CN101204661A - Efficient oxidation catalyst catalyzing disinfection under room temperature and preparation method thereof - Google Patents
Efficient oxidation catalyst catalyzing disinfection under room temperature and preparation method thereof Download PDFInfo
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- CN101204661A CN101204661A CNA2006101654323A CN200610165432A CN101204661A CN 101204661 A CN101204661 A CN 101204661A CN A2006101654323 A CNA2006101654323 A CN A2006101654323A CN 200610165432 A CN200610165432 A CN 200610165432A CN 101204661 A CN101204661 A CN 101204661A
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Abstract
The invention provides an oxidation catalyst for high efficiency catalytic disinfecting in water at room temperature and a preparation method thereof. The catalyst is composed of common metal phosphate supporting a little active metal component of which the capacity is 1 to 6 percent (equivalent value of metal weight) respectively and a certain proportion of lanthanon adulterated. The metal phosphate is generated from the reaction of metal oxide and phosphoric acid at a certain temperature, which supports active metal component by impregnation. The invention can realize an efficient catalytic oxidation disinfecting water source polluted by pathogenic microorganism, which is applicable to filtration and purification devices such as filter screen and filter core of drinking water dispensers, water clarifier and mineral pot, etc. The catalyst of the invention can be used without additional external condition, which is energy saving, easy recycling, in accord with economic and environmental protection requirement and possessing promotion value.
Description
Technical field
The present invention is applied to the environmental catalysis technical field, relates under the room temperature condition catalytic oxidation of invasive organism is removed, and realizes sterilization and purification to drinking water, reduces the harm of disease to human body.
Background technology
Because the existence of bacterium, virus and other pollutant in the water brings great harm for human life.According to statistics, human 80% disease is polluted by water and is caused, and it then is the main killer who causes disease that invasive organism wherein pollutes.Wreaking havoc of SARS virus in 2003 and bird flu epidemic situation following closely more aroused the strong consciousness of the public to self living environment sterilization, sterilization, promoted the R and D to antiseptic of environment and medical field.
Use more drinking water disinfection technology at present disinfection by chlorine method, ozone disinfection and ultraviolet sterilization etc. are arranged.Wherein use time traditional disinfection by chlorine method at most through current research show very easily with water in the organic pollution reaction produce carcinogenic accessory substances such as chloroform, the ozonization rule is easy to the bromide ion in the water is oxidized to harmful accessory substances such as bromate, employed ultraviolet ray and ozone all need in situ preparation in the disinfecting process in addition, the equipment complexity.
In recent years, with the especially nontoxic TiO of semi-conducting material
2For the photocatalysis oxidation technique of catalyst becomes drinking water disinfection Study on Technology focus, but the problem of its existence in actual applications is, is to guarantee advantages of high catalytic activity, except will be with TiO
2Nano-powder or film still need use ultraviolet light or near ultraviolet excitation TiO as outside the photochemical catalyst
2Produce strong oxidizing property intermediate kill microorganisms, this just makes not only method for preparing raw material complexity of this kind technology, the specification requirement height, and also the integral device complexity causes cost higher, as patent 96197457.5 and 98240831.5.These tangible deficiencies have limited this kind technology applying in extensive water factory.
Summary of the invention
The present invention is directed to the problems referred to above, provide a kind of ultraviolet light that do not need also not need other photoelectricity energy at room temperature just can realize the catalyst that the thorough catalytic oxidation of pathogenic microorganisms is removed, be issued to the purpose of killing microorganisms and purified water source in environmental protection and energy-conservation prerequisite.This catalyst use be simple and easy to metal oxide and small amount of precious metals and transition metal be raw material, the preparation method is simple.And bactericidal action is lasting, does not need complicated auxiliary device and external condition.
The principles of science of the present invention is described below: the result of study of modern Surface Science shows, oxygen is adsorbed on oxygen atom or charged peroxide or the superoxide radical that a lot of transition metal and some precious metal surfaces can be dissociated into adsorbed state under the room temperature.These free radicals have extremely strong oxidisability, thereby bactericidal activity is high.We have found a kind of load nanoscale high dispersion metal catalyst in recent research, can at room temperature airborne microorganism and formaldehyde exhaustive oxidation be decomposed into water and carbon dioxide, these scientific discoveries have been confirmed more and have been utilized airborne oxygen or oxygen in water to be oxidant, realize the possibility of efficient killing microorganisms on the specific catalyst surface.Studies show that further simultaneously that the doping of an amount of rare earth element can effectively suppress the reunion of active metal component, promotes its dispersion at carrier surface, make catalyst performance stable more and not easy to change.And this catalytic oxidation disinfective action, can not produce any side effect to human body and environment.
Catalyst of the present invention is based on metal phosphate, the active metal component of load 1～6%, and a certain proportion of rare earth element that mixes.Wherein metal phosphate is obtained by the phosphoric acid of at least a metal oxide and 1～5mol/L in alundum (Al (boehmite, zeolite), the silica (diatomite) stirring reaction 1～3h under 50～60 ℃, condition of normal pressure.Phosphate itself is a kind of excellent carrier with adsorption function and catalysis, and the phosphate carrier of in situ preparation has bigger specific area and activity under experiment condition.Active metal component is loaded on the phosphate carrier simultaneously or with any sequencing by one or more metals in silver, copper, the zinc.Infusion process is adopted in load, promptly directly join in the above-mentioned carrier solution according to the ratio of 1～6% (metallic element weight scaled value) load capacity nitrate solution with this metal, be 1: 1 the ratio adding rare-earth element cerium or the nitrate solution of lanthanum according to active metal component and rare earth element atom number ratio simultaneously, abundant at ambient temperature stirring reaction 1～3h.After load is finished, evaporate moisture in 60 ℃, put into baking oven again and spend the night, after Muffle furnace roasting 3～8h in 600 ℃ of air promptly makes catalyst in 120 ℃ of oven dry with Rotary Evaporators.The particle that catalyst is sieved as required certain order number is standby.
Aforesaid catalyst according to different needs, can be made various structures, as loads on various metal honeycombs or the mesh structure wall surface, and on the cellulosic filter screen, filter cloth, or open-celled foams also can be as the structural carrier of catalyst.The filtering and purifying that is used for article such as various water dispensers, water purifier and mineral pot.
Preparation process of the present invention is simple, and is easy to operate.Compare with prior art, the present invention has following advantage:
(1) cheap being easy to get of Preparation of Catalyst raw material of the present invention, preparation technology is simple, can effectively be applied under the room temperature condition oxidation removal of pathogenic microorganisms in the drinking water, and heat-resisting high temperature resistant, not easy to change, stable performance.
When (2) catalyst of the present invention uses, with the oxygen in water is oxidant, need not promptly have efficient, lasting bactericidal activity under the illumination condition in room temperature, and can further the microorganism exhaustive oxidation be decomposed into harmless little molecules such as water and carbon dioxide, thereby reach the purpose of sterilizing and purifying.
(3) catalyst of the present invention can reach 100% sterilizing rate to objective microbe Escherichia coli and staphylococcus aureus in shorter action time under experiment condition, sterilizing ability is with the remarkable enhancing of the rising of temperature and can keep antibacterial for a long time, can not cause any harm to human body and ecological environment.
(4) catalyst amount of the present invention is few, and each metal ion species of stripping and does not need ultraviolet source and thermal source all less than the limit value of national drinking water sanitary standard (GB5749-85) defined in the water, equipment is simple, operating cost is low, energy savings, safety economy.
The specific embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to scope of the present invention.
Embodiment 1
Accurately take by weighing the 11.77g boehmite and join slowly in 50 ℃ the phosphate aqueous solution of 1mol/L, the limit edged stirs, and after treating fully to react 1h, cools to room temperature naturally, contains AgNO to adding simultaneously wherein
30.1575g silver nitrate aqueous solution and contain Ce (NO
3)
36H
2The cerous nitrate aqueous solution of O0.4023g, behind abundant stirring reaction 3h under the room temperature, mixed solution is added Rotary Evaporators evaporate moisture in 60 ℃, next putting into baking oven spends the night in 120 ℃ of oven dry, put into Muffle furnace at last in 450 ℃ of roasting 3h, 600 ℃ of roasting 3h, it is standby for 40-60 purpose particle to reduce to after the room temperature screening.The silver components load capacity of manufactured goods catalyst is 1% (metallic element weight scaled value), and cerium is 1: 1 with the atom number ratio of silver.2 times and 4 times of the interpolation quality of proportional increase silver nitrate and cerous nitrate promptly obtain silver components content respectively and are 2% and 4% catalyst.
Embodiment 2
Accurately take by weighing γ-Al
2O
310.00g join slowly in 50 ℃ the phosphate aqueous solution of 1mol/L, the limit edged stirs, and after treating fully to react 1h, cools to room temperature naturally, contains Cu (NO to adding simultaneously wherein
3)
26H
2The copper nitrate aqueous solution of O 1.8472g and contain Ce (NO
3)
26H
2The cerous nitrate aqueous solution of O2.7140g, making the cerium and the atom number ratio of copper is 1: 1, behind abundant stirring reaction 3h under the room temperature, mixed solution is added Rotary Evaporators evaporate moisture in 60 ℃, next putting into baking oven spends the night in 120 ℃ of oven dry, put into Muffle furnace at last in 450 ℃ of roasting 3h, 600 ℃ of roasting 3h, it is standby for 40-60 purpose particle to reduce to after the room temperature screening.Promptly obtain the copper constituent content and be 4% catalyst.
Embodiment 3
Get each 0.005g of catalyst of various active components among the embodiment 1 respectively, adding fills in the 100ml conical flask of 100ml aseptic deionized water, and promptly catalyst concn is 50mg/L, to wherein adding the initial bacterium liquid of Escherichia coli, adjusting final bacterial concentration is 6E+06CFU/ml, in 25 ℃ of room temperatures, O
2Flow is to carry out the bactericidal activity test under the 60ml/min aeration condition, adopts magnetic stirring apparatus that system is constantly stirred in the course of reaction.Culture experiment result shows that silver carrying amount is 1%, 2% and 4% catalyst, and sterilizing rate can reach 99.8%, 99.9% and 100% respectively behind reaction 2h.And bactericidal action is lasting, and not seeing in the 48h has bacteria growing.And control experiment shows, not adding catalyst under the similarity condition and only adding the phosphoric acid alumina supporter does not then have bactericidal effect.
Embodiment 4
Get silver components content among the embodiment 1 and be 4% catalyst 0.005g, add and fill in the 100ml conical flask of 100ml aseptic deionized water, be that catalyst concn is 50mg/L, to wherein adding the initial bacterium liquid of Escherichia coli, adjusting final bacterial concentration is 6E+06CFU/ml, reaction system is put into the magnetic agitation thermostat water bath, and accurate temperature controlling carries out the bactericidal activity test respectively under 25 ℃, 35 ℃ and the 40 ℃ of conditions.Culture experiment result shows that bactericidal activity significantly strengthens with the rising of reaction temperature, under reaction temperature is 25 ℃, 35 ℃ and 40 ℃ of conditions, after reacting 3h, 1h and 0.5h respectively, sterilizing rate can reach 100%, and bactericidal action is lasting, and not seeing in the 48h has bacteria growing.And control experiment shows, not adding catalyst under the similarity condition and only adding the phosphoric acid alumina supporter does not then have bactericidal effect.
Catalyst is to the colibacillary activity of killing under the table 1 differential responses temperature
Embodiment 5
Get silver components content among the embodiment 1 and be 4% catalyst 0.2g, under 20 atmospheric pressure, be pressed into the disk of one centimetre of diameter, under 25 ℃ of conditions of room temperature, be that agar medium after Escherichia coli bacteria liquid and the heating of 6E+06CFU/ml evenly mixes in culture dish with bacterial concentration, to be cooled solidify to the incubated at room temperature base after, be placed on agar surface in the culture dish at a certain distance with the catalyst disk with as the onesize filter paper dick of blank, behind 37 ℃ of cultivation 24h, asepsis growth around the catalyst, and bacteriostasis continues 48h and does not see have bacterium to grow, as around the filter paper of blank then with a large amount of bacterium colonies of the equally even growth in other positions.
Embodiment 6
Get copper content among the embodiment 2 and be 4% catalyst 0.2g, under 20 atmospheric pressure, be pressed into the disk of one centimetre of diameter, behind high-temperature sterilization, pour into agar medium in the sterile petri dish, treat its cool off naturally be condensed into solid-state plane after, under 25 ℃ of conditions of room temperature, is that the staphylococcus aureus bacterium liquid of 6E+06CFU/ml is uniformly coated on its surface with aseptic glass slicker with concentration, be placed on agar surface in the culture dish at a certain distance with the catalyst disk with as the onesize filter paper dick of blank, behind 37 ℃ of cultivation 24h, asepsis growth around the catalyst, and bacteriostasis continues 48h and does not see have bacterium to grow, as around the filter paper of blank then with a large amount of bacterium colonies of the equally even growth in other positions.
Claims (9)
1. a water source that at ambient temperature invasive organism is polluted carries out effective catalyst of catalytic oxidation sterilization and preparation method thereof, it is characterized in that this catalyst is to obtain a small amount of active metal component of load on the metal phosphate carrier by metal oxide and phosphatase reaction, and a certain proportion of rare earth element that mixes constitutes.
2. the described catalyst of claim 1 as described above, it is characterized in that, the aforementioned metal oxide component is at least a in alundum (Al, the silica, and aforementioned active metal component is at least a in silver, copper, the zinc, and aforementioned rare earth element component is at least a in cerium, the lanthanum.
3. the described method for preparing catalyst of claim 1 as described above, it is characterized in that, aforementioned metal phosphate carrier is obtained by the metal oxide and the phosphatase reaction of correspondence, and active metal component and Doped Rare Earth component load on the metal phosphate carrier by infusion process.
4. as described above among the described preparation method of claim 3, during preparation phosphate carrier, water-bath control reaction temperature is 50～70 ℃, under fully stirring metal oxide is added in the phosphoric acid of 1～5mol/L, and the reaction time is 1～3h.
5. as described above among the described preparation method of claim 3, adopt infusion process, it is characterized in that after different activities component metals and the nitrate of rare earth element aqueous solution, join in the carrier solution for preparing, behind abundant at ambient temperature stirring reaction 1～3h, at first, place 120 ℃ of oven dry to spend the night then, roasting 3～8 hours in 600 ℃ of air at last at 60 ℃ of rotation evaporates to dryness.
6. as described above among the described preparation method of claim 3, be the nitrate solution that 1: 1 ratio adds rare-earth element cerium or lanthanum according to active metal component and rare earth element atom number ratio during doped with rare-earth elements.
7. as described above among the described preparation method of claim 3, it is characterized in that the load capacity of the active metal component on the aforementioned metal phosphate carrier is 1～6% by the metal element wt.
8. the described catalyst of claim 1 as described above is characterized in that invasive organism is meant Escherichia coli and staphylococcus aureus.
9. the described catalyst of claim 1 as described above, it is characterized in that, be oxidant with the oxygen in water in the application process, need not promptly have efficient, lasting bactericidal activity under the illumination condition in room temperature, and can further the microorganism exhaustive oxidation be decomposed into harmless little molecule.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101654323A CN101204661A (en) | 2006-12-20 | 2006-12-20 | Efficient oxidation catalyst catalyzing disinfection under room temperature and preparation method thereof |
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| CNA2006101654323A CN101204661A (en) | 2006-12-20 | 2006-12-20 | Efficient oxidation catalyst catalyzing disinfection under room temperature and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252365A (en) * | 2019-04-26 | 2019-09-20 | 宁波市雨辰环保科技有限公司 | The catalyst system and its application of air generation hydroxyl free radical |
| CN115301254A (en) * | 2022-09-29 | 2022-11-08 | 山东华城工程技术有限公司 | Ozone oxidation catalyst, preparation and application thereof in water treatment |
-
2006
- 2006-12-20 CN CNA2006101654323A patent/CN101204661A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252365A (en) * | 2019-04-26 | 2019-09-20 | 宁波市雨辰环保科技有限公司 | The catalyst system and its application of air generation hydroxyl free radical |
| CN115301254A (en) * | 2022-09-29 | 2022-11-08 | 山东华城工程技术有限公司 | Ozone oxidation catalyst, preparation and application thereof in water treatment |
| CN115301254B (en) * | 2022-09-29 | 2022-12-23 | 山东华城工程技术有限公司 | Ozone oxidation catalyst, preparation and application thereof in water treatment |
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Open date: 20080625 |