CN105561953A - Compound adsorbent PANI-CMC and application thereof to dye wastewater treatment - Google Patents
Compound adsorbent PANI-CMC and application thereof to dye wastewater treatment Download PDFInfo
- Publication number
- CN105561953A CN105561953A CN201610067536.4A CN201610067536A CN105561953A CN 105561953 A CN105561953 A CN 105561953A CN 201610067536 A CN201610067536 A CN 201610067536A CN 105561953 A CN105561953 A CN 105561953A
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- cmc
- pani
- compound adsorbent
- aniline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a compound adsorbent PANI-CMC and an application thereof to dye wastewater treatment. A preparing method of the compound adsorbent includes the following steps that in a buffer system, a certain mass ratio of aniline, a certain mass ratio of hemin and a certain mass ratio of CMC are added and evenly dispersed; at the room temperature, the mixture is continually stirred, and a certain amount of H2O2 is added into the system every 15-20 min; the mixture is continuously reacted for 0.5 h or longer, a certain amount of hydrochloric acid is added into the system, the mixture is continuously reacted under the sealed condition, and is subjected to standing, washed, dried and ground, and the powder-shaped product is obtained. The PANI-CMC has the good adsorption performance for anionic dye containing sulfonic acid groups and cationic dye, and has the good adsorption effect within the wide pH range (pH=3-11), and the application range is expanded.
Description
Technical field
The present invention relates to bionic catalysis and water-treatment technology field, be specifically related to a kind of the compound adsorbent PANI-CMC and the application thereof that can be used for dye wastewater treatment.
Background technology
Polyaniline (PANI) has unique physicochemical property and certain absorption property, is the novel substance that a class being is is being researched and developed.The people such as Mahanta adopt chemical method to prepare polyaniline under strongly acidic conditions, and it shows better absorption property for containing sulfonic anionic dye, for then not showing good absorption property containing sulfonic dyestuff.The people such as Ai under strongly acidic conditions, adopt chemical method to prepare the polyaniline microsphere that average grain diameter is 2.2 μm, and are applied to the Adsorption of methyl orange in water.But because polyaniline particles particle diameter is less, easily reunite, adsorbed rear separation difficulty or fixed bed resistance comparatively large, be not suitable for continuous adsorption or the Dynamic Adsorption process of industrial wastewater.
Research finds, PANI and large biological molecule interphase interaction, can give PANI-bimolecular complexes better performance.The large biological molecule that report attempts using has the extracellular polymeric, starch etc. of shitosan, bacterium.As Janaki etc. in acid condition, polyaniline/the Chitosan Composites that utilized chemical oxidization method to prepare, with pure polyaniline compound seemingly, have selective to the absorption of dyestuff in water, better to the adsorption effect containing sulfonic anionic dyes, but to cationic dyes less effective.Starch/the polyaniline nano-composite material that utilized chemical oxidization method to prepare such as Janaki, for containing sulfonic dyestuff, there is good absorption property in acid condition, when optimal adsorption effect appears at pH=3, its practical application that is restricted to of service condition is made troubles.
The preparation method of current polyaniline mainly contains chemical method, electrochemical process and biological enzyme three class.Wherein, biological enzyme is a kind of method of comparatively environmental protection, but biology enzyme is owing to limiting by factors such as environment, source and prices, fails extensively to be applied.Imitative enzyme process, by building the system similar to biology enzyme, carries out the synthesis of polyaniline under mild conditions, turn avoid enzyme easy in inactivation, to shortcomings such as requirement for environmental conditions are higher simultaneously.Hemin (Hemin) is the Small molecular with ferriporphyrin structure, and have the character similar to peroxidase, early-stage Study shows, it can be used to the polymerization carrying out aniline.
Cellulose is the abundantest on the earth, reproducible natural polymer biological material.China is as a large agricultural country, the annual production of crop material is huge (can reach about 700,000,000 tons), and current straw utilization rate is very low, wherein major part also just directly utilizes as fuel etc., brings the problems comprising atmospheric haze thus.In plant material, content of cellulose is the highest, can account for 40 ~ 50%, so based on cellulose exploitation new material, the prospect realizing the higher value application of living beings is boundless.Carboxyl methyl cellulose is nonpoisonous and tasteless, wide material sources, be at present most important, output is maximum, use cellulosic products the most easily.
Summary of the invention
The invention provides a kind of eco-friendly imitative enzymatic and prepare PANI-CMC compound, and as adsorbent, be applied to the process of waste water from dyestuff.
A PANI-CMC compound adsorbent prepared by imitative enzymatic, prepared by following steps:
In buffer system, add the aniline of certain mass ratio, X-factor (Hemin) and CMC, make it be uniformly dispersed; At room temperature, constantly stir, in system, add a certain amount of H every 15-20min
2o
2; Continue reaction more than 0.5h, in system, add a certain amount of hydrochloric acid, make reaction continue to react more than 30min in sealing situation, leave standstill by water and ethanol washed product after a period of time, and by product drying at not higher than 60 DEG C, after grinding, obtain powdery product.
In above-mentioned reaction, buffer system is selected from the one in acetic acid-sodium acetate, citric acid-sodium citrate, and pH value range is 3 ~ 6; The mass ratio of aniline, Hemin and CMC is 1:0.01:0.2 ~ 0.8; Aniline, hydrochloric acid and H
2o
2mol ratio be 1:6 ~ 30:0.15 ~ 1.5; Time of repose is 10 ~ 20h.
The application of above-mentioned compound adsorbent PANI-CMC in dye wastewater treatment.
Compared with prior art, tool of the present invention has the following advantages:
1, catalystic converter system environmental protection, reaction condition is gentle.
2, compared with polyaniline, the product P ANI-CMC obtained not only has good absorption property for containing sulfonic anionic dye, also has good absorption property for the dye of positive ion.
3, product P ANI-CMC (pH=3 ~ 11) under wider pH condition has better adsorption effect simultaneously, and range of application is expanded.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of products obtained therefrom in embodiment 1, and A-D label is corresponding with each sample in embodiment 1.
Detailed description of the invention
The application utilizes imitative enzyme technology, with carboxymethyl cellulose and aniline monomer for raw material, prepare efficient, economic, eco-friendly composite PANI-CMC, and provide treatment process and the effect of dye wastewater, for dye wastewater treatment provides new technology and material.
Embodiment 1
In the citric acid-sodium citrate buffer system of 200mLpH=4.00, slowly add 0g, 0.200g, 0.500g and 0.800gCMC successively, after CMC is dispersed, respectively add the Hemin solution that 1mL is 10mg/L through the aniline of distillation purifying and 1mL concentration.Reaction system is placed in 25 DEG C, the shaking table of 150r/min reacts, and in system, add 0.2mL30%H every 15min
2o
2, add 7 times altogether.Etc. whole H
2o
2after adding, continue reaction 0.5h, in reaction system, then add the 37%HCl of 25mL, sealing leaves standstill 16h, makes to react completely after continuing reaction 0.5h.Centrifugally obtain solid product, and wash with deionized water and absolute ethyl alcohol, product is dried at 60 DEG C, grinds for subsequent use.
The product labelling obtained during different CMC consumption is designated as A, B, C and D respectively.Product quality is followed successively by 0.4123g, 0.8670g, 0.9469g and 1.0616g.
Result shows, when same aniline consumption, adds CMC and can prepare more product.
The ESEM of product as shown in Figure 1.
Embodiment 2
Be in the methyl orange solution of 20mg/L at 100mL initial concentration, add 50mg product A, B, C and D respectively, and in 25 DEG C, the shaking table of 150r/min carries out adsorption reaction, at regular intervals, get supernatant and measure its absorbance under 464nm, calculate the concentration of residual methyl orange.During result display absorption 10min, A, B, C and D are 62.29%, 74.20%, 83.52% and 70.42% to the clearance of methyl orange respectively; During absorption 30min, A, B, C and D clearance to methyl orange is respectively 74.4%, 86.08%, 90.96% and 82.14%; During absorption 60min, A, B, C and D clearance to methyl orange is respectively 85.56%, 90.67%, 93.29% and 86.46%.
Result shows, the product obtained after adding CMC is for the Dye Adsorption performance enhancement in waste water, and removal speed and clearance are all significantly increased.
Embodiment 3
The product A and the C that add 50mg in the methyl orange of 20mg/L, Coomassie brilliant blue, rhodamine and methyl blue solution is respectively at 100mL initial concentration, in 25 DEG C, the shaking table of 150r/min carries out adsorption reaction, after 30min, get supernatant, measure absorbance respectively under 464nm, 582nm, 552nm and 578nm, calculate residual each dye strength, calculate removal effect.
Experimental result shows, and product A (PANI) clearance to methyl orange, Coomassie brilliant blue, rhodamine and methyl blue is followed successively by 89.20%, 83.98%, 86.69% and 24.77%, shows the selective absorption to dyestuff.Products C (PANI-CMC) clearance to methyl orange, Coomassie brilliant blue, rhodamine and methyl blue is followed successively by 91.89%, 88.69%, 88.61% and 84.40%.
Embodiment 4
Be 20mg/L at 100mL initial concentration, initial pH is respectively in the methyl orange solution of 3,4,5,6,7,8,9,10,11 and 12, add the products C of 50mg respectively, in 25 DEG C, the shaking table of 150r/min carries out adsorption reaction, after 30min, gets supernatant, measure its absorbance, calculate the concentration of residual methyl orange.
After experimental result display 30min, products C (PANI-CMC) is the clearance of the methyl orange solution of 12 to initial pH is 20%, and can reach 85.97% (pH=5.00) ~ 91.09% (pH=6.00) to initial pH at the clearance of the methyl orange solution of 3 ~ 11.
Embodiment 5
Be 20mg/L at 100mL initial concentration, initial pH is respectively 3,4,5,6,7,8,9,10, in the rhodamine liquor of 11 and 12, add the products C of 50mg respectively, in 25 DEG C, the shaking table of 150r/min carries out adsorption reaction, after 30min, gets supernatant, measure its absorbance, calculate the concentration of residual rhodamine.
After experimental result display 30min, products C (PANI-CMC) is the clearance of the rhodamine liquor of 12 to initial pH is 77.17%, and can reach 88.63% (pH=3.00) ~ 93.92% (pH=11.00) to initial pH at the clearance of the rhodamine liquor of 3 ~ 11.
Claims (7)
1. a compound adsorbent PANI-CMC, is characterized in that, is prepared by following steps:
In buffer system, add aniline, X-factor and carboxymethyl cellulose, make it be uniformly dispersed; At room temperature, constantly stir, in system, add H every 15-20min
2o
2; Continue reaction more than 0.5h, in system, add hydrochloric acid, make reaction continue to react more than 30min in sealing situation, leave standstill, by water and ethanol washed product, and by product drying at not higher than 60 DEG C, after grinding, obtain powdery product.
2. compound adsorbent PANI-CMC as claimed in claim 1, it is characterized in that, buffer system is selected from the one in acetic acid-sodium acetate, citric acid-sodium citrate, and pH value range is 3 ~ 6.
3. compound adsorbent PANI-CMC as claimed in claim 1, it is characterized in that, the mass ratio of aniline, X-factor and carboxymethyl cellulose is 1:0.01:0.2 ~ 0.8.
4. compound adsorbent PANI-CMC as claimed in claim 1, is characterized in that, aniline, hydrochloric acid and H
2o
2mol ratio be 1:6 ~ 30:0.15 ~ 1.5.
5. compound adsorbent PANI-CMC as claimed in claim 1, it is characterized in that, time of repose is 10 ~ 20h.
6. the preparation method of the compound adsorbent PANI-CMC as described in as arbitrary in claim 1-5.
7. the application of compound adsorbent PANI-CMC in dye wastewater treatment as described in as arbitrary in claim 1-5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169717A (en) * | 2020-09-30 | 2021-01-05 | 深圳大学 | Microencapsulated hemin and preparation method and application thereof |
Citations (5)
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|---|---|---|---|---|
| CN102604084A (en) * | 2012-01-13 | 2012-07-25 | 上海师范大学 | Method for preparing water-soluble conducting polyaniline |
| CN103433484A (en) * | 2013-08-22 | 2013-12-11 | 福建医科大学 | Bovine serum albumin-platinum composite nanomaterial mimetic peroxidase |
| CN103613756A (en) * | 2013-11-08 | 2014-03-05 | 上海师范大学 | Method for preparing chiral polyaniline by protein induction |
| CN103936985A (en) * | 2014-04-29 | 2014-07-23 | 中国科学院长春应用化学研究所 | Preparation method and application of polyaniline nanoparticles |
| CN105170115A (en) * | 2015-08-20 | 2015-12-23 | 黑龙江大学 | Preparation method and applications of ternary polyaniline-titanium dioxide-hollow bead composite nano material |
-
2016
- 2016-01-29 CN CN201610067536.4A patent/CN105561953A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604084A (en) * | 2012-01-13 | 2012-07-25 | 上海师范大学 | Method for preparing water-soluble conducting polyaniline |
| CN103433484A (en) * | 2013-08-22 | 2013-12-11 | 福建医科大学 | Bovine serum albumin-platinum composite nanomaterial mimetic peroxidase |
| CN103613756A (en) * | 2013-11-08 | 2014-03-05 | 上海师范大学 | Method for preparing chiral polyaniline by protein induction |
| CN103936985A (en) * | 2014-04-29 | 2014-07-23 | 中国科学院长春应用化学研究所 | Preparation method and application of polyaniline nanoparticles |
| CN105170115A (en) * | 2015-08-20 | 2015-12-23 | 黑龙江大学 | Preparation method and applications of ternary polyaniline-titanium dioxide-hollow bead composite nano material |
Non-Patent Citations (1)
| Title |
|---|
| YING ZHAO，ET AL: "Hierarchical MWCNTs/Fe3O4/PANI magnetic composite as adsorbent for methyl orange removal", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169717A (en) * | 2020-09-30 | 2021-01-05 | 深圳大学 | Microencapsulated hemin and preparation method and application thereof |
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Application publication date: 20160511 |
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