CN110270302A - One kind is for adsorbing S in industrial wastewater2-Material preparation method - Google Patents

Abstract

The invention belongs to the field of industrial wastewater material preparation, in particular to a method for preparing a ZnO@FeOOH material that can adsorb S ^2- in industrial wastewater. _In this method, FeCl3 solution, sodium dodecyl sulfate (SDS) solution, nano-ZnO particles and NaOH solution are mixed in a certain proportion and put into a hydrothermal reaction kettle for reaction, and after the reaction, the sediment in the kettle is filtered and washed. , The final product is obtained after drying. The advantages of the present invention are that the raw materials are cheap and easy to obtain, the technological process is simple, and the ^product has good ^S The removal rate of S ^2- can reach 80%-99%, which can be widely used in the field of industrial wastewater treatment.

Description

A kind of material preparation method for adsorbing S2- in industrial wastewater

technical field

The invention belongs to the field of industrial wastewater adsorption material preparation, in particular to a preparation method of a ZnO@FeOOH material capable of adsorbing S ^2- .

Background technique

Oil refining, petrochemical, pharmaceutical and tanning industries will produce a large amount of sulfur-containing wastewater in the production process. S ^2- in such wastewater can corrode metal materials, poison the human body, and release malodorous gases, causing great harm to the environment. . At present, biological methods and precipitation methods are mostly used for the removal of sulfide in wastewater. The removal rate of S ^2- by biological method is close to 100%, but it is not suitable for high-concentration wastewater, and the generated sulfate is easy to cause secondary pollution to the environment; the precipitation method mainly forms FeS precipitation through the interaction of Fe ²⁺ and S ^2- , which will S ^2- removal, although this technology is widely used in industry, it is mostly used for high-sulfur wastewater, because the generated precipitate particles are too small, it is not easy to settle, and other anions are introduced. Sulfur-containing wastewater treatment. Compared with the above technologies, the adsorption technology has the advantages of stable operation, strong impact load resistance, and no introduction of other interfering ions. However, the current industrial sulfur-containing wastewater treatment lacks adsorption materials for S ^2- , so it is cheap and easy to develop. S ² - desulfurization materials with large fluctuations in influent concentration become particularly important;

Chinese patent 201610674614.7

Chinese patent 201510772205.6

Chinese Patent 201410444573.3

Chinese patent 201410755660.0

Chinese Patent 201811617006.8

Chinese Patent 201620116413.0

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a ZnO@FeOOH material capable of adsorbing S ^2- . The raw materials of the method are cheap and easy to obtain, the technological process is easy to realize, the product has good S ^2- adsorption performance, and can be widely used in the field of environmental protection.

In order to achieve the above purpose, the preparation method of the present invention uses FeCl ₃ and nano-ZnO as raw materials, and the whole preparation method is composed of the following steps:

Step 1, configure 0.8-1.3mol/L FeCl ₃ solution, weigh a certain amount of nano-ZnO, and place the nano-ZnO in the FeCl ₃ solution to prepare a mixed solution of FeCl ₃ and nano-ZnO;

Step 2, add 0.2-0.4mol/L CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na solution dropwise to the FeCl ₃ and nano-ZnO mixed solution prepared in step 1 at a speed of 3-6ml/min to prepare FeCl _3. The mixed solution of nano-ZnO and CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na is added dropwise and the solution is continuously stirred;

In step 3, 1.0-1.5mol/L NaOH solution was added dropwise to the mixed solution of FeCl ₃ , nano-ZnO and CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na prepared in step 2 with continuous stirring. Stop the titration when the pH value of the mixed solution is 9.0-12.0, continue stirring for 40-80min, transfer the solution with precipitation into the reaction kettle, place the reaction kettle in a -115 ℃ oven at 100, react for 8.0-12h and then cool down to Take out at room temperature;

In step 4, the solid-liquid mixture in the reaction kettle is subjected to suction filtration, washing, and drying for 18-26 hours, and the drying temperature is 50-70° C., to obtain the ZnO@FeOOH material.

Wherein, in the preparation method described in step 1, the concentration of FeCl ₃ solution is preferably 1.0 mol/L, and the particle size of the nano-ZnO is between 10-50 nm.

Wherein, in the preparation method described in step 2, the concentration of CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na solution is preferably 0.25-0.35 mol/L, and the amount ratio of FeCl ₃ , nano-ZnO and CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na is 4:1:1.2.

In the preparation method described in step 3, the concentration of the NaOH solution is preferably 1.2mol/L, the titration is stopped when the pH value is preferably 9.0-10.5, the continuous stirring time is preferably 40-50min, and the temperature of the oven is preferentially set is 105-110 ℃, and the reaction time is preferably 8.0-10h.

In the preparation method described in step 4, the drying time is preferably 20-24h, and the drying temperature is preferably 55-65°C.

The advantages of the present invention are as follows:

In the preparation process of this material, the raw materials are cheap and easy to obtain, the process is easy to realize, and it is suitable for industrial scale production; the product has good adsorption performance of S ^2- , and is suitable for the treatment of industrial wastewater with large fluctuation of S ^2- influent concentration, and can be widely used In the fields of oil refining, petrochemical, pharmaceutical and tanning.

Description of drawings

Figure 1 is the infrared spectrum of ZnO@FeOOH;

Figure 2 is the XRD pattern of ZnO@FeOOH.

Detailed ways

Example 1:

Dissolve 5.40g FeCl ₃ ·6H ₂ O and 1.728g CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na in 20ml of deionized water respectively, stir and dissolve with a magnetic stirrer, and add 0.40g of nano-ZnO to the FeCl ₃ solution after fully dissolving and mix well , add CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na solution dropwise to the continuously stirring FeCl ₃ and nano-ZnO mixed solution at 5ml/min and continue stirring for 15min, and add 1.5mol/L NaOH solution dropwise to the continuously stirring FeCl _3. In the mixed solution of nano-ZnO and CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na, after precipitation appears, stop the titration when the pH value of the mixed solution is 12.0, and continue stirring for 60 minutes to transfer the solution with the precipitation into the reaction kettle , the reaction kettle was placed in an oven at 110 °C, cooled to room temperature after 10 h of water heating, and taken out. The precipitate in the reaction kettle was suction filtered, washed, and dried at 60 °C for 24 h to obtain the ZnO@FeOOH material. It can be seen from the infrared spectrum of Fig. 1 that the absorption peaks with wave numbers around 787cm ^-1 and 895cm ^-1 belong to the vibration peaks between Fe-OH of FeOOH, and the stretching vibration peaks of Fe-O appear at 601cm ^-1 ; It can be seen from the XRD diffraction pattern of 2θ that there is a diffraction peak at 35.3°, which proves that FeOOH exists on the surface of the material. Since the nano-ZnO is encapsulated inside FeOOH, the existence of nano-ZnO was not detected;

Take 1L of wastewater containing S ^2- 100mg/L and put 1g of desulfurizer into it, after adsorption for 1h, take a water sample for detection, and the S ^2- removal rate is 98.2%.

Example 2:

Dissolve 8.10g FeCl ₃ ·6H ₂ O and 2.592g CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na in 30ml of deionized water respectively, stir and dissolve with a magnetic stirrer, and add 0.60g of nano-ZnO to the FeCl ₃ solution after fully dissolving and mix well , the CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na solution was added dropwise at 3ml/min to the continuously stirred FeCl ₃ and nano-ZnO mixed solution and continued to stir for 15min, and the 1.0mol/L NaOH solution was added dropwise to the continuously stirred FeCl _3. In the mixed solution of nano-ZnO and CH ₃ (CH ₂ ) ₁₁ OSO ₃ Na, after precipitation appears, stop the titration when the pH value of the mixed solution is 11.0, and continue stirring for 70 minutes to transfer the solution with the precipitation into the reaction kettle , the reaction kettle was placed in an oven at 108 °C, cooled to room temperature after 9 hours of water heating, and taken out. The precipitate in the reaction kettle was suction filtered, washed, and dried at 70 °C for 20 h to obtain ZnO@FeOOH;

Take 1L of wastewater containing S ^2- 200mg/L and put 1g of desulfurizer into it, after adsorption for 1 hour, take a water sample for detection, and the S ^2- removal rate is 90.6%.

Claims (7)

1. one kind is for adsorbing S in industrial wastewater^2-ZnO@FeOOH material preparation method, it is characterised in that with FeCl₃And nanometer ZnO is raw material, is prepared using hydro-thermal method, and preparation method is made of following steps:

Step 1 configures the FeCl of 0.8-1.3mol/L₃Solution, weighs a certain amount of nano-ZnO, and nano-ZnO is placed in FeCl₃ In solution, FeCl is made₃With nano-ZnO mixed liquor；

Step 2, by the CH of 0.2-0.4mol/L₃(CH₂)₁₁OSO₃Na solution is added drop-wise to step 1 institute with the speed of 3-6ml/min The FeCl of system₃In nano-ZnO mixed liquor, it is prepared into FeCl₃, nano-ZnO and CH₃(CH₂)₁₁OSO₃Process is added dropwise in Na mixed liquor Solution persistently stirs；

Step 3, the step of NaOH solution of 1.0-1.5mol/L is added drop-wise to lasting stirring two made FeCl₃, nano-ZnO and CH₃(CH₂)₁₁OSO₃In Na mixed liquor, after thering is precipitating to occur, drops to when mixed solution pH value is 9.0-12.0 and stop titration, continue Solution with precipitating is transferred in reaction kettle by stirring 40-80min, and reaction kettle is placed in 100-115 DEG C of baking oven, is reacted 8.0-12h taking-up is cooled to room temperature after;

Step 4 filters the solidliquid mixture in reaction kettle, washing, and dry 18-26h, drying temperature is 50-70 DEG C, Obtain ZnO FeOOH material.

2. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that FeCl in step 1₃Solution concentration It is preferably 1.0mol/L.

3. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that nanometer described in step 1 The partial size of ZnO is between 10-50nm.

4. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that CH in step 2₃(CH₂)₁₁OSO₃Na solution concentration is preferably 0.25-0.35mol/L, FeCl₃, nano-ZnO and CH₃(CH₂)₁₁OSO₃Na the mass ratio of the material is 4:1:1.2。

5. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that NaOH solution is dense in step 3 Degree is preferably 1.2mol/L, is titrated to and stops titration when pH value is preferably 9.0-10.5, and continuing mixing time is preferably 40- 50min, the temperature prioritised of baking oven are set as 105-110 DEG C, and the reaction time is preferably 8.0-10h.

6. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that drying time is preferential in step 4 For 20-24h, drying temperature is preferably 55-65 DEG C.

7. material is suitable for containing S^2-Concentration is in the industrial wastewater of 5-200mg/L.