CN111517325A - Preparation method and application of polydopamine modified biomass carbon material - Google Patents
Preparation method and application of polydopamine modified biomass carbon material Download PDFInfo
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- 229920001690 polydopamine Polymers 0.000 title claims abstract description 65
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 24
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 18
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 244000146553 Ceiba pentandra Species 0.000 claims abstract description 12
- 235000003301 Ceiba pentandra Nutrition 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000004043 dyeing Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 2
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- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
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- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 48
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 19
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229960003638 dopamine Drugs 0.000 abstract description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 2
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- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
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- 150000001721 carbon Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
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- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000003344 environmental pollutant Substances 0.000 description 2
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- 238000006386 neutralization reaction Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000332382 Ceiba Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
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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
- 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
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Abstract
The invention provides a preparation method and application of a polydopamine modified biomass carbon material, and belongs to the field of adsorption materials. The material is obtained by carrying out oxidative polymerization on an acid-treated biomass carbon material (coconut shell carbon or kapok fiber is taken as an example) and then dopamine serving as a precursor. The invention has the characteristics of simple preparation method and stable property; besides the porous structure of the biomass carbon material, the modified polydopamine endows the material with imino and phenolic hydroxyl adsorption groups; the adsorbent prepared by the invention has low operation cost for treating wastewater and is environment-friendly; the removal efficiency of methylene blue with the concentration of 20-400 ppm is as high as 99.15%, and the adsorbent achieves adsorption balance in a wider pH value range and a quicker adsorption time, so that the method can be widely applied to the printing and dyeing wastewater treatment industry.
Description
Technical Field
The invention belongs to a new material, relates to an adsorbent, and particularly relates to a preparation method and application of a polydopamine modified biomass carbon material.
Background
With the continuous development of the printing and dyeing industry, the type and the amount of dye pollution in the environment are continuously increased, the chemical structure of the dye pollution is increasingly complex, and the dye pollution causes great harm to the environment, particularly the water environment. Dye wastewater can affect the growth and reproduction of aquatic organism populations, cause ecological imbalance and further endanger human health. Most of the printing and dyeing wastewater is complex aromatic hydrocarbon compounds, has the characteristics of large sewage quantity, deep chroma, complex components, difficult degradation, strong toxicity and the like, and is difficult to treat.
At present, the treatment methods of dye wastewater mainly comprise adsorption, chemical precipitation, membrane separation, biological methods and the like. The adsorption method is a widely used method for removing pollutants difficult to degrade in water, and has the advantages of large treatment capacity, short time and no secondary pollution. The adsorption method has the advantages of simple operation, low investment cost, good removal effect on various dyes and the like, and is widely applied to dye wastewater treatment. The selection of the adsorbent plays an important role in treating the dye wastewater by an adsorption method.
The adsorption method is an important method for treating pollutants in printing and dyeing wastewater, and the activated carbon and the carbon nano tube are the most widely used adsorbents at present, but the price and the operation cost of the activated carbon are relatively high, and the regeneration is difficult, so that the large-scale application of the activated carbon in the dye wastewater is hindered.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a preparation method of a polydopamine modified biomass carbon material, which utilizes a cheap and easily available biomass carbon material as a carbon source, and the polydopamine modification is carried out, so that the porous structure of the biomass carbon material is maintained, more chemical adsorption sites are provided for the carbon material, and the purposes of reducing cost and efficiently adsorbing are achieved.
The technical scheme adopted by the invention is as follows: a preparation method of a polydopamine modified biomass carbon material specifically comprises the following steps:
s1, placing the crushed biomass carbon material in concentrated sulfuric acid, and stirring to fully carbonize the biomass carbon material;
s2, washing to be neutral, filtering, and drying at 70-90 ℃ to obtain acidified biomass carbon;
and S3, adding the trihydroxymethyl aminomethane into distilled water, adjusting the pH value to 8.5, adding dopamine hydrochloride and acidified biomass carbon in a mass ratio of 3:5, and stirring at room temperature for more than 6-48h to obtain the polydopamine modified biomass carbon material.
The biomass carbon material is coconut shell, corn straw, rape straw or kapok fiber.
Preferably, the mass ratio of the tris (hydroxymethyl) aminomethane to the distilled water is 0.12: 100, and adding dopamine hydrochloride according to the mass ratio of 1:0.8 to the trihydroxymethyl aminomethane.
Preferably, in S3, the pH is adjusted by using a 1 mol/L NaOH solution.
Preferably, in S3, the reaction is stirred at room temperature for 24 hours.
Preferably, in S3, drying is carried out in an oven at 80 ℃.
The invention relates to an application of a polydopamine modified biomass carbon material in treatment of printing and dyeing wastewater.
The structural characterization and performance of the polydopamine modified biomass carbon material of the invention were tested as follows:
(1) and (3) testing the micro-morphology of the coconut shell carbon material before and after poly-dopamine modification:
FIG. 1 is a scanning electron micrograph of a coconut shell carbon material before and after modification with polydopamine, wherein a large number of pore structures appear after the coconut shell carbon is etched by concentrated sulfuric acid (FIG. 1 a). Uneven on the outer surface, a fish-scale-like appearance appears. Acidification is often used to build micro/nano hierarchical structures and, at the same time, facilitates the further modification of the material surface. The activation of the acid serves two purposes: firstly, concentrated sulfuric acid is dispersed in a biomass carbon precursor and is immersed into the biomass carbon precursor, and sulfuric acid is washed out after activation, so that gaps are left in activated carbon; secondly, the biomass carbon material is made into small molecules by the catalytic decomposition of sulfuric acid, and then a gas escape reaction system is formed in the sulfuric acid solution along with the processes of continuous stirring and diluted heat release, so that pores are left in the carbon.
As can be seen from the scanning electron micrograph of the surface of the polydopamine modified carbon material (fig. 1 b), the coated surface has a loose porous structure. After the polydopamine modification, the porous structure of the original biomass carbon material can be kept, and more chemical adsorption sites are endowed to the carbon material.
(2) The infrared spectrogram analysis of the polydopamine-coated coconut shell carbon material comprises the following steps:
FIG. 2 is an infrared spectrum of a polydopamine-coated coconut shell carbon material, wherein 3420 cm is observed from the infrared spectrum-1The strong absorption peak is a stretching vibration absorption peak of phenolic hydroxyl functional groups in catechol formed after the polydopamine coats the surface of the biomass carbon material. 1609 cm-1And 1509 cm-1The absorption peaks appeared at the position are respectively the stretching vibration peak of C = C and the shearing vibration of N-H bond in the polydopamine aromatic ring. The infrared spectrogram proves that the polydopamine successfully coats the acidified coconut shell carbon surface, and lays a foundation for the next adsorption research.
(3) Adsorption experiments of polydopamine coated carbon materials on methylene blue solutions with different concentrations:
as can be seen from FIG. 3, the methylene blue dye is highly colored, and even if only 10 mg of water (FIG. 3a, first reagent bottle from the right) in 1 liter of water can dye the water blue, the solution becomes poor in transmittance as the concentration increases. After the adsorption experiment of the polydopamine-coated coconut shell carbon material on dyes with different concentrations, the adsorbent is found to have higher removal efficiency on the low-concentration dye with the concentration of 10-100 ppm, the aqueous solution becomes colorless and transparent, and the particles of the modified carbon material can be seen to be dispersed in the supernatant and precipitated at the bottom of a reagent bottle. In the color comparison before and after the adsorption of the methylene blue solution with the concentration of 200-400 ppm, the polydopamine coated carbon material has very excellent adsorption effect. When the concentration reached a maximum of 500 ppm, the removal effect was not satisfactory.
(4) The removal efficiency of the polydopamine coated carbon material on dyes with different concentrations is as follows:
and measuring the absorbance values before and after adsorption by using an ultraviolet-visible spectrophotometer to quantitatively analyze the removal efficiency of the polydopamine-coated coconut shell carbon material on dyes with different concentrations. As can be seen from FIG. 4, the removal efficiency reached 100% when the concentration of the methylene blue solution was 100 ppm. The removal efficiency still remains at a high value when the concentration of the methylene blue solution is between 100 and 400 ppm. At a concentration of 400 ppm, the removal efficiency was still as high as 99.15%. However, when the concentration value was 500 ppm, the removal efficiency dropped to 93.01%. The excellent removal efficiency is attributed to the combined effect of the micro-nano-scale hierarchical structure of the polydopamine coated carbon material and the poly-functional group modified by polydopamine.
Phenolic hydroxyl, amino and aromatic ring structures are introduced after the poly-dopamine is modified, so that the poly-dopamine coats the carbon material and methylene blue dye moleculesπ-πBonds, hydrogen bonds and electrostatic interactions. The bonding mode of the chemical bond obviously improves the bonding degree of dye molecules in the wastewater and the carbon material. The adsorption process can be carried out at a pH of 4-12, and the adsorption effect is good. Adsorption equilibrium was reached within 5 minutes. This paves the way for the use of adsorbents in practically complex environments.
(5) The water dispersibility of the polydopamine-coated kapok fiber carbon material and the adsorption processes of different dyes are compared as follows:
FIG. 5 is a photograph showing the comparison of water dispersibility of polydopamine-coated kapok fiber carbon material and adsorption process of different dyes, before adsorption, after adsorption and neutralization of 100ppm Congo red and methylene blue, wherein columns 1 and 2 are Congo red dye, columns 3 and 4 are methylene blue dye, and the middle two columns are experimental groups, and as can be seen from the comparison photograph before adsorption, after adsorption and neutralization, the polydopamine-coated carbon material can be uniformly dispersed in the aqueous solution of the two dyes, thereby providing guarantee for the next adsorption process (the first line in FIG. 5). When the carbon material was placed (second row of fig. 5), the bottom of the vial containing 100ppm methylene blue dye became clear and transparent, and due to the light weight of kapok fiber, the coated carbon material floated on top of the dye solution with no significant change in the bottom of the vial containing 100ppm congo red dye. The carbon material shows different adsorption effects on the two dyes, and the adsorption effect is based on polydopamine modified kapok fiberZetaThe potential was-41.4/mV, indicating anionic properties. Congo red dye is an anionic dye and methylene blue is a cationic dye. Besides the function of chemical bonds, the dye adsorption process also has the electrostatic function of anions and cations.
Therefore, the polydopamine modified kapok fiber shows excellent selective adsorption to the cationic dye methylene blue. After adsorption balance is achieved, supernatant liquid is respectively transferred, the concentration of Congo red is basically unchanged, methylene blue dye becomes colorless and transparent after the polydopamine modified carbon material is adsorbed, and the coated ceiba fiber can be seen to be dispersed in the supernatant liquid. The experimental process shows that the carbon material coated with polydopamine shows excellent adsorption performance on methylene blue dye.
In conclusion, the polydopamine-coated carbon material prepared by the invention endows the coating material with a more ideal three-dimensional pore structure and abundant chemical bonding sites, and realizes the application in printing and dyeing wastewater treatment.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is obtained by using acid to treat biomass carbon materials (coconut shell carbon and kapok fiber) and then using dopamine as a precursor to carry out oxidative polymerization; has the advantages of simple preparation method, cheap and easily obtained raw materials and the like; in the material obtained by the invention, besides the porous structure of the biomass carbon material, the polydopamine modified material is endowed with imino and phenolic hydroxyl adsorption groups, so that the adsorption effect is greatly improved, and the rapid and efficient adsorption of wastewater in a large concentration range is realized.
2. The invention utilizes the simple acid treatment and the adsorbent prepared by coating the biomass carbon with dopamine autoxidation, and the operation cost for treating the wastewater is low and the invention is environment-friendly; the removal efficiency of methylene blue with the concentration of 20-400 ppm is as high as 99.15%, and the adsorbent achieves adsorption balance in a wider pH value range and a quicker adsorption time, so that the method can be widely applied to the printing and dyeing wastewater treatment industry.
Drawings
FIG. 1 is a scanning electron microscope image of coconut shell carbon material before and after polydopamine modification;
FIG. 2 is an infrared spectrum of a carbon material of coconut shell coated with polydopamine;
FIG. 3 is a comparison graph of poly-dopamine coated coconut shell carbon material before and after adsorption on methylene blue solutions of different concentrations;
FIG. 4 is a graph of the removal efficiency of polydopamine coated carbon material for different concentrations of dye;
FIG. 5 is a comparison graph of the dispersibility of polydopamine coated kapok fiber carbon material in water and adsorption effects of polydopamine coated kapok fiber carbon material on different dyes.
Detailed Description
The preparation of the polydopamine-coated biomass carbon material of the invention is further explained by the following specific examples;
example 1
A preparation method of a polydopamine modified biomass carbon material comprises the steps of putting 1 g of crushed coconut shell carbon into 1 mL of concentrated sulfuric acid, stirring for 0.5 hour, and uniformly mixing and fully carbonizing. Washing to neutrality, filtering, and drying in an oven at 80 ℃ to obtain the acidified biomass carbon. Adding 0.24 g of tris (hydroxymethyl) aminomethane into 200 g of distilled water, adjusting the pH value to 8.5 by using 1 mol/L NaOH solution, adding 0.3 g of dopamine hydrochloride and 0.5 g of acidified biomass carbon, stirring at room temperature for reacting for 6 hours, and drying in an oven at 80 ℃ to obtain the polydopamine modified biomass carbon material. The polydopamine solution is light brown, and the autoxidation reaction is not completely carried out.
For cationic dye methylene blue adsorption experiments:
50 mg of the polydopamine modified biomass carbon material obtained in the previous step is put into 10 mL of 400 ppm methylene solution, stirred at 150 rpm for 30 minutes at room temperature, centrifuged at 3000 rpm, supernatant is removed, absorbance value is measured, and removal efficiency is calculated to be only 50.5%. The coated carbon material is agglomerated in dye aqueous solution, so that the dispersibility is poor and the adsorption effect is poor.
Example 2
A preparation method of a polydopamine modified biomass carbon material comprises the steps of putting 1 g of crushed coconut shell carbon into 1 mL of concentrated sulfuric acid, stirring for 0.5 hour, uniformly mixing and fully carbonizing. Washing to neutrality, filtering, and drying in an oven at 80 ℃ to obtain the acidified biomass carbon. 0.24 g of tris (hydroxymethyl) aminomethane is added into 200 g of distilled water, 0.3 g of dopamine hydrochloride and 0.5 g of acidified biomass carbon are added when the pH value is adjusted to 8.5 by using 1 mol/L NaOH solution, and the mixture is stirred and reacted for 24 hours at room temperature to obtain the polydopamine modified carbon material. And drying in an oven at 80 ℃ to obtain the polydopamine modified biomass carbon material. The polydopamine solution changes from light brown to black, and the autoxidation reaction is completely carried out.
For cationic dye methylene blue adsorption experiments:
50 mg of the polydopamine modified biomass carbon material obtained above is put into 10 mL of 400 ppm methylene solution, stirred at 150 rpm for 30 minutes at room temperature, centrifuged at 3000 rpm, and the supernatant is removed to measure the absorbance value, and the removal efficiency is calculated to be 99.15%. The coated carbon material has good dispersibility in dye aqueous solution and good adsorption effect.
Example 3
A preparation method of a polydopamine modified biomass carbon material comprises the steps of putting 1 g of crushed biomass carbon material (coconut shell carbon or kapok fiber) into 1 mL of concentrated sulfuric acid, stirring for 0.5 hour, uniformly mixing and fully carbonizing. Washing to neutrality, filtering, and drying in an oven at 80 ℃ to obtain the acidified biomass carbon. 0.24 g of tris (hydroxymethyl) aminomethane is added into 200 g of distilled water, 0.3 g of dopamine hydrochloride and 0.5 g of acidified biomass carbon are added when the pH value is adjusted to 8.5 by using 1 mol/L NaOH solution, and the mixture is stirred and reacted for 48 hours at room temperature to obtain the polydopamine modified carbon material. And drying in an oven at 80 ℃ to obtain the polydopamine modified biomass carbon material. The polydopamine solution changes from light brown to black, and the autoxidation reaction is completely carried out.
For cationic dye methylene blue adsorption experiments:
50 mg of the polydopamine modified biomass carbon material obtained above is put into 10 mL of 400 ppm methylene solution, stirred at 150 rpm for 30 minutes at room temperature, centrifuged at 3000 rpm, supernatant is removed, absorbance value is measured, and removal efficiency is calculated to be 70.23%. The coated carbon material has good dispersibility in a dye aqueous solution, but the thickness of the coating layer is thickened along with the prolonging of the reaction time of the polydopamine, the three-dimensional pore structure of the carbon material is damaged, and in the adsorption process, the carbon material has no physical adsorption effect of pores, only has chemical bonding and electrostatic effect, and has no advantages of being used as a substrate carbon material, so that the adsorption effect is not ideal, and the removal efficiency is poor.
Claims (7)
1. A preparation method of a polydopamine modified biomass carbon material is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, placing the crushed biomass carbon material in concentrated sulfuric acid, and stirring to fully carbonize the biomass carbon material;
s2, washing to be neutral, filtering, and drying at 70-90 ℃ to obtain acidified biomass carbon;
and S3, adding the trihydroxymethyl aminomethane into distilled water, adjusting the pH value to 8.5, adding dopamine hydrochloride and acidified biomass carbon in a mass ratio of 3:5, and stirring at room temperature for more than 6-48h to obtain the polydopamine modified biomass carbon material.
2. The preparation method of polydopamine modified biomass carbon material according to claim 1
The method is characterized in that: the biomass carbon material is coconut shell, corn straw, rape straw or kapok fiber.
3. Preparation of polydopamine-modified biomass carbon material according to claim 1 or 2
The method is characterized in that: in S3, the mass ratio of the trihydroxymethyl aminomethane to the distilled water is 0.12: 100, and adding dopamine hydrochloride according to the mass ratio of 1:0.8 to the trihydroxymethyl aminomethane.
4. The preparation method of polydopamine modified biomass carbon material according to claim 3
The method is characterized in that: in S3, the pH was adjusted with a 1 mol/L NaOH solution.
5. The method for preparing polydopamine-modified biomass carbon material according to claim 1, 2 or 4, wherein: in S3, the reaction was stirred at room temperature for 24 hours.
6. The method for preparing the polydopamine-modified biomass carbon material as claimed in claim 5, wherein: and S3, drying at 80 ℃ by using an oven.
7. Use of a polydopamine modified biomass carbon material prepared according to the method of claim 1, 2, 4 or 6 for treating printing and dyeing wastewater.
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