CN103319212B - Preparation method of filtering material having arsenic and heavy metal adsorbing and fixing functions - Google Patents
Preparation method of filtering material having arsenic and heavy metal adsorbing and fixing functions Download PDFInfo
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Abstract
The invention relates to a preparation method of a filtering material having arsenic and heavy metal adsorbing and fixing functions. The method comprises the following steps: adsorbing divalent iron ions on a porous ceramic matrix, carrying out in-situ reduction of the divalent iron ions adsorbed on the porous ceramic matrix by a reducing agent, and carrying out anoxic sintering of the porous ceramic matrix at 400-500DEG C, wherein the amount of porosity of the porous ceramic matrix is 35-85%, and the porous ceramic matrix comprises at least 25wt% of diatomite. The filtering material obtained in the invention forms a porous fluff filtering structure in the microstructure and generates an adsorption membrane, so the adsorption efficiency is greatly improved, and the filtering material is adapted to the chemical environment change of water. The shedding or heavy metal precipitation of the used filtering material does not appear, and the use safety is good.
Description
Technical field
The invention belongs to filtering material preparation field, particularly a kind of preparation method with the filtering material of absorption and fixed arsenic and heavy metal function, the trivalent arsenic contained in fluid such as water and pentavalent arsenic can effectively remove by gained filtering material.
Background technology
Arsenic is one of element that toxicity is very strong, the main inorganic toxins removed in Ye Shi various countries drinking water standard.Exist mainly with trivalent and pentavalent state in nature water body.But it is as a kind of metallic element, not exist with the state of common cation, and mainly exist with arsenous anion and arsenate form.Even if the technology in modern times is only about 50% as reverse osmosis membrane (RO) to arsenious clearance, the filtration needs to arsenic can not be met.In addition, filtering material filters arsenic and the great heavy metal of toxicity, must take into account the fixation problem after absorption.
Conventional porous pottery and ceramic element utilize diatomaceous natural porous structure can remove bacterium and larger molecular organics, but can not remove arsenic and the heavy metal of ionic condition.On the other hand, Zero-valent Iron/nano zero valence iron is less than 6 at low pH() in water, slowly corrode and contribute two free charges, arsenic and heavy metal are reduced and symbiosis precipitation (co-precipitation), thus reach the object of removal heavy metal.But, the independent application of Zero-valent Iron, bring following problem: one, corrosion reaction must could occur under pH is less than the environment of 7, regulation and control pH is the application limitations of Drinking Water Filtration; Two, certain dissolved oxygen (being greater than 2 mg/litre) ability sustained reaction must be had in water; Three, form harmful mud in reaction process, can not heavy metal be fixed, need further harmless treatment; Four, produce ferric iron or the ferrous ion of great quantities of spare in use procedure, water is presented red or orange, must process further.
In order to solve these application limitations problems of Zero-valent Iron, some researchs take Zero-valent Iron or nano zero valence iron to be formed on porous ceramic particles prepared by gac, natural diatomaceous earth, kaolin and kaolin in the mode of coating.But the way of coating still exists some problems, the coating prepared as gac hybrid system easily comes off when pH change or change of water quality, and this can cause acute poisoning in tap water; In addition, filtering material easily produces zeroth order iron powder and comes off and the problem of surface oxidation, thus reduces its adsorptive power.
Chinese invention patent ZL200680052402.X discloses a kind of method and composition removing arsenic and heavy metal from water, kaolin ceramic particle is wherein used to carry out the method for Zero-valent Iron coating, can effectively remove arsenic and heavy metal, and realize heavy metal at ceramic surface and fix, but the method also only can utilize ceramic surface structure, adsorption efficiency also needs further raising.
Sum up, in the removal of arsenic, the main drawback of prior art is: one, traditional ceramics oxidizing roasting only can provide vesicular structure filter bacteria and macromolecular substance to carry out physical filtering; Two, zeroth order iron powder applies voluminous pig iron ion and harmful waste; Three, there is the problem that comes off in gac iron powder coating; Four, ceramic grain surface coating only can utilize surface tissue.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of preparation method with the novel filter material of arsenic removal function.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
Have a preparation method for the filtering material of absorption and fixed arsenic and heavy metal function, it comprises the steps:
(1) porous ceramic matrices suitable is dipped into pH7.0 ~ 8.0, containing in the aqueous phase mixed solution of ferrous ion and tackifier, after porous ceramic matrices suitable complete wetting, take out porous ceramic matrices suitable, dry for subsequent use, wherein, the porosity of described porous ceramic matrices suitable is 35% ~ 85%, and at least 25wt% forming the ceramics component of porous ceramic matrices suitable is diatomite;
(2) porous ceramic matrices suitable through step (1) is immersed in pH8.5 ~ 9.5, the aqueous solution containing sodium borohydride 0.1wt% ~ 5wt%, takes out after 2 ~ 8 minutes, dry for subsequent use;
(3) porous ceramic matrices suitable through step (2) is put in anaerobic stove carry out anaerobic sintering, heat-up rate is 80 ~ 100 DEG C/h, be warming up to 300 DEG C ~ 500 DEG C, be incubated 0.5 ~ 3 hour, there is described in obtaining the filtering material of absorption and fixed arsenic and heavy metal function.
Further, in step (1), described tackifier can for being selected from one or more the combination in glucose, sucrose, starch, and the content of tackifier in aqueous phase mixed solution is 0.2wt% ~ 15wt%;
In step (1), the content of ferrous ion in aqueous phase mixed solution is preferably 0.1wt% ~ 5wt%, is more preferably 0.2wt% ~ 2wt%.Ferrous ion can the form of such as iron protochloride or ferrous sulfate be incorporated in solution.
In the aqueous solution described in step (2), the content of sodium borohydride is preferably 2wt% ~ 5wt%.
According to a concrete and preferred aspect of the present invention: in step (1), regulate pH with Trisodium Citrate.
According to another concrete and preferred aspect of the present invention: in step (2), use winestone acid for adjusting pH.
Preferably, in step (3), described sintering is carried out under nitrogen or hydrogen shield.
Preferably, in step (3), sintering temperature is 380 DEG C ~ 420 DEG C.More preferably, sintering temperature is 400 DEG C.
Preferably, in the aqueous solution of step (2), the content of sodium borohydride is 2wt% ~ 5wt%.
According to a preferred aspect of the present invention: forming the ceramics component of porous ceramic matrices suitable be all diatomite, or be diatomite and the combination being selected from a kind of in kaolin, wilkinite or two kinds, wherein at least 25% of ceramics component is diatomite.Preferably, also at least wilkinite is contained in ceramics component.These porous ceramic matrices suitables can obtain in accordance with known methods.
According to a concrete aspect of the present invention, with parts by weight, the material of porous ceramic matrices suitable consists of: 55 ~ 65 parts, diatomite; Calcium-base bentonite 12 ~ 15 parts, powdered carbon 7 ~ 12 parts, starch 2 ~ 3 parts, kaolin 4 ~ 6 parts.
According to another concrete aspect of the present invention: with parts by weight, the material of porous ceramic matrices suitable consists of: 50 ~ 55 parts, diatomite, wilkinite 6 ~ 8 parts, starch 3 ~ 4 parts, kaolin 3 ~ 5 parts, liquid wax 1 ~ 2 part, iron powder 1 ~ 3 part, powdered carbon 13 ~ 15 parts.
According to an also concrete aspect of the present invention: with parts by weight, the material of porous ceramic matrices suitable consists of: 75 ~ 85 parts, diatomite, powdered carbon 8 ~ 10 parts, wilkinite 1 ~ 3 part, kaolin 3 ~ 5 parts.
Preferably, the porosity of described porous ceramic matrices suitable is 50% ~ 70%.
The filtering material that the inventive method gained has absorption and fixed arsenic and heavy metal function has following features:
(1) be the porous ceramic matrices suitable of 35% ~ 85% by porosity and form at the nanometer nulvalent iron particle that the internal in-situ of porous ceramic matrices suitable generates, the micropore size of porous ceramic matrices suitable is 2 ~ 10 microns, and in described micropore, be formed with velvet-like unformed silicon-iron-carbon structure, and this structure can form adsorption film after absorbing water.
(2) surface of filtering material is iron cyan or Steel Gray, and fresh section is blue, and filtering material becomes black after water suction or immersion.Below 0.1mm Y25 ferromagnetic powder can adsorb by filtering material.Filtering material is after scraping off top layer powder, and the pH measured by NY/T 1377-2007 Soil standard is 7.2 ~ 8.5.
Gained filtering material of the present invention can be used for except middle trivalent arsenic, pentavalent arsenic and the heavy metal ion of anhydrating.Described heavy metal ion includes but not limited to lead, cadmium, mercury, chromium etc.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
1, the inventive method gained filtering material has high absorption fixed function to trivalent arsenic and pentavalent arsenic, and the filter core be made up of the present invention, when 15 seconds duration of contact of waterpower, can be removed arsenic plumbous chromium mercury mn ion clearance and reach more than 90%;
2, the glassware for drinking water after the filtering material obtained through the inventive method filters has stable weakly alkaline;
3, take the inventive method, can form stable Nanoscale Iron in the micropore of porous ceramic matrices suitable, zeroth order nanometer iron powder is in the formation of microtexture, and have reductibility environment C to protect, heavy metal positively charged ion has metathesis fast: Fe
0+ X
+→ Fe
++ X; Fe
+the form that can form (FeOOH) at silica sphere is fixed, and wherein X can be lead, cadmium, mercury ion, but is not limited to these heavy metal ion, and after fixing, waste water filtering material is under simulation landfill yard condition, does not separate out heavy metal.Used civilian Filtration Filtration material, does not come off or separates out heavy metal, ensure that its safety in utilization;
4, gained filtering material of the present invention has strong reducing property to hexavalent chromium.Due to the existence of Zero-valent Iron, to poisonous sexavalent chrome, nontoxic and useful trivalent chromium can be reduced to;
5, the silicon-iron-carbon structure of gained filtering material of the present invention and hole active surface thereof are to the chlorine residue gas in water and chemical disinfection byproducts, also have removal effect.At 1.2 liters/min, the clearance of 90% when 12 seconds duration of contact, can be reached;
6, water and waste water filtration mainly applied by gained filtering material of the present invention, but also has filteration for the gas containing arsenic mercury and radiocesium;
7, gained filtering material of the present invention after a procedure, can be smashed as soil improvement agent, realize material circulation;
8, preparation method's reaction conditions provided by the invention is gentle, and simple to operate, cost is low.
Accompanying drawing explanation
Fig. 1 shows the scanning electron microscope (SEM) photograph of porous ceramic matrices suitable and material for core in embodiment 1, and wherein (A-1) is porous ceramic matrices suitable (5 μm of scales); (A-2) be porous ceramic matrices suitable (20 μm of scales); (A-3) be porous ceramic matrices suitable (50 μm of scales); (A-4) be porous ceramic matrices suitable (100 μm of scales); (B-1) be filtering material finished product (5 μm of scales); (B-2) be filtering material finished product (10 μm of scales); (B-3) be filtering material finished product (50 μm of scales); (B-4) be filtering material finished product (100 μm of scales); (C-1) be filtering material finished product (after water suction, 5 μm of scales); (C-2) be filtering material finished product (after water suction, 10 μm of scales); (C-3) be filtering material finished product (after water suction, 50 μm of scales); (C-4) be filtering material finished product (after water suction, 100 μm of scales);
Fig. 2 shows the scanning electron microscope (SEM) photograph of material for core in embodiment 2, and wherein (2A) is filtering material finished product; (2B) be filtering material finished product (after water suction);
Fig. 3 shows the scanning electron microscope (SEM) photograph of a micropore of embodiment 3 gained material for core;
Fig. 4 is test pattern when testing the strainability of filtering material.
Embodiment
Known common porous ceramic filter element, such as ordinary white Diatomite ceramic filter core, because micropore is flourishing, have good permeability, can for physically to bacteriological filter.But heavy metal ion can not filter.Although the existing method in ceramic surface formation coating can make pottery obtain the function of arsenic-adsorbing and heavy metal ion, there is coating and easily come off, generate harmful waste and the dissatisfactory problem of adsorption effect.Invention thinking of the present invention is mainly to provide a kind of internal in-situ at porous ceramic filter element to generate the method for nano-iron particle, the filtering material obtained not only has very high removal effect to arsenic and heavy metal ion, and absorption arsenic and heavy metal ion highly stable, do not come off, meanwhile, also there is not coating shedding problem in this filtering material.The present invention also according to the different application field of filtering material, is optimized design to the composition of porous ceramic matrices suitable and the preparation condition of filtering material simultaneously.
Provided by the inventionly can be specifically implemented as follows the method that porous ceramic matrices suitable carries out Nanoscale Iron modification:
The first step: the sugar solution (such as glucose, sucrose) of preparation 0.2% ~ 15% or Zulkovsky starch solution, preferred weakly alkaline pH7.5 ~ 8.0 of pH7 ~ 8.0(are adjusted to) with Trisodium Citrate, add sulfurous acid iron or iron protochloride (consumption such as 0.2% ~ 10%), dissolve completely;
Second step: porous ceramic matrices suitable (such as common Diatomite ceramic filter core) is fully immersed in solution prepared by the first step, makes it completely moistening, more than 15 minutes, pull out dry stand-by;
3rd step: preparation sodium borohydride aqueous solution (sodium borohydride content is not low by 0.1%), dissolves completely, preferably regulates pH to 8.5 ~ 9.5 with such as tartaric acid solution, stand-by;
4th step: in the sodium borohydride aqueous solution that the porous ceramic matrices suitable rapid soaking dried by second step is prepared in the 3rd step, ceramic element generation surface chemical reaction, taking-up in 2 to 5 minutes is dried.
5th step: the porous ceramic matrices suitable that the 4th step is dried is placed in the anaerobic stove of nitrogen protection or hydrogen shield and is heated to 300 DEG C ~ 500 DEG C; optimum temps about 400 DEG C; 80 ~ 120 DEG C per hour of temperature rise rate (such as 100 DEG C); be incubated 0.5 ~ 3 hour; obtain filtering material; be cooled to less than 120 DEG C, take out.
The filtering material physics generated according to the method described above and structure as follows:
1) color: be Steel Gray or iron cyan, fresh section is blue, meets water (absorb water or soak rear) and becomes black;
2) pH: scrape off top layer powder, is determined as 7.2 ~ 8.5 by NY/T 1377-2007 Soil standard.
3) material section structure: show under 5000 times of electron microscopes is 2 ~ 10 micrometer Millipore, inside has Si-Fe-C unformed (amorphous, amorphous) migrated first dopant, Nanoscale Iron structure, forms infiltrative type interlayer film after absorbing water.
4) magnetic testing: to Y25 (3800GS) magnet, can be less than the powder particle absorption of 0.1 millimeter.
Known, the nose of human or animal is perfect strainer, because it has a unique structure: 1, electrostatic vibrissa absorption macrobead and dust; 2, the adsorbable bacterium in nasal cavity built-in fine fleece surface; 3, the strong adsorption of chemical species of bronchia mucosal constantly generated and fixing.In microtexture, the porous ceramic matrices suitable (kaolin, diatomite, wilkinite etc.) that the present invention adopts loses crystal water and forms vesicular structure after high-temperature calcination, but under certain control condition, water can be absorbed again and be reduced into membranaceous interlayer structure containing crystal water.Therefore, gained filtering material of the present invention, in microtexture, forms the porous of similar nose, fine hair filtration generate adsorption film, thus will increase substantially adsorption efficiency, adapts to hydrochemistry environmental change.
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.Content involved below, without when defining especially, refers to mass content.
Embodiment 1
The present embodiment provides a kind of filtering material for heavy metal lead mercury cadmium chromium in filtering drinking water, and its preparation method is as follows:
The first step: normal temperature preparation sucrose solution, adds sulfurous acid water solution, adjusts pH to 7.5 ~ 8.0 with Trisodium Citrate, obtain the aqueous solution of sucrose content 10%, ferrous ion content 3%;
Second step: porous ceramic matrices suitable is fully immersed in solution prepared by the first step, makes it completely moistening, more than 15 minutes, pull out dry stand-by;
3rd step: preparation 2.5wt% sodium borohydride aqueous solution, regulates pH to 8.5 ~ 9.5 with 0.1% tartaric acid solution, stand-by;
4th step: in the sodium borohydride aqueous solution that the porous ceramic matrices suitable rapid soaking dried by second step is prepared in the 3rd step, ceramic element generation surface chemical reaction, taking-up in 5 minutes is dried.
5th step: be placed in the kiln of nitrogen protection or hydrogen shield by the porous ceramic matrices suitable that the 4th step is dried, is heated to about 400 DEG C with the temperature rise rate of 100 DEG C/h, is incubated 2 hours, and sintering obtains filtering material, is cooled to less than 120 DEG C, takes out.
In this example, with parts by weight, porous ceramic matrices suitable used is formed with anaerobic side's sintering by 55 parts, diatomite, calcium-base bentonite 7 parts, kaolin 4 parts, starch 3 parts, powdered carbon 14 parts, liquid wax 2 parts, iron powder 2 parts, sintering temperature 400 DEG C.The porosity of porous ceramic matrices suitable is 70%, pH is about 7.5, and color is white, becomes base shape to be the spherical of 1 ~ 2mm.
physical properties and the structure of this routine gained filtering material are as follows:
1) color: be Steel Gray or iron cyan, fresh section is blue, meets water (absorb water or soak rear) and becomes black; The spheroidal particle that shape: 1 ~ 2mm is large.
2) pH: scrape off top layer powder, is determined as 7.8 ~ 8.0 by NY/T1377-2007 Soil standard.
3) material section structure: be shown as 2 ~ 10 micrometer Millipore under 5000 times of electron microscopes, inside has Si-Fe-C unformed (amorphous, amorphous) migrated first dopant, Nanoscale Iron structure, forms infiltrative type interlayer film (see Fig. 1) after absorbing water.
4) magnetic testing: to Y25 (3800GS) magnet, can be less than the powder particle absorption of 0.1 millimeter.
this routine gained filtering material is to the filter effect of tap water
1. testing method
Lead, arsenic, chromium clearance: with reference to MOH " Drinking Water water quality treater hygienic safety and functional evaluation specification-general water quality treater " & EPA200.8ICP/MS;
Mercury clearance: with reference to MOH " Drinking Water water quality treater hygienic safety and functional evaluation specification-general water quality treater " & GB/T 5750.6-2006 drinking water standard method of inspection metal index atomic fluorescence method;
Hexavalent chromium removal rate: with reference to MOH " Drinking Water water quality treater hygienic safety and functional evaluation specification-general water quality treater " & GB/T5750.6-2006 drinking water standard method of inspection metal index;
Test pattern is see Fig. 4.
2. test result: see table 1.
Table 1
stability test after this routine gained filtering material uses
According to international standard: EPA TCLP CD-ROM 1311-1 July 1992
METHOD 1311 TOXICITY CHARACTERISTIC LEACHING PROCEDURE carries out simulation test.The heavy metals such as the plumbous cadmium of arsenic cadmium mercury that detected result absorption is fixing do not exceed standard or do not detect.
Embodiment 2
The present embodiment provides a kind of filtering material for arsenic in filtering drinking water and heavy metal lead mercury cadmium chromium, and its preparation method is as follows:
The first step: normal temperature preparation Zulkovsky starch solution, adds ferrous chloride aqueous solution, adjusts pH to 7.5 ~ 8.0 with Trisodium Citrate, obtain the aqueous solution of starch content 5%, ferrous ion content 2%;
Second step: porous ceramic matrices suitable is fully immersed in solution prepared by the first step, makes it completely moistening, more than 15 minutes, pull out dry stand-by;
3rd step: preparation 2wt% sodium borohydride aqueous solution, regulates pH to 8.5 ~ 9.5 with 0.1% tartaric acid solution, stand-by;
4th step: in the sodium borohydride aqueous solution that the porous ceramic matrices suitable rapid soaking dried by second step is prepared in the 3rd step, ceramic element generation surface chemical reaction, taking-up in 5 minutes is dried.
5th step: be placed in the kiln of nitrogen protection or hydrogen shield by the porous ceramic matrices suitable that the 4th step is dried, is heated to about 400 DEG C with the temperature rise rate of 90 DEG C/h, is incubated 2 hours, and sintering obtains filtering material, is cooled to less than 120 DEG C, takes out.
In this example, with parts by weight, porous ceramic matrices suitable used is formed with anaerobic side's sintering by 80 parts, diatomite, calcium-base bentonite 2 parts, kaolin 5 parts, powdered carbon 10 parts, sintering temperature 800 DEG C, porosity 65%, pH8.5, color is Steel Gray, and one-tenth base shape is the single radial cut tubulose of long 200mm, outside diameter 40mm, interior diameter 33mm.
physical properties and the structure of this routine gained filtering material are as follows:
1) color: be Steel Gray or iron cyan, fresh section is blue, meets water (absorb water or soak rear) and becomes black; Shape: the filter core of external diameter 40mm, internal diameter 35mm, length 200mm.
2) pH: scrape off top layer powder, is determined as 8.3 ~ 8.5 by NY/T 1377-2007 Soil standard.
3) material section structure: show under 5000 times of electron microscopes is 2 ~ 10 micrometer Millipore, inside has Si-Fe-C unformed (amorphous, amorphous) migrated first dopant, Nanoscale Iron structure, forms infiltrative type interlayer film (see Fig. 2) after absorbing water.
4) magnetic testing: to Y25 (3800GS) magnet, can be less than the powder particle absorption of 0.1 millimeter.
this routine gained filtering material is to the filter effect of tap water
1. testing method:
Arsenic, chromium clearance: with reference to MOH " Drinking Water water quality treater hygienic safety and functional evaluation specification-general water quality treater " & EPA200.8ICP/MS;
Mercury clearance: with reference to MOH " Drinking Water water quality treater hygienic safety and functional evaluation specification-general water quality treater " & GB/T 5750.6-2006 drinking water standard method of inspection metal index atomic fluorescence method;
Test pattern is see Fig. 4.
2. test result: see table 2.
Table 2
stability test after this routine gained filtering material uses
According to international standard: EPA TCLP CD-ROM 1311-1 July 1992
METHOD 1311 TOXICITY CHARACTERISTIC LEACHING PROCEDURE carries out simulation test.The heavy metals such as the plumbous cadmium of arsenic cadmium mercury that detected result absorption is fixing do not exceed standard or do not detect.
Embodiment 3
The present embodiment provides a kind of for the treatment of the filtering material containing arsenic, selenium metalloid and heavy metal wastewater thereby, and its preparation method is as follows:
The first step: normal temperature preparation Zulkovsky starch solution, adds ferrous sulfate aqueous solution, adjusts pH to 7.5 ~ 8.0 with Trisodium Citrate, obtain the aqueous solution of starch content 5%, ferrous ion content 4%;
Second step: porous ceramic matrices suitable is fully immersed in solution prepared by the first step, makes it completely moistening, more than 15 minutes, pull out dry stand-by;
3rd step: preparation 4wt% sodium borohydride aqueous solution, regulates pH to 8.5 ~ 9.5 with 0.1% tartaric acid solution, stand-by;
4th step: in the sodium borohydride aqueous solution that the porous ceramic matrices suitable rapid soaking dried by second step is prepared in the 3rd step, ceramic element generation surface chemical reaction, taking-up in 5 minutes is dried.
5th step: be placed in the kiln of nitrogen protection or hydrogen shield by the porous ceramic matrices suitable that the 4th step is dried, is heated to about 380 DEG C with the temperature rise rate of 100 DEG C/h, is incubated 2.5 hours, and sintering obtains filtering material, is cooled to less than 120 DEG C, takes out.
In this example, with parts by weight, porous ceramic matrices suitable used is formed with anaerobic side's sintering by 60 parts, diatomite, calcium-base bentonite 13 parts, kaolin 5 parts, powdered carbon 10 parts, starch 2.5 parts, and sintering temperature 980 DEG C, porosity 62%, pH8, color is black.
physical properties and the structure of this routine gained filtering material are as follows:
1) color: be Steel Gray or iron cyan, fresh section is blue, meets water (absorb water or soak rear) and becomes black; Shape: the filter core of external diameter 40mm, internal diameter 35mm, length 200mm.
2) pH: scrape off top layer powder, is determined as 8.1 ~ 8.3 by NY/T1377-2007 Soil standard.
3) material section structure: show under 5000 times of electron microscopes is 2 ~ 10 micrometer Millipore, inside has Si-Fe-C unformed (amorphous, amorphous) migrated first dopant, Nanoscale Iron structure, forms infiltrative type interlayer film (see Fig. 3) after absorbing water.
4) magnetic testing: to Y25 (3800GS) magnet, can be less than the powder particle absorption of 0.1 millimeter.
this routine gained filtering material is to the filter effect of waste water
1. wastewater sample: Hawaii AlaWai Canal-water.
2. testing method: see the test pattern of Fig. 4, by waste water one way by being equipped with the water inlet device of filtering material, 9.5 minutes time, measures its Inlet and outlet water concentration.
3. test result: the results are shown in Table 3.Result shows, and filtering material has good removal effect to cadmium, cobalt, strontium, copper, nickel, zinc, silver-colored plasma simultaneously.Measuring using this water as isothermal adsorption, is 5mg/l to the comprehensive loading capacity of complicated metal ion.
Table 3
stability test after this routine gained filtering material uses
According to international standard: EPA TCLP CD-ROM 1311-1 July 1992
METHOD 1311 TOXICITY CHARACTERISTIC LEACHING PROCEDURE carries out simulation test.The heavy metals such as the plumbous cadmium of arsenic cadmium mercury that detected result absorption is fixing do not exceed standard or do not detect.
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (10)
1. one kind has the preparation method of the filtering material of absorption and fixed arsenic and heavy metal function, it is characterized in that: described filtering material is the porous ceramic matrices suitable of 35% ~ 85% by porosity and forms at the nanometer nulvalent iron particle that the internal in-situ of porous ceramic matrices suitable generates, the micropore size of porous ceramic matrices suitable is 2 ~ 10 microns, and in described micropore, be formed with velvet-like unformed silicon-iron-carbon structure, and this structure can form adsorption film after absorbing water, described preparation method comprises the steps:
(1) porous ceramic matrices suitable is dipped into pH 7.0 ~ 8.0, containing in the aqueous phase mixed solution of ferrous ion and tackifier, after porous ceramic matrices suitable complete wetting, take out porous ceramic matrices suitable, dry for subsequent use, wherein, the porosity of described porous ceramic matrices suitable is 35% ~ 85%, and at least 25wt% forming the ceramics component of porous ceramic matrices suitable is diatomite;
(2) porous ceramic matrices suitable through step (1) is immersed in pH 8.5 ~ 9.5, the aqueous solution containing sodium borohydride 0.1wt% ~ 5wt%, takes out after 2 ~ 8 minutes, dry for subsequent use;
(3) porous ceramic matrices suitable through step (2) is put in anaerobic stove carry out anaerobic sintering, heat-up rate is 80 ~ 100 DEG C/h, be warming up to 300 DEG C ~ 500 DEG C, be incubated 0.5 ~ 3 hour, there is described in obtaining the filtering material of absorption and fixed arsenic and heavy metal function.
2. preparation method according to claim 1, is characterized in that: in step (1), and described tackifier are one or more the combination in glucose, sucrose and Zulkovsky starch, and the content of tackifier in aqueous phase mixed solution is 0.2wt% ~ 15wt%.
3. preparation method according to claim 1, is characterized in that: in step (1), and the content of described ferrous ion in aqueous phase mixed solution is 0.1wt% ~ 5wt%.
4. preparation method according to claim 3, is characterized in that: in step (1), and the content of described ferrous ion in aqueous phase mixed solution is 0.2wt% ~ 2wt%.
5. preparation method according to claim 1, is characterized in that: in the aqueous solution described in step (2), the content of sodium borohydride is 2wt% ~ 5wt%.
6. preparation method according to claim 1, is characterized in that: in step (1), regulate pH with Trisodium Citrate, in step (2), uses winestone acid for adjusting pH.
7. preparation method according to claim 1, is characterized in that: in step (3), and described sintering is carried out under nitrogen or hydrogen shield.
8. preparation method according to claim 1, is characterized in that: in step (3), and sintering temperature is 380 DEG C ~ 420 DEG C.
9. preparation method according to claim 1, is characterized in that: the ceramics component forming described porous ceramic matrices suitable is all diatomite, or is diatomite and the combination being selected from a kind of in kaolin, wilkinite or two kinds.
10. preparation method according to claim 1, is characterized in that: the porosity of described porous ceramic matrices suitable is 50% ~ 70%.
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| CN106732337A (en) * | 2016-12-29 | 2017-05-31 | 德清华得环保设备有限公司 | A kind of waste water high-efficiency inorganic agent and preparation method thereof |
| CN107188627A (en) * | 2017-07-17 | 2017-09-22 | 湖南七纬科技有限公司 | A kind of water hyacinth culture medium of edible fungus and preparation method thereof |
| CN111795984B (en) * | 2020-06-22 | 2022-05-10 | 中国科学院上海硅酸盐研究所 | Sample preparation method for observing microstructure inside ceramic by scanning electron microscope |
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| US8361920B2 (en) * | 2005-12-29 | 2013-01-29 | Micronose Technologies, Llc | Methods and compositions for removal of arsenic and heavy metals from water |
| CN101347717B (en) * | 2007-07-18 | 2010-05-19 | 中国科学院沈阳应用生态研究所 | Method for preparing load type nano arsenic-removing sorbent for drinking water |
| CN102153329B (en) * | 2010-11-22 | 2013-09-04 | 甘肃省灌溉试验培训中心 | Ceramic filter element and production process thereof |
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