CN107983300A - Biological carbon composite of manganese dioxide modification and its preparation method and application - Google Patents
Biological carbon composite of manganese dioxide modification and its preparation method and application Download PDFInfo
- Publication number
- CN107983300A CN107983300A CN201610954702.2A CN201610954702A CN107983300A CN 107983300 A CN107983300 A CN 107983300A CN 201610954702 A CN201610954702 A CN 201610954702A CN 107983300 A CN107983300 A CN 107983300A
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- heavy metal
- carbon composite
- charcoal
- biological carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
Biological carbon composite the invention discloses a kind of modification of manganese dioxide and its preparation method and application, which includes manganese dioxide and charcoal；The biological carbon composite of manganese dioxide modification is will to be prepared by the comproportionation reaction of permanganate and manganese element in manganous salt on the manganese dioxide load of generation to charcoal.The composite material of manganese dioxide of the present invention modification has the advantages that strong to the adsorption capacity of heavy metal lead or cadmium, adsorption effect is obvious, manufacturing cost is low etc., it is a kind of ideal heavy metal wastewater thereby adsorbent, its preparation method has the advantages that technique is simple, raw material is cheap, material makes full use of, production cost is low etc..The composite material of manganese dioxide of the present invention modification can be used for handling heavy metal wastewater thereby, have that big to the adsorption capacity of heavy metal, adsorption efficiency is high, to low toxin biological in environment, can mass produce and apply.
Description
Technical field
The invention belongs to material and environmental area, and in particular to a kind of manganese dioxide modification biological carbon composite and
Its preparation method and application.
Background technology
With the fast development of modern industrial or agricultural, heavy metal passes through mining, intermetallic composite coating and chemical production wastewater etc.
Industrial pollution source, the man-made pollution source such as the use of agriculture chemical and house refuse, and the natural source form such as geologic erosion, weathering
Into water body, serious threat is caused to publilc health and ecological environment.More seriously, heavy metal pollution has hidden
The features such as property, chronicity, irreversibility and consequence seriousness, human body can be eventually entered into by ecologic food chain, physiology can be caused
On disease, endanger human health.
At present, existing many treatment technologies are applied in heavy metal-polluted water harnessing, mainly have phytoremediation technology, animal to repair
Recovering technology, microorganism remediation technology, chemical precipitation method, membranous system and absorption method.Compared with other methods, absorption method is grasped because of it
Work convenience, the wide variety of adsorbent, operating cost are low, efficient, flexible design, regenerating easily, the waste water of processing are suitable for back
Receipts the advantage such as utilize and are widely used as one and efficient processing method.
Charcoal is one kind that waste biomass material is formed by the method for Pintsch process under conditions of anoxic or few oxygen
Highly difficult fragrance insoluble solid material.Because its preparing raw material source is wide, preparation process is relatively easy, and specific surface area is big, surface
The high preferably physicochemical property of energy, has been widely used in adsorbing the research of the pollutants such as heavy metal in waste water.Such as maize straw
The charcoal of preparation is to Cd2+The research of adsorption mechanism；Charcoal prepared by peanut shell is to Pb2+Removal research；In addition with core
Charcoal prepared by the raw materials such as peach green peel, bagasse, fowl poultry kind excrement, activated sludge is applied in the absorption to Heavy Metals in Waters
Research.
However, single charcoal can not show a candle to the adsorption effect of heavy metal in the composite material after being combined with other materials
Adsorption effect.Composite material is by two or more material of different nature, utilizes physics, the tool being chemically synthesized
There is the material of new capability, its comprehensive performance is better than former composition material and meets a variety of requirements.In recent years, charcoal is compound
Material causes the research interest of numerous scholars, and existing research includes nano zero valence iron, magnetic iron oxide, carbon nanotubes, stone
The compound of black alkene, AlOOH, clay, magnesia etc. and charcoal, these composite materials all have good physical property, and
And it can efficiently remove various pollutants in water body.
Mn oxide includes Mn oxide-absorbent charcoal material, Mn oxide-tree as composite material prepared by modified material
The materials such as fat, Mn oxide-nano material and Mn oxide-charcoal, but in the material of existing Mn oxide-charcoal, greatly
It is that composite material, this complex method are obtained by high-temperature calcination after charcoal or biological carbon feedstock are immersed manganese containing solution mostly
It is difficult to control load capacity of the Mn oxide on charcoal, it is impossible to make full use of the manganese element in manganese containing solution, raw material can be caused
Waste.How to optimize Mn oxide-charcoal mode of loading, save financial cost, it is also necessary to further research.
The content of the invention
The technical problems to be solved by the invention are in view of the deficiencies of the prior art, there is provided a kind of heavy metal adsorption capacity
Greatly, the biological carbon composite for the manganese dioxide modification that adsorption efficiency is high, manufacturing cost is low, it is simple, former also to provide a kind of technique
Expect the preparation method of the biological carbon composite of the manganese dioxide modification cheap, material makes full use of, production cost is low and be somebody's turn to do
Application of the biological carbon composite of manganese dioxide modification in heavy metal wastewater thereby is handled.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of biological carbon composite of manganese dioxide modification, including manganese dioxide and charcoal；The manganese dioxide is repaiied
The biological carbon composite of decorations is by the manganese dioxide of generation by the comproportionation reaction of manganese element in permanganate and manganous salt
Load on charcoal and be prepared.
The technical concept total as one, the biological carbon composite modified present invention also offers a kind of manganese dioxide
Preparation method, comprises the following steps：Manganous salt is added in being returned in the mixed liquor containing charcoal and permanganate anti-
Should, obtain the biological carbon composite of manganese dioxide modification.
In above-mentioned preparation method, it is preferred that charcoal, permanganate in the manganous salt and the mixed liquor
Mass ratio is 2.45~9.80: 15: 1.06~4.22.
In above-mentioned preparation method, it is preferred that the preparation method of the charcoal comprises the following steps：
(1) fowl and animal excrement and sawdust are mixed into row aerobic compost, obtain mixture；
(2) mixture in step (1) is calcined, obtains charcoal.
In above-mentioned preparation method, it is preferred that in the step (1)：The mass ratio of the fowl and animal excrement and sawdust for 3~
5∶1；The time of the aerobic compost is 56 days~92 days；
And/or in the step (2)：The calcining carries out under nitrogen protection atmosphere；The calcining is with 5 DEG C/min
The speed of~15 DEG C/min is warming up to 400 DEG C~700 DEG C calcining 1.5h~2.5h.
In above-mentioned preparation method, it is preferred that the comproportionation reaction carries out under agitation；The comproportionation reaction is completed
After further include following processing：The biological carbon composite suspension that manganese dioxide obtained by comproportionation reaction is modified is heated to 70 DEG C
~90 DEG C and 30min~60min is kept, be washed till neutral, drying.
The technical concept total as one, present invention also offers a kind of charcoal of above-mentioned manganese dioxide modification is compound
The biological carbon composite that manganese dioxide made from material or above-mentioned preparation method is modified answering in heavy metal wastewater thereby is handled
With comprising the following steps：The biological carbon composite that the manganese dioxide is modified is mixed with heavy metal wastewater thereby carries out vibration suction
Reaction enclosure, completes the processing to heavy metal wastewater thereby；
The additive amount of the biological carbon composite of manganese dioxide modification is adds institute in heavy metal wastewater thereby every liter described
State biological carbon composite 0.2g~4.0g of manganese dioxide modification.
In above-mentioned application, it is preferred that the heavy metal wastewater thereby is leaded heavy metal wastewater thereby or heavy metal wastewater thereby containing cadmium；Institute
The initial concentration for stating lead in leaded heavy metal wastewater thereby is 0.5mg/L~1500.0mg/L；Cadmium in the heavy metal wastewater thereby containing cadmium
Initial concentration is 0.5mg/L~250.0mg/L.
In above-mentioned application, it is preferred that the pH value of the heavy metal wastewater thereby is 2.0~8.0；The heavy metal wastewater thereby from
Sub- intensity is 0.01mol/L~0.1mol/L.It is further preferred that the pH value of the heavy metal wastewater thereby is 5.0 ± 0.2.
In above-mentioned application, it is preferred that it is described vibration adsorption reaction temperature be 25 DEG C~45 DEG C, rotating speed for 150rpm~
180rpm, time are 10h~14h.It is further preferred that the temperature of the vibration adsorption reaction is 25 DEG C, rotating speed 170rpm,
Time is 12h.
In the preparation method of the biological carbon composite of manganese dioxide of the present invention modification, it is preferred that the permanganate is
Potassium permanganate or sodium permanganate, but it is not limited only to this.
In the preparation method of the biological carbon composite of manganese dioxide of the present invention modification, it is preferred that the manganous salt is
Four hydration manganese acetates or four chloride hydrate manganese, but it is not limited only to this.
It is described to contain charcoal and permanganic acid in the present invention in the preparation method for the biological carbon composite that manganese dioxide is modified
The mixed liquor of salt is mixed by charcoal, permanganate with deionized water, is made after sonic oscillation；The time of the sonic oscillation
For 30min~60min.In the present invention, after charcoal is mixed with permanganate, the MnO4 in permanganate can be with biology
Charcoal forms hydrogen bond, promotes the combination of charcoal and MnO4, so that load of the manganese dioxide on charcoal is more scattered；
In addition, the purpose for carrying out sonic oscillation is to allow charcoal to be come into full contact with liquor potassic permanganate, reaches Load Balanced and disperse
Effect.
In the preparation method of charcoal of the present invention, it is preferred that the fowl and animal excrement is pig manure or cow dung, but is not limited only to
This.
In the preparation method of charcoal of the present invention, it is preferred that the sawdust is camphorwood dust, but is not limited only to this.
In the preparation method of charcoal of the present invention, the mixture further includes following processing before being calcined：By mixture
Cleaned, dried with deionized water, grinding, crosses 100 mesh sieves.
In the application of the present invention, according to actual needs, 0.1mol/L sodium nitrate solutions can be used to adjust heavy metal wastewater thereby
Ionic strength, but it is not limited only to this.
In the application of the present invention, according to actual needs, NaOH solution or HNO can be used3Solution adjusts heavy metal wastewater thereby
PH value, but it is not limited only to this.
The innovative point of the present invention is：
Fowl and animal excrement (such as pig manure) is mixed laggard oxygen heap of acting charitably with sawdust (camphorwood dust) in mass ratio 3~5: 1 by the present invention
Fertilizer, adds the oxide content prepared in charcoal raw material, and the process control system, easy to operate, fast, resource impact of degrading
Good, reaction process is as follows：
Organic matter+aerobic bacteria+oxygen+water → carbon dioxide+water (water vapour state)+nitrate+sulfate+oxide
Then take compost late-stage products dry after under nitrogen protection atmosphere, the heating of the speed of 5 DEG C/min~15 DEG C/min
To 400 DEG C~700 DEG C calcining 1.5h~2.5h, charcoal is obtained.Finally, permanganate (such as potassium permanganate) and bivalent manganese are passed through
The comproportionation reaction of manganese element obtains titanium dioxide by the manganese dioxide load of generation to charcoal in salt (such as four hydration manganese acetates)
The biological carbon composite of manganese modification, its chemical equation are：
3Mn2++2MnO4 -+2H2O=5MnO2↓+4H+
The biological carbon composite for the manganese dioxide modification that the present invention obtains, the main function of manganese dioxide is modified biological
The surface of charcoal, reduces the effect between the Van der Waals force and pi-pi bond between charcoal, makes charcoal be not easy to reunite, so as to increase
The specific surface area of charcoal, improves adsorption capacity of the composite material to heavy metal (such as lead, cadmium).
Compared with prior art, the advantage of the invention is that：
(1) the present invention provides a kind of biological carbon composite of manganese dioxide modification, including manganese dioxide and charcoal,
The composite material is to giving birth to by the comproportionation reaction of manganese element in permanganate and manganous salt by the manganese dioxide load of generation
It is prepared on thing charcoal.The biological carbon composite of the manganese dioxide modification of the present invention has the adsorption energy to heavy metal lead or cadmium
The advantages such as power is strong, adsorption effect is obvious, manufacturing cost is low, are a kind of ideal heavy metal wastewater thereby adsorbents.
(2) the present invention provides a kind of modification of manganese dioxide biological carbon composite preparation method, by by divalence
Manganese salt be added in the mixed liquor containing charcoal and permanganate carry out comproportionation reaction be made manganese dioxide modification charcoal answer
Condensation material, the load capacity for overcoming Mn oxide in the charcoal method for synthesizing composite material of existing Mn oxide load be not easily-controllable
Make and big deficiency is lost in manganese containing solution.The method of the present invention can be according to actual needs, by adjusting permanganate and manganous salt
Dosage change the growing amount of manganese dioxide, and then control manganese dioxide not only to realize to two in the load capacity of charcoal
Effective control of manganese oxide load amount, also improves the utilization rate of raw material, reduces production cost.
(3) charcoal of the invention is made by fowl and animal excrement and sawdust through aerobic compost, after nitrogen protective atmosphere encloses lower calcining
.The charcoal directly prepared in compared with the prior art by pig manure, oxide content is more in charcoal of the invention, has
Beneficial to the formation of charcoal inside hydrogen bond, increase the stability of biological carbon structure, while increase the avtive spot of biological carbon surface.
And the yield higher of charcoal of the present invention, calcined under 400 DEG C~700 DEG C cracking temperatures, make the charcoal of the present invention have more
Big specific surface area and micro pore volume.
(4) preparation method for the biological carbon composite modified the present invention provides a kind of manganese dioxide, has technique letter
The advantages such as single, raw material is inexpensively, material makes full use of, production cost is low.
(5) the biological carbon composite of manganese dioxide modification provided by the invention can be used for processing heavy metal (such as lead, cadmium)
Waste water, it is big to the adsorption capacity of heavy metal, adsorption efficiency is high, it is low to toxicity biological in environment, it can mass produce and answer
With.
Brief description of the drawings
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, clear, complete description is carried out to the technical solution in the embodiment of the present invention.
Fig. 1 is the scanning electron microscope (SEM) photograph of the biological carbon composite that manganese dioxide is modified in the embodiment of the present invention 1.
Fig. 2 is the energy spectrum diagram of the biological carbon composite that manganese dioxide is modified in the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope picture of the biological carbon composite that manganese dioxide is modified in the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of the charcoal of unsupported manganese dioxide in comparative example 1.
Fig. 5 is the energy spectrum diagram of the charcoal of unsupported manganese dioxide in comparative example 1.
Fig. 6 is the transmission electron microscope picture of the charcoal of unsupported manganese dioxide in comparative example 1.
Fig. 7 is that the manganese dioxide in comparative example 1 in the charcoal (a) of unsupported manganese dioxide and the embodiment of the present invention 1 is repaiied
The X-ray diffractogram of the biological carbon composite (b) of decorations.
Fig. 8 is that the manganese dioxide in comparative example 1 in the charcoal (a) of unsupported manganese dioxide and the embodiment of the present invention 1 is repaiied
The infrared spectrogram of the biological carbon composite (b) of decorations.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material and instrument employed in following embodiments are commercially available.
Embodiment 1：
A kind of biological carbon composite of manganese dioxide modification of the invention, including manganese dioxide and charcoal；The dioxy
The biological carbon composite for changing manganese modification will be generated by the comproportionation reaction of manganese element in potassium permanganate and four hydration manganese acetates
Manganese dioxide load to being prepared on charcoal.
A kind of preparation method of the biological carbon composite of the manganese dioxide modification of above-mentioned the present embodiment, including following step
Suddenly：
S1, mix pig manure with camphorwood dust with mass ratio 4: 1, carries out aerobic compost 60 days, obtains mixture, and will mixing
Thing is cleaned for several times with deionized water, is dried at 80 DEG C, and grinding, crosses 100 mesh sieves, be put into hermetic bag and save backup.
S2, will cross the mixture after 100 mesh sieves and be placed in quartz boat in step S1, then quartz boat is put in tube furnace,
Calcined under nitrogen protection atmosphere, calcination process is specially：400 DEG C (400~700 is warming up to the speed of 10 DEG C/min
DEG C can implement) calcined, residence time 2h, obtains charcoal.
S3, take the charcoal in 15g steps S2 to be mixed with 3.16g potassium permanganate, with the deionized water dissolving of 150mL,
Sonic oscillation 30min (30min~1h can be implemented) at room temperature, obtains the mixed liquor containing charcoal and potassium permanganate；In magnetic force
Blender continues under stirring condition, and 100mL, the four hydration acetic acid manganese solutions that concentration is 0.3mol/L are slowly added into containing biology
Comproportionation reaction, generation dark brown precipitation are carried out in the mixed liquor of charcoal and potassium permanganate, the charcoal for obtaining manganese dioxide modification is answered
Condensation material suspension；The biological carbon composite suspension that manganese dioxide is modified finally is heated to 80 DEG C, and at such a temperature
30min (30min~1h can be implemented) is kept, makes the manganese dioxide stabilization of generation in biological carbon surface, with deionized water rinse
Until rinse liquid is in neutrality, 80 DEG C of drying, obtain the biological carbon composite of manganese dioxide modification, save backup.
The scanning electron microscope (SEM) photograph (SEM figures) for the biological carbon composite that Fig. 1 modifies for manganese dioxide in the present embodiment, its China and foreign countries
Figure is the SEM figures of 2000 times of amplification, and interior figure is to amplify the figures of the SEM after 10 times in outer figure at black box again (to amplify 20000
Times).Fig. 2 is the energy spectrum diagram (EDAX figures) of the biological carbon composite that manganese dioxide is modified in the present embodiment.Fig. 3 is the present embodiment
The transmission electron microscope picture (TEM figures) of the biological carbon composite of middle manganese dioxide modification.
Comparative example 1：
A kind of charcoal of unsupported manganese dioxide, is the charcoal prepared in the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM figures) of the charcoal of unsupported manganese dioxide in comparative example 1, its China and foreign countries' figure is to put
Big 2000 times of SEM figures, interior figure are to amplify the figures of the SEM after 10 times (amplifying 20000 times) in outer figure at black box again.Fig. 5
For the energy spectrum diagram (EDAX figures) of the charcoal of unsupported manganese dioxide in comparative example 1.Fig. 6 is unsupported titanium dioxide in comparative example 1
The transmission electron microscope picture (TEM figures) of the charcoal of manganese.
According to the scanning electron microscope (SEM) photograph of Fig. 1 and Fig. 4, the life of charcoal and the manganese dioxide modification of unsupported manganese dioxide
Thing carbon composite is all aperture structure.In the biological carbon composite of manganese dioxide modification, manganese dioxide is distributed widely in
Biological carbon surface, charcoal still maintain initial structural form, while increase the specific surface area of charcoal, make manganese dioxide
The adsorption efficiency of the biological carbon composite counterweight metal (such as lead, cadmium) of modification is significantly improved.After testing, comparative example 1
In the specific surface area of charcoal of unsupported manganese dioxide be 5.0831m2/ g, and the manganese dioxide in the embodiment of the present invention 1 is repaiied
The specific surface area of the biological carbon composite of decorations is 70.9096m2The charcoal of unsupported manganese dioxide in/g, about comparative example 1
13 times, it is seen then that the biological carbon composite of manganese dioxide produced by the present invention modification, its specific surface area are significantly increased.
According to the energy spectrum diagram of Fig. 2 and Fig. 5, the mass fraction of oxygen element is in the charcoal of unsupported manganese dioxide
21.66%, the mass fraction of manganese element is then less than test limit 0.1%~0.2%；And manganese member in the charcoal of manganese dioxide modification
The mass fraction of element is up to 47.98%, and the mass fraction of oxygen element is 23.93%, it is seen that charcoal is successfully repaiied by Mn oxide
Decorations.
According to the transmission electron microscope picture of Fig. 3 and Fig. 6, the form in two kinds of biological carbon materials transmission electron microscopes is all with each sweeping
The form presented in electron microscope is retouched mutually to unify, wherein bright part illustrates electronics by material surface, and dark portion
It is as caused by electron scattering to divide.The charcoal of unsupported manganese dioxide has an obvious border, and the life of manganese dioxide modification
Thing charcoal is substantially change compared to the surface of unsupported manganese dioxide charcoal and border, it is seen that manganese dioxide load to life
Influence is generated on composite material entirety pattern after on thing charcoal.
The biology modified respectively the manganese dioxide in the charcoal and embodiment 1 of unsupported manganese dioxide in comparative example 1
Carbon composite carries out X-ray diffraction analysis, and the results are shown in Figure 7.Fig. 7 is the biology of unsupported manganese dioxide in comparative example 1
The X-ray diffractogram (XRD diagram) of the biological carbon composite (b) of manganese dioxide modification in charcoal (a) and the embodiment of the present invention 1.
As can be seen from Figure 7, the charcoal of unsupported manganese dioxide has more peak in comparative example 1, and the dioxy of generation is reacted in embodiment 1
It is a kind of non-stoichiometric amorphous phase to change manganese, when manganese dioxide largely loads on charcoal the titanium dioxide obtained in embodiment 1
The biological carbon composite of manganese modification, the peak value of composite material reduce.
The biology modified respectively the manganese dioxide in the charcoal and embodiment 1 of unsupported manganese dioxide in comparative example 1
Carbon composite carries out infrared spectrum analysis, and the results are shown in Figure 8.Fig. 8 is the charcoal of unsupported manganese dioxide in comparative example 1
(a) infrared spectrogram (FTIR figures) of the biological carbon composite (b) of the manganese dioxide modification and in the embodiment of the present invention 1.From
Fig. 8 understands that the stretching vibration of the C=O bases contained by the biological carbon composite of manganese dioxide modification is stronger, while has more
Hydroxyl, more vivaciously；511cm-1The adsorption peak at place discloses the vibration characteristics of Mn-O bands, this is clearly depositing by manganese dioxide
Caused by, illustrate that the biological carbon composite of manganese dioxide modification has generated.
Embodiment 2：
A kind of application of biological carbon composite of manganese dioxide modification of the invention in heavy metal wastewater thereby is handled, wherein
The biological carbon composite of manganese dioxide modification derives from embodiment 1, and heavy metal wastewater thereby is leaded heavy metal wastewater thereby or weight containing cadmium
Metallic wastewater.
Leaded heavy metal wastewater thereby is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 13 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is in conical flask, and addition ionic strength is 0.01mol/L, pH value is 5.0 ± 0.2
Leaded heavy metal wastewater thereby, wherein in leaded heavy metal wastewater thereby lead initial concentration be respectively 0.5mg/L, 1.0mg/L, 5.0mg/L,
10.0mg/L、20.0mg/L、40.0mg/L、60.0mg/L、80.0mg/L、100.0mg/L、120.0mg/L、150.0mg/L、
180.0mg/L and 210.0mg/L.Adsorption reaction 12h is vibrated after mixing under conditions of rotating speed is 170rpm, temperature is 25 DEG C,
Complete the processing to heavy metal wastewater thereby.
Heavy metal wastewater thereby containing cadmium is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 13 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is in conical flask, and addition ionic strength is 0.01mol/L, pH value is 5.0 ± 0.2
Heavy metal wastewater thereby containing cadmium, wherein in heavy metal wastewater thereby containing cadmium cadmium initial concentration be respectively 0.5mg/L, 1.0mg/L, 2.0mg/L,
5.0mg/L、10.0mg/L、15.0mg/L、20.0mg/L、30.0mg/L、40.0mg/L、50.0mg/L、60.0mg/L、
80.0mg/L and 100.0mg/L.Adsorption reaction 12h is vibrated after mixing under conditions of rotating speed is 170rpm, temperature is 25 DEG C, it is complete
The processing of paired heavy metal wastewater thereby.
After the completion of vibrating adsorption reaction, suspension is poured into syringe, crosses the life that 0.22 μm of filter membrane modifies manganese dioxide
Thing carbon composite is separated with mixed liquor, and solution is appropriate after taking filtering, with dust technology constant volume, utilizes NITRATE BY FLAME ATOMIC spectrophotometer
The concentration of lead or cadmium in solution, the charcoal that manganese dioxide modification is calculated using following equation (1) are compound after measure adsorption equilibrium
The removal rate to lead or cadmium of material, to judge the treatment effect of the adsorbent synthesized by the present invention.
In formula (1)：A is removal rate (%)；
C0For the initial concentration (unit of lead in solution before absorption or cadmium：mg/L)；
C is absorption up to the concentration (unit of lead or cadmium in solution after balance：mg/L)；
Table 1 is removal effect of the biological carbon composite of manganese dioxide of the present invention modification to lead at different concentrations or cadmium waste water
Fruit.
Removal effect of the biological carbon composite of 1 manganese dioxide of the present invention of table modification to lead at different concentrations or cadmium waste water
| Lead concentration (mg/L) | Removal rate (%) | Cadmium concentration (mg/L) | Removal rate (%) |
| 0.5 | 100.00 | 0.5 | 94.80 |
| 1.0 | 93.90 | 1.0 | 94.10 |
| 5.0 | 95.20 | 2.0 | 91.50 |
| 10.0 | 96.54 | 5.0 | 90.26 |
| 20.0 | 97.38 | 10.0 | 81.04 |
| 40.0 | 98.12 | 15.0 | 71.47 |
| 60.0 | 98.67 | 20.0 | 61.85 |
| 80.0 | 98.50 | 30.0 | 49.67 |
| 100.0 | 98.00 | 40.0 | 42.19 |
| 120.0 | 86.14 | 50.0 | 36.55 |
| 150.0 | 72.20 | 60.0 | 31.83 |
| 180.0 | 60.89 | 80.0 | 24.94 |
| 210.0 | 52.57 | 100.0 | 20.10 |
As can be seen from Table 1, when the additive amount of the biological carbon composite of manganese dioxide modification of the present invention is 0.40g/L,
With the increase of heavy metal (lead or cadmium) concentration, the biological carbon composite of manganese dioxide modification is overall to the removal rate of lead or cadmium
Into downward trend, 100% is reached to the maximum material removal rate of lead, has 94.80% to the maximum material removal rate of cadmium.
Embodiment 3：
A kind of application of biological carbon composite of manganese dioxide modification of the invention in heavy metal wastewater thereby is handled, this two
The biological carbon composite of manganese oxide modification derives from embodiment 1, and heavy metal wastewater thereby is for leaded heavy metal wastewater thereby or containing a cadmium huge sum of money
Belong to waste water.
Leaded heavy metal wastewater thereby is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 39 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is divided into three groups in 39 conical flasks.Ionic strength is added in every group of conical flask
The leaded heavy metal wastewater thereby for being 5.0 ± 0.2 for 0.01mol/L, pH value, wherein lead initial concentration is distinguished in leaded heavy metal wastewater thereby
For 0.5mg/L, 1.0mg/L, 5.0mg/L, 10.0mg/L, 20.0mg/L, 40.0mg/L, 60.0mg/L, 80.0mg/L,
100.0mg/L, 120.0mg/L, 150.0mg/L, 180.0mg/L and 210.0mg/L.After mixing, three groups of conical flasks are put by more than
It it is respectively 25 DEG C, 35 DEG C, 45 DEG C in temperature on constant-temperature table, rotating speed is that adsorption reaction 12h is vibrated under 170rpm, is completed pair
The processing of heavy metal wastewater thereby.
Heavy metal wastewater thereby containing cadmium is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 39 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is divided into three groups in 39 conical flasks.Ionic strength is added in every group of conical flask
The heavy metal wastewater thereby containing cadmium for being 5.0 ± 0.2 for 0.01mol/L, pH value, wherein cadmium initial concentration is distinguished in heavy metal wastewater thereby containing cadmium
For 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 10.0mg/L, 15.0mg/L, 20.0mg/L, 30.0mg/L, 40.0mg/
L, 50.0mg/L, 60.0mg/L, 80.0mg/L and 100.0mg/L.After mixing, three groups of conical flasks are placed in constant-temperature table by more than
On, it is respectively 25 DEG C, 35 DEG C, 45 DEG C in temperature, rotating speed is that adsorption reaction 12h is vibrated under 170rpm, is completed to heavy metal wastewater thereby
Processing.
After the completion of vibrating adsorption reaction, suspension is poured into syringe, crosses the life that 0.22 μm of filter membrane modifies manganese dioxide
Thing carbon composite is separated with mixed liquor, and solution is appropriate after taking filtering, with dust technology constant volume, utilizes NITRATE BY FLAME ATOMIC spectrophotometer
The concentration of lead or cadmium in solution after measure adsorption equilibrium, using following equation (2), calculates the manganese dioxide modification of the present invention
Biological the carbon composite change of adsorbance and its adsorption effect at different temperatures.
In formula (2)：Q is adsorbance (unit：mg/g)；
C0For the initial concentration (unit of lead in solution before absorption or cadmium：mg/L)；
C is absorption up to the concentration (unit of lead or cadmium in solution after balance：mg/L)；
M is adsorbent amount (unit：mg)；
V is aqueous solution volume (unit：mL).
The biological carbon composite of manganese dioxide of the present invention modification at different temperatures to the adsorbance (mg/g) of lead or cadmium,
It is shown in Table 2.
The biological carbon composite of 2 manganese dioxide of the present invention of table modification is at different temperatures to the adsorbance of lead or cadmium
As shown in Table 2, when temperature is 45 DEG C, the biological carbon composite of manganese dioxide of the invention modification is initial to lead
Concentration is the adsorbance highest of the heavy metal wastewater thereby of 210.0mg/L, can reach 305.75mg/g, is to cadmium initial concentration
The adsorbance of the heavy metal wastewater thereby of 100.0mg/L reaches as high as 55.80mg/g.Under identical lead or cadmium initial concentration, this hair
The adsorbance of biological the carbon composite counterweight metallic lead or cadmium of bright manganese dioxide modification increases with the rise of temperature, this table
Bright adsorption process is endothermic process, as temperature raises, the increased activity in adsorbent activity site, so as to promote heavy metal
Absorption.Therefore, when temperature is higher than 45 DEG C, the biological carbon composite of manganese dioxide modification will to the adsorbance of lead or cadmium
Improve, but temperature it is excessive be unfavorable for reduce production cost.
Embodiment 4：
A kind of application of biological carbon composite of manganese dioxide modification of the invention in heavy metal wastewater thereby is handled, this two
The biological carbon composite of manganese oxide modification derives from embodiment 1, and heavy metal wastewater thereby is for leaded heavy metal wastewater thereby or containing a cadmium huge sum of money
Belong to waste water.
Leaded heavy metal wastewater thereby is handled, is comprised the following steps：By additive amount for 0.20g/L, 0.40g/L, 1.0g/L,
2.0g/L and 4.0g/L weigh in 5 parts of embodiments 1 manganese dioxide modification biological carbon composite in conical flask, add from
The leaded heavy metal wastewater thereby that sub- intensity is 0.01mol/L, pH value is 5.0 ± 0.2, wherein lead is initially dense in leaded heavy metal wastewater thereby
Spend for 1500.0mg/L.Mixing is placed in constant temperature oscillation case, is vibrated and is inhaled under the conditions of being 170rpm by 25 DEG C, rotating speed of temperature
Reaction enclosure 12h, completes the processing to heavy metal wastewater thereby.
Heavy metal wastewater thereby containing cadmium is handled, is comprised the following steps：By additive amount for 0.20g/L, 0.40g/L, 1.0g/L,
2.0g/L and 4.0g/L weigh in 5 parts of embodiments 1 manganese dioxide modification biological carbon composite in conical flask, add from
The heavy metal wastewater thereby containing cadmium that sub- intensity is 0.01mol/L, pH value is 5.0 ± 0.2, wherein cadmium is initially dense in heavy metal wastewater thereby containing cadmium
Spend for 250.0mg/L.Mixing is placed in constant temperature oscillation case, is vibrated and is inhaled under the conditions of being 170rpm by 25 DEG C, rotating speed of temperature
Reaction enclosure 12h, completes the processing to heavy metal wastewater thereby.
After the completion of vibrating adsorption reaction, suspension is poured into syringe, crosses the life that 0.22 μm of filter membrane modifies manganese dioxide
Thing carbon composite is separated with mixed liquor, and solution is appropriate after taking filtering, with dust technology constant volume, utilizes NITRATE BY FLAME ATOMIC spectrophotometer
Measure after adsorption equilibrium the concentration of lead or cadmium in solution, the charcoal of the manganese dioxide modification of Different adding amount is answered in the present embodiment
Condensation material is shown in Table 3 to the adsorption effect (being represented with adsorbance) of lead or cadmium.
Adsorption effect of the biological carbon composite of the manganese dioxide modification of 3 Different adding amount of the present invention of table to lead or cadmium
| Additive amount (g/L) | 0.20 | 0.40 | 1.00 | 2.00 | 4.00 |
| Lead adsorption (mg/g) | 349.72 | 342.50 | 304.00 | 256.25 | 226.58 |
| Cadmium adsorbance (mg/g) | 142.32 | 138.25 | 68.60 | 47.85 | 38.68 |
As can be seen from Table 3, the biological carbon composite of manganese dioxide of the present invention modification to the adsorbance of lead or cadmium with
The increase of composite material additive amount and reduce, when composite material additive amount is 0.20g/L and 0.40g/L, composite material is to lead
Adsorbance is suitable, and to the adsorbance of cadmium without larger difference, this is probably because composite material adding in 0.20g/L and 0.40g/L
Under dosage, having been able to come into full contact with heavy metal standard solution, the adsorption site of material in itself has made full use of, and with
The increase of composite material additive amount, composite material is in adsorption process, probably due to making composite material to lead the reason for reunion
Or the adsorbance of cadmium declines.
Embodiment 5：
A kind of application of biological carbon composite of manganese dioxide modification of the invention in heavy metal wastewater thereby is handled, this two
The biological carbon composite of manganese oxide modification derives from embodiment 1, and heavy metal wastewater thereby is for leaded heavy metal wastewater thereby or containing a cadmium huge sum of money
Belong to waste water.
Leaded heavy metal wastewater thereby is handled, is comprised the following steps：By additive amount for 0.40g/L weigh in 7 parts of embodiments 1 two
The biological carbon composite of manganese oxide modification is in conical flask, and addition ionic strength is 0.01mol/L, lead initial concentration is
The leaded heavy metal wastewater thereby of 150mg/L, wherein the pH value of leaded heavy metal wastewater thereby is respectively 2.0,3.0,4.0,5.0,6.0,
7.0th, 8.0 (deviation is no more than 0.2).Mixing is placed in constant temperature oscillation case, is 170rpm conditions by 25 DEG C, rotating speed of temperature
Lower vibration adsorption reaction 12h, completes the processing to heavy metal wastewater thereby.
Heavy metal wastewater thereby containing cadmium is handled, is comprised the following steps：By additive amount for 0.40g/L weigh in 7 parts of embodiments 1 two
The biological carbon composite of manganese oxide modification is in conical flask, and addition ionic strength is 0.01mol/L, cadmium initial concentration is
The heavy metal wastewater thereby containing cadmium of 50mg/L, wherein the pH value of the heavy metal wastewater thereby containing cadmium is respectively 2.0,3.0,4.0,5.0,6.0,7.0,
8.0 (deviation is no more than 0.2).Mixing is placed in constant temperature oscillation case, is shaken under the conditions of being 170rpm as 25 DEG C, rotating speed using temperature
Adsorption reaction 12h is swung, completes the processing to heavy metal wastewater thereby.
After the completion of vibrating adsorption reaction, suspension is poured into syringe, crosses the life that 0.22 μm of filter membrane modifies manganese dioxide
Thing carbon composite is separated with mixed liquor, and solution is appropriate after taking filtering, with dust technology constant volume, utilizes NITRATE BY FLAME ATOMIC spectrophotometer
Measure after adsorption equilibrium the concentration of lead or cadmium in solution, the biological carbon composite that manganese dioxide is modified in the present embodiment is in difference
To the adsorption effect (being represented with adsorbance) of lead or cadmium under the conditions of pH, 4 are shown in Table.
The biological carbon composite of 4 manganese dioxide of the present invention of table modification is under different pH to the adsorption effect of lead or cadmium
| pH | 2.0 | 3.0 | 4.0 | 5.0 | 6.0 | 7.0 | 8.0 |
| Lead adsorption (mg/g) | 90.38 | 167.25 | 236.88 | 267.13 | 284.50 | 333.75 | 361.88 |
| Cadmium adsorbance (mg/g) | 10.13 | 17.88 | 25.44 | 45.94 | 52.56 | 76.75 | 102.50 |
Obtained by table 4, the biological carbon composite that manganese dioxide of the present invention is modified is to the adsorbance of lead or cadmium all with solution
The increase of pH and increase；When pH is between 2.0~4.0, composite material increases obvious increase to the adsorbance of lead with pH, and right
The adsorbance increase of cadmium is slow；When pH is between 5.0~8.0, the increase compared to before is slightly slow to the adsorbance of lead for composite material,
And to adsorbance obvious increase compared to before of cadmium.When pH is 8, composite material is reachable respectively to the adsorbance of lead and cadmium
316.88mg/g, 102.50mg/g, hence it is evident that composite material is to the adsorbance of lead and cadmium when higher than pH being 2, and therefore, pH value rise has
Beneficial to the raising of adsorbance, when pH is higher than 8, adsorbance can increased, and be issued to saturation absorption in certain pH value.
One group of blank separately is set, leaded or cadmium heavy metal wastewater thereby is replaced with the ultra-pure water of equivalent, remaining operation is identical.With
After the measurement absorption of Malvern zetasizer particle size analyzers in solution the biological carbon composite that manganese dioxide is modified zeta
Current potential, the results are shown in Table 5.
Zeta current potential (unit of the biological carbon composite of 5 manganese dioxide of the present invention of table modification under condition of different pH：
mV)
| pH | 2.0 | 3.0 | 4.0 | 5.0 | 6.0 | 7.0 | 8.0 |
| Blank | -5.79 | -19.67 | -25.30 | -27.90 | -28.77 | -29.40 | -30.1 |
| Experimental group (lead) | 4.18 | 7.21 | 17.30 | 18.23 | 17.27 | 4.04 | 8.03 |
| Experimental group (cadmium) | 1.58 | -12.60 | -17.27 | -18.23 | -17.70 | -18.13 | -18.00 |
As can be seen from Table 5, blank group zeta current potentials are negative value, therefore the charcoal of manganese dioxide of the present invention modification is answered
Condensation material itself is negatively charged；Under the conditions of identical pH, the zeta current potentials of experimental group are higher than blank group, illustrate the two of the present invention
The biological carbon composite of manganese oxide modification has absorption behavior really to lead and cadmium, and is adsorbed in the form of cation
's.
With reference to table 4, table 5, with the increase of pH value, the zeta current potentials of blank group reduce；And the zeta current potentials of lead experimental group
In the range of pH is 2.0~5.0, zeta current potentials increase and increase with pH, illustrate change of the suction-operated at this time to zeta current potentials
Play a leading role, in the range of pH is 5..0~8.0, zeta current potentials increase and reduce with pH, but the value of zeta current potentials remains above
Blank group and value are just, to illustrate that zeta current potentials at this time are still influenced by the leading of suction-operated, but the change of pH value is to zeta
The influence of potential change is gradually strengthened；And the zeta current potentials of cadmium experimental group higher than blank group zeta current potentials and value be it is negative,
Illustrate the presence of absorption behavior, but zeta potential changes are mainly influenced by pH value change.
Embodiment 6：
A kind of application of biological carbon composite of manganese dioxide modification of the invention in heavy metal wastewater thereby is handled, this two
The biological carbon composite of manganese oxide modification derives from embodiment 1, and heavy metal wastewater thereby is for leaded heavy metal wastewater thereby or containing a cadmium huge sum of money
Belong to waste water.
Leaded heavy metal wastewater thereby is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 10 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is in conical flask, and addition ionic strength is 0.01mol/L, pH value is 5.0 ± 0.2
Leaded heavy metal wastewater thereby, wherein lead initial concentration is 150mg/L in leaded heavy metal wastewater thereby.Mixing is placed on constant temperature oscillation case
In, carry out vibration adsorption reaction under the conditions of being 170rpm as 25 DEG C, rotating speed using temperature, the reaction time be respectively 5min, 15min,
30min, 1h, 2h, 4h, 8h, 12h, 18h, 24h, complete the processing to heavy metal wastewater thereby.
Heavy metal wastewater thereby containing cadmium is handled, is comprised the following steps：Weighed by additive amount for 0.40g/L in 10 parts of embodiments 1
The biological carbon composite of manganese dioxide modification is in conical flask, and addition ionic strength is 0.01mol/L, pH value is 5.0 ± 0.2
Heavy metal wastewater thereby containing cadmium, wherein the initial concentration of cadmium is 50mg/L in heavy metal wastewater thereby containing cadmium.Mixing is placed on constant temperature oscillation
In case, carry out vibration adsorption reaction under the conditions of being 170rpm as 25 DEG C, rotating speed using temperature, the reaction time be respectively 5min,
15min, 30min, 1h, 2h, 4h, 8h, 12h, 18h, 24h, complete the processing to heavy metal wastewater thereby.
In addition, the manganese dioxide in the embodiment of the present invention 1 is substituted with the charcoal of the unsupported manganese dioxide in comparative example 1
The biological carbon composite of modification, and in this, as control group, heavy metal wastewater thereby is handled under the same conditions.
After the completion of vibrating adsorption reaction, suspension is poured into syringe, crosses the life that 0.22 μm of filter membrane modifies manganese dioxide
Thing carbon composite is separated with mixed liquor, and solution is appropriate after taking filtering, with dust technology constant volume, utilizes NITRATE BY FLAME ATOMIC spectrophotometer
Measure after adsorption equilibrium the concentration of lead or cadmium in solution, the biological carbon composite and contrast that manganese dioxide is modified in embodiment 1
The charcoal of unsupported manganese dioxide (uses absorption scale under the conditions of different adsorption times to the adsorption effect of lead or cadmium in example 1
Show), it is shown in Table 6.
Table 6：Embodiment 1 and the biological carbon materials in comparative example 1 are under different adsorption times to the adsorption effect of lead or cadmium
As shown in Table 6, when two kinds of adsorbents handle heavy metal in waste water lead or cadmium, adsorption time is inhaled for 12h up to saturation
Attached, the biological carbon composite that manganese dioxide is modified in embodiment 1 at this time is reachable respectively to the maximal absorptive capacity of lead, cadmium
268.00mg/g, 45.80mg/g be far above in comparative example 1 charcoal to the maximal absorptive capacity 127.75mg/g of lead, cadmium,
14.413mg/g。
In conclusion the biological carbon composite of the manganese dioxide modification of the present invention has the absorption to heavy metal lead or cadmium
The advantages such as ability is strong, adsorption effect is obvious, manufacturing cost is low, are a kind of ideal heavy metal wastewater thereby adsorbents, it is prepared
Method has the advantages that synthetic method is simple, synthesis cycle is short, raw material is cheap, material makes full use of.The manganese dioxide of the present invention
The biological carbon composite of modification can be used for processing heavy metal (such as lead, cadmium) waste water, and, absorption big to the adsorption capacity of heavy metal is imitated
Rate is high, low to toxicity biological in environment, can mass produce and apply.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention.Though
So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from the Spirit Essence of the present invention and technical solution, all using in the methods and techniques of the disclosure above
Appearance makes technical solution of the present invention many possible changes and modifications, or is revised as the equivalent embodiment of equivalent variations.Therefore,
Every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to made for any of the above embodiments any simple
Modification, equivalent substitution, equivalence changes and modification, still fall within technical solution of the present invention protection in the range of.
Claims (10)
1. a kind of biological carbon composite of manganese dioxide modification, it is characterised in that including manganese dioxide and charcoal；Described two
The biological carbon composite of manganese oxide modification is by generation by the comproportionation reaction of manganese element in permanganate and manganous salt
Manganese dioxide load is to being prepared on charcoal.
2. a kind of preparation method of the biological carbon composite of manganese dioxide modification, it is characterised in that comprise the following steps：By two
Valency manganese salt, which is added in the mixed liquor containing charcoal and permanganate, carries out comproportionation reaction, obtains the charcoal of manganese dioxide modification
Composite material.
3. preparation method according to claim 2, it is characterised in that the manganous salt and the biology in the mixed liquor
Charcoal, the mass ratio of permanganate are 2.45~9.80: 15: 1.06~4.22.
4. preparation method according to claim 3, it is characterised in that the preparation method of the charcoal includes following step
Suddenly：
(1) fowl and animal excrement and sawdust are mixed into row aerobic compost, obtain mixture；
(2) mixture in step (1) is calcined, obtains charcoal.
5. preparation method according to claim 4, it is characterised in that in the step (1)：The fowl and animal excrement and sawdust
Mass ratio be 3~5: 1；The time of the aerobic compost is 56 days~92 days；
And/or in the step (2)：The calcining carries out under nitrogen protection atmosphere；The calcining is with 5 DEG C/min~15
DEG C/speed of min is warming up to 400 DEG C~700 DEG C calcining 1.5h~2.5h.
6. the preparation method according to any one of claim 2~5, it is characterised in that the comproportionation reaction is in stirring bar
Carried out under part；Following processing is further included after the completion of the comproportionation reaction：The biology that manganese dioxide obtained by comproportionation reaction is modified
Carbon composite suspension is heated to 70 DEG C~90 DEG C and keeps 30min~60min, is washed till neutral, drying.
7. any one of a kind of biological carbon composite of manganese dioxide modification as claimed in claim 1 or claim 2~6
Application of the biological carbon composite that manganese dioxide made from the preparation method is modified in heavy metal wastewater thereby is handled, it is special
Sign is, comprises the following steps：The biological carbon composite that the manganese dioxide is modified is mixed with heavy metal wastewater thereby to shake
Adsorption reaction is swung, completes the processing to heavy metal wastewater thereby；
The additive amount of the biological carbon composite of the manganese dioxide modification is to add described two in every liter of heavy metal wastewater thereby
Biological carbon composite 0.2g~4.0g of manganese oxide modification.
8. application according to claim 7, it is characterised in that the heavy metal wastewater thereby is for leaded heavy metal wastewater thereby or containing cadmium
Heavy metal wastewater thereby；The initial concentration of lead is 0.5mg/L~1500.0mg/L in the leaded heavy metal wastewater thereby；It is described to contain a cadmium huge sum of money
The initial concentration for belonging to cadmium in waste water is 0.5mg/L~250.0mg/L.
9. application according to claim 8, it is characterised in that the pH value of the heavy metal wastewater thereby is 2.0~8.0；It is described
The ionic strength of heavy metal wastewater thereby is 0.01mol/L~0.1mol/L.
10. the application according to any one of claim 7~9, it is characterised in that it is described vibration adsorption reaction temperature be
25 DEG C~45 DEG C, rotating speed is 150rpm~180rpm, and the time is 10h~14h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610954702.2A CN107983300B (en) | 2016-10-27 | 2016-10-27 | The charcoal composite material and preparation method and application of manganese dioxide modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610954702.2A CN107983300B (en) | 2016-10-27 | 2016-10-27 | The charcoal composite material and preparation method and application of manganese dioxide modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107983300A true CN107983300A (en) | 2018-05-04 |
| CN107983300B CN107983300B (en) | 2019-11-05 |
Family
ID=62028476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610954702.2A Active CN107983300B (en) | 2016-10-27 | 2016-10-27 | The charcoal composite material and preparation method and application of manganese dioxide modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107983300B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927107A (en) * | 2018-07-25 | 2018-12-04 | 中央民族大学 | A kind of straw base heavy-metal adsorption material and preparation method thereof |
| CN109173984A (en) * | 2018-08-14 | 2019-01-11 | 华南理工大学 | A method of Pb In Exhausted Water is removed using composite material |
| CN109270152A (en) * | 2018-10-18 | 2019-01-25 | 郑州市宇驰检测技术有限公司 | The visualization of presence detection method of heavy metal arsenic in a kind of environmental water sample |
| CN109926021A (en) * | 2019-03-15 | 2019-06-25 | 新疆农业大学 | A kind of preparation method and applications of ball milling modification chicken manure charcoal |
| CN109939661A (en) * | 2019-03-15 | 2019-06-28 | 农业农村部环境保护科研监测所 | A kind of adsorbent and its preparation method and application of adsorbable fixed heavy metal lead ion |
| CN110075785A (en) * | 2019-05-08 | 2019-08-02 | 河南城建学院 | The MnO of lead ion in a kind of removing water2Composite material and preparation method |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
| CN110898804A (en) * | 2019-11-25 | 2020-03-24 | 湖南第一师范学院 | Biochar composite material and preparation method and application thereof |
| CN110975809A (en) * | 2019-12-12 | 2020-04-10 | 广东工业大学 | Tangerine-based biochar and application thereof |
| CN111266084A (en) * | 2020-01-08 | 2020-06-12 | 江苏大学 | Porous aquatic plant-based biomass charcoal material and application thereof |
| CN111617739A (en) * | 2020-05-09 | 2020-09-04 | 齐鲁工业大学 | Al-Mn modified biomass charcoal and preparation method and application thereof |
| CN111874984A (en) * | 2020-07-28 | 2020-11-03 | 上海泽耀环保科技有限公司 | Water body restoration rope and preparation method and application thereof |
| CN112044399A (en) * | 2020-09-10 | 2020-12-08 | 江西农业大学 | Manganese oxide-biological bamboo charcoal composite material and preparation method thereof |
| CN112058232A (en) * | 2020-09-21 | 2020-12-11 | 河南大学 | Manganese dioxide modified activated carbon composite adsorbent, preparation method thereof and application thereof in arsenic removal |
| CN112117517A (en) * | 2020-09-01 | 2020-12-22 | 威海广泰空港设备股份有限公司 | Flexible zinc-air battery for electric passenger boarding ladder and preparation method |
| CN112296084A (en) * | 2020-10-14 | 2021-02-02 | 成都市四友生物科技有限公司 | Soil restoration and improvement agent and preparation process thereof |
| CN112619601A (en) * | 2020-10-26 | 2021-04-09 | 广东省农业科学院农产品公共监测中心 | Manganese modified biochar capable of reducing arsenic absorption of rice and application method thereof |
| CN112679246A (en) * | 2021-01-26 | 2021-04-20 | 东北农业大学 | Method for improving humic acid content of organic solid waste compost by utilizing sustainable catalytic material |
| CN113321255A (en) * | 2021-04-30 | 2021-08-31 | 国家地质实验测试中心 | Preparation method and application of manganese oxide-biochar composite solar interface evaporation material |
| CN115138332A (en) * | 2022-06-23 | 2022-10-04 | 华中农业大学 | Preparation method and application of manganese-acid-modified composite biochar passivation material |
| CN115785957A (en) * | 2022-12-19 | 2023-03-14 | 中国地质科学院水文地质环境地质研究所 | Preparation method and application of nano manganese dioxide modified biochar passivator |
| CN116272841A (en) * | 2023-05-11 | 2023-06-23 | 中南大学 | Manganese dioxide/ferric hydroxide porous adsorption material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198405A (en) * | 2011-04-01 | 2011-09-28 | 天津工业大学 | Composite catalyst for purifying indoor formaldehyde and preparation method of composite catalyst |
| CN105148842A (en) * | 2015-09-07 | 2015-12-16 | 河北师范大学 | Preparing method of manganese oxide-charcoal composite adsorbent |
-
2016
- 2016-10-27 CN CN201610954702.2A patent/CN107983300B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198405A (en) * | 2011-04-01 | 2011-09-28 | 天津工业大学 | Composite catalyst for purifying indoor formaldehyde and preparation method of composite catalyst |
| CN105148842A (en) * | 2015-09-07 | 2015-12-16 | 河北师范大学 | Preparing method of manganese oxide-charcoal composite adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| UN MENG ET AL.: ""Physicochemical properties of biochar produced from aerobically composted swine manure and its potential use as an environmental amendment"", 《BIORESOURCE TECHNOLOGY》 * |
| 叶正钱等: "《生物炭环境修复实用技术》", 30 November 2015 * |
| 马越: ""改性活性炭/纳米羟基氧化铝对水中氟离子的去除研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927107A (en) * | 2018-07-25 | 2018-12-04 | 中央民族大学 | A kind of straw base heavy-metal adsorption material and preparation method thereof |
| CN109173984A (en) * | 2018-08-14 | 2019-01-11 | 华南理工大学 | A method of Pb In Exhausted Water is removed using composite material |
| CN109270152B (en) * | 2018-10-18 | 2020-08-04 | 郑州市宇驰检测技术有限公司 | On-site visual detection method for heavy metal arsenic in environmental water sample |
| CN109270152A (en) * | 2018-10-18 | 2019-01-25 | 郑州市宇驰检测技术有限公司 | The visualization of presence detection method of heavy metal arsenic in a kind of environmental water sample |
| CN109926021A (en) * | 2019-03-15 | 2019-06-25 | 新疆农业大学 | A kind of preparation method and applications of ball milling modification chicken manure charcoal |
| CN109939661A (en) * | 2019-03-15 | 2019-06-28 | 农业农村部环境保护科研监测所 | A kind of adsorbent and its preparation method and application of adsorbable fixed heavy metal lead ion |
| CN110075785A (en) * | 2019-05-08 | 2019-08-02 | 河南城建学院 | The MnO of lead ion in a kind of removing water2Composite material and preparation method |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
| CN110898804A (en) * | 2019-11-25 | 2020-03-24 | 湖南第一师范学院 | Biochar composite material and preparation method and application thereof |
| CN110975809A (en) * | 2019-12-12 | 2020-04-10 | 广东工业大学 | Tangerine-based biochar and application thereof |
| CN111266084A (en) * | 2020-01-08 | 2020-06-12 | 江苏大学 | Porous aquatic plant-based biomass charcoal material and application thereof |
| CN111617739A (en) * | 2020-05-09 | 2020-09-04 | 齐鲁工业大学 | Al-Mn modified biomass charcoal and preparation method and application thereof |
| CN111617739B (en) * | 2020-05-09 | 2022-06-28 | 齐鲁工业大学 | Al-Mn modified biomass charcoal and preparation method and application thereof |
| CN111874984A (en) * | 2020-07-28 | 2020-11-03 | 上海泽耀环保科技有限公司 | Water body restoration rope and preparation method and application thereof |
| CN112117517A (en) * | 2020-09-01 | 2020-12-22 | 威海广泰空港设备股份有限公司 | Flexible zinc-air battery for electric passenger boarding ladder and preparation method |
| CN112044399A (en) * | 2020-09-10 | 2020-12-08 | 江西农业大学 | Manganese oxide-biological bamboo charcoal composite material and preparation method thereof |
| CN112058232A (en) * | 2020-09-21 | 2020-12-11 | 河南大学 | Manganese dioxide modified activated carbon composite adsorbent, preparation method thereof and application thereof in arsenic removal |
| CN112296084A (en) * | 2020-10-14 | 2021-02-02 | 成都市四友生物科技有限公司 | Soil restoration and improvement agent and preparation process thereof |
| CN112619601A (en) * | 2020-10-26 | 2021-04-09 | 广东省农业科学院农产品公共监测中心 | Manganese modified biochar capable of reducing arsenic absorption of rice and application method thereof |
| CN112679246A (en) * | 2021-01-26 | 2021-04-20 | 东北农业大学 | Method for improving humic acid content of organic solid waste compost by utilizing sustainable catalytic material |
| CN113321255A (en) * | 2021-04-30 | 2021-08-31 | 国家地质实验测试中心 | Preparation method and application of manganese oxide-biochar composite solar interface evaporation material |
| CN113321255B (en) * | 2021-04-30 | 2022-09-20 | 国家地质实验测试中心 | Preparation method and application of manganese oxide-biochar composite solar interface evaporation material |
| CN115138332A (en) * | 2022-06-23 | 2022-10-04 | 华中农业大学 | Preparation method and application of manganese-acid-modified composite biochar passivation material |
| CN115785957A (en) * | 2022-12-19 | 2023-03-14 | 中国地质科学院水文地质环境地质研究所 | Preparation method and application of nano manganese dioxide modified biochar passivator |
| CN116272841A (en) * | 2023-05-11 | 2023-06-23 | 中南大学 | Manganese dioxide/ferric hydroxide porous adsorption material and preparation method and application thereof |
| CN116272841B (en) * | 2023-05-11 | 2024-04-19 | 中南大学 | Manganese dioxide/ferric hydroxide porous adsorption material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107983300B (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107983300B (en) | The charcoal composite material and preparation method and application of manganese dioxide modification | |
| CN106362685A (en) | Modified biochar material for removing arsenic, and preparation and application thereof | |
| Chen et al. | Biosorption of fluoride from drinking water using spent mushroom compost biochar coated with aluminum hydroxide | |
| CN106362690A (en) | Magnetic biochar adsorbing material and preparation method thereof | |
| CN105797693A (en) | Magnetic chaff charcoal for removing lead and cadmium in water and preparation and application method thereof | |
| CN108483444A (en) | A kind of preparation method of the multiporous biological carbon composite of alpha-FeOOH nano-rod load | |
| CN109158084A (en) | Metal peroxides modification biological charcoal dephosphorization material and its preparation method and application | |
| Çoruh et al. | Adsorption of basic dye from wastewater using raw and activated red mud | |
| CN107262037B (en) | A kind of preparation and application of sepiolite FeOOH active carbon compound adsorbent | |
| CN106390940B (en) | Modified biomass charcoal and the preparation method and application thereof | |
| CN107626283B (en) | Utilize the method for antibiotic in multi-walled carbon nanotube/metal organic framework composite material adsorbed water body | |
| CN109225134A (en) | A kind of preparation method of needle-shaped Fe-Mn-S ternary nano material load multiporous biological carbon composite | |
| CN105236507A (en) | Method for removing hexavalent chromium in wastewater by using beta-cyclodextrin chitosan and walnut shell biochar compounded adsorbent | |
| CN106517341B (en) | A kind of method and its application for preparing manganese dioxide nano catalyst | |
| CN106423051A (en) | Preparation method and application of magnetic activated hydrothermal biochar microspheres | |
| CN105056949B (en) | A kind of fiber-loaded type Fenton catalyst of plant hollow, preparation method and applications | |
| CN106732375A (en) | A kind of preparation method and applications of clay mineral modification biological charcoal | |
| CN108176373A (en) | A kind of graphene oxide corn straw modification charcoal and preparation method thereof and in sewage is removed heavy metal application | |
| CN109967033A (en) | A kind of modified rice husk biomass carbon and preparation method thereof | |
| CN110142032A (en) | Chitosan biological carbon composite and its preparation method and application | |
| CN108671886A (en) | A kind of magnetic active carbon adsorbent and the preparation method and application thereof based on abandoned biomass | |
| CN104549146A (en) | Aluminum oxide modified multiwalled carbon nanotube nano composite material as well as preparation method and application thereof | |
| CN109569525A (en) | A kind of preparation of amido modified magnetic rice husk charcoal and method using uranium in its adsorbed water body | |
| CN101486769A (en) | Preparation of amidoxime group bacteria cellulose | |
| Liu et al. | Sulfur-modified Pleurotus ostreatus spent substrate biochar enhances the removal of cadmium in aqueous solution: Characterization, performance, mechanism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |