CN101565298B - Oxide ceramic powder capable of perpetually releasing active oxygen when suffering from water - Google Patents
Oxide ceramic powder capable of perpetually releasing active oxygen when suffering from water Download PDFInfo
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- CN101565298B CN101565298B CN2008101045127A CN200810104512A CN101565298B CN 101565298 B CN101565298 B CN 101565298B CN 2008101045127 A CN2008101045127 A CN 2008101045127A CN 200810104512 A CN200810104512 A CN 200810104512A CN 101565298 B CN101565298 B CN 101565298B
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- active oxygen
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Abstract
The invention discloses inorganic ceramic powder and discloses the performance of the inorganic ceramic powder for slowing hydrolyzing and releasing active oxygen when suffering from water and a preparation method thereof. Through controlling the sintering temperature and time and performing surface packaging treatment by different methods, the hydrolization process can be ensured to be performed slowly and the active oxygen can be released for a long time, thereby the application value of the powder on engineering is ensured. The release of the active oxygen can provide a powerful oxygenationmechanism for sterilizing, killing algae and lowering the pollution in water (lowering the COD index). When the powder is used for preparing various other water treatment filter materials, the range of the powder applied to the field of water treatment engineer can be expanded.
Description
Technical field
What the present invention relates to is the inorganic non-metallic professional domain, uses the natural crystal sintering to form, interior alkaline including earth metal, and activated oxygen released in hydrolytic process can be used for the multiple water treatment system, also can be used as major ingredient, is used to prepare various water treatment ceramic filter materials.
The background of invention
In recent years, paid special attention to some new oxide ceramics abroad, be characterized under certain conditions, can activated oxygen released, play the oxidation catalysis effect of organic matter degradation.Be used for environment purification, effect is fine.Such as, 14CaO7Al
2O
3Constitute complicated structure cell, under certain conditions, the free oxygen in the structure possibly discharge, and becomes active oxygen, (US6,818,192B2) [8] and the structure of structure cell remains unchanged.When the sintering environment was different, the concentration of free oxygen can improve two one magnitude.The crystalline structure Ca of other cubic system
12Al
10Si
4O
35Also in crystal, comprising a lot of free oxygen (US2006/0045834A1) [9], when temperature was enough high, active oxygen can move out, had the ability of decomposition and voloxidation organic matter.
On the other hand; In the document also relevant for the report [10-12] of alkaline earth metal oxide with anti-microbial activity; Natural manganese dioxide (MgO), quicklime (CaO), zinc oxide (ZnO) and suplical are arranged, and it can burn till in powder and the natural crystal etc. at pottery, oyster, fan tool etc. and find.It is injured until death because of receiving the external force effect that its antibacterial mechanisms is considered to bacterium.Also there is work [17] to use to O
2 -Responsive chemiluminescent indicator (PMAC) has proved that the ultra oxygen base of a kind of negatively charged ion is the hydrolysis that is accompanied by alkaline earth metal oxide really, in pH is from neutrality to the alkaline range, can obtain.And subsequently, the ultra oxygen base of this negatively charged ion can be converted into the strongest active oxygen of oxidation capacity under the alkaline environment more than 8.5, hydroxyl radical free radical (OH).Active oxygen radical can obtain check through chemiluminescent method, and its existence is confirmed.
Beaune science and technology is used to prepare ceramic filter material to oxide ceramics, is called water health ceramic ball, has delivered multinomial patent (patent No. CN 1392115A, CN 1724112A, CN 1733678A).Title is uniform-distribution with inorganic antibacterial material in the surface and the inside of this ceramic filter material, because the self poling effect is in active condition highly, contacts with water, and moment produces a large amount of active oxygens.Produce the strong oxidation of non-selectivity thus, make organic matter degradation, killing bacteria and other mikrobes.This product principal constituent is silicon oxide and aluminum oxide.
Part applicant of the present invention has applied for that before one is the oxide ceramic filtering material of staple with quicklime and Natural manganese dioxide.This filtrate ultimate principle is to accomplish deep oxidation and filtration treatment to various water quality through the function of the physical filtering of absorption and stupalith chance water activated oxygen released.Can solve the caused water quality deterioration of all contaminations in the water body very effectively, effectively reduce chemical oxygen demand index (COD) in the water, possess very strong sterilization algae removal performance simultaneously.Sterilizing rate to Miyun Reservoir water can reach 100%, and algaecidal rate also reaches more than 99%.The disadvantage of the patented product is higher energy consumption.One of step of preparation technology is: the particle that will make is put into muffle furnace and is toasted, and heats up between 500 ℃～1150 ℃, is incubated 0.5 to 48 hour.In this invention process, lot of test work shows, keeps one of important symbol of ceramic filter material activated oxygen released, is whether the pH value in its place solution of test can remain on more than 8.5.And the important symbol that guarantees ceramic filter material activated oxygen released consistency of performance property is that pH maintains below 10.
The present invention takes directly to calcine the method for natural crystal, burns till suitable powder, makes it reach the chance water activated oxygen released performance of previous patent product.Gordian technique wherein is how to control the hydrolysis rate of earth alkali metal in the ceramics powder, the performance of its activated oxygen released is kept for a long time as much as possible, effectively.
The present invention both can directly be used for the suitable field of water treatment, and also the unburned knot ceramic filter material grain for preparation chance water activated oxygen released provides important material.
Summary of the invention
One of the object of the invention provides high performance oxide ceramic, is formed by multiple natural crystal mixed sintering, has the performance of meeting the water activated oxygen released.Ceramics powder self promptly can be filtered dirty taste removal, reduces COD, multiple function such as sterilization algae removal.Be applicable to water treatment, also be applicable to the preparation of ceramic filter material particulate.But, through the ore powder of activation treatment, meet the water posthydrolysis, when discharging active oxygen, important problem is a hydrolysis rate.Too fast hydrolysis rate is accompanied by the release of a large amount of active oxygens, has also determined the life-span of short duration that oxide ceramics divides.Below be the theoretical analysis and the verification experimental verification in alkalimetal oxide hydrolysis rate and life-span, we find, can agree well between the two.
Use 5 gram agglomerated powders, put into the container that 200ml water is housed, hydrolytic process is hydrolyzed to example with CaO:
CaO+H
2O＝＝＝Ca
+++2OH
-
Can get molecular weight CaO: 2OH by following formula
-==56: 34
Be not difficult to calculate 5 gram CaO hydrolysis, the OH of 3 grams in corresponding the water thus
-Ion,
In the process of the test, change 30 day Total Water 6000 milliliter==6 liter changing new water in the container that 5 gram filtrates are housed every day.
Calculate OH
-Ionic concn, and be converted into volumetric molar concentration, and calculate pH value of aqueous solution.
Through calculating, obtain conclusion: 5 gram agglomerated powder all hydrolysis in 6 liter water, pH can reach 12.5, and in other words, under the situation that keeps pH12.5,5 gram activatory ceramics powders need whole hydrolysis in 6L water.If pH is dropped to 9.5, can derive out, the hydrolysis of 5 gram ceramics powders should be at 6000L (6 * 10
-6ML) accomplish in the water.100 tons of ceramics powders can hydrolysis to 1.2 * 10
4In ten thousand tons of water, guarantee that its pH 9.5, reaches the level of effective processing.So calculate, suppose 100,000 tons of water of treating water every day, but the time of 100 tons of ceramics powder treating water is more than 3 years.As previously mentioned, activated oxygen released is the performance that earth alkali metal possesses along with the hydrolysis of self.Hydrolysis rate is slow, the perhaps trim point of hydrolysis low (such as being equilibrated at pH9.5, rather than 12.5), and a hydrolysis institute retainable time limit (life-span) is just long, and active oxygen will discharge for a long time and reposefully.Can reach under the prerequisite that active oxygen discharges minimum requirements (critical level), the hydrolysis rate of control earth alkali metal makes it can satisfy the water treatment demand, is not too fast consumption again, the present invention that Here it is the purpose that will reach.
For realizing above-mentioned purpose, the present invention takes following technical solution:
Use natural crystal, comprise magnesite ore, rhombspar, zeolite, illite, medical stone, the difference sintering, mix according to certain ratio burned back.Various embodiment is used conditions such as different raw materials combination and sintering temperature.
Mix after the sintering, resultant powder possesses following various component contents:
CaO：0.34～60；MgO：20～90；SiO
2：5～20；Al
2O
3：0.13～5.5；TiO
2：0.1～10；ZnO：0～10；Fe
2O
3：0.1～5；K
2O：0.1～1；Na
2O：0.1～1；Mn
2O
3：0.1～1
It is characterized in that: be main with quicklime, these two kinds of alkaline earth metal oxides of Natural manganese dioxide in the said oxide ceramic.
A kind of optimal technical scheme is characterized in that: comprise (weight part) CaO:20～40 in the said oxide ceramic, MgO:20～50, Al
2O
3: 0.1～0.3, TiO
2: 0.1～5, ZnO:0～10, SiO
2: 0.1～2.0, Fe
2O
3: 0.1～0.5, K
2O:0.0～0.5, Na
2O:0～0.2.
A kind of optimal technical scheme is characterized in that: in the powder behind the sintering, comprise carbonate some amount, that be evenly distributed.In the oxide compound hydrolytic process, carbonate and other insoluble oxide compound play the effect that strengthens the hydrolysis resistance.Whether carbonate exists in powder, can use the structure analysis method of X-line diffraction to confirm.
Another object of the present invention provides the preparation method of above-mentioned oxide ceramic.
A kind of preparation method of oxide ceramic filtering material powder, its step is following:
(1) get rhombspar respectively, magnesite, zeolite, illite, medical stone carries out sintering.Sintering temperature is at 500～1600 ℃, and the time is 1～12 hour.Active during sintering for guaranteeing, suitably control the various atmosphere dividing potential drops in the stove.
(2) according to different ratios, get calcining good ground dolomite, magnesite ore powder and zeolite powder, add titanium oxide in addition; Powders such as zinc oxide are perhaps only got wherein 1～2 kind, thorough mixing, grinding; Fineness reaches the 20-300 order, promptly constitutes main material of the present invention and forms;
(3), carry out the surface parcel and handle with being dipped in the different environment after the powder mixing; The envrionment conditions of handling can be: organic resin (vinyl resin) adds organic solvent or diluent (N-BUTYL ACETATE, diacetone alcohol etc.); Water-based emulsion (ACRYLIC EMULSION) adds a certain proportion of water; Dissolve in the aqueous solution of other tensio-active agents and certain atmosphere.
(4) surface treatment is good ceramics powder takes out from processing environment, dries processing.Flash-off time is not less than 2 hours.
(5) use baking oven that ceramics powder is dried in case of necessity; Oven temperature is raised to 200～260 ℃, is incubated 0.5～5 hour.
Oxide ceramics powder of the present invention possesses the porousness of material, and the oxidisability after the raw material slaking possesses the water of chance and discharges the property of dissimilar active oxygens and enough work-ing life.When the active oxygen that discharges was hydroxy radical qiao, filtrate had the strongest oxidation susceptibility.At this moment powder has possessed the effect of degraded toxic organic compound, possesses the function of the robe of killing mikrobe and algae.Hydrolysis rate is slow and steady, long perfomance life.
Through embodiment the present invention is further specified below, but and do not mean that restriction protection domain of the present invention.
Description of drawings
The X-ray diffraction peak of Fig. 1 Comparative Examples 1 powder
The X-ray diffraction peak of Fig. 2 embodiment 1 powder
The chemoluminescence check of Fig. 3 embodiment 1 prepared powder
Embodiment
Comparative Examples
The burnt dolomite powder, sintering mound magnesium ore becomes powder, and 1000～1150 ℃ of sintering temperatures, soaking time are 5 hours.Mix by a certain percentage, do not carry out surface treatment.
Staple: CaO:34～45; MgO:45～55; SiO
2: 0.5～2; Al
2O
3: 0.13～1; Fe
2O
3: 0.1～0.5, add TiO
2: 0.1～1
The primary structure of this material and corresponding semi-quantitative analysis are seen Fig. 1.
Diffraction maximum based among the figure obtains quantitative analysis results:
CaO～49％，MgO～51％
Use this powder 5 grams, immerse 200ml check pH, obtain the result of pH12, sustainable 20 days.After 20 days, pH drops to below 8 rapidly.Hydrolysis rate is too fast, and the life-span is too short, does not have actual use value.
Embodiment 1
Burnt dolomite, temperature are 800～1100 ℃, soaking time 4 hours; Use water phase surfactant mixture to do the surface and handle, use Walocel MT 20.000PV, process the aqueous solution 1%, soak the agglomerating powder, dry then.
Fig. 2 is seen at the X-ray diffraction peak.
The powder that burns till obtains quantitative analysis results through diffraction peak:
CaO～28％，MgO～43％，CaCO3～22％，SiO2～7％
Use this powder 5 grams, immerse 200ml check pH, obtain the result of pH10, continue after 300 days, pH still can reach 9-10.
Embodiment 2
Sintering magnesite ore, temperature are 700-900 ℃, soaking time 6 hours; Use vinyl resin to dissolve in N-BUTYL ACETATE according to the ratio of 2:8, process is with the breeze surface treatment, and the back is 260 ℃ of bakings.Baking finishes, and ceramics powder is placed on indoor drying.
Use this powder 5 grams, immerse 200ml check pH, obtain the result of pH10, continue after 300 days, pH is still more than 9.
The check of embodiment 3 activated oxygen released and sterilising effect check
Gained ceramic powder of the present invention is carried out the check of activated oxygen released, use the chemoluminescence method of inspection that Chemiluminescence Apparatus provided.The assay that obtains is (Fig. 3) as follows:
Ceramic powder embodiment 1 of the present invention carries out the sterilization algae removal service check with gained, and the result sees table 1.
Table 1 drops into the sterilization experiment of ceramics powder
| Numbering | Dosage (g/L) | Settling time (min) | Total plate count (individual/m l) | Coliform (individual/L) |
| 1 | 0 | - | ＞100 | ＞100 |
| 2 | 5 | 10 | 0 | 0 |
| 3 | 10 | 10 | 0 | 0 |
| 4 | 5 | 30 | 0 | 0 |
| 5 | 5 | 600 | 0 | 0 |
Annotate: numbering 1 is for containing bacterium sewage.
Can confirm the performance and the sterilization algae removal function thereof of ceramic powder activated oxygen released of the present invention thus.
Embodiment 4
According to 20-40 burnt dolomite powder, 50-70 sintering magnesite ore, the source of powder is embodiment 1 and embodiment 2, adds oxide powder and zinc 5-10 part again, carries out each item check of water treatment after the mixing.As a result, for the processing of petrochemical wastewater, once filter, COD descends more than 80%.
Claims (2)
1. oxide ceramic, it comprises following component:
CaO：0.34～60；MgO：20～90；SiO
2：5～20；Al
2O
3：0.13～5.5；TiO
2：0.1～10；ZnO：0～10；Fe
2O
3：0.1～5；K
2O：0.1～1；Na
2O：0.1～1；Mn
2O
3：0.1～1，
It is characterized in that: be main with quicklime, these two kinds of alkaline earth metal oxides of Natural manganese dioxide in the said oxide ceramic.
2. an oxide ceramic is characterized in that, comprises by weight: CaO:20～40, MgO:20～50, Al
2O
3: 0.1～0.3, TiO
2: 0.1～5, ZnO:0～10, SiO
2: 0.1～2.0, Fe
2O
3: 0.1～0.5, K
2O:0.0～0.5, Na
2O:0～0.2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101045127A CN101565298B (en) | 2008-04-21 | 2008-04-21 | Oxide ceramic powder capable of perpetually releasing active oxygen when suffering from water |
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|---|---|---|---|
| CN2008101045127A CN101565298B (en) | 2008-04-21 | 2008-04-21 | Oxide ceramic powder capable of perpetually releasing active oxygen when suffering from water |
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| CN101565298B true CN101565298B (en) | 2012-07-11 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722163B (en) * | 2013-12-18 | 2017-05-03 | 宁波市雨辰环保科技有限公司 | Air purifier |
| CN109095886A (en) * | 2018-10-09 | 2018-12-28 | 揭阳市腾晟科技咨询有限公司 | A kind of anti-bacteria ceramic raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392115A (en) * | 2002-08-13 | 2003-01-22 | 河北工业大学 | Multifunctinoal health ceramic material and its preparing method and use |
| CN1724112A (en) * | 2005-06-02 | 2006-01-25 | 淄博博纳科技发展有限公司 | Microporous ceramic filtering element with antibacterial water activating function |
| CN1733648A (en) * | 2005-07-20 | 2006-02-15 | 淄博博纳科技发展有限公司 | Ceramic products possessing antisepsis and water mineralization and activation functions, and its preparation method and uses |
-
2008
- 2008-04-21 CN CN2008101045127A patent/CN101565298B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392115A (en) * | 2002-08-13 | 2003-01-22 | 河北工业大学 | Multifunctinoal health ceramic material and its preparing method and use |
| CN1724112A (en) * | 2005-06-02 | 2006-01-25 | 淄博博纳科技发展有限公司 | Microporous ceramic filtering element with antibacterial water activating function |
| CN1733648A (en) * | 2005-07-20 | 2006-02-15 | 淄博博纳科技发展有限公司 | Ceramic products possessing antisepsis and water mineralization and activation functions, and its preparation method and uses |
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