CN107626322A - A kind of preparation method of heterogeneous catalysis and its application in degradation of dye waste water - Google Patents

Abstract

Application the invention discloses a kind of preparation method of heterogeneous catalysis and its in degradation of dye waste water, first by CoCl₂▪6H₂O、(NH₄)₆MoO₂₄▪4H₂O and CO (NH₂)₂It is mixed and added into deionized water dissolving, stirring, obtained mixture, which is put into reactor, carries out hydro-thermal reaction, product after reaction is filtered, deionized water and ethanol are washed to colourless, obtained colourless product drying, high-temperature calcination, finally obtains cobalt molybdenum oxide CoMoO₄, by cobalt molybdenum oxide CoMoO made from the technique₄Catalytic effect in advanced oxidation processes is notable, and in catalytic degradation organic dye waste water, by being catalyzed and aoxidizing, organic dyestuff is decomposed into the material without pollution, CoMoO to environment₄As a kind of new heterogeneous catalysis, to the obvious processing effect of organic dyestuff in wastewater.

Description

A kind of preparation method of heterogeneous catalysis and its application in degradation of dye waste water

Technical field

The invention belongs to field of waste water treatment, and in particular to a kind of heterogeneous catalysis CoMoO₄Preparation method and its Application in degradation of dye waste water.

Background technology

The organic dyestuff of various high concentrations is usually contained in the sewage of weaving and printing and dyeing industry, is directly discharged to meeting in environment Huge harm is caused to environment and health.In in the past few decades, traditional processing method includes：Physical, change Method and biotechnology etc..But these processing methods are all very low in the efficiency of organic dye waste water degradation process.Then, it is domestic Outer researcher begins to focus on the application in degrading organic dye waste water in high-level oxidation technology.In high-level oxidation technology, hydroxyl Free radical is a kind of typical oxidation group of tradition, and it can degrade many organic pollutions, but because its generation process is answered Miscellaneous and uneconomical, pH restricted applications and sludge energy shortcoming may be produced, researcher is begun to focus in potentiometric titrations, Potentiometric titrations have very high oxidation-reduction potential, can be with the organic dyestuff in oxidation Decomposition waste water, while sulfate radical is certainly Can continue longer time after being produced by base is present, and this can lengthen with organic matter continuous contact and lift the effect of degraded, can be with Oxidation is set to carry out time lengthening,

Peroxy-monosulfate can be catalyzed in view of cobalt molybdenum oxide and produces potentiometric titrations, shone in theory under kindred circumstances than hydroxyl The palliating degradation degree of free radical can improve, and potentiometric titrations can also process part hydroxy radical itself can not aoxidize it is organic Thing, removal ability are wider.By synthesizing heterogeneous catalysis cobalt molybdenum oxide CoMoO₄, applied to peroxy-monosulfate advanced oxidation System processing contains organic organic dye waste water, can be greatly enhanced the removal effect to organic dyestuff.

The content of the invention

The technical problem of solution：The application is mainly to propose a kind of preparation method of heterogeneous catalysis and its contaminated in degraded Expect the application in waste water, solution has the technical problems such as cost height, effect difference in the prior art.

Technical scheme：A kind of preparation method of heterogeneous catalysis, comprises the following steps：

The first step, CoMoO is prepared using hydrothermal synthesis method₄Presoma：By CoCl₂▪6H₂O、(NH₄)₆MoO₂₄▪4H₂O and CO (NH₂)₂Deionized water dissolving, stirring are mixed and added into, obtained mixture, which is put into reactor, carries out hydro-thermal reaction, described CoCl₂▪6H₂O、(NH₄)₆MoO₂₄▪4H₂O and CO (NH₂)₂Mass ratio be 0.119:0.877:0.3003.

Second step, calcining prepare CoMoO₄Compound：The product that hydro-thermal reaction obtains later is filtered, then uses deionized water Washed with ethanol to colourless, obtained colourless product, which is maintained at 60-80 DEG C, dries 12-24h, and dried product is in 450- 3-6h is calcined at 500 DEG C, heterogeneous catalysis cobalt molybdenum oxide CoMoO is obtained after calcined₄。

As a preferred technical solution of the present invention：CoCl in the first step₂▪6H₂O usage amount be 0.119g, (NH₄)₆MoO₂₄▪4H₂O usage amount is 0.877g, CO (NH₂)₂Usage amount be 0.3003g, the volume 36mL of deionized water, Hydrothermal temperature is 120-150 DEG C, reaction time 12-24h.

As a preferred technical solution of the present invention：The speed control that temperature rises during the calcining is in 1-2 DEG C/min.

As a preferred technical solution of the present invention：The filter paper filter footpath of the second step filtering is 30-50 microns, washing Order is washed with ethanol again to be first washed with deionized water.

On the other hand, present invention also offers heterogeneous catalysis made of the method using this law in degradation of dye waste water In application.

Beneficial effect：The preparation method of herein described heterogeneous catalysis and its in degradation of dye waste water application use with Upper technical scheme compared with prior art, has following technique effect：

1st, raw material obtain simple, cheap, no danger.

2nd, the preparation technology is simple, to dyestuff high treating effect.

3rd, for single PSM after the 60min that reaction starts, the discoloration rate of methylene blue has only reached 32.2%；Do not adding In the case of adding PSM, CoMoO₄Can not degradation of methylene blue dyestuff；PSM and CoMoO are added when simultaneously₄When, methylene blue dye Clearance substantially increase, after catalytic oxidation starts 40min, the clearance of methylene blue dye has reached 100%.

4th, as catalyst CoMoO₄Dosage when being 0.01g, PSM-CoMoO after reaction 60 minutes₄Catalyzing oxidizing degrading is sub- The speed of methyl blue has reached 95.3%；As catalyst CoMoO₄Dosage when being 2.00g, PSM-CoMoO after reaction 25 minutes₄ The speed of catalyzing oxidizing degrading methylene blue has reached 100%.With the increase of catalyst amountses, the removal of methylene blue is imitated Rate significantly improves.

Brief description of the drawings：

Fig. 1 is the preparation technology schematic flow sheet of the application heterogeneous catalysis.

Embodiment

The embodiment of the present invention is described in further detail with reference to Figure of description.

Embodiment 1

As shown in figure 1, the preparation method of heterogeneous catalysis, comprises the following steps：

The first step, CoMoO is prepared using hydrothermal synthesis method₄Presoma：By 0.119g CoCl₂▪6H₂O, 0.877g (NH₄)₆MoO₂₄▪4H₂O and 0.3003g CO (NH₂)₂Mixing, and add 36mL deionized water dissolvings, stirring, obtained mixing Thing, which is put into reactor, carries out hydro-thermal reaction, and hydrothermal temperature is 120 DEG C, reaction time 12h.

Second step, calcining prepare CoMoO4 compounds：The product that hydro-thermal reaction obtains later is through filtering the filter that footpath is 30 microns Paper is filtered, and filter residue is first washed with deionized water to be washed to colourless with ethanol again, and obtained colourless product is maintained at 60 DEG C and dried 12h, dried product calcine 3h at 450 DEG C, and the speed control that temperature rises finally obtains heterogeneous urge in 1 DEG C/min Agent cobalt molybdenum oxide CoMoO₄。

Catalytic oxidation process：All catalytic reaction experiments are carried out in 100 mL beaker, first in room temperature 25 50mL waste water is added at DEG C into beaker, adds 5.0 mg catalyst PSM, CoMoO₄And PSM-CoMoO₄It is scattered in In 50mL, 100mg/L methylene blue solution, and controlled with the min of magnetic stirrer 30, magnetic stirring speed 400 R/min, ensure that reaction solution fully reacts and reach absorption-desorption balance；Oxidizing process starts from adding into beaker 2.0mmol PSM, in given reaction time interval, take that 0.4mL's is anti-in 0,10,20,30,40,50,60min respectively Solution is answered, while saturation Na is added into reaction solution₂S₂O₃Solution terminating reaction, surveyed with spectrophotometer at wavelength 664nm Determine methylene blue dye concentration degradation efficiency.

Catalytic result shows：Single PSM is after the 60min that reaction starts, and the discoloration rate of methylene blue is only Reach 32.2%；In the case of no addition PSM, CoMoO₄Can not degradation of methylene blue dyestuff；When simultaneously add PSM and CoMoO₄When, the clearance of methylene blue dye substantially increases, after catalytic oxidation starts 40min, methylene blue dye Clearance reached 100%.

Embodiment 2

As shown in figure 1, heterogeneous catalysis CoMoO₄Preparation method, comprise the following steps：

The first step, CoMoO is prepared using hydrothermal synthesis method₄Presoma：By 0.119g CoCl₂▪6H₂O, 0.877g (NH₄)₆MoO₂₄▪4H₂O and 0.3003g CO (NH₂)₂Mixing, and add 36mL deionized water dissolvings, stirring, obtained mixing Thing, which is put into reactor, carries out hydro-thermal reaction, and hydrothermal temperature is 150 DEG C, reaction time 24h.

Second step, calcining prepare CoMoO4 compounds：The product that hydro-thermal reaction obtains later is through filtering the filter that footpath is 50 microns Paper is filtered, and filter residue is first washed with deionized water to be washed to colourless with ethanol again, and obtained colourless product is maintained at 80 DEG C and dried 24h, dried product calcine 6h at 500 DEG C, and the speed control that temperature rises finally obtains heterogeneous urge in 2 DEG C/min Agent cobalt molybdenum oxide CoMoO₄。

All catalytic oxidation experiments are carried out in 100 mL beaker, first to beaker at 25 DEG C of room temperature 50 mL of middle addition waste water, add 5.0 mg catalyst CoMoO₄It is scattered in 50mL, 100mg/L methylene blue solution In, and fully reacted in 400 r/min, guarantee reaction solution with the min of magnetic stirrer 30, magnetic stirring speed control Reach absorption-desorption balance；Oxidizing process：0.5 mmol, 1.0 mmol, 1.5 mmol, 2.0 are separately added into beaker Mmol, 2.5 mmol PSM, in given reaction time interval, take 0.4 in 0,10,20,30,40,50,60 min respectively ML reaction solution, while saturation Na is added into reaction solution₂S₂O₃Solution terminating reaction, with spectrophotometer in wavelength 664 Methylene blue dye concentration degradation efficiency is determined at nm.

Test result indicates that：PSM-CoMoO₄The speed of catalyzing oxidizing degrading methylene blue is with the increase of PSM dosages And substantially increase.Behind 30 minutes that reaction starts, when PSM dosage increases to 2.5mmol from 0.5mmol, methylene The degradation rate of blue dyestuff increases to 95.3% from 80.5%.

Embodiment 3

As shown in figure 1, heterogeneous catalysis CoMoO₄Preparation method, comprise the following steps：

The first step, CoMoO is prepared using hydrothermal synthesis method₄Presoma：By 0.119g CoCl₂▪6H₂O, 0.877g (NH₄)₆MoO₂₄▪4H₂O and 0.3003g CO (NH₂)₂Mixing, and add 36mL deionized water dissolvings, stirring, obtained mixing Thing, which is put into reactor, carries out hydro-thermal reaction, and hydrothermal temperature is 140 DEG C, reaction time 18h.

Second step, calcining prepare CoMoO4 compounds：The product that hydro-thermal reaction obtains later is through filtering the filter that footpath is 40 microns Paper is filtered, and filter residue is first washed with deionized water to be washed to colourless with ethanol again, and obtained colourless product is maintained at 70 DEG C and dried 18h, dried product calcine 5h at 480 DEG C, and the speed control that temperature rises finally obtains heterogeneous urge in 1 DEG C/min Agent cobalt molybdenum oxide CoMoO₄。

All catalytic oxidation experiments are carried out in 100 mL beaker, first to beaker at 25 DEG C of room temperature Middle addition 50mL waste water, it is separately added into 0.01g, 0.05g, 2.00 g, 3.00g catalyst CoMoO₄Be scattered in 50mL, In 100mg/L methylene blue solution, and controlled with the min of magnetic stirrer 30, magnetic stirring speed in 400 r/min, Ensure that reaction solution fully reacts and reach absorption-desorption balance；Oxidizing process：Into beaker add 2.0mmol, PSM, to In fixed reaction time interval, 0.4mL reaction solution is taken in 0,10,20,30,40,50,60min respectively, while to reaction Saturation Na is added in solution₂S₂O₃Solution terminating reaction, it is dense that methylene blue dye is determined at wavelength 664nm with spectrophotometer Spend degradation efficiency.

Test result indicates that：As catalyst CoMoO₄Dosage when being 0.01g, PSM-CoMoO after reaction 60 minutes₄Urge The speed for changing oxidative degradation methylene blue has reached 95.3%；As catalyst CoMoO₄Dosage when being 2.00g, react 25 points PSM-CoMoO after clock₄The speed of catalyzing oxidizing degrading methylene blue has reached 100%.

Embodiments of the present invention are explained in detail above in conjunction with accompanying drawing, but the present invention is not limited to above-mentioned implementation Mode, can also be on the premise of present inventive concept not be departed from those of ordinary skill in the art's possessed knowledge Make a variety of changes.

Claims (5)

1. a kind of preparation method of heterogeneous catalysis, it is characterised in that comprise the following steps：

The first step, CoMoO is prepared using hydrothermal synthesis method₄Presoma：By CoCl₂▪6H₂O、(NH₄)₆MoO₂₄▪4H₂O and CO (NH₂)₂Deionized water dissolving, stirring are mixed and added into, obtained mixture, which is put into reactor, carries out hydro-thermal reaction, described CoCl₂▪6H₂O、(NH₄)₆MoO₂₄▪4H₂O and CO (NH₂)₂Mass ratio be 0.119:0.877:0.3003；

Second step, calcining prepare CoMoO₄Compound：Obtained product is filtered later for hydro-thermal reaction, then with deionized water and second Alcohol is washed to colourless, and obtained colourless product, which is maintained at 60-80 DEG C, dries 12-24h, and dried product is at 450-500 DEG C Lower calcining 3-6h, heterogeneous catalysis cobalt molybdenum oxide CoMoO is obtained after calcined₄。

2. CoMoO according to claim 1₄The preparation method of/GAC sorbing materials, it is characterised in that：In the first step CoCl₂▪6H₂O usage amount is 0.119g, (NH₄)₆MoO₂₄▪4H₂O usage amount is 0.877g, CO (NH₂)₂Usage amount be 0.3003g, the volume 36mL of deionized water, hydrothermal temperature are 120-150 DEG C, reaction time 12-24h.

3. CoMoO according to claim 1₄The preparation method of/GAC sorbing materials, it is characterised in that：The temperature during calcining The speed control risen is spent in 1-2 DEG C/min.

4. CoMoO according to claim 1₄The preparation method of/GAC sorbing materials, it is characterised in that：The second step mistake The filter paper filter footpath of filter is 30-50 microns, and washing sequence is washed with ethanol again to be first washed with deionized water.

A kind of 5. application of the heterogeneous catalysis in degradation of dye waste water made of any methods describeds of claim 1-4.