CN101310854B - Filter media and preparation method, filter element, purifier and drinking machine using the filter media - Google Patents
Filter media and preparation method, filter element, purifier and drinking machine using the filter media Download PDFInfo
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Abstract
The invention discloses a method for preparing a filtering medium which is used for removing pesticides in water and includes the steps as follows: a) raw materials containing ultrahigh molecular weight polyethylene, active carbon, sepiolite powder, zeolite powder and a hole opening agent are mixed, and the step (a) is characterized in that the weight ratio of the ultrahigh molecular weight polyethylene to the active carbon, the sepiolite powder, the zeolite powder and the hole opening agent is equal to 100-300:100-300:50-100:50-100:10-50; b) the obtained mixture obtained in the step a) is compacted, sintered and cooled in a mould. The method for preparing the filtering medium to remove the pesticides in the water is simple with low cost and good performance.
Description
Technical field
The present invention relates to a kind of filter medium of removing agricultural chemicals in the water and preparation method thereof, use filter core, the water purifying plant and drinking Fountains of this filter medium.
Background technology
Industry and developing rapidly of agricultural cause water resource to be seriously damaged, industrial wastewater discharge is in rivers, lake, agricultural chemicals, agrochemical be the discharging wantonly of use and house refuse and sanitary wastewater in a large number, the water quality variation that these all cause underground water and surface water causes producing in the water a lot of harmful materials.Water pollutes more and more becomes the severe problem that influences people's life.
From worldwide, the water resource of nearly all country has all suffered the pollution of agricultural chemicals, and China is large agricultural country, and the agricultural chemicals of use is then more, and the pollution that is subjected to agricultural chemicals is even more serious.Some experts of ministry of Health of China from early 1980s to the end of the nineties, the water quality situation of national water resource is investigated analysis to be found afterwards: the Yellow River, Taihu Lake etc. is subjected to the generally pollution of agricultural chemicals, pesticide concentration is many in the water, kind is many, for example BHC, DDT, Atrazine, ametryn etc.Wherein based on BHC and DDT.In addition, the Atrazine in the Guanting reservoir of Beijing exceeds standard.
In China, BHC is the most serious agricultural chemicals that is detrimental to health that contains in the agricultural chemicals water.BHC is the trade name of lindane, and English abbreviates BHC as, and molecular formula is C
6H
6Cl
6,, therefore must be called BHC because carbon, hydrogen, chlorine atom respectively are 6 in the molecule.Lindane normal temperature for white crystal, has 8 kinds of isomers down, is respectively α, β, γ, δ, ε, η, θ and ξ.Lindane insect is had tag, smoked kill and stomach poison function, wherein the gamma isomer desinsection is renderd a service the highlyest, αYi Gouti takes second place, the δ isomers takes second place again, beta isomer efficient is extremely low.Human body mainly show as when poisoning headache, dizziness, hidrosis, unable, tremble, upper and lower extremities is epileptoid convulsion, astasia, ataxia, consciousness is blunt even stupor, also can produce respiratory failure because of the respiratory center inhibition.To digestive system can produce hydrostomia, feel sick, symptoms such as vomiting, epigastric discomfort pain and diarrhoea.The breathing and the circulatory system can cause pharynx, larynx, schneiderian membrane because of sucking agricultural chemicals hyperemia, and there is foreign body sensation in throat, and there are oedema in the frothy sputum that spues, the band trace of blood, expiratory dyspnea, lung, pale, blood pressure drops, body temperature rises, cardiac arrhythmia, tachycardia even ventricular fibrillation.To skin, eye irritation, flush is arranged, produce papule, blister, dermatitis, generation allergic dermatitis; Eye is shed tears, blepharospasm and having an intense pain.
DDT is the another kind of agricultural chemicals that is detrimental to health.The structural formula of DDT is as follows:
The English of DDT abbreviates DDT as, and Chinese is again 1,1,1-three chloro-2, and two (rubigan) ethane of 2-, it is white or pale yellow powder at normal temperatures.DDT is first a large amount of organic synthesis pesticides that use.As far back as 1874, Qi Dele just found, generates a kind of material with chlorobenzene and trichloroacetaldehyde reaction, has desinsection and renders a service.1936～1938, the Miu Le of Switzerland repeated the reaction of Qi Dele in the laboratory, had obtained this material with desinsection effectiveness, and had applied for patent for it.This material formally put into production in nineteen forty-three, was extensive use of for people in the forties in 20th century.DDT has extremely strong tagging and stomach poison function to insect, for various insects good effect is arranged all, and purposes is extremely wide.Therefore in 30 years of its appearance, be important pesticide always.Yet in long-term the use, it has also exposed the shortcoming of oneself, and the most serious is that it is difficult for being decomposed by biological, can left behind, and causes environmental pollution.Symptom has headache, dizzy, nauseating, vomiting, meropresthesia, incoordination during acute poisoning; The rising of weight person's body temperature, tachycardia, expiratory dyspnea, stupor even death.Skin there is spread effect.
The standard GB 5749-1985 of China has stipulated the standard of water quality in the Drinking Water, wherein DDT and BHC are limited the quantity of and be respectively: 1 μ g/L (micrograms per litre) and 5 μ g/L, concrete bioassay standard is referring to the 85th～87 page of standard GB 5750-1985.Utilizing traditional treatment process is the poor effect that coagulation-precipitation-filtering technique is removed the agricultural chemicals that exceeds standard, and utilizes the effect of granular active carbon filtration absorption also undesirable.Electrodialysis, NF membrane, RO film (reverse osmosis membrane) are though treatment effect is fine, and investment such as complex treatment process, equipment is expensive, has limited their application on sizable degree.
Summary of the invention
An object of the present invention is to provide a kind of filter medium, be mainly used in and remove agricultural chemicals in the water, thereby reach the purpose of improving water quality.
Another object of the present invention provides a kind of preparation method of filter medium that is used for removing the water agricultural chemicals.
In order to reach above goal of the invention, the present invention by the following technical solutions:
A kind of preparation method of filter medium that is used for removing the water agricultural chemicals comprises the steps:
A) raw material that will comprise ultra-high molecular weight polyethylene, active carbon, sepiolite powder, zeolite powder and gas generation agent mixes, and it is characterized in that: the weight ratio of ultra-high molecular weight polyethylene, active carbon, sepiolite powder, zeolite powder and gas generation agent is: 100～300: 100～300: 50～100: 50～100: 10～50;
B) mixture of step a) gained is suppressed sintering, cooling in mould.
Described ultra-high molecular weight polyethylene is a weight average molecular weight greater than 1,000,000 polyethylene, and preferably using weight average molecular weight is 250～4,000,000 polyethylene.Ultra-high molecular weight polyethylene can obtain from domestic production producer, and the product of M-I (molecular weight is 150 ± 500,000), M-II (molecular weight is 250 ± 500,000), M-III (molecular weight is 350 ± 500,000), M-IV specifications such as (molecular weight are greater than 4,000,000) can be provided as Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be.An effect of ultra-high molecular weight polyethylene is bonding and the effect that forms the filter medium skeleton, utilizes ultra-high molecular weight polyethylene to pass through compacting in addition, and the filter medium that sintering obtains forms micropore easily, can play the effect of impurity in the adsorbed water.
Active carbon is a kind of porous material, and it has as cellular pore structure, huge specific area, special surface functional group, stable physics and chemical property, is good adsorbent, catalyst or catalyst carrier.Can be divided into wood activated charcoal according to raw material sources different activities charcoal, as cocoanut active charcoal, apricot shell active carbon, wooden burgy etc.; The mineral raw material active carbon is the active carbon that raw material is made as various coals and oil and elaboration products thereof; The active carbon that other raw material is made, the active carbon of making as scrap rubber, waste plastics etc.Be that the active carbon intensity in source is higher, absorption property is better wherein with the coconut husk material.The specific area of preferred active carbon is not less than 500 meters squared per gram, more preferably is not less than 1000 meters squared per gram.
Active carbon is organic matter, the especially medical activated carbon in the adsorbed water efficiently, and as the product by the relevant drug surveilance standard of country, impurity content is lower, and surface area is bigger, and adsorption effect is also better, and is good especially to the suction-operated of agricultural chemicals.Select for use medical activated carbon can guarantee that filter medium is directly used in the processing of drinking water.Preferred use particle diameter is 38～250 microns a medical activated carbon.
Sepiolite can be divided into two types of hot-liquid type sepiolite and appositional pattern sepiolites according to the reason that forms, and is commonly referred to α-type sepiolite and β-type sepiolite.The hot-liquid type sepiolite ore deposit is formed by the hydrothermal solution direct crystallization or is formed through the low temperature hot liquid alteration by volcanic glass, the mineral that contain magnesium, often originates in the dolomitic limestone that is rich in magnesium, the white clouds matter Dali rock; Normal and the carbonate rock of appositional pattern sepiolite deposit, clay rock symbiosis are generated by diagenesis.Hot-liquid type sepiolite is the fibre bundle shape, MgO (magnesia) and SiO
2(silica) content height, Al
2O
3(aluminium oxide) content is low, is rich magnesium sepiolite; The appositional pattern sepiolite is argillaceous, still is fibrous, modified meerschaum Al but observe under electron microscope
2O
3The content height, Mg and SiO
2Content is low, is rich meerschalminite.Sepiolite has big specific area and pore volume, and passage and the space of running through total are arranged, and there are three class activated centres in the sepiolite surface: the oxygen atom in (1) silicon-oxy tetrahedron layer, thus the electric charge a little less than oxygen atom provides carries out the absorption to adsorbate; (2) at the hydrone of edge and magnesium ion coordination, they can form hydrogen bond with adsorbate; (3) at tetrahedral outer surface, Si-O-Si bond fission and the Si-OH ion cluster that produces, come the electric charge of compensate for residual by a proton or a polyhydroxylated molecule, these ion clusters distribute along the spacing of fiber axis with 5 dusts, and its quantity depends on the size of fiber and the scarce cave of crystal.These Si-OH ion clusters can with the interaction of molecules that is attracted on the sepiolite outer surface, can also form covalent bond with some organic reagents.These activated centres make that the absorption property of sepiolite is fabulous, comprise the organic compound that adsorbs nonpolar or low pole.Preferred use particle diameter is 18～150 microns a sepiolite powder.The sepiolite powder specific area that particle diameter is little is big, easier performance suction-operated.Better through the sepiolite powder effect of activation processing, can make acid activation, for example working concentration be 0.1～20% sulfuric acid 20～100 ℃ of immersion treatment 1～15h of temperature (hour).
Natural zeolite is the general name of moisture porous silicate, its crystalline texture mainly is to be made of silicon-oxy tetrahedron, wherein part tetravalence silicon ion is replaced by trivalent aluminium ion, cause the negative electrical charge surplus, the ion that therefore alkali metal or alkaline-earth metal isoequilibrium electric charge are arranged in the structure, the vestibule and the duct of certain pore size are arranged in the zeolite framework simultaneously, determined it to have character such as absorption, ion-exchange.
The modification of natural zeolite can be adopted following method: earlier natural zeolite powder is cleaned up with deionized water, dry, take by weighing the zeolite of certain mass, be immersed in the certain density modifier solution, fully stirring is no less than 2 hours, and filter the neutralization back, clean up dry for standby with deionized water.
Modifier can be the HCl of 0.05～0.30mol/L (mol), the H of 0.01～0.05mol/L
2SO
4, the NaCl of 0.2～1.0mol/L, the NaOH of 0.05～0.25mol/L, or the mixed solution of the NaCl of the HCl of 0.03～0.15mol/L and 0.2～1.0mol/L.When modifier was HCl and NaCl mixed solution, optium concentration NaCl was 0.8mol/L, and HCl is 0.09mol/L, adopted modifier should be no less than 2 hours usually to the time that zeolite carries out the modification processing, preferably was no less than 4 hours, and this moment, correctability was fully complete.
Natural zeolite can also carry out modification by following technology to be handled: natural zeolite is crushed to 5～80 orders, is the hydrochloric acid of 4～10wt% or sulfuric acid impregnation process 10～20 hours with concentration, in sodium carbonate or caustic alkali and after wash, poach 30～60 minutes; Zeolite dehydration after will boiling at 350～580 ℃ of roasting temperatures, is crushed to needed granularity then then.
Zeolite can be removed impurity contained in the mineral and DDGS after modification is handled, etch abundant hole and vestibule in mineral structure, increases its contact area, thus character such as the absorption of raising zeolite, ion-exchange.In the present invention, modified zeolite powder also has extremely strong adsorption capacity to halogen acetic acid.As preferably, modified zeolite powder is the using natural clinoptilolite powder, and particle diameter can be selected 44～124 microns.
Gas generation agent is selected at least a in Celogen Az, food-grade carbonic hydroammonium, the oxalic acid.As preferably, gas generation agent is Celogen Az or food-grade carbonic hydroammonium.Wherein, food-grade carbonic hydroammonium also claims AMMONIUM BICARBONATE FOOD GRADE, distinguishes mutually with technical grade carbonic hydroammonium.Though technical grade carbonic hydroammonium also has the effect of sending out the hole, it may contain the impurity of insalubrity, should not be as the raw materials for production of drinking water filter medium.Gas generation agent is that a class is easily decomposed a large amount of gases of generation and caused a material of sending out the hole effect, and wherein azo compound, sodium acid carbonate, carbonic hydroammonium, ammonium carbonate, sulphonyl nitrile compounds, oxalic acid etc. are its typical representatives.
Pressing pressure can be chosen as 0.4～1.0MPa, and sintering temperature is: 190～300 ℃, sintering time is 10～200 minutes, and being cooled to can the demoulding below 70 ℃.
Though the present invention has carried out comparatively detailed description for several raw materials used in the step a) among the above-mentioned preparation method, the present invention is not limited to this kind theory.Still can not determine for the concrete chemical change between them, the variation of structure in preparation process.The filter medium that these several raw materials are prepared through above-mentioned PROCESS FOR TREATMENT can effectively be removed the agricultural chemicals in the water, and synergy is arranged, and the agricultural chemicals in the water fully can be absorbed, and obtains pure drinking water.
In the present invention, for blend step, can think that any low shear mixer or agitator that can significantly not change diameter of particle and size distribution all is suitable for, such as the agitator with blunt impeller blade, drum-type blender, spiral agitator etc., rotating speed will be decided on the type of blender, but is advisable with the dust of avoiding kicking up.
Mixed powder is filled in the pre-designed mould, and with its compacting, pressure generally is not more than 2MPa by pressurization, and adapts with the material of mould therefor; Mould can be by aluminium, cast iron, steel or any suitable material manufacturing that can bear relevant pressure and temperature.Can be in the mould inner surface release agent application, that can select silicone oil or any other for use can be adsorbed onto commercially available releasing agent on the filter medium hardly, also can use processing release papers such as aluminium foil.
The present invention also provides following technical scheme: a kind of filter core that uses above-mentioned filter medium.
The present invention also provides following technical scheme: a kind of purifier comprises above-mentioned filter medium or filter core.
The present invention also provides a kind of water dispenser that comprises above-mentioned purifier.
With respect to prior art, the invention has the advantages that the technical scheme that is proposed can remove agricultural chemicals in the water, thereby reach the purpose of improving water quality, and method is simple, cost is low.
The specific embodiment
For further understanding the present invention, above-mentioned technical scheme is further elaborated and illustrates below in conjunction with embodiment.
Embodiment 1
(1) take by weighing ultra-high molecular weight polyethylene powder 220 grams, described ultra-high molecular weight polyethylene is the M-III type product of Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be, and its molecular weight is 3,500,000;
(2) take by weighing medicinal active powdered carbon 180 grams, the particle diameter of described medical activated carbon is 38～250 microns;
(3) take by weighing sepiolite powder 80 grams, the particle diameter of described sepiolite powder is 18～150 microns, the acidified activation processing of this sepiolite powder, concrete acidification technology is: working concentration is that 10% sulfuric acid is at 60 ℃ of immersion treatment 12h of temperature, it is clean to spend deionised water then, and at 300 ℃ of following roasting 3h;
(4) take by weighing using natural clinoptilolite powder 60 grams, the particle diameter of described using natural clinoptilolite powder is 44～124 microns, the acidified activation processing of this using natural clinoptilolite powder, concrete processing acidification technology is: use HCl and NaCl mixed solution to soak 6h, wherein NaCl concentration is 0.8mol/L, and HCl concentration is 0.09mol/L, utilizes the NaOH solution neutralization of 0.1mol/L then, clean up with deionized water, then 100 ℃ of oven dry down;
(5) take by weighing food-grade carbonic hydroammonium 20 grams, purity reaches more than 99.99%;
(6) above-mentioned five kinds of powder are put into the mechanical agitator stirring mixed in 10 minutes;
(7) being packed into diameter is in the 50mm tubular die, suppresses under the hydraulic pressure of 0.8MPa, 260 ℃ of sintering temperatures 180 minutes.
(8) naturally cool to 50 ℃ of demouldings then, promptly get the tubulose filter core of many minute apertures.
Embodiment 2
(1) take by weighing ultra-high molecular weight polyethylene powder 150 grams, described ultra-high molecular weight polyethylene is the M-III type product of Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be, and its molecular weight is 3,500,000;
(2) take by weighing medicinal active powdered carbon 140 grams, the particle diameter of described medical activated carbon is 178～250 microns;
(3) take by weighing sepiolite powder 70 grams, the particle diameter of described sepiolite powder is 38～150 microns, the acidified activation processing of this sepiolite powder, concrete acidification technology is: working concentration is that 10% sulfuric acid is at 60 ℃ of immersion treatment 12h of temperature, it is clean to spend deionised water then, and at 300 ℃ of following roasting 3h;
(4) take by weighing using natural clinoptilolite powder 65 grams, the particle diameter of described using natural clinoptilolite powder is 44～124 microns, the acidified activation processing of this using natural clinoptilolite powder, concrete processing acidification technology is: use HCl and NaCl mixed solution to soak 6h, wherein NaCl concentration is 0.6mol/L, and HCl concentration is 0.07mol/L, utilizes the NaOH solution neutralization of 0.1mol/L then, clean up with deionized water, then 100 ℃ of oven dry down;
(5) take by weighing food-grade carbonic hydroammonium 15 grams, purity reaches more than 99.99%;
All the other steps are identical with embodiment 1.
Embodiment 3
(1) take by weighing ultra-high molecular weight polyethylene powder 180 grams, described ultra-high molecular weight polyethylene is the M-II type product of Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be, and its molecular weight is 2,500,000;
(2) take by weighing medicinal active powdered carbon 170 grams, the particle diameter of described medical activated carbon is 89～178 microns;
(3) take by weighing sepiolite powder 60 grams, the particle diameter of described sepiolite powder is 38～178 microns, the acidified activation processing of this sepiolite powder, concrete acidification technology is: working concentration is that 10% sulfuric acid is at 60 ℃ of immersion treatment 12h of temperature, it is clean to spend deionised water then, and at 300 ℃ of following roasting 3h;
(4) take by weighing using natural clinoptilolite powder 80 grams, the particle diameter of described using natural clinoptilolite powder is 44～124 microns, the acidified activation processing of this using natural clinoptilolite powder, concrete processing acidification technology is: use HCl and NaCl mixed solution to soak 6h, wherein NaCl concentration is 0.6mol/L, and HCl concentration is 0.07mol/L, utilizes the NaOH solution neutralization of 0.1mol/L then, clean up with deionized water, then 100 ℃ of oven dry down;
(5) take by weighing Celogen Az 14 grams, it is pure that its purity reaches analysis;
All the other steps are identical with embodiment 1.
Embodiment 4
(1) take by weighing ultra-high molecular weight polyethylene powder 250 grams, described ultra-high molecular weight polyethylene is the M-I type product of Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be, and its molecular weight is 1,500,000;
(2) take by weighing medicinal active powdered carbon 200 grams, the particle diameter of described medical activated carbon is 38～178 microns;
(3) take by weighing sepiolite powder 75 grams, the particle diameter of described sepiolite powder is 38～178 microns, the acidified activation processing of this sepiolite powder, concrete acidification technology is: working concentration is that 10% sulfuric acid is at 60 ℃ of immersion treatment 12h of temperature, it is clean to spend deionised water then, and at 300 ℃ of following roasting 3h;
(4) take by weighing zeolite powder 60 grams, the particle diameter of described zeolite powder is 44～124 microns, the acidified activation processing of this using natural clinoptilolite powder, concrete processing acidification technology is: use HCl and NaCl mixed solution to soak 7h, wherein NaCl concentration is 0.8mol/L, and HCl concentration is 0.05mol/L, utilizes the NaOH solution neutralization of 0.1mol/L then, clean up with deionized water, then 100 ℃ of oven dry down;
(5) take by weighing oxalic acid 35 grams, it is pure that its purity reaches analysis;
All the other steps are identical with embodiment 1.
Embodiment 5
Get the tubulose filter core 1,2,3 of the many minute apertures of embodiment 1～4 gained, 4, the liner two-layer nonwoven, the outsourcing two-layer nonwoven wraps polypropylene porous net at skin again, bonding the going up in filter core two ends connects end cap, be positioned in stainless steel or the plastic casing, be used for Drinking Water, after testing, this filter core is good, as shown in table 1 to the removal effect of BHC in the drinking water and DDT.The needs that are fit to very much the home terminal drinking water treatment.
Table 1 uses filter core to handle the water of front and back, and method of testing adopts GB5750-1985 unit: μ g/L
As can be seen from Table 1, the agricultural chemicals that utilizes filter core of the present invention to remove in the water has been obtained good effect.
More than filter medium provided by the present invention and preparation method thereof and the filter core made by this filter medium are described in detail.Used specific embodiment in this specification principle of the present invention and embodiment have been set forth, for one of ordinary skill in the art, according to the thought of the present invention part that may in implementation process, can change in specific embodiments and applications.Therefore, the content of this specification record should not be construed as limitation of the present invention.
Claims (11)
1. a preparation method of filter medium that is used for removing the water agricultural chemicals comprises the steps:
A) raw material that will comprise ultra-high molecular weight polyethylene, active carbon, sepiolite powder, zeolite powder and gas generation agent mixes, it is characterized in that: the weight ratio of ultra-high molecular weight polyethylene, active carbon, sepiolite powder, zeolite powder and gas generation agent is: 100～300: 100～300: 50～100: 50～100: 10～50, and the acidified activation processing of described sepiolite powder;
B) mixture of step a) gained is suppressed sintering, cooling in mould.
2. preparation method according to claim 1 is characterized in that: the molecular weight of ultra-high molecular weight polyethylene is 250～4,000,000.
3. preparation method according to claim 1 is characterized in that: active carbon is a medical activated carbon, and its particle diameter is 38～250 microns.
4. preparation method according to claim 1 is characterized in that: the particle diameter of sepiolite powder is 18～150 microns.
5. preparation method according to claim 1 is characterized in that: zeolite powder is the acid-treated using natural clinoptilolite powder of process.
6. preparation method according to claim 1 is characterized in that: gas generation agent is at least a in Celogen Az, food-grade carbonic hydroammonium, the oxalic acid.
7. preparation method according to claim 1 is characterized in that: the temperature of sintering is 190～300 ℃.
8. the filter medium that obtains according to each described preparation method in the claim 1～7.
9. use the filter core of the described filter medium of claim 8.
10. a purifier comprises and uses described filter medium of claim 8 or the described filter core of claim 9.
11. a water dispenser comprises the described purifier of claim 10.
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| CN101844007B (en) * | 2009-03-27 | 2011-10-26 | 周奇迪 | Filter medium and preparation method thereof, filter element and water purification device |
| CN101844011B (en) * | 2009-03-27 | 2012-07-04 | 奇迪电器集团有限公司 | Filter medium for removing nitrobenzene from drinking water and preparation method thereof |
| CN101844009B (en) * | 2009-03-27 | 2012-06-13 | 奇迪电器集团有限公司 | Filter medium for removing organophosphorus pesticide from water and preparation method thereof |
| CN101844005B (en) * | 2009-03-27 | 2012-05-23 | 奇迪电器集团有限公司 | Filter medium for removing benzene and homologous compounds thereof from drinking water and preparation method thereof |
| WO2010139816A1 (en) * | 2009-06-05 | 2010-12-09 | Desarrollos Tecnicos Mc, S.L. | Composition and use of an adsorbent material for filtering toxic components during the process of incineration and/or distillation of glycerine generated from the production of biodiesel |
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