CN105016576A - Method for degrading azo dye in water body by using activated carbon nanotube immobilized azo reductase - Google Patents
Method for degrading azo dye in water body by using activated carbon nanotube immobilized azo reductase Download PDFInfo
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Abstract
The invention discloses a method for degrading azo dye in a water body by using activated carbon nanotube immobilized azo reductase. The method comprises: firstly adjusting the pH value of a to-be-treated water body containing the azo dye to 5.0-8.0 and adjusting the initial concentration of the azo dye of the water body containing the azo dye to 20-100 mg/L; then putting the activated carbon nanotube immobilized azo reductase in the water body, wherein the content of the activated carbon nanotube immobilized azo reductase added into the water body containing the azo dye per ml is not less than 0.5 mg; then carrying out oscillatory reaction on a mixed liquid for 10-30 minutes at 10-50 DEG C; and recovering the activated carbon nanotube immobilized azo reductase through suction filtration and adjusting the water body to neutral and discharging the water body. According to the method disclosed by the invention, azo reductase of the azo dye is degraded in an immobilized manner by using an activated carbon nanotube, so that the mass transfer effect of the azo reductase is favorably fixed by virtue of a relatively large specific surface area and abundant porous structures of an activated carbon nanotube material; the degradation efficiency of the azo dye wastewater is greatly improved as the mass transfer effect is cooperated with the catalytic action of the azo reductase. The repeated utilization ratio of the azo reductase is improved as the azo reductase is recovered through suction filtration.
Description
Technical field
The invention belongs to sewage treatment area, particularly a kind of method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body.
Background technology
Of a great variety and the complex structure of azoic dyestuff, still greater activity can be kept there is oxygenant existent condition in water surrounding under, in addition azoic dyestuff greatly and mesostate thereof is had to be the toxic compounds of pole difficult degradation, steady chemical structure, there is teratogenesis, carcinogenic, mutagenic " three cause " effect, have a strong impact on the healthy and safe of contactee.In recent years, Chinese scholars had done large quantifier elimination to its Degradation and Transformation method.At present, mainly contain Physical, chemical method and biological process to process dye wastewater, compare with chemical method with Physical, biological process have stable, easy to operate simple, working cost is low and not easily produce the features such as secondary pollution, enjoys investigator to favor.
Biological process comprises again microbiological deterioration and enzyme liberating, there are some researches show, the effect of the decoloring ability of bacterium azo dyes mainly its azo reductase produced, enzyme liberating method is compared with biological degradation method, have easy and simple to handle, reaction process easily control, advantage that processing efficiency is high.But resolvase because of poor stability, be difficult to reclaim, be easily mixed into sample and not easily the shortcoming such as recycle make it apply to be restricted, after resolvase being fixed on carrier by certain method, the shortcoming of resolvase can be overcome, be convenient to serialization and the automatization of production technique, have broad application prospects.Fixation techniques for enzyme is generally divided into absorption method, crosslinking, covalently bonded are legal, entrapping method, directional at-tachment etc., wherein physisorphtion is compared all the other several technology and is had easy and simple to handle, the feature such as mild condition, the variation inactivation that can not cause enzyme.The inorganic carrier of early stage immobilized enzyme application is mainly divided into wilkinite, aluminum oxide, glass and marine alga stone etc., and these materials are owing to being subject to the restriction of the factors such as aperture, specific surface area, grain graininess, and the ability of desmoenzyme is quite low.
Carbon nanotube owing to having stronger absorption property, at present as water treatment practice in type material.But carbon nanotube is due to self, its specific surface area is relatively little, and easily self-reunion affects its dispersing property in water surrounding, and then affects its adsorption effect further.Effectively can be increased specific surface area and the pore volume of carbon nanotube by the carbon nanotube after activation of potassium hydroxide, and greatly strengthen its dissemination in water body, for enzyme immobilizatio study on the carrier provides great potential.
And utilize immobilized azo reductase to process the research containing azo dye wastewater also to there is not yet bibliographical information at present.
Summary of the invention
Goal of the invention: the invention provides a kind of method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, to solve the problems of the prior art.
Technical scheme: to achieve these goals, the present invention by the following technical solutions:
A kind of method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, comprise the following steps: first the pending water pH value containing azoic dyestuff is adjusted to 5.0 ~ 8.0, and regulates the azoic dyestuff starting point concentration containing azoic dyestuff water body to be 20 ~ 100mg/L; Then drop in above-mentioned water body by immobilized for activated carbon nano-tube azo reductase, every milliliter is not less than 0.5mg containing the immobilized azo reductase of activated carbon nano-tube added in the water body of azoic dyestuff; Subsequently at the temperature of 10 ~ 50 DEG C to above-mentioned mixed solution oscillatory reaction 10 ~ 30min; Reclaim the immobilized azo reductase of activated carbon nano-tube by suction filtration again, finally water body is adjusted to neutral rear discharge.
Further, during described adjustment azoic dyestuff starting point concentration, be add 10ml phosphate buffer solution in the azo dye wastewater of 0.2 ~ 1g/L by 1ml containing concentration.
Further, described azoic dyestuff is any one in simple chemical structure and low-molecular-weight methyl red, tropeolin-D, orange I.
Further, the immobilized azo reductase of described activated carbon nano-tube is that azo reductase is fixed on activated carbon nano-tube by physical adsorption.
Preferably, the quality proportioning of described activated carbon nano-tube and azo reductase is 1:1 ~ 3.
Further, the immobilized azo reductase of described activated carbon nano-tube obtains by the following method: be first dissolved in 50mL phosphoric acid buffer by 0.1 ~ 0.3g activated carbon nano-tube powder, ultrasonic 10 ~ 35min in ultrasonic cleaner; Then add resolvase, fix 30 ~ 240min and obtain mixed solution in the water bath with thermostatic control of 10 ~ 50 DEG C, mixing speed is 50 ~ 400rpm; Subsequently by mixed solution suction filtration and with phosphoric acid buffer washing, wash away the resolvase do not adsorbed, dry filter under room temperature condition, the azo reductase of being fixed.
Further, described activated carbon nano-tube obtains by the following method: be that 1:5 ~ 6 mix with potassium hydroxide according to mass ratio by carbon nanotube, and be warming up to 800 DEG C of calcination 1.5 ~ 3h by the speed of 10 DEG C/min afterwards, whole process lasts leads to nitrogen; After being cooled to room temperature, the material deionized water obtained is cleaned repeatedly, after filtration, resulting materials is dried 4 ~ 6h under 100 ~ 120 DEG C of conditions.
Preferably, described nitrogen passes into speed is 35 ~ 45mL/min.
Preferably, the specific surface area of described activated carbon nano-tube is 600 ~ 1200m
2/ g, pore volume is 0.40 ~ 1.80cm
3/ g.
Preferably, described activated carbon nano-tube has orderly graphite microcrystalline structure.
Preferably, the starting point concentration of described azo reductase is 0.1 ~ 0.9mg/mL, and the pH value of described phosphoric acid buffer is 6.5 ~ 7.5.
Beneficial effect: the present invention utilizes activated carbon nano-tube to fix the azo reductase of degrade azo dyestuff, the specific surface area that activated carbon nano-tube material is larger and abundant pore passage structure are conducive to the effect of mass transmitting of immobilized enzyme, work in coordination with the katalysis of enzyme the degradation efficiency substantially increasing azo dye wastewater.In addition, reclaim immobilized enzyme by suction filtration, improve the repeating utilization factor of enzyme; The present invention utilizes azoic dyestuff in immobilized azo reductase degraded water body, and removal efficiency is higher, and between optimal ph 6.0 ~ 7.0, under the condition of initial azoic dyestuff concentration 50mg/L, within 30min, the clearance of paramethyl red is more than 85%; The present invention is simple to operate, investment and working cost lower.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Utilize a method for azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, comprise the following steps:
A. prepare activated carbon nano-tube: be that 1:5 mix with potassium hydroxide according to mass ratio by carbon nanotube, heating up by the speed of 10 DEG C/min is afterwards heated to 800 DEG C of calcination 2h, and whole process lasts leads to nitrogen (40mL/min).After being cooled to room temperature, the material deionized water obtained being cleaned repeatedly, after filtration, resulting materials is dried 4h under 100 DEG C of conditions.
B. the immobilized azo reductase of activated carbon nano-tube is prepared: first 0.15g activated carbon nano-tube powder is dissolved in (pH value is 7.0) in 50ml phosphoric acid buffer, ultrasonic 10min in ultrasonic cleaner; Then add the resolvase of 0.5mg/mL, fix 40min and obtain mixed solution in the water bath with thermostatic control of 37 DEG C, mixing speed is 250rpm; Subsequently by mixed solution suction filtration and with phosphoric acid buffer washing, wash away the resolvase do not adsorbed, dry filter under room temperature condition, the azo reductase of being fixed.
C. degraded is containing azo dye wastewater: activated carbon nano-tube is mixed to come obtained immobilized enzyme with azo reductase with the quality proportioning of 1:2.Waste water containing 0.5g/L methyl red is added in sample, the methyl red solution of 10mL is obtained by damping fluid configuration, starting point concentration is 50mg/L, pH value is 6.5, and added respectively in sample by above-mentioned obtained immobilized enzyme, control temperature is at 37 DEG C, with the rotating speed of 150rpm oscillatory reaction 30min in constant temperature culture, then be separated back the immobilized azo reductase of activated carbon nano-tube by suction filtration, regulate waste water to be after neutrality, discharge.After measured, the degradation rate of methyl red reaches more than 90%.
Comparative example 1
With free azo reductase as a comparison, simultaneous test is carried out to above-mentioned obtained immobilization azo reductase and the subject range that free azo reductase carries out pH
The subject range of pH value: the enzyme activity measuring free azo reductase and immobilized azo reductase respectively under different pH condition, as shown in table 1, as seen from table, resolvase is between 5 ~ 8 in pH value, there is higher activity, under meta-acid or slight alkali environment, free enzyme activity is lower, almost loses activity; And immobilized enzyme is between 5 ~ 8 in pH value, the activity of enzyme all higher than the activity of resolvase, and when pH value is 3 and 9, compares resolvase, and activity has higher lifting.Illustrate that immobilized enzyme is not remarkable by the impact of pH, compare resolvase and there is more wide in range pH value subject range.(in table, relative reactivity represents with %)
The relative reactivity of free azo reductase and immobilized azo reductase under table 1 different pH condition
Comparative example 2
With free azo reductase as a comparison, simultaneous test is carried out to above-mentioned obtained immobilization azo reductase and the subject range that free azo reductase carries out temperature.
The subject range of temperature: the enzyme activity measuring free azo reductase and immobilized azo reductase respectively under condition of different temperatures, as shown in table 2, as seen from table, resolvase is at 0 ~ 50 DEG C, enzyme relative reactivity higher (more than 70%), when temperature is more than 50 DEG C, the rapid sex change of protein, enzyme is lived and is significantly reduced, and the catalytic capability of enzyme declines; In contrast, immobilized enzyme is at 0 ~ 50 DEG C of temperature, and the relative reactivity of enzyme comparatively resolvase promotes to some extent, and 60 DEG C time, still keeps relatively high enzyme to live.Illustrate that immobilized enzyme is compared with resolvase, more can the actual environment of adaptive temperature complexity.(in table, the unit of temperature is DEG C, and relative reactivity represents with %)
The relative reactivity of free azo reductase and immobilized azo reductase under table 2 condition of different temperatures
With the standard that the enzyme activity contrasting free azo reductase and immobilization azo reductase is tested as a comparison, reaction system comprises following component: the phosphate buffered saline buffer (pH value is 7.0) of 1.5mL 100mM, 0.2mL 1mM NADH, 0.2mM methyl red, 0.2mL enzyme liquid.
Measuring method is: after the reaction system not adding NADH being placed in 37 DEG C of water-bath 5min, in system, add NADH fast and timing.With spectrophotometer (U-2800Hitachi) detect under 485nm enzyme liquid and methyl red at room temperature react 1min after the variable quantity of light absorption value, calculate the activity of azo reductase.1 unit azo reductase enzyme live (U) be defined as: in the reaction system of 1mL, 1min degrades the enzyme amount (the highest enzyme is lived and is set as 100%) required for 1 μm of ol dyestuff.
Comparative example 3
The degradation efficiency of immobilized azo reductase paramethyl red under research different pH condition.
Be that the methyl red solution of 0.5g/L is divided into 5 groups by concentration, often organize sample 10ml, methyl red concentration is made to be 50mg/L, pH of mixed is regulated with citrate buffer solution or phosphoric acid buffer, pH of mixed is made to be respectively 3.0, 4.0, 5.0, 6.0 and 7.0, then the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube and azo reductase quality proportioning are 1:2) is added to often organizing in sample, control temperature is at 37 DEG C, with the rotating speed of 150rpm oscillatory reaction 30min in constant temperature culture, then by suction filtration Separation and Recovery immobilized enzyme, waste water is regulated to be after neutrality, discharge.
The degradation efficiency of immobilized azo reductase paramethyl red is measured respectively under different pH condition, as shown in table 3 below, as seen from table, pH value is when 6 or 7, and the degradation efficiency of immobilization azo reductase paramethyl red is the highest, when pH is lower, lower efficiency not good, therefore, optimum pH scope is 6.0 ~ 7.0, within optimum pH scope.(in table, degradation rate represents with %)
The degradation efficiency of immobilized azo reductase paramethyl red under table 3 different pH condition
Comparative example 4
The different initial azoic dyestuff concentration of research is on the impact of immobilization azo reductase degradation efficiency.
Be that the methyl red waste water of 0.5g/L, 0.7g/L and 1g/L adds in sample respectively by concentration, often organize sample 10ml, sample concentration is respectively 50mg/L, 70mg/L and 100mg/L, pH value is 6.5, then the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube and azo reductase quality proportioning are 1:2) is added to often organizing in sample, control temperature is at 37 DEG C, with the rotating speed of 150rpm oscillatory reaction 30min in constant temperature culture, then by suction filtration Separation and Recovery immobilized enzyme, waste water is regulated to be after neutrality, discharge.
Under the initial azoic dyestuff concentration conditions of difference, measure the degradation efficiency of immobilized azo reductase paramethyl red.After measured, when the starting point concentration of methyl red is 50mg/L, degradation rate is more than 90%, and when starting point concentration is 100mg/L, degradation rate is down to about 75%.When showing that the starting point concentration of methyl red is lower, the degradation rate of immobilized azo reductase paramethyl red is higher, and best starting point concentration is 50mg/L, and this concentration is within optimum concentration scope.
Comparative example 5
The research differential responses time is on the impact of immobilization azo reductase degradation efficiency.
Waste water containing methyl red is added in sample, the methyl red solution of 10mL is obtained by damping fluid configuration, starting point concentration is 50mg/L, pH value is 6.5, then in sample, add the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube and azo reductase quality proportioning are 1:2), control temperature is at 37 DEG C, vibrate in constant temperature culture with the rotating speed of 150rpm and continue 1h, take out a certain amount of mixed solution at set intervals, by spectrophotometer measurement residue methyl red concentration, then by suction filtration Separation and Recovery immobilized enzyme, waste water is regulated to be after neutrality, discharge.
Respectively under differential responses time conditions, measure the degradation efficiency of immobilized azo reductase paramethyl red.After measured, reaction is when proceeding to 5 minutes, and immobilized enzyme paramethyl red has higher degradation rate, when proceeding to 30min, degradation rate more than 90%, pending to 60min time, degradation rate does not have a greater change.May be within 5min, it is very abundant that methyl-red dye has been degraded.
Comparative example 6
The impact reused immobilization azo reductase degradation efficiency of research immobilized enzyme.
Waste water containing methyl red is added in sample, the methyl red solution of 10mL is obtained by damping fluid configuration, starting point concentration is 50mg/L, pH value is 6.5, then in sample, add the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube and azo reductase quality proportioning are 1:2), control temperature is at 37 DEG C, vibrate in constant temperature culture with the rotating speed of 150rpm and continue 1h, by spectrophotometer measurement residue methyl red concentration, then by suction filtration Separation and Recovery immobilized enzyme, then the enzyme of recovery is rejoined in new above-mentioned solution, same reaction process measures residue methyl red concentration, so move in circles, measure the reusability of the immobilized azo reductase of activated carbon nano-tube.After measured, reuse after reaction carries out 5 times, the degradation rate of immobilized enzyme paramethyl red, still up to about 60%, shows that this immobilized enzyme has certain operational stability, can reuse.
Embodiment 2
Utilize a method for azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, comprise the following steps:
A. prepare activated carbon nano-tube: mixed with the mass ratio of potassium hydroxide according to 1:6 by carbon nanotube, heating up by the speed of 10 DEG C/min is afterwards heated to 800 DEG C of calcination 1.5h, and whole process lasts leads to nitrogen (35mL/min).After being cooled to room temperature, the material deionized water obtained being cleaned repeatedly, after filtration, resulting materials is dried 5h under 120 DEG C of conditions.
B. the immobilized azo reductase of activated carbon nano-tube is prepared: first 0.1g activated carbon nano-tube powder is dissolved in (pH value is 6.5) in 50ml phosphoric acid buffer, ultrasonic 35min in ultrasonic cleaner; Then add the resolvase of 0.5mg/mL, fix 240min and obtain mixed solution in the water bath with thermostatic control of 10 DEG C, mixing speed is 50rpm; Subsequently by mixed solution suction filtration and with phosphoric acid buffer washing, wash away the resolvase do not adsorbed, dry filter under room temperature condition, the azo reductase of being fixed.
C. degraded is containing azo dye wastewater: activated carbon nano-tube is mixed to come obtained immobilized enzyme with azo reductase with the quality proportioning of 1:1.Waste water containing 0.2g/L tropeolin-D is added in sample, the methyl orange solution of 10mL is obtained by damping fluid configuration, starting point concentration is 100mg/L, pH value is 8.0, and added respectively in sample by above-mentioned obtained immobilized enzyme, control temperature is at 10 DEG C, with the rotating speed of 150rpm oscillatory reaction 30min in constant temperature culture, then by the immobilized azo reductase of suction filtration Separation and Recovery activated carbon nano-tube, waste water is regulated to be after neutrality, discharge.After measured, the degradation rate of tropeolin-D reaches more than 90%.
Comparative example 7
Under research different pH condition, immobilized azo reductase is to the degradation efficiency of tropeolin-D.
Concrete operations are as described in comparative example 3, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:1.
The degradation efficiency of immobilized azo reductase to tropeolin-D is measured respectively under different pH condition, as shown in table 4 below, as seen from table, pH value is when 6 or 7, and the degradation efficiency of immobilization azo reductase to tropeolin-D is the highest, when pH is lower, lower efficiency not good, therefore, optimum pH scope is 6.0 ~ 7.0, within optimum pH scope.(in table, degradation rate represents with %)
Under table 4 different pH condition, immobilized azo reductase is to the degradation efficiency of tropeolin-D
Comparative example 8
The different initial azoic dyestuff concentration of research is on the impact of immobilization azo reductase degradation efficiency.
Concrete operations are as described in comparative example 4, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:1.
Under the initial azoic dyestuff concentration conditions of difference, measure the degradation efficiency of immobilized azo reductase to tropeolin-D.After measured, when the starting point concentration of tropeolin-D is 50mg/L, degradation rate is more than 90%, and when starting point concentration is 100mg/L, degradation rate is down to about 70%.When showing that the starting point concentration of tropeolin-D is lower, the degradation rate of immobilized azo reductase to tropeolin-D is higher, and best starting point concentration is 50mg/L, and this concentration is within optimum concentration scope.
Comparative example 9
The research differential responses time is on the impact of immobilization azo reductase degradation efficiency.
Concrete operations are as described in comparative example 5, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:1.
Respectively under differential responses time conditions, measure the degradation efficiency of immobilized azo reductase to tropeolin-D.After measured, reaction is when proceeding to about 30min, degradation rate more than 90%, pending to 60min time, degradation rate does not have a greater change.May be within 30, methyl orange dye be fully degraded.
Embodiment 3
Utilize a method for azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, comprise the following steps:
A. prepare activated carbon nano-tube: mixed with the mass ratio of potassium hydroxide according to 1:5 by carbon nanotube, heating up by the speed of 10 DEG C/min is afterwards heated to 800 DEG C of calcination 3h, and whole process lasts leads to nitrogen (45mL/min).After being cooled to room temperature, the material deionized water obtained being cleaned repeatedly, after filtration, resulting materials is dried 6h under 100 DEG C of conditions.
B. the immobilized azo reductase of activated carbon nano-tube is prepared: first 0.3g activated carbon nano-tube powder is dissolved in (pH value is 7.5) in 50ml phosphoric acid buffer, ultrasonic 20min in ultrasonic cleaner; Then add the resolvase of 0.5mg/mL, fix 30min and obtain mixed solution in the water bath with thermostatic control of 50 DEG C, mixing speed is 400rpm; Subsequently by mixed solution suction filtration and with phosphoric acid buffer washing, wash away the resolvase do not adsorbed, dry filter under room temperature condition, the azo reductase of being fixed.
C. degraded is containing azo dye wastewater: activated carbon nano-tube is mixed to come obtained immobilized enzyme with azo reductase with the quality proportioning of 1:3.Waste water containing the orange I of 1g/L is added in sample, the orange I solution of 10mL is obtained by damping fluid configuration, starting point concentration is 20mg/L, pH value is 5.0, and added respectively in sample by above-mentioned obtained immobilized enzyme, control temperature is at 50 DEG C, with the rotating speed of 150rpm oscillatory reaction 10min in constant temperature culture, then by the immobilized azo reductase of suction filtration Separation and Recovery activated carbon nano-tube, waste water is regulated to be after neutrality, discharge.After measured, the degradation rate of orange I reaches more than 85%.
Comparative example 10
Under research different pH condition, immobilized azo reductase is to the degradation efficiency of orange I.
Concrete operations are as described in comparative example 3, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:3.
The degradation efficiency of immobilized azo reductase to orange I is measured respectively under different pH condition, as shown in table 5 below, as seen from table, pH value is when 6 or 7, and the degradation efficiency of immobilization azo reductase to orange I is the highest, when pH is lower, lower efficiency not good, therefore, optimum pH scope is 6.0 ~ 7.0, within optimum pH scope.(in table, degradation rate represents with %)
Under table 5 different pH condition, immobilized azo reductase is to the degradation efficiency of orange I
Comparative example 11
The different initial azoic dyestuff concentration of research is on the impact of immobilization azo reductase degradation efficiency.
Concrete operations are as described in comparative example 4, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:3.
Under the initial azoic dyestuff concentration conditions of difference, measure the degradation efficiency of immobilized azo reductase to orange I.After measured, when the starting point concentration of orange I is 50mg/L, degradation rate is more than 85%, and when starting point concentration is 100mg/L, degradation rate is down to about 60%.When showing that the starting point concentration of orange I is lower, the degradation rate of immobilized azo reductase to orange I is higher, and best starting point concentration is 50mg/L, and this concentration is within optimum concentration scope.
Comparative example 12
The research differential responses time is on the impact of immobilization azo reductase degradation efficiency.
Concrete operations are as described in comparative example 5, and difference is activated carbon nano-tube and azo reductase quality proportioning is 1:3.
Respectively under differential responses time conditions, measure the degradation efficiency of immobilized azo reductase to orange I.After measured, reaction is when proceeding to about 30min, degradation rate more than 85%, pending to 60min time, degradation rate does not have a greater change.May be within 30, it is very abundant that orange I dyestuff has been degraded.
Can be found out by embodiment 1-3 and comparative example 1-12, utilize the immobilized azo reductase of activated carbon nano-tube, have stronger adaptability to temperature, pH, and the repeat usage of immobilized enzyme be higher; Utilize immobilized enzyme degrading azoic dye waste water, there is the advantages such as operating process is easy, degradation efficiency is remarkable.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. one kind utilizes the method for azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body, it is characterized in that, comprise the following steps: first the pending water pH value containing azoic dyestuff is adjusted to 5.0 ~ 8.0, and regulates the azoic dyestuff starting point concentration containing azoic dyestuff water body to be 20 ~ 100mg/L; Then drop in above-mentioned water body by immobilized for activated carbon nano-tube azo reductase, every milliliter is not less than 0.5mg containing the immobilized azo reductase of activated carbon nano-tube added in the water body of azoic dyestuff; Subsequently at the temperature of 10 ~ 50 DEG C to above-mentioned mixed solution oscillatory reaction 10 ~ 30min; Reclaim the immobilized azo reductase of activated carbon nano-tube by suction filtration again, finally water body is adjusted to neutral rear discharge.
2. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 1, it is characterized in that: during described adjustment azoic dyestuff starting point concentration, is add 10mL phosphate buffer solution in the azo dye wastewater of 0.2 ~ 1g/L by 1ml containing concentration.
3. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 1, is characterized in that: described azoic dyestuff is any one in simple chemical structure and low-molecular-weight methyl red, tropeolin-D, orange I.
4. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 1, is characterized in that: the immobilized azo reductase of described activated carbon nano-tube is that azo reductase is fixed on activated carbon nano-tube by physical adsorption.
5. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 1 or 4, is characterized in that: the quality proportioning of described activated carbon nano-tube and azo reductase is 1:1 ~ 3.
6. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 5, it is characterized in that, the immobilized azo reductase of described activated carbon nano-tube obtains by the following method: be first dissolved in 50mL phosphoric acid buffer by 0.1 ~ 0.3g activated carbon nano-tube powder, ultrasonic 10 ~ 35min in ultrasonic cleaner; Then add resolvase, fix 30 ~ 240min and obtain mixed solution in the water bath with thermostatic control of 10 ~ 50 DEG C, mixing speed is 50 ~ 400rpm; Subsequently by mixed solution suction filtration and with phosphoric acid buffer washing, wash away the resolvase do not adsorbed, dry filter under room temperature condition, the azo reductase of being fixed.
7. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 6, it is characterized in that, described activated carbon nano-tube obtains by the following method: be that 1:5 ~ 6 mix with potassium hydroxide according to mass ratio by carbon nanotube, be warming up to 800 DEG C of calcination 1.5 ~ 3h by the speed of 10 DEG C/min afterwards, whole process lasts leads to nitrogen; After being cooled to room temperature, the material deionized water obtained is cleaned repeatedly, after filtration, resulting materials is dried 4 ~ 6h under 100 ~ 120 DEG C of conditions.
8. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 7, is characterized in that: it is 35 ~ 45mL/min that described nitrogen passes into speed.
9. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 6, is characterized in that: the specific surface area of described activated carbon nano-tube is 600 ~ 1200m
2/ g, pore volume is 0.40 ~ 1.80cm
3/ g; Described activated carbon nano-tube has orderly graphite microcrystalline structure.
10. the method utilizing azoic dyestuff in activated carbon nano-tube immobilized azo reductase degraded water body according to claim 6, it is characterized in that, the starting point concentration of described azo reductase is 0.1 ~ 0.9mg/mL, and the pH value of described phosphoric acid buffer is 6.5 ~ 7.5.
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