CN103785345B - A kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water - Google Patents

A kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water Download PDF

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CN103785345B
CN103785345B CN201410076283.8A CN201410076283A CN103785345B CN 103785345 B CN103785345 B CN 103785345B CN 201410076283 A CN201410076283 A CN 201410076283A CN 103785345 B CN103785345 B CN 103785345B
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manganese dioxide
waste water
support type
adsorbent
dioxide adsorbent
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CN103785345A (en
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肖巍
汪的华
徐寅
刘文婷
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Wuhan University WHU
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Abstract

The present invention relates to a kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water, belong to technical field of waste water processing.This adsorbent comprises nano-sheet birnessite manganese dioxide and transition metal oxide carrier, and the particle diameter stating carrier is 100 ~ 3000nm, and the thickness of sheet manganese dioxide is 1-100nm, and its content is 15-20wt.%.The method of its pretreatment aniline waste water is utilized to be: the shape characteristic of the method material therefor is: adopt hydro-thermal method to prepare support type manganese dioxide adsorbent, being joined pH value is in the aniline waste water of 3 ~ 14, fully shakes, centrifugation.The attached capacity of adsorbent of the present invention is large, and not easily reunite, adsorption efficiency is high, can realize recycling, and the concentration of the aniline waste water of high concentration can be down to 5-700mg/L.Method of the present invention has that method of operating is easy, recycling is convenient, cheaper starting materials is easy to get.

Description

A kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water
Technical field
The present invention relates to a kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water, belong to technical field of waste water processing.
Background technology
Growing along with chemical industry, quantity and the kind of organic pollution increase year by year, and a large amount of poisonous and hazardous organic pollution is discharged in river, causes the severe contamination of water body.Aniline is the most representative material of aromatic amine, it is a kind of colourless oil liquid with aromatic odor, be widely used in the industry such as national defence, printing and dyeing, plastics, agricultural chemicals and medicine, also the material being serious environment pollution simultaneously and being detrimental to health, be a kind of " carcinogenic, teratogenesis, mutagenesis " three cause material, listed in " Chinese environmental priority pollutant blacklist ".Domestication factory is many in process of production can produce aniline waste water, and its mass concentration can reach thousands of milligrams per liter, and is very likely leaked in process of production in environment.The discharge of China to aniline waste water has strict demand, and its highest permission concentration of emission is 5.0mg/L.
At present, the processing method of aniline organic wastewater mainly contains physics, chemistry and biological method, comprises extraction, membrane separation process, absorption method, oxidizing process, electrolysis, sonication and biological degradation method etc.In the processing method of various aniline waste water, chemical method and bioanalysis can not recycle aniline, and chemical method cost is high, and bioanalysis needs to carry out Macrodilution to waste water.And absorption method have simple to operate, treatment effect good, be beneficial to the features such as aniline recovery.Adsorbent conventional at present mainly contains several large class of carbonaceous adsorbent, adsorbent of molecular sieve and polymeric adsorbent.But its adsorption capacity is all lower, the adsorbent of development of new is significant for aniline sewage process.
Nano adsorber has the features such as specific area is large, active adsorption sites is many, has great advantage in Adsorption waste water in organic impurities.But nanoscale adsorbent because of its particle too small, and exist and easily reunite, side reaction easily occurs, to be difficultly separated, easily to produce the shortcomings such as secondary pollution.And nano/submicron level or Nano/micron level composite adsorbing material, both there is the feature that the particle diameter of sub-micron or micro materials is large, there is again the advantage that specific area is high and adsorption site is many of nano material, therefore, not only remain the advantageous property of nano material as adsorbent, and also overcome many defects of nano material to a great extent.
Simple physics or chemisorbed limit absorption potential and the stability of adsorbent to a great extent, and based on the suction-operated that cationic ion exchanges, can significantly improve the absorption property of adsorbent.
Summary of the invention
The object of the present invention is to provide a kind of support type manganese dioxide adsorbent;
Another object of the present invention is to provide a kind of method utilizing above-mentioned adsorbent pretreatment aniline waste water.
Adsorbent of the present invention is the support type manganese dioxide of nano-sheet manganese dioxide oriented growth on transition metal oxide, can utilize its high-efficiency pretreatment aniline waste water.This adsorbent has high-efficiency pretreatment High Concentration Aniline Wastewater, adsorbent has various controlled, and adsorption capacity is large, not easily reunites, to the feature such as environment and body harmless, method is simple to utilize its pretreated waste water.
Object of the present invention is achieved through the following technical solutions:
A kind of support type manganese dioxide adsorbent, comprises nano-sheet birnessite manganese dioxide and carrier thereof; Described carrier is transition metal oxide, and its particle diameter is 100 ~ 3000nm.
The thickness of described sheet manganese dioxide is 1-100nm, and its content is 15-20wt.%.
Described transition metal oxide is mangano-manganic oxide, manganese sesquioxide managnic oxide, iron oxide, tri-iron tetroxide, tin ash, titanium dioxide, zinc oxide or cupric oxide.
Utilize a method for above-mentioned support type manganese dioxide adsorbent pretreatment aniline waste water, comprise the steps:
(1) hydro-thermal method is adopted to prepare support type manganese dioxide adsorbent;
(2) regulate pH value to 3 ~ 14 of aniline waste water, add the support type manganese dioxide adsorbent prepared by step (1), the content forming support type manganese dioxide adsorbent is the mixture of 0.05 ~ 10g/L, fully shakes, centrifugation.
Hydro-thermal method in described step (1) comprises the steps: transition metal oxide powder to be distributed in deionized water, add the hydrochloric acid of solubility permanganate and 37%, stir, 80-110 DEG C of hydro-thermal reaction 4-23h, centrifugal, removal of impurities, obtains support type manganese dioxide adsorbent; The mass ratio of described transition metal oxide powder and solubility permanganate is 0.05-0.15:0.1-0.4, and the addition of the hydrochloric acid of described 37% is 0.01-0.04mol/L.
Described solubility permanganate is potassium permanganate or sodium permanganate.
Described concussion is shaking table concussion.
Described shaking table concussion condition is: temperature 5 ~ 40 DEG C, rotating speed 30 ~ 300 rpms.
Support type manganese dioxide adsorbent provided by the invention is that the aniline waste water pretreating effect of high concentration is better to concentration, the concentration of this case waste water can be down to 5-700mg/L from 3000-7100mg/L.In addition, also organic dye waste water can be processed, as methylene blue and Congo red.
Birnessite is a kind of manganese oxide mineral that nature extensively exists, and is the mixed valence Mn oxide be made up of manganic and tetravalent manganese, and structure composition is complicated.In its structure, MnO 6octahedra to be interconnected formation lamella by common edge in ab plane.By this MnO 6octahedra lamella is piled up along c-axis direction and is formed layered crystal structure.At two MnO 6na is filled with between octahedral layer +and water molecule layer, have ion-exchange character, the cation namely between octahedral layer can with other cations (as K +, Cu 2+, Sn 2+, Fe 2+, Fe 3+or Zn 2+deng) there is ion exchange.
The basal plane spacing (about 0.73 nanometer) of birnessite manganese dioxide is slightly larger than the diameter (about 0.58nm) of anilinium cations, in aniline waste water preprocessing process, metal cation contained by birnessite manganese dioxide interlayer and the anilinium cations in aniline waste water carry out ion-exchange, anilinium cations enters the interlayer of adsorbent, and anilinium cations absorption on the sorbent.And the manganese dioxide of sheet increases surface area and the adsorption site of adsorbent, thus realize efficient adsorption.
In the present invention, the method for testing of the absorption property of resulting materials is: utilize ultraviolet-visible spectrophotometer to measure the absorbance of sorbent treatment aniline waste water in the different disposal time, according to aniline absorbance-concentration standard curve, measure the concentration of aniline in different time waste water, and then obtain the absorption property of adsorbent.
The invention has the beneficial effects as follows:
1. support type manganese dioxide adsorbent needed raw material provided by the invention is non-rare element (base metal), with low cost.
2. support type manganese dioxide adsorbent provided by the invention has the advantages that surface area is high and absorption property is good, shows good removal effect to High Concentration Aniline Wastewater.
3. the own safety of support type manganese dioxide adsorbent provided by the invention, main component is the Mn oxide extensively existed in soil, and has submicron order or micron scale construction, to natural environment and health without harm.
4. support type manganese dioxide adsorbent provided by the invention is to the process of waste water, and method is simple, and regeneration effect is good.
5. support type manganese dioxide adsorbent stable in properties provided by the invention, because adsorption capacity is huge, use amount is considerably less, is convenient to especially store and transport.
6. the synergy of sheet birnessite manganese dioxide to the ion-exchange of the ammonium radical ion in the physical absorption of aniline and contained metal cation and aniline waste water thereof makes it have the feature of efficient adsorption high concentration aniline.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of mangano-manganic oxide load manganese dioxide adsorbent prepared by the embodiment of the present invention 1.
Fig. 2 is the adsorption curve of mangano-manganic oxide load manganese dioxide adsorbent prepared by the embodiment of the present invention 1.
Detailed description of the invention
Below by embodiment, illustrate outstanding feature of the present invention and marked improvement further, be only the present invention is described and never limits the present invention.
Embodiment 1
Take 0.674g potassium permanganate dissolution of solid in 40mL deionized water, add 2mL ethylene glycol under magnetic stirring, stir dissolution homogeneity after 20 minutes.Being joined volume is in the autoclave of 100mL, 160 DEG C of heated sealed 10 hours.After autoclave is cooled to room temperature, adopt centrifugal (7000rpm, 10min) mode to be separated by brown powder shape solid, remove the impurity in product successively with water, ethanol, washing.Vacuum drying 5 hours in 80 DEG C of vacuum drying chambers, obtain mangano-manganic oxide sub-micron octahedral build powder, its particle diameter is 100-800nm.
The ultrasonic method of 0.1g mangano-manganic oxide powder obtained is distributed in 50mL deionized water, adds 0.25g potassium permanganate and 0.8mmol37% hydrochloric acid, stir.Under magnetic agitation condition, 80 DEG C of oil bath seal heat 5 hours.Treat that container is cooled to room temperature, by solidliquid mixture with the centrifugal 10min of the rotating speed of 7000rpm, use deionized water, ethanol, deionized water centrifuge washing under the same conditions successively; Grind after 5 hours through 80 DEG C of vacuum drying, obtain brown powder solid, be i.e. mangano-manganic oxide load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 1-50nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 3191mg/L, regulates its pH value to be 12.0, add the mangano-manganic oxide load manganese dioxide adsorbent powder prepared by 30mg embodiment 1, be 25 DEG C in shaking table temperature, rotating speed is shake under 150rmp, results of regular determination aqueous concentration.After 1 hour, water outlet concentration of aniline is 292mg/L, and adsorption capacity is 2.703g aniline/g adsorbent.
Embodiment 2
Take 0.674g potassium permanganate dissolution of solid in 40mL deionized water, under magnetic stirring, add 2mL ethylene glycol, stir dissolution homogeneity after 40 minutes.Being poured into volume is in the autoclave of 100mL, 160 DEG C of heated sealed 10 hours.After autoclave is cooled to room temperature, adopt centrifugal (10000rpm, 5min) mode brown powder to be separated, wash away the impurity in product successively with water, water, ethanol.Vacuum drying 8 hours in 70 DEG C of vacuum drying chambers, obtain mangano-manganic oxide sub-micron octahedral build powder, its particle diameter is 100-800nm.
The ultrasonic method of 0.1g mangano-manganic oxide powder obtained be distributed in 50mL deionized water, add 0.25g potassium permanganate and 1.0mmol37% hydrochloric acid, stir, under magnetic stirring, 95 DEG C of oil bath seal heat 23 hours.Treat that container is cooled to room temperature, by solidliquid mixture with the centrifugal 5min of the rotating speed of 10000rpm, use deionized water, deionized water, ethanol centrifuge washing under the same conditions successively; Grind after 8 hours through 70 DEG C of vacuum drying, obtain brown powder solid, be i.e. mangano-manganic oxide load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 1-50nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 7092mg/L, regulates its pH value to 12.0, add mangano-manganic oxide load manganese dioxide adsorbent prepared by 30mg embodiment 2, be 25 DEG C in shaking table temperature, rotating speed is shake under 150rmp, results of regular determination aqueous concentration.24 hours water outlet concentration of anilines are 53.37mg/L, and adsorption capacity is 7.039g aniline/g adsorbent.
Embodiment 3
Take 0.606g sodium permanganate dissolution of solid in 30mL deionized water, under magnetic stirring, add 1.5mL ethylene glycol, stir dissolution homogeneity after 30 minutes.Mixed liquor being poured into volume is in the autoclave of 50mL, 160 DEG C of heated sealed 10 hours.After autoclave is cooled to room temperature, adopt centrifugal (8000rpm, 8min) mode brown powder to be separated, wash away the impurity in product successively with water, water, ethanol.Vacuum drying 12 hours in 50 DEG C of vacuum drying chambers, obtain octahedral build mangano-manganic oxide submicron powder, its particle diameter is 100-800nm.
The ultrasonic method of 0.1g mangano-manganic oxide powder obtained be distributed in 50mL deionized water, add 0.25g sodium permanganate and 1.5mmol37% hydrochloric acid, stir, 105 DEG C of oil bath seal heat 8 hours.Treat that container is cooled to room temperature, by solidliquid mixture with after the centrifugal 8min of the rotating speed of 8000rpm, use deionized water, ethanol, deionized water centrifuge washing under the same conditions successively; Grind after 12 hours through 50 DEG C of vacuum drying, obtain brown powder solid, be i.e. mangano-manganic oxide load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 1-50nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 4069mg/L, regulates its pH value to be 12.0, add mangano-manganic oxide load manganese dioxide adsorbent powder prepared by 30mg embodiment 3, be 25 DEG C in shaking table temperature, rotating speed is shake under 120rmp, results of regular determination aqueous concentration.24 hours water outlet concentration of anilines are 361mg/L, and adsorption capacity is 4.248g aniline/g adsorbent.
Embodiment 4
Take 0.674g potassium permanganate dissolution of solid in 40mL deionized water, under magnetic stirring, add 2mL ethylene glycol, stir dissolution homogeneity after 40 minutes.Mixed liquor being poured into volume is in the autoclave of 100mL, 160 DEG C of heated sealed 10 hours.After autoclave is cooled to room temperature, adopt centrifugal (10000rpm, 5min) mode brown powder to be separated, wash away the impurity in product successively with water, water, ethanol.Vacuum drying 8 hours in 70 DEG C of vacuum drying chambers, obtain mangano-manganic oxide sub-micron octahedral build powder, its particle diameter is 100-800nm.
Go in ionized water by the 0.05g mangano-manganic oxide powder ultrasonic method obtained dispersion 50mL, add 0.1g potassium permanganate and 0.5mmol37% hydrochloric acid, stir, under magnetic stirring, 85 DEG C of oil bath seal heat 5 hours.Treat that container is cooled to room temperature, by solidliquid mixture with the centrifugal 8min of the rotating speed of 7000rpm, use deionized water, deionized water, ethanol centrifuge washing under the same conditions successively; Grind after 8 hours through 70 DEG C of vacuum drying, obtain brown powder solid, be i.e. mangano-manganic oxide load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 1-50nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 4255mg/L, regulates its pH value to 12.0, add mangano-manganic oxide load manganese dioxide adsorbent prepared by 1.5mg embodiment 4, be 40 DEG C in shaking table temperature, rotating speed is shake under 30rmp, results of regular determination aqueous concentration.2 hours water outlet concentration of anilines are 438mg/L, and adsorption capacity is 3.817g aniline/g adsorbent.
Embodiment 5
Take 0.674g potassium permanganate dissolution of solid in 40mL deionized water, under magnetic stirring, add 2mL ethylene glycol, stir dissolution homogeneity after 40 minutes.Mixed liquor being poured into volume is in the autoclave of 100mL, 160 DEG C of heated sealed 10 hours.After autoclave is cooled to room temperature, adopt centrifugal (10000rpm, 5min) mode brown powder to be separated, wash away the impurity in product successively with water, water, ethanol.Vacuum drying 8 hours in 70 DEG C of vacuum drying chambers, obtain mangano-manganic oxide sub-micron octahedral build powder, its particle diameter is 100-800nm.
The ultrasonic method of 0.15g mangano-manganic oxide powder obtained be distributed in 50mL deionized water, add 0.4g potassium permanganate and 2.0mmol37% hydrochloric acid, stir, under magnetic stirring, 110 DEG C of oil bath seal heat 8 hours.Treat that container is cooled to room temperature, by solidliquid mixture with the centrifugal 8min of the rotating speed of 7000rpm, use deionized water, deionized water, ethanol centrifuge washing under the same conditions successively; Grind after 8 hours through 70 DEG C of vacuum drying, obtain brown powder solid, be i.e. mangano-manganic oxide load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 1-50nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 7092mg/L, regulates its pH value to 12.0, add mangano-manganic oxide load manganese dioxide adsorbent prepared by 300mg embodiment 5, be 5 DEG C in shaking table temperature, rotating speed is shake under 300rmp, results of regular determination aqueous concentration.48 hours water outlet concentration of anilines are 5.1mg/L, and adsorption capacity is 708.7g aniline/g adsorbent.
Embodiment 6
Take 0.12g hum silicon dioxide titanium powder (its particle diameter is 500-3000nm), be distributed in 50mL deionized water by ultrasonic method, add 0.25g potassium permanganate and 2.0mmol37% hydrochloric acid, stir and form uniform solution.Under magnetic stirring, after 95 DEG C of oil bath seal heat 10 hours.Treat that container is cooled to room temperature, by solidliquid mixture with the centrifugal 10min of the rotating speed of 7000rpm, use deionized water, ethanol, deionized water centrifuge washing under the same conditions successively; Grind after 5 hours through 80 DEG C of vacuum drying, obtain brown powder solid, be i.e. titanium dichloride load manganese dioxide adsorbent, in adsorbent, the thickness of sheet manganese dioxide is 20-100nm.
In flask, add 30mL aniline waste water, the concentration of aniline is 3901mg/L, regulates its pH value to be 12.0, add titanium dichloride load manganese dioxide adsorbent powder prepared by 30mg embodiment 6, be 25 DEG C in shaking table temperature, rotating speed is shake under 180rmp, results of regular determination aqueous concentration.12 hours water outlet concentration of anilines are 250mg/L, and adsorption capacity is 3.651g aniline/g adsorbent.
Embodiment 7
Contrast different aniline waste water solution ph to the impact of the adsorption capacity of support type manganese dioxide adsorbent.
Take 2.7g Iron(III) chloride hexahydrate and 27mg sodium dihydrogen phosphate, join and fill in the closed glass container of 500mL deionized water, 105 DEG C of heated sealed 48 hours, after container naturally cools to room temperature, adopt centrifugal (7000rpm, 10min) pulverulent solids is separated by mode, removes the impurity in product successively with water, ethanol, washing.In 80 DEG C of vacuum drying chambers, vacuum drying 5 hours, obtains croci, and its particle diameter is 100-1500nm.
The 0.12g croci obtained is distributed in 50mL deionized water by ultrasonic method, adds 0.25g potassium permanganate and 1.0mmol37% hydrochloric acid, stir and form uniform solution.Under magnetic stirring, 95 DEG C of oil bath seal heat 4 hours.Treat that container is cooled to room temperature, by solidliquid mixture with after the centrifugal 10min of the rotating speed of 7000rpm, use deionized water, ethanol, deionized water centrifuge washing under the same conditions successively; Grind after 5 hours through 80 DEG C of vacuum drying, obtain brown powder shape solid, i.e. iron oxide load manganese dioxide adsorbent, the thickness of sheet manganese dioxide is 10-70nm.
In flask, add 50mL aniline waste water, the concentration of aniline is 4710.1mg/L, regulates its pH, and add 50mg iron oxide load manganese dioxide powder, temperature is 25 DEG C, rotating speed be 120rmp shaking table on shake, determine water concentration.The impact of aniline waste water solution ph on the adsorption capacity of support type manganese dioxide adsorbent is as shown in table 1.
Table 1 aniline waste water solution ph is on the impact of the adsorption capacity of support type birnessite manganese dioxide adsorbent.
The pH of aniline solution Water outlet concentration of aniline (mg/L) after 18 hours Adsorption capacity (g aniline/g adsorbent)
3.0 668 4.042
13.1 393 4.392
7.1 552 4.158
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (5)

1. a method for support type manganese dioxide adsorbent pretreatment aniline waste water, is characterized in that comprising the steps:
(1) hydro-thermal method is adopted to prepare support type manganese dioxide adsorbent;
(2) regulate pH value to 3 ~ 14 of aniline waste water, add the support type manganese dioxide adsorbent prepared by step (1), the content forming support type manganese dioxide adsorbent is the mixture of 0.05 ~ 10g/L, fully shakes, centrifugation;
Support type manganese dioxide adsorbent in described step (1), comprises nano-sheet birnessite manganese dioxide and carrier thereof; Described carrier is transition metal oxide, and its particle diameter is 100 ~ 3000nm;
The thickness of described sheet manganese dioxide is 1-100nm, and its content is 15-20wt.%;
Hydro-thermal method in described step (1) comprises the steps: transition metal oxide powder to be distributed in deionized water, add the hydrochloric acid of solubility permanganate and 37%, stir, 80-110 DEG C of hydro-thermal reaction 4-23h, centrifugal, removal of impurities, obtains support type manganese dioxide adsorbent; The mass ratio of described transition metal oxide powder and solubility permanganate is 0.05-0.15:0.1-0.4, and the addition of the hydrochloric acid of described 37% is 0.01-0.04mol/L.
2. the method for a kind of support type manganese dioxide adsorbent pretreatment aniline waste water according to claim 1, is characterized in that: described transition metal oxide is mangano-manganic oxide, manganese sesquioxide managnic oxide, iron oxide, tri-iron tetroxide, tin ash, titanium dioxide, zinc oxide or cupric oxide.
3. the method for a kind of support type manganese dioxide adsorbent pretreatment aniline waste water according to claim 1, is characterized in that: described solubility permanganate is potassium permanganate or sodium permanganate.
4. the method for a kind of support type manganese dioxide adsorbent pretreatment aniline waste water according to claim 1, is characterized in that: described concussion is shaking table concussion.
5. the method for a kind of support type manganese dioxide adsorbent pretreatment aniline waste water according to claim 4, is characterized in that: described shaking table concussion condition is: concussion temperature 5 ~ 40 DEG C, rotating speed is 30 ~ 300 revs/min.
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