CN104984737A - Adsorbing agent for treating cationic dye waste water and preparation method and application thereof - Google Patents
Adsorbing agent for treating cationic dye waste water and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of waste water treatment, and particularly relates to an adsorbing agent for treating cationic dye waste water and a preparation method and application thereof. The adsorbing agent comprises a hybridization adsorbing agent prepared by a hybridization reaction conducted by congo red and calcium fluoride. The hybridization adsorbing agent is prepared of, by molar mass, the following raw materials of 0.05 to 0.10 part of the congo red, 0.5 to 8 parts of the calcium and 1.25 to 25 parts of sodium fluoride. The adsorbing agent further comprises ferroferric oxide. The mass ratio of the hybridization adsorbing agent and the ferroferric oxide is 2 to 10:1. According to the adsorbing agent for treating cationic dye waste water and the preparation method and application thereof, the hybridization adsorbing agent is prepared by the hybridization reaction conducted by the organic dye ligand congo red and the inorganic framework material CaF2, an environmental-protection hybridization adsorbing agent is prepared after mixing the hybridization adsorbing agent and the ferroferric oxide, the cost is low, the producing technology is simple, the adsorbing treatment is conducted on the cationic dye waste water through a traditional adsorbing method, the prepared hybridization material is green and environmentally friendly, sustainable development is met, and the green chemistry concept of using waste for treating waste can be reached.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of adsorbent processing cationic dye wastewater and its preparation method and application.
Background technology
With the develop rapidly of industrial technology, kind and the number of dyestuff constantly increase, and data show, world's dyestuff annual production is about 800kt ~ 900kt.China is the rich and influential family of industrial wastewater discharge, and dyestuff annual production is about 150kt, and position is at the forefront in the world, and dyestuff is widely used in the industries such as printing and dyeing, medicine, cosmetics and food.Developing rapidly of industry makes various new dye constantly be put into operation, and waste water from dyestuff water quality also becomes increasingly complex thereupon, and its pollution on the environment is on the rise.Different qualities according to dyestuff can carry out different classification to dyestuff, dyestuff can be divided into: direct dyes, sulfur dye, reducing dye, acid dyes, acidic complex dye, chemically-reactive dyes, azoic dyes, oxidation dye, disperse dyes, basic-dyeable fibre according to application characteristic during dyeing; The ionic state of often dissociating out in aqueous according to dye molecule in field of environment engineering and being divided into: anionic dye, as direct dyes, acid dyes; The dye of positive ion, as basic-dyeable fibre; Nonionic dye, as disperse dyes.Kind of dyes is thousands of, though bring bright and colourful color and produce huge economic benefit to the life of people, is discharged into a large amount of waste water from dyestuff in water body environment, but causes immeasurable destruction to natural water.
Waste water from dyestuff generally has following features: (1) no matter unit product displacement or whole industry draining total amount all has the feature that the water yield is large; (2) organic matter is the main constituent of pollutant, but wherein easily the ratio of degraded is very little, thus uses bioremediation intractability larger; (3) substantially, pollutant all has poisonous and harmful character; (4) its chroma in waste water difference produced of different dyes is comparatively large, but the color and luster of overall waste water from dyestuff is all deep; (5) belong to high concentrated organic wastewater, wherein the operation such as destarch, kiering waste water belongs to high concentration especially.Nowadays, both at home and abroad to the improvement of industrial wastewater from the simple disposal of three wastes turn to adopt few useless, without useless production technology, the theory of " treatment of wastes with processes of wastes against one another " Green Chemistry obtains the high praise of various countries scientist especially.Waste water from dyestuff has the features such as colourity is high, complicated component, salt content are high, the Congo red concentration of COD is high, biodegradability is poor, is difficult to adopt traditional waste water treatment process and material to administer, and becomes the difficult point of current Industrial Wastewater Treatment.Therefore, research and develop advantages of good adsorption effect, cost low, manipulate simple novel environmental functional material and be applied to dye wastewater treatment there is important practical significance and wide application prospect.
In order to reach the object of effective waste water from dyestuff, for the large quantifier elimination that the technology of dye wastewater treatment is carried out in prior art, and achieving certain achievement, existing dye wastewater treatment method mainly contains membrane separation process, extraction, radiation method, oxidizing process, Coagulation Method, bioanalysis and absorption method.Absorption method the characteristic of optionally some compound of enrichment can have special status in field of waste water treatment with it.Absorption refers to that the molecule of the surface of solids or atom have remaining surface energy because of discontinuity equalization, when Cucumber colliding solid surface, is subject to the attraction of these out-of-balance forces and stops on a solid surface.The result of absorption is that adsorbate concentrates on the sorbent, and the surface energy of absorption reduces.Adsorption technology utilizes porous solid to adsorb in waste water certain or several pollutant exactly, to reclaim or to remove some pollutant, thus is also that adsorbent conventional in the method absorption method that waste water is purified has active carbon, resin, mineral, discarded object etc.The adsorption bleaching of waste water from dyestuff has two kinds of mechanism: absorption and ion-exchange, adsorption efficiency by the impact of a lot of chemical factors, as the particle size of the specific area of the interaction of dyestuff-adsorbent, adsorbent, adsorbent, temperature, pH value and adsorption time etc.But existing adsorbent needs to obtain through tediously long chemical modification through complicated preparation process and plurality of raw materials, and not high for the adsorption efficiency of waste water from dyestuff, and complicated process of preparation cost is high, is unfavorable for promoting.The environment-friendly materials finding Cheap highly effective are applied to dye wastewater treatment, greatly can not only improve the water resources comprehensive utilization benefit of dyeing, and have very important meaning to China's economy " green consumption " and " sustainable development ".
As can be seen here, a kind of novel adsorbent for waste water from dyestuff can be invented, make it have raw material to be easy to get, cost is low, preparation technology is simple, and the adsorbent of preparation is pointed, the advantage high to corresponding dye wastewater treatment efficiency, becomes the technical barrier that those skilled in the art are urgently to be resolved hurrily.
Summary of the invention
The present invention, in order to solve the problems of the technologies described above, provided a kind of adsorbent for waste water from dyestuff and its preparation method and application, utilized organic dyestuff part Congo red with inorganic skeleton material C aF
2carry out hydridization reaction and be prepared into hybrid sorbents, hybrid sorbents is prepared into environmental protection hybrid sorbents of the present invention with tri-iron tetroxide is blended, its cost is low, manufacture craft is simple, and adopt traditional absorption method to carry out adsorption treatment to cationic dye wastewater, the hybrid material environmental protection of preparing, meet sustainable development, the green chemical concept of " treatment of wastes with processes of wastes against one another " can be reached.
" organic/inorganic hybridization material " refers to the material of a kind of heterogeneous structure that organic matter and inorganic matter combine with physics or chemical action, have a phase in this material at least or have the size of one dimension to be nano level, thus organic/inorganic hybridization material and traditional composite have obviously different on Structure and Properties.Compared with the organic and inorganic polymer that structure is single, the obvious performance advantage of organic-inorganic hybrid material optical transparence, tunable refractive index, mechanical property, heat resistance, wearability, pliability, functional etc. in.
In order to reach above-mentioned technique effect, technical scheme of the present invention comprises:
Process an adsorbent for cationic dye wastewater, described adsorbent comprises the hybrid sorbents that Congo red and calcirm-fluoride carries out preparation after hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 ~ 0.10 part
0.5 ~ 8 part, calcium chloride
Sodium fluoride 1.25 ~ 25 parts.
Preferably, described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 ~ 0.06 part
0.8 ~ 5 part, calcium chloride
Sodium fluoride 2.5 ~ 12.5 parts.
More preferably, described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.052 part
1 part, calcium chloride
Sodium fluoride 2.5 parts.
Described adsorbent also comprises tri-iron tetroxide, and described hybrid sorbents is 2 ~ 10:1 with the molal weight ratio of tri-iron tetroxide.
Process a preparation method for the adsorbent of cationic dye wastewater, comprise the following steps:
Step one: prepare hybrid sorbents: take Congo red, the calcium chloride of 0.5 ~ 8 part, the sodium fluoride of 1.25 ~ 25 parts that molal weight number is 0.05 ~ 0.10 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, Congo red solution, Fluorinse and calcium chloride solution is added successively, reaction 15min in beaker.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, and the suspension of rear obtained hybrid sorbents;
Step 2: prepare tri-iron tetroxide: get FeCl
36H
2o is dissolved in distilled water, N
2vibrate under protection 30min, gets FeCl
24H
2after O is dissolved in distilled water, add above-mentioned solution, after vibration 30min, make mixed solution, be added dropwise to by NaOH in described mixed solution, after dropwising, vibration 60min, is then heated to 90 DEG C, then reacts 2h, and Magneto separate obtains Fe
3o
4, Bian use water, ethanol and acetone washing successively, dry obtained at 40 DEG C;
Step 3: the preparation of adsorbent: get the Fe that molal weight number is 1 part
3o
4join in distilled water, joining molal weight number after ultrasonic is in the suspension of 2 ~ 10 parts of hybrid sorbents, continues ultrasonic, vibrates into homogeneous, drying is obtained under room temperature.
A kind of application processing the adsorbent of cationic dye wastewater, described adsorbent is above-mentioned adsorbent, the method of described sorbent treatment cationic dye wastewater is utilized to comprise the following steps: at room temperature, when adsorbent addition is 15 ~ 25mg, when dye of positive ion initial concentration is 200 ~ 300mg/L, solution ion strength is 0.06 ~ 2mol/L, regulates the pH value of described cationic dye wastewater to be 7, absorption 30min.
The addition of described adsorbent is 17.77mg, and described dye of positive ion initial concentration is 240mg/L, and described solution ion strength is 0.06mol/L.
Described cationic dye wastewater is ethyl violet waste water from dyestuff.
Beneficial effect of the present invention comprises: the present invention utilizes organic dyestuff part Congo red with inorganic skeleton material C aF
2carry out hydridization reaction, prepare a kind of environmental protection hybrid sorbents, its cost is low, manufacture craft is simple, and adopt traditional absorption method to carry out adsorption treatment to cationic dye wastewater, the hybrid material environmental protection of preparing, meet sustainable development, the green chemical concept of " treatment of wastes with processes of wastes against one another " can be reached, simultaneously also blended in adsorbent of the present invention have tri-iron tetroxide, adsorption capacity for cationic dye wastewater is strengthened, especially for ethyl violet waste water from dyestuff, there is preferably treatment effect.The present invention with Congo red with inorganic skeleton material C aF
2carry out hydridization reaction and make hybrid sorbents, by hybrid sorbents with the blended preparation of tri-iron tetroxide adsorbent of the present invention, sorbing material product has been synthesized by the selection of reaction raw materials, pulp furnish experiment, mensuration product forms, and organic adsorption effect under having investigated different condition, judge optimum adsorption conditions.Make adsorbent of the present invention when processing cationic dye wastewater, there is preferably effect.
Accompanying drawing explanation
Figure 1 shows that calcirm-fluoride multiplication factor is the SEM figure of 50,000.
Figure 2 shows that calcirm-fluoride multiplication factor is the SEM figure of 100,000.
Figure 3 shows that calcirm-fluoride multiplication factor is the SEM figure of 200,000.
Figure 4 shows that adsorbent multiplication factor prepared by the embodiment of the present invention 1 is the SEM figure of 50,000.
Figure 5 shows that adsorbent multiplication factor prepared by the embodiment of the present invention 1 is the SEM figure of 100,000.
Figure 6 shows that adsorbent multiplication factor prepared by the embodiment of the present invention 1 is the SEM figure of 200,000.
Figure 7 shows that CaF of the present invention
2and CaF
2the infrared spectrum curve map of-CR.
Figure 8 shows that CaF of the present invention
2and CaF
2-CR hybrid material carries out TGA analysis chart.
Figure 9 shows that calcirm-fluoride inorganic skeleton of the present invention embeds Congo red adsorption curve figure.
Figure 10 shows that adsorbent amount q prepared by the embodiment of the present invention 3
ewith percent of decolourization R with dyestuff initial concentration change curve.
Figure 11 shows that adsorbent amount q prepared by the embodiment of the present invention 3
ewith adsorption time t change curve.
Figure 12 shows that adsorbent amount q prepared by the embodiment of the present invention 3
ewith temperature T change curve.
Figure 13 shows that adsorbent amount q prepared by the embodiment of the present invention 3
ewith suction ionic strength change curve.
Figure 14 shows that adsorbent amount q prepared by the embodiment of the present invention 3
ewith pH change curve.
Figure 15 shows that the addition of adsorbent prepared by the embodiment of the present invention 3 and the graph of relation of clearance (%).
Detailed description of the invention
Hereafter will describe the specific embodiment of the invention in detail in conjunction with concrete accompanying drawing.It should be noted that the combination of technical characteristic or the technical characteristic described in following embodiment should not be considered to isolated, they can mutually be combined thus be reached better technique effect.
CaF described in following content
2-CR hybrid material adsorbent is that calcirm-fluoride and Congo red hydridization of carrying out react rear prepared adsorbent of the present invention.
Embodiment 1
Process an adsorbent for cationic dye wastewater, described adsorbent is Congo red and calcirm-fluoride carries out the rear hybrid sorbents prepared of hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 part
0.5 part, calcium chloride
Sodium fluoride 1.25 parts.
A kind of preparation method processing the adsorbent of cationic dye wastewater, comprise the following steps: take Congo red, the calcium chloride of 0.5 part, the sodium fluoride of 1.25 parts that molal weight number is 0.05 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, in beaker, add Congo red solution, Fluorinse and calcium chloride solution successively, reaction 15min.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, obtained after dry.
Embodiment 1 is prepared adsorbent and carries out Treatment of Cationic Dyestuff Wastewater, the method comprises the following steps: at room temperature, when adsorbent addition is 15mg, when dye of positive ion initial concentration is 200mg/L, solution ion strength is 0.06mol/L, the pH value of described cationic dye wastewater is regulated to be 7, get supernatant liquor after absorption 30min and survey its absorbance, calculated the concentration of residual Crystal Violet Dye by the relation of absorbance and concentration, calculating adsorbent prepared by embodiment is thus 94.8% to the clearance of Crystal Violet Dye waste water.
Embodiment 2
Process an adsorbent for cationic dye wastewater, described adsorbent comprises the hybrid sorbents that Congo red and calcirm-fluoride carries out preparation after hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 part
0.8 part, calcium chloride
Sodium fluoride 2.5 parts.
Described adsorbent also comprises tri-iron tetroxide, and described hybrid sorbents is 2:1 with the molal weight ratio of tri-iron tetroxide.
Process a preparation method for the adsorbent of cationic dye wastewater, comprise the following steps:
Step one: prepare hybrid sorbents: take Congo red, the calcium chloride of 0.8 part, the sodium fluoride of 2.5 parts that molal weight number is 0.05 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, Congo red solution, Fluorinse and calcium chloride solution is added successively, reaction 15min in beaker.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, and the suspension of rear obtained hybrid sorbents;
Step 2: prepare tri-iron tetroxide: get 0.08moL FeCl
36H
2o is dissolved in 100mL distilled water, N
2vibrate under protection 30min, gets 0.04moL FeCl
24H
2after O is dissolved in 100mL distilled water, add above-mentioned solution, after vibration 30min, make mixed solution, be added dropwise in described mixed solution by the 10M NaOH of 100mL, after dropwising, vibration 60min, is then heated to 90 DEG C, then reacts 2h, and Magneto separate obtains Fe
3o
4, Bian use water, ethanol and acetone washing successively, dry obtained at 40 DEG C;
Step 3: the preparation of adsorbent: get the Fe that molal weight number is 1 part
3o
4join in distilled water, joining molal weight number after ultrasonic 10min is in the suspension of 2 parts of hybrid sorbents, continues ultrasonic 30min, and the 1h that vibrates under room temperature becomes homogeneous, drying obtains.
Embodiment 2 is prepared adsorbent and carries out Treatment of Cationic Dyestuff Wastewater, the method comprises the following steps: at room temperature, when adsorbent addition is 16mg, when dye of positive ion initial concentration is 250mg/L, solution ion strength is 0.08mol/L, the pH value of described cationic dye wastewater is regulated to be 7, get supernatant liquor after absorption 30min and survey its absorbance, calculated the concentration of residual Crystal Violet Dye by the relation of absorbance and concentration, calculating adsorbent prepared by embodiment is thus 96.1% to the clearance of Crystal Violet Dye waste water.
Embodiment 3
Process an adsorbent for cationic dye wastewater, described adsorbent comprises the hybrid sorbents that Congo red and calcirm-fluoride carries out preparation after hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.052 part
1 part, calcium chloride
Sodium fluoride 2.5 parts.
Described adsorbent also comprises tri-iron tetroxide, and described hybrid sorbents is 8:1 with the molal weight ratio of tri-iron tetroxide.
Process a preparation method for the adsorbent of cationic dye wastewater, comprise the following steps:
Step one: prepare hybrid sorbents: take Congo red, the calcium chloride of 1 part, the sodium fluoride of 2.5 parts that molal weight number is 0.052 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, Congo red solution, Fluorinse and calcium chloride solution is added successively, reaction 15min in beaker.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, and the suspension of rear obtained hybrid sorbents;
Step 2: prepare tri-iron tetroxide: get 0.08moL FeCl
36H
2o is dissolved in 100mL distilled water, N
2vibrate under protection 30min, gets 0.04moL FeCl
24H
2after O is dissolved in 100mL distilled water, add above-mentioned solution, after vibration 30min, make mixed solution, be added dropwise in described mixed solution by the 10M NaOH of 100mL, after dropwising, vibration 60min, is then heated to 90 DEG C, then reacts 2h, and Magneto separate obtains Fe
3o
4, Bian use water, ethanol and acetone washing successively, dry obtained at 40 DEG C;
Step 3: the preparation of adsorbent: get the Fe that molal weight number is 1 part
3o
4join in distilled water, joining molal weight number after ultrasonic 10min is in the suspension of 8 parts of hybrid sorbents, continues ultrasonic 30min, and the 1h that vibrates under room temperature becomes homogeneous, drying obtains.
Embodiment 3 is prepared adsorbent and carries out Treatment of Cationic Dyestuff Wastewater, the method comprises the following steps: at room temperature, when adsorbent addition is 17.77mg, when dye of positive ion initial concentration is 240mg/L, solution ion strength is 0.06mol/L, the pH value of described cationic dye wastewater is regulated to be 7, get supernatant liquor after absorption 30min and survey its absorbance, calculated the concentration of residual Crystal Violet Dye by the relation of absorbance and concentration, calculating adsorbent prepared by embodiment is thus 97.8% to the clearance of Crystal Violet Dye waste water.
Embodiment 4
Process an adsorbent for cationic dye wastewater, described adsorbent comprises the hybrid sorbents that Congo red and calcirm-fluoride carries out preparation after hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.06 part
5 parts, calcium chloride
Sodium fluoride 12.5 parts.
Described adsorbent also comprises tri-iron tetroxide, and described hybrid sorbents is 10:1 with the molal weight ratio of tri-iron tetroxide.
Process a preparation method for the adsorbent of cationic dye wastewater, comprise the following steps:
Step one: prepare hybrid sorbents: take Congo red, the calcium chloride of 5 parts, the sodium fluoride of 12.5 parts that molal weight number is 0.06 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, Congo red solution, Fluorinse and calcium chloride solution is added successively, reaction 15min in beaker.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, and the suspension of rear obtained hybrid sorbents;
Step 2: prepare tri-iron tetroxide: get 0.08moL FeCl
36H
2o is dissolved in 100mL distilled water, N
2vibrate under protection 30min, gets 0.04moL FeCl
24H
2after O is dissolved in 100mL distilled water, add above-mentioned solution, after vibration 30min, make mixed solution, be added dropwise in described mixed solution by the 10M NaOH of 100mL, after dropwising, vibration 60min, is then heated to 90 DEG C, then reacts 2h, and Magneto separate obtains Fe
3o
4, Bian use water, ethanol and acetone washing successively, dry obtained at 40 DEG C;
Step 3: the preparation of adsorbent: get the Fe that molal weight number is 1 part
3o
4join in distilled water, joining molal weight number after ultrasonic 10min is in the suspension of 10 parts of hybrid sorbents, continues ultrasonic 30min, and the 1h that vibrates under room temperature becomes homogeneous, drying obtains.
Embodiment 4 is prepared adsorbent and carries out Treatment of Cationic Dyestuff Wastewater, the method comprises the following steps: at room temperature, when adsorbent addition is 20mg, when dye of positive ion initial concentration is 245mg/L, solution ion strength is 1mol/L, the pH value of described cationic dye wastewater is regulated to be 7, get supernatant liquor after absorption 30min and survey its absorbance, calculated the concentration of residual Crystal Violet Dye by the relation of absorbance and concentration, calculating adsorbent prepared by embodiment is thus 96.5% to the clearance of Crystal Violet Dye waste water.
Embodiment 5
Process an adsorbent for cationic dye wastewater, described adsorbent is Congo red and calcirm-fluoride carries out the rear hybrid sorbents prepared of hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.10 part
8 parts, calcium chloride
Sodium fluoride 25 parts.
A kind of preparation method processing the adsorbent of cationic dye wastewater, comprise the following steps: take Congo red, the calcium chloride of 8 parts, the sodium fluoride of 25 parts that molal weight number is 0.10 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, in beaker, add Congo red solution, Fluorinse and calcium chloride solution successively, reaction 15min.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, obtained after dry.
Embodiment 5 is prepared adsorbent and carries out Treatment of Cationic Dyestuff Wastewater, the method comprises the following steps: at room temperature, when adsorbent addition is 25mg, when dye of positive ion initial concentration is 300mg/L, solution ion strength is 2mol/L, the pH value of described cationic dye wastewater is regulated to be 7, get supernatant liquor after absorption 30min and survey its absorbance, calculated the concentration of residual Crystal Violet Dye by the relation of absorbance and concentration, calculating adsorbent prepared by embodiment is thus 95.1% to the clearance of Crystal Violet Dye waste water.
The material of the adsorbent of embodiment 6 embodiment 1 preparation characterizes
1, sem analysis
For embodiment 1, calcium chloride and sodium fluoride are amplified 50,000,100,000 and 200,000 times as the calcirm-fluoride prepared by reactant and carries out ESEM, the SEM figure as Fig. 1 ~ 3 is known, CaF
2intergranular fillet is relatively more sticky glutinous, and border is not clearly, mainly because CaF
2for colloidal solid precipitation.CaF
2sample is ellipsoid shape, and their shape matching rule, size is basically identical.
Adsorbent multiplication factor embodiment 1 prepared is the ESEM of 50,000,100,000 and 200,000, SEM figure as Fig. 4 ~ 6 is known, and calcirm-fluoride and Congo red hybrid material are adsorbent, and its border is also not obvious, shape is also the ellipsoid shape of comparison rule, and size is basically identical.But by the photo comparison before and after hydridization, can CaF be found
2after hydridization is Congo red, absorbent particles becomes large to some extent, and inter-grain boundary is more loose, illustrates that Congo red is likely be embedded into CaF as interlayer
2in particle, Congo red participation inhibits CaF
2from stacking.
2, FTIR analyzes
Be illustrated in figure 7 CaF
2and CaF
2the infrared spectrum curve of-CR, CaF
2-CR is calcirm-fluoride and Congo redly carries out the reacted adsorbent of hydridization, as can be known from Fig. 7, and CaF
2at 3624 ~ 3245cm
-1and 1684cm
-1place has characteristic absorption peak.At CaF
2in-CR hybrid sorbents, existing CaF
2characteristic absorption peak have again the characteristic absorption peak of CR functional group.CaF
2jointly there is organic and inorganic two-phase in-CR hybrid sorbents, make between the infrared absorption peak of hybrid material overlapped.Can clearly find out from figure: at 3461cm
-1locate the stretching vibration absworption peak for N-H produces; At 1633cm
-1and 1491cm
-1place is the stretching vibration peak absworption peak of naphthalene derivatives C=C; At 1388cm
-1and 1276cm
-1the stretching vibration absworption peak that place produces for conjugated system in aromatic amine compounds; At 1192cm
-1and 1059cm
-1locate the stretching vibration absworption peak for fragrant sulfonate produces.Result shows, CR hydridization enters CaF
2facilitate the increase of material structure, do not change CaF
2this is consistent with sem analysis result for the basic structure of particle.
3, TG analyzes
By CaF
2and CaF
2-CR hybrid material carries out TGA analysis, and result is as shown in Figure 8, known, CaF
2and CaF
2-CR sample is had the individual loss in weight before 100 DEG C in temperature, and this process is the process that the water of sample surfaces is removed, and the evaporation being moisture residual in sample caused.In the temperature range of 100 ~ 800 DEG C, CaF
2sample almost zero gravity loss, TGA curve is almost a horizontal linear, and this illustrates CaF
2there is organo-functional group hardly in sample, be only CaF
2inorganic skeleton, at 800 ~ 1000 DEG C, occur an obvious weightless peak, this process is CaF
2the Bound moisture of colloid inside is by the process of evaporating.And CaF
2the thermogravimetric curve generation significant change of-CR sample: in the temperature range of 100 ~ 1000 DEG C, weightlessness is 12.56%, and this process is that organic molecule causes, but to end from decomposition, decomposable process is comparatively slow and speed is even, can illustrate that CR hydridization enters CaF
2embedded into CaF layer by layer in inorganic skeleton
2inorganic skeleton is inner.
In embodiment 7 adsorbent, hydridization inhales the choice experiment of material optimum proportioning and solid content
For embodiment 1, carry out hydridization in adsorbent and inhale the choice experiment of material optimum proportioning and solid content, CaF
2the adsorbent of-CR hydridization utilizes calcirm-fluoride to carry out hydridization reaction for inorganic skeleton and organic dyestuff part CR, and the percent of decolourization of solution is high, and illustrate that being embedded into calcirm-fluoride is that the CR of inorganic skeleton is more, the negative ion intensities in material is larger, the CaF prepared
2the adsorption capacity of adsorbent to the dye of positive ion of-CR hydridization is stronger.The adsorption curve of calcirm-fluoride inorganic skeleton embedding CR dyestuff and congo red as shown in Figure 9.
Known as shown in Figure 9, curve forward part presents platform-like substantially, and when concentration increases to 1800mg/L, percent of decolourization R declines rapidly; When CR concentration is 1500mg/L, adsorbance reaches maximum, and clearance is 96.939%, and data are more stable, precipitates more stable.Analysis draws, under this hybridization ratios, being embedded into calcirm-fluoride is that the CR of inorganic skeleton is maximum, and this ratio is decided to be best hybridization ratios.Calculating optimum molar ratio (mol) is CaCl
2: NaF:CR=1:2.5:0.052.According to formula
obtain obtained CaF
2the solid content X of the adsorbent suspension of-CR hydridization is 35.54g/L.
Embodiment 8 adsorbent is to the selection of different dyes waste water adsorptivity
Absorption situation is observed after adding adsorbent prepared by embodiment 3 in acid green 27, azogeramine 38, methylene blue, ethyl violet four kinds of dye solutions, show that adsorbent has better adsorption effect to the dye of positive ion, after absorption, methylene blue and ethyl violet solution are almost clarified, to acid green 27, azogeramine 38 solution without adsorption effect.Result shows that adsorbent of the present invention has good adsorption effect to the dye of positive ion, wherein adsorbs ethyl violet effect better, and does not substantially possess suction-operated to anionic dye.Its reason may be adsorbent of the present invention is by electrostatic interaction absorbing dye, and adsorbent surface, with a large amount of negative electrical charge, attracts each other with the dye of positive ion in solution, makes the dye of positive ion by adsorption precipitation.
Under embodiment 9 Different factor condition, adsorbent is tested the impact of Dye Adsorption
1, under dyestuff initial concentration condition adsorbent on the impact of Dye Adsorption
As shown in Figure 10, for adsorbent prepared by embodiment 3, under carrying out dyestuff initial concentration condition, adsorbent is tested the impact of Dye Adsorption, adsorbance increases with the increase adding dyestuff initial concentration as shown in Figure 10, this is because dye concentration is higher, the chance that dye ions is contacted with adsorbent surface increases, and is conducive to the adsorption site making full use of adsorbent, higher concentration can promote the electrostatic interaction between EV molecule and adsorbent, adsorbs more polycation dyestuff.But the adsorption site number of a certain amount of adsorbent is certain, when reaching adsorption equilibrium, adsorbance no longer increases after reaching maximum, and maximal absorptive capacity is about 93mg/g.Because the increase of dyestuff initial concentration can make not increased by the dye quantity adsorbed in dye solution, thus cause percent of decolourization to decline, work as c
0when being increased to 240mg/L from 100mg/L, percent of decolourization significantly decreases trend.
2, under different adsorption time condition adsorbent on the impact of Dye Adsorption
For adsorbent prepared by embodiment 3, under measuring different adsorption time condition, adsorbent is on the impact of Dye Adsorption, as shown in figure 11, known adsorbent of the present invention to ethyl violet be adsorbed on t=0min time adsorbance can reach 91.02mg/g, 95.13mg/g can be reached when t=30min, when substantially reaching balance, equilibrium adsorption capacity is 98mg/g, and further testimonial material causes due to positive and negative charge effect the absorption of dyestuff.
3, under condition of different temperatures adsorbent on the impact of Dye Adsorption
As shown in figure 12, for adsorbent prepared by embodiment 3, under carrying out condition of different temperatures, adsorbent is tested the impact of Dye Adsorption, adsorbent of the present invention can have the trend of increase along with temperature to the adsorbance of EV as shown in Figure 12, because the rising of temperature makes the warm-up movement of molecule aggravate, be conducive to the carrying out adsorbed, but not obvious from the figure impact effect of known temperature.Result shows that raised temperature is to CaF
2-CR hydridization sorbing material absorption EV has the effect of promotion, but acts on not obvious, and adsorption reaction can at room temperature be carried out.
4, under different ionic strength condition adsorbent on the impact of Dye Adsorption
For adsorbent prepared by embodiment 3, under carrying out condition of different temperatures, adsorbent is tested the impact of Dye Adsorption, experimentation finds, NaCl is on the impact of adsorbent nothing itself, but NaCl has impact to EV, when the NaCl concentration added is higher, EV amount of precipitation is more, in such cases, carry out control experiment, namely adsorbent, EV stoste are added to same concentration NaCl and makes blank.Experimental result as shown in figure 13.Containing a large amount of Na, K, Cu, Cr plasmas in known actual industrial dye waste water, salt content, usually in 0.1mol/L, produces important impact to adsorption process.Experiment studies the impact of ionic strength on adsorption effect by the NaCl adding variable concentrations, known as shown in figure 13, when salinity is increased to 0.06mol/L from 0.02, there is obvious ascendant trend in Dye Adsorption amount, adsorbance 98.37mg/g rises to 103.47mg/g, along with the further rising of salting liquid, adsorbance slightly rises, but kept stable.Result shows, this adsorbent can use in the industrial dye waste water that salt content is higher, has higher practicality.
5, under condition of different pH adsorbent on the impact of Dye Adsorption
For adsorbent prepared by embodiment 3, under carrying out condition of different pH, adsorbent is tested the impact of Dye Adsorption, adsorbent of the present invention causes due to positive and negative charge effect the absorption of dyestuff, residing for adsorbent, the pH of environment is easy to the distribution of charges composition changing its surface, on the other hand, the ionization of dyestuff is also affected.Therefore, the pH of solution is the key factor affecting adsorbent effect of the present invention.Consider that pH is on the impact of EV, carries out control experiment, namely the HCl of same pH is added to adsorbent, EV stoste and NaOH solution makes blank, use adsorbance q
eperformance variation tendency.
PH to the change of adsorbance as shown in figure 14.As shown in Figure 14, the adsorbance q of EV when the initial pH of dyestuff is elevated to 4 by 2
esharply rise, between pH 4 ~ 8, Dye Adsorption amount is kept stable, reduce gradually along with pH continues to increase adsorbance.That is, adsorbent of the present invention adsorption effect under partial neutral condition is better.The reason of impact is, under strongly acidic conditions the amino that contains of adsorbent of the present invention and sulfonic acid group and H
+in conjunction with, there is the protonated adsorbent surface that makes positively charged, due to electrostatic interaction, mutually repel with dye of positive ion EV, thus cause the reduction of adsorbance.On the other hand, the C-H group on dye of positive ion molecule also can with H
+in conjunction with, occur protonatedly to make dyestuff unitary strip positive charge, result also in adsorbance and reduce.Under strongly alkaline conditions, too much OH
-be combined with the dye of positive ion, hinder the absorption of adsorbent to EV, cause adsorbance to decline.
Embodiment 10 simulated wastewater COD measures
For adsorbent prepared by embodiment 3, carry out simulated wastewater COD determination experiment, COD (COD) refers under certain condition, by the amount of strong oxidizer process water sample time institute oxygen consumed agent, result this be counted as the content (in mg/L) of oxygen.It characterizes the composite target that in water body, reducing substances pollutes.COD index divides again potassium bichromate (COD
cr) and potassium permanganate salt index (COD
mn), the former is used for the detection of industrial wastewater, and the latter is mainly for the detection of some surface water.This paper discusses COD
crmensuration.As can be seen from described in Figure 15 and table 1 data, adsorbent of the present invention has good adsorption effect, with initial COD to simulation EV waste water
crfor the simulated wastewater of 150.11mg/L, when addition is 17.6mg, COD
crbe reduced to 40.92mg/L, COD
crclearance is 72.74%, and percent of decolourization is up to 99.16%.This shows that adsorbent of the present invention has a good application prospect in reality printing and dyeing or dye wastewater treatment.
Table 1 adsorbent of the present invention is to the treatment effect of simulation EV waste water
| CaF 2-CR addition (mg) | 0 | 3.52 | 7.04 | 10.56 | 17.6 |
| Percent of decolourization (%) | -- | 55.00 | 88.70 | 97.84 | 99.16 |
| COD Cr(mg/L) | 150.11 | 102.52 | 75.54 | 47.54 | 40.92 |
| COD CrClearance (%) | -- | 31.70 | 49.68 | 68.33 | 72.74 |
The present invention utilizes organic dyestuff part Congo red with inorganic skeleton material C aF
2carry out hydridization reaction, prepare a kind of environmental protection hybrid sorbents, its cost is low, manufacture craft is simple, and adopt traditional absorption method to carry out adsorption treatment to cationic dye wastewater, the hybrid material environmental protection of preparing, meet sustainable development, the green chemical concept of " treatment of wastes with processes of wastes against one another " can be reached, simultaneously also blended in adsorbent of the present invention have tri-iron tetroxide, adsorption capacity for cationic dye wastewater is strengthened, especially for ethyl violet waste water from dyestuff, there is preferably treatment effect.The present invention with Congo red with inorganic skeleton material C aF
2carry out hydridization reaction and make hybrid sorbents, by hybrid sorbents with the blended preparation of tri-iron tetroxide adsorbent of the present invention, sorbing material product has been synthesized by the selection of reaction raw materials, pulp furnish experiment, mensuration product forms, and organic adsorption effect under having investigated different condition, judge optimum adsorption conditions.Make adsorbent of the present invention when processing cationic dye wastewater, there is preferably effect.
Above-mentioned detailed description is the illustrating of possible embodiments for invention, and this embodiment is also not used to limit the scope of the claims of the present invention, does not allly depart from equivalence of the present invention and implements or change, and all should be contained in the scope of the claims of the present invention.
In addition, those skilled in the art also can make various amendments in other form and details, interpolation and replacement in the claims in the present invention scope of disclosure and spirit.Certainly, the changes such as these various amendments made according to the present invention's spirit, interpolation and replacement, all should be included within the present invention's scope required for protection.
Claims (8)
1. process an adsorbent for cationic dye wastewater, it is characterized in that, described adsorbent comprises the hybrid sorbents that Congo red and calcirm-fluoride carries out preparation after hydridization reaction, and described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 ~ 0.10 part
0.5 ~ 8 part, calcium chloride
Sodium fluoride 1.25 ~ 25 parts.
2. a kind of adsorbent processing cationic dye wastewater according to claim 1, is characterized in that, described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.05 ~ 0.06 part
0.8 ~ 5 part, calcium chloride
Sodium fluoride 2.5 ~ 12.5 parts.
3. a kind of adsorbent processing cationic dye wastewater according to claim 1, is characterized in that, described hybrid sorbents is made up of the raw material of following molal weight number:
Congo red 0.052 part
1 part, calcium chloride
Sodium fluoride 2.5 parts.
4. the adsorbent of the kind process cationic dye wastewater according to any one of claims 1 to 3, it is characterized in that, described adsorbent also comprises tri-iron tetroxide, and described hybrid sorbents is 2 ~ 10:1 with the molal weight ratio of tri-iron tetroxide.
5. process a preparation method for the adsorbent of cationic dye wastewater, it is characterized in that, comprise the following steps:
Step one: prepare hybrid sorbents: take Congo red, the calcium chloride of 0.5 ~ 8 part, the sodium fluoride of 1.25 ~ 25 parts that molal weight number is 0.05 ~ 0.10 part, be dissolved in respectively in distilled water, under the condition of magnetic agitation, be prepared into Congo red solution, calcium chloride solution and Fluorinse, according to reactant addition sequence, Congo red solution, Fluorinse and calcium chloride solution is added successively, reaction 15min in beaker.Natural subsidence 20 ~ 24 hours, removes supernatant, with distilled water cleaning 2-3 time, and the suspension of rear obtained hybrid sorbents;
Step 2: prepare tri-iron tetroxide: get FeCl
36H
2o is dissolved in distilled water, N
2vibrate under protection 30min, gets FeCl
24H
2after O is dissolved in distilled water, add above-mentioned solution, after vibration 30min, make mixed solution, be added dropwise to by NaOH in described mixed solution, after dropwising, vibration 60min, is then heated to 90 DEG C, then reacts 2h, and Magneto separate obtains Fe
3o
4, Bian use water, ethanol and acetone washing successively, dry obtained at 40 DEG C;
Step 3: the preparation of adsorbent: get the Fe that molal weight number is 1 part
3o
4join in distilled water, joining molal weight number after ultrasonic is in the suspension of 2 ~ 10 parts of hybrid sorbents, continues ultrasonic, vibrates into homogeneous, drying is obtained under room temperature.
6. one kind processes the application of the adsorbent of cationic dye wastewater, it is characterized in that, described adsorbent is the adsorbent described in any one of Claims 1 to 4, the method of described sorbent treatment cationic dye wastewater is utilized to comprise the following steps: at room temperature, when adsorbent addition is 15 ~ 25mg, when dye of positive ion initial concentration is 200 ~ 300mg/L, solution ion strength is 0.06 ~ 2mol/L, the pH value of described cationic dye wastewater is regulated to be 7, absorption 30min.
7. a kind of application processing the adsorbent of cationic dye wastewater according to claim 6, is characterized in that, the addition of described adsorbent is 17.77mg, and described dye of positive ion initial concentration is 240mg/L, and described solution ion strength is 0.06mol/L.
8. a kind of application processing the adsorbent of cationic dye wastewater according to any one of claim 6 ~ 7, is characterized in that, described cationic dye wastewater is ethyl violet waste water from dyestuff.
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| CN107473326A (en) * | 2017-09-16 | 2017-12-15 | 济南大学 | A kind of acid TiO2The hydrosol regenerates the method for combined use of aerobic particle mud degradation of dye waste water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5464855A (en) * | 1977-10-31 | 1979-05-25 | Matsushita Electric Works Ltd | Waste water treating method |
| CN103752281A (en) * | 2014-01-21 | 2014-04-30 | 南京林业大学 | Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5464855A (en) * | 1977-10-31 | 1979-05-25 | Matsushita Electric Works Ltd | Waste water treating method |
| CN103752281A (en) * | 2014-01-21 | 2014-04-30 | 南京林业大学 | Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material |
Non-Patent Citations (2)
| Title |
|---|
| DANHUA ZHAO ET AL: "Preparation of Highly Effective Hybrid Adsorbent by Anionic Dye Wastewater and Its Use in Cationic Dye Wastewater", 《J. ENVIRON. ENG.》 * |
| KAH AIK TAN ET AL: "Removal of Cationic Dye by Magnetic Nanoparticle (Fe3O4) Impregnated onto Activated Maize Cob Powder and Kinetic Study of Dye Waste Adsorption", 《APCBEE PROCEDIA》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473326A (en) * | 2017-09-16 | 2017-12-15 | 济南大学 | A kind of acid TiO2The hydrosol regenerates the method for combined use of aerobic particle mud degradation of dye waste water |
| CN107473326B (en) * | 2017-09-16 | 2020-11-27 | 济南大学 | Acidic TiO2Combined method for degrading dye wastewater by hydrosol regeneration aerobic granular sludge |
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