CN103449529A - Method for preparing ferrate through pulsed ultrasound and hydraulic power cavitation coupled synergistic activation - Google Patents
Method for preparing ferrate through pulsed ultrasound and hydraulic power cavitation coupled synergistic activation Download PDFInfo
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- CN103449529A CN103449529A CN2013103542356A CN201310354235A CN103449529A CN 103449529 A CN103449529 A CN 103449529A CN 2013103542356 A CN2013103542356 A CN 2013103542356A CN 201310354235 A CN201310354235 A CN 201310354235A CN 103449529 A CN103449529 A CN 103449529A
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- ferrate
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Abstract
The invention provides a preparation method of a water treatment agent, which can be used for preparation of a high-efficiency water treatment agent ferrate and belongs to the technical field of environmental protection. The method comprises the following steps: under the condition of sufficient stirring, adding an iron salt solution into a strongly alkaline solution, thus generating iron hydroxide; under the condition of sufficient stirring, adding a right amount of stabilizer, adding a hypochlorite solution, adding strong alkali solid powder until the powder is dissolved to saturation, performing cavitation treatment on the reaction materials through a pulsed ultrasound and hydraulic power cavitation coupled reactor, and ensuring that Fe(OH)3 is sufficiently oxidized, thus generating a ferrate product; and cooling the solution, performing solid-liquid separation, purifying the ferrate in the solid phase to obtain the ferrate product, and recovering and returning the alkaline solution of the liquid phase. The method has the characteristics of low cost, high yield, high product purity, less equipment investment and the like, and is very suitable for preparation of ferrate.
Description
[technical field]
The present invention relates to a kind of method of preparation of water conditioner, can be used for the preparation of High-efficient Water treatment agent ferrate, belong to environmental technology field.
[background technology]
Ferrate refers to and contains Fe (VI) O
4the salt that acid group and metal ion form, it possesses very strong oxidisability, and its redox potential is 2.20V under acidic conditions, under alkaline condition, is 0.72V, compares KMnO
4, O
3, Cl
2the oxygenant of relatively commonly using Deng these also is eager to excel.New and effective disinfection of drinking water agent and water conditioner as a kind of non-chlorine, it can be removed traditional water conditioner and be difficult to thoroughly remove harmful chloro pollutent, especially phenol and sulfide are had to obvious oxidation removal effect, the CN in oxidizing water safely and effectively
-.Except thering is extremely strong oxidisability, generate the Fe with height adsorption activity after reaction
3+, most of ion, organism and suspended substance can flocculate at very wide pH value scope internal adsorption.Potassium ferrate integrates oxidation, sterilization, absorption, it is solidifying to flocculate, help, decolouring, deodorizing etc. are multi-functional, and final product is nontoxic ferric ion, can not produce induced gene sudden change and carcinogenic effect, is eco-friendly treatment agent.Ferrate not only can be used as water conditioner, but also at aspects such as electrode active material, petrochemical catalysts, a lot of application is arranged, and therefore, the preparation method of research ferrate has become an important problem.
The preparation method of existing ferrate mainly contains three kinds of high temperature peroxide oxidation method, electrolytic process and hypochlorite methods.High temperature peroxide oxidation method is that the metal oxide with oxidisability is reacted to the ferrate method that generates with the oxide compound of iron, molysite or iron under the heat condition, this method needs strict red-tape operati condition, production cost is high, more dangerous and certainly be difficult to realize the there be limited evidence currently of employing.Electrolytic process is that oxidizing reaction occurs on iron anode. make iron or iron ion be oxidized to the method for high ferro acid group, this method exists the problems such as energy consumption is high, byproduct is more to have to be solved.Hypochlorite method is in the strong alkali solution environment, take saturated hypochlorite solutions and molysite as raw material, by hypochlorite, the oxidizing reaction of iron is generated the method for ferrate, this method mature production technology, facility investment is less, easily realizing, is a kind of preparation method commonly used, but because its oxidising process efficiency is lower, need to add excessive oxygenant, the cost that this not only increases, accelerated equipment corrosion, but also the difficulty of the product purification process strengthened.Therefore, strengthening its oxidising process, promote its oxidation efficiency, is that the reduction hypochlorite method prepares the cost of ferrate, an important channel of improving product quality.
[summary of the invention]
Purpose of the present invention is exactly by the oxidising process of impulse ultrasound and Hydrodynamic cavitation coupling and intensifying hypochlorite, improves oxidation efficiency, effectively solves the defect of above-mentioned alkali hypochlorite method.Existing hypochlorite method is that hypochlorite and molysite are added in strong alkali solution, and molysite first generates ferric hydroxide precipitate, and then by the hypochlorite oxidation.Its chemical reaction is:
Fe
3++3OH
-＝Fe(OH)
3↓
2Fe(OH)
3+3ClO
-+4OH
-＝2FeO
4 2-+5H
2O+3Cl
-
Because oxidizing reaction occurs in the ironic hydroxide solid surface, this liquid and solid phase reaction process is easy to restriction, solid state reaction surface due to the liquid-solid phase mass transfer process and former the obstruction such as is passivated, and reaction efficiency is reduced.
If now material is carried out to cavitation process by impulse ultrasound and Hydrodynamic cavitation coupled reactor, because the coupling of impulse ultrasound and Hydrodynamic cavitation can produce high-intensity cavatition, this cavatition can produce local high speed micro jet flow, the ironic hydroxide solid surface issues life-stylize in the impact of this high speed micro jet flow, on the solid surface of this activation, the oxidation reaction process of solid liquid phase is accelerated, on the other hand, micro jet flow has also accelerated the mass transfer process of solid-liquid phase reaction, therefore, no matter be that reaction is controlled or the solid liquid phase oxidising process of diffusion control, under cavatition, its reaction all is accelerated, reaction efficiency is improved.
Therefore present method can be divided into following steps:
1, under well-beaten condition, iron salt solutions is added in strong alkali solution, generate ironic hydroxide.
2, under well-beaten condition, first add appropriate stablizer, then add hypochlorite solutions, finally supplementing the highly basic pressed powder, that it is dissolved to is saturated.
3, reaction mass is carried out to cavitation process by impulse ultrasound and Hydrodynamic cavitation coupling cavitation reactor, allow Fe (OH)
3by fully oxidation, generate the ferrate product.
4, cooling, solid-liquid separation, carry out purifying by the ferrate generated in solid phase, obtains the ferrate product, the recycle of alkali liquor of liquid phase reuse.
The characteristics such as present method has low cost, high yield, product purity is high, facility investment is little, be well suited for the preparation of ferrate.
[embodiment]
Further illustrate the specific embodiment of the present invention and effect with following indefiniteness embodiment:
Embodiment 1
1, in the reactor of 1000 liters, add 120 liters of saturated potassium hydroxide solutions, under well-beaten condition, add gradually 60 liters of 45% liquor ferri trichloridis, more fully stir half an hour.
2, under well-beaten condition, first add 5 liters of 50% Cupric Chloride Solutions, then add 200 liters of potassium hypochlorite 3, the solution of 10% (available chlorine), finally add granularity to be less than 300 kilograms, 600 purpose potassium hydroxide powder, then stir half an hour.
3, by reaction mass repeatedly ultrasonic the and Hydrodynamic cavitation of input pulse coupling cavitation reactor carry out cavitation process, control the accumulated process time of slurry in cavitation reactor and reach one hour.After cavitation process completes, it is transparent that solution is.Impulse ultrasound and Hydrodynamic cavitation coupling cavitation process device and processing condition are as follows:
Hydrodynamic cavitation mechanism adopts two front and back porous plates in succession, first porous plate aperture 3.0mm, thickness of slab 12mm, 0.085, the second porous plate aperture 2.5mm of ratio that hole area is long-pending with the cavitation reactor cross-section of pipeline, thickness of slab 10mm, the ratio 0.125 that hole area is long-pending with the cavitation reactor cross-section of pipeline, the ratio 2.5 that the distance of two porous plates is long-pending with the cavitation reactor cross-section of pipeline, cavitation reactor inlet feed pressure is 0.80Mpa, top hole pressure is 0.15Mpa.
Adopt two in cavitation reactor and lay respectively at two porous plate downstream probe type ultrasonic wave producers as ultrasonic wave generating source, first probe is 10mm apart from first porous plate distance, the ratio 1.5w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 60kH, recurrence interval 200ms, dutycycle is 0.05.Second probe is 15mm apart from second porous plate distance, the ratio 2.0w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 100kH, recurrence interval 150ms, dutycycle is 0.03.
4, cooling solution to 0 ℃, the centrifugal solid phase that obtains is the thick product of potassium ferrate, the liquid phase recycle of alkali liquor is also reused.Saturated potassium hydroxide solution washing 5 times for thick product, washings is cooling, can also obtain potassium ferrate solid.By reaching the cooling potassium ferrate solid obtained of washings after washing successively with methyl alcohol, ether washing, can obtain pure potassium ferrate product after suction filtration, drying.
Prepare potassium ferrate according to above-mentioned steps, yield reaches 96.8%, and product purity reaches 98.7%.
Embodiment 2
1, in the reactor of 1000 liters, add 120 liters of saturated sodium hydroxide solutions, at audio frequency, be under 22kHz, the power Ultrasonic Radiation that is 1.2kw, well-beaten condition, add gradually 100 liters of saturated iron nitrate solutions, more fully stir 40 minutes.
2, under well-beaten condition, first add 15 liters of 15% sodium silicate solutions, then add 150 liters of the chlorine bleach liquores of 10% (available chlorine), finally add granularity to be less than 300 kilograms of 600 purpose sodium hydroxide powder, then stir half an hour.
3, by reaction mass repeatedly ultrasonic the and Hydrodynamic cavitation of input pulse coupling cavitation reactor carry out cavitation process, control the accumulated process time of slurry in cavitation reactor and reach one and a half hours.After cavitation process completes, it is transparent that solution is.Impulse ultrasound and Hydrodynamic cavitation coupling cavitation process device and processing condition are as follows:
Hydrodynamic cavitation mechanism adopts two front and back porous plates in succession, first porous plate aperture 3.0mm, thickness of slab 12mm, the ratio 0.080 that hole area is long-pending with the cavitation reactor cross-section of pipeline, first porous plate aperture 2.5mm, thickness of slab 10mm, the ratio 0.12 that hole area is long-pending with the cavitation reactor cross-section of pipeline, the ratio 2 that the distance of two porous plates is long-pending with the cavitation reactor cross-section of pipeline, cavitation reactor inlet feed pressure is 0.85Mpa, top hole pressure is 0.15Mpa.
Adopt two in cavitation reactor and lay respectively at two porous plate downstream probe type ultrasonic wave producers as ultrasonic wave generating source, first probe is 10mm apart from first porous plate distance, the ratio 2w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 60kH, recurrence interval 100ms, dutycycle is 0.05.Second probe is 15mm apart from second porous plate distance, the ratio 2.5w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 100kH, recurrence interval 150ms, dutycycle is 0.03.
4, cooling solution to 0 ℃, the centrifugal thick product of Na2Fe04 that obtains, then wash 5 times with saturated sodium hydroxide solution, washings is cooling, can obtain the Na2Fe04 solid.By reaching the cooling Na2Fe04 solid obtained of washings after washing successively with methyl alcohol, ether washing, can obtain pure Na2Fe04 product after the suction filtration drying.
Prepare Na2Fe04 according to above-mentioned steps, yield reaches 96.3%, and product purity reaches 98.5%.
Embodiment 3
1, in the reactor of 1000 liters, add 100 liters of saturated potassium hydroxide solutions, at audio frequency, be under 25kHz, the power Ultrasonic Radiation that is 1.5kw, well-beaten condition, add gradually 100 liters of saturated iron nitrate solutions, more fully stir half an hour.
2, under well-beaten condition, add successively 5 liters of 15% sodium silicate solutions, 2 liters of 50 Cupric Chloride Solutions, 200 liters of the chlorine bleach liquores of 10% (available chlorine), finally add granularity to be less than 350 kilograms, 600 purpose potassium hydroxide powder, then stir half an hour.
3, by reaction mass repeatedly ultrasonic the and Hydrodynamic cavitation of input pulse coupling cavitation reactor carry out cavitation process, control the accumulated process time of slurry in cavitation reactor and reach two hours.After cavitation process completes, it is transparent that solution is.Impulse ultrasound and Hydrodynamic cavitation coupling cavitation process device and processing condition are as follows:
Hydrodynamic cavitation mechanism adopts two front and back porous plates in succession, first porous plate aperture 3.0mm, thickness of slab 12mm, 0.085, the second porous plate aperture 2.5mm of ratio that hole area is long-pending with the cavitation reactor cross-section of pipeline, thickness of slab 10mm, the ratio 0.125 that hole area is long-pending with the cavitation reactor cross-section of pipeline, the ratio 2 that the distance of two porous plates is long-pending with the cavitation reactor cross-section of pipeline, cavitation reactor inlet feed pressure is 0.75Mpa, top hole pressure is 0.15Mpa.
Adopt two in cavitation reactor and lay respectively at two porous plate downstream probe type ultrasonic wave producers as ultrasonic wave generating source, first probe is 10mm apart from first porous plate distance, the ratio 1.5w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 40kH, recurrence interval 200ms, dutycycle is 0.1.Second probe is 15mm apart from second porous plate distance, the ratio 2.0w/cm that ultrasonic power is long-pending with the cavitation reactor cross-section of pipeline
2, frequency 60kH, recurrence interval 150ms, dutycycle is 0.08.
4, cooling solution to 0 ℃, the centrifugal thick product of potassium ferrate that obtains, then wash 5 times with saturated potassium hydroxide solution, washings is cooling, can obtain potassium ferrate solid.By reaching the cooling potassium ferrate solid obtained of washings after washing successively with methyl alcohol, ether washing, can obtain pure potassium ferrate product after the suction filtration drying.
Prepare potassium ferrate according to above-mentioned steps, yield reaches 95.6%, and product purity reaches 98.2%.
Above-described embodiment has only expressed the preferred embodiment of the present invention, can not be interpreted as the restriction to the scope of the claims of the present invention, so the present invention is not limited to this concrete technical process.Those skilled in the art, according to technical scheme of the present invention and design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.So all other embodiments that draw according to the claims in the present invention scope, all should belong to the scope that the present invention is contained.
Claims (6)
1. an impulse ultrasound and the collaborative activation of Hydrodynamic cavitation coupling prepare the method for ferrate, it is characterized in that comprising following steps:
(1), under well-beaten condition, iron salt solutions is added in strong alkali solution, generate ironic hydroxide.
(2), under well-beaten condition, first add appropriate stablizer, then add hypochlorite solutions, finally supplementing the highly basic pressed powder, that it is dissolved to is saturated.
(3) reaction mass is carried out to cavitation process by impulse ultrasound and Hydrodynamic cavitation coupled reactor, allow Fe (OH)
3by fully oxidation, generate the ferrate product.
(4), cooling, solid-liquid separation, carry out purifying by the ferrate generated in solid phase, obtains the ferrate product, the recycle of alkali liquor of liquid phase reuse.
2. preparation method according to claim 1, it is characterized in that: described pulse ultrasonic wave generating source is placed in Hydrodynamic cavitation mechanism downstream, and Hydrodynamic cavitation mechanism is orifice fitting, and the pulse ultrasonic wave generating source is titanium system probe.
3. preparation method according to claim 1 is characterized in that: described highly basic is a kind of in potassium hydroxide or sodium hydroxide.
4. preparation method according to claim 1 is characterized in that: the molysite of described (1) step is a kind of in iron(ic) chloride or iron nitrate.
5. preparation method according to claim 1 is characterized in that: the hypochlorite of described (2) step is a kind of in clorox or potassium hypochlorite.
6. preparation method according to claim 1, it is characterized in that: the stablizer of described (2) step is a kind of or or its mixture in cupric chloride, water glass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193050A (en) * | 2014-08-21 | 2014-12-10 | 华南理工大学 | Method for deeply removing thallium in water body through impulse ultrasound and hydrodynamic cavitation coupled, synergetic and assisted oxidation |
| WO2015109683A1 (en) * | 2014-01-22 | 2015-07-30 | 哈尔滨工业大学 | Method for efficiently preparing ferrate based on nascent interfacial activity |
| CN110449109A (en) * | 2019-03-21 | 2019-11-15 | 东北电力大学 | A kind of preparation method and device for wet oxidation process continuous production of high-concentration ferrate |
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| US5746994A (en) * | 1996-08-09 | 1998-05-05 | New Mexico State University Technology Transfer Corporation | Method for synthesizing ferrate and ferrate produced thereby |
| US20060097086A1 (en) * | 2004-07-21 | 2006-05-11 | Sergiy Zakharchenko | Cavitation-generating attachment |
| CN102059070A (en) * | 2010-12-02 | 2011-05-18 | 广州市新栋力超声电子设备有限公司 | Hydraulic/ultrasonic coupling cavitation device |
| CN103145189A (en) * | 2013-03-01 | 2013-06-12 | 凤台精兴生物科技有限公司 | Preparation method of potassium ferrate |
-
2013
- 2013-08-09 CN CN2013103542356A patent/CN103449529A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5746994A (en) * | 1996-08-09 | 1998-05-05 | New Mexico State University Technology Transfer Corporation | Method for synthesizing ferrate and ferrate produced thereby |
| US20060097086A1 (en) * | 2004-07-21 | 2006-05-11 | Sergiy Zakharchenko | Cavitation-generating attachment |
| CN102059070A (en) * | 2010-12-02 | 2011-05-18 | 广州市新栋力超声电子设备有限公司 | Hydraulic/ultrasonic coupling cavitation device |
| CN103145189A (en) * | 2013-03-01 | 2013-06-12 | 凤台精兴生物科技有限公司 | Preparation method of potassium ferrate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109683A1 (en) * | 2014-01-22 | 2015-07-30 | 哈尔滨工业大学 | Method for efficiently preparing ferrate based on nascent interfacial activity |
| WO2015110050A1 (en) * | 2014-01-22 | 2015-07-30 | 哈尔滨工业大学 | Method for efficiently preparing ferrate based on nascent interfacial activity |
| CN104193050A (en) * | 2014-08-21 | 2014-12-10 | 华南理工大学 | Method for deeply removing thallium in water body through impulse ultrasound and hydrodynamic cavitation coupled, synergetic and assisted oxidation |
| CN110449109A (en) * | 2019-03-21 | 2019-11-15 | 东北电力大学 | A kind of preparation method and device for wet oxidation process continuous production of high-concentration ferrate |
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Application publication date: 20131218 |