CN106215862A - A kind of preparation method and applications of iron oxyhydroxide/graphenoxide oxide composite material - Google Patents

Abstract

The invention relates to a preparation method and application of an iron oxyhydroxide/graphene oxide composite material. The iron oxyhydroxide/graphene oxide composite material is composed of a suspension of graphene oxide and a suspension of iron oxyhydroxide in a volume ratio of 1:1-2, mixed and dispersed, and compounded by a hydrothermal method. The obtained iron oxyhydroxide/graphene oxide composite material is used for the treatment of phenol-containing wastewater, and 0.5-5 g of the iron oxyhydroxide/graphene oxide composite adsorption material is put into 1000 ml of 10-60 mg/l p-chlorophenol In the wastewater, shake fully on a constant temperature shaker, control the water temperature at 25°C, and filter the wastewater after 3 hours of reaction. The removal rate of p-chlorophenol is detected to be 87-93.2%, the concentration of chlorophenol in the effluent is 1.3-5.2mg/l, and the adsorption capacity is 11～17.4mg/l.

Description

A kind of preparation method and application of iron oxyhydroxide/graphene oxide composite material

technical field

The invention relates to the technical field of water pollution control, in particular to a preparation method of an iron oxyhydroxide/graphene oxide composite material and its application in water treatment.

Background technique

With the rapid development of the chemical industry, organochlorine compounds have been widely used in the fields of medicine, agricultural supplies, textiles, daily chemicals, and public health, but they have also caused serious environmental pollution. Many organochlorine compounds are highly toxic, difficult to biodegrade, have a long half-life, have "three effects" and genotoxicity, and the long-term residue of these organochlorine compounds in the environment will affect the environment and endanger the health of various organisms and human beings.

Chlorophenol aromatic compounds are a type of typical organochlorine compounds, which can cause poisonous effects on various organisms after entering the environment, and even lead to the destruction of the entire ecosystem in severe cases. At the same time, studies in recent years have shown that most chlorophenol compounds are endocrine disruptors or potential endocrine disruptors. When they exist in organisms for a long time, they will cause endocrine disorders of organisms and can affect various organisms and human reproduction. Systemic toxic effects that can be harmful to organisms even at low concentrations. Studies have shown that chlorophenols can have toxic effects on aquatic organisms. When the concentration in fresh water or ocean reaches 1-10μg/L, it will cause acute poisoning to aquatic organisms.

Chlorophenols in the environment mainly come from natural synthesis in the environment, degradation of chlorinated organic substances, by-products in processing or purification processes, and artificially synthesized chlorinated compounds.

At present, the control of p-chlorophenol in my country is mainly in the field of water pollution control. According to my country's "Surface Water Environmental Quality Standards" (GB-3838-2002), the maximum allowable concentration of volatile phenols in surface water V water bodies is 0.1mg/L; my country's "Drinking Water Quality Standards" (GB5749-2006) The concentration of volatile phenols in drinking water shall not exceed 0.002mg/L; my country's "Urban Water Supply Quality Standard" (CJ/T206-2005) stipulates that the total amount of chlorophenols (including 2-chlorophenol, 2,4-dichlorophenol , 2,4,6-trichlorophenol) shall not exceed 0.01mg/L.

At present, conventional methods for controlling chlorophenol pollutants include chemical oxidation, photocatalysis, membrane separation, biodegradation, and adsorption. The chemical oxidation method uses strong oxidants such as O ₃ , Fenton reagent, etc. for oxidation treatment. The treatment of phenol-containing wastewater has obvious effects, but the oxidant cost is high and the technical equipment requirements are high; the photocatalytic oxidation method oxidizes chlorophenols by catalyzing the generation of hydroxyl radicals. Although the treatment effect is good and the reaction time is short, more toxic intermediate products may be produced in some treatment processes, making it difficult for chemical treatment of chlorinated phenols to be widely used; membrane separation method is to treat phenol-containing wastewater through synthetic membrane filtration , but the membrane is easy to be blocked after long-term operation, resulting in a decrease in the permeability of the membrane, and frequent replacement of the membrane module, resulting in high operating costs. These problems make the membrane separation technology have certain limitations in practical application; biological treatment Although the cost of phenol-containing wastewater is low and there is no secondary pollution, the biological system has low treatment efficiency and poor operation stability, which limits the application of biological methods to treat phenol-containing wastewater. Adsorption treatment of phenol-containing wastewater will not be affected by water volume and impact, and has the advantages of low operating cost, no intermediate product production, and high efficiency. Using adsorption method to treat phenol-containing wastewater can overcome many of the above shortcomings.

At present, there are many kinds of materials for treating chlorophenol by adsorption method, such as activated carbon and carbon fiber based on carbon matrix, resins based on organic matter/polymer, chitosan microspheres, etc., and montmorillonite based on inorganic mineral matrix, Hydrotalcite etc.

This method provides a method for treating phenol-containing wastewater by iron oxyhydroxide and graphene oxide composite materials. Graphene oxide is a graphene derivative and a new type of two-dimensional nanomaterial with a huge specific surface area and a large amount of The oxygen-containing functional groups make it a good adsorbent. Two-dimensional nanomaterials are prone to irreversible stacking and agglomeration in practical applications. This method modifies graphene oxide through iron oxyhydroxide to make it an excellent water treatment adsorbent with stable performance and effectively treat Phenol wastewater.

Invention content:

The purpose of the present invention is to provide a preparation method of iron oxyhydroxide/graphene oxide composite material and apply it to treat phenolic wastewater.

The technical scheme that the present invention takes is realized through the following steps:

An iron oxyhydroxide/graphene oxide composite material is formed by mixing and dispersing graphene oxide suspension and iron oxyhydroxide suspension at a volume ratio of 1:1 to 2 and compounding them by a hydrothermal method.

An iron oxyhydroxide component in an iron oxyhydroxide/graphene oxide composite material is obtained by adding Fe(NO ₃ ) _3` 2H ₂ O and NaOH into 100ml deionized water according to a mass ratio of 0.5-1.2:1 and mixing them by hydrothermal method 30min, kept in an oven at 120-150°C for 24 hours, centrifuged and dried.

Graphite oxide in an iron oxyhydroxide/graphene oxide composite material is graphite powder and potassium permanganate according to the mass ratio of 1:1 to 3, adding concentrated sulfuric acid and concentrated phosphoric acid with a volume ratio of 6 to 8:1 mixed acid, 50 ℃ water bath heating 2h, the system.

A composite step of iron oxyhydroxide/graphene oxide composite material:

(1) Take 1 g of graphite oxide solid, add 50 ml of deionized water, and disperse for 5 to 10 minutes to obtain a graphene oxide suspension with a mass volume fraction of about 0.02 g/ml;

(2) Disperse 0.5-1 g of ferric oxyhydroxide in 50 ml of deionized water for 5 minutes to obtain a suspension with a mass volume fraction of 0.1-0.2 g/ml of ferric oxyhydroxide;

(3) Add the uniformly dispersed ferric oxyhydroxide suspension to the dispersed graphene oxide suspension, and disperse the mixed solution for 5-10 minutes, keep it in an oven at 120°C for 12-24 hours, and centrifuge and dry it. The composite material is produced.

The above-mentioned graphene oxide is combined by the electrostatic force between the group on the graphene and the iron oxyhydroxide group to form an iron oxyhydroxide/graphene oxide composite material.

The obtained ferric oxyhydroxide/graphene oxide composite material is used for the treatment of phenol-containing wastewater, and the specific steps are as follows: Take 0.5-5 g of ferric oxyhydroxide/graphene oxide composite adsorption material and put it into 1000 ml of p-chlorophenol containing 10-5 g In the 60mg/l waste water, fully shake it on a constant temperature shaker, control the water temperature at 25°C, filter the waste water after 3 hours of reaction, and detect that the removal rate of p-chlorophenol is 87-93.2%, and the concentration of chlorophenol in the effluent is 1.3-5.2mg/l , the adsorption capacity is 11-17.4mg/l.

The iron oxyhydroxide/graphene oxide composite material prepared by the present invention has the following advantages:

1. The composite of graphene oxide and iron oxyhydroxide in the iron oxyhydroxide/graphene oxide composite material of the present invention can effectively avoid the agglomeration of graphene oxide, and graphene oxide can effectively maintain a two-dimensional structure;

2. The graphene oxide used in the present invention is moderately oxidized graphene, which has abundant oxygen-containing groups and a large specific surface area, and can efficiently adsorb chlorophenols;

3. The iron oxyhydroxide in the iron oxyhydroxide/graphene oxide composite material is used as the substrate, which has a certain adsorption and oxidation effect, and can absorb and oxidize part of chlorophenol.

detailed description

Example 1

Graphite powder and potassium permanganate are in a mass ratio of 1:1, add sulfuric acid and phosphoric acid with a volume ratio of 8:1 mixed acid, and heat in a water bath at 50°C for 2 hours. The oxidized graphite is filtered, dried and ground into powder for later use.

The mass of graphite oxide and the volume of deionized water are 1g:50ml, mixed and dispersed for 5-10min to prepare a 0.02g/ml graphene oxide suspension.

Fe(NO ₃ ) _3` 2H ₂ O and NaOH were added into 100ml deionized water according to the mass ratio of 1.2:1, mixed for 30 minutes, and kept in an oven at 150°C for 24 hours.

Mix the obtained iron oxyhydroxide mass with deionized water volume according to 0.5g:50ml, and disperse for 5 minutes to prepare 0.1g/ml iron oxyhydroxide suspension. The uniformly dispersed iron oxyhydroxide suspension was added to the dispersed graphene oxide suspension, and the mixed solution was dispersed for 5-10 minutes, and kept in an oven at 120° C. for 24 hours.

The obtained ferric oxyhydroxide/graphene oxide composite material is used for the treatment of phenol-containing wastewater, and the specific steps are as follows: 0.5 g of ferric oxyhydroxide/graphene oxide composite adsorption material is dropped into 1000 ml containing p-chlorophenol with a concentration of 10 mg/l In the waste water, shake fully on a constant temperature shaker, control the water temperature at 25°C, and filter the waste water after reacting for 3 hours. The concentration of chlorophenol in the effluent is 1.3 mg/l, and the adsorption capacity is 17.4 mg/g. Detection of p-chlorophenol removal rate of 87%

Example 2

Graphite powder and potassium permanganate are in a mass ratio of 1:2, add sulfuric acid and phosphoric acid with a volume ratio of 7:1 mixed acid, and heat in a water bath at 50°C for 2 hours. The oxidized graphite is filtered, dried and ground into powder for later use.

The mass of graphite oxide and the volume of deionized water were mixed according to 1g:50ml, and dispersed for 5-10min to prepare a 0.02g/ml graphene oxide suspension.

Fe(NO ₃ ) _3` 2H ₂ O and NaOH were added into 100ml deionized water according to the mass ratio of 1:1, mixed for 30 minutes, and kept in an oven at 120°C for 24 hours.

The mass of the obtained iron oxyhydroxide and the volume of deionized water were mixed according to 1g:50ml, and dispersed for 5 minutes to prepare a 0.2g/ml iron oxyhydroxide suspension. The uniformly dispersed iron oxyhydroxide suspension was added to the dispersed graphene oxide suspension, and the mixed solution was dispersed for 5-10 minutes, and kept in an oven at 120° C. for 24 hours.

The obtained ferric oxyhydroxide/graphene oxide composite material is used for the treatment of phenol-containing wastewater, and the specific steps are as follows: get 3 g of ferric oxyhydroxide/graphene oxide composite adsorbent material and drop into 1000 ml of chlorophenol containing p-chlorophenol concentration of 50 mg/l In the wastewater, shake fully on a constant temperature shaker, control the water temperature at 25°C, and filter the wastewater after reacting for 3 hours. The concentration of chlorophenol in the effluent is 3.4mg/l, and the adsorption capacity is 15.5mg/g. Detection of p-chlorophenol removal rate of 93.2%

Example 3

Graphite powder and potassium permanganate are in a mass ratio of 1:3, add sulfuric acid and phosphoric acid with a volume ratio of 6:1 mixed acid, and bathe in water at 50°C for 2 hours. The oxidized graphite is filtered, dried and ground into powder for later use.

The mass of graphite oxide and the volume of deionized water are 1g:50ml, mixed and dispersed for 5-10min to prepare a 0.02g/ml graphene oxide suspension.

Fe(NO ₃ ) _3` 2H ₂ O and NaOH were added into 100ml deionized water according to the mass ratio of 0.5:1, mixed for 30 minutes, and kept in an oven at 120°C for 24 hours.

The mass of the obtained iron oxyhydroxide and the volume of deionized water were mixed according to 1g:50ml, and dispersed for 5 minutes to prepare a 0.2g/ml iron oxyhydroxide suspension. The uniformly dispersed iron oxyhydroxide suspension was added to the dispersed graphene oxide suspension, and the mixed solution was dispersed for 5-10 minutes, and kept in an oven at 120° C. for 24 hours.

The obtained ferric oxyhydroxide/graphene oxide composite material is used for the treatment of phenol-containing wastewater, and the specific steps are as follows: get 5 g of ferric oxyhydroxide/graphene oxide composite adsorbent material and drop into 1000 ml of 60 mg/l p-chlorophenol In the wastewater, shake fully on a constant temperature shaker, control the water temperature at 25°C, and filter the wastewater after reacting for 3 hours. The concentration of chlorophenol in the effluent is 5.2mg/l, and the adsorption capacity is 11mg/g. The removal rate of p-chlorophenol was detected to be 91.3%.

The preparation method of an iron oxyhydroxide/graphene oxide composite material disclosed and proposed by the present invention and its application in water treatment can be realized by those skilled in the art by referring to the content of this article and appropriately changing the conditions and routes. Although the present invention The methods and preparation techniques have been described through preferred implementation examples, and those skilled in the art can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit and scope of the present invention to achieve the final Preparation technology. In particular, it should be pointed out that all similar substitutions and modifications will be obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.

Claims (5)

1. the preparation method of an iron oxyhydroxide/graphenoxide oxide composite material；It is characterized in that by graphene oxide is suspended The suspension of liquid and FeOOH is composited by hydro-thermal method after according to volume ratio 1:1～2 mixing, dispersion.

2. the method for claim 1, is characterized in that FeOOH component is to utilize hydro-thermal method by Fe (NO₃)_3`2H₂O with NaOH adds according to mass ratio 0.5～1.2:1 and mixes 30min in 100ml deionized water, keeps in the baking oven of 120～150 DEG C 24 hours, prepare after centrifugal drying.

3. the method for claim 1, it is characterized in that graphite oxide be graphite powder with potassium permanganate according to mass ratio 1:1～ 3, add concentrated sulphuric acid and the nitration mixture that strong phosphoric acid volume ratio is 6～8:1,50 DEG C of heating in water bath 2h prepare.

4. the method for claim 1, is characterized in that step is as follows:

1) take the oxidation graphite solid of 1g, add 50ml deionized water, disperse 5～10min, i.e. prepare mass body fraction and be about The graphene oxide suspension of 0.02g/ml；

2) by taking the FeOOH of 0.5～1g in 50ml deionized water, disperse 5min, i.e. prepare mass body fraction 0.1 ～the suspension of 0.2g/ml FeOOH；

3) finely dispersed FeOOH suspension is joined in the most scattered graphene oxide suspension, and will mixing Liquid dispersion 5～10min, keeps 12～24h in the baking oven of 120 DEG C, i.e. prepares described composite after centrifugal drying.

5. utilize iron oxyhydroxide/graphenoxide oxide composite material to carry out the processing method of phenol wastewater, it is characterized in that taking hydroxyl What ferrum oxide/graphene oxide composite adsorption material 0.5～5g put into 1000ml is 10～60mg/l containing parachlorophenol concentration In waste water, shaking on constant-temperature table, control water temperature is at 25 DEG C, and by waste water filtering after reaction 3h, detection parachlorophenol clearance is 87～93.2%, water outlet chlorophenol concentration is 1.3～5.2mg/l, and adsorbance is 11～17.4mg/l.