CN102107980A - 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 sorbent material 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 and pollution have become the important factor of restriction national economy sustainable development.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, chemical oxygen demand (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 pollutant has persistence, can remain in the environment midium or long term, and environment is caused serious harm.
At present, in the majority in the waste water containing dye treatment process at the treatment process of Acid Dye Wastewater.Yet basic dyestuff waste water is the same with acid waste water, all is modal a kind of waste water in all trade effluents, 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 water resources to reduce or destroy.
At present, alkaline waste water physical chemistry treatment process mainly contains: (1) flocculence; (2) acid-base neutralisation 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 neutralisation method need expend in a large amount of acid and the alkali in the waste water; High-level oxidation technology then needs to use a large amount of oxidising agents, cost height; Membrane separation technique exists the relative too high problem of complicated operation, starting 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 constituents.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 product or agricultural wastes such as gac, resin and clay, zeolite, wilkinite, flyash, sawdust.Gac at present research is the most extensive, comprises granular carbon, powdered carbon and activated carbon fiber etc., but in the practical application because its solid-liquid separation is difficult, to reclaiming and recycle has brought very big inconvenience.Therefore, in recent years, environmental engineering circle is more and more paid attention to the research and the application of cheapness, efficient, low-cost sorbent material.
In recent years, because good selectivity, higher loading capacity, be easy to characteristics such as regeneration, transition metal ion and macromolecular title complex have demonstrated great application prospect in wastewater treatment, utilize the title complex of chemically modified starch and copper to be successfully applied to removal (Equilibrium and molecular mechanism of anionic dyes adsorption onto Copper (II) the Complex of dithiocarbamate-modified starch of dyestuff in the waste water, Cheng R., Ou S., Xiang B., Li Y., Liao Q., Langmuir, 2010,26,752-758).Yet the optimum handling pH value of this sorbent material is 4, that is to say that this sorbent material 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 dyestuff wastewater treatment.
Chitosan be by chitin through deacetylated and a kind of natural biological polymer 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 sequestering action and is subject to people's attention.Yet the absorption property of chitosan mainly depends on the positive charge of its polar group amino, An Ji rate of ionization just, and like this, chitosan class sorbent material 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 dyestuff waste water to chitosan.Have in the chitosan molecule-OH and-NH
2Side group, it is typical Lewis basic group, on conformation, they all are equatorial bonds, this special construction makes them have sequestering action to some metal ions with certain ionic radius under certain pH value condition, be a kind of natural sequestrant, can be used as part and metal ion and form inner complex, effectively the dye molecule in capture or the absorption alkaline waste water.
Summary of the invention
The invention provides a kind of chitosan magnetic sorbent material and remove the method that contains the sulfonic group dyestuff in the alkaline waste water, contain the sulfonic group dyestuff in this method environmental friendliness, simple to operate, the waste water and remove and the organic efficiency height, the recyclable utilization of sorbent material, cost recovery is low.
A kind of chitosan magnetic sorbent material is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, comprising:
(1) chitosan magnetic preparation of adsorbent: chitosan is dissolved in the ferric chloride in aqueous solution that concentration is 0.1-0.2mol/L, the mol ratio of chitosan and iron(ic) chloride is 2-3: 1, stirring at room 120～150 minutes, separate out solid after adding ethanol, solid after filtration, washing is back and nano-magnetic Z 250 (Fe
3O
4) mix, carried out crosslinking reaction 120～150 minutes with glutaraldehyde water solution then, the weight percent concentration of glutaraldehyde is 10～15% in the control reaction system, crosslinking reaction is finished after aftertreatment obtains the chitosan magnetic sorbent material;
(2) contain the absorption of sulfonic group dyestuff in the alkaline waste water: the above-mentioned chitosan magnetic sorbent material 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 sorbent material (chitosan magnetic-iron adsorbent) of absorbing dye then through magneticseparation, oven dry;
(3) regeneration of Xi Fu recovery that contains the sulfonic group dyestuff and chitosan magnetic sorbent material: the chitosan magnetic sorbent material of absorbing dye is joined in the aqueous solution that contains desorbing agent, stirred at least 50 minutes, filter then, filtrate being that filtration obtains reclaimed the solution that contains the sulfonic group dyestuff, the chitosan magnetic sorbent material 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 sequestering action (A magnetic study of an Fe-chitosan complex and its relevance to other biomolecules between its sequestering action: Fe3+ and the chitosan, 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 adsorptive power of chitosan.Because dye molecule mostly has sulfonic acid group, in alkaline aqueous solution, exist with electronegative form, be easy to the ferric ion chelating in chitosan-iron complex, thus among the present invention chitosan magnetic-iron adsorbent to the adsorption of dyestuff in the alkaline waste water mainly by dyestuff and Fe
3+The sequestering action that produces is realized.
Described nano-magnetic Fe
3O
4Can select the solid nano particulate matter of selling on the market for use, nano-magnetic Fe
3O
4With the mass ratio of chitosan 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 sorbent material 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 sequestering action of the iron in chitosan magnetic-iron adsorbent, optionally desorbing agent comprises sodium hydroxide, yellow soda ash, sodium bicarbonate, sodium acetate, Sodium phosphate dibasic, ethylenediamine tetraacetic acid (EDTA), methyl alcohol, ethanol or ammoniacal liquor; Experiment shows that the desorption effect of sodium hydroxide wherein is best, and the existence of desorbing agent has destroyed the sequestering action power between chitosan 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 aqueous sodium hydroxide solution of 1mol/L; Sorbent material behind the desorption can be by recycling after the regenerated liquid regeneration, the strong basicity of considering NaOH is to Fe-CS (chitosan, 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: sorbent material in utilizing the NaOH desorption process, produce with chitosan-iron coordinate hydroxyl, utilize in the acetate and make the adsorption activity bit recovery, thus the activation adsorption agent, 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 sorbent material is directly put in the alkaline waste water that contains the sulfonic group dyestuff, stir under the room temperature and can finish adsorption process, utilize magnetic field separate sorbent and processed waste water quickly and easily, do not need to 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.Using chitosan can be selected from molecular weight 80～120,000, deacetylation among the present invention is 85～95% chitosan.
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 sorbent material of the present invention only to need just can remove fully, and be easy in 5 minutes to utilize magnetic field to realize separating fast as the active red dye of 200mg/L;
(2) preparation method of chitosan magnetic-iron adsorbent of the present 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 chitosan;
(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 sorbent material 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.
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 chitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes chitosan 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 chitosan-iron complex precipitation generates gradually after, the unreacted Fe of dehydrated 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 crosslinking reaction 2h reuses dehydrated alcohol at last and cleans glutaraldehyde, magneticseparation, 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 chitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes chitosan 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 chitosan-iron complex precipitation generates gradually after, the unreacted Fe of dehydrated 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 crosslinking reaction 2h reuses dehydrated alcohol at last and cleans glutaraldehyde, magneticseparation, 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 chitosan 2.67g (molecular weight is 1,000,000, and deacetylation is 91%), makes chitosan 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 chitosan-iron complex precipitation generates gradually after, the unreacted Fe of dehydrated 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 crosslinking reaction 2h reuses dehydrated alcohol at last and cleans glutaraldehyde, magneticseparation, 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 chitosan 3.56g (molecular weight is 1,000,000, and deacetylation is 91%), makes chitosan 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 chitosan-iron complex precipitation generates gradually after, the unreacted Fe of dehydrated 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 crosslinking reaction 2h reuses dehydrated alcohol at last and cleans glutaraldehyde, magneticseparation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 1
The HCl solution 50mL of preparation 0.1mol/L, (molecular weight is 1,000,000 slowly to add chitosan 2.67g, deacetylation is 91%), continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, stir simultaneously slowly, treat that the chitosan precipitation generates gradually after, centrifugation, use the unreacted HCl of dehydrated alcohol flush away, add the 0.067g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and crosslinking reaction 2h uses dehydrated alcohol to clean glutaraldehyde at last, magneticseparation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 2
The HCl solution 50mL of preparation 0.1mol/L, (molecular weight is 1,000,000 slowly to add chitosan 2.67g, deacetylation is 91%), continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, stir simultaneously slowly, treat that the chitosan precipitation generates gradually after, centrifugation, use the unreacted HCl of dehydrated alcohol flush away, add the 0.133g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and crosslinking reaction 2h uses dehydrated alcohol to clean glutaraldehyde at last, magneticseparation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Comparative Examples 3
The HCl solution 50mL of preparation 0.1mol/L, (molecular weight is 1,000,000 slowly to add chitosan 2.67g, deacetylation is 91%), continue to stir 2h, both are fully reacted, then 50mL ethanol is slowly added, stir simultaneously slowly, treat that the chitosan precipitation generates gradually after, centrifugation, use the unreacted HCl of dehydrated alcohol flush away, add the 0.67g nanometer Fe immediately
3O
4Stirring and evenly mixing adds 25% glutaraldehyde 5mL then, and crosslinking reaction 2h uses dehydrated alcohol to clean glutaraldehyde at last, magneticseparation, and 80 ℃ of oven dry, levigate, prepare chitosan magnetic-iron adsorbent.
Absorption test case 1
The sorbent material 0.2g that gets respectively by embodiment 1～4 and Comparative Examples 1～3 preparation adds respectively in 100mg/L Xylene Red 73 dye solutions of 100mL, pH=8, room temperature vibration 5 minutes, magneticseparation, use the dye strength in the spectrophotometry solution, dyestuff clearance test result is as shown in table 1 in the waste water, by the test result of table 1 as can be known, 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 sorbent material 0.2g respectively by embodiment 2 and Comparative Examples 2 preparations, adding the 100mL dye strength is 100mg/L, and pH value is respectively in 8,10,12 Xylene Red 73 dye solutions, and room temperature was vibrated 5 minutes, magneticseparation 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, remove the efficient height at pH=8-12 scope inner dye, Xylene 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 only is 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 sorbent material 0.2g respectively by embodiment 2 preparations, add 100mL, pH=12, dye strength is respectively in Xylene Red 73 dye solutions of 25mg/L, 50mg/L, 100mg/L, 200mg/L, room temperature vibration 30 minutes, magneticseparation 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 starting point 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 sorbent material 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 (Xylene Red 73), RR24 (reactive red 24), RY2 (reactive yellow 2), RB74 (Reactive blue 74), RB194 (Reactive Blue 19 100 4), RR11 (reactive red 11), RY18 (REACTIVE YELLOW 18) solution of 50mg/L, room temperature vibration 30 minutes, magneticseparation 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, various waste water from dyestuff at pH=12 are removed the efficient height, and the clearance of dye strength 50mg/L all remains on more than 90%, and applied widely to dyestuff of sorbent material 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 sorbent material 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 magneticseparation 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 manipulation of regeneration, chitosan magnetic-iron adsorbent that the after-filtration drying of finishing dealing with obtains reclaiming, the absorbing dye that the chitosan magnetic-iron adsorbent that obtains reclaiming carries out in the same step (1) is tested, and test result sees Table 5.As shown in Table 5, the sorbent material of manipulation of regeneration not, the dyestuff clearance only has 30.6% during reuse for the second time, and sorbent material is after the HAc of 0.1mol/L solution manipulation of regeneration, can reach to reach the dyestuff clearance again up to 94.4% adsorption effect.
Table 5
Desorption test case 2
(1) get the sorbent material 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 magneticseparation 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 manipulation of regeneration, chitosan magnetic-iron adsorbent that the after-filtration drying of finishing dealing with obtains reclaiming, chitosan magnetic-the iron adsorbent that obtains reclaiming is recycled, and the absorption of carrying out same step (1) is simultaneously tested and the desorption test of same step (2), test result sees Table 6, as shown in Table 6, chitosan magnetic after the absorption-iron adsorbent is through the desorption of the NaOH aqueous solution, again after the HAc of 0.1mol/L solution manipulation of regeneration, just can reach good desorption effect, help reclaiming usefulness again, reduce and handle cost for wastewater treatment.
Table 6
Claims (5)
1. a chitosan magnetic sorbent material is removed the method that contains the sulfonic group dyestuff in the alkaline waste water, comprising:
(1) chitosan is dissolved in the ferric chloride in aqueous solution that concentration is 0.1-0.2mol/L, the mol ratio of chitosan and iron(ic) chloride is 2-3: 1, stirring at room 120～150 minutes, separate out solid after adding ethanol, solid after filtration, washing is back mixes with the nano-magnetic Z 250, carried out crosslinking reaction 120～150 minutes with glutaraldehyde water solution then, the weight percent concentration of glutaraldehyde is 10～15% in the control reaction system, and crosslinking reaction is finished after aftertreatment obtains the chitosan magnetic sorbent material;
(2) the chitosan magnetic sorbent material 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 sorbent material of absorbing dye then through magneticseparation, oven dry;
(3) the chitosan magnetic sorbent material 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 filtrate that obtains, the chitosan magnetic sorbent material that the solid that filtration obtains obtains reclaiming after regenerated liquid regeneration for reclaiming.
2. chitosan magnetic sorbent material 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 Z 250 and chitosan is 0.05～0.5: 2.
3. chitosan magnetic sorbent material 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 aqueous sodium hydroxide solution of 1mol/L; Described regenerated liquid is that concentration is the acetic acid solution of 0.02-0.2mol/L.
4. chitosan magnetic sorbent material 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 sorbent material 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 sorbent material of described step (2) and the waste water.
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| 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 |
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