CN102060334A - Preparation of ferrous compound in polyhydroxy structural state and application of ferrous compound in wastewater reduction pretreatment - Google Patents
Preparation of ferrous compound in polyhydroxy structural state and application of ferrous compound in wastewater reduction pretreatment Download PDFInfo
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Abstract
The invention relates to preparation of a ferrous compound in a polyhydroxy structural state and an application of the ferrous compound in wastewater reduction pretreatment. The preparation method comprises the following steps: dissolving a certain amount of ferrite in water without dissolved oxygen; and then gradually dropping oxygen-free alkaline solution in the obtained solution while stirring continuously, and generating structural state ferrous hydroxy complex (FHC) by controlling the molar ratio of ferrous ions to hydroxyls. The FHC prepared by the invention has high reduction activation and high reaction rate with pollutants and can fast reduce and convert harmful and poisonous pollutants in wastewater; and dissolved ferrous state is converted to structural ferrous state so as to obviously increase the reduction performance of the ferrous state. The FHC is used in the wastewater reduction pretreatment; and the scope of application of pH is wide, and the FHC has good effect when the pH value is 4-10. In addition, the FHC is more convenient to add compared with catalyzed iron filler; the wastewater treatment process is easy to operate, manage and maintain, and the cost is low; and the FHC is suitable for the large-scale reduction pretreatment of industrial wastewater.
Description
Technical field
The invention belongs to environmental protection technical field, relate to a kind of preparation method and the application in trade effluent reduction pre-treatment thereof of poly-hydroxy structure attitude ferrous compound.
Background technology
The annual quantity discharged of China's all types of industries waste water reaches 25,000,000,000 tons, and trade effluent is the big but also composition complexity of quantity discharged not only, contains a large amount of recalcitrant substances and toxic pollutent, and its characteristic feature is BOD
5/ COD value is very low, is difficult to biological degradation and handles.And many trade effluents generally are strongly-acid or strong basicity, and have typical difficult features such as high density, high salinity, high chroma, high toxicity.Therefore, the processing of trade effluent has caused both domestic and external showing great attention to, becomes world-famous puzzle.Because trade effluent generally has stronger bio-toxicity, so single aerobe oxidation processing technique is difficult to meet the demands.Present technology for treating industrial waste water mainly is to carry out pre-treatment before biological treatment earlier.Pretreatment process mainly comprises anaerobic hydrolysis-acidification and physical chemistry method, materialization and biochemistry combination process become the typical process of Industrial Wastewater Treatment gradually, improve the biological treatment performance of waste water by physico-chemical process, and then pass through the further oxidative degradation pollutants in waste water of bio-oxidation.Materialization pretreatment method mainly comprises absorption method, coagulating sedimentation/air supporting method and advanced oxidation reduction technique etc.The trade effluent reduction preconditioning technique that at present with the reduction by catalytic iron is representative becomes research gradually and uses focus, the reduction preconditioning technique can with the complementation of bio-oxidation treatment technology, form coupling technique.The core concept of reduction preconditioning technique is by poisoning the redox reaction of contact scar thing in reductive agent and the waste water, pollutent reduction in the waste water is transformed, generate the less relatively biodegradable material of bio-toxicity, thereby improve the biodegradable property of wastewater energy.Chinese patent " method of the treating used water difficult to degradate by catalytic internal electrolysis of iron " (patent No.: ZL02111901.5) invented a kind of use iron, copper and cation-modified zeolite are formed catalytic reduction system, the method of pre-treating difficultly-degradable trade effluent, catalytic reduction effect by iron can make the hard-degraded substance in the waste water be reduced to easy biochemical degradation material, obtained large-scale engineering applications at present, be considered to a kind of reduction of waste water preferably preconditioning technique, but because the use of metallic copper causes cost higher, and the engineering application cost of catalysis iron filler and management maintenance measure need continue research.
Ferrous salt as a kind of traditional inorganic coagulant because cheap and easy to get, treatment effect good, can the large-scale engineering application etc. advantage, therefore extensively apply to wastewater treatment, aspect decolorizing printing and dyeing waste water, have good effect especially.Research is arranged in the process that the decolouring of contrast dyeing waste water coagulating sedimentation is handled, show that ferrous salt has the better coagulation decolorizing effect than other inorganic coagulant.Ferrous salt has been brought into play vital role as coagulating agent in the treating processes of waste water, specialize in report although in the ferrous salt coagulation-settlement process, may exist the ferrous reductive action still to yet there are no, be commonly considered as the Coagulation and Adsorption effect of ferrous salt about the application of ferrous reduction in the trade effluent pre-treatment.Seminar discovers, by changing the ferrous morphological structure, makes it to form structure attitude ferrous complex and can significantly improve the ferrous reducing property, can develop and be applicable to the pretreated ferrous reductive agent of indegradable industrial effluent.Ferrously in environment, can exist with variform, under low pH condition with Fe
2+Form exists, and high pH condition is with Fe (OH)
2Perhaps the oligomerization iron carbonyl is such as Fe (OH)
4 2-, Fe (OH)
4 -, alpha-feooh, ≡ FeOFeOH
0, FeOH
+, coordination compound such as green embroidery, and FeO, FeS, FeOOH, Fe
3O
4, FeCO
3Exist etc. the multi mineral form.People such as Refait adopt Fe (II) and Fe (III) to use coprecipitation method to prepare structural formula under the anoxybiotic condition to be Fe
II 3Fe
III(OH)
8C1nH
2Green embroidery (the Refait P. of O, Abdelmoula M., G é nin J-M.R.mechanisms of formation andstructure of green rust one in aqueous corrosion in the presence of chloride ions[J] CorrosionScience.1998,40 (9): 1547-1560.).Green embroidery is a kind of mixture that contains Fe (II) and Fe (III) with multilayered structure, often contain the negatively charged ion interlayer, it generally is iron oxidation corrosion intermediate product or exists with sedimentary form in anaerobism soil and settling, experimental results show that patina has very strong adsorptivity and reducing power, can be with the hydrochloric ether reduction dechlorination, with nitrobenzene reduction is aniline etc., and the ferrous structural form changes the transformation that causes its reducing power.Chinese patent " a kind of preparation method of green embroidery " (CN 101259970A) discloses the method for a kind of Fe (II) and the green embroidery of Fe (III) co-precipitation formation, the preparation procedure more complicated, and do not mention its reduction industrial wastewater pretreatment function.In addition, patina is ferric iron and ferrous mixture, contains three more valence state iron, and ferric iron can't be brought into play reductive action when being used to go back parent pollutant, so restoring function is restricted.Document does not also have the report about structure attitude ferrous complex (FHC) reduction pretreated waste water at present.
Summary of the invention
In order to improve the ferrous reducing property, and be applied to the reduction pre-treatment of trade effluent, form a kind of new waste water reduction pretreatment process, at the insufficient shortcoming of green embroidery reducing power, the objective of the invention is to disclose the simple preparation method of the strong pure ferrous hydroxo complex of structure attitude of a kind of reducing property, and be used for waste water reduction processing.
Technical scheme of the present invention is: only use perferrite solution, by the pH of the hierarchy of control, determine different [Fe (II)]: [OH
-] mol ratio, make and ferrously combine with hydroxyl, it is ferrous all to be converted into the structure attitude, formation has poly-hydroxy structure attitude ferrous complex (the Ferrous Hydroxy Complex of strong reducing property energy, FHC), promptly, improve its reducing property, be developed to ferrous class reductive agent with very strong reducing power by changing the ferrous structural form.By in dye solution and actual dying, adding FHC, estimate the reducing property of FHC, and optimize processing condition, form waste water reduction novel process for pretreating method.
A kind of preparation method of poly-hydroxy structure attitude ferrous compound comprises step:
(1) taking by weighing a certain amount of ferrous salt is dissolved in it in water that does not contain dissolved oxygen;
(2) in above-mentioned solution, drip the anaerobic basic solution gradually, stir, by control ferrous ion and mol ratio hydroxy, generating structure attitude ferrous precipitation thing while dripping;
Described ferrous salt is from FeSO
47H
2O, FeSO
4, FeCl
2Perhaps Fe (NO
3)
2
Fe in the described perferrite solution
2+Volumetric molar concentration be 0.1～0.8mol/L;
Described alkaline matter is from NaOH, KOH, Ca (OH)
2, Na
2CO
3, ammoniacal liquor;
The mol ratio of described ferrous ion and hydroxide ion is 0.1～1.0.
Described entire operation process is carried out under anaerobic state.
A kind of poly-hydroxy structure attitude ferrous compound that utilizes above-mentioned preparation carries out waste water and reduces pretreated method, comprises step:
(1) the dyestuff simulated wastewater or the actual waste water of getting certain volume joins in the reactor, and the pH that regulates waste water is 4～10;
(2) add FHC in waste water, it adds concentration is 20～200mg/L (in ferrous content), at a slow speed behind stirring reaction 10～60min, and the water sampling analysis.
Described pH regulator agent is from NaOH, KOH, Ca (OH)
2, CaO, Na
2CO
3Or ammoniacal liquor.
Described FHC comes from and obtains containing the sedimentary liquid of FHC in the above-mentioned FHC preparation process, and maybe the FHC liquid with preparation also can filter earlier, starvation drying then, obtain pressed powder after, be added in the waste water reactor.
A kind of poly-hydroxy structure attitude ferrous compound that utilizes above-mentioned preparation carries out waste water and reduces pretreated method, comprises step:
(1) use alkaline matter earlier wastewater pH to be adjusted to 8～12;
(2) adding Fe (II) concentration then gradually in waste water is the ferrous aqueous solution of 0.1～0.8mol/L, make the concentration of Fe in the waste water (II) reach 20～200mg/L, Fe (II) forms structure attitude ferrous (FHC), stirring reaction 10～60min, water sampling analysis in waste water.
Described alkaline matter is selected from NaOH, KOH, CaO, Ca (OH)
2Or Na
2CO
3A kind of poly-hydroxy structure attitude ferrous compound that utilizes above-mentioned preparation carries out waste water and reduces pretreated method, comprises step:
(1) directly adding Fe (II) concentration in waste water is the ferrous aqueous solution of 0.1～0.8mol/L, makes that ferrous concentration reaches 20～200mg/L in the waste water;
(2) use pH regulator to 8～10 of alkaline matter with waste water then, Fe (II) forms structure attitude ferrous (FHC) in waste water, behind stirring reaction 10～60min, and the water sampling analysis.
Described alkaline matter is selected from NaOH, KOH, Ca (OH)
2, CaO, Na
2CO
3Or ammoniacal liquor.
Advantage of the present invention comprises:
The FHC reducing activity height of preparation, the structure attitude is ferrous to be improved greatly than solubilised state ferrous reducing property, can reduce the toxic pollutent of conversion in the waste water, has given full play to the ferrous reducing property.
Iron among the FHC of preparation all is that the structure attitude is ferrous, and the reducing property that contains ferric structure attitude iron cpd than patina etc. obviously strengthens.
The FHC and the pollutant reaction speed of preparation are fast, and being generally 10min with reaction times of pollutent can finish, and the reaction times of wastewater preprocessing process is 10～60min, has significantly reduced the volume of reaction tank in the waste water treatment process.
The FHC of preparation is used for waste water reduction pre-treatment, and to adapt to the pH scope wide, can both obtain good effect in pH is 4～10 scope, expanded its range of application.
The FHC of preparation adds conveniently than catalysis iron filler, and the waste water treatment process Operation Administration and Maintenance is simple, and is with low cost, is applicable to the reduction pre-treatment of large-scale industry waste water.
Description of drawings
Fig. 1 is ferrous morphological structure is removed influence to RB5 a synoptic diagram.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
The preparation of FHC: the FeSO that takes by weighing 2.78g
47H
2O is dissolved in 50mL and removes in the deionized water of dissolved oxygen, then Fe in the water
2+Concentration is 0.2mol/L, dropwise adds the NaOH of the 8mol/L of 2.15mL then to this solution, makes [Fe (II)]: [OH
-]=0.58 mixes, and the pH value of mixed solution sees that tangible blackish green throw out generates about 8.0.
The reduction of pollutent is handled: get reactive black 5 (the reactive black 5 that two parts of 250mL remove dissolved oxygen, RB5) the dyestuff simulated wastewater joins in the 500mL beaker, the dyestuff starting point concentration is 100mg/L, the solution initial pH value is 6.5, adds the FeSO of 112mg/L (in Fe (II) content) in a copy of it waste water from dyestuff
47H
2O, ferrous with solubilised state Fe
2+Exist.The FHC that in other a waste water, adds 112mg/L (in Fe (II) content), this moment is ferrous in the system to be existed with the ferrous form of structure attitude hydroxyl, opens stirred reactor, in setting-up time point sampling, the concentration of RB5 in the detection processed waste water.Fig. 1 illustrates only 10% RB5 of the ferrous removal of solubilised state, and ferrous 90% the RB5 that can remove of structure attitude, the ferrous reducing property of description architecture attitude is ferrous far above solubilised state.
Embodiment 2:
The reactive brilliant red x-3b simulated wastewater of getting four parts of 250mL removal dissolved oxygens joins in the 500mL beaker, regulate the initial pH to 4 of dye solution, 6,8,10, the FHC (according to method preparation among the embodiment 1) that adds 67.2mg/L (in Fe (II) content), open six agitators, in the sampling of setting-up time point, detect the concentration and the reacted pH of reactive brilliant red x-3b in the processed waste water.It is wider to know that by table 1 FHC handles the appropriate pH scope of reactive brilliant red x-3b simulated wastewater, in the pH value is all to have good reducing dyes removal effect under 4～10 the condition.
The different initial pH of table 1 solution are to the influence of FHC reducing activity bright red X-3B
Embodiment 3:
Different [Fe]/[OH
-] the FHC preparation of mol ratio: the ferrous sulfate aqueous solution that in the beaker of 5 100mL, adds the 0.2mol/L of 25mL respectively, the NaOH solution 1mL, 1.33mL, 2mL, 4mL, the 10mL that add 5mol/L then respectively, stir at a slow speed and form blackish green throw out FHC, then [Fe]/[OH of FHC
-] mol ratio is respectively 1,0.75,0.5,0.25,0.10.The reduction of waste water from dyestuff is handled: get the beaker of 5 200ml, be labeled as A, B, C, D, E, and add reactive black 5 (RB5) the dyestuff simulated wastewater 100ml of 100mg/L respectively, regulate the initial pH=8.0 of simulated wastewater, add [Fe]/[OH then respectively
-] mol ratio is 1,0.75,0.5,0.25,0.10 FHC 112mg/L (in ferrous content), opens six agitators and stirs at a slow speed, reaction 30min gets the 10mL water sample and be used for assay determination behind the membrane filtration of 0.45 μ m, and the result is as shown in table 2.
The reduction removal effect of table 2 reactive black 5 dye
| Water sample | A | B | C | D | E |
| [Fe]/[OH -] mol ratio | 1 | 0.75 | 0.5 | 0.25 | 0.10 |
| RB5 clearance/% | 0.25 | 0.34 | 0.82 | 0.81 | 0.84 |
Embodiment 4:
The preparation of FHC: the FeSO that takes by weighing 1.39g
47H
2O is dissolved in 50mL and removes in the deionized water of dissolved oxygen, then Fe in the water
2+Concentration is 0.1mol/L, dropwise adds the KOH of the 4mol/L of 2.15mL then in this solution, makes [Fe (II)]: [OH
-]=0.58 mixes, and the pH value of mixed solution sees that tangible blackish green throw out generates about 8.0.
The reduction of pollutent is handled: get the 3 parts of purplish red GRL dyestuff of neutrality simulated wastewaters, and dyestuff starting point concentration 100mg/L, the initial pH on wastewater value is FHC, GR, the Fe that adds 224mg/L (in Fe content) in 9.0,3 parts of waste water respectively
2(SO
4)
3GR according to literature method with FeSO
4And Fe
2(SO
4)
3According to certain ratio preparation.Because initial pH on wastewater is 9.0, add Fe
2(SO
4)
3After, will form Fe (OH)
3, the coagulating sedimentation effect takes place, contrast FHC, GR, the Fe (OH) of identical dosage
3To the decolorizing effect of dyestuff, table 3 as can be seen, FHC has tangible performance advantage.
Table 3FHC, GR, Fe (OH)
3To dye decolored effect comparison
Embodiment 5
The preparation of FHC: the Fe (NO that takes by weighing 5.4g
3)
2Be dissolved in 50mL and remove in the deionized water of dissolved oxygen, then Fe in the water
2+Concentration is 0.6mol/L, dropwise adds the NaOH that 6ml concentration is 10mol/L then in this solution, makes [Fe (II)]: [OH
-Stir while dripping]=0.50, sees that tangible blackish green throw out generates.
Wastewater treatment: adopt reactive brilliant red x-3b, Acid Brilliant Scarlet GR and three kinds of dye ligand moldings of Cationic Red X-GRL to intend waste water respectively, the dyestuff starting point concentration is 100mg/L, getting the 250mL simulated wastewater respectively joins in three 500mL beakers, regulating initial pH value is 9.0, and the FHC dosage is 89.6mg/L.The concentration of dyestuff in the sampling analysis waste water behind the stirring reaction 30min at a slow speed.Find out that by table 4 FHC has decolorizing effect preferably to multiple soluble azo dyes.
Table 4FHC is to the decolorizing effect of dissimilar dyestuffs
| Dye class | Clearance/% |
| Reactive brilliant red x-3b | 68.78 |
| Acid Brilliant Scarlet GR | 97.95 |
| Cationic Red X-GRL | 99.85 |
Embodiment 6:
The RB5 dyestuff simulated wastewater of getting two parts of 250mL removal dissolved oxygens joins in the 500mL beaker, and dyestuff starting point concentration 100mg/L after wherein A part elder generation adjusting waste water ph is 9.0, adds FHC (according to the preparation of embodiment 1 method) again, and B part adds a certain amount of FeSO
4(the 0.8mol/L aqueous solution) back re-adjustment pH value is that the content of Fe (II) in 9.0, two parts of waste water is 112mg/L.Turn on agitator stirs at a slow speed, the concentration and the reduzate aniline category matter concentration of dyestuff in the sampling analysis waste water behind the reaction 10min.RB5 belongs to soluble azo dyes, and azo bond can be reduced the generation aniline category matter.As shown in Table 5, two kinds of dosing methods, the clearance of RB5 and aniline generation are much at one.
Table 5FHC reduction transforms RB5 clearance and reduzate aniline growing amount
Embodiment 7:
The dyeing waste water of getting six parts of 1L is adjusted to 10 with waste water ph earlier in 6 beakers, slowly add a certain amount of FeCl then respectively
2The aqueous solution is opened six agitators, makes the ferrous structure attitude ferrous complex that forms in waste water, sees that tangible floss produces, and is quiet heavy behind the reaction 30min, gets the supernatant liquor analysis.The initial water quality of waste water: pH=8.88, COD
Cr=1064mg/L, BOD
5=338mg/L, BOD
5/ COD
Cr=0.32.By data in the table 6 as can be seen, the COD of waste water when ferrous dosage is 120mg/L
CrClearance can reach 49%, the BOD of waste water
5/ COD
CrCan bring up to 0.62 by 0.32, can significantly improve wastewater biodegradability.
Table 6FHC is to the treatment effect of actual industrial waste water
| Ferrous |
0 | 30 | 60 | 90 | 120 | 200 |
| Reaction back pH value | 9.98 | 8.9 | 8.87 | 8.6 | 8.3 | 8.23 |
| Reaction back COD/mg.L -1 | 950 | 858 | 722 | 570 | 544 | 572 |
| COD clearance/% | 10.7 | 19.4 | 32.1 | 46.4 | 48.9 | 46.2 |
| Reaction back BOD 5 | 292 | 290 | 342 | 313 | 338 | 329 |
| BOD 5/COD Cr | 0.31 | 0.34 | 0.47 | 0.55 | 0.62 | 0.58 |
FHC reduction pretreated waste water is not limited only to dyeing waste water, and is equally suitable for other trade effluents.
Above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (8)
1. the preparation method of a poly-hydroxy structure attitude ferrous compound is characterized in that: comprise step:
(1) taking by weighing a certain amount of ferrous salt is dissolved in it in water that does not contain dissolved oxygen;
(2) in above-mentioned solution, drip the anaerobic basic solution gradually, stir, by control ferrous ion and mol ratio hydroxy, generating structure attitude ferrous precipitation thing while dripping.
2. method according to claim 1 is characterized in that: described ferrous salt is from FeSO
47H
2O, FeSO
4, FeCl
2Perhaps Fe (NO
3)
2Fe in the described perferrite solution
2+Volumetric molar concentration be 0.1～0.8mol/L.
3. method according to claim 1 is characterized in that: the mol ratio of described ferrous ion and hydroxide ion is 0.1～1.0.
4. method according to claim 1 is characterized in that: described entire operation process is carried out under anaerobic state.
5. one kind is utilized poly-hydroxy structure attitude ferrous compound to carry out waste water to reduce pretreated method, it is characterized in that: comprise step:
(1) the dyestuff simulated wastewater or the actual waste water of getting certain volume joins in the reactor, and the pH that regulates waste water is 4～10;
(2) add FHC in waste water, it adds concentration is 20～200mg/L, in ferrous content, and at a slow speed behind stirring reaction 10～60min, the water sampling analysis.
6. one kind is utilized poly-hydroxy structure attitude ferrous compound to carry out waste water to reduce pretreated method, it is characterized in that: comprise step:
(1) the pH value of using alkaline matter to regulate waste water is 8～12;
(2) in above-mentioned waste water, add Fe then gradually
2+Concentration is the ferrous aqueous solution of 0.1～0.8mol/L, makes that the concentration of ferrous ion reaches 20～200mg/L in the waste water, stirs water sampling analysis behind 10～60min.
7. one kind is utilized poly-hydroxy structure attitude ferrous compound to carry out waste water to reduce pretreated method, it is characterized in that: comprise step:
(1) in waste water, directly adds Fe
2+Concentration is the ferrous aqueous solution of 0.1～0.8mol/L, makes that ferrous concentration reaches 20～200mg/L in the waste water;
(2) use pH regulator to 8～10 of alkaline matter then with waste water, behind stirring reaction 10～60min, the water sampling analysis.
8. according to the described method of arbitrary claim in the claim 1,5,6 or 7, it is characterized in that: described alkaline matter is NaOH, KOH, Ca (OH)
2, CaO, Na
2CO
3Or ammoniacal liquor.
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| CN102616913B (en) * | 2012-03-26 | 2013-10-16 | 同济大学 | Polyhydroxy ferrous complex reduction system, and preparation method and application thereof |
| CN103224278A (en) * | 2012-03-27 | 2013-07-31 | 同济大学 | Method for removing pollutant in water by palladium-catalyzed polyhydroxy ferrous-reduced method |
| CN103224278B (en) * | 2012-03-27 | 2014-08-13 | 同济大学 | Method for removing pollutant in water by palladium-catalyzed polyhydroxy ferrous-reduced method |
| CN105585099A (en) * | 2015-12-23 | 2016-05-18 | 中国科学院烟台海岸带研究所 | Decolorization treatment method for colored liquid waste |
| CN106927547A (en) * | 2017-04-05 | 2017-07-07 | 同济大学 | A kind of method that magnetic iron-based material reduction contact break removes complex state heavy metal |
| CN111072123A (en) * | 2019-12-19 | 2020-04-28 | 南京理工大学 | Method for removing complex lead by ferrous phosphate under anoxic condition |
| CN111233198A (en) * | 2020-02-11 | 2020-06-05 | 武汉轻工大学 | Industrial wastewater treatment method and device |
| CN111233198B (en) * | 2020-02-11 | 2022-09-23 | 武汉轻工大学 | Industrial wastewater treatment method and device |
| CN112570441A (en) * | 2020-10-28 | 2021-03-30 | 暨南大学 | Buffering repair medicament for degrading pollutants and preparation and application thereof |
| CN114751580A (en) * | 2021-03-23 | 2022-07-15 | 哈尔滨工业大学（深圳） | Method and system for treating refractory wastewater by advanced reduction pretreatment-biochemical coupling technology |
| CN114751580B (en) * | 2021-03-23 | 2023-10-24 | 哈尔滨工业大学（深圳） | Method and system for treating refractory wastewater by advanced reduction pretreatment-biochemical coupling technology |
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