CN102107980B - Method for removing sulfonic-group-containing dye in alkaline waste water by using magnetic chitosan adsorbent - Google Patents
Method for removing sulfonic-group-containing dye in alkaline waste water by using magnetic chitosan adsorbent Download PDFInfo
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Abstract
The invention discloses a method for removing sulfonic-group-containing dye in alkaline waste water by using a magnetic chitosan adsorbent, which comprises the following steps: (1) dissolving chitosan in an iron chloride water solution, stirring, adding ethanol to precipitate a solid, filtering out the solid, washing, mixing the solid with nano magnetic ferroferric oxide, carrying out cross-linking reaction with a glutaric dialdehyde water solution, and carrying out after-treatment to obtain a magnetic chitosan adsorbent; (2) adding the obtained magnetic chitosan adsorbent into an alkaline waste water solution containing the sulfonic-group-containing dye, stirring, carrying out magnetic separation, and drying to obtain the dye-adsorbed magnetic chitosan adsorbent; and (3) adding the dye-adsorbed magnetic chitosan adsorbent into a water solution containing a desorbing agent, stirring, and filtering to obtain a dye recovered solution and the recovered magnetic chitosan adsorbent. The method disclosed by the invention is simple to operate, has the advantages of environment friendliness and low cost, and has wide industrial application prospects.
Description
Technical field
The invention belongs to waste water post-processing technology field, specifically relate to a kind of chitosan magnetic adsorbent and remove the method that contains the sulfonic group dyestuff in the alkaline waste water.
Background technology
Along with the high speed development and the urbanization process of China's economic society are constantly accelerated, shortage of water resources has become the key factor that restricts national economy sustainable development with polluting.Textile printing and dyeing industry is the industrial wastewater discharge rich and influential family; Not only the water yield is big, variation water quality is big, contaminant component is complicated for dyeing waste water, content is high; Colourity, COD (COD) and biochemical oxygen demand (BOD) (BOD) are all higher, but also contain a large amount of poisonous hardly degraded organic substances.This type of organic pollution has persistence, can remain in the environment midium or long term, and environment is caused serious harm.
At present, the processing method to Acid Dye Wastewater is in the majority in the waste water containing dye processing method.Yet basic-dyeable fibre waste water is the same with acid waste water, all is modal a kind of waste water in all industrial wastewaters, is mainly derived from the production and use of dyestuff.If without just handling directly discharging, with corrosion pipeline, channel and hydraulic structure; Enter the pH value that will change water body behind the water body, influence the self purification of water body, destroy the natural, ecological in river, cause aquatic resources to reduce or destroy.
At present, alkaline waste water physical chemistry processing method mainly contains: (1) flocculence; (2) acid-base neutralization method; (3) absorption method; (4) membrane separation technique; (5) (Liu Jianming, Wu Shubing, alkaline waste water handle and recycle progress, Chinese comprehensive utilization of resources, 2008,26 (9): 36-39) for high-level oxidation technology etc.But above-mentioned these methods all exist some drawback and irrationality, and for example a large amount of mud of flocculence processing generation may cause second environmental pollution; The acid-base neutralization method need the acid of labor come in waste water in alkali; High-level oxidation technology then need use a large amount of oxidising agents, and cost is high; Membrane separation technique exists the too high relatively problem of complicated operation, raw material and running cost.And because dye species is many, and develop towards anti-photodissociation, anti-oxidant, antibiont oxidation direction, conventional oxidized waste water treatment technology is difficult to remove these organic components.And absorption method is particularly suitable for the processing of difficult waste water from dyestuff of biochemical degradation.The sorbent systems of test is also a lot, for example, and low value article or agricultural wastes such as active carbon, resin and clay, zeolite, bentonite, flyash, sawdust.Active carbon at present research is the most extensive, comprises granular active carbon, powdered activated carbon and NACF etc., but in the practical application because its Separation of Solid and Liquid is difficult, to reclaiming and recycle has brought very big inconvenience.Therefore, in recent years, environmental project circle is more and more paid attention to the research and the application of cheapness, efficient, low-cost adsorbent.
In recent years, owing to good selectivity, higher adsorption capacity, be easy to characteristics such as regeneration, transition metal ions and macromolecular complex have demonstrated great application prospect in wastewater treatment; Utilize the complex of chemical modification starch and copper to be successfully applied to removal (Equilibrium and molecular mechanism of anionic dyes adsorption onto Copper (II) Complex of dithiocarbamate-modified starch, Cheng R., the Ou S. of dyestuff in the waste water; Xiang B., Li Y., Liao Q.; Langmuir; 2010,26,752-758).Yet the optimization process pH value of this adsorbent is 4, that is to say that this adsorbent can only adapt to the processing with Acid Dye Wastewater.Therefore, be badly in need of the high-efficiency adsorbent that exploitation is applicable to the basic-dyeable fibre wastewater treatment.
Shitosan be by chitin through deacetylated and a kind of natural biological macromolecule that obtain, have complicated double-spiral structure, have in the molecular structure-OH ,-NH
2Group, it is nontoxic, and is harmless to animal, plant, has good adsorption and chelation and receives people's attention.Yet the absorption property of shitosan mainly depends on the amino positive charge property of its polar group, just amino rate of ionization, and like this, shitosan class adsorbent is applicable to the waste water from dyestuff of pH＜5 mostly.Therefore, need carry out modifying and decorating to be adapted to the processing of basic-dyeable fibre waste water to shitosan.Have in the chitosan molecule-OH and-NH
2Side group; Be typical Lewis basic group, in view of conformation, they all are equatorial bonds; This special construction makes them under certain pH value condition, have chelation to some metal ions with certain ionic radius; Be a kind of natural chelating agent, can be used as part and metal ion and form chelate, effectively the dye molecule in capture or the absorption alkaline waste water.
Summary of the invention
The invention provides a kind of chitosan magnetic adsorbent and remove the method that contains the sulfonic group dyestuff in the alkaline waste water, contain in this method environmental friendliness, simple to operate, the waste water that the sulfonic group dyestuff is removed and organic efficiency is high, the recyclable utilization of adsorbent, cost recovery is low.
A kind of chitosan magnetic adsorbent is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, comprising:
(1) chitosan magnetic preparation of adsorbent: shitosan is dissolved in the ferric chloride in aqueous solution that concentration is 0.1-0.2mol/L; The mol ratio of shitosan and iron chloride is 2-3: 1; Stirring at room 120～150 minutes; Separate out solid after adding ethanol, solid through filter, washing back and nano-magnetic tri-iron tetroxide (Fe
3O
4) mix, carried out cross-linking reaction 120～150 minutes with glutaraldehyde water solution then, the weight percent concentration of glutaraldehyde is 10～15% in the control reaction system, cross-linking reaction is accomplished after post processing obtains the chitosan magnetic adsorbent;
(2) contain the absorption of sulfonic group dyestuff in the alkaline waste water: the above-mentioned chitosan magnetic adsorbent for preparing is joined to contain the sulfonic group dye strength be 25～200mg/L; The pH value is in 8～12 the aqueous solution; Stirred at least 30 minutes, and obtained the chitosan magnetic adsorbent (chitosan magnetic-iron adsorbent) of absorbing dye then through magnetic separation, oven dry;
(3) recovery that contains the sulfonic group dyestuff of absorption and the regeneration of chitosan magnetic adsorbent: the chitosan magnetic adsorbent of absorbing dye is joined in the aqueous solution that contains desorbing agent; Stirred at least 50 minutes; Filter then; Filtrating being that filtration obtains reclaimed the solution that contains the sulfonic group dyestuff, the chitosan magnetic adsorbent that the solid that filtration obtains obtains reclaiming after regenerated liquid regeneration.
Chitosan magnetic-iron adsorbent is removed the process that contains the sulfonic group dye molecule in the alkaline waste water and mainly is chelation (the A magnetic study of an Fe-chitosan complex and its relevance to other biomolecules between its chelation: Fe3+ and the shitosan; Subhash C.Bhatia and Natarajan Ravi; Biomacromolecules 2000; 1; 413-417) effectively reduce the chance that forms hydrogen bond between the chitosan molecule, increased the stability and the adsorption capacity of shitosan.Because dye molecule mostly has sulfonic acid group; In alkaline aqueous solution, exist with electronegative form; Be easy to the ferric ion chelating in shitosan-iron complex, so dyestuff and Fe are mainly passed through in the suction-operated to dyestuff in the alkaline waste water of chitosan magnetic-iron adsorbent among the present invention
3+The chelation that produces is realized.
Described nano-magnetic Fe
3O
4Can select the solid nano particle of selling on the market for use, nano-magnetic Fe
3O
4With the mass ratio of shitosan be 0.05～0.5: 2.Adopt nano level magnetic Fe
3O
4, Fe
3O
4Uniform particles is distributed in the chitosan absorbent system, utilizes the magnetic of chitosan absorbent, guarantees that the last handling process of adsorbent preparation, adsorbents adsorb and desorption is simple, has avoided centrifugal and has waited operation with filtration.It is 25% or 50% glutaraldehyde water solution commercially available prod that described glutaraldehyde can be selected mass percent concentration common on the market for use.
Described desorbing agent can be selected alkaline desorbing agent for use; With the sulfonic acid group of destruction dye molecule and the chelation of the iron in chitosan magnetic-iron adsorbent, optional desorbing agent comprises NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, sodium hydrogen phosphate, ethylenediamine tetra-acetic acid, methyl alcohol, ethanol or ammoniacal liquor; Experiment shows that the desorption effect of NaOH wherein is best, and the existence of desorbing agent has destroyed the chelation power between shitosan and dyestuff, thereby makes adsorbed material carry out desorption, has realized the reuse of chitosan magnetic-iron adsorbent and the recovery of dyestuff.Show according to a large amount of experiments, in the desorbing agent aqueous solution desorption effect best for concentration be the sodium hydrate aqueous solution of 1mol/L; Adsorbent behind the desorption can be through recycling after the regenerated liquid regeneration; The strong basicity of considering NaOH is to Fe-CS (shitosan; Chitosan) influence; Described regenerated liquid is preferably the acetic acid aqueous solution that concentration is 0.02-0.2mol/L, and further preferred regenerated liquid is acetate (HAc) aqueous solution of 0.1mol/L.The regeneration mechanism of regenerated liquid is: adsorbent that in utilizing the NaOH desorption process, produce with hydroxyl shitosan-iron coordination, utilize in the acetate and make the adsorption activity bit recovery, thus the activation adsorbent, mechanism is shown below:
Above-mentioned chitosan magnetic-iron adsorbent contains when using in the sulfonic group waste water from dyestuff in alkalescence; Simple to operate; Only need adsorbent is directly put in the alkaline waste water that contains the sulfonic group dyestuff, stir under the room temperature and can accomplish adsorption process, utilize magnetic field separating adsorbent and the waste water that is processed quickly and easily; Need not carry out centrifugal treating, the amount that adds chitosan magnetic-iron adsorbent can be adjusted according to the concentration that contains dyestuff in the actual waste water.The consumption of chitosan magnetic-iron adsorbent is generally speaking: 100mg contains the sulfonic group dyestuff and needs 1g chitosan magnetic-iron adsorbent.Use among the present invention shitosan optional from molecular weight 80～120,000, deacetylation is 85～95% shitosan.
Beneficial effect of the present invention is embodied in:
(1) chitosan magnetic-iron adsorbent of the present invention; In alkaline waste water, contain in the absorption place to go process of sulfonic group dyestuff; Can remove dyestuff in the water apace; Adopt adsorbent of the present invention only to need just can remove fully, and be easy in 5 minutes to utilize magnetic field to realize separation fast like the active red dye of 200mg/L;
(2) preparation method of chitosan magnetic-iron adsorbent according to the invention is simple to operate, and environmental friendliness is with low cost, and its absorption property has more the application prospect of industrialization than obviously not improving through pretreated shitosan;
(3) chitosan magnetic-iron adsorbent of preparing of the present invention can use the NaOH aqueous solution to carry out desorption behind the absorbing dye, utilizes the HAc aqueous solution to carry out the regeneration of adsorbent then, and regeneration is easy, and cost recovery is low;
(4) chitosan magnetic-iron adsorbent of preparing of the present invention is applicable to that the alkaline waste water containing dye of various concentration is handled, and is simple to operate.
The specific embodiment
Below in conjunction with embodiment the present invention is specified, but be not that the present invention is made restriction.
Embodiment 1
The FeCl of preparation 0.1mol/L
3Solution 50mL (0.005mol) slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes shitosan and Fe
3+Mol ratio be 3: 1, continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, slowly stir simultaneously, treat that shitosan-iron complex deposition generates gradually after, the unreacted Fe of absolute ethyl alcohol flush away is used in centrifugation
3+, add the 0.067g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h reuses absolute ethyl alcohol at last and cleans glutaraldehyde, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Embodiment 2
The FeCl of preparation 0.1mol/L
3Solution 50mL (0.005mol) slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes shitosan and Fe
3+Mol ratio be 3: 1, continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, slowly stir simultaneously, treat that shitosan-iron complex deposition generates gradually after, the unreacted Fe of absolute ethyl alcohol flush away is used in centrifugation
3+, add the 0.133g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h reuses absolute ethyl alcohol at last and cleans glutaraldehyde, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Embodiment 3
The FeCl of preparation 0.1mol/L
3Solution 50mL (0.005mol) slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes shitosan and Fe
3+Mol ratio be 3: 1, continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, slowly stir simultaneously, treat that shitosan-iron complex deposition generates gradually after, the unreacted Fe of absolute ethyl alcohol flush away is used in centrifugation
3+, add the 0.67g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h reuses absolute ethyl alcohol at last and cleans glutaraldehyde, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Embodiment 4
The FeCl of preparation 0.2mol/L
3Solution 50mL (0.005mol) slowly adds shitosan 3.56g (molecular weight is 1,000,000, and deacetylation is 91%), makes shitosan and Fe
3+Mol ratio be 2: 1, continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, slowly stir simultaneously, treat that shitosan-iron complex deposition generates gradually after, the unreacted Fe of absolute ethyl alcohol flush away is used in centrifugation
3+, add the 0.134g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h reuses absolute ethyl alcohol at last and cleans glutaraldehyde, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 1
The HCl solution 50mL of preparation 0.1mol/L slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%); Continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added; Stir simultaneously slowly, treat that the shitosan deposition generates gradually after, centrifugation; Use the unreacted HCl of absolute ethyl alcohol flush away, add the 0.067g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h uses absolute ethyl alcohol to clean glutaraldehyde at last, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 2
The HCl solution 50mL of preparation 0.1mol/L slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%); Continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added; Stir simultaneously slowly, treat that the shitosan deposition generates gradually after, centrifugation; Use the unreacted HCl of absolute ethyl alcohol flush away, add the 0.133g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h uses absolute ethyl alcohol to clean glutaraldehyde at last, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 3
The HCl solution 50mL of preparation 0.1mol/L slowly adds shitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%); Continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added; Stir simultaneously slowly, treat that the shitosan deposition generates gradually after, centrifugation; Use the unreacted HCl of absolute ethyl alcohol flush away, add the 0.67g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and cross-linking reaction 2h uses absolute ethyl alcohol to clean glutaraldehyde at last, magnetic separation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Absorption test case 1
Get respectively by the embodiment 1～4 and the adsorbent 0.2g of Comparative Examples 1～3 preparation and add respectively in 100mg/L acid red 73 dye solutions of 100mL, pH=8; Room temperature vibration 5 minutes, magnetic separation is used the dye strength in the spectrophotometry solution; Dyestuff clearance test result is as shown in table 1 in the waste water; Test result by table 1 can know that with respect to chitosan magnetic, chitosan magnetic-iron adsorbent can obviously improve the removal efficient of chitosan molecule to dyestuff.Nano-magnetic Fe
3O
4With chitosan mass than in (g/g) 0.05～0.5: 2 scopes, it is all better that chitosan magnetic-iron adsorbent is removed the effect of dyestuff in the alkaline waste water.
Table 1
Absorption test case 2
Get the adsorbent 0.2g with Comparative Examples 2 preparations respectively by embodiment 2; Adding the 100mL dye strength is 100mg/L, and pH value is respectively in 8,10,12 acid red 73 dye solutions, and room temperature was vibrated 5 minutes; Magnetic separation is used the dye strength in the spectrophotometry solution.The clearance result of dyestuff is as shown in table 2 in the waste water.By shown in the table 2, use the chitosan magnetic-iron adsorbent of the present invention's preparation, it is high to remove efficient at pH=8-12 scope inner dye, and acid red 73 dyestuffs of 100mg/L all can reach 85% above clearance.And without FeCl
3Under the chitosan modified similarity condition, the dyestuff clearance is very low: during pH=8, and dyestuff clearance 34%, the above dyestuff clearance of pH=10 is merely 2～5%.
Table 2
| Chitosan magnetic-iron adsorbent | pH | Dyestuff clearance (%) |
| Embodiment 2 | 8 | 95.4 |
| Embodiment 2 | 10 | 91.7 |
| Embodiment 2 | 12 | 88.4 |
| Comparative Examples 2 | 8 | 34.1 |
| Comparative Examples 2 | 10 | 5.3 |
| Comparative Examples 2 | 12 | 2.2 |
Absorption test case 3
Get adsorbent 0.2g respectively by embodiment 2 preparations; Add 100mL, pH=12, dye strength is respectively in acid red 73 dye solutions of 25mg/L, 50mg/L, 100mg/L, 200mg/L, room temperature vibration 30 minutes; Magnetic separation is used the dye strength in the spectrophotometry solution.Dyestuff clearance test result is as shown in table 3 in the waste water.By shown in the table 3, use the chitosan magnetic-iron adsorbent of the present invention's preparation, it is all higher to remove efficient at the waste water from dyestuff of pH=12, and dye strength is that the clearance of 25～200mg/L all remains on more than 85%.
Table 3
| Chitosan magnetic-iron adsorbent | Dyestuff initial concentration (mg/L) | Dyestuff clearance (%) |
| Embodiment 2 | 25 | 98.7 |
| Embodiment 2 | 50 | 96.9 |
| Embodiment 2 | 100 | 88.4 |
| Embodiment 2 | 200 | 85.7 |
Absorption test case 4
Get adsorbent 0.2g respectively by embodiment 2 preparations; Add pH=12,100mL dye strength and be among the dyestuff AB25 (acid blue 25), AB40 (Acid Blue 40), AB62 (acid blue 62), AB113 (Acid blue 113), AB193 (acid blue 193), AR73 (acid red 73), RR24 (reactive red 24), RY2 (reactive yellow 2), RB74 (reactive blue 74), RB194 (active blue 19 4), RR11 (reactive red 11), RY18 (REACTIVE YELLOW 18) solution of 50mg/L; Room temperature vibration 30 minutes; Magnetic separation is used the dye strength in the spectrophotometry solution.Dyestuff clearance test result is as shown in table 4 in the waste water.By shown in the table 4; Use the chitosan magnetic-iron adsorbent of the present invention's preparation; It is high to remove efficient at the various waste water from dyestuff of pH=12, and the clearance of dye strength 50mg/L all remains on more than 90%, and applied widely to dyestuff of adsorbent that the present invention prepares be described.
Table 4
| Chitosan magnetic-iron adsorbent | The dyestuff title | Dyestuff clearance (%) |
| Embodiment 2 | AB25 | 96.5 |
| Embodiment 2 | AB40 | 95.7 |
| Embodiment 2 | AB62 | 93.1 |
| Embodiment 2 | AB113 | 97.9 |
| Embodiment 2 | AB193 | 96.3 |
| Embodiment 2 | AR73 | 96.9 |
| Embodiment 2 | RR24 | 98.5 |
| Embodiment 2 | RY2 | 95.2 |
| Embodiment 2 | RB74 | 97.2 |
| Embodiment 2 | RB194 | 98.5 |
| Embodiment 2 | RR11 | 97.8 |
| Embodiment 2 | RY18 | 94.1 |
Desorption test case 1
(1) get the adsorbent 0.2g that is prepared by embodiment 2, adding pH=12,100mL dye strength are in the dyestuff AR73 solution of 50mg/L, room temperature vibration 30 minutes, and magnetic separation is used the dye strength in the spectrophotometry solution.Collect residue,, obtained adsorbing the chitosan magnetic-iron adsorbent powder of dyestuff 80 ℃ of oven dry down.
(2) this above-mentioned chitosan magnetic-iron adsorbent that has adsorbed dyestuff is put into respectively in the NaOH aqueous solution of 25mL1mol/L, stirred 30min under the room temperature, the dyestuff of desorption chitosan magnetic-iron adsorbent.
(3) chitosan magnetic-iron adsorbent behind the desorption being joined concentration is respectively in the HAc solution of 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L; Stir 30min and carry out Regeneration Treatment; Chitosan magnetic-iron adsorbent that the back filtration drying of finishing dealing with obtains reclaiming; Chitosan magnetic-the iron adsorbent that obtains reclaiming is carried out the absorbing dye test in the same step (1), and test result is seen table 5.Can know by table 5, the adsorbent of Regeneration Treatment not, the dyestuff clearance only has 30.6% during reuse for the second time, and adsorbent is after the HAc of 0.1mol/L solution Regeneration Treatment, can reach to reach the dyestuff clearance again up to 94.4% adsorption effect.
Table 5
Desorption test case 2
(1) get the adsorbent 0.2g that is prepared by embodiment 2, adding pH=12,100mL dye strength are in the dyestuff AR73 solution of 50mg/L, room temperature vibration 30 minutes, and magnetic separation is used the dye strength in the spectrophotometry solution.Collect residue, 80 ℃ of oven dry down, obtained adsorbing the chitosan magnetic-iron adsorbent powder of dyestuff, dyestuff clearance test result is as shown in table 6 in the waste water.
(2) this above-mentioned chitosan magnetic-iron adsorbent that has adsorbed dyestuff is put into respectively in the NaOH aqueous solution of 25mL1mol/L, stirred 30min under the room temperature, the dyestuff of desorption chitosan magnetic-iron adsorbent, dyestuff desorption rate test result is as shown in table 6.
(3) chitosan magnetic-iron adsorbent behind the desorption is joined in the HAc solution of 0.1mol/L, stir 30min and carry out Regeneration Treatment, chitosan magnetic-iron adsorbent that the back filtration drying of finishing dealing with obtains reclaiming; Chitosan magnetic-the iron adsorbent that obtains reclaiming is recycled, and carry out the absorption test of same step (1) and the desorption test of same step (2) simultaneously, test result is seen table 6; Can know by table 6; Chitosan magnetic after the absorption-iron adsorbent after the HAc of 0.1mol/L solution Regeneration Treatment, just can reach good desorption effect again through the desorption of the NaOH aqueous solution; Help reclaiming usefulness again, reduce and handle cost for wastewater treatment.
Table 6
Claims (5)
1. a chitosan magnetic adsorbent is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, comprising:
(1) shitosan is dissolved in the ferric chloride in aqueous solution that concentration is 0.1-0.2mol/L, the mol ratio of shitosan and iron chloride is 2-3: 1, and stirring at room 120～150 minutes; Separate out solid after adding ethanol, solid mixes with the nano-magnetic tri-iron tetroxide after filtering, washing, and carries out cross-linking reaction 120～150 minutes with glutaraldehyde water solution then; The weight percent concentration of glutaraldehyde is 10～15% in the control reaction system; After accomplishing, cross-linking reaction use absolute ethyl alcohol to clean glutaraldehyde, magnetic separation, 80 ℃ of oven dry; Levigate, obtain the chitosan magnetic adsorbent;
(2) the chitosan magnetic adsorbent for preparing is joined to contain the sulfonic group dye strength be 25～200mg/L, the pH value is in 8～12 the aqueous solution, to stir at least 30 minutes, obtains the chitosan magnetic adsorbent of absorbing dye then through magnetic separation, oven dry;
(3) the chitosan magnetic adsorbent with absorbing dye joins in the aqueous solution that contains desorbing agent; Stirred at least 50 minutes; Filter then, filter the solution that contains sulfonic group dyestuff of filtrating that obtains, the chitosan magnetic adsorbent that the solid that filtration obtains obtains reclaiming after regenerated liquid regeneration for reclaiming.
2. chitosan magnetic adsorbent according to claim 1 is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, it is characterized in that the mass ratio of described nano-magnetic tri-iron tetroxide and shitosan is 0.05～0.5: 2.
3. chitosan magnetic adsorbent according to claim 1 is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, it is characterized in that the aqueous solution of described desorbing agent is that concentration is the sodium hydrate aqueous solution of 1mol/L; Described regenerated liquid is that concentration is the acetic acid solution of 0.02-0.2mol/L.
4. chitosan magnetic adsorbent according to claim 3 is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, it is characterized in that described regenerated liquid is that concentration is the acetic acid aqueous solution of 0.1mol/L.
5. chitosan magnetic adsorbent according to claim 1 is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, it is characterized in that, the mass ratio of sulfonic group dyestuff is 10: 1 in middle chitosan magnetic adsorbent of described step (2) and the waste water.
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| CN106947020B (en) * | 2017-04-19 | 2019-01-22 | 福州大学 | A kind of preparation method of the chitosan-based hydrogel of high intensity |
| CN111534644A (en) * | 2020-05-26 | 2020-08-14 | 广西大学 | Method for removing alkaline degradation pigments of sugar beet sugar-making dilute juice hexose |
| CN114307949A (en) * | 2022-01-25 | 2022-04-12 | 湖南海澍环保科技有限公司 | Efficient compound water purifying agent and processing method thereof |
| CN115007115A (en) * | 2022-06-06 | 2022-09-06 | 昆明理工大学 | Synchronous purification of tetracycline and Cu 2+ Preparation method of adsorbent |
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| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
| CN101279776A (en) * | 2008-05-21 | 2008-10-08 | 东华大学 | Novel method for fast removing cupric ion with magnetic sorbent |
| CN101882496A (en) * | 2009-05-04 | 2010-11-10 | 杨琥 | Chitosan-polyacrylamide magnetic composite microsphere material, preparation method and application thereof |
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| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
| CN101279776A (en) * | 2008-05-21 | 2008-10-08 | 东华大学 | Novel method for fast removing cupric ion with magnetic sorbent |
| CN101882496A (en) * | 2009-05-04 | 2010-11-10 | 杨琥 | Chitosan-polyacrylamide magnetic composite microsphere material, preparation method and application thereof |
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