CN110538639A - Preparation and application of high-purity magnetic peanut shell biomass adsorbing material - Google Patents
Preparation and application of high-purity magnetic peanut shell biomass adsorbing material Download PDFInfo
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- CN110538639A CN110538639A CN201910907191.2A CN201910907191A CN110538639A CN 110538639 A CN110538639 A CN 110538639A CN 201910907191 A CN201910907191 A CN 201910907191A CN 110538639 A CN110538639 A CN 110538639A
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/40—Organic compounds containing sulfur
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method and application of a high-purity magnetic peanut shell biomass adsorbing material. The adsorbent takes crushed and sieved peanut shells as raw materials, soluble ferric salt and ferrous salt such as FeSO4.7H2O, Fe2(SO4)3 and the like are introduced to provide Fe2+ and Fe3+, the peanut shells and the salt solution are separated after being fully mixed in ultrasonic, a solid part is directly added into ammonia water for ultrasonic reaction, and magnetic nano ferrite can be loaded on the peanut shells through washing and drying, SO that the peanut shells are converted into a biomass adsorbing material with magnetism and excellent adsorption performance, and the biomass adsorbing material is applied to adsorption treatment of methylene blue dye wastewater. The biomass magnetic adsorbent prepared by the method has the characteristics of high purity and high reagent utilization rate, effectively reduces the generation of non-loaded magnetic ferrite, has larger unit adsorption amount to methylene blue and higher adsorption efficiency, and can be separated from a polluted water body more easily.
Description
Technical Field
The invention relates to the technical field of preparation and application of biomass-based magnetic adsorbents made of agricultural and forestry wastes, in particular to preparation and application of a high-purity magnetic peanut shell biomass adsorbing material.
Background
In the current social production process, organic synthetic dyes are widely applied to various industries such as textile, dyeing, paper making and the like, according to relevant statistical data, the industries produce about 10 ten thousand tons of dyes every year, more than 10% of the dyes are discharged into the natural environment, and the serious environmental pollution problem is caused. The dye wastewater has the characteristics of complex components, high chromaticity, poor biodegradability, high chemical stability and the like, so that the removal of organic pollutants in the dye wastewater becomes a worldwide problem. The common treatment methods of the dye wastewater comprise a flocculation precipitation method, a chemical oxidation method, an advanced oxidation method, a biological method, an adsorption method and the like, wherein the adsorption method is an ideal treatment technology due to simplicity, practicability, good purification performance and the like. Meanwhile, in order to improve the feasibility of the adsorption technology applied to dye wastewater treatment on a large scale, a trend is formed for biomass materials with the advantages of low cost, rich content, reproducibility and the like to be used as adsorbent precursors.
China is a big agricultural country, the crop yield is huge, and a large amount of agricultural and forestry waste is generated. The agricultural and forestry waste (peanut shells, rice husks, straws, corncobs and the like) contains a large number of functional groups (-COOH, -NH2, -OH, -SH, -OCH 3) in cellulose, lignin and other components, and can adsorb pollutants through electrostatic adsorption and chemical bond action, and meanwhile, the agricultural and forestry waste has the characteristics of rough surface structure, looseness, porosity, large specific surface area, high porosity, good hydrophilicity and the like, so the agricultural and forestry waste can be used as a good water treatment material.
In recent years, partial research focuses on the development and application of magnetic adsorbents, namely, magnetic substances are loaded on adsorption materials to enable the adsorbents to show corresponding magnetism, so that a magnetic separation technology is applied to separation and recovery of saturated adsorbents in liquid-phase pollutants after adsorption is completed, long-time filtration or centrifugal operation is omitted, and the magnetic adsorbent has the advantages of high treatment and separation speed, high efficiency, simplicity and convenience in equipment operation, low construction and maintenance cost and the like. The commonly used magnetic substances are metallic simple substances, alloys or compounds such as Fe, Ni, Pd and the like, wherein the magnetic ferrite is the most simple, easily obtained and stable paramagnetic material.
CN105642241A discloses a magnetic biomass-based adsorbing material for removing harmful anions in water, firstly, biomass material powder is required to be fully mixed with Fe3+ and Fe2+ solutions to expose nitrogen, then alkali liquor is added into the mixed solution to cause coprecipitation reaction, so as to prepare a magnetic biomass adsorbent, and the process has a large amount of free Fe3+ and Fe2+ in the mixed solution, so that a large amount of non-loaded magnetic ferrite is also generated in the process of generating the loaded magnetic biomass adsorbent.
Disclosure of Invention
The magnetic biomass adsorbing material takes peanut shells as raw materials, soluble ferric salt and ferrous salt are introduced to provide Fe2+ and Fe3+, the peanut shells are separated after being fully soaked in a Fe3 +/Fe 2+ mixed salt solution, and a solid part is directly added into ammonia water for mixing reaction.
The present invention adopts the following technical means to achieve the above object.
1. The preparation method of the high-purity peanut shell magnetic adsorption material comprises the following steps: (1) treating peanut shells: repeatedly washing peanut shells with deionized water for 2-3 times, drying at 100-120 ℃ for 12 h to constant weight, crushing with a crusher, sieving to obtain peanut shell powder with the particle size of 30-40 meshes, sealing, drying and storing for later use; (2) preparing a certain amount of FeSO4.7H2O, Fe2(SO4)3 and deionized water into a Fe3 +/Fe 2+ mixed salt solution, fully aerating nitrogen to remove dissolved oxygen in the deionized water before using, adding a certain amount of the peanut shell powder obtained in the step (1) into the mixed solution, carrying out ultrasonic impregnation for 30min until the mixture is uniformly mixed, and starting timing after the peanut shell powder is fully soaked; (3) after the ultrasonic treatment, rapidly performing suction filtration on the suspension, recovering filtrate, quickly putting filter residues (peanut shell powder) into ammonia water, stirring and performing ultrasonic treatment, separating solid from liquid by using a magnet after the ultrasonic treatment is finished, pouring and recovering concentrated ammonia water, and repeatedly washing solid particles with deionized water until the pH value is neutral; (4) and drying the solid particles in an oven after washing to obtain the high-purity peanut shell magnetic adsorption material with clear particles.
The amount ratio of the Fe2+ and Fe3+ substances added in the step (2) is 1:1, and the concentrations of Fe2+ and Fe3+ are 0.4-0.65 mol/L.
The deionized water is preferably exposed to nitrogen for more than 15min in the step (2).
The ratio of the added peanut shells to the Fe2 +/Fe 3+ mixed solution in the step (2) is not more than 6g/100 mL.
And (4) putting the filter residue into ammonia water in the step (3), and then carrying out ultrasonic treatment for 60 min.
The concentration of the ammonia water in the step (3) is 25-28%.
In the step (4), the temperature of the oven needs to be kept at 50-70 ℃, and the drying time is 4-6 h.
2. The high-purity magnetic peanut shell adsorbing material is applied to the purification of methylene blue dye wastewater: adding 1g of prepared high-purity peanut shell magnetic adsorbing material into 100mL of methylene blue solution with the concentration of 100mg/L, putting the peanut shell magnetic adsorbing material into a constant-temperature water bath oscillator, continuously oscillating for 30min at the temperature of 30-40 ℃, wherein the removal rate can reach 97.8%, and finally, under the action of a magnetic field, the treated methylene blue solution is easy to separate from solid particles.
The invention has the beneficial effects that: compared with the traditional coprecipitation preparation method of dripping alkali liquor, the peanut shell magnetic adsorption material prepared by the method has higher purity of a target product, effectively avoids the generation of a large amount of non-loaded magnetic ferrite, and can recycle high-concentration alkali liquor ammonia water, thereby reducing the consumption of medicine reagents and greatly reducing the manufacturing cost; meanwhile, the peanut shell magnetic adsorbent with higher purity is used, so that the unit adsorption capacity of the peanut shell is increased, and the adsorption effect is further improved.
Detailed Description
The invention relates to a preparation and application of a high-purity peanut shell biomass magnetic adsorption material, which comprises the following steps: repeatedly washing peanut shells with deionized water for 2-3 times, drying at 100-120 ℃ for 12 hours, crushing with a crusher, sieving to obtain peanut shell powder with the particle size of 30-40 meshes, sealing, drying and storing for later use; preparing a certain amount of mixed solution of Fe2+ and Fe3+ by taking 26.00 g of FeSO4.7H2O and 18.07 g of Fe2(SO4)3 and 100mL of deionized water, wherein the deionized water used in the invention is aerated with nitrogen for 15min before use, then 5g of sieved peanut shell powder is added into the mixed solution, and the ultrasonic treatment is carried out for 30min, and timing is started after the peanut shell powder is fully soaked; after ultrasonic treatment, rapidly performing suction filtration on the suspension, recovering filtrate, quickly putting filter residues (peanut shell powder) into ammonia water (the concentration is 25-28%, the pH value is approximately equal to 11), performing ultrasonic treatment for 60min while stirring, separating solid from liquid by using a magnet after the ultrasonic treatment is finished, pouring and recovering concentrated ammonia water, and repeatedly washing solid particles with deionized water until the pH value is neutral; and drying the solid particles in a drying oven at 50-70 ℃ after washing to obtain the high-purity peanut shell magnetic adsorbing material with clear particles. Then 1.0g of the magnetic peanut shell is accurately weighed and put into 100mL of methylene blue solution with the concentration of 100mg/L, the temperature is adjusted to 30 ℃ in a constant-temperature water bath oscillator for oscillating back and forth, and then the concentration of the methylene blue in the residual liquid is measured, so that the removal rate can be calculated. Experiments show that the removal rates of 5min, 10min, 20min, 30min, 40min and 60min in water bath oscillation respectively reach 88.9%, 95.1%, 96.5%, 97.8%, 97.6% and 98.2%, solid-liquid separation is obvious under the action of an external magnetic field, but the removal rate of methylene blue only reaches 84.3% after a single peanut shell without a magnetic material is oscillated in water bath for 60 min.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned embodiments, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The high-purity magnetic peanut shell biomass adsorbing material is characterized by being clear in particle size and high in purity, and no non-loaded magnetic ferrite is generated in the preparation process.
2. The preparation method of the high-purity magnetic peanut shell biomass adsorbing material as claimed in claim 1, which is characterized by comprising the following steps: step 1, crushing clean peanut shell to 30-40 meshes, and drying for later use; step 2, preparing a certain amount of FeSO4.7H2O, Fe2(SO4)3 and deionized water fully aerated with nitrogen into Fe3 +/Fe 2+ mixed salt solution, adding a certain amount of peanut shell powder obtained in the step 1 into the mixed solution, and carrying out ultrasonic dipping until the mixture is uniformly mixed; step 3, after ultrasonic treatment, rapidly performing suction filtration on the suspension, quickly putting filter residues (peanut shell powder) into ammonia water, stirring and performing ultrasonic treatment, separating solid from liquid by using a magnet after the ultrasonic treatment is finished, pouring and recovering concentrated ammonia water, and repeatedly washing solid particles with deionized water until the pH value is neutral; and 4, drying the solid particles in an oven after washing to obtain the high-purity peanut shell magnetic adsorption material with clear particles.
3. The preparation method of the high-purity magnetic peanut shell biomass adsorbing material as claimed in claim 2, wherein the amount ratio of Fe2+ to Fe3+ added in the step 2 is 1:1, and the concentrations of Fe2+ and Fe3+ are 0.4 mol/L-0.65 mol/L.
4. The method for preparing the high-purity magnetic peanut shell biomass adsorbing material as claimed in claim 2, wherein the ratio of the peanut shells added in the step 2 to the Fe2 +/Fe 3+ mixed solution is not more than 6g/100 mL.
5. The preparation method of the high-purity magnetic peanut shell biomass adsorbing material as claimed in claim 2, wherein the ultrasonic treatment time of the filter residue in the step 3 after being put into the ammonia water is 60min, and the concentration of the ammonia water is 25% -28%.
6. The application of the high-purity magnetic peanut shell biomass adsorbing material based on the claim 1 in organic dye wastewater treatment.
7. The use of claim 6, wherein the wastewater is methylene blue solution with an initial concentration of 100-800 mg/L.
8. The use of claim 6, wherein the high purity magnetic peanut shell biomass adsorbent material is added to the methylene blue solution in a ratio of 1g to 100 mL.
9. Use according to claim 6, wherein the adsorption is carried out at a temperature of 30-40 ℃ for a period of 30 min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101642699A (en) * | 2009-08-06 | 2010-02-10 | 浙江大学 | Method for preparing magnetic biological carbon adsorbing material and usage thereof |
| CN102266750A (en) * | 2011-08-01 | 2011-12-07 | 武汉工程大学 | In situ preparation method of magnetic bio-absorbent |
| CN104014317A (en) * | 2014-06-19 | 2014-09-03 | 山东大学 | Preparation and application of modified magnetic straw anion adsorbent |
| CN105642241A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院理化技术研究所 | A biomass-based adsorption material used for removing harmful anions from water and a preparing method thereof |
| WO2016172755A1 (en) * | 2015-04-28 | 2016-11-03 | Monash University | Non-covalent magnetic graphene oxide composite material and method of production thereof |
| CN109046247A (en) * | 2018-09-08 | 2018-12-21 | 重庆大学 | Strengthen the modification biological charcoal and preparation method thereof of absorption organic dyestuff |
| CN109499538A (en) * | 2018-12-28 | 2019-03-22 | 天津大学 | A kind of iron modified peanut magnetic bio charcoal and its preparation method and application |
-
2019
- 2019-09-24 CN CN201910907191.2A patent/CN110538639A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101642699A (en) * | 2009-08-06 | 2010-02-10 | 浙江大学 | Method for preparing magnetic biological carbon adsorbing material and usage thereof |
| CN102266750A (en) * | 2011-08-01 | 2011-12-07 | 武汉工程大学 | In situ preparation method of magnetic bio-absorbent |
| CN104014317A (en) * | 2014-06-19 | 2014-09-03 | 山东大学 | Preparation and application of modified magnetic straw anion adsorbent |
| CN105642241A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院理化技术研究所 | A biomass-based adsorption material used for removing harmful anions from water and a preparing method thereof |
| WO2016172755A1 (en) * | 2015-04-28 | 2016-11-03 | Monash University | Non-covalent magnetic graphene oxide composite material and method of production thereof |
| CN109046247A (en) * | 2018-09-08 | 2018-12-21 | 重庆大学 | Strengthen the modification biological charcoal and preparation method thereof of absorption organic dyestuff |
| CN109499538A (en) * | 2018-12-28 | 2019-03-22 | 天津大学 | A kind of iron modified peanut magnetic bio charcoal and its preparation method and application |
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Application publication date: 20191206 |