CN1500737A - Technique for treating water using magnetic absorbent - Google Patents
Technique for treating water using magnetic absorbent Download PDFInfo
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- CN1500737A CN1500737A CNA021493588A CN02149358A CN1500737A CN 1500737 A CN1500737 A CN 1500737A CN A021493588 A CNA021493588 A CN A021493588A CN 02149358 A CN02149358 A CN 02149358A CN 1500737 A CN1500737 A CN 1500737A
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- magnetic
- oxidation
- water
- catalytic oxidation
- sorbent material
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Abstract
The present invention provides one kind of water processing magnetic adsorbent adsorption-magnetic separation and catalytic oxidation process to eliminate organic pollutant from water, and belongs to the field of water processing technology. The adsorbing elimination and oxidizing decomposition of organic matter in water are completed separately in different systems. Especially, organic matter in water is first adsorbed with ferrite-type composite metal oxide or magnetic active carbon as adsorbent, and the adsorbent is then recovered via magnetic separation and regenerated in catalytic oxidation system for reuse, with the loaded organic matter being oxidized completely to avoid secondary pollution.
Description
The present invention relates to a kind ofly adsorb with magnetic adsorbent--the water technology of-magnetic separation-catalyzed oxidation is removed organic pollutant in the water.Particularly utilize wustite type complex metal oxides or compose magnetic active carbon and be organism in the adsorbents adsorb water, separate through magnetic then, sorbent material is separated from water, place catalytic oxidation system to regenerate again, simultaneously with load organism complete oxidation, avoid secondary pollution, sorbent material can be recycled after magnetic separates.
The method of organic pollutant is divided into physics method, chemical method and biological process and their combination in the common removal water; The physics method has absorption method, coagulant sedimentation etc., and chemical method has chemical oxidization method, catalytic oxidation etc.Existing chemical method and biological process all are to carry out in former water, and water outlet can not guarantee to reach fully requirement, sometimes even the stronger by product of toxigenicity.And remove in the physics method with granular carbon through absorption---manipulation of regeneration, organism is destroyed fall outside, other method does not all destroy organic pollutant, just transfers to another system from an individual system, still has secondary pollution hidden danger; Even adopt granular carbon absorption---manipulation of regeneration, the thermal regeneration method that generally adopts also exists the problems such as loss that process is numerous and diverse, energy consumption is high, gac has 5%--10% now, and during the powder application shaped activated carbon, these problems are just more outstanding, often can only disposablely use, cause huge waste.
In addition, well-known, as sorbent material and rigid granules thing, except that the structure factor, its particle diameter is more little, specific surface area is big more, and performance is good more; But the consequent more little then difficult more separation that is particle diameter, treatment effect is reduced, running cost increases, and easily causes the wasting of resources, so that the application of the sorbent material (as powdered carbon) that some particles are little, specific surface is big, rate of adsorption is fast, capacity is high is restricted.Pursue efficient and solid-liquid separation contradictory problems so in technologies such as absorption, precipitation, often exist,
Magnetic separation technique has been widely used in fields such as mining industry, microbiology, environmental protection as a kind of method of efficient, quick, economic separation magnetic-particle thing, therefore can utilize magnetic separation technique to solve the Separation and Recovery problem of small-particle sorbent material.
The objective of the invention is: make full use of that small grain size adsorbents adsorb speed is fast, capacity is big and catalytic wet oxidation decomposing organic matter technology is simple, the advantage of control easily, separate in conjunction with magnetic, can fast and efficiently organic matter removal in the former water and branch be taken off, not have secondary pollution again.Method is that the organic removal of Jiang Yuanshui places different systems to carry out with oxygenolysis: utilize magnetic adsorbent good adsorption performance and easy magnetic separation property, quickly organic pollutant is adsorbed from former water and separate, adopt catalytic wet oxidation or electrochemical oxidation that the oxidation operation that is adsorbed is fallen again, and the while reproducing adsorbent.This technology makes former water treatment effect only relevant with absorption, not oxidated reaction influence.
Water technology as shown in drawings.Concrete grammar is: to have the MFe of magnetic
2O
4(M=Fe, Cu, Mn) or be loaded with the gac of these magnetic substances, particularly powdered carbon is a sorbent material, according to the concentration of organic pollutant in the water, gets an amount of sorbent material it is dispersed in the water that contains organic pollutant, under agitation adsorb, until reaching adsorption equilibrium or water outlet requirement; Then this mixed system is carried out solid-liquid separation by magnetic separator, reclaim the organic sorbent material of load, and the organic concentration of water outlet is reduced greatly.The sorbent material that reclaims can return absorbing process once more, or places catalytic oxidation system that the oxidation operation that is adsorbed is fallen, and sorbent material obtains regeneration simultaneously; After magnetic separated, reproducing adsorbent returned absorbing process and recycles through washing; The oxidation mother liquor of separating can be done next oxide treatment and use.
The present invention is sorbent used to be the MFe that has than bigger serface
2O
4(M=Fe, Cu, Mn) magnetic substance or be loaded with the gac of these magnetic substances, its granularity is 0.1-1000 μ m.These magnetic substances can make easily with known coprecipitation method, and used gac is granular, powdery or activated carbon fiber; Preferred powder shaped activated carbon wherein.
Absorbing process involved in the present invention can be continuously or intermittent mode carry out, as long as can reach complete mixed effect.And the optimal ph, sorbent material dosage and the adsorption time that are suitable for different solutions are determined by experiment.
Separation method involved in the present invention is that the mixed solution that will contain magnetic adsorbent directly carries out solid-liquid separation by magnetic separator.Used magnetic separator is permanent magnetism or electromagnetic induction high gradient magnetic separator, and background magnetic field intensity is more than 1000 Gausses, and filtering velocity is 20-200m/h.
The adsorbed organism of sorbent material is removed with the catalytic wet oxidation method, simultaneously reproducing adsorbent.Used oxidized catalyst precursor is Fe
2+/ H
2O
2Or catalytic oxidation method.Fe
2+/ H
2O
2System catalytic oxidation condition: according to sorbent material and adsorbed organism difference, reaction conditions is different, generally speaking, solid-liquid volume ratio 1: 5-1: 20, the pH value is 2-6, preferably 3-4.5; H
2O
2Concentration 0.1-2mol/l, Fe
2+/ H
2O
2Mol ratio be 1: 20-1: 2, be preferably 1: 12-1: 5.10--40 ℃ of down vibration or with other method hybrid reaction 10-120 minute.Carry out magnetic then and separate, the aqueous solution adds an amount of Fe
2+And H
2O
2After can do next oxide treatment and use; Isolated sorbent material recycles with returning absorbing process after washing 2-3 time on a small quantity.
The catalytic oxidation method is to carry out at electrochemical cell, room temperature, and negative electrode is right China ink or platinum electrode, anode is titanium ruthenium or platinum electrode; Distance is 3--10cm between the electrode, the organic sorbent material of load is filled therebetween, and be supporting electrolyte with 2--5%NaCl solution, voltage 2-10V, electric current are 50-2500mA, electrolysis time 1-5 hour.Electrolysis finishes, and carries out solid-liquid separation with magnetism separate method, can return absorbing process after sorbent material washes 2-3 time with water and recycle; Electrolyte solution then can continue to use.
Advantage of the present invention is, (1) adopts magnetic adsorbent, and rate of adsorption is fast, and the organic efficiency height is not limited by granular size substantially; (2) organic removal is to carry out in different systems with oxidation, and former water treatment effect is only relevant with absorption, not oxidated reaction influence; (3) catalytic oxidation system separates with the former aqueous systems of processing, and oxidation mother liquor and sorbent material all can be recycled, non-secondary pollution.(4) this technology not only can be used for to water treatment but also can be used for wastewater treatment.
Embodiment
Example 1, certain waste water from dyestuff mainly contain Acid Red B 200mg/l, and pH5.2 gets 1 liter of waste water, add 10gMnFe
2O
4Sorbent material mixes and carries out the magnetic separation after 30 minutes, records water outlet Acid Red B concentration less than 5mg/l.Isolated sorbent material is dropped into 30ml pH4, H
2O
2In the aqueous solution of concentration 0.5-2.0mol/l, stir adding 0.4g FeSO down
47H
2O reacts and carries out the magnetic separation after 1 hour, and aqueous solution TOC≤10mg/l can continue on for the next batch oxidation regeneration and (add an amount of H during use
2O
2And FeSO
47H
2O); Sorbent material steeped 30 minutes with the 20ml water logging, returned adsorption operations after magnetic separates, and recycled.The result shows that the adsorbents adsorb ability strengthens to some extent behind oxidation regeneration, and absorption back water outlet Acid Red B concentration is less than 2mg/l.
Example 2, waste water from dyestuff and adsorption operations are the same, and different is, the organic sorbent material of load directly drops into new waste water from dyestuff and carries out adsorption operations once more after magnetic separates, and after magnetic separated, water outlet dropped into new sorbent material and does second adsorption; The sorbent material that reclaims then carries out oxidation regeneration by example 1 method.Can make outlet water organic substance concentration lower like this, the utilization ratio of sorbent material is higher.
Example 3, waste water from dyestuff are the same, add CuFe
2O
4Sorbent material 10g, other condition is the same, records absorption back water outlet dye strength at last less than 5mg/l.The adsorbents adsorb ability strengthens equally behind oxidation regeneration, recycles, and absorption back water outlet Acid Red B concentration is less than 2mg/l.
Example 4, waste water from dyestuff are the same, add to contain CuFe
2O
430% CuFe
2O
4-powdered carbon magnetic adsorbent 5g, other condition is the same, records absorption back water outlet dye strength at last less than 3mg/l.The adsorbents adsorb ability is constant substantially behind oxidation regeneration, recycles, and absorption back water outlet Acid Red B concentration is less than 3mg/l.
Example 5, with containing CuFe
2O
430% CuFe
2O
4-powdered carbon magnetic adsorbent is done adsorption experiment, and other condition is the same, and absorption finishes, and after magnetic separated, the organic sorbent material of load was regenerated with electrochemical method.Sorbent material is placed electrolyzer, room temperature, negative electrode is a Graphite Electrodes, anode is a platinum electrode; Distance is 3cm between the electrode, is supporting electrolyte with 2--5%NaCl solution, and voltage 10V, electric current are 200mA, electrolysis time 4 hours.Electrolysis finishes, and carries out solid-liquid separation with magnetism separate method, and electrolyte solution can continue to use.Can return absorbing process after sorbent material washes 2-3 time with water recycles; After the result showed regeneration, the loading capacity of sorbent material can reach more than 80% of former loading capacity.
Claims (6)
1, a kind of water technology is characterized in that, utilizes the organism in the former water of magnetic adsorbent absorption removal earlier, decomposes with the oxidation operation of catalytic oxidation with load again.Organic removal places different systems with oxygenolysis in the former water, makes the treatment effect of former water only relevant with absorption, is not subjected to the influence of catalytic oxidation, non-secondary pollution.
2, in accordance with the method for claim 1, it is characterized in that, be used for adsorbing remove the organic sorbent material of former water be have good magnetic, be easy to the MFe that separates and reclaim, have good adsorption properties with magnetism separate method
2O
4(M=Fe, Cu, Mn) or be loaded with the gac of these magnetic substances.
3, in accordance with the method for claim 1, it is characterized in that catalytic oxidation treatment is to carry out in the another one system, used catalysed oxidation processes is Fe
2+/ H
2O
2Oxidation system or electrochemical catalytic oxidation method.
4, in accordance with the method for claim 2, it is characterized in that, carry out solid-liquid separation, reclaim magnetic adsorbent with magnetism separate method.Specifically be to separate with permanent magnetism or electromagnetic induction high gradient magnetic separator, background magnetic field intensity is more than 1000 Gausses.
5, according to the described method of claim 3, it is characterized in that, be used for the Fe of catalyzed oxidation
2+/ H
2O
2The system pH value is 2-6, preferably 3-4.5; Fe
2+/ H
2O
2Mol ratio be 1: 20-1: 2, be preferably 1: 12-1: 5.Reaction times 10-120 minute.
According to the described method of claim 3, it is characterized in that 6, the used negative electrode of electrochemical catalytic oxidation method is graphite or platinum electrode, anode is titanium ruthenium or platinum electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02149358 CN1247466C (en) | 2002-11-13 | 2002-11-13 | Technique for treating water using magnetic absorbent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02149358 CN1247466C (en) | 2002-11-13 | 2002-11-13 | Technique for treating water using magnetic absorbent |
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|---|---|
| CN1500737A true CN1500737A (en) | 2004-06-02 |
| CN1247466C CN1247466C (en) | 2006-03-29 |
Family
ID=34233617
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02149358 Expired - Fee Related CN1247466C (en) | 2002-11-13 | 2002-11-13 | Technique for treating water using magnetic absorbent |
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| CN (1) | CN1247466C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009009942A1 (en) * | 2007-07-13 | 2009-01-22 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Ferrimanganic composite oxide absorbent, method for preparing the same, and method for utilizing the same |
| CN102795736A (en) * | 2011-05-25 | 2012-11-28 | 四川环能德美科技股份有限公司 | Deep treatment method for anion exchange resin regeneration waste solution |
| CN103007881A (en) * | 2012-12-10 | 2013-04-03 | 衢州学院 | Magnetically separated bamboo charcoal-based wastewater treatment agent and preparation method and application thereof |
| CN103611496A (en) * | 2013-11-12 | 2014-03-05 | 南京工业大学 | Magnetic carbon-based adsorbent and application thereof |
| CN104150540A (en) * | 2014-07-14 | 2014-11-19 | 河南大学 | Heavy metal ion adsorbent ferrite hollow spheres MFe2O4 |
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| CN106745367A (en) * | 2016-12-06 | 2017-05-31 | 苏州科技大学 | A kind of iron-based nanometer sewage-treating agent |
| CN112387249A (en) * | 2020-11-11 | 2021-02-23 | 内蒙古科技大学 | Porous biochar/zinc ferrite composite material and preparation method and application thereof |
| CN113713770A (en) * | 2021-09-08 | 2021-11-30 | 江西省科学院微生物研究所 | Composite adsorption material, preparation method and application thereof, and recycling method of composite adsorption material |
-
2002
- 2002-11-13 CN CN 02149358 patent/CN1247466C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8207087B2 (en) | 2007-07-13 | 2012-06-26 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Method for making ferric and manganese binary oxide based adsorbent |
| WO2009009942A1 (en) * | 2007-07-13 | 2009-01-22 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Ferrimanganic composite oxide absorbent, method for preparing the same, and method for utilizing the same |
| CN102795736B (en) * | 2011-05-25 | 2014-08-13 | 四川环能德美科技股份有限公司 | Deep treatment method for anion exchange resin regeneration waste solution |
| CN102795736A (en) * | 2011-05-25 | 2012-11-28 | 四川环能德美科技股份有限公司 | Deep treatment method for anion exchange resin regeneration waste solution |
| CN103007881A (en) * | 2012-12-10 | 2013-04-03 | 衢州学院 | Magnetically separated bamboo charcoal-based wastewater treatment agent and preparation method and application thereof |
| CN103611496B (en) * | 2013-11-12 | 2016-08-17 | 南京工业大学 | A kind of magnetic carbon-supported catalyst and application |
| CN103611496A (en) * | 2013-11-12 | 2014-03-05 | 南京工业大学 | Magnetic carbon-based adsorbent and application thereof |
| CN104150540A (en) * | 2014-07-14 | 2014-11-19 | 河南大学 | Heavy metal ion adsorbent ferrite hollow spheres MFe2O4 |
| CN104150540B (en) * | 2014-07-14 | 2016-01-20 | 河南大学 | A kind of adsorbent for heavy metal ferrite hollow ball MFe 2o 4 |
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| CN106745367A (en) * | 2016-12-06 | 2017-05-31 | 苏州科技大学 | A kind of iron-based nanometer sewage-treating agent |
| CN112387249A (en) * | 2020-11-11 | 2021-02-23 | 内蒙古科技大学 | Porous biochar/zinc ferrite composite material and preparation method and application thereof |
| CN113713770A (en) * | 2021-09-08 | 2021-11-30 | 江西省科学院微生物研究所 | Composite adsorption material, preparation method and application thereof, and recycling method of composite adsorption material |
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| Publication number | Publication date |
|---|---|
| CN1247466C (en) | 2006-03-29 |
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