Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of method removing malachite green.The method utilizes the synergy of TMT15 and PAM to be removed by malachite green, and remove speed fast, removal efficiency is high, simple to operate, is with a wide range of applications in dyeing wastewater process field.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method removing malachite green, and it is characterized in that, the method comprises the following steps:
Step one, TMT15, PAM, malachite green and deionized water to be mixed, obtain mixed solution, in often liter of mixed solution, the add-on of TMT15, PAM, malachite green and deionized water is respectively: 560mg ~ 800mg TMT15,360mg ~ 480mg PAM, 80mg malachite green, surplus is deionized water;
The pH value of mixed solution described in step one is adjusted to 8 ~ 12 by the method that step 2, employing drip alkali lye, then by pH value be 8 ~ 12 mixed solution be incubated 0.5h ~ 8.0h under the condition of 30 DEG C ~ 75 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
A kind of above-mentioned method removing malachite green, is characterized in that, in step one, in often liter of mixed solution, the add-on of TMT15 is the add-on of 672mg, PAM is 400mg.
A kind of above-mentioned method removing malachite green, is characterized in that, the sodium hydroxide solution of to be concentration the be 0.5mol/L ~ 1mol/L of alkali lye described in step 2.
A kind of above-mentioned method removing malachite green, is characterized in that, after regulating in step 2, the pH value of mixed solution is 10.
A kind of above-mentioned method removing malachite green, is characterized in that, the time be incubated described in step 2 is 0.5h.
The mechanism that the present invention removes malachite green is: TMT15 can be successfully used in removing malachite green, its mechanism is, malachite green molecular structure is on the surface with stronger positive charge, and this form with stronger positive charge causes high density malachite green to be easy to be dissolved in water body and the root place of long-term stability just.TMT15, as a kind of sulfur-bearing sequestrant, has electronegativity polarity, and on TMT15 molecule, institute is electrically charged electrically charged contrary with malachite green molecule institute, the positive and negative charge of malachite green and TMT15 is attracting, cause the electrically charged counteracting of both sides, thus form larger crumb structure, and then form precipitation.PAM, as a kind of linear polymeric watersoluble organic polymer of synthetic, has good flocculence.PAM can adsorb little for the throw out formed in solution scattered fragment further, is bound up in the lump, is bonded to larger particle, forms flocs unit, thus serves good promoter action to TMT15 chelating precipitation malachite green.Therefore, under the synergy of TMT15 and PAM, malachite green can farthest be removed.
The present invention compared with prior art has the following advantages:
1, present invention process is simple, and processing cost is low, and removal efficiency is high, consuming time short, is suitable for large-scale industrial production.
2, the present invention utilizes the synergy of TMT15 and PAM to be removed by malachite green.Wherein, TMT15, to environment non-secondary pollution, belongs to environmentally friendly organosulfur medicament, and it can form precipitation with the powerful chelating of malachite green, and treatment effect is good; PAM serves good promoter action for TMT15 chelating precipitation malachite green.Adopt process 0.5h of the present invention that the clearance of malachite green can be made up to more than 99%, remove thorough, complete.
3, treatment process of the present invention is simple, without the need to increasing cost of equipment, having significant social benefit and environmental benefit, being highly suitable for industrial dye waste water industry and applying.
4, malachite green effectively can be removed from containing the dyeing waste water of malachite green by the present invention, and malachite green concentration residual in the dyeing waste water after process is well below discharging standards, and the dyeing waste water after process gets final product safety dumping without the need to neutralizing treatment.
5, the present invention has the advantages such as treatment effect is good, simple to operate, working cost is low, is with a wide range of applications in dyeing wastewater process.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
The present embodiment removes the method for malachite green:
Step one, 672mg TMT15,400mg PAM and 80mg malachite green to be added in 1L volumetric flask, add after deionized water is diluted to graticule and fully shake up, obtain mixed solution;
The pH value of mixed solution described in step one is adjusted to 10 by the method that step 2, employing drip the sodium hydroxide solution that concentration is 0.8mol/L, then by pH value be 10 mixed solution be incubated 0.5h under the condition of 75 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
The clearance of the present embodiment malachite green is 99.96%.
Embodiment 2
The present embodiment removes the method for malachite green:
Step one, 672mg TMT15,400mg PAM and 80mg malachite green to be added in 1L volumetric flask, add after deionized water is diluted to graticule and fully shake up, obtain mixed solution;
The pH value of mixed solution described in step one is adjusted to 10 by the method that step 2, employing drip the sodium hydroxide solution that concentration is 0.6mol/L, then by pH value be 10 mixed solution be incubated 3h under the condition of 50 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
The clearance of the present embodiment malachite green is 99.54%.
Embodiment 3
The present embodiment removes the method for malachite green:
Step one, 560mg TMT15,360mgmg PAM, 80mg malachite green to be added in 1L volumetric flask, add after deionized water is diluted to graticule and fully shake up, obtain mixed solution;
The pH value of mixed solution described in step one is adjusted to 12 by the method that step 2, employing drip the sodium hydroxide solution that concentration is 1mol/L, then by pH value be 12 mixed solution be incubated 8h under the condition of 75 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
The clearance of the present embodiment malachite green is 99.38%.
Embodiment 4
The present embodiment removes the method for malachite green:
Step one, 800mg TMT15,480mg PAM, 80mg malachite green to be added in 1L volumetric flask, add after deionized water is diluted to graticule and fully shake up, obtain mixed solution;
The pH value of mixed solution described in step one is adjusted to 8 by the method that step 2, employing drip the sodium hydroxide solution that concentration is 0.5mol/L, then by pH value be 8 mixed solution be incubated 1.5h under the condition of 30 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
The clearance of the present embodiment malachite green is 99.04%.
Embodiment 5
The present embodiment removes the method for malachite green:
Step one, 784mg TMT15,420mg PAM, 80mg malachite green to be added in 1L volumetric flask, add after deionized water is diluted to graticule and fully shake up, obtain mixed solution;
The pH value of mixed solution described in step one is adjusted to 9 by the method that step 2, employing drip the sodium hydroxide solution that concentration is 0.8mol/L, then by pH value be 9 mixed solution be incubated 5h under the condition of 65 DEG C in temperature, malachite green in mixed solution is separated out with precipitation forms under the synergy of TMT15 and PAM, finally adopts the method for filtration to be removed by malachite green.
The clearance of the present embodiment malachite green is 99.37%.
The clearance of malachite green of the present invention is measured by ultraviolet visible spectrophotometry, and detailed process is as follows:
One, the absorbancy-concentration standard curve of malachite green is drawn:
First, accurately take 1.0000g malachite green to add in 1L volumetric flask, add after redistilled water is settled to graticule and fully shake up, obtain the Standard Reserving Solution that concentration is 1000.00mg/L, place 1 ~ 2 angel's malachite green to dissolve completely, ensure that the absorbancy of Standard Reserving Solution keeps stable; Then, pipette 0 respectively, 0.50mL, 1.00mL, 2.00mL, 5.00mL, 10.00mL and 20.00mL Standard Reserving Solution is in 100mL volumetric flask, add after redistilled water is diluted to graticule and fully shake up, obtain that mass concentration is respectively 0, the malachite green reference liquid of 5.00mg/L, 10.00mg/L, 20.00mg/L, 50.00mg/L, 100.00mg/L and 200.00mg/L series; Afterwards, the malachite green reference liquid series pipetting 5mL different concns respectively, in the dry colorimetric cylinder of 10mL, adds redistilled water and fully shakes up to colorimetric cylinder scale marks; After ambient temperatare puts 10min, use 1cm quartz colorimetric utensil, in wavelength 614nm place, measure the absorbance A of different concns malachite green reference liquid series
i; Finally, with the absorbance A of different concns malachite green reference liquid series
ifor ordinate zou, corresponding malachite green mass concentration is X-coordinate, draws the absorbancy-concentration standard curve of malachite green.
Two, the concentration of malachite green before and after assaying reaction:
Before the reaction with reaction after, all pipette 5mL mixed solution in the dry colorimetric cylinder of 10mL, add redistilled water and fully shake up to colorimetric cylinder scale marks; After ambient temperatare puts 10min, use 1cm quartz colorimetric utensil, in wavelength 614nm place, measure the absorbance A of mixed solution
x; Finally by A
xbe incorporated in the absorbancy-concentration standard curve of malachite green, calculate the concentration of mixed solution Malachite Green before and after reaction.
Three, the clearance of malachite green is measured:
By formula
record the clearance of malachite green; Wherein, η is the clearance of malachite green, C
0for reacting the concentration of front malachite green solution, C is the concentration of malachite green solution after reaction, C
0mg/L is with the unit of C.
Optimal ph and the optimal reaction temperature of the optimal addn of TMT15 of the present invention, the optimal addn of PAM, mixed solution are optimized by following test.
One, the selection of TMT15 optimal addn
It is the malachite green aqueous solution of 80mg/L is research object that the present invention chooses starting point concentration, TMT15 is only adopted to remove malachite green as remover, react under the condition of non-adjust ph at normal temperature (20 DEG C) environment, record the removal effect of different concns TMT15 to malachite green in table 1.
Table 1 different concns TMT15 is to the removal effect of malachite green
As shown in Table 1, under the condition of non-adjust ph at normal temperature (20 DEG C) environment, react and reach stable at about 8h, when the add-on of TMT15 in mixed solution is 672mg/L, the clearance of malachite green reaches the highest (clearance is 93.29%).Along with the increase of TMT15 add-on, the clearance of malachite green progressively increases, and when TMT15 add-on is 672mg/L, clearance reaches maximum, and that continues increase TMT15 adds concentration, and the clearance of malachite green declines on the contrary.
Two, the selection of PAM optimal addn under independent role
It is the malachite green aqueous solution of 80mg/L is research object that the present invention chooses starting point concentration, PAM is only adopted to remove malachite green as remover, react under the condition of non-adjust ph at normal temperature (20 DEG C) environment, record the removal effect of different concns PAM to malachite green in table 2.
Table 2 different concns PAM is to the removal effect of malachite green
As shown in Table 2, under the condition of non-adjust ph at normal temperature (20 DEG C) environment, react and reach stable at about 2.5h, when in mixed solution, the add-on of PAM is 120mg/L, the clearance of malachite green reaches the highest (clearance is 19.25%).After the flocculation agent PAM of high molecular polymerization state is added to water body, its form is relatively stable, because it is that inertia stable state can not continue hydrolysis thus keep existing polymeric species, stronger charge neutrality cohesion and net is had to catch bridge formation function than traditional flocculation agent, best flocculation can be played, thus part malachite green can be removed.
Three, the selection of the lower PAM optimal addn of synergy
It is the malachite green aqueous solution of 80mg/L is research object that the present invention chooses starting point concentration, adopt TMT15 and PAM as remover, by synergy, malachite green is removed, the add-on of TMT15 is 672mg/L, react under the condition of non-adjust ph at normal temperature (20 DEG C) environment, record the lower different concns PAM of synergy to the removal effect of malachite green in table 3.
Table 3 acts synergistically lower different concns PAM to the removal effect of malachite green
As shown in Table 3, at normal temperature (20 DEG C) environment and under the condition of non-adjust ph, when the add-on of mixed solution Malachite Green is 80mg/L, the add-on of TMT15 is 672mg/L, when the add-on of PAM is 400mg/L, reaction reaches stable at about 8h, and the removal efficiency of malachite green is the highest (clearance is 97.14%).
Four, the selection of optimal ph
It is the malachite green aqueous solution of 80mg/L is research object that the present invention chooses starting point concentration, adopt TMT15 and PAM as remover, by synergy, malachite green is removed, the add-on of TMT15 is 672mg/L, the add-on of PAM is 400mg/L, react under normal temperature (20 DEG C) condition, record the removal effect of different pH value to malachite green in table 4.
The different pH value of table 4 is to the removal effect of malachite green
As shown in Table 4, under normal temperature (20 DEG C) condition, when the add-on of mixed solution Malachite Green is 80mg/L, the add-on of TMT15 is 672mg/L, when the add-on of PAM is 400mg/L, reaction reaches stable at about 5.0h, and the pH regulating mixed solution is 10, and the removal efficiency of malachite green can be made to reach the highest (clearance is 97.91%).
Five, the selection of optimal reaction temperature
It is the malachite green aqueous solution of 80mg/L is research object that the present invention chooses starting point concentration, adopt TMT15 and PAM as remover, by synergy, malachite green is removed, the add-on of TMT15 is 672mg/L, the add-on of PAM is 400mg/L, be react under the condition of 10 in pH value, record the removal effect of differential responses temperature to malachite green in table 5.
Table 5 differential responses temperature is to the removal effect of malachite green
As shown in Table 5, the add-on being 80mg/L, TMT15 when the add-on of mixed solution Malachite Green is 672mg/L, the add-on of PAM is 400mg/L, and the pH value of mixed solution is 10, and temperature of reaction is 0.5h, when temperature of reaction is 30 DEG C ~ 75 DEG C, the removal efficiency of malachite green is all more than 99%.
Six, sum up
The present invention finds through large quantity research, and malachite green can be removed by synergy by TMT15 and PAM, and removal efficiency is high, removes speed fast.In addition, the present invention is directed to starting point concentration is that the malachite green aqueous solution of 80mg/L is studied, determine that at the optimal addn of TMT15 be 672mg/L, the optimal addn of PAM is 400mg/L, the optimal ph of mixed solution is 10, optimal reaction temperature is react 0.5h under the condition of 30 DEG C ~ 75 DEG C, and the removal effect of malachite green is up to more than 99%.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.