Eastman Kodak Company | Method of electrolysis employing a doped diamond anode to oxidize solutes in wastewater |
| CN101054679A (en) * | 2007-02-14 | 2007-10-17 | 浙江工业大学 | Method of preparing ozone by low-voltage electrolysis method |
| CN101223885A (en) * | 2008-02-01 | 2008-07-23 | 中国农业大学 | Micro electrolysis disinfecting preparation and preparing method thereof |
| US20100126879A1 (en) * | 2006-09-05 | 2010-05-27 | Jonathan James Wilman | Solid Electrode |
| CN102021602A (en) * | 2010-07-19 | 2011-04-20 | 江苏泽宇环境工程有限公司 | Sodium hypochlorite generator |
| CN103282551A (en) * | 2010-10-14 | 2013-09-04 | 六号元素有限公司 | A bipolar cell for a reactor |
| CN103328690A (en) * | 2010-12-03 | 2013-09-25 | 电解臭氧有限公司 | Electrolytic cell for ozone production |
| CN104710056A (en) * | 2015-04-02 | 2015-06-17 | 金刚宝石水高科技有限公司 | System and method for producing electrolytic treatment solutions |
-
2015
- 2015-12-17 CN CN201510945875.3A patent/CN105525307A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399247A (en) * | 1993-12-22 | 1995-03-21 | Eastman Kodak Company | Method of electrolysis employing a doped diamond anode to oxidize solutes in wastewater |
| US20100126879A1 (en) * | 2006-09-05 | 2010-05-27 | Jonathan James Wilman | Solid Electrode |
| CN101054679A (en) * | 2007-02-14 | 2007-10-17 | 浙江工业大学 | Method of preparing ozone by low-voltage electrolysis method |
| CN101223885A (en) * | 2008-02-01 | 2008-07-23 | 中国农业大学 | Micro electrolysis disinfecting preparation and preparing method thereof |
| CN102021602A (en) * | 2010-07-19 | 2011-04-20 | 江苏泽宇环境工程有限公司 | Sodium hypochlorite generator |
| CN103282551A (en) * | 2010-10-14 | 2013-09-04 | 六号元素有限公司 | A bipolar cell for a reactor |
| CN103328690A (en) * | 2010-12-03 | 2013-09-25 | 电解臭氧有限公司 | Electrolytic cell for ozone production |
| CN104710056A (en) * | 2015-04-02 | 2015-06-17 | 金刚宝石水高科技有限公司 | System and method for producing electrolytic treatment solutions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158116A (en) * | 2019-05-31 | 2019-08-23 | 凯莱英医药集团（天津）股份有限公司 | Electrolysis unit and electrolysis system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2563725B1 (en) | Membrane-electrode assembly, electrolytic cell using the same, method and apparatus for producing ozone water, method for disinfection and method for wastewater or waste fluid treatment | |
| US20060076248A1 (en) | Apparatus and method for producing electrolyzed water | |
| CN101634035B (en) | Electrochemical method and electrochemical device for synergistically generating ozone and hydrogen peroxide in neutral medium | |
| JP5640266B1 (en) | Electrolyzed water production apparatus and electrolyzed water production method using the same | |
| MXPA03007923A (en) | Method and apparatus for producing negative and positive oxidative reductive potential (orp) water. | |
| RU2297980C1 (en) | Method of the electroactivation of the water solutions | |
| JP2013108104A (en) | Electrolytic synthesis device, electrolytic treating device, electrolytic synthesis method, and electrolytic treatment method | |
| Girenko et al. | Selection of the optimal cathode material to synthesize medical sodium hypochlorite solutions in a membraneless electrolyzer | |
| JP2012107331A (en) | Water electrolysis system | |
| KR101312879B1 (en) | Three-Compartment-Cell and One-Port typed Electrolysis Apparatus | |
| KR101506951B1 (en) | Manufacturing equipment of electrolyte for redox flow battery and manufacturing method thereof | |
| CN105293642A (en) | Multi-electrode multi-diaphragm electrolytic cell for treating high-salinity industrial wastewater | |
| CN105525307A (en) | Method and device for preparing composite oxidizing agent | |
| KR20120139515A (en) | Electrolytically ionized water generator | |
| CN205204884U (en) | Handle many diaphragm electrolysis of multi -electrode groove of high salt industrial waste water | |
| JP4597263B1 (en) | Electrolyzed water production apparatus and electrolyzed water production method using the same | |
| JPH11123381A (en) | Preparation of electrolytic ionic water and prepared water | |
| KR20080040659A (en) | Induction catalyst and electrolysis system | |
| CN108193226B (en) | Composite electrode assembly | |
| JP2017047362A (en) | Generation apparatus and generation method of weak-acidic hypochlorous acid solution | |
| JP2892120B2 (en) | Method for producing sterile water containing hypochlorous acid by electrolysis | |
| US20090081077A1 (en) | Alkaline water sterilizer and alkaline sterilizing water production method | |
| JP3893693B2 (en) | Electrolyzed water production equipment | |
| JPH11319831A (en) | Production of electrolytic function water and its apparatus | |
| JP7212978B1 (en) | electrolytic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160427 |