Be used for filter medium of removing the drinking water halogenated nitromethane and preparation method thereof
Technical field
The present invention relates to a kind of filter medium of removing halogenated nitromethane in the drinking water and preparation method thereof, the filter core, the water purifying plant and drinking Fountains that constitute by this filter medium.
Background technology
Because urban population is concentrated, chemical fertilizer is used in industrial production accident and agricultural production in a large number, make the surface water body of China contain the organonitrogen compound of higher concentration, water body generally has peculiar smell, colourity height, alga microbial raised growth.Over nearly 30 years, people have relatively paid attention to the control and the elimination of cholorination accessory substance in the water such as haloform, carbon tetrachloride, halogen acetonitrile, halogen acetic acid etc., but often ignored in the water by soluble organic nitrogen compound and chlorine generation halogenation the nitrogenous DBPs (N-DBPs) that the toxicity of generation is bigger.
Coagulation in the conventional treatment process of waterworks-precipitation clarification-filtration-sterilization is pointed out in many researchs, and the organic nitrogen compound of soluble organic nitrogen thing clearance<more than 10%, 90% is still remained in the output water.Increasing nitrogenous DBPs is detected in output water, halogenated nitromethane (HNMs) is representative wherein, the hydrophily of halogenated nitromethane is better than general DBPs, its carcinogenic risk is apparently higher than haloform and halogen acetic acid, have strong cytogenetic toxicity and mutagenicity, bigger harmfulness is arranged, thereby to having higher requirement for water technology material etc.
The general membrane technology that uses is not fine to the removal effect of halogenated nitromethane in the water; The clearance of oxidation technology is also lower; The counter-infiltration complex structure, power consumption and waste a large amount of water sources.
Summary of the invention
The technical problem that the present invention solves provides a kind of filter medium and preparation method thereof, and this filter medium also provides the filter core, purifier and the water dispenser that are made of this filter medium to the clearance height of the halogenated nitromethane in the drinking water.
For addressing the above problem, the present invention by the following technical solutions:
A kind of preparation method of filter medium that is used for removing the drinking water halogenated nitromethane comprises the steps:
A) raw material that will comprise activated carbon powder, ultra-high molecular weight polyethylene powder, attapulgite powder and gas generation agent mixes, and the weight ratio of described activated carbon powder, ultra-high molecular weight polyethylene powder, attapulgite powder, magnesium chloride hexahydrate, aluminium chloride and gas generation agent is: 50~300: 100~400: 50~300: 50~150;
B) mixture of step a) gained is suppressed sintering, cooling in mould.
As preferably, the weight ratio of activated carbon powder, ultra-high molecular weight polyethylene powder, attapulgite powder, magnesium chloride hexahydrate, aluminium chloride and gas generation agent is: 120~130: 290~300: 90~100: 120~130.
Pressing pressure is 0.4~1.0MPa, and sintering temperature is 200 ℃~300 ℃, and sintering time is 120~150 minutes, is cooled to 40 ℃~60 ℃ demouldings behind the sintering.In this manufacturing process, after inventor's test many times, draw the filter medium of in 200~300 ℃, producing in sintering range, filter effect is better.
Active carbon is a kind of porous carbon adsorbent, and it has as cellular abundant 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.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 can efficiently adsorb organic matter, heavy metal, the heterochromatic peculiar smell in the drinking-water, especially medical activated carbon, as product by the relevant drug surveilance standard of country, impurity content is lower, surface area is bigger, adsorption effect is also better, and is good especially to the absorption of color and smell, selects for use medical activated carbon can guarantee that filter medium is directly used in the processing of drinking water.The molecular weight of halogenated nitromethane is less, and active carbon has very strong absorption property to it, mainly occurs on the surface of activated carbon powder, and the mesopore of active carbon inside, fine holes also have many adsorbances.
As preferably, it is 74~104 microns medical activated carbon that active carbon is selected particle diameter for use.
Described ultra-high molecular weight polyethylene is a weight average molecular weight greater than 1,000,000 polyethylene, and preferred particle diameter is 89~104 microns.Ultra-high molecular weight polyethylene can obtain from domestic production producer, and the product of M-I type (molecular weight is 150 ± 500,000), M-II type (molecular weight is 250 ± 500,000), M-III type (molecular weight is 350 ± 500,000), M-IV type 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, because the molecular weight of ultra-high molecular weight polyethylene is big, melt viscosity is very high, fusion can not be flowed later, so utilize ultra-high molecular weight polyethylene to pass through compacting, the filter medium that sintering obtains forms micropore easily, can play the effect of chloro-acetamide in the adsorbed water.
Attapulgite is a monoclinic system, and its desirable chemical formula is; Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, the chemical composition theoretical value is MgO 23.83%, SiO
256.96%, H
2O 19.21%.The attapulgite of occurring in nature often has Al
3+, Fe
3+Deng isomorphous replacement, rich Al
3+, Fe
3+Mutation be called aluminium attapulgite and iron attapulgite.Composition as the aluminium attapulgite powder of the Dragon King of Xuyi County, Jiangsu Province mountain products is SiO
258.38%, MgO 12.10%, Al
2O
39.50%, CaO 0.40%, TiO
20.56%, MnO 0.05%, Fe
2O
3+ FeO 5.26%, Na
2O 1.10%, K
2O 1.24%.Because attapulgite has the major path of similar zeolite in structure, therefore have good adsorption and decoloration performance, the organism that decomposes and hydrogen sulfide etc. all there are the good adsorption performance.SiO in the absorption property of attapulgite powder and the mineral
2Content relevant, the high more absorption affinity of content is strong more, the performance of the attapulgite powder after acid activation is handled is better.
The acid activation method of attapulgite powder is more, and sulfuric acid process, salt acid system, sulfuric acid-mixed in hydrochloric acid method etc. are arranged.As application number is the acid soak activating process that the patent of invention of CN90105849.1 discloses a kind of attapulgite powder, comprises the about 0.5~100cm of the volume of fritter
3The Concave-convex clay rod raw ore, with concentration is the inorganic acid solution of 1~15wt% (weight fraction), as sulfuric acid, hydrochloric acid solution etc., static immersion 2~100 hours, filter extruding in flakes, 280~350 ℃ of down activation 30~50 minutes, be ground into decolorizing ability and be 250 ± 5 active attapulgite stone flour with revolving drier.
As preferably, the attapulgite powder is 74~104 microns active attapulgite stone flour for the particle diameter of handling through acid activation, attapulgite powder after the modification has very big specific area, has outer surface absorption, colloid absorption, ion-exchange absorption to echo multiple suction types such as its duct inner surface absorption to halogenated nitromethane.Preferred use phosphoric acid modification attapulgite powder.
Gas generation agent of the present invention 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.As preferably, gas generation agent is at least a in Celogen Az, food-grade carbonic hydroammonium, the oxalic acid.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.
The present invention has carried out comparatively detailed description for several raw materials used in the step a) among the above-mentioned preparation method, and under the collaborative adduction of these several raw materials, the halogenated nitromethane in the water can fully be adsorbed.
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 paper.
The present invention also provides following technical scheme: the filter core of halogenated nitromethane in a kind of removal drinking water that is made of 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 clearance height of the filter medium of preparation to the halogenated nitromethane in the water, be applicable to the drinking water that is subjected to its pollution, exempt the injury that halogenated nitromethane produces human body, easy to use, cost is low, be filter core owing to what use in addition, not powder,, be fit to home terminal drinking-water and handle so need not subsequent treatment.This filter medium is more than 93% to the clearance of halogenated nitromethane in the drinking water after testing.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment 1:
(1) take by weighing medicinal active powdered carbon 60g, the particle diameter of described medical activated carbon is 74~104 microns;
(2) take by weighing ultra-high molecular weight polyethylene powder 130g, 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;
(3) take by weighing the attapulgite powder 80g of phosphoric acid acidification;
(4) take by weighing food-grade carbonic hydroammonium 70g, purity reaches more than 99.99%;
(5) above-mentioned four kinds of powder are put into the mechanical agitator stirring mixed in 10 minutes;
(6) mixed powder packing is gone in the tubular die, under the hydraulic pressure of 0.9MPa, suppress, 250 ℃ of sintering temperatures 140 minutes;
(7) naturally cool to 50 ℃ of demouldings then, promptly get the tubulose filter core of many minute apertures.
The diameter of the filter core of preparation is 50mm, and length is 200mm.
Embodiment 2:
(1) take by weighing medicinal active powdered carbon 125g, the particle diameter of described medical activated carbon is 74~104 microns;
(2) take by weighing ultra-high molecular weight polyethylene powder 295g, 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;
(3) take by weighing the attapulgite powder 95g of phosphoric acid acidification;
(4) take by weighing food-grade carbonic hydroammonium 85g, purity reaches more than 99.99%;
(5) above-mentioned four kinds of powder are put into the mechanical agitator stirring mixed in 10 minutes;
(6) mixed powder packing is gone in the tubular die, under the hydraulic pressure of 0.8MPa, suppress, 280 ℃ of sintering temperatures 130 minutes;
(7) naturally cool to 60 ℃ of demouldings then, promptly get the tubulose filter core of many minute apertures.
The diameter of the filter core of preparation is 50mm, and length is 200mm.
Embodiment 3:
(1) take by weighing medicinal active powdered carbon 200g, the particle diameter of described medical activated carbon is 74~104 microns;
(2) take by weighing ultra-high molecular weight polyethylene powder 350g, 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;
(3) take by weighing the attapulgite powder 150g of phosphoric acid acidification;
(4) take by weighing Celogen Az 135g, purity reaches more than 99.99%;
(5) above-mentioned four kinds of powder are put into the mechanical agitator stirring mixed in 10 minutes;
(6) mixed powder packing is gone in the tubular die, under the hydraulic pressure of 0.6MPa, suppress, 220 ℃ of sintering temperatures 150 minutes;
(7) naturally cool to 40 ℃ of demouldings then, promptly get the tubulose filter core of many minute apertures.
The diameter of the filter core of preparation is 50mm, and length is 200mm.
Embodiment 4:
(1) take by weighing medicinal active powdered carbon 280g, the particle diameter of described medical activated carbon is 74~104 microns;
(2) take by weighing ultra-high molecular weight polyethylene powder 370g, 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;
(3) take by weighing the attapulgite powder 280g of phosphoric acid acidification;
(4) take by weighing oxalic acid 150g, purity reaches more than 99.99%;
(5) above-mentioned four kinds of powder are put into the mechanical agitator stirring mixed in 10 minutes;
(6) mixed powder packing is gone in the tubular die, under the hydraulic pressure of 0.4MPa, suppress, 300 ℃ of sintering temperatures 120 minutes;
(7) naturally cool to 40 ℃ of demouldings then, promptly get the tubulose filter core of many minute apertures.
The diameter of the filter core of preparation is 50mm, and length is 200mm.
Embodiment 5:
Get the tubulose filter core 1 of the many minute apertures of embodiment 1~4 gained, 2,3,4, the liner two-layer nonwoven, the outsourcing two-layer nonwoven wraps polypropylene porous net at skin again, and 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 to the removal effect of the halogenated nitromethane in the drinking water.With the trichloronitromethane is example, as shown in table 1, and for adopting filter core that embodiment 1~4 the provides content to the trichloronitromethane before and after the drinking water treatment, the result shows that filter core provided by the invention is fit to the needs of home terminal drinking water treatment very much.
Table 1 uses the trichloronitromethane content in the water of filter core processing front and back, unit: mg/L
As can be seen from Table 1, the halogenated nitromethane that utilizes filter core of the present invention to remove in the water has been obtained good effect.
More than filter medium that is used for removing the drinking water halogenated nitromethane provided by the present invention and preparation method thereof and the filter core that is made of this filter medium are described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.