CN105016576B - Method using azo dye in activated carbon nano-tube immobilized azo reductase degraded water body - Google Patents
Method using azo dye in activated carbon nano-tube immobilized azo reductase degraded water body Download PDFInfo
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Abstract
The method of azo dye in the water body the invention discloses a kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded, first the pending water pH value containing azo dye is adjusted to 5.0～8.0, adjusting the azo dye initial concentration containing azo dye water body is 20～100mg/L；Then immobilized for activated carbon nano-tube azo reductase is put in above-mentioned water body, every milliliter contains the immobilized azo reductase of activated carbon nano-tube adding in the water body of azo dye and is not less than 0.5mg；Subsequently to above-mentioned mixed liquor oscillating reactionss 10～30min at a temperature of 10～50 DEG C；The immobilized azo reductase of activated carbon nano-tube is reclaimed by sucking filtration, water body is adjusted to discharge after neutrality；The present invention fixes the azo reductase of degraded azo dye using activated carbon nano-tube, the larger specific surface area of activated carbon nano-tube material is conducive to the effect of mass transmitting of immobilized enzyme with abundant pore passage structure, the degradation efficiency substantially increasing azo dye wastewater is worked in coordination with catalytic action with enzyme, reclaims the recycling rate of waterused that improve enzyme by sucking filtration.
Description
Technical field
The invention belongs to sewage treatment area, utilize the immobilized azo reductase of activated carbon nano-tube particularly to a kind of
The method of azo dye in degraded water body.
Background technology
Azo dye species is various and complex structure, in water environment with the presence of oxidant under conditions of remain to keep higher
Activity, has substantial portion of azo dye and its toxic compounds that mesostate is extremely difficult degraded in addition, chemistry knot
Structure is stable, has teratogenesis, carcinogenic, mutagenic " three causes " effect, has a strong impact on the healthy and safe of contactee.In recent years, domestic
Outer scholar has done substantial amounts of research to its Degradation and Transformation method.At present, Physical, chemical method and bioanalysises are mainly had to process idol
Nitrogen waste water, compared with Physical and chemical method, bioanalysises have stable, easy to operate simple, operating cost is low and is difficult
The features such as produce secondary pollution, enjoys researcher to favor.
Bioanalysises include microbial degradation and enzymatic degradation again, there are some researches show, the decoloring ability master of antibacterial azo dyes
If the effect of azo reductase produced by it, enzymatic degradation method, compared with biological degradation method, has easy and simple to handle, reacted
The advantage that journey is easily controlled, treatment effeciency is high.But resolvase because stability is poor, be difficult to reclaim, be easily mixed into sample and be difficult to follow
Ring using the shortcomings of make it apply to be restricted, be fixed on after carrier by certain method by resolvase, resolvase can be overcome
Shortcoming, be easy to serialization and the automatization of production technology, have broad application prospects.Fixation techniques for enzyme is typically divided
For absorption method, cross-linking method, covalently bonded be legal, investment, directional at-tachment etc., wherein physisorphtion compares remaining several technology
The features such as there is easy and simple to handle, mild condition, the variation of enzyme will not be caused to inactivate.The inorganic carrier master of early stage immobilized enzyme application
It is divided into and has bentonite, aluminium oxide, glass and seaweed stone etc., these materials are due to by aperture, specific surface area, grain graininess etc.
The restriction of factor, the ability of desmoenzyme is quite low.
The new material due to having stronger absorption property, in putting into practice currently as water process for the CNT.But carbon
, due to itself, its specific surface area is relatively small for nanotube, and its dispersibility of impact of easily self reuniting in water environment
Can, and then affect its adsorption effect further.CNT after activation of potassium hydroxide can increase CNT effectively
Specific surface area and pore volume, and greatly enhance its peptizaiton in water body, provide for enzyme immobilizatio study on the carrier
Great potential.
And document report is not yet shown in the research being processed using immobilized azo reductase containing azo dye wastewater at present
Road.
Content of the invention
Goal of the invention：The invention provides in a kind of degraded water body using activated carbon nano-tube immobilized azo reductase
The method of azo dye, to solve the problems of the prior art.
Technical scheme：To achieve these goals, the present invention employs the following technical solutions：
A kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded the method for azo dye in water body, including with
Lower step：First the pending water pH value containing azo dye is adjusted to 5.0～8.0, and adjusts containing azo dye water body
Azo dye initial concentration is 20～100mg/L；Then immobilized for activated carbon nano-tube azo reductase is put into above-mentioned water
In body, every milliliter contains the immobilized azo reductase of activated carbon nano-tube adding in the water body of azo dye and is not less than 0.5mg；
Subsequently to above-mentioned mixed liquor oscillating reactionss 10～30min at a temperature of 10～50 DEG C；Again activated carbon nanometer is reclaimed by sucking filtration
Manage immobilized azo reductase, finally water body is adjusted to discharge after neutrality.
Further, during described regulation azo dye initial concentration, the azo dye that 1ml is 0.2～1g/L containing concentration
10ml phosphate buffer solution is added in material waste water.
Further, described azo dye be the C.I. 13020. of simple chemical constitution and low-molecular-weight, methyl orange, orange I
In any one.
Further, the immobilized azo reductase of described activated carbon nano-tube is that azo reductase is passed through physical absorption
It is fixed on activated carbon nano-tube.
Preferably, described activated carbon nano-tube and the quality proportioning of azo reductase are 1：1～3.
Further, the immobilized azo reductase of described activated carbon nano-tube is obtained by the following method：First by 0.1
～0.3g activated carbon nano-tube powder is dissolved in 50mL phosphate buffer, ultrasonic 10～35min in ultrasonic cleaner；Then
Add resolvase, 10～50 DEG C of water bath with thermostatic control is fixed 30～240min and obtains mixed liquor, speed of agitator be 50～
400rpm；Subsequently wash by mixed liquor sucking filtration and with phosphate buffer, wash away unadsorbed resolvase, dried under room temperature condition
Filter, the azo reductase of being fixed.
Further, described activated carbon nano-tube is obtained by the following method：By CNT with potassium hydroxide according to matter
Amount ratio is 1：5～6 mixing, are warming up to 800 DEG C of calcination 1.5～3h by the speed of 10 DEG C/min afterwards, and whole process persistently leads to nitrogen
Gas；After being cooled to room temperature, the material obtaining deionized water is cleaned repeatedly, by resulting materials in 100～120 DEG C of bars after filtration
4～6h is dried under part.
Preferably, described nitrogen is passed through speed is 35～45mL/min.
Preferably, the specific surface area of described activated carbon nano-tube is 600～1200m2/ g, pore volume is 0.40～1.80cm3/
g.
Preferably, described activated carbon nano-tube has orderly graphite microcrystalline structure.
Preferably, the initial concentration of described azo reductase is 0.1～0.9mg/mL, and the pH value of described phosphate buffer is
6.5～7.5.
Beneficial effect：The present invention fixes the azo reductase of degraded azo dye, activated carbon using activated carbon nano-tube
The larger specific surface area of nano-tube material is conducive to the effect of mass transmitting of immobilized enzyme, the catalytic action with enzyme with abundant pore passage structure
The collaborative degradation efficiency substantially increasing azo dye wastewater.Additionally, immobilized enzyme is reclaimed by sucking filtration, improve the repetition of enzyme
Utilization rate；The present invention utilizes azo dye in immobilized azo reductase degraded water body, and removal efficiency is higher, in optimal ph
Between 6.0～7.0, under conditions of initial azo dye concentration 50mg/L, within 30min, the clearance of paramethyl red exceedes
85%；The present invention is simple to operate, and investment and operating cost are relatively low.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
A kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded the method for azo dye in water body, including with
Lower step：
A. prepare activated carbon nano-tube：CNT and potassium hydroxide are 1 according to mass ratio：5 mixing, press 10 afterwards
DEG C/speed of min heats up and is heated to 800 DEG C of calcination 2h, whole process maintaining nitrogen purge (40mL/min).After being cooled to room temperature,
The material obtaining deionized water is cleaned repeatedly, after filtration, resulting materials is dried under the conditions of 100 DEG C 4h.
B. prepare the immobilized azo reductase of activated carbon nano-tube：First 0.15g activated carbon nano-tube powder is dissolved in
(pH value is 7.0), ultrasonic 10min in ultrasonic cleaner in 50ml phosphate buffer；It is subsequently adding the free of 0.5mg/mL
Enzyme, fixes 40min in 37 DEG C of water bath with thermostatic control and obtains mixed liquor, and speed of agitator is 250rpm；Subsequently by mixed liquor sucking filtration simultaneously
Washed with phosphate buffer, wash away unadsorbed resolvase, dry filter under room temperature condition, the azo reduction of being fixed
Enzyme.
C. degraded contains azo dye wastewater：By activated carbon nano-tube and azo reductase with 1:2 quality proportioning mixing comes
Prepared immobilized enzyme.Waste water containing 0.5g/L C.I. 13020. is added in sample, the C.I. 13020. obtaining 10mL by buffer configuration is molten
Liquid, initial concentration is 50mg/L, and pH value is 6.5, and above-mentioned prepared immobilized enzyme is separately added in sample, controls temperature 37
DEG C, with the rotating speed of 150rpm in constant temperature culture oscillating reactionss 30min, then activated carbon nano-tube is separated back by sucking filtration and fixes
The azo reductase changed, after regulation waste water is neutrality, discharge.After measured, the degradation rate of C.I. 13020. reaches more than 90%.
Comparative example 1
With free azo reductase as a comparison, to above-mentioned prepared immobilization azo reductase with free azo also
The subject range that protoenzyme carries out pH carries out contrast test
The subject range of pH value：Measure free azo reductase and immobilized azo respectively also under different pH condition
The enzyme activity of protoenzyme, as shown in table 1, as seen from table, resolvase is between 5～8 in pH value, has higher activity, meta-acid or inclined
Under alkaline environment, free enzyme activity is relatively low, almost loses activity；And immobilized enzyme is between 5～8 in pH value, the activity of enzyme is all
Higher than the activity of resolvase, and in the case that pH value is 3 and 9, compare resolvase, activity has higher lifting.Illustrate to fix
Change enzyme is affected not notable by pH, compares resolvase and has more wide in range pH value subject range.(in table, relative activity is with % table
Show)
The relative activity of free azo reductase and immobilized azo reductase under table 1 different pH condition
Comparative example 2
With free azo reductase as a comparison, to above-mentioned prepared immobilization azo reductase with free azo also
The subject range that protoenzyme enters trip temperature carries out contrast test.
The subject range of temperature：Measure free azo reductase and immobilized azo respectively also under condition of different temperatures
The enzyme activity of protoenzyme, as shown in table 2, as seen from table, resolvase at 0～50 DEG C, enzyme relative activity higher (more than 70%), temperature
During more than 50 DEG C, the rapid degeneration of protein, enzyme activity significantly reduces, and the catalytic capability of enzyme declines；In contrast, immobilized enzyme is 0
At a temperature of～50 DEG C, the relative activity of enzyme has been lifted compared with resolvase, and when 60 DEG C, remains in that of a relatively high enzyme activity.
Immobilized enzyme is described compared with resolvase, is suitable for the complicated actual environment of temperature.(in table, the unit of temperature is DEG C, relatively
Activity is represented with %)
The relative activity of free azo reductase and immobilized azo reductase under table 2 condition of different temperatures
The standard tested as a comparison with the enzyme activity compareing free azo reductase and immobilization azo reductase, reaction
System includes following components：The phosphate buffer (pH value is 7.0) of 1.5mL 100mM, 0.2mL 1mM NADH, 0.2mM first
Base is red, 0.2mL enzyme liquid.
Assay method is：The reaction system not adding NADH is placed in after water-bath 5min in 37 DEG C, quickly adds in system
Enter NADH timing.Detect that enzyme liquid is reacted at room temperature with C.I. 13020. under 485nm with spectrophotometer (U-2800Hitachi)
The variable quantity of light absorption value after 1min, calculates the activity of azo reductase.The definition of 1 unit azo reductase enzyme activity (U) is：
Enzyme amount (highest enzyme activity is set as 100%) required for 1 μm of ol dyestuff of 1min degraded in the reaction system of 1mL.
Comparative example 3
The degradation efficiency of immobilized azo reductase paramethyl red under research different pH condition.
The C.I. 13020. solution for 0.5g/L for the concentration is divided into 5 groups, every group of sample 10ml is so that C.I. 13020. concentration is 50mg/
L, adjusts pH of mixed with citrate buffer solution or phosphate buffer, makes pH of mixed be respectively 3.0,4.0,5.0,6.0 and
7.0, in every group of sample, then add 5g above-mentioned immobilized azo reductase (activated carbon nano-tube and azo reductase quality
Proportioning is 1:2), control temperature at 37 DEG C, with the rotating speed of 150rpm in constant temperature culture oscillating reactionss 30min, then pass through take out
Filter separation and recovery immobilized enzyme, after regulation waste water is neutrality, discharge.
Measure the degradation efficiency of immobilized azo reductase paramethyl red respectively under different pH condition, such as table 3 below
Shown, as seen from table, pH value when 6 or 7, the degradation efficiency highest of immobilization azo reductase paramethyl red, when pH is relatively low, fall
Poor efficiency is not good, and therefore, optimum pH scope is 6.0～7.0, within the scope of optimum pH.(in table, degradation rate is with % table
Show)
The degradation efficiency of immobilized azo reductase paramethyl red under table 3 different pH condition
Comparative example 4
The different initial impact to immobilization azo reductase degradation efficiency for the azo dye concentration of research.
By concentration, the C.I. 13020. waste water for 0.5g/L, 0.7g/L and 1g/L adds in sample respectively, every group of sample 10ml, sample
Product concentration is respectively 50mg/L, 70mg/L and 100mg/L, and pH value is 6.5, then adds the above-mentioned immobilization of 5g in every group of sample
Azo reductase (activated carbon nano-tube and azo reductase quality proportioning are 1:2), control temperature at 37 DEG C, with 150rpm's
Rotating speed oscillating reactionss 30min in constant temperature culture, then separates and recovers immobilized enzyme by sucking filtration, after regulation waste water is neutrality,
Discharge.
Under different initial azo dye concentration conditions, measure the degraded effect of immobilized azo reductase paramethyl red
Rate.After measured, when the initial concentration of C.I. 13020. is 50mg/L, degradation rate, more than 90%, when initial concentration is for 100mg/L, drops
Solution rate is down to 75% about.When showing that the initial concentration of C.I. 13020. is lower, the degraded of immobilized azo reductase paramethyl red
Rate is higher, and optimal initial concentration is 50mg/L, and this concentration is within the scope of optimum concentration.
Comparative example 5
The research impact to immobilization azo reductase degradation efficiency for the differential responses time.
Waste water containing C.I. 13020. is added in sample, obtains the C.I. 13020. solution of 10mL by buffer configuration, initially dense
Spend for 50mg/L, pH value is 6.5, then add in sample the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube with
Azo reductase quality proportioning is 1:2), control temperature at 37 DEG C, vibrated in constant temperature culture with the rotating speed of 150rpm and continue 1h,
Take out a certain amount of mixed liquor at set intervals, with spectrophotometer measurement residue C.I. 13020. concentration, then divided by sucking filtration
From reclaiming immobilized enzyme, after regulation waste water is neutrality, discharge.
Respectively under differential responses time conditions, measure the degradation efficiency of immobilized azo reductase paramethyl red.Warp
Measure, when reaction proceeds to 5 minutes, the higher degradation rate of immobilized enzyme paramethyl red, when proceeding to 30min, degradation rate surpasses
Cross 90%, pending to 60min when, degradation rate does not have a greater change.It is probably that within 5min, methyl-red dye is dropped
Solve is very abundant.
Comparative example 6
The impact to immobilization azo reductase degradation efficiency for the reuse of research immobilized enzyme.
Waste water containing C.I. 13020. is added in sample, obtains the C.I. 13020. solution of 10mL by buffer configuration, initially dense
Spend for 50mg/L, pH value is 6.5, then add in sample the above-mentioned immobilized azo reductase of 5g (activated carbon nano-tube with
Azo reductase quality proportioning is 1:2), control temperature at 37 DEG C, vibrated in constant temperature culture with the rotating speed of 150rpm and continue 1h,
With spectrophotometer measurement residue C.I. 13020. concentration, then immobilized enzyme is separated and recovered by sucking filtration, the enzyme weight that then will reclaim
In the new above-mentioned solution of new addition, same course of reaction measures remaining C.I. 13020. concentration, so moves in circles, and measures activated carbon
The reusability of the immobilized azo reductase of nanotube.After measured, after reuse reaction carries out 5 times, immobilized enzyme pair
The degradation rate of C.I. 13020. is still up to 60% about, shows that this immobilized enzyme has certain operational stability, can reuse.
Embodiment 2
A kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded the method for azo dye in water body, including with
Lower step：
A. prepare activated carbon nano-tube：By CNT and potassium hydroxide according to 1：6 mass ratio mixing, presses 10 afterwards
DEG C/speed of min heats up and is heated to 800 DEG C of calcination 1.5h, whole process maintaining nitrogen purge (35mL/min).It is cooled to room temperature
Afterwards, the material obtaining deionized water is cleaned repeatedly, after filtration, resulting materials are dried under the conditions of 120 DEG C 5h.
B. prepare the immobilized azo reductase of activated carbon nano-tube：First 0.1g activated carbon nano-tube powder is dissolved in
(pH value is 6.5), ultrasonic 35min in ultrasonic cleaner in 50ml phosphate buffer；It is subsequently adding the free of 0.5mg/mL
Enzyme, fixes 240min in 10 DEG C of water bath with thermostatic control and obtains mixed liquor, and speed of agitator is 50rpm；Subsequently by mixed liquor sucking filtration simultaneously
Washed with phosphate buffer, wash away unadsorbed resolvase, dry filter under room temperature condition, the azo reduction of being fixed
Enzyme.
C. degraded contains azo dye wastewater：By activated carbon nano-tube and azo reductase with 1:1 quality proportioning mixing comes
Prepared immobilized enzyme.Waste water containing 0.2g/L methyl orange is added in sample, the methyl orange obtaining 10mL by buffer configuration is molten
Liquid, initial concentration is 100mg/L, and pH value is 8.0, and above-mentioned prepared immobilized enzyme is separately added in sample, controls temperature 10
DEG C, with the rotating speed of 150rpm in constant temperature culture oscillating reactionss 30min, then activated carbon nano-tube is separated and recovered by sucking filtration solid
The azo reductase of fixedization, after regulation waste water is neutrality, discharge.After measured, the degradation rate of methyl orange reaches more than 90%.
Comparative example 7
The degradation efficiency to methyl orange for the immobilized azo reductase under research different pH condition.
Concrete operations are as described in comparative example 3, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
1.
Measure the degradation efficiency to methyl orange for the immobilized azo reductase respectively under different pH condition, such as table 4 below
Shown, as seen from table, pH value when 6 or 7, the degradation efficiency highest to methyl orange for the immobilization azo reductase, when pH is relatively low, fall
Poor efficiency is not good, and therefore, optimum pH scope is 6.0～7.0, within the scope of optimum pH.(in table, degradation rate is with % table
Show)
The degradation efficiency to methyl orange for the immobilized azo reductase under table 4 different pH condition
Comparative example 8
The different initial impact to immobilization azo reductase degradation efficiency for the azo dye concentration of research.
Concrete operations are as described in comparative example 4, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
1.
Under different initial azo dye concentration conditions, measure immobilized azo reductase and the degraded of methyl orange is imitated
Rate.After measured, when methyl orange initial concentration be 50mg/L when, degradation rate more than 90%, when initial concentration is for 100mg/L,
Degradation rate is down to 70% about.When showing that the initial concentration of methyl orange is lower, the fall to methyl orange for the immobilized azo reductase
Solution rate is higher, and optimal initial concentration is 50mg/L, and this concentration is within the scope of optimum concentration.
Comparative example 9
The research impact to immobilization azo reductase degradation efficiency for the differential responses time.
Concrete operations are as described in comparative example 5, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
1.
Respectively under differential responses time conditions, measure the degradation efficiency to methyl orange for the immobilized azo reductase.Warp
Measure, reaction proceed to 30min about when, degradation rate more than 90%, pending to 60min when, degradation rate does not have larger
Change.It is probably that within 30, methyl orange dye is fully degraded.
Embodiment 3
A kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded the method for azo dye in water body, including with
Lower step：
A. prepare activated carbon nano-tube：By CNT and potassium hydroxide according to 1：5 mass ratio mixing, presses 10 afterwards
DEG C/speed of min heats up and is heated to 800 DEG C of calcination 3h, whole process maintaining nitrogen purge (45mL/min).After being cooled to room temperature,
The material obtaining deionized water is cleaned repeatedly, after filtration, resulting materials is dried under the conditions of 100 DEG C 6h.
B. prepare the immobilized azo reductase of activated carbon nano-tube：First 0.3g activated carbon nano-tube powder is dissolved in
(pH value is 7.5), ultrasonic 20min in ultrasonic cleaner in 50ml phosphate buffer；It is subsequently adding the free of 0.5mg/mL
Enzyme, fixes 30min in 50 DEG C of water bath with thermostatic control and obtains mixed liquor, and speed of agitator is 400rpm；Subsequently by mixed liquor sucking filtration simultaneously
Washed with phosphate buffer, wash away unadsorbed resolvase, dry filter under room temperature condition, the azo reduction of being fixed
Enzyme.
C. degraded contains azo dye wastewater：By activated carbon nano-tube and azo reductase with 1:3 quality proportioning mixing comes
Prepared immobilized enzyme.Waste water containing the orange I of 1g/L is added in sample, obtains the orange I solution of 10mL by buffer configuration, just
Beginning concentration is 20mg/L, and pH value is 5.0, and above-mentioned prepared immobilized enzyme is separately added in sample, controls temperature at 50 DEG C, with
The rotating speed of 150rpm oscillating reactionss 10min in constant temperature culture, then separates and recovers activated carbon nano-tube immobilization by sucking filtration
Azo reductase, adjust waste water be neutrality after, discharge.After measured, the degradation rate of orange I reaches more than 85%.
Comparative example 10
The degradation efficiency to orange I for the immobilized azo reductase under research different pH condition.
Concrete operations are as described in comparative example 3, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
3.
Measure the degradation efficiency to orange I for the immobilized azo reductase respectively under different pH condition, as table 5 below institute
Show, as seen from table, pH value when 6 or 7, the degradation efficiency highest to orange I for the immobilization azo reductase, when pH is relatively low, reduce
Efficiency is not good, and therefore, optimum pH scope is 6.0～7.0, within the scope of optimum pH.(in table, degradation rate is represented with %)
The degradation efficiency to orange I for the immobilized azo reductase under table 5 different pH condition
Comparative example 11
The different initial impact to immobilization azo reductase degradation efficiency for the azo dye concentration of research.
Concrete operations are as described in comparative example 4, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
3.
Under different initial azo dye concentration conditions, measure the degradation efficiency to orange I for the immobilized azo reductase.
After measured, when the initial concentration of orange I is 50mg/L, degradation rate, more than 85%, when initial concentration is for 100mg/L, is degraded
Rate is down to 60% about.When showing that the initial concentration of orange I is lower, immobilized azo reductase is got over to the degradation rate of orange I
Height, optimal initial concentration is 50mg/L, and this concentration is within the scope of optimum concentration.
Comparative example 12
The research impact to immobilization azo reductase degradation efficiency for the differential responses time.
Concrete operations are as described in comparative example 5, except that activated carbon nano-tube and azo reductase quality proportioning are 1:
3.
Respectively under differential responses time conditions, measure the degradation efficiency to orange I for the immobilized azo reductase.Through surveying
Fixed, reaction proceed to 30min about when, degradation rate more than 85%, pending to 60min when, degradation rate does not have larger change
Change.Be probably 30 within, the degraded of orange I dyestuff very abundant.
Can be seen that using the immobilized azo reductase of activated carbon nano-tube by embodiment 1-3 and comparative example 1-12,
There is stronger adaptability to temperature, pH, and the repeat usage of immobilized enzyme is higher；Given up using immobilized enzyme degraded azo dye
Water, has the advantages that operating process simplicity, degradation efficiency are notable.
The above be only the preferred embodiment of the present invention it should be pointed out that：Ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of immobilized azo reductase of utilization activated carbon nano-tube is degraded the method for azo dye in water body, and its feature exists
In comprising the following steps：First the pending water pH value containing azo dye is adjusted to 5.0 ~ 8.0, and adjusts containing azo dye
The azo dye initial concentration of material water body is 20 ~ 100mg/L；Then immobilized for activated carbon nano-tube azo reductase is put into
In above-mentioned water body, the immobilized azo reductase of activated carbon nano-tube adding in every milliliter of water body containing azo dye is not low
In 0.5mg；Subsequently to above-mentioned mixed liquor oscillating reactionss 10 ~ 30min at a temperature of 10 ~ 50 DEG C；Again activation is reclaimed by sucking filtration
Water body is finally adjusted to discharge after neutrality by the immobilized azo reductase of CNT；
The immobilized azo reductase of described activated carbon nano-tube is obtained by the following method：First 0.1 ~ 0.3g activated carbon is received
Mitron powder is dissolved in 50 mL phosphate buffers, ultrasonic 10 ~ 35min in ultrasonic cleaner；It is subsequently adding resolvase,
Fix 30 ~ 240 min in 10 ~ 50 DEG C of water bath with thermostatic control and obtain mixed liquor, speed of agitator is 50 ~ 400rpm；Subsequently by mixed liquor
Sucking filtration is simultaneously washed with phosphate buffer, washes away unadsorbed resolvase, dry filter under room temperature condition, the azo of being fixed
Reductase；
Described activated carbon nano-tube is obtained by the following method：CNT and potassium hydroxide are 1 according to mass ratio：5 ~ 6 mix
Close, be warming up to 800 DEG C of calcination 1.5 ~ 3h, whole process maintaining nitrogen purge by the speed of 10 DEG C/min afterwards；After being cooled to room temperature,
The material obtaining deionized water is cleaned repeatedly, resulting materials are dried after filtration under the conditions of 100 ~ 120 DEG C 4 ~ 6 h is
Can.
2. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that：During described regulation azo dye initial concentration, 1ml is contained the azo dye that concentration is 0.2 ~ 1g/L
10mL phosphate buffer solution is added in material waste water.
3. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that：Described azo dye is the C.I. 13020. of simple chemical constitution and low-molecular-weight, methyl orange, orange I
In any one.
4. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that：The immobilized azo reductase of described activated carbon nano-tube is to inhale azo reductase by physics
Attached it is fixed on activated carbon nano-tube.
5. azo in the utilization activated carbon nano-tube immobilized azo reductase degraded water body according to claim 1 or 4
The method of dyestuff it is characterised in that：Described activated carbon nano-tube is 1 with the quality proportioning of azo reductase：1~3.
6. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that：It is 35 ~ 45 mL/min that described nitrogen is passed through speed.
7. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that：The specific surface area of described activated carbon nano-tube is 600 ~ 1200 m2/ g, pore volume is 0.40 ~ 1.80
cm3/g；Described activated carbon nano-tube has orderly graphite microcrystalline structure.
8. azo dye in utilization activated carbon nano-tube according to claim 1 immobilized azo reductase degraded water body
Method it is characterised in that described azo reductase initial concentration be 0.1 ~ 0.9mg/mL, the pH value of described phosphate buffer
For 6.5 ~ 7.5.
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