CN101348297B - Processing method for heavy metal ion-containing waste water - Google Patents
Processing method for heavy metal ion-containing waste water Download PDFInfo
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- CN101348297B CN101348297B CN200710075261XA CN200710075261A CN101348297B CN 101348297 B CN101348297 B CN 101348297B CN 200710075261X A CN200710075261X A CN 200710075261XA CN 200710075261 A CN200710075261 A CN 200710075261A CN 101348297 B CN101348297 B CN 101348297B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 27
- 238000003672 processing method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000006722 reduction reaction Methods 0.000 claims abstract description 25
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 52
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 45
- 150000002500 ions Chemical class 0.000 claims description 31
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 230000002829 reductive effect Effects 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 230000003321 amplification Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009991 scouring Methods 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 30
- 239000006249 magnetic particle Substances 0.000 abstract 2
- 230000003617 peroxidasic effect Effects 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 24
- 230000000274 adsorptive effect Effects 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- -1 thiourea peroxide Chemical class 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
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- 238000000967 suction filtration Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
A method for treating waste water containing chromium ion comprises the following steps that a magnetic particle is used to adsorb heavy metal ion in waste water; the particle contains ferroferric oxide and adsorbs sexivalent chromium ion or trivalent chromium ion in the waste water so as to form a complex with the sexivalent chromium ion or reducing body of the sexivalent chromium ion, namely trivalent chromium ion in the waste water; moreover, the capacity of the particle containing ferroferric oxide for adsorbing chromium ion is gradually enlarged through stepwise reduction reaction till the capacity is saturated; and finally, the magnetic particle is separated from the adsorbed chromium ion through peroxidatic reaction. The particle containing ferroferric oxide can effectively adsorb poisonous heavy metal ion in the waste water, and can reclaim heavy metal, thereby realizing effective treatment of the waste water and protecting the environment.
Description
Technical field
The present invention relates to field of waste water treatment, especially about handling the method for heavy metal ions in wastewater.
Background technology
Chromium metal is a kind of harmful heavy metal, and especially sexavalent chrome is the most malicious.Chromate waste water is a kind of trade effluent that environment is had significant damage, and chromate waste water is mainly derived from smelting, electroplates mechanical workout and leather processing industries.For a long time, administer pollution of chromium and attracted attention by the whole world always, various countries drop into manpower and materials for this reason and carry out extensive studies, and obtain certain achievement in research and patent of invention.Up to the present, be used to administer the method for hexavalent chromium wastewater mainly based on chemical method, its process comprises: with reductive agent such as iron protochloride, ferrous sulfate etc. it is reduced to trivalent chromium and makes it generate chromium hydroxide precipitation with alkali and trivalent chromium reaction then, thereby it is removed from waste water.The ferrite coprecipitation method of widespread use recently also belongs to this category in fact.Though this method can effectively be removed sexavalent chrome, process length consuming time, facility takes up an area of big, produces a large amount of mud simultaneously, causes secondary pollution easily.Except that chemical method, also have some other technology sequential use to handle in chromate waste water, these comprise: electrolytic process, absorption method, ion exchange method, membrane separation process, though these technology all have certain advantage separately to handling chromium metal waste water, but still there are shortcomings such as the too high or reliability of cost is not enough.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiencies in the prior art, and a kind of nontoxic, method of wastewater treatment that cost is low is provided.
The technical solution adopted for the present invention to solve the technical problems is: a kind of treatment process of heavy metal ion-containing waste water, utilize the heavy metal ion in the particulate absorption waste water with magnetic, and this particulate chemistry composition is a Z 250.
The described particulate that contains Z 250 adsorbs hexavalent chromium or the trivalent chromic ion in the waste water.
Specifically, described particulate that contains Z 250 and the hexavalent chromium in the waste water or and going back of it form water-fast complex body between the substance trivalent chromic ion.
Described Z 250 obtains by iron(ic) chloride, iron protochloride and sodium hydroxide are synthetic.
A kind of treatment process of heavy metal ion-containing waste water, core content are exactly that the capacity that contains the particulate absorption chromium ion of Z 250 is to reach progressively amplification by the step-by-step reduction reaction, up to saturated; The chromium ion that separates little magnetic grain and absorption again by oxidizing reaction.
Reduction reaction is meant the process of little magnetic grain Z 250 electron gain.
The reduction reaction process is meant: mix by the little magnetic grain slurry mud that adsorbs chromium ion of ratio with reductant solution and recovery, regulate PH to alkalescence, normal temperature condition reaction is down adsorbed little magnetic grain slurry mud by magnetic field, removes the liquid that contains reductive agent, washing.
Specifically, mix by little magnetic grain slurry mud of 1:1 ratio with the adsorbing hexavalent chromium ions of reductant solution and recovery exactly, with sodium hydroxide the pH value is transferred to more than 8.0, reaction is 1 hour under normal temperature condition.Adsorb little magnetic grain slurry mud by magnetic field, remove the liquid that contains reductive agent, wash and get final product for twice.
Oxidizing reaction is meant that Z 250-chromium metal complex body loses the process of electronics.
The oxidation sepn process is meant: mix by little magnetic grain slurry mud of ratio with the adsorbing hexavalent chromium ions of oxygenant and recovery, regulate PH to alkalescence, normal temperature is reaction down, makes its solid-liquid separation by vacuum filtration, finds chromic trace until nothing for several times with the washing lotion washing.
Specifically, by the ratio of 1:1.5 little magnetic grain of the adsorbing hexavalent chromium of oxygenant and recovery being starched mud exactly mixes, with sodium hydroxide the pH value is transferred to 10.0, reacted at normal temperatures 20 minutes, make its solid-liquid separation by vacuum filtration, find chromic trace until nothing for several times with the washing lotion washing of 1:1 volume.
Reductive agent is that concentration is 1.3% thiourea dioxide water solution.
Reductive agent can also be a Sodium Pyrosulfite, Sodium Thiosulfate,-sulfinic acid and time sodium bisulfite.
Oxygenant is 10% hydrogen peroxide.
Oxygenant can also be ozone, chlorine, dioxide peroxide and hypochlorite.
The washing lotion of reaction after scouring is the solution that contains 0.04% sodium hydroxide and 1% hydrogen peroxide, the pH=9.0 of this solution.
Oxidizing reaction is directly used in the recovery of sexavalent chrome and emblem grain.
The particulate that reclaims by oxidizing reaction can recycle.
The invention has the beneficial effects as follows, can adsorb the ion of the deleterious heavy metal of waste water effectively, heavy metal is reclaimed, thereby can handle waste water effectively, the protection environment by this particulate.
Description of drawings
Fig. 1 is the dynamic change that little magnetic grain repeats adsorbing hexavalent chromium;
Fig. 2 is initial saturation capacity and the maximum saturation amount that little magnetic grain repeats adsorbing hexavalent chromium.
Embodiment
The processing of present embodiment waste water is chromium (Cr) ion in the heavy metal ion of utilizing in the little magnetic grain absorption waste water that contains Z 250 (Fe304), particularly waste water.Contain sexavalent chrome (Cr6+) ion in the little magnetic grain absorption waste water of Z 250 (Fe304) or trivalent chromium (Cr3+) ion and be by sexavalent chrome (Cr6+) ion in Z 250 (Fe304) particulate and the waste water or and its water-fast complex body of formation of going back between substance trivalent chromium (Cr3+) ion realize.Z 250 (Fe304) is synthesized into by iron(ic) chloride (FeCl3), iron protochloride (FeCl2) and sodium hydroxide (NaOH).
The present embodiment wastewater treatment method, be to utilize particulate absorption chromium (Cr) ion that contains Z 250 (Fe304), the capacity of its absorption is to reach progressively amplification by the step-by-step reduction reaction, up to saturated: promptly when little magnetic grain adsorbing hexavalent chromium (Cr6+) ion that contains Z 250 (Fe304) reaches capacity state, itself can not further adsorb chromium (Cr) ion, but will be in this state contain the little magnetic grain of Z 250 (Fe304) through with reductive agent thiourea peroxide (CH4N202S) reaction after can recover initial adsorbed state, when the approaching initial saturated capacity of loading capacity, repeat above process again, and such process can repeat 3-4 time, makes last absorption total amount reach primary 4-5 doubly.
In such reduction reaction process, there is no heavy metal ion and deviate from, illustrate that each treating processes by reductive agent is exactly the primary sorption dilation process, make final saturated adsorption capacity increase to original 4-5 doubly.Because contain ferric iron (Fe3+) and ferrous iron (Fe2+) in Z 250 (Fe304) crystal, number is than being 2:1.The composition that plays the effect of absorption heavy metal is ferrous iron (Fe2+).Its adsorption process is that ferrous iron (Fe2+) reduces the sexavalent chrome in the waste water (Cr6+) ion earlier, thereby form the mixture of complex compound or other form on the surface of ferrous iron (Fe2+), after the surperficial useful space of ferrous iron (Fe2+) was taken, little magnetic grain sorbent material reached temporary or interim state of saturation; When with reductive agent thiourea peroxide (CH4N202S) when its reaction, the part ferric iron (Fe3+) in the little magnetic grain of Z 250 (Fe304) is reduced to ferrous iron (Fe2+), from and new adsorption space is provided.Because Z 250 (Fe304) structure needs certain ferric iron (Fe3+) and ferrous iron (Fe2+) ratio to maintain its stability of structure, therefore a reduction reaction can not be reduced to ferrous iron (Fe2+) with most of or whole ferric irons (Fe3+), so need be through repeatedly reduction reaction several times. and adsorption process just can reach final state of saturation.
Containing in the process of the little magnetic grain of Z 250 (Fe304) with the reductive agent reduction, thiourea peroxide (CH4N202S) is a kind of ideal reductive agent, thiourea peroxide (CH4N202S) safety non-toxic, performance at normal temperatures is stable, and consumption is few, and reaction is fast, effective, expense is low; Some other reductive agent such as Sodium Pyrosulfite (Na2S205), Sodium Thiosulfate (Na2S204),-sulfinic acid (CH2=CH-S03H), inferior sodium bisulfite (NaHS204) also can be used for above-mentioned reduction reaction.
After chromium (Cr) ion in containing the little magnetic grain absorption of Z 250 (Fe304) waste water reaches complete state of saturation, separate chromium (Cr) ion that contains little magnetic grain of Z 250 (Fe304) and absorption by oxidizing reaction again, originally the chromium metal (Cr) that is attracted to the little magnetic grain of Z 250 (Fe304) surface in oxidizing reaction through reduction is oxidized, thereby complex compound that originally forms or mixture are broken and allowed chromium metal (Cr) dissociate out again.
Contain in chromium (Cr) the ionic process of little magnetic grain of Z 250 (Fe304) and absorption in the oxidizing reaction separation, hydrogen peroxide (H202) is a kind of ideal oxygenant, hydrogen peroxide (H202) safety non-toxic, and consumption is few, and reaction is fast, and effective, expense is low; Some other oxygenant such as ozone (03), chlorine (C12), dioxide peroxide (C102) and hypochlorite (XC10n) also can be used for above-mentioned oxidizing reaction.
Contain the little magnetic grain of Z 250 (Fe304) sorbent material and can stand repeatedly recycling elution and absorption, in each circulation, be accompanied by the reduction reaction process, containing the little magnetic grain of Z 250 (Fe304) can be repeatedly used, saturated up to reaching last absorption.Use this technology not only can effectively remove chromium metal in the waste water, but also not produce mud, can not cause secondary pollution, can also from waste water, reclaim chromium metal simultaneously.
A kind of concrete processing mode is as follows:
The reduction reaction process; be meant the process of the little magnetic grain electron gain that contains Z 250 (Fe304): mix by little magnetic grain slurry mud of 1:1 ratio with the adsorbing hexavalent chromium ions of reductant solution and recovery; with sodium hydroxide the pH value is transferred to more than 8.0, reaction is 1 hour under normal temperature condition.Adsorb little magnetic grain slurry mud by magnetic field, remove the liquid that contains reductive agent, wash and get final product for twice.Reductive agent is that concentration is 1.3% thiourea peroxide (CH4N202S) aqueous solution, can also be Sodium Pyrosulfite (Na2S205) Sodium Thiosulfate (Na2S204),-sulfinic acid (CH2=CH-S03H), inferior sodium bisulfite (NaHS204).
The oxidation sepn process is an oxidizing reaction, be meant that Z 250-chromium metal complex body loses the process of electronics: by the ratio of 1:1.5 little magnetic grain of the adsorbing hexavalent chromium of oxygenant and recovery is starched mud and mix, with sodium hydroxide the pH value is transferred to 10.0, reacted at normal temperatures 20 minutes, make its solid-liquid separation by vacuum filtration, find chromic trace until nothing for several times with the washing lotion washing of 1:1 volume.Oxygenant is that concentration is 10% hydrogen peroxide (H202), can also be ozone (03), chlorine (C12), dioxide peroxide (C102) and hypochlorite (XC10n).Washing lotion is the solution of 0.04% sodium hydroxide (NaOH) and 1% hydrogen peroxide (H202), the pH=9.0 of this solution.
Adsorption process is used for adsorbing the chromium ion of waste water, the oxidation sepn process is used for separating the chromium (Cr) that contains the little magnetic grain of Z 250 (Fe304) and be adsorbed, can be directly used in the little magnetic grain that reclaims sexavalent chrome (Cr6+) and contain Z 250 (Fe304), the little magnetic grain that contains Z 250 (Fe304) that reclaims by the oxidation sepn process can be recycled, and has so just increased adsorptive capacity, has stopped secondary pollution, has reduced the cost of wastewater treatment.
For beneficial effect of the present invention is described, done following experiment:
Testing used ferroferric oxide micro-magnetic grain is made by following method: respectively 0.5 mole of iron(ic) chloride (FeCl3) and iron protochloride (FeCl2) are dissolved in 1 liter of distilled water, then add the sodium hydroxide that concentration is 1 mol (NaOH) lentamente in stirring and rise to 7.5 until the pH value.At this moment all iron(ic) chloride (FeCl3) and iron protochloride iron protochloride (FeCl2) all are converted into Z 250 (Fe304) particulate of not allowing and be black basically, and particle is very small, to between tens microns, has very strong magnetropism at several microns.Z 250 in the solution (Fe304) can be collected by vacuum filtration or by magnetic field.
Testing 1: one usefulness contains the ferroferric oxide micro-magnetic grain and handle the experiment of hexavalent chromium wastewater and follow these steps to carry out: it is in 250 ml beakers that sexavalent chrome (Cr6+) the ionic waste water that to get 200 milliliters of content respectively be 250,500,1000 mg/litre is poured capacity into, adding over dry in each beaker heavily is that the 1 little magnetic grain of Z 250 (Fe304) that restrains also stirred 10 minutes at normal temperatures gently, the bottom that is placed on beaker with a permanent magnet inhales little magnetic grain toward the bottom then, gets clarifying water sample and carries out sexavalent chrome and detect.The difference of sexavalent chrome (Cr6+) ion content is used for estimating that the little magnetic grain of unit is to sexavalent chrome (Cr6+) ionic adsorptive capacity before and after the wastewater treatment.Table 1 result shows that the little magnetic grain of Z 250 (Fe304) is the 36-37 mg/litre to sexavalent chrome (Cr6+) the ionic adsorptive capacity of these three kinds of different concns, and is very little to the absorption difference between different concns, basically all in the scope of error.
Table 1: the variation of three kinds of different concns hexavalent chromium wastewater chrome contents and little magnetic grain are to chromic adsorptive capacity after little magnetic grain is handled
Data presentation in the table 1: concerning the sexavalent chrome of different concns, emblem magnetic grain is little to its adsorptive capacity difference.Little magnetic grain is distinguished the chromic absorption difference of 250,500 and 1000 mg/litre all in limit of error to concentration.For the sexavalent chrome below concentration is 250 mg/litre, consumption is that little magnetic grain of 0.6% can make its content reduce to below 0.5 mg/litre.According to this consumption, it is that the waste water of 250 mg/litre dechromises up to standard that the disposable processing of emblem magnetic grain just can make content of 6-valence Cr ions.Z 250 emblem magnetic grain has very strong magnetropism, after the absorption chromium metal reaches capacity, and formed little magnetic grain. the chromium metal complex body still has same magnetropism, thereby is easy to by magnetic field it be collected, thereby reaches the effect of purifying liquid waste.This shows that little magnetic grain of being made up of Z 250 is very good as the hexavalent chromium wastewater scavenging agent.
Experiment 2:(experiment 1 experiment that continues) reductant solution that will contain 1.3% thiourea peroxide (CH4N202S) in the ratio of 1:1 joins in little magnetic grain slurry mud (water content about 85%) of the adsorbing hexavalent chromium of collecting by magnetic field (Cr6+), the pH value is transferred to 8.0, fully be allowed to condition at behind the mixing and carried out reduction reaction in the normal temperature 1 hour.After reaction finishes, collect emblem magnetic grain, remove reductive agent, wash twice with magnet.Method by experiment 1 continues to handle corresponding sexavalent chrome (Cr6+) waste water with it then, repeats these two processes 3 times.Asking when prolonging reaction in reduction reaction and increasing the reductive agent consumption does not influence reaction effect.Little magnetic grain repeatedly repeat to reduce and adsorption process to the dynamic change of sexavalent chrome absorption.See Fig. 1 its for the first time saturated extent of adsorption and final saturation adsorptive capacity relatively see Fig. 2.
Experiment 3:(experiment 2 experiments that continue) 8 milliliter 10%, the hydrogen peroxide (H202) of PH=11 are joined in little magnetic grain of last collection its oxidizing reaction of mixing relief 20 minutes respectively.The phenomenon that can occur the temperature rising in reaction process belongs to normal.After reaction finishes, collect liquid, use washing lotion (0.04% sodium hydroxide (Na0H), 1% hydrogen peroxide (H202), PH=9.0) washing more for several times until no chromium metal (Cr) trace by suction filtration.Detect chromium metal (Cr) content that all collect liquid.Through oxidizing reaction and washing, the sexavalent chrome that is adsorbed (Cr6+) is come out by wash-out basically entirely, and the rate of recovery is greater than 97%.Little magnetic grain part after oxidizing reaction removes sexavalent chrome (Cr6+) is directly used in adsorbing hexavalent chromium (Cr6+), and another part then passes through as being used further to adsorbing hexavalent chromium (Cr6+) after the example 2 described reduction reactions.Little in both cases magnetic grain sees Table 2 to the adsorptive capacity of sexavalent chrome (Cr6+).The result shows: the little magnetic grain that does not pass through reduction reaction is very low to sexavalent chrome (Cr6+) adsorptive capacity, and less than 10% of initial adsorptive capacity, little magnetic grain of process reduction reaction then reaches more than 95% of initial adsorptive capacity to the adsorptive capacity of sexavalent chrome (Cr6+).
Table 2: the little magnetic grain behind the wash-out chromium metal is handled the effect of hexavalent chromium wastewater once more
| The wash-out aftertreatment | Not reduction | Reduction |
| Content (mg/litre) before handling | 250 | 250 |
| Handle back content (mg/litre) | 230 | 75 |
| Adsorptive capacity (mg/litre) | 4 | 35 |
Not reduction group data declaration in the table 2 is in oxidation removing heavy-metal process, and except chromium metal was oxidized, the ferrous iron of considerable part was also oxidized and be converted into ferric iron in the magnetic grain of emblem, and its process is just in time opposite with reduction reaction.Show just and to remove chromic little magnetic grain through oxidizing reaction the capacity of adsorbing hexavalent chromium is very little once more, it only is below 10% of initial capacity, little magnetic grain of this state obviously can not be directly used in adsorbing hexavalent chromium, must be by just being reused for adsorbing hexavalent chromium after the above-mentioned reduction process regeneration.The ability of reduction group data declaration little magnetic grain adsorbing hexavalent chromium behind reducing/regenerating returns to original state substantially.
Utilize method of wastewater treatment of the present invention, utilize Fe 3 O 4 magnetic particulate absorption chromium metal to reach the purpose of from waste water, removing this harmful heavy metal, not only can be used for hexavalent chromium wastewater improvement and also can be used for the recovery of chromium metal, thereby reach the effect of purifying liquid waste; Provide not only cheap but also reliable and can a recycle method for administering chrome waste water, used this method not only can effectively remove chromium metal in the waste water, but also not produce mud, can not cause secondary pollution, can also from waste water, reclaim chromium metal simultaneously.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. the treatment process of a heavy metal ion-containing waste water is characterized in that: utilize the heavy metal ion in the particulate absorption waste water with magnetic, this particulate contains Z 250, and described Z 250 is synthetic by iron(ic) chloride, iron protochloride and sodium hydroxide; The described particulate that contains Z 250 adsorbs hexavalent chromium or the trivalent chromic ion in the waste water; Described particulate that contains Z 250 and the hexavalent chromium in the waste water or and going back of it form water-fast complex body between the substance trivalent chromic ion; The capacity that contains the particulate absorption chromium ion of Z 250 is to reach progressively amplification by the step-by-step reduction reaction, up to saturated, passes through the chromium ion of oxidizing reaction separating particles and absorption again; Reduction reaction is meant the process of particulate Z 250 electron gain, reduction process is for to mix by the particulate slurry mud that adsorbs chromium ion of ratio with reductant solution and recovery, regulate pH to alkalescence, normal temperature condition is reaction down, by magnetic field adsorbent particles slurry mud, remove the liquid that contains reductive agent, washing; Oxidizing reaction is meant that Z 250-chromium metal complex body loses the process of electronics, the oxidation sepn process is for to mix by the particulate slurry mud of ratio with the adsorbing hexavalent chromium ions of oxygenant and recovery, regulate pH to alkalescence, normal temperature is reaction down, make its solid-liquid separation by vacuum filtration, find chromic trace until nothing for several times with the washing lotion washing.
2. the treatment process of heavy metal ion-containing waste water according to claim 1, it is characterized in that: reduction process is, mix by 1: 1 ratio particulate slurry mud the adsorbing hexavalent chromium ions of reductant solution and recovery, with sodium hydroxide the pH value is transferred to more than 8.0, reaction is 1 hour under normal temperature condition; By magnetic field adsorbent particles slurry mud, remove the liquid that contains reductive agent, wash and get final product for twice.
3. the treatment process of heavy metal ion-containing waste water according to claim 1, it is characterized in that: the oxidation sepn process is, mix by the particulate slurry mud of 1: 1.5 ratio the adsorbing hexavalent chromium of oxygenant and recovery, with sodium hydroxide the pH value is transferred to 10.0, reacted at normal temperatures 20 minutes, make its solid-liquid separation by vacuum filtration, find chromic trace until nothing for several times with the washing lotion washing of 1: 1 volume.
4. the treatment process of heavy metal ion-containing waste water according to claim 1 and 2, it is characterized in that: reductive agent is that concentration is 1.3% thiourea dioxide water solution.
5. the treatment process of heavy metal ion-containing waste water according to claim 1 and 2, it is characterized in that: reductive agent is a Sodium Pyrosulfite, Sodium Thiosulfate,-sulfinic acid and time sodium bisulfite.
6. according to the treatment process of claim 1 or 3 described heavy metal ion-containing waste waters, it is characterized in that: oxygenant is 10% hydrogen peroxide.
7. according to the treatment process of claim 1 or 3 described heavy metal ion-containing waste waters, it is characterized in that: oxygenant is ozone, chlorine, dioxide peroxide and hypochlorite.
8. according to the treatment process of each described heavy metal ion-containing waste water of claim 1～3, it is characterized in that: the washing lotion of reaction after scouring is the solution that contains 0.04% sodium hydroxide and 1% hydrogen peroxide, the pH=9.0 of this solution.
9. according to the treatment process of any described heavy metal ion-containing waste water of claim 1～3, it is characterized in that: oxidizing reaction is directly used in the recovery of sexavalent chrome and particulate.
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| CN103021491B (en) * | 2012-12-12 | 2015-04-29 | 华东理工大学 | Method for treating wastewater generated by nuclear power plant by utilizing chemical precipitation |
| CN104370392A (en) * | 2014-12-03 | 2015-02-25 | 广州蓝涛水处理有限公司 | Treatment method for smelting waste water containing sulfuric acid and heavy metal |
| CN105859014A (en) * | 2016-05-25 | 2016-08-17 | 安徽普氏生态环境工程有限公司 | Magnetic separation special industry water treatment device |
| CN106946382B (en) * | 2017-05-18 | 2019-09-13 | 上海聚丰热镀锌有限公司 | A kind of environment-friendly treatment method of heavy metal chromium ion waste water |
| CN108640247A (en) * | 2018-04-26 | 2018-10-12 | 温州医科大学 | A kind of administering method of hexavalent chromium wastewater |
| US20200299850A1 (en) * | 2019-03-22 | 2020-09-24 | Eco-Tec Limited | Processes for treating electrolyte from an electrorefining process |
| CN110776042B (en) * | 2019-09-29 | 2022-10-28 | 中冶华天工程技术有限公司 | Bifunctional material for reducing and removing chromium (VI) in water and preparation method thereof |
| CN112225381B (en) * | 2020-07-09 | 2022-04-26 | 桂林理工大学 | Treatment method of chromium-containing wastewater |
| CN112159025A (en) * | 2020-10-28 | 2021-01-01 | 中国科学院生态环境研究中心 | Treatment method and application of hexavalent chromium-containing wastewater |
| CN112371098A (en) * | 2020-11-12 | 2021-02-19 | 北京新风航天装备有限公司 | Recovery method of magnetic adsorption particles |
| CN114314997B (en) * | 2022-03-14 | 2022-06-21 | 中南大学 | Electroplating chromium-containing wastewater resource treatment method based on interface coordination regulation |
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