CN110404504A - Cu for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application - Google Patents
Cu for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application Download PDFInfo
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- CN110404504A CN110404504A CN201810387224.0A CN201810387224A CN110404504A CN 110404504 A CN110404504 A CN 110404504A CN 201810387224 A CN201810387224 A CN 201810387224A CN 110404504 A CN110404504 A CN 110404504A
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- walnut shell
- active carbon
- dyeing
- doping
- adulterates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The Cu that the invention discloses a kind of for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application.The preparation method of the Cu doping walnut shell active carbon for handling dyeing and printing sewage includes: that walnut shell is successively obtained Cu doping walnut shell active carbon through mantoquita processing, charing process, activation processing and high-temperature heat treatment.Preparation method, the preparation process flow that Cu provided by the present invention for handling dyeing and printing sewage adulterates walnut shell active carbon are simple, the Cu doping walnut shell active carbon that preparation is formed easily regenerates, by recycled for multiple times, adsorption efficiency is still stable, large amount of adsorption, speed is fast, using walnut shell as raw material, low in cost, good biocompatibility, advantages of environment protection have a good application prospect.
Description
Technical field
The Cu that the present invention is more particularly directed to a kind of for handling dyeing and printing sewage adulterates walnut shell active carbon and its preparation method and application,
Belong to technical field of sewage.
Background technique
With the continuous quickening of industrialization and urbanization process, a large amount of trade effluents and sanitary sewage are unprocessed just direct
Discharge, according to data statistics, about 700000 tons of waste water from dyestuff are discharged in the whole world every year, and wherein the annual usage amount of industrial textile dyestuff is super
10000 tons are crossed, is directly used in dyeing more than 90% textile dyestuff, more than 1000 tons waste water from dyestuff direct emissions are in water body
(Bouaziz F,Koubaa M,Kallel F,et al.Adsorptive removal of malachite green from
aqueous solutions by almond gum:Kinetic study and equilibrium isotherms[J]
.International Journal of Biological Macromolecules,2017.).These industrial wastewaters and life
Containing organic matter, the heavy metal particles etc. being largely harmful to the human body in sewage, water environment pollution is caused to aggravate.Dyeing discharge
Sewage composition it is complicated, concentration is big, toxicity is big, biochemical degradation is difficult to handle, discharge amount is big etc., be China's water pollution main source
One of, dye wastewater enters natural water, will cause the decline of water body translucency, slows down photosynthesis, and then influence aquatic dynamic plant
The chelation of the growth of object and the dyestuff and metal ion that are discharged into natural water causes toxicity and right to aquatic animal
The mankind cause to poison even carcinogenic, mutagenesis, teratogenesis (Zhang X, Lin Q, Luo S, et al.Preparation of
novel oxidized mesoporous carbon with excellent adsorption performance for
removal of malachite green and lead ion[J].Applied Surface Science,2018,442)。
Studies have shown that triphenylmethane dye has carcinogenic property, wherein malachite green (MG) is a kind of toxic triphenylmethane
Object is closed, there are the harmfulness such as residual quantity is big, toxicity is high, carcinogenic, teratogenesis, it is micro- that high toxicity causes it to be difficult in the treatment of waste water
Biodegrade, the metabolite in aquatic organism is leucomalachite green, and leucomalachite green is not soluble in water, residual toxicity
It is more stronger than malachite green.Attached method because its is simple and easy to do, investment it is small and fruitful, become the important method of dye wastewater treatment
(Ghaedi M,Shojaeipour E,Ghaedi A M,et al.Isotherm and kinetics study of
malachite green adsorption onto copper nanowires loaded on activated carbon:
artificial neural network modeling and genetic algorithm optimization.[J]
.Spectrochim Acta A Mol Biomol Spectrosc,2015,142:135-149.Wang D,Liu L,Jiang
X,et al.Adsorption and removal of malachite green from aqueous solution using
magneticβ-cyclodextrin-graphene oxide nanocomposites as adsorbents[J]
.Colloids&Surfaces A Physicochemical&Engineering Aspects,2015,466(6):166-
173).Active carbon is a kind of porosity carbonaceous material, has flourishing pore structure, huge specific surface area and excellent absorption
Performance is widely used in the fields such as environmental protection, chemical industry (Yu M, Li J, Wang L.KOH-activated carbon
aerogels derived from sodium carboxymethyl cellulose for high-performance
supercapacitors and dye adsorption[J].Chemical Engineering Journal,2016,310)。
As water environment pollution increasingly aggravates, attention to the working process of sewage by various countries researcher, and achieve
Certain progress.Existing processing technique mostly uses smashed wheat husk or pecan shell-corn stover is that raw material prepares adsorbent material
To cope with malachite green in waste water etc., there is the disadvantages of complex process, treatment conditions are harsh more in right existing processing technique, unfavorable
In large-scale industrial production and application, and the adsorbent material obtained is to lower containing pollutant components adsorbances such as malachite greens.
It is asked therefore it provides a kind of quick, the efficient absorption material of reply malachite green (MG) pollution processing are still that industry is urgently to be resolved
Topic.
Summary of the invention
The main purpose of the present invention is to provide it is a kind of for handle dyeing and printing sewage Cu adulterate walnut shell active carbon and its
Preparation method and application, with overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The Cu that the embodiment of the invention provides a kind of for handling dyeing and printing sewage adulterates the preparation method of walnut shell active carbon,
Include:
(1) by walnut shell and containing Cu2+Inorganic salt solution uniformly mix, be dried later, obtain inorganic salts-
Walnut shell mixture;
(2) inorganic salts-walnut shell mixture is subjected to carbonization treatment, the temperature of carbonization treatment in protective atmosphere
It is 400~600 DEG C, the time is 0.5~2h, obtains Cu and adulterates walnut shell carbide;
(3) Cu doping walnut shell carbide is uniformly mixed with alkaline solution, is dried later, obtains Cu
Adulterate walnut shell activated product;
(4) Cu doping walnut shell activity compound is heat-treated in protective atmosphere, the temperature of heat treatment is
700~900 DEG C, the time is 1~3h, then post-treated, obtains Cu and adulterates walnut shell active carbon.
Walnut shell active carbon is adulterated the embodiment of the invention also provides the Cu by the preparation method preparation.
The embodiment of the invention also provides Cu doping walnut shell active carbons in the application of dyeing and printing sewage process field.
The embodiment of the invention also provides a kind of methods of dyeing and printing sewage processing, comprising:
The Cu is provided and adulterates walnut shell active carbon;
Cu doping walnut shell active carbon is added in dyeing and printing sewage and is sufficiently mixed;
Wherein, the dyeing and printing sewage contains any one in malachite green malachite green, methyl red and methylene blue
Or two or more combination.
Compared with prior art, the invention has the advantages that being adulterated provided by the present invention for the Cu for handling dyeing and printing sewage
Walnut shell active carbon and its preparation method and application.Cu for handling dyeing and printing sewage adulterates the preparation method packet of walnut shell active carbon
It includes: walnut shell successively being obtained into Cu doping walnut shell activity through inorganic salt treatment, charing process, activation processing and high-temperature heat treatment
Charcoal.Provided by the present invention for handling preparation method, the preparation process flow letter of the Cu doping walnut shell active carbon of dyeing and printing sewage
Single, Cu doping walnut shell active carbon easily regenerates, and by recycled for multiple times, adsorption efficiency is still stable, large amount of adsorption, speed
Fastly, using walnut shell as raw material, low in cost, good biocompatibility, advantages of environment protection have a good application prospect.
Detailed description of the invention
Fig. 1 is the elemental analysis figure that Cu adulterates walnut shell active carbon in the embodiment of the present invention 1;
Fig. 2 is the microscopic appearance figure that Cu adulterates walnut shell active carbon in the embodiment of the present invention 1;
Fig. 3 is the microscopic appearance figure that Cu adulterates walnut shell active carbon in comparative example 1 of the present invention;
Fig. 4 is the adsorbance curve graph that Cu adulterates walnut shell active carbon in the embodiment of the present invention 1 and comparative example 1;
Fig. 5 is the N that Cu adulterates walnut shell active carbon in the embodiment of the present invention 12Adsorption-desorption curve graph;
Cu adulterates the X-ray powder diffraction collection of walnut shell active carbon in Fig. 6 embodiment of the present invention 1 and comparative example 1.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
The Cu that the embodiment of the invention provides a kind of for handling dyeing and printing sewage adulterates the preparation method of walnut shell active carbon,
Include:
(1) by walnut shell and containing Cu2+Inorganic salt solution uniformly mix, be dried later, obtain inorganic salts-
Walnut shell mixture;
(2) inorganic salts-walnut shell mixture is subjected to carbonization treatment, the temperature of carbonization treatment in protective atmosphere
It is 400~600 DEG C, the time is 0.5~2h, obtains Cu and adulterates walnut shell carbide;
(3) Cu doping walnut shell carbide is uniformly mixed with alkaline solution, is dried later, obtains Cu
Adulterate walnut shell activated product;
(4) Cu doping walnut shell activity compound is heat-treated in protective atmosphere, the temperature of heat treatment is
600~800 DEG C, the time is 2~4h, then post-treated, obtains Cu and adulterates walnut shell active carbon.
Further, the partial size of walnut shell is 100~200 mesh in step (1).
Further, the walnut shell is by dried, and the temperature of drying process is 100~120 DEG C, when
Between be 12~36h.
Further, described to contain Cu2+Inorganic salt solution concentration be 5~15mmol-1。
Further, the walnut shell with contain Cu2+Inorganic salt solution mass volume ratio be 1~3g:100~
300ml。
Further, Cu in the inorganic salt solution2+Source include copper nitrate, it is copper sulphate, any in copper chloride
A combination of one or more, but not limited to this.
In some more specific embodiments, step (1) is specifically included: under conditions of temperature is 20~40 DEG C,
Walnut shell is added and contains Cu2+Inorganic salt solution in, and with 200~400r min-1Mixing speed persistently stir 12~
For 24 hours, later by gained mixture in temperature be 60~100 DEG C under conditions of be dried, and be dried time
For 0.5~1h.
In some more specific embodiments, the step (2) includes: by the inorganic salts-walnut shell mixture
It is placed in protective atmosphere, and with 2~10 DEG C of min-1Heating rate be warming up to 500~700 DEG C of progress carbonization treatments, and carbon
The time for changing processing is 0.5~1h.
Preferably, the protective atmosphere includes nitrogen atmosphere, but not limited to this.
Preferably, the nitrogen flow for being used to form the protective atmosphere is 100~200mL min-1。
In some more specific embodiments, Cu described in step (3) adulterates walnut shell carbide and alkaline solution
Mass ratio be 1:(1~3).
Further, the concentration of the alkaline solution is 5~10mmol L-1。
Further, the alkaline solution include sodium hydroxide solution, it is potassium hydroxide solution, any one in ammonia spirit
Kind or two or more combinations, but not limited to this.
In some more specifically embodiments, the step (3) is specifically included: the condition for being 20~40 DEG C in temperature
Under, alkaline solution is added in Cu doping walnut shell carbide, and with 200~400r min-1Speed persistently stir 2~
Gained mixture is dried in 60~100 DEG C later by 4h, and the time of drying process is 2~4h.
In some more specific embodiments, the step (4) is specifically included: by Cu doping walnut shell activity
Compound is placed in protective atmosphere, and with 2~10 DEG C of min-1Heating rate be warming up to 700~900 DEG C and be heat-treated, at heat
The time of reason is 1~3h.
Preferably, the protective atmosphere includes nitrogen atmosphere, but not limited to this.
Preferably, the nitrogen flow for being used to form the protective atmosphere is 100~200mL min-1。
In some more specifically embodiments, the step (4) further include: after the completion of heat treatment, production will be obtained
Object is washed to neutrality, then at 100~140 DEG C of 4~6h of drying process, is obtained Cu and is adulterated walnut shell active carbon.
The embodiment of the invention also provides the Cu prepared by the method to adulterate walnut shell active carbon.
Further, the inside and surface of the Cu doping walnut shell active carbon are distributed with meso-hole structure, total pore volume
For 0.5~1.0cm3g-1, specific surface area is 1000~2000m2g-1, the aperture of the meso-hole structure is 1~3nm, Cu therein
Constituent content is 5~10wt%.
The embodiment of the invention also provides Cu doping walnut shell active carbons in the application of dyeing and printing sewage process field.
The embodiment of the invention also provides a kind of methods of dyeing and printing sewage processing, comprising:
The Cu is provided and adulterates walnut shell active carbon;
Cu doping walnut shell active carbon is added in dyeing and printing sewage and is sufficiently mixed;
Wherein, the dyeing and printing sewage contain any one or two kinds in malachite green, methyl red and methylene blue with
On combination, but not limited to this.
Preferably, the concentration of the dyeing and printing sewage is 500~2000mg L-1。
Preferably, the amount ratio of the Cu doping walnut shell active carbon and dyeing and printing sewage is 1g:(1000~2000) ml.
Preferably, the mixed reaction time that dyeing and printing sewage is added in the Cu doping walnut shell active carbon is 10~360min.
Preferably, the dyeing and printing sewage processing method further include: the Cu after above-mentioned adsorption treatment dyeing and printing sewage is adulterated into core
Peach shell active carbon carries out circular regeneration processing;The circular regeneration processing includes: by the Cu doping after adsorption treatment dyeing and printing sewage
Walnut shell active carbon cleaning after in 100~140 DEG C of 4~6h of drying process, later in protective atmosphere from room temperature with 2~10 DEG C
min-1Heating rate be warming up to 400~600 DEG C and be heat-treated, the time of heat treatment be 1~3h after be cooled to room temperature, obtain
It regenerates Cu and adulterates walnut shell carbide;
Preferably, the protective atmosphere includes nitrogen atmosphere;Preferably, it is used to form the nitrogen of the protective atmosphere
Flow is 50~200mL min-1。
Preferably, which comprises the Cu doping walnut shell active carbon after above-mentioned adsorption treatment dyeing and printing sewage is carried out 4
~6 circular regeneration processing.
The technical solution, its implementation process and principle etc. will be further explained in conjunction with specific embodiments as follows
It is bright.
Embodiment 1
(1) impregnation: taking 100~200 mesh raw material walnut shells, place it in drying box in 110 DEG C it is dry for 24 hours, with
Remove moisture;Preparation 200mL concentration is 10mmol L-1CuCl2Solution weighs the aforementioned walnut shell of 2.0g, by the walnut shell
CuCl is added2In solution, later with 300r min at 25 DEG C-1Rate temperature constant magnetic stirring 12h, with ensure walnut shell with
CuCl2Solution is sufficiently mixed, and then rotates obtained mixture to powdered by Rotary Evaporators;
(2) charing process: the mixture of the walnut shell-inorganic salts is weighed, is added in quartz ampoule, in fixed bed reaction
With 100mL min in device-1Flow be continually fed into N2, from room temperature with 5 DEG C of min-1Heating rate be warming up to 600 DEG C, keep
It is cooled to room temperature after 0.5h, obtains Cu doping walnut shell carbide;
(3) be activated: compound concentration is 6mol L-1KOH solution, by obtained Cu doping walnut shell carbide with
6molL-1KOH solution mixed with the mass ratio of 1:1, with 300r min at 25 DEG C-1Rate temperature constant magnetic stirring 2h,
Later in 60 DEG C of dry 12h, Cu doping walnut shell activated product is obtained;
(4) obtained Cu is adulterated into walnut shell activated product, be added in quartz ampoule, with 100mL in fixed bed reactors
min-1Flow be continually fed into N2,And with 5 DEG C of min-1Heating rate be warming up to 800 DEG C and keep the temperature 2h, then cool to room temperature;
Gained absorbent charcoal material is washed with deionized several times, until neutral, in 120 DEG C of drying process 5h in drying box, it
After be cooled to room temperature, obtain Cu doping walnut shell active carbon.
The doping walnut shell absorbent charcoal material of Cu made from the present embodiment is named as Cu-AC, and wherein Cu adulterates walnut shell activity
The constituent content of charcoal is as shown in table 1.
Handling malachite green sewage using Cu doping walnut shell activated-carbon catalyst in the embodiment of the present invention 1 includes following step
It is rapid:
Cu in the embodiment 1 of 0.0150g is taken to adulterate walnut shell active carbon and 15ml initial concentration is added as 1000mg L-1's
Malachite green solution is put it into the small test tube of 50ml, and small test tube is put into magnetic agitation water-bath with 300r min-1It carries out
Stirring, keeping bath temperature is 25 DEG C.Then 5min, 10min, 15min, 20min, 30min, 60min, 120min,
The times such as 180min, 240min, 360min measure malachite green solution concentration after taking its upper liquid to be centrifuged.
As can be seen from Figure 4 the Cu doping walnut shell active carbon that embodiment 1 provides has stronger suction to malachite green
Attached effect, malachite green solution initial concentration are 1000mg L-1In the case where, adsorbance reaches 997.37mg g in 5min-1,
Removal rate, which reaches, reaches adsorption saturation in 99.74%, 10min.
It adulterates walnut shell active carbon using Cu in embodiment 1 regenerate after adsorbing malachite green: will be through
The Cu doping walnut shell active carbon for crossing absorption is collected, and is dried 5h after ethyl alcohol centrifuge washing at 105 DEG C, is then placed in fixation
In bed reactor, it is continually fed into 100mL min-1N2, from room temperature with 5 DEG C of min-1Heating rate be warming up to 500 DEG C, keep 2h
After be cooled to room temperature, obtain regeneration Cu doping walnut shell carbide, altogether carry out five circular regenerations.
The result shows that being adsorbed using regeneration Cu doping walnut shell carbide to malachite green, treatment conditions and Cu
The treatment process that doping walnut shell carbide adsorbs malachite green is identical with condition:
When first time circular regeneration, adsorbance reaches 997.37mg g in 5min-1, removal rate reaches 99.74%, 10min
Inside reach adsorption saturation.
When second of circular regeneration, solution is clarified substantially in 5min, and adsorption saturation is reached in 30min, and adsorbance reaches
997.25mgg-1, removal rate reaches 99.73%.
When third time circular regeneration, solution is clarified substantially in 5min, and adsorption saturation is reached in 30min, and adsorbance reaches
996.45mgg-1, removal rate reaches 99.65%.
When the 4th circular regeneration, solution is clarified substantially in 5min, and adsorption saturation is reached in 30min, and adsorbance reaches
997.31mgg-1, removal rate reaches 99.73%.
When the 5th circular regeneration, solution is clarified substantially in 5min, and adsorption saturation is reached in 30min, and adsorbance reaches
997.31mgg-1, removal rate reaches 99.73%.
Table 1 is the elemental analysis table that Cu adulterates walnut shell active carbon in the embodiment of the present invention 1
Embodiment 2
Its preparation process and condition and embodiment 1 are almost the same, the difference is that preparing 200mL concentration in step (1)
For 5mmol L-1CuCl2Solution carries out impregnation.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 2
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 2 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 884.19mg g-1。
Embodiment 3
Its preparation process and condition and embodiment 1 are almost the same, the difference is that preparing 200mL concentration in step (1)
For 15mmol L-1CuCl2Solution carries out impregnation.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 3
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 3 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 891.99mg g-1。
Embodiment 4
Its preparation process and condition and embodiment 1 are almost the same, the difference is that preparing 200mL concentration in step (1)
For 10mmol L-1Cu (NO3)2Solution carries out impregnation.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 4
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 4 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 889.76mg g-1。
Embodiment 5
Its preparation process and condition and embodiment 1 are almost the same, the difference is that preparing 200mL concentration in step (3)
For 10mmol L-1CuSO4Solution carries out impregnation.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 5
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 5 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 907.57mg g-1。
Embodiment 6
Its preparation process and condition and embodiment 1 are almost the same, the difference is that Cu is adulterated walnut shell charcoal by step (3)
Compound and 6mol L-1KOH solution mixed with the mass ratio of 1:2.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 6
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 6 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 933.18mg g-1。
Embodiment 7
Its preparation process and condition and embodiment 1 are almost the same, the difference is that Cu is adulterated walnut shell charcoal by step (3)
Compound and 6mol L-1KOH solution mixed with the mass ratio of 1:3.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by embodiment 7
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the Cu in embodiment 7 adulterates walnut shell active carbon pair
The maximal absorptive capacity of malachite green solution is 893.10mg g-1。
Comparative example 1:
The step of comparative example 1 is with embodiment 1 is almost the same, the difference is that without CuCl in step (2)2Solution dipping
Processing, obtained absorbent charcoal material are named as AC.
It is to initial concentration according to condition same as Example 1 by Cu doping walnut shell active carbon prepared by comparative example 1
500~1500mg L-1Carry out malachite green solution absorption.The result shows that the undoped Cu walnut shell active carbon in comparative example 1
Maximal absorptive capacity to malachite green solution is 783.32mg g-1。
Comparative example 2
It uses CN105664849A a kind of and prepares mixed base activated carbon from activated sludge by raw material of pecan shell-corn stover
Method obtains 0.0150g mixed base activated carbon from activated sludge, and is added into the malachite that 15ml initial concentration is 1000mg L-1
Green solution, the rate of adsorption is slow, adsorbance is extremely low;The mixed base activated carbon from activated sludge provided in comparative example 2 is provided after tested
Adsorption rate to malachite green is 65%-93% effect, but the initial concentration of its malachite green solution being directed to is up to 300mg
L-1And adsorption time is longer.
As shown in figures 1 to 6, Cu doping walnut shell active carbon contains Cu in embodiment 1, and has significant absorption effect
Fruit.The scanning electron microscope (SEM) photograph that Fig. 2,3 adulterate walnut shell active carbon and 1 walnut shell active carbon of comparative example for Cu in embodiment 1.From Fig. 2,
It can be seen that the surface of Cu doping walnut shell active carbon is increased through NaOH activation rear surface duct in the embodiment of the present invention 1 in 3, have
There is cellular structure abundant, these ducts become the primary attachment site of absorption malachite green solution, and duct is more, is more conducive to
Absorption.In conjunction with Fig. 5, (Cu adulterates walnut shell activated-carbon catalyst N in the embodiment of the present invention 12Adsorption-desorption figure) it can be seen that Cu
Adulterating Cu mass fraction in walnut shell active carbon inside is 5.50wt%, internal and surface meso-hole structure rich in,
Specific surface area reaches 1015.3924m2g-1, total pore volume reach 0.55cm3g-1, average pore sizes reach 2.16nm, for its absorption malachite
It is green that sufficient place is provided.There is less hole on the walnut shell activated-carbon catalyst surface undoped with Cu as can be seen from Figure 3, and
There is more protrusion on surface, and its specific surface area is smaller, cannot provide sufficient active site for absorption malachite green.
Fig. 4 is the adsorbance curve graph that Cu adulterates walnut shell active carbon in the embodiment of the present invention 1 and comparative example 1.From figure
It can be seen that Cu doping walnut shell active carbon has stronger suction-operated, malachite green solution to malachite green in embodiment 1
Initial concentration is 1000mg L-1In the case where, adsorbance reaches 997.37mg g in 5min-1, removal rate reaches 97.74%,
Reach adsorption saturation in 10min.Undoped Cu walnut shell active carbon maximal absorptive capacity is 783.32mg g in comparative example 1-1, remove
Rate is 78.33%.Cu doping walnut shell active carbon makees malachite green with stronger absorption in embodiment 1 known to by contrast
With.
When adsorb malachite green using Cu of the present invention doping walnut shell active carbon, discovery adsorption effect is more
Significantly, the rate of adsorption is 1000mg L in malachite green solution initial concentration faster-1In the case where, to the maximum of malachite green
Adsorbance reaches 997.37mg g-1, adsorption time only has 5min, and removal rate, which reaches, reaches adsorption saturation in 99.74%, 10min.
On the one hand since duct abundant and biggish specific surface area are conducive to adsorb;One side copper plays important in adsorption process
Catalytic action, be distributed in the inside and surface of active carbon, change the polarity of active carbon, increase oxygen-containing functional group, it is right
Malachite green macromolecular shows extremely strong coordination binding force, improves adsorption capacity;Additionally, because malachite green is cationic dye
Material, the copper atom on surface are shown strong electronics and are received tendency due to electronics unsaturation energy level discretization, are had extremely strong
Activity, it is extremely unstable, it is easily absorbing tool malachite green molecule or forms complex compound therewith and tend towards stability.
In addition, finding that other embodiments of the invention obtained product is for the hole in dyeing waste water by similar experiment
Sparrow malachite green also has excellent adsorption rate and adsorption capacity.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. the preparation method that a kind of Cu for handling dyeing and printing sewage adulterates walnut shell active carbon, characterized by comprising:
(1) by walnut shell and containing Cu2+Inorganic salt solution uniformly mix, be dried later, obtain inorganic salts-walnut
Shell mixture;
(2) inorganic salts-walnut shell mixture is subjected to carbonization treatment in protective atmosphere, the temperature of carbonization treatment is
400~600 DEG C, the time is 0.5~2h, obtains Cu and adulterates walnut shell carbide;
(3) Cu doping walnut shell carbide is uniformly mixed with alkaline solution, is dried later, obtains Cu doping
Walnut shell activated product;
(4) Cu doping walnut shell activity compound being heat-treated in protective atmosphere, the temperature of heat treatment is 600~
800 DEG C, the time is 2~4h, then post-treated, obtains Cu and adulterates walnut shell active carbon.
2. preparation method according to claim 1, it is characterised in that: the partial size of walnut shell is 100~200 in step (1)
Mesh;And/or the walnut shell is by dried, and the temperature of drying process is 100~120 DEG C, the time is 12~
36h;And/or it is described containing Cu2+Inorganic salt solution concentration be 5~15mmol-1;And/or the walnut shell with contain Cu2+
Inorganic salt solution mass volume ratio be 1~3g:100~300ml;And/or Cu in the inorganic salt solution2+
Source includes copper nitrate, copper sulphate, any one or two or more combinations in copper chloride.
3. preparation method according to claim 1 or 2, which is characterized in that step (1) specifically includes: temperature be 20~
Under conditions of 40 DEG C, walnut shell is added and contains Cu2+Inorganic salt solution in, and with 200~400r min-1Mixing speed
Persistently stirring 12~for 24 hours, later by gained mixture be 60~100 DEG C in temperature under conditions of be dried, and do
The time of dry processing is 0.5~1h.
4. preparation method according to claim 1, which is characterized in that the step (2) includes: by the inorganic salts-core
Peach shell mixture is placed in protective atmosphere, and with 2~10 DEG C of min-1Heating rate be warming up to 500~700 DEG C and be carbonized
Processing, and the time of carbonization treatment is 0.5~1h;And/or the protective atmosphere includes nitrogen atmosphere;And/or it is used for
The nitrogen flow for forming the protective atmosphere is 100~200mL min-1。
5. preparation method according to claim 1, it is characterised in that: Cu described in step (3) adulterates walnut shell carbide
Mass ratio with alkaline solution is 1:(1~3);And/or the concentration of the alkaline solution is 5~10mmol L-1;And/or institute
Stating alkaline solution includes sodium hydroxide solution, potassium hydroxide solution, any one or two or more combinations in ammonia spirit;
And/or the step (3) specifically includes: under conditions of temperature is 20~40 DEG C, Cu doping walnut shell carbide being added
Enter alkaline solution, and with 200~400r min-1Speed persistently stir 2~4h, later by gained mixture in 60~100 DEG C
It is dried, the time of drying process is 2~4h.
6. preparation method according to claim 1, which is characterized in that the step (4) specifically includes: the Cu is adulterated
Walnut shell activity compound is placed in protective atmosphere, and with 2~10 DEG C of min-1Heating rate be warming up to 700~900 DEG C of progress
Heat treatment, the time of heat treatment are 1~3h;And/or the protective atmosphere includes nitrogen atmosphere;And/or it is used to form institute
The nitrogen flow for stating protective atmosphere is 100~200mL min-1;And/or the step (4) further include: completed in heat treatment
Afterwards, obtained product is washed to neutrality, then at 100~140 DEG C of 4~6h of drying process, obtains Cu and adulterate walnut shell active carbon.
7. adulterating walnut shell active carbon by the Cu of any one of claim 1-6 the method preparation.
8. Cu according to claim 7 adulterates walnut shell active carbon, it is characterised in that: the Cu adulterates walnut shell active carbon
Inside and surface be distributed with meso-hole structure, total pore volume is 0.5~1.0cm3g-1, specific surface area is 1000~2000m2g-1, the aperture of the meso-hole structure is 1~3nm, and Cu constituent content therein is 5~10wt%.
9. Cu doping walnut shell active carbon as claimed in claim 7 or 8 is in the application of dyeing and printing sewage process field.
10. a kind of method of dyeing and printing sewage processing, characterized by comprising:
Cu described in claim 7 or 8 is provided and adulterates walnut shell active carbon;
Cu doping walnut shell active carbon is added in dyeing and printing sewage and is sufficiently mixed;
Wherein, the dyeing and printing sewage contain in malachite green, methyl red and methylene blue any one or it is two or more
Combination;
Preferably, the concentration of the dyeing and printing sewage is 500~2000mg L-1;
Preferably, the amount ratio of the Cu doping walnut shell active carbon and dyeing and printing sewage is 1g:(1000~2000) ml;
Preferably, the mixed reaction time that dyeing and printing sewage is added in the Cu doping walnut shell active carbon is 10~360min;
Preferably, the dyeing and printing sewage processing method further include: the Cu after above-mentioned adsorption treatment dyeing and printing sewage is adulterated into walnut shell
Active carbon carries out circular regeneration processing;The circular regeneration processing includes: that the Cu after adsorption treatment dyeing and printing sewage is adulterated walnut
Shell active carbon cleaning after in 100~140 DEG C of 4~6h of drying process, later in protective atmosphere from room temperature with 2~10 DEG C of min-1
Heating rate be warming up to 400~600 DEG C and be heat-treated, the time of heat treatment be 1~3h after be cooled to room temperature, regenerated
Cu adulterates walnut shell carbide;
Preferably, the protective atmosphere includes nitrogen atmosphere;Preferably, it is used to form the nitrogen flow of the protective atmosphere
For 50~200mL min-1;
Preferably, which comprises the Cu doping walnut shell active carbon after above-mentioned adsorption treatment dyeing and printing sewage is carried out 4~6
Secondary circular regeneration processing.
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