CN102616913B - Polyhydroxy ferrous complex reduction system, and preparation method and application thereof - Google Patents
Polyhydroxy ferrous complex reduction system, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental engineering, and particularly relates to a preparation method and application of a polyhydroxy ferrous complex reduction system. The preparation method comprises the following steps: dropwisely adding an alkaline matter into an oxygen-free ferrite aqueous solution, stirring to react, and combining ferrous ions with all hydroxyl ions byregulating different ferrous ion/hydroxyl ion mol ratios and the type and content of anions, thereby forming a polyhydroxy ferrous complex (FHC); and adding a silver nitrate solution, a dispersant and a protective agent to form an Ag/FHC reduction system, thereby greatly enhancing the reducibility of the FHC. The Ag/FHC reduction system has the advantages of high reduction activity and high reaction rate, is convenient to add, and can be used for treating wastewater containing multiple nondegradable pollutants.
Description
Technical field
The invention belongs to the environment-friendly engineering technical field, be specifically related to a kind of poly-hydroxy ferrous complex
(FHC) reduction system and preparation method thereof and application.
Background technology
In recent years, China's chemical industry development is rapid, and the wastewater from chemical industry of discharging is cumulative year after year also.The waste water major part of the discharges such as chemical industry such as oil, papermaking, printing and dyeing, coking belongs to indegradable industrial effluent, these wastewater from chemical industry BOD
5/ COD is very low, and has the typical difficult features such as high density, high salinity, high chroma, high toxicity, and is very large to Ecotoxicology, is difficult to biological degradation, and the single aerobic treatment process of tradition is difficult to process up to standard.For this type of waste water, present treatment technology is that preconditioning technique is combined with biologic treating technique, namely carries out first pre-treatment before biological treatment, improves after the wastewater biodegradability, carries out a biological disposal upon again.Preconditioning technique generally includes anaerobic hydrolysis-acidification method and physico-chemical process.Physico-chemical process commonly used comprises ultrasonic method, absorption method, coagulating sedimentation/By Bubble-floating Method, oxidation style, reduction method etc.Because the ultrasonic method energy consumption is larger, absorption method, Coagulation Method, By Bubble-floating Method have the risk of secondary pollution, and using at present more is oxidation style and reduction method.Because oxidation style is more effective to the lower pollutent of redox potential; the redox potential of general indegradable industrial effluent is higher; usual conditions are relatively harsher during with oxidative treatment; often can cause the rising of processing costs or produce other by products etc., become the key constraints of oxidation style industrial wastewater pretreatment.With respect to oxidation style, reduction method has the advantages such as by product is few, and speed of response is fast.The reduction pretreatment technology is by difficult degradation pollutent generation redox reaction in reductive agent and the waste water, and the Pollutants in Wastewater reduction is transformed, and generates the biodegradable material of bio-toxicity less, thereby improves the biodegradable performance of waste water.Reductive agent commonly used is zero-valent metal, particularly Zero-valent Iron and other metal couplings at present, and treatment effect is better.The mode that the utilizations such as Wu Deli plate silver at iron surface forms Ag/Fe bimetal system and processes in the water hydrochloric ether and obtained good effect (Wu Deli etc., the Ag/Fe catalytic reduction system is processed the research of hydrochloric ether in the water body, environmental science, 2006,27(9)), this explanation bimetal system can obviously improve rate of reduction.But because metallic iron and waste water contact area are limited, reduction reaction rate is limited.And, will use catalysis iron filler, in the reaction tank inconvenience that often changes the outfit, affected its application.
Ferrous salt often uses as a kind of coagulating agent, has the advantages that coagulation effect is good, the source is wide, expense is low.The ferrous reducing power of free state is very low, and it be it is generally acknowledged removal of pollutants and mainly leans on its coagulation to realize.Research is found, can significantly improve ferrous reducing power by changing ferrous structural form, and multiple difficult degradation pollutent is all had preferably reduction effect.Under different pH conditions, there is variform in ferrous iron, under low pH, mainly with Fe
2+Exist, under high pH, can be with Fe (OH)
2Or the existence of ferrous poly-hydroxy complex compound (FHC) state, such as Fe (OH)
4 2-, the existence such as alpha-feooh, patina.The ferrous oxy-compound reduction pretreatment of the use structure attitudes such as Feng Yong dyeing waste water has been obtained good effect (Feng Yong etc., effect and the mechanism of the ferrous oxy-compound reduction pretreatment of structure attitude dyeing waste water, Journal of Chemical Industry and Engineering, 2011,62(7)), this illustrates that ferrous poly-hydroxy complex compound has good reducing property, is applicable to the pre-treatment of the multiple indegradable industrial effluents such as dyeing waste water.But it is not very high only adopting FHC reduction pretreatment indegradable industrial effluent speed, and not good to baroque difficult degradation pollutent reduction effect, has limited its application.
Summary of the invention
The object of the invention is to propose good poly-hydroxy ferrous complex reduction system of a kind of reducing property and preparation method thereof and application.
Technical scheme of the present invention is: in the perferrite solution of anaerobic, dropwise add alkaline matter, and carry out stirring reaction, by regulating ferrous ion mol ratio and anion species and the content different from hydroxide ion, ferrous and whole hydroxide radicals are combined, form poly-hydroxy ferrous complex FHC.Then add therein silver nitrate solution and dispersion agent and protective material, consist of the Ag/FHC catalytic reduction system, fully improve the reducing power of FHC.
The preparation method of the poly-hydroxy ferrous complex reduction system that the present invention proposes, concrete steps are:
The first step: take by weighing a certain amount of FeSO
47H
2O is dissolved in it in water that does not contain dissolved oxygen, and adds tripoly phosphate sodium STPP as dispersion agent, and dosage is 0.1-0.5g/L, and (alkaline matter can be NaOH, KOH or Ca (OH) to add gradually the anaerobic basic solution in the mentioned solution
2Deng), stir while adding, generate FHC suspension liquid dispersion system.The dosage of anaerobic basic solution is for making Fe
2+With OH
-Mol ratio reaches 0.1-0.8;
Second step: add a certain amount of anaerobic silver nitrate solution in prepared FHC system, stir, the mol ratio of control silver ions and ferrous iron is between 0.1-0.5%, and stirring reaction 0.1-0.5h forms strong, the finely dispersed Ag/FHC system of reducing power;
The 3rd step: in the Ag/FHC system, add a certain amount of anaerobic sodium borohydride solution as protective material, be conducive to the formation of Ag/FHC with stable, and play the reinforcement reductive action.The dosage of sodium borohydride is the 1-10% of Fe (II) total amount.Form final target reduction system, be designated as the Ag/FHC reduction system.
The present invention can be used for the processing of difficult degradation sewage with the reduction system of aforesaid method preparation, and specific practice is:
Get a certain amount of Ag/FHC reduction system and directly be added in the waste water that contains pollutent, perhaps the Ag/FHC suspension liquid is filtered under oxygen free condition, drying, get the Ag/FHC powder, get the Ag/FHC powder and join in the waste water; The dosage of Ag/FHC and waste water ratio are that 50 ~ 200mg/L(is in iron level).Stirring reaction 0.2-3h.Sampling analysis shows, utilizes Ag/FHC can process difficult degradation pollutent in the waste water, improves wastewater biodegradability.
Main advantage of the present invention comprises:
The Ag/FHC reduction system of preparation possesses stronger reducing power than traditional FHC, can reduce to transform multiple toxic pollutent, has equally stronger reducing power for the irreducible a lot of pollutents of FHC, has expanded the range of application of FHC.Can effectively keep Ag/FHC suspension liquid dispersion system after adding dispersion agent, what be conducive to Ag/FHC and pollutent contacts the raising speed of reaction.The Ag/FHC reducing activity is high, and speed of reaction is fast, adds conveniently, can be used for containing the processing of the waste water of multiple difficult degradation pollutent.
Embodiment
Embodiment 1:
The preparation of FHC: the FeSO that takes by weighing 27.8g
47H
2O is dissolved in the distilled water that 200ml do not contain dissolved oxygen, and adds the 0.1g tripoly phosphate sodium STPP as dispersion agent, and then dropwise adds the anaerobic aqueous sodium hydroxide solution of 25ml 5mol/L, Fe (II) and OH
-Mol ratio is 0.8, stirs while dripping, until form cyan FHC suspension liquid system.
The preparation of Ag/FHC: according to the preparation method of FHC, prepare first the FHC system, then add the silver nitrate solution 1mL of 0.1mol/L in the FHC system, so that the mol ratio of Ag and Fe is 0.1%, stirring reaction 0.2h.The anaerobic sodium borohydride solution 1ml that adds 1mol/L in the Ag/FHC system is conducive to the formation of Ag/FHC with stable, and plays the reinforcement reductive action as protective material.
Hexachloroethane in the reducing waste water: get the FHC for preparing and Ag/FHC suspension liquid and directly be added to respectively in two reactors that contain hexachloroethane waste water, the ratio of adding is 100mg/L (in iron level), staticly settle behind the stirring reaction 3h, then get supernatant liquor and analyze the content of hexachloroethane and the chlorion in the waste water, with reflection FHC and Ag/FHC the reduction of hexachloroethane is removed.
Embodiment 2:
The preparation of FHC: the FeSO that takes by weighing 27.8g
47H
2O is dissolved in the distilled water that 100ml do not contain dissolved oxygen, and adds the 0.01g tripoly phosphate sodium STPP as dispersion agent, and then dropwise adds the anaerobic aqueous sodium hydroxide solution of 40ml 5mol/L, Fe (II) and OH
-Mol ratio is 0.5, stirs while dripping, until form cyan FHC suspension liquid system.
The preparation of Ag/FHC: according to the preparation method of FHC, prepare first the FHC system, then add the silver nitrate solution 5mL of 0.1mol/L in the FHC system, so that the mol ratio of Ag and Fe is 0.5%, stirring reaction 0.5h.The anaerobic sodium borohydride solution 10ml that adds 1mol/L in the Ag/FHC system is conducive to the formation of Ag/FHC with stable, and plays the reinforcement reductive action as protective material.
In the reduction Cationic Red X-GRL waste water from dyestuff: get the FHC for preparing and Ag/FHC suspension liquid and directly be added to respectively two and contain in the Cationic Red X-GRL waste water from dyestuff reactor that 250mL concentration is 200mg/L, FHC and Ag/FHC add ratio and are 200mg/L (in iron level), difference sampling analysis dye strength behind stirring reaction 0.2h and the 0.5h, analytical results is as shown in table 1.
Table 1 Ag/FHC system and FHC system are processed Cationic Red X-GRL waste water from dyestuff result
This shows that the Ag/FHC system can obviously be accelerated dye decolored speed, it is complete substantially to have decoloured in basic 30 minutes, and FHC then can only remove the dyestuff about 63% in 30 minutes.This explanation, the reducing power of Ag/FHC catalytic reduction system is stronger than FHC, and the speed of reduction reaction is faster.
Embodiment 3:
The preparation of FHC: the FeSO that takes by weighing 13.9g
47H
2O is dissolved in the distilled water that 100ml do not contain dissolved oxygen, and adds the 0.02g tripoly phosphate sodium STPP as dispersion agent, and then dropwise adds the anaerobic potassium hydroxide aqueous solution of 20ml 4mol/L, Fe (II) and OH
-Mol ratio is 0.625, stirs while dripping, until form cyan FHC suspension liquid system.
The preparation of Ag/FHC: according to the preparation method of FHC, prepare first the FHC system, then add the silver nitrate solution 2mL of 0.1mol/L in the FHC system, so that the mol ratio of Ag and Fe is 0.4%, stirring reaction 0.1h.The anaerobic sodium borohydride solution 2ml that adds 1mol/L in the Ag/FHC system is conducive to the formation of Ag/FHC with stable, and plays the reinforcement reductive action as protective material.
Dibromo aniline in the reducing waste water: get the FHC for preparing and Ag/FHC suspension liquid and directly be added to respectively two and contain in the dibromo aniline waste water reactor that 250mL concentration is 50mg/L, FHC and Ag/FHC add ratio and are 120mg/L (in iron level), difference sampling analysis dibromo aniline concentration and bromide ion concentration behind stirring reaction 1h and the 2h, analytical results is as shown in table 2.
The dibromo aniline in the waste water is removed in table 2 FHC and Ag/FHC reduction
Can find thus, simple FHC can not make the dibromo aniline reduction-debromination, the removal of its paradibromobenzene amine may mainly be by its adsorption, the Ag/FHC system then removal of paradibromobenzene amine is very obvious, be higher than the FHC single mass system far away, this explanation Ag/FHC system can be with the dibromo aniline reduction-debromination.Therefore, the reducing power of Ag/FHC system is far above the FHC system.
Embodiment 4:
The preparation of FHC: the FeSO that takes by weighing 27.8g
47H
2O is dissolved in the distilled water that 300ml do not contain dissolved oxygen, and adds the 0.1g tripoly phosphate sodium STPP as dispersion agent, and then dropwise adds the anaerobic potassium hydroxide aqueous solution of 25ml 10mol/L, Fe (II) and OH
-Mol ratio is 0.4, stirs while dripping, until form cyan FHC suspension liquid system.
The preparation of Ag/FHC: according to the preparation method of FHC, prepare first the FHC system, then add the silver nitrate solution 3mL of 0.1mol/L in the FHC system, so that the mol ratio of Ag and Fe is 0.3%, stirring reaction 0.2h.The anaerobic sodium borohydride solution 5ml that adds 0.6mol/L in the Ag/FHC system is conducive to the formation of Ag/FHC with stable, and plays the reinforcement reductive action as protective material.
Reduction dechlorination to diclofenac in the water: get the FHC and the Ag/FHC suspension liquid that prepare and directly be added to respectively among the diclofenac waste water 250ml that concentration is 200mg/L, FHC and Ag/FHC add ratio and are 50mg/L (in iron level), difference sampling analysis diclofenac and chlorine ion concentration behind stirring reaction 0.5h and the 0.1h, analytical results is as shown in table 3, can find out Ag/FHC to the reduction dechlorination speed of reaction of diclofenac pollutent obviously faster than FHC.
The reduction dechlorination of table 3 diclofenac
Embodiment 5:
Take by weighing the FeSO of 556g
47H
2O is dissolved in the tap water that 2l do not contain dissolved oxygen, and adds the 0.2g tripoly phosphate sodium STPP as dispersion agent, and then adds gradually the anaerobic calcium hydroxide aqueous solution of 1000ml 10mol/L, Fe (II) and OH
-Mol ratio is 0.1, stirs while dripping, until form cyan FHC suspension liquid system.Then the silver nitrate solution 20mL that adds 0.1mol/L in the FHC system, so that the mol ratio of Ag and Fe is 0.1%, stirring reaction 0.1h.In the Ag/FHC system, add the anaerobic sodium borohydride solution 40ml of 0.5mol/L as protective material.To obtain the Ag/FHC suspension liquid at the oxygen free operation condition filter, and vacuum freezedrying, the Ag/FHC pressed powder obtained.Pressed powder is added in actual wastewater from chemical industry, carry out the reduction pretreatment of waste water, dosage is that 80mg/L(is in iron level).
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 (5)
1. the preparation method of a poly-hydroxy ferrous complex reduction system is characterized in that concrete steps are as follows:
The first step: with FeSO
47H
2O is dissolved in the water that does not contain dissolved oxygen, obtains FeSO
4The aqueous solution; Add tripoly phosphate sodium STPP as dispersion agent, the dosage of tripoly phosphate sodium STPP and FeSO
4The ratio of the aqueous solution is 0.1-0.5g/L; In mentioned solution, add gradually the anaerobic basic solution, stir while adding, generate FHC suspension liquid dispersion system; The dosage of anaerobic basic solution makes Fe (II) and OH
-Mol ratio is 0.1-0.8;
Second step: add the anaerobic silver nitrate solution in above-mentioned FHC suspension liquid dispersion system, the control silver ions is 0.1-0.5% with the molar percentage of ferrous iron, and stirring reaction 0.1-0.5h forms the Ag/FHC system;
The 3rd step: add the anaerobic sodium borohydride solution in above-mentioned Ag/FHC system, as protective material, the dosage of sodium borohydride is the 1-10% of Fe (II) total amount, forms the ultimate aim reduction system, is designated as the Ag/FHC reduction system;
Wherein, symbol FHC is the poly-hydroxy ferrous complex.
2. the preparation method of poly-hydroxy ferrous complex reduction system according to claim 1, the alkaline matter that it is characterized in that basic solution described in the first step is NaOH, KOH or Ca (OH)
2
3. the reduction system that is prepared by the described method of claim 1 is designated as the Ag/FHC reduction system.
4. the application of reduction system as claimed in claim 3 in the difficult degradation sewage disposal.
5. application as claimed in claim 4 is characterized in that concrete steps are:
Get the Ag/FHC reduction system and directly be added in the waste water that contains pollutent, perhaps the Ag/FHC reduction system is filtered under oxygen free condition, drying, get the Ag/FHC powder, get the Ag/FHC powder and join and contain in the pollutent waste water; The dosage of Ag/FHC and waste water ratio are counted 50 ~ 200mg/L with iron level; Stirring reaction 0.2-3h.
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| CN104944564B (en) * | 2015-06-19 | 2016-09-14 | 四川师范大学 | A kind of remove the preparation method of the reducing agent of nitrate in water |
| CN105396590A (en) * | 2015-11-03 | 2016-03-16 | 同济大学 | Method for preparing ozonation catalyst by scrap iron surface modifying, and application of ozonation catalyst |
| CN109311837B (en) * | 2016-03-31 | 2022-09-30 | 英国神盾Tx股份有限公司 | Method for producing a maltoferric composition from ferrous hydroxide |
| CN107324587B (en) * | 2017-07-12 | 2020-08-18 | 同济大学 | Method for synchronously removing heavy metals and organic matters in wastewater |
| CN109692970A (en) * | 2018-11-26 | 2019-04-30 | 合肥学院 | A kind of quick method for preparing Fe/Ag composite nano powder |
| CN110357240B (en) * | 2019-05-15 | 2022-05-03 | 浙江工业大学 | Water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron |
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| CN102060334A (en) * | 2010-11-22 | 2011-05-18 | 同济大学 | Preparation of ferrous compound in polyhydroxy structural state and application of ferrous compound in wastewater reduction pretreatment |
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| CN102060334A (en) * | 2010-11-22 | 2011-05-18 | 同济大学 | Preparation of ferrous compound in polyhydroxy structural state and application of ferrous compound in wastewater reduction pretreatment |
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