阅读说明：本技术 一种近常温热敏催化剂及其制备方法 (Near-normal-temperature thermosensitive catalyst and preparation method thereof ) 是由 丁凤 于 2020-12-23 设计创作，主要内容包括：本发明公开了一种近常温热敏催化剂及其制备方法,该催化剂的原料包括硝酸铋、硝酸银、氯化亚铁和单质硫,该制备方法包括以下步骤：制备载体BiOCl；制备载体BiOCl/Ag-3PO-4；制备BiOCl/Ag-3PO-4/FeS-2；本发明制备的热敏催化剂具有廉价、简单可操作和高效降解有机废水的优良降解效果,该催化剂对亚甲基蓝去除率达到99.2％。(The invention discloses a near normal temperature heat-sensitive catalyst and a preparation method thereof, wherein the raw materials of the catalyst comprise bismuth nitrate, silver nitrate, ferrous chloride and elemental sulfur, and the preparation method comprises the following steps: preparing a carrier BiOCl; preparation of the Carrier BiOCl/Ag 3 PO 4 (ii) a Preparation of BiOCl/Ag 3 PO 4 /FeS 2 (ii) a The thermosensitive catalyst prepared by the invention has the advantages of low price, simple operation and excellent degradation effect of efficiently degrading organic wastewater, and the removal rate of the catalyst to methylene blue reaches 99.2%.)

1. A near-normal-temperature thermosensitive catalyst is characterized in that: the raw materials of the catalyst comprise bismuth nitrate, silver nitrate, ferrous chloride and elemental sulfur.

2. The preparation method for realizing the near-normal-temperature thermosensitive catalyst of claim 1 is characterized by comprising the following steps of: the preparation method comprises the following steps:

step one, preparing a carrier BiOCl:

dissolving 1-1.2 mol of bismuth nitrate in deionized water, stirring continuously, adding 2-2.4 mol of sodium sulfide, mixing uniformly, adjusting the pH value of the solution to 7.0-7.5, stirring and ultrasonically treating, keeping the temperature at 80 ℃, heating and refluxing, washing after the solution is cooled, and drying for 2 times;

step two, preparing a carrier BiOCl/Ag₃PO₄：

Adding 1-1.2 mol of silver nitrate into the solution obtained in the step one, stirring continuously to dissolve the silver nitrate, and then dropwise adding 1-1.3 mol of disodium hydrogen phosphate solution to obtain a precipitate; keeping the precipitate at a certain temperature for several hours, cooling, and cleaning with ultrapure water and ethanol for 3 times respectively;

step three, preparing BiOCl/Ag₃PO₄/FeS₂：

Adding 5.6-6.1 mol of ferrous chloride and 2.2-2.5 m of ferrous chloride into the solution obtained in the second step in sequenceAdjusting the pH value of the reaction solution to 7.0-7.2 by using ammonia water, carrying out hydrothermal reaction, cooling, washing 3 times by using deionized water and ethanol respectively, and drying to obtain BiOCl/Ag₃PO₄/FeS₂And (3) powder.

3. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: in the first step, 0.1mol/L hydrochloric acid is used for adjusting the pH value of the solution to 7.0-7.5.

4. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: stirring and ultrasonic treatment are carried out for 3-4 h in the first step, then the temperature is kept at 80-90 ℃, and heating reflux is carried out for 10-12 h.

5. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: and in the second step, keeping the precipitate at 120-140 ℃ for 3-4 h.

6. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: and in the third step, 0.1mol/L ammonia water is adopted to adjust the pH value of the reaction liquid to 7.0-7.2.

7. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: the hydrothermal reaction in the third step is a hydrothermal reaction at 130-145 ℃ for 12-15 h.

8. The method for preparing a near-normal-temperature thermosensitive catalyst according to claim 2, wherein the method comprises the following steps: the drying treatment in the third step comprises the following steps: drying for 10-12 h at 50-60 ℃.

Technical Field

The invention relates to the technical field of metal salt and a compound thereof and organic wastewater degradation, in particular to a near-normal-temperature thermosensitive catalyst and a preparation method thereof.

Background

The dye is produced into tens of thousands of tons every year in China, and is divided into 11 types, namely sulfuration, acidity, alkalinity, reduction, activity, dispersion, direct, neutral, ice dyeing, cation and the like. In addition, ten thousand tons of organic pigments, assistants and intermediates are produced, the variety reaches more than 550, and the waste water amount is 1.57 multiplied by 10⁸m³A, the wastewater treatment rate is only about 22.5%.

Most of organic components in the dye wastewater take aromatic hydrocarbon and heterocyclic compounds as matrixes, and the organic components have color development and polar groups. The waste water also contains more raw materials and byproducts, such as aniline, phenols, inorganic salts and the like. The dye wastewater has the characteristics of large water quality and water quantity change range, complex components, high concentration, deep color and the like, so that the dye wastewater treatment difficulty is increased. In general, organic wastewater treatment is mainly difficult as follows: high COD and difficult degradation; the COD of the wastewater is high, the BOD/COD is low, generally between 0.2 and 0.4, and the wastewater can be subjected to biochemical treatment and is not easy to be subjected to biochemical treatment.

Methods commonly used for treating organic wastewater are: the methods of photodegradation, physical degradation, electrochemical degradation and biodegradation still have the defects of low degradation rate, complex operation, high price and the like. The thermosensitive catalyst prepared by the method is efficient and low in price, so that pollution caused by dye wastewater is reduced, environmental pollution is reduced, and environmental contradiction is relieved.

Disclosure of Invention

The invention aims to provide a near-normal-temperature thermosensitive catalyst and a preparation method thereof, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the near normal temperature heat sensitive catalyst has material including bismuth nitrate, silver nitrate, ferrous chloride and simple substance sulfur.

Preferably, the preparation method comprises the following steps:

step one, preparing a carrier BiOCl:

dissolving 1-1.2 mol of bismuth nitrate in deionized water, stirring continuously, adding 2-2.4 mol of sodium sulfide, mixing uniformly, adjusting the pH value of the solution to 7.0-7.5, stirring and ultrasonically treating, keeping the temperature at 80 ℃, heating and refluxing, washing after the solution is cooled, and drying for 2 times;

step two, preparing a carrier BiOCl/Ag₃PO₄：

Adding 1-1.2 mol of silver nitrate into the solution obtained in the step one, stirring continuously to dissolve the silver nitrate, and then dropwise adding 1-1.3 mol of disodium hydrogen phosphate solution to obtain a precipitate; keeping the precipitate at a certain temperature for several hours, cooling, and cleaning with ultrapure water and ethanol for 3 times respectively;

step three, preparing BiOCl/Ag₃PO₄/FeS₂：

Adding 5.6-6.1 mol of ferrous chloride and 2.2-2.5 mol of elemental sulfur into the solution obtained in the step two in sequence, and adjusting the reaction by using ammonia waterThe pH value of the reaction solution is 7.0-7.2, carrying out hydrothermal reaction, cooling, washing with deionized water and ethanol for 3 times respectively, and drying to obtain BiOCl/Ag₃PO₄/FeS₂And (3) powder.

Preferably, in the step one, 0.1mol/L hydrochloric acid is used for adjusting the pH value of the solution to 7.0-7.5.

Preferably, stirring and ultrasonic treatment are carried out for 3-4 h in the first step, then the temperature is kept at 80-90 ℃, and heating reflux is carried out for 10-12 h.

Preferably, the precipitate is kept at 120-140 ℃ for 3-4 h in the second step.

Preferably, in the third step, 0.1mol/L ammonia water is adopted to adjust the pH value of the reaction solution to 7.0-7.2.

Preferably, the hydrothermal reaction in the third step is a hydrothermal reaction at 130-145 ℃ for 12-15 h.

Preferably, the drying treatment in the third step is as follows: drying for 10-12 h at 50-60 ℃.

Compared with the prior art, the invention has the beneficial effects that: the thermosensitive catalyst prepared by the invention has the advantages of low price, simple operation and excellent degradation effect of efficiently degrading organic wastewater, and the removal rate of the catalyst to methylene blue reaches 99.2%.

Drawings

FIG. 1 is a synthetic route diagram according to the present invention;

FIG. 2 is a schematic view of the internal structure of the present invention;

FIG. 3 is a graph of degradation curves for an embodiment of the present invention;

FIG. 4 is a graph of degradation curves for an embodiment of the present invention;

FIG. 5 is a graph of degradation curves for an embodiment of the present invention;

FIG. 6 is a graph of degradation curves for an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1-2, the present invention provides the following technical solutions: the near normal temperature heat sensitive catalyst has material including bismuth nitrate, silver nitrate, ferrous chloride and simple substance sulfur.

The preparation method comprises the following steps:

step one, preparing a carrier BiOCl:

dissolving 1-1.2 mol of bismuth nitrate in deionized water, stirring continuously, adding 2-2.4 mol of sodium sulfide, mixing uniformly, adjusting the pH value of the solution to 7.0-7.5, stirring and ultrasonically treating, keeping the temperature at 80 ℃, heating and refluxing, washing after the solution is cooled, and drying for 2 times;

step two, preparing a carrier BiOCl/Ag₃PO₄：

Adding 1-1.2 mol of silver nitrate into the solution obtained in the step one, stirring continuously to dissolve the silver nitrate, and then dropwise adding 1-1.3 mol of disodium hydrogen phosphate solution to obtain a precipitate; keeping the precipitate at a certain temperature for several hours, cooling, and cleaning with ultrapure water and ethanol for 3 times respectively;

step three, preparing BiOCl/Ag₃PO₄/FeS₂：

Sequentially adding 5.6-6.1 mol of ferrous chloride and 2.2-2.5 mol of elemental sulfur into the solution obtained in the step two, adjusting the pH value of the reaction solution to 7.0-7.2 by using ammonia water, carrying out hydrothermal reaction, respectively cleaning 3 times by using deionized water and ethanol after cooling, and then drying to obtain BiOCl/Ag₃PO₄/FeS₂And (3) powder.

Example 1:

weighing 1mol of initial reactant bismuth nitrate in deionized water according to the formula in sequence, stirring continuously, adding 5 drops of 0.1mol/L hydrochloric acid to adjust the pH value of the mixed solution to 7.0, stirring and carrying out ultrasonic treatment for 4 hours, and heating and refluxing for 12 hours. Then adding 1mol of silver nitrate into the solution, stirring the solution continuously to dissolve the silver nitrate, and then adding 1mol of disodium hydrogen phosphate solution dropwise to obtain BiOCl/Ag₃PO₄Transferring the precipitate to polytetrafluoroThe hydrothermal reaction kettle for ethylene is kept at 140 ℃ for several hours. Thirdly, sequentially adding 1.1mol of ferrous chloride and 1.1mol of elemental sulfur into the solution, then adding 3 drops of 0.1mol/L ammonia water to adjust the pH value of the solution to 7.0, carrying out hydrothermal reaction for 12 hours at 130 ℃, respectively cleaning 3 times by using deionized water and ethanol after cooling, and then drying for 10 hours at 60 ℃ to obtain BiOCl/Ag₃PO₄/FeS₂And (3) powder.

Example 2

Weighing 1.1mol of initial reactant bismuth nitrate in deionized water according to the formula in sequence, stirring continuously, adding 4 drops of 0.1mol/L hydrochloric acid to adjust the pH value of the mixed solution to 7.2, stirring and carrying out ultrasonic treatment for 3h, and heating and refluxing for 12 h. Then adding 1.1mol of silver nitrate into the solution, stirring the solution continuously to dissolve the silver nitrate, and then adding 1.1mol of disodium hydrogen phosphate solution dropwise to obtain BiOCl/Ag₃PO₄The precipitate was transferred to a hydrothermal polytetrafluoroethylene reactor and held at 140 ℃ for several hours. Thirdly, sequentially adding 1.1mol of ferrous chloride and 1.1mol of elemental sulfur into the solution, then adding 3 drops of 0.1mol/L ammonia water to adjust the pH value of the solution to 7.2, carrying out hydrothermal reaction for 12 hours at 120 ℃, respectively cleaning 3 times by using deionized water and ethanol after cooling, and then drying for 10 hours at 60 ℃ to obtain BiOCl/Ag₃PO₄/FeS₂And (3) powder.

Example 3

Under the shading condition, the reaction temperature is controlled to be 30 ℃, and BiOCl/Ag prepared in the example 1 is taken₃PO₄/FeS₂10mg of methylene blue solution with the degradation concentration of 30mg/L is subjected to adsorption experiment while the rotating speed is kept at 10 r/min, degradation experiment is carried out after the absorbance is unchanged, degradation is carried out for 12min under the conditions, the degradation rate reaches 95.2%, and the degradation curve is shown in figure 3.

Example 4

Under the shading condition, the reaction temperature is controlled to be 35 ℃, and BiOCl/Ag prepared in the example 1 is taken₃PO₄/FeS₂Performing adsorption experiment on 8mg of methylene blue solution with degradation concentration of 35mg/L at rotation speed of 10 rpm, performing degradation experiment after absorbance is unchanged, degrading for 12min under the above conditions, and reducingThe degradation rate reaches 99.0 percent, and the degradation curve is shown in figure 4.

Example 5

The BiOCl/Ag obtained in example 2 was collected by controlling the reaction temperature at 30 ℃ under a light-shielding condition₃PO₄/FeS₂And (3) performing an adsorption experiment on 10mg of a methyl orange solution with a degradation concentration of 30mg/L in the powder at a rotation speed of 10 rpm, performing a degradation experiment after the absorbance is unchanged, degrading for 12min under the conditions, wherein the degradation rate reaches 98.6%, and the degradation curve is shown in figure 5.

Example 6

Under the shading condition, the reaction temperature is controlled to be 30 ℃, and the BiOCl/Ag prepared in the example 2 is taken₃PO₄/FeS₂10mg of powder of methyl blue and methyl orange solution with degradation concentration of 40mg/L is subjected to adsorption experiment while maintaining the rotating speed of 10 r/min, degradation experiment is carried out after the absorbance is unchanged, degradation is carried out for 12min under the conditions, the degradation rate reaches 99.6%, and the degradation curve is shown in figure 6.

Example 7

The catalyst of example 1 was reused 3 times for a recycling experiment. The procedure of example 1 was followed, and the degraded catalyst was collected by filtration, washed with ethanol and acetone 3 times in sequence, and dried at 40 ℃. And then repeating the step 2 times again under the same condition, wherein the degradation rate reaches 95.5% after the degradation is finished, which shows that the thermal sensitive catalyst prepared by the method has good stability and is beneficial to recycling.

Example 8

The catalyst of example 2 was reused 3 times for a recycle experiment. The procedure of example 1 was followed, and the degraded catalyst was collected by filtration, washed with ethanol and acetone 3 times in sequence, and dried at 40 ℃. And then repeating the step 2 times again under the same condition, wherein the degradation rate reaches 93.2% after the degradation is finished, which shows that the thermal sensitive catalyst prepared by the method has good stability and is beneficial to recycling.

In conclusion, the thermosensitive catalyst prepared by the invention has excellent degradation effect of cheap, simple and operable and high-efficiency degradation of organic wastewater, and the removal rate of methylene blue of the catalyst reaches 99.2%.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.