CN106000340A - Preparation method of manganese dioxide cellulose nanofiber mixed compound - Google Patents
Preparation method of manganese dioxide cellulose nanofiber mixed compound Download PDFInfo
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- CN106000340A CN106000340A CN201610420938.8A CN201610420938A CN106000340A CN 106000340 A CN106000340 A CN 106000340A CN 201610420938 A CN201610420938 A CN 201610420938A CN 106000340 A CN106000340 A CN 106000340A
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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
- B01J20/02—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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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a material preparation method, in particular to a preparation method of a manganese dioxide cellulose nanofiber mixed compound. Cellulose is prepared into cellulose suspension, ultrasound is conducted for one hour at the power of 1,000 w through an ultrasonic cell crushing instrument, and cellulose nanofibers are prepared; 10 mmol of alkaline potassium permanganate is dissolved in 100 mL of water, and 300 mL of the cellulose nanofibers with the concentration being 1 wt% is added to the mixture; stirring is conducted for eight hours at the room temperature, washing is conducted to remove impurities, and the mixture is concentrated into pulp. According to the method, the raw material cellulose is wide in source and is green and sustainable resources, manganese dioxide grows on the nano-crystalline cellulose fibers in an in-situ mode, a reducing agent does not need to be added, synthesis cost is low, and the process is simple. Adsorption of the manganese dioxide/cellulose nanofiber mixed compound to methylthionine chloride and conversion of oxidation and decoloration can be achieved by adjusting the pH, decoloration efficiency of the prepared manganese dioxide/cellulose nanofiber mixed compound on the methylthionine chloride is high, and consumption of a decolorising agent is small. The manganese dioxide cellulose nanofiber mixed compound has good application prospect on the aspects of industrial wastewater treatment and environmental repair.
Description
Technical field
The present invention relates to material preparation method, specially manganese dioxide cellulose nano-fibrous hybrid preparation method.
Technical background
It is reported, annual produced worldwide nearly 7 × 105Ton dyestuff.Because of some dyestuffs have that colourity is high, concentration big, the feature such as strong toxicity, difficult degradation, water quality and quantity fluctuation are big and unstable, cause dye wastewater treatment difficulty big.And the discharge beyond standards of waste water from dyestuff not only causes serious environmental pollution, and health even life security is constituted a threat to.Therefore, how carry out efficient removal processing to Wastewater Dyes is a problem demanding prompt solution.Although flocculation, filtering, the removal of the various dyestuff such as Electrochemical adsorption and photooxidation has either physically or chemically obtained widely studied.But, a kind of low energy consumption, the ionic dye decoloring material of low cost still remains a stern challenge for environment remediation.Recently, nanosecond science and technology show that a lot of water treatment problems can pass through nano adsorber, nanocatalyst, and biological nanoparticle or nano-structure film etc. are improved.Wherein, nano-manganese dioxide, as the adsorbent of organic pollution and catalyst, can adsorb catalysis oxidation organic dyestuff then at a lower temperature.
Decolouring for methylene blue plasma dyestuff is removed, and nano-manganese dioxide can play many effects: (i) is as catalyst hydrogen peroxide, the antioxidant dye such as oxygen or TBHP；(ii) physical absorption；(iii) manganese dioxide self is directly as oxidizing dyestuff.But, the manganese dioxide of major part synthesis is powder, this strongly limits its application in engineering: (i) is difficult to solid-liquid separation；(ii) it is difficult to reclaim decoloring material；(iii) easily reuniting thus reduce the contact area of dyestuff and decolorising agent, decolorizing efficiency reduces.
The gathering of nanoparticle and dust pollution can be avoided by being fixed on by nanoparticle on other matrixes.Cellulose, as one of most important natural macromolecular material, is close to inexhaustible, is the important sustainable resource in commercial production.Cellulose nano-fibrous due to its special nano-scale structure and rheologic behavio(u)r, (aeroge is 400-500m to high specific surface area2·L-1), low-density (0.004g cm-3), excellent mechanical performance and optical property, the feature such as environmental friendliness, it is widely used and makees carrier material.
Therefore, use cellulose nano-fibrous network structure for supporting, by the longest for sheet manganese dioxide on cellulose nano-fibrous surface, while avoiding dust pollution question, also achieving the higher value application of cellulose resource, the ionic dye Quick Oxidation in waste water can be made to fade for synthesized hybrid material and absorption is faded.
Summary of the invention
It is an object of the invention to realize the high-valued application of nano-cellulose, a kind of manganese dioxide/cellulose nano-fibrous hybrid of synthesis, energy-efficient solution ionic dye purification of waste water problem.
The purpose of the present invention is realized by techniques below measure.
Manganese dioxide cellulose nano-fibrous hybrid preparation method, comprises the following steps:
(1) preparation of nano-cellulose
Cellulose preparation cellulose suspension, with ultrasonic cell disrupte instrument with the ultrasonic 1h of 1000w, is prepared as cellulose nano-fibrous；
(2) preparation of manganese dioxide/cellulose nano-fibrous hybrid
Potassium permanganate: the mol ratio of alkali=1:1 prepares alkalinity potassium permanganate, and 10mmol alkalinity potassium permanganate is dissolved in 100mL water, is added thereto to the cellulose nano-fibrous of 300mL 1wt%；8h, ion are stirred at room temperature, concentrate pulping.
Described cellulose origin is waste cotton fiber, bamboo pulp, wood pulp, cardboard, filter paper.
Described alkali is the one of sodium hydroxide, potassium hydroxide.
The manganese dioxide cellulose nano-fibrous hybrid preparation method that the present invention provides, raw cellulose wide material sources, are green sustainable resources, use manganese dioxide the longest on nano-cellulose fiber, need not add reducing agent again, synthesize low cost, and process is simple.Can realize the absorption to methylene blue of the manganese dioxide/cellulose nano-fibrous hybrid and the conversion of oxidative decoloration by regulation pH, the manganese dioxide prepared/cellulose nano-fibrous hybrid is high to the decolorizing efficiency of methylene blue, and decolorising agent usage amount is little.In Industrial Wastewater Treatment, environment remediation aspect has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment intermediate product and end product thereof；
Fig. 2 is the transmission electron microscope view of embodiment intermediate product and end product thereof；
Fig. 3 is that embodiment product is to the ultra-violet absorption spectrum of different time under the adsorption bleaching effect-room temperature of methylene blue.
Detailed description of the invention
Below by example, the present invention is specifically described; be necessary it is pointed out here that be that following example are served only for being further described the present invention; it is not intended that limiting the scope of the invention, the present invention can be made some nonessential improvement and adjustment according to foregoing by the person skilled in the art in this field.
Embodiment 1
Manganese dioxide cellulose nano-fibrous hybrid preparation method, comprises the following steps:
(1) preparation of nano-cellulose
Waste cotton fiber preparation cellulose suspension, with ultrasonic cell disrupte instrument with the ultrasonic 1h of 1000w, is prepared as cellulose nano-fibrous；
(2) preparation of manganese dioxide/cellulose nano-fibrous hybrid
Potassium permanganate: the mol ratio of potassium hydroxide=1:1 prepares alkalinity potassium permanganate, and 10mmol alkalinity potassium permanganate is dissolved in 100mL water, is added thereto to the cellulose nano-fibrous of 300mL 1wt%；8h, ion are stirred at room temperature, concentrate pulping, solid content 9.3wt%.
Embodiment 2
Manganese dioxide cellulose nano-fibrous hybrid preparation method, comprises the following steps:
(1) preparation of nano-cellulose
Bamboo pulp, wood pulp cellulose preparation cellulose suspension, with ultrasonic cell disrupte instrument with the ultrasonic 1h of 1000w, is prepared as cellulose nano-fibrous；
(2) preparation of manganese dioxide/cellulose nano-fibrous hybrid
Potassium permanganate: the mol ratio of sodium hydroxide=1:1 prepares alkalinity potassium permanganate, and 10mmol alkalinity potassium permanganate is dissolved in 100mL water, is added thereto to the cellulose nano-fibrous of 300mL 1wt%；8h, ion are stirred at room temperature, concentrate pulping, solid content 9.3wt%.
Embodiment 1 products therefrom is carried out performance test:
1, XRD observes crystal formation
A, b, c of Fig. 1 are the most cellulose nano-fibrous, manganese dioxide/cellulose nano-fibrous hybrid and from manganese dioxide/cellulose nano-fibrous hybrid isolated manganese dioxide XRD figure spectrum, 2 θ=16 ° and the characteristic peak that 22.4 ° is I fiber type element, and c shows the birnessite structure that manganese dioxide is stratiform of fabricated in situ.
2, TEM microscopic appearance observed result
The a of Fig. 2, b is respectively undressed cellulose fibre transmission electron microscope photo and manganese dioxide/cellulose nano-fibrous hybrid transmission electron microscope photo, contrast understands, cellulose fibre remains in that its filamentary structure, but it is owing to the attachment of manganese dioxide causes that part colours deepens this, but the fold of the cellulose fiber surface after DMAc/LiCl swelling pretreatment and slight crack showed increased, this is by more useful Yu follow-up mechanical stripping process.In Fig. 2, c and d is the partial enlarged drawing of b, can to manganese dioxide length on nano-cellulose fiber, and be layer structure.
3, manganese dioxide/cellulose nano-fibrous hybrid decolorizing effect to methylene blue
Initial concentration is 80mg L-1Methylene blue solution in add 25mg (in terms of dry weight) the present embodiment prepare manganese dioxide/cellulose nano-fibrous hybrid, regulation original ph is 9.6, methylene blue is filtered at a certain time interval by syringe filters, measuring the uv absorption of methylene blue, Fig. 3 is that manganese dioxide/cellulose nano-fibrous hybrid is to the ultra-violet absorption spectrum of different time under the adsorption bleaching effect-room temperature of methylene blue.Embedded figure be initial concentration be 80mg L-1With in 5min after the pictorial diagram of aqueous solution of methylene blue.From the figure 3, it may be seen that this manganese dioxide/cellulose nano-fibrous hybrid can make aqueous solution of methylene blue can reach clarification in 5min.
Claims (3)
1. manganese dioxide cellulose nano-fibrous hybrid preparation method, it is characterised in that comprise the following steps:
(1) preparation of nano-cellulose
Cellulose preparation cellulose suspension, with ultrasonic cell disrupte instrument with the ultrasonic 1h of 1000w, is prepared as cellulose nano-fibrous；
(2) preparation of manganese dioxide/cellulose nano-fibrous hybrid
Potassium permanganate: the mol ratio of alkali=1:1 prepares alkalinity potassium permanganate, and 10mmol alkalinity potassium permanganate is dissolved in 100mL water,
It is added thereto to the cellulose nano-fibrous of 300mL 1wt%；8h, ion are stirred at room temperature, concentrate pulping.
Manganese dioxide the most according to claim 1 cellulose nano-fibrous hybrid preparation method, it is characterised in that described
Cellulose origin be waste cotton fiber, bamboo pulp, wood pulp, cardboard, filter paper.
Manganese dioxide the most according to claim 1 and 2 cellulose nano-fibrous hybrid preparation method, it is characterised in that
Described alkali is the one of sodium hydroxide, potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610420938.8A CN106000340A (en) | 2016-06-13 | 2016-06-13 | Preparation method of manganese dioxide cellulose nanofiber mixed compound |
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| CN201610420938.8A CN106000340A (en) | 2016-06-13 | 2016-06-13 | Preparation method of manganese dioxide cellulose nanofiber mixed compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289782A (en) * | 2018-10-10 | 2019-02-01 | 太原工业学院 | A kind of manganese dioxide/corn stover nano material and its preparation method and application |
| CN111111620A (en) * | 2020-01-09 | 2020-05-08 | 青岛科技大学 | Efficient, green and environment-friendly adsorption degradation material and preparation method and application thereof |
| CN111533172A (en) * | 2020-05-09 | 2020-08-14 | 上海大学 | Mesoporous manganese dioxide prepared based on biological material and preparation method thereof |
| CN113426418A (en) * | 2021-06-16 | 2021-09-24 | 山东银鹰股份有限公司 | Nano-cellulose/nano-double transition metal oxide ternary composite material and preparation method and application thereof |
Citations (3)
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| DE2409951A1 (en) * | 1973-03-02 | 1974-09-05 | Joergensen S E | ION EXCHANGE MATERIAL |
| CN101974848A (en) * | 2010-08-27 | 2011-02-16 | 山东海龙股份有限公司 | Preparation method of cellulose-based ion exchange fiber |
| CN103131033A (en) * | 2013-03-20 | 2013-06-05 | 福建农林大学 | Method for preparing nano manganese dioxide/nano microcrystalline cellulose composite films |
-
2016
- 2016-06-13 CN CN201610420938.8A patent/CN106000340A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2409951A1 (en) * | 1973-03-02 | 1974-09-05 | Joergensen S E | ION EXCHANGE MATERIAL |
| CN101974848A (en) * | 2010-08-27 | 2011-02-16 | 山东海龙股份有限公司 | Preparation method of cellulose-based ion exchange fiber |
| CN103131033A (en) * | 2013-03-20 | 2013-06-05 | 福建农林大学 | Method for preparing nano manganese dioxide/nano microcrystalline cellulose composite films |
Non-Patent Citations (1)
| Title |
|---|
| YARU WANG,ET AL: "In situ synthesis of MnO2 coated cellulose nanofibers hybrid for effective removal of methylene blue", 《CARBOHYDRATE POLYMERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289782A (en) * | 2018-10-10 | 2019-02-01 | 太原工业学院 | A kind of manganese dioxide/corn stover nano material and its preparation method and application |
| CN111111620A (en) * | 2020-01-09 | 2020-05-08 | 青岛科技大学 | Efficient, green and environment-friendly adsorption degradation material and preparation method and application thereof |
| CN111533172A (en) * | 2020-05-09 | 2020-08-14 | 上海大学 | Mesoporous manganese dioxide prepared based on biological material and preparation method thereof |
| CN113426418A (en) * | 2021-06-16 | 2021-09-24 | 山东银鹰股份有限公司 | Nano-cellulose/nano-double transition metal oxide ternary composite material and preparation method and application thereof |
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