CN101486506B - Arsenic removing apparatus for drinking water - Google Patents
Arsenic removing apparatus for drinking water Download PDFInfo
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- CN101486506B CN101486506B CN2008100101609A CN200810010160A CN101486506B CN 101486506 B CN101486506 B CN 101486506B CN 2008100101609 A CN2008100101609 A CN 2008100101609A CN 200810010160 A CN200810010160 A CN 200810010160A CN 101486506 B CN101486506 B CN 101486506B
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Abstract
The invention relates to the removal of arsenic in drinking water, in particular to a drinking-water arsenic-removing device which comprises a closed hollow cylinder; the upper part of the cylinder is provided with a water outlet, and the lower part of the cylinder is provided with a water inlet; two cylindrical filter elements are vertically arranged inside the cylinder in parallel; the bottom of the filter element on the right is communicated with the water inlet of the cylinder, and the top thereof is provided with a water outlet; the middle and upper part, the middle part and the middle and lower part of the filter element on the right are respectively provided with a detachable hole-born supporting board along radial direction; the three supporting boards divide the cavity in the filter element on the right into four parts which are a filter bed A, a filter bed B, a filter C and a filter D from top to bottom; the bottom of the filter element on the left is provided with a water inlet, and the top of the filter element on the left is communicated with the water outlet of the cylinder; and loaded drinking-water arsenic-removing nano-adsorbing agent is filled in the filter element on the left. The arsenic-removing device has wide application range and can reduce arsenic content in the drinking water to safe standard, thus being suitable for the drinking requirement of scattered towns and citizens.
Description
Technical field
The present invention relates to the removal of arsenic in the tap water water, specifically a kind of arsenic removing apparatus for drinking water.
Background technology
Arsenic is one of hypertoxic element, and the pollution of underground water arsenic has in recent years caused that people pay close attention to widely. regional underground water arsenic content severe overweights such as the Taiwan of China, Xinjiang and the Inner Mongol, arsenic content reaches as high as 2000 μ gL
-1, the area that influenced by Arsenic Contamination in Groundwater reaches more than ten province, autonomous region, and population is up to more than 1,500 ten thousand; There are India, Bangladesh, Vietnam, Argentina, Chile, Mexico, Hungary etc. in the country that Arsenic Contamination in Groundwater is serious in the world.Secular arsenic exposes the canceration that can cause skin, lung, liver, kidney and bladder.The World Health Organization revised the maximum permissible concentration of tap water arsenic in 1993 again, was defined as 10 μ gL
-1The European Union and the U.S. have reformulated the content standard of tap water arsenic, and the maximum permissible concentration of arsenic is from 50 μ gL in the tap water
-1Drop to 10 μ gL
-1New hygienic standard has proposed requirements at the higher level to the removal and the technology of arsenic.
How removed both at home and abroad at present and dropped into very big strength in the water aspect the arsenic technological development, also formed some otherwise effective technique, existing exploitation both at home and abroad in recent years and some treatment technologies that use are summarized as follows.
1. absorption method: absorption method is one of effective ways that arsenic is removed in the tap water, and sorbent material commonly used has activated alumina, gac, functional resin, metal oxide such as ferric oxide and various natural mineral such as zeolite etc.Adopt the ion exchange resin method, the interference of constant disturbances quite well ion pair arsenic such as sulfate ion is big.Activated alumina has strict requirement to former water pH, can only could effectively remove arsenic in narrower scope.The natural mineral low price, wide material sources, but loading capacity is generally very low, it is not high to remove efficient, and there is some trace element in it, may have other health risks. comprise the oxide compound of rare earth oxide such as lanthanum, zirconium, cerium with various metal oxides, the oxide compound of iron such as pyrrhosiderite, rhombohedral iron ore, amorphous ferric hydroxide etc. are removed arsenic, but these oxide compounds mostly do not possess good pore structure, and difficulty is applied to fixed bed.Arsenic from underwater acid group and arsenous anion ion all have a certain proportion of existence, above-mentioned sorbent material mostly can not effectively be removed the arsenous anion ion, therefore when removing arsenic, must operation easier and expense have been increased through preoxidation process as with chlorine and potassium permanganate oxidation etc. with them.A patent of Germany is that the oxyhydroxide granulation with iron obtains granular arsenic-removing adsorption agent, but it is not wear-resisting, and in the column operation process caking easily.
2. direct precipitation method: domestic drinking-water dearsenicating method commonly used mainly contains coagulant sedimentation and filtering layer absorption method etc.Coagulant sedimentation mainly adopts medicine arsenic removals such as ferric flocculant, and this method needn't increase treatment facility in addition, has the reduced investment convenience operation, but also has dosage big simultaneously, and the mud generation is big, introduces shortcomings such as other material in treating water.Consider that high arsenic water area mostly is remote districts, backward in economy, do not possess public drinking water treatment system, therefore dearsenicating method has bigger practical value cost-effectively.
3. ion exchange method: the advantage of this technology is that treatment unit is simple, easy to use, treatment capacity is big.When handling arsenic-containing water in water body, former quality is had relatively high expectations, mainly be applicable to and handle ion component tap water or process water single and that effluent quality is had relatively high expectations with anionite-exchange resin (because of arsenic exists with anionic form).If when containing negatively charged ion such as a large amount of sulfate radicals, phosphate radical, nitrate radical in the former water, resin will soon lose efficacy.
4. embrane method: membrane technique is a selection perviousness of utilizing film, according to the different purposes that reach separate substance by higher external pressure with water molecules of contaminant molecule size.Molecular dimension is effectively removed greater than all contaminants matter of membrane pore size.Big I according to membrane pore size is divided into: microfiltration membrane, ultra-filtration membrane, nanofiltration membrane, reverse osmosis membrane.This technology is all very harsh to the requirement of equipment, film, operational condition, and present studies show that, the electronegative film in blocking layer is effective for the removal of As (V), and it is unsatisfactory to the removal effect that is present in the As (III) in the water body with the electric neutrality form, also need source water is carried out pre-oxidation treatment, cost is very high undoubtedly.This technology be mainly used in demand less relatively, to extra high pure water of water quality requirement and PREPARATION OF ULTRA-PURE WATER.So it is ripe to use this technology to administer on a large scale that opportunity of water body arsenic contamination, is that all right at present.
5. electroosmose process: this technology is that arsenic-containing waste water is placed between two semi-permeable membraness, and outside two semi-permeable membraness, respectively insert a not same sex electrode, feed direct current, zwitterion moves to the two poles of the earth under the electrical forces effect in the water, two semi-permeable membraness only allow a kind of passing through in negatively charged ion or the positively charged ion, have so just reached the purpose of purifying water body.This technology to consume a large amount of electric energy, long processing period, big to equipment corrosion, treatment capacity is little, and is very uneconomical at present.This technology mainly applies to the purifying of material, is in the laboratory exploratory stage at present with the improvement of water body arsenic contamination.
6. biological process: the complicated mechanism of microorganism and the effect of arsenic contamination thing mainly contains the direct mechanism of action and indirect action mechanism at present.Directly mechanism is that various microorganisms absorb arsenic or microorganism consumes the organotrophy source as the carrier of electronics and receptor and makes As (III) oxidation.Indirect mechanism is that a series of biochemical reaction takes place various biological enzymes and the arsenic that microorganism secretion goes out, and arsenic is removed from water body with the form of various organic compound.
This technology is particularly useful for handling routine techniquess such as various physics, chemistry can't be handled or the unfavorable water body of treatment effect, and this technology also is applicable to the processing of underground arsenic polluted water body.Biology belongs to renewable resources, the environmental pollution degree is little, relevant research Showed Very Brisk; And the adaptability of arsenic contamination can be strengthened along with the environmental stimulus effect, and this reinforcement can be hereditary, so biotechnology has huge development potentiality.But this technology still in research, also has certain gap with application.
7. photocatalytic oxidation: photocatalysis oxidation technique is to utilize photocatalyst to absorb luminous energy to discharge with certain wavelengths under certain conditions then, makes the oxygen in water ionization, and then makes As (III) obtain oxidation.After the advantage of this technology was that photocatalyst adds system for handling, catalyzed reaction can comparatively fast be carried out, and photocatalyst can forever use in theory.This technology is just carried out pre-treatment to arsenic polluted water body, also needs to cooperate other technologies just can reach the purpose of removing arsenic.Present research is confined to photocatalyst more and absorbs the catalyzed oxidation that UV-light is emitted energy realization As (III) then, and is unsatisfactory for the effect that absorbs the visible light and the oxidation As (III) that releases energy.
The existing ubiquitous problem of treatment technology:
● can not satisfy the comparatively complicated practical situation of domestic groundwater quality, perhaps actual motion effect instability;
● fixed investment is relative with running cost higher, and some sorbing material is short work-ing life, is difficult for regeneration;
● can not remove As (III) and As (V) simultaneously.
Therefore the present invention is directed to the problem that existing treatment technology exists, be intended to develop a kind of economy and the practical high arsenic of suitable China (As (III) and As (V)) phreatic efficient nano level sorbent material and device thereof, to solve the processing difficult problem of China's some areas tap water arsenic contamination.
At present. the water source of China's living standard of urban and rural population water is subjected to pollution in various degree mostly, and the drinking water quality problem becomes the focus that people pay close attention to.In this case. in order to improve the quality of tap water, household water filter arises at the historic moment, and becomes another focus of household consumption.Household water filter is by physical method amounts of increasing water quality such as cascade filtration and absorption.Can make water quality reach the drinking water standard of national regulation except that the material of harmful human bodies such as some bacterium in anhydrating, virus, suspended substance, heavy metal with it.
Now, household water filter roughly is divided three classes according to its principle of work: adsorption filtration, membrane sepn filter, mineralization and magnetization is handled.Adsorption filtration mainly is to utilize the absorption of the absorption property of gac except that the impurity in anhydrating, hazardous compound etc.; It then is to utilize special finished film (a lot of very tiny holes of its existence that membrane sepn filters, only can pass through water molecules, and other detrimental impurity, biology and heavy metal ion etc. can not by) water is carried out separating treatment, send pure water, polluted water after concentrating is discharged from other water pipe: it then is that the ion component the water is adjusted that mineralization and magnetization is handled, and the dissolving part is to human body beneficial's ion.Reach the effect of whole water.The integrated application of part household water filter above three kinds of principle of work, thereby can be purified water preferably.
Summary of the invention
The objective of the invention is to provides the arsenic removing apparatus for drinking water that a kind of cost is low, can be reduced to the arsenic in the tap water safety standards for the geographic resident of high arsenic; It uses nano level that homemade a kind of functional, loading capacity is big, absorption/parsing speed is fast except that arsenic adsorbent material it to be applied in the economical and practical device, can be fit to disperse resident's drinking-water demand.
For achieving the above object, the technical solution used in the present invention is:
A kind of arsenic removing apparatus for drinking water comprises airtight hollow cylinder, and the top of described cylindrical shell is provided with water port, is provided with water-in in the bottom of cylindrical shell; Vertically be set side by side with two cylindric filter cores in the inside of cylindrical shell;
The bottom of right side filter core is connected with the water-in of cylindrical shell, and the top is provided with water outlet; The middle and upper part of right side filter core, middle part, middle and lower part radially are provided with back up pad dismountable, that have aperture respectively, three back up pads are divided into four parts with the cavity in the filter core of right side, be followed successively by filter bed A, B, C, D from bottom to up, they get final product separate spliting, can be combined into an integral body again, it mainly acts on is that water is handled, and comprises bulk processing and depths reason, and the filter core on the left side only carries out arsenic removal to water to be handled;
Radially be equipped with the nonwoven layer more than 2 layers or 2 layers in the filter bed A, former water is by non-woven fabrics (10-250 gram/square metre), filters materials such as large granular impurity in the filtering water, colloid, alleviates the gac working load;
Be filled with granulated active carbon, natural zeolite and/or medical stone in the filter bed B; Intercept absorption by granulated active carbon, zeolite or medical stone and remove relative smaller particles impurity, colloid, bacterium etc.;
Be filled with the commercially available powder sintered block absorbent charcoal in city in the filter bed C, by powder sintered active carbon layer, small granule foreign, colloid, harmful organic ion, bacterium etc. are removed in absorption;
Radially be equipped with the microfiltration membrane more than 2 layers or 2 layers in the filter bed D, about 0.002～0.1 μ m in the aperture of film, molecular weight cut-off is the impurity of 500-500000, its working pressure is about 0.07-0.7Mpa; Granule foreign, colloid, harmful organic ion, bacterium that the further filtering of microfiltration membrane is trickle guarantee the pure of effluent quality; Micro-filtration (MF) claim millipore filtration again, and it belongs to secondary filter, and its ultimate principle is the sieve aperture sepn process.The material of microfiltration membrane is divided into organic and inorganic two big classes, and organic polymer has cellulose acetate, polypropylene, polycarbonate, polysulfones or polymeric amide etc.; Inorganic material film has pottery and metal etc.;
The bottom of left side filter core is provided with water-in, and the top is connected with the water port of cylindrical shell; Be filled with load type nano arsenic-removing sorbent for drinking water in filter core inside, left side.
Be provided with plastic mesh respectively between nonwoven layer in described filter bed A and the microfiltration membrane in the filter bed D; Be provided with vertical current baffle plate at described filter bed B and filter bed C inside; Be provided with between the water-in of described left side filter core and the water outlet of right side filter core and be connected flexible pipe.
The particle diameter of described granulated active carbon, natural zeolite and/or medical stone is the 10-100 order; The particle diameter of described load type nano arsenic-removing sorbent for drinking water is the 1-100 order.
Below back up pad between filter bed B and filter bed C and filter bed C and filter bed D, be respectively arranged with the common hospital gauze of 1-4 layer; Aperture on the back up pad is circular or square, and the aperture is 1-10mm, aperture be distributed as 1-10/cm
2
Be provided with magnetic material layer on the inwall of described right side filter core and left side filter core respectively.
Described load type nano arsenic-removing sorbent for drinking water can prepare as follows:
1. choosing pore volume is 0.100-0.500cm
3The commercially available gac of/g is used soluble ferric iron salt solution soaking gac 10-120 minute earlier, and the volume ratio of soluble iron salts solution and gac is 5: 1-20: 1;
2. in iron salt solutions, add alcoholic solution as dispersion agent; The volume ratio of dispersion agent and soluble iron salts solution is 0.5: 1-5: 1;
3. under the room temperature protection of inert gas, strong reductant POTASSIUM BOROHYDRIDE or sodium borohydride titration molysite with concentration 0.01-0.28M, for guaranteeing that molysite is fully reduced, the strong reductant amount of substance is 3-10 a times of molysite amount of substance, rate of titration is the 0.1-5 ml/min, protection of inert gas is stirred;
After POTASSIUM BOROHYDRIDE or sodium borohydride solution titration finish, continue to stir 10-120 minute;
5. after stirring finished, centrifugal 5-20 minute, rotating speed was 400-4000 rev/min; With oxygen-free water washing 1-3 time, use organic solvent washing 1-3 time more earlier, 40-100 ℃ of following vacuum-drying 12-48h gets product.
The matrix source of described absorbent charcoal material can be ature of coal, shell or wooden.
Described alcoholic solution is low-carbon (LC) 2-4 unit's alcohol and/or the molecular weight 200-40000 polyoxyethylene glycol of C1-C6 monohydroxy-alcohol, C2-C8; Described soluble iron salts solution is ferric sulfate 0.01-0.038M, ferrous sulfate 0.01-0.07M, iron(ic) chloride 0.1-0.56M or iron protochloride 0.01-0.8M; Step is the flow velocity 10-200 ml/min of middle rare gas element 4., stirs revolution 10-1000/ minute.
The present invention has following advantage:
1. the loading capacity of nano adsorption material is big in the filter core of left side.The present invention selects the gac of suitable pore size distribution from the gac of numerous different substrates, can make nanometer iron enter into gac inside; Utilize strong reductant reduction molysite, and select the particle diameter of the appropriate reaction conditions control nanometer iron that generates, enable to load on the aforesaid gac; Select suitable loading condition such as reaction times, dispersion agent etc., make the ideal position that loads to gac that nanometer iron can be uniform and stable; Prepared nano adsorption material can be used for the arsenic in the absorption method removal tap water.Its loading capacity can be up to the 20mg/g sorbent material; Be the sorbent material of commercially available single component and natural adsorbent 3-200 doubly; Its adsorption/desorption speed is fast, can effectively remove As (III) and As (V) simultaneously.
2. the nano adsorption material preparation method is simple, with low cost in the filter core of left side.
1. reaction conditions gentleness: reaction at normal temperatures and pressures, common laboratory, medium-sized and small enterprises can prepare, and can not burn, hazardous condition such as blast.
2. sorbent material itself is safe, economical, does not contain the harm element.This sorbent material main component is iron (and oxide compound), charcoal, and HUMAN HEALTH is safe from harm.Enter public drinking water source system even leaking appears in something unexpected happened (as Act for God factor such as earthquake, tsunami, wind spout), sorbent material, also can not pollute the water source.Though and commercially available compound adsorbent loading capacity is big, usually contain transition element or rare elements such as cerium, lanthanum, and this dvielement itself is still waiting assessment to the health risk of human body.
3. cost of investment is low, easily transforms and goes into operation.It is simple that this sorbent material is produced required equipment, invest for a short time, and general medium-sized and small enterprises can be realized batch process.And usually economy is backward relatively in high arsenic area, and this point has realistic meaning and economic implications especially.
3. the nano adsorption material application life is long in the filter core of left side, is easy to regeneration.Compare with other commercially available sorbent material, this sorbent material is long service life not only, and regeneration easily, and regeneration back adsorptive power can improve the economic performance of this sorbent material greatly up to more than 91.7% of former adsorptive power; Its proterties safety and stability is easy to store, transport simultaneously.
4. this apparatus structure is reasonable.The arsenic removing apparatus that designs and produces is reasonable in design: water-purifying process by thick to essence; About two filter core functions distribute rationally, promptly can unite use and can use one of them separately with reference to water quality again; Baffle plate can effectively prevent the current short circuit; Screen cloth not only plays effective supporting role to gauze and other filtering layer, but also can prevent the radial flow of sealing; Magneticsubstance can effectively be prevented sealing fouling obstruction water stream channel.The associated plant that employing can be dismantled is flexibly dismantled, cleans, repairs easy.
5. the arsenic removing apparatus cost is low, and effect is good.The present invention is directed to the physicochemical property of arsenic, descend the difficult point of water constituent complexity in combination, utilize homemade nano material to adsorb to remove the most of arsenic in the underground water of area, high arsenic water source, its effluent quality has reached the tap water arsenic content standard of the European Union and the U.S., guarantees high arsenic area resident's drinking water safety; The gac that the present invention is used and other material, amount is easy to get greatly in China, can satisfy need of industrial production fully; The arsenic removing apparatus arsenic removal efficient height that designs and produces, cost is lower, installation, conveniently moving, being fit to each family disperses use (promptly to can be used for high arsenic area, also can be used for common cities and towns uses), can effectively solve area, high arsenic water source owing to the backward in economy and sparsely populated high practical difficulty of central water supply cost that causes of resident.
Description of drawings
Fig. 1 is the influence of different substrates gac to the arsenic adsorption efficiency;
Fig. 2 is the influence to the arsenic adsorption efficiency of different dispersion agents and ratio;
Fig. 3 is the influences of different molysite to the arsenic adsorption efficiency;
Fig. 4 is the influence of gac different-grain diameter to the arsenic adsorption efficiency;
Fig. 5 is the influence of iron(ic) chloride different concns to the arsenic adsorption efficiency;
Fig. 6 is the arsenic adsorption effect contrast of different sorbent materials.
The kinetic curve of Fig. 7 sorbent material intermittent type arsenic-adsorbing.
Fig. 8 is the diagrammatic cross-section of arsenic removing apparatus for drinking water of the present invention.
Embodiment
The preparation of nano adsorption material in the filter core of left side:
At room temperature, carry out the intermittent type arsenic removal with made nano adsorption material.Is arsenic concentration that the water sample of 2000 μ g/L is crossed post, and the clearance of arsenic is up to more than 99.5%, and the arsenic concentration in the water outlet has reached the new arsenic content standard of formulating of the European Union and the U.S. less than 10 μ g/L.
Select materials is: select the different substrates gac: (pore volume is 0.326cm to the coconut husk charcoal
3/ g), (pore volume is 0.145cm to the ature of coal charcoal
3/ g), (pore volume is 0.250cm to bone black
3/ g); Iron(ic) chloride, POTASSIUM BOROHYDRIDE, organic solvent (common), single alcohol (C
1-C
10), the many alcohol series of low-carbon (LC) (C
1-C
10), polyoxyethylene glycol series (200-40000), oxygen-free water, rare gas element (common) etc.
Concrete steps are:
(1) (pore volume is 0.326cm to choose commercially available coconut husk charcoal
3/ g), (pore volume is 0.145cm to the ature of coal charcoal
3/ g), (pore volume is 0.250cm to bone black
3/ g) isoreactivity raw material of wood-charcoal material, with deionized water wash 3 times, supersound process 30min then;
(2) at room temperature, in the there-necked flask of the 250ml that magnetic stirring apparatus, gac, dropping funnel are housed, add 30 milliliters of the ferric chloride Solutions (coconut husk charcoal, ature of coal charcoal, bone black soaked 60 minutes with iron(ic) chloride in advance) of 0.15M, add 45 milliliters of dispersion agents (volume ratio of ethanol, glycerol, Macrogol 4000 is 1: 1: 0.5) then.
(3) under rare gas element (flow velocity 40 ml/min) protection, drip solution of potassium borohydride (rate of titration is 1.5 ml/min), stir simultaneously by (revolution 30/ minute) by certain flow rate.
(4) after reaction finished, vigorous stirring was 30 minutes again.Use 15 milliliters of oxygen-free waters and 15 milliliters of cleanings of acetone then respectively.
(5) carried out dry certain hour 12 hours under nitrogen protection, temperature is 80 ℃.
As can be seen from Figure 1: the gac of different substrates has remarkable difference to the effect of arsenic absorption, and wherein coal mass active carbon is because of having suitable pore volume, and nanometer iron can on its surface and load be carried out in inside and make it have good arsenic absorption property.
Select materials is: (obtained by the processing of ature of coal charcoal, pore volume is 0.168cm to gac
3/ g), ferrous sulfate, POTASSIUM BOROHYDRIDE, organic solvent (common), ethanol, glycerol, Macrogol 200, Macrogol 4000, oxygen-free water, rare gas element (common) etc.
Concrete steps are:
(1) choosing pore volume is 0.168cm
3The commercially available ature of coal activated carbon of/g is used deionized water wash 3 times, then supersound process 30min;
(2) at room temperature, in the there-necked flask of the 250ml that magnetic stirring apparatus, gac, dropping funnel are housed, 30 milliliters of the copperas solutions (the ature of coal charcoal soaked 60 minutes with ferrous sulfate in advance) that add 0.2M add 45 milliliters of dispersion agents (ethanol, glycerol, Macrogol 200 and 4000 ratio 1 are that 1: 1: 1, ratio 2 are that 2: 2: 0.5, ratio 3 are 2: 1: 0.1) then.
(3) under rare gas element (flow velocity 60 ml/min) protection, drip solution of potassium borohydride (rate of titration is 2.0 ml/min), stir simultaneously by (revolution 50/ minute) by certain flow rate.
(4) after reaction finished, vigorous stirring was 90 minutes again.Use 20 milliliters of oxygen-free waters and 200 milliliters of cleanings of organic solvent then respectively.(4) carried out dry certain hour 18 hours under nitrogen protection, temperature is 100 ℃.
The used dispersion agent of the present invention is a nonionogenic tenside, and its dispersion mechanism can be summarized as high electrostatic effect and space steric effect.The dispersion agent add-on very little, not only intergranular electrostatic repulsion is strong inadequately, nor thorough non-bridge formation hydroxyl and the planar water between screening granules can't reach good dispersion effect; The dispersion agent add-on is excessive, obviously do not improve dispersion effect, and the trend that makes particle thick is arranged, and too much dispersion agent also will improve the cost of product.In addition, dispersant molecule chain length is influenced by its molecular weight.The molecular chain of Macrogol 4000 is longer, so if its concentration is bigger, long molecular chain twines mutually and forms annular, thereby the direction of growth and the pattern that can influence nano iron particles influence its size.Fully take into account of the influence of dispersant molecule chain length to nanometer abrasive grit footpath size, single alcohol (molecular chain is shorter), poly(oxyethylene glycol) 400, Macrogol 4000 0 (molecular chain is longer) are adopted in this research, and its optimum mix of optimization, guarantee prepared nanometer abrasive grit footpath size to fit.
From accompanying drawing 2 as can be seen: the dispersion agent of different ratios has remarkable difference to the effect of arsenic absorption, wherein coal mass active carbon is because of having suitable pore volume for the dispersion agent of suitable proportion, and nanometer iron can on its surface and load be carried out in inside and make it have good arsenic absorption property.
Embodiment 3
Select materials is: (obtained by the processing of ature of coal charcoal, pore volume is 0.214cm to gac
3/ g), molysite (iron(ic) chloride, ferrous sulfate, ferric sulfate), POTASSIUM BOROHYDRIDE, organic solvent (common), ethanol, glycerol, polyoxyethylene glycol series 200, oxygen-free water, rare gas element (common) etc.
Concrete steps are:
(1) choosing pore volume is 0.214cm
3The commercially available coal mass active carbon of/g is used deionized water wash 3 times, then supersound process 30min;
(2) at room temperature, in the there-necked flask of the 250ml that magnetic stirring apparatus, gac, dropping funnel are housed, 30 milliliters of iron(ic) chloride, ferric sulfate, the copperas solutions (the ature of coal charcoal soaked 60 minutes with molysite in advance) that add 0.1M respectively add 60 milliliters of dispersion agents (ethanol, glycerol, Macrogol 4000 ratio 2: 1: 0.1) then.
(3) under nitrogen (flow velocity 60 ml/min) protection, drip solution of potassium borohydride (rate of titration is 1 ml/min), stir simultaneously by (revolution 30/ minute) by certain flow rate.
(4) after reaction finished, vigorous stirring was 30 minutes again.Use 10 milliliters of oxygen-free waters and 10 milliliters of cleanings of organic solvent then respectively.
(5) temperature is 110 ℃ and carried out drying 24 hours under nitrogen protection.
From accompanying drawing 3 as can be seen: adopt different types of molysite as source of iron, the performance of made sorbent material is had remarkably influenced, the arsenic removal impact of performance of made sorbent material is best when wherein being source of iron with the ferrous sulfate.
Embodiment 4
Select materials is: (obtained by the processing of ature of coal charcoal, pore volume is 0.100cm to gac
3/ g) particle diameter is respectively 10-20 order, 20-40 order, 40-60 order, 60-100 order, ferric sulfate, POTASSIUM BOROHYDRIDE, organic solvent (common), ethanol, glycerol, polyoxyethylene glycol series 2000, oxygen-free water, rare gas element (common) etc.
Concrete steps are:
(1) choosing pore volume is 0.100cm
3The commercially available coal mass active carbon of/g is used deionized water wash 3 times, then supersound process 30min;
(2) at room temperature, in the there-necked flask of the 250ml of 30 milliliters of the ferrum sulfuricum oxydatum solutums that 0.1M is housed, magnetic stirring apparatus, gac, dropping funnel, add 10-20 order, 20-40 order, 40-60 order, 60-100 purpose gac (the ature of coal charcoal soaked 60 minutes with molysite in advance) respectively, add 60 milliliters of dispersion agents (ethanol, glycerol, Macrogol 4000 ratio 2: 2: 1) then.
(3) under nitrogen (flow velocity 90 ml/min) protection, drip solution of potassium borohydride (rate of titration is 2.5 ml/min), stir simultaneously by (revolution 45/ minute) by certain flow rate.
(4) after reaction finished, vigorous stirring was 25 minutes again.Use 10 milliliters of oxygen-free waters and 10 milliliters of cleanings of organic solvent then respectively.
(5) carried out dry certain hour 18 hours under nitrogen protection, temperature is 90 ℃.
Total mass one timing of gac, its particle diameter is more little, and specific surface area is just big more, and then its portative nanometer iron of surface institute is many more, and the effect of arsenic absorption is also just good more.Accompanying drawing 4 has also illustrated this point.But particle diameter is too little, influences the rate of recovery and the engineering using value of its preparation.Take into account the best combination of practical application and adsorption effect, 40-60 purpose gac has been adopted in this research.
Select materials is: the concentration of iron(ic) chloride is respectively 0.1M, 0.3M, 0.6M, POTASSIUM BOROHYDRIDE, organic solvent (common), ethanol, glycerol, polyoxyethylene glycol series 9000, oxygen-free water, rare gas element (common) etc.
Concrete steps are:
(1) choosing pore volume is 0.100cm
3The commercially available coal mass active carbon of/g is used deionized water wash 3 times, then supersound process 30min;
(2) at room temperature, in the there-necked flask of the 250ml that magnetic stirring apparatus, 10-20 order gac, dropping funnel are housed, the ferric sulfate (the ature of coal charcoal soaked 60 minutes with molysite in advance) that adds 0.1M, 0.3M, 0.6M respectively adds 60 milliliters of dispersion agents (ethanol, glycerol, Macrogol 4000 ratio 2: 1: 1.2) then.
(3) under nitrogen (flow velocity 75 ml/min) protection, drip solution of potassium borohydride (rate of titration is 0.5 ml/min), simultaneously vigorous stirring (revolution 60/ minute) by certain flow rate.
(4) after reaction finishes, restir 75 minutes.Use 10 milliliters of oxygen-free waters and 10 milliliters of cleanings of organic solvent then respectively.
(5) carried out dry certain hour 18 hours under nitrogen protection, temperature is 90 ℃.
From accompanying drawing 5 as can be seen: the molysite that adopts different concns is as source of iron, and the performance of made sorbent material is had remarkably influenced, and the arsenic removal impact of performance of made sorbent material is best when wherein being source of iron with the iron(ic) chloride of 0.3M.
Embodiment 6
Select materials is: the concentration of ferric sulfate is 0.025M, POTASSIUM BOROHYDRIDE, organic solvent (common), ethanol, glycerol, polyoxyethylene glycol series 9000, oxygen-free water, rare gas element (common), common iron powder, gac etc.
Concrete steps are:
(1) choosing pore volume is 0.214cm
3The commercially available coal mass active carbon of/g is used deionized water wash 3 times, then supersound process 30min;
(2) at room temperature, in the there-necked flask of the 250ml that magnetic stirring apparatus, 10-20 order gac, dropping funnel are housed, the ferric sulfate (the ature of coal charcoal soaked 60 minutes with molysite in advance) that adds 0.025M adds 60 milliliters of dispersion agents (ethanol, glycerol, Macrogol 4000 ratio 1: 2: 0.5) then.
(3) under nitrogen (flow velocity 50 ml/min) protection, drip solution of potassium borohydride (rate of titration is 1.5 ml/min), stir simultaneously by (revolution 50/ minute) by certain flow rate.
(4) after reaction finished, vigorous stirring was 75 minutes again.Use 10 milliliters of oxygen-free waters and 10 milliliters of cleanings of organic solvent then respectively.(4) carried out dry certain hour 18 hours under nitrogen protection, temperature is 90 ℃.
A series of chemical reaction takes place in fe in water, its converted product is ferrous iron, ferric oxide compound and oxyhydroxide, and above-claimed cpd all has to a certain degree adsorption (external existing utilization simple substance iron powder contains the case history of arsenic drinking water treatment success) to arsenic.From accompanying drawing 6 as can be seen: the effect of removing arsenic of the nano adsorber of being developed is significantly better than common simple substance iron powder and activated carbon of sorbent commonly used.So the nano adsorber of this development test has application promise in clinical practice.
Embodiment 7
This arsenic concentration of testing used solution is 2000 μ gL
-1, 120 rev/mins of shaking speed, temperature of reaction are room temperature, and the sorbent material particle diameter is the 20-40 order, and total reaction time is 72h.
As can be seen from Figure 7, the arsenic adsorption rate of this sorbent material is fast, and loading capacity is big, not only can be competent at fully regional underground water arsenic content severe overweights such as China Taiwan, Xinjiang and the Inner Mongol (arsenic content reaches as high as 2000 μ gL
-1) the arsenic removal task, and can remove organic pollutant effectively.
Embodiment 8
A kind of arsenic removing apparatus for drinking water comprises airtight hollow cylinder, and the top of described cylindrical shell is provided with water port, is provided with water-in in the bottom of cylindrical shell; Vertically be set side by side with two cylindric filter cores in the inside of cylindrical shell;
Radially lay the nonwoven layer that haves three layers (50 grams/square metre) in the filter bed A; Be filled with granulated active carbon (20 order) in the filter bed B; Be filled with commercially available powder sintered block absorbent charcoal in the filter bed C; Radially lay the microfiltration membrane that haves three layers in the filter bed D, the about 0.006 μ m in the aperture of film, working pressure is about 0.5Mpa;
The bottom of left side filter core is provided with water-in, and the top is connected with the water port of cylindrical shell; Be filled with load type nano arsenic-removing sorbent for drinking water (20 order) in filter core inside, left side.
At room temperature, fill the left side filter core with the made nano adsorption material of the foregoing description 1-6 method.Is arsenic concentration the water sample intermittent type arsenic removal of 2000 μ g/L, and the clearance of arsenic is up to more than 99.5%, and the arsenic concentration in the water outlet＜10 μ g/L has reached the new arsenic hygienic standard of formulating of the European Union and the U.S..
Purifier in the filter core on apparatus of the present invention right side can be finished the water purification operation; The filter core in left side further carries out arsenic removal to the water from the filter core on right side to be handled, and can reach and drink quality standards for water.This device arsenic removal efficient height, cost is lower, and installation, conveniently moving are applicable to the geographic numerous residents in high arsenic water source.
Claims (8)
1. an arsenic removing apparatus for drinking water comprises airtight hollow cylinder (1), it is characterized in that:
The top of described hollow cylinder (1) is provided with water port (4), is provided with first water-in (3) in the bottom of hollow cylinder (1); Vertically be set side by side with two cylindric filter cores in the inside of hollow cylinder (1);
The bottom of right side filter core is connected with first water-in (3) of hollow cylinder (1), and the top is provided with water outlet (5); The middle and upper part of right side filter core, middle part, middle and lower part radially are provided with dismountable, as to have aperture back up pad (2) respectively, and three back up pads (2) are divided into four parts with the cavity in the filter core of right side, are followed successively by filter bed A, B, C, D from bottom to up;
Radially be equipped with the nonwoven layer more than 2 layers in the filter bed A; Be filled with granulated active carbon, natural zeolite and/or medical stone in the filter bed B; Be filled with commercially available powder sintered block absorbent charcoal in the filter bed C; Radially be equipped with the microfiltration membrane more than 2 layers in the filter bed D, aperture 0.002～0.1 μ m of film, molecular weight cut-off is 500-500000, its working pressure is at 0.07-0.7MPa;
The bottom of left side filter core is provided with second water-in (6), and the top is connected with the water port (4) of hollow cylinder (1); Be filled with load type nano arsenic-removing sorbent for drinking water in filter core inside, left side;
Described load type nano arsenic-removing sorbent for drinking water prepares as follows,
1. choosing pore volume is 0.100-0.500cm
3The commercially available gac of/g is used soluble ferric iron salt solution soaking gac 10-120 minute earlier, and the volume ratio of soluble iron salts solution and gac is 5: 1-20: 1;
2. in iron salt solutions, add alcoholic solution as dispersion agent; The volume ratio of dispersion agent and soluble iron salts solution is 0.5: 1-5: 1;
3. under the room temperature protection of inert gas, strong reductant POTASSIUM BOROHYDRIDE or sodium borohydride titration molysite with concentration 0.01-0.28M, for guaranteeing that molysite is fully reduced, the strong reductant amount of substance is 3-10 a times of molysite amount of substance, rate of titration is the 0.1-5 ml/min, protection of inert gas is stirred;
After POTASSIUM BOROHYDRIDE or sodium borohydride solution titration finish, continue to stir 10-120 minute;
4. after stirring finished, centrifugal 5-20 minute, rotating speed was 400-4000 rev/min; With oxygen-free water washing 1-3 time, use organic solvent washing 1-3 time more earlier, 40-100 ℃ of following vacuum-drying 12-48h gets product;
The matrix source of described absorbent charcoal material is ature of coal, shell or wooden;
Described alcoholic solution is low-carbon (LC) 2-4 unit's alcohol and/or the molecular weight 200-40000 polyoxyethylene glycol of C1-C6 monohydroxy-alcohol, C2-C8; Described soluble iron salts solution is ferric sulfate 0.01-0.038M, ferrous sulfate 0.01-0.07M, iron(ic) chloride 0.1-0.56M or iron protochloride 0.01-0.8M.
2. according to the described arsenic removing apparatus of claim 1, it is characterized in that: be provided with plastic mesh respectively between nonwoven layer in described filter bed A and the microfiltration membrane in the filter bed D.
3. according to the described arsenic removing apparatus of claim 1, it is characterized in that: be provided with vertical current baffle plate at described filter bed B and filter bed C inside.
4. according to the described arsenic removing apparatus of claim 1, it is characterized in that: be provided with between second water-in (6) of described left side filter core and the water outlet (5) of right side filter core and be connected flexible pipe.
5. according to the described arsenic removing apparatus of claim 1, it is characterized in that: the particle diameter of described granulated active carbon, natural zeolite and/or medical stone is the 10-100 order; The particle diameter of described load type nano arsenic-removing sorbent for drinking water is the 1-100 order.
6. according to the described arsenic removing apparatus of claim 1, it is characterized in that: the below of back up pad (2) is respectively arranged with the common hospital gauze of 1-4 layer between filter bed B and filter bed C and filter bed C and filter bed D; Aperture on the back up pad (2) is circular, and the aperture is 1-10mm, aperture be distributed as 1-10/cm
2
7. according to the described arsenic removing apparatus of claim 1, it is characterized in that: be provided with magnetic material layer respectively on the inwall of described right side filter core and left side filter core.
8. according to the described arsenic removing apparatus of claim 1, it is characterized in that: described step is the flow velocity 10-200 ml/min of middle rare gas element 3., stirs revolution 10-1000/ minute.
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| CN101818253B (en) * | 2010-05-11 | 2011-10-05 | 贵州铝城铝业原材料研究发展有限公司 | Separation and purification method of electrolytic aluminum scraps |
| CN101948194A (en) * | 2010-09-07 | 2011-01-19 | 中国市政工程西北设计研究院有限公司 | Method and system for removing arsenic from drinking water |
| CN102151543B (en) * | 2011-03-16 | 2012-08-22 | 浙江大学 | Preparation method, product and application of catalytic activity nano particle loaded absorbent |
| CN102645511B (en) * | 2012-05-18 | 2015-02-04 | 河海大学 | Device for detecting adsorption capacity of powdered active carbon |
| CN103386231B (en) * | 2013-07-12 | 2015-02-04 | 苏州微陶重金属过滤科技有限公司 | Filter core material of household filter and preparation method thereof |
| CN104478155B (en) * | 2014-12-02 | 2016-04-06 | 河海大学 | A kind of device utilizing nano-magnetic chitin and the arsenic removal of iron powder compound |
| CN106745645B (en) * | 2016-12-20 | 2020-09-22 | 山西省环境科学研究院 | Preparation method and application of nano zero-valent iron composite material |
| CN106630075B (en) * | 2017-02-23 | 2020-03-31 | 广西金投环境科技有限公司 | Polymer heavy metal flocculation device |
| CN114849641B (en) * | 2022-04-18 | 2023-03-10 | 河南大学 | Petal-shaped nano iron hydroxide and preparation method and application thereof |
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| CN85102296A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院长春应用化学研究所 | The purifying method of waste water containing arsenic |
| US5149437A (en) * | 1991-03-29 | 1992-09-22 | Wilkinson Theodore L | Water filter |
| CN2205378Y (en) * | 1993-10-17 | 1995-08-16 | 内蒙古自治区地方病防治研究所 | Household device for removing arsenic from water |
| CN101200324A (en) * | 2006-12-12 | 2008-06-18 | 美安得（天津）建筑环保工程设计研究有限公司 | Arsenic removal technology without secondary pollution and outfit |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102296A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院长春应用化学研究所 | The purifying method of waste water containing arsenic |
| US5149437A (en) * | 1991-03-29 | 1992-09-22 | Wilkinson Theodore L | Water filter |
| CN2205378Y (en) * | 1993-10-17 | 1995-08-16 | 内蒙古自治区地方病防治研究所 | Household device for removing arsenic from water |
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