CN110327885A - A kind of absorbent charcoal composite material and its preparation method and application - Google Patents

A kind of absorbent charcoal composite material and its preparation method and application Download PDF

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Publication number
CN110327885A
CN110327885A CN201910666059.7A CN201910666059A CN110327885A CN 110327885 A CN110327885 A CN 110327885A CN 201910666059 A CN201910666059 A CN 201910666059A CN 110327885 A CN110327885 A CN 110327885A
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China
Prior art keywords
sewage
active carbon
absorbent charcoal
composite material
charcoal composite
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CN201910666059.7A
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CN110327885B (en
Inventor
贾文娟
丁爱中
王大扬
刘宝蕴
梁信
孙跃林
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Bo Chuan Environmental Rehabilitation (beijing) Co Ltd
Beijing Normal University
Poten Environment Group Co Ltd
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Bo Chuan Environmental Rehabilitation (beijing) Co Ltd
Beijing Normal University
Poten Environment Group Co Ltd
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Publication of CN110327885A publication Critical patent/CN110327885A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2101/105—Phosphorus compounds
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to a kind of absorbent charcoal composite materials and its preparation method and application.The preparation method includes the following steps: 1) to stir in the solution of active carbon addition ferrous salt, obtains active carbon particle；The wherein active carbon: the quality molar ratio of ferrous salt is (20-100) g:1mol；2) the resulting active carbon particle of step 1) is added in solvent, stirs, is drying to obtain in the presence of a reducing agent.Absorbent charcoal composite material provided by the present invention, mechanical strength is good, and recycling number is high, and the cleanser as sewage has biggish advantage.It is used for the absorbent charcoal composite material to handle sewage, can reach to ammonia nitrogen in sewage, organic matter, total phosphorus effectively removes.After processing, the content of total organic carbon reduces 40% or more, and fluorescent characteristic has obtained significant removal, and ammonia nitrogen reduces 70% or more, and total phosphorus reduces 80% or more.

Description

A kind of absorbent charcoal composite material and its preparation method and application
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of absorbent charcoal composite material and preparation method thereof and answers With.
Background technique
At this stage, China is faced with the baptism of water resources problems.The sewage of city outlet is added as second water source With reuse, it can greatly improve China's shortage of water resources status.In secondary effluent reuse, problem in need of consideration is mainly difficult drop Solve organic matter, ammonia nitrogen and total phosphorus, there are still a large amount of noxious materials and potential carcinogenic contaminant, such as surface in secondary effluent Activating agent, additive and dyestuff etc..Moreover, the content of ammonia nitrogen and total phosphorus in secondary effluent is higher.
The technology of current removal ammonia nitrogen mainly has vaporizing extract process, the guanite precipitation method, ion-exchange, breakpoint chloridising, height Grade oxidizing process etc..Chemical phosphorus removal method has coagulating sedimentation, electrolysis method, crystallisation, ion-exchange, absorption method these types.It goes Except the method for hardly degraded organic substance is mainly advanced oxidation processes, current research is mostly to the respective removal skill of these three pollutants Art research, few technical studies that can remove these three pollutants simultaneously.
Summary of the invention
Defect based on the prior art, the present invention provide one kind (for purifying sewage) absorbent charcoal composite material and its system Preparation Method and application.
A method of absorbent charcoal composite material is prepared, is included the following steps:
1) active carbon is added in the solution of ferrous salt and is stirred, obtain active carbon particle；The wherein active carbon: ferrous salt Quality molar ratio be (17-100) g:1mol；
2) the resulting active carbon particle of step 1) is added in solvent, stirs, is drying to obtain in the presence of a reducing agent.
The method of the present invention for preparing absorbent charcoal composite material, about step 1):
Preferably, the active carbon: the quality molar ratio of ferrous salt is (30-80) g:1mol；
More preferably 50g:1mol；Or, the concentration of the solution of the ferrous salt is in 0.5-2mol/L.
Under the range of above-mentioned restriction, advantage is, while energy processability more excellent material, prepares the material The dosage of chemical reagent needed for expecting is few, also reduces production cost and subsequent processing problem.
It is further preferable that the ferrous salt is selected from one or more of ferrous sulfate, frerrous chloride；Wherein, with iron member The quality meter of plain Fe and the quality meter of active carbon C, iron-carbon ratio are Fe:C=(1-3): (1-2)；
It is further preferred that Fe:C is (2-3): 1 or Fe:C is (1-2): (1-2)；
Most preferably, Fe:C is 3:1, and or, Fe:C is (1-1.5): 2, or, Fe:C is 2:(1-1.5).
When handling sewage using the absorbent charcoal composite material, when Fe:C is 3:1, to the removal effect of ammonia nitrogen compared with It is good；Fe:C is (1-1.5): preferable to the removal effect of ammonia nitrogen when 2；Fe:C is 2:(1-1.5) when, to the removal effect of TOC compared with It is good.
Preferably, the active carbon is cylindricality active carbon.Inventor once attempted granular active carbon, tree in development phase Rouge active carbon etc., it is all more excellent not as good as the effect of cylindricality active carbon.
The method of the present invention for preparing absorbent charcoal composite material, about step 2):
About solvent:
Preferably, the solvent is selected from one of alcohol, ultrapure water of C1-C3 etc. or at least two；Preferably ultrapure water.
About reducing agent:
Preferably, the reducing agent is potassium borohydride；The mole dosage ratio of the more preferable reducing agent and the ferrous salt For 1:(300-600).
It will be understood by those skilled in the art that the reducing agent is added in a manner of being added dropwise dropwise as a solution.
About drying:
Preferably, one of heating, drying or freeze-drying can be selected in the drying；More preferably it is freeze-dried；Specifically Ground, the drying are to be freeze-dried 5-10h under the conditions of -80 DEG C.
As the optimal technical scheme of preparation method, include the following steps:
Column-shaped active carbon is placed in the ferrous sulfate solution that concentration is 1mol/L and stirs 1-3h, after cleaning, by active carbon Particle is placed in (appropriate) ultrapure water and stirs, while the reducing agent being added dropwise dropwise, continue after dripping off stir 20-30h, then in In freeze drier be lyophilized to get.
The absorbent charcoal composite material haveing excellent performance, and holistic approach can be not only prepared in method provided by the present invention Have the advantages that low in cost, not harsh to operating environment requirement.
Present invention simultaneously provides a kind of absorbent charcoal composite materials, are prepared by activated carbon supported Zero-valent Iron, the zeroth order Iron (at least) includes amorphous form and is attached to activated carbon surface.
Preferably, there is following characterization information: specific surface area 160-220m2/ g (more preferably 180 ± 10m2/ g), hole Diameter range is 1.7-300nm；
It is further preferred that the average pore size of the absorbent charcoal composite material is 2.438nm, most probable pore size is 1.8nm。
Preferably, prepared by absorbent charcoal composite material preparation method as described in above-mentioned any one technical solution It obtains.
Absorbent charcoal composite material provided by the present invention, mechanical strength is good, and recycling number is high, the purification as sewage Agent has biggish advantage, and there are also aoxidize organic pollutants and good ammonia nitrogen effect.
Pair it need to be explained, heretofore described cleanser, can be this field cleanser to understand, i.e., Sewage has the inorganic agent of certain suction-operated and/or oxidation.
The present invention further provides above-mentioned absorbent charcoal composite material sewage treatment field application, specifically, the work Cleanser of the property carbon composite as sewage.
A kind of heterogeneous advanced oxidization method handling sewage, it is multiple using active carbon described in above-mentioned any one technical solution Cleanser of the condensation material as sewage.
Preferably, include the following steps:
S1, persulfate is added in the first sewage, obtains the second sewage；In second sewage, persulfate it is dense Degree is 5-50mmol/L；
S2, so that second sewage is in contact with the absorbent charcoal composite material to get.
As explanation and illustration, in step S2, in " second sewage is made to be in contact with the absorbent charcoal composite material " " contact " can be referred to that the absorbent charcoal composite material is immersed in second sewage, the second sewage flows through the activity The acceptable way of contact of carbon composite or any other this field.
Heterogeneous advanced oxidization method of the present invention, about step S1:
The concentration of the persulfate is 5-40mmol/L；The concentration of the more preferable persulfate is 5-25mmol/L.
In first sewage, at least contain following ion: chloride ion and/or carbanion, it is preferable that chloride ion Concentration is 2-20mmol/L.
When first sewage contains chloride ion and carbanion, using heterogeneous advanced oxidation side of the present invention Method can more effectively remove pollutant.
Preferably, the pH value of first sewage is 3-11；It is highly preferred that 7 (the pH value of pH value < of first sewage For within the scope of 3-7, do not include 7) or > 7 (pH value is not include 7) within the scope of 7-11, or is 7.
As optimal technical scheme, in heterogeneous advanced oxidization method: the content of the persulfate is 10-20mmol/ L,
PH value is 10-11；
Or,
PH value is 3-4；
Or,
PH value is 6-8.
As another optimal technical scheme, in heterogeneous advanced oxidization method:
The iron-carbon ratio is 1:2, and the dosage of the persulfate is 7-25mmol/L；
Or,
The iron-carbon ratio is 3:1, and the dosage of the persulfate is 10-20mmol/L.
Heterogeneous advanced oxidization method of the present invention, about step S2:
Contact of second sewage with absorbent charcoal composite material for example the second sewage flows through the absorbent charcoal composite material, Then flow velocity is the conventional flow velocity of this field, does not do special restriction herein.
Heterogeneous advanced oxidization method of the present invention is that nano zero valence iron is supported on activated carbon surface, will be mixed with over cure The sewage of hydrochlorate is passed through the absorbent charcoal composite material, and ammonia nitrogen in sewage, organic matter can be realized, and total phosphorus effectively removes.Make For those skilled in the art, which can be filled in adsorption column, the sewage for being mixed with persulfate is led to Enter adsorption column.
In the reaction, nano zero valence iron can activate persulfate and generate potentiometric titrations, aoxidize the ammonia nitrogen in sewage And organic matter, active carbon can be with the phosphorus in absorption effluent.After treatment by using the treatment method, the content of total organic carbon reduce 40% with On, fluorescent characteristic has obtained significant removal.Ammonia nitrogen reduces 70% or more, and total phosphorus reduces 80% or more.
Certainly, implement any of the products of the present invention or method it is not absolutely required at the same reach all the above excellent Point.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.
Fig. 1-1 and Fig. 1-2 is the scanning electron microscope (SEM) photograph of absorbent charcoal composite material of the invention；
Fig. 2 is the XRD diagram of absorbent charcoal composite material of the invention；
Fig. 3 is the full spectrogram of XPS of absorbent charcoal composite material of the invention；
Fig. 4 is the XPS open score figure of the iron of absorbent charcoal composite material of the invention；
Fig. 5 is the FTIR spectrum figure of absorbent charcoal composite material of the invention；
Fig. 6 is absorbent charcoal composite material described in embodiment 1-4 in test example 1 to the removal rate schematic diagram of ammonia nitrogen；
Fig. 7 is absorbent charcoal composite material described in embodiment 1-4 in test example 1 to the removal rate schematic diagram of total phosphorus；
Fig. 8 is absorbent charcoal composite material described in embodiment 1-4 in test example 1 to the removal rate schematic diagram of TOC；
Fig. 9 is by under the different persulfate contents that measure in test example 3, absorbent charcoal composite material of the invention is to total phosphorus Removal rate schematic diagram；
Figure 10 is by the embodiment 1 that measures in test example 3 as the three-dimensional fluorescence figure after cleanser；
Figure 11 is by the embodiment 6 that measures in test example 3 as the three-dimensional fluorescence figure after cleanser；
Figure 12 is absorbent charcoal composite material described in embodiment 8-11 in test example 4 for the removal rate schematic diagram of ammonia nitrogen；
Figure 13 is absorbent charcoal composite material described in embodiment 8-11 in test example 4 for the removal rate schematic diagram of total phosphorus；
Figure 14 is absorbent charcoal composite material described in embodiment 8-11 in test example 4 for the removal rate schematic diagram of TOC；
Figure 15 is in test example 5, and the reuse number of absorbent charcoal composite material described in embodiment 1 is to ammonia nitrogen removal frank Influence diagram；
Figure 16 is in test example 5, and the reuse number of absorbent charcoal composite material described in embodiment 1 is to total tp removal rate Influence diagram；
Figure 17 is in test example 5, and the reuse number of absorbent charcoal composite material described in embodiment 1 is to TOC removal rate Influence diagram；
Figure 18 be test example 6 in, embodiment 7, the processing method of embodiment 12-21 for total tp removal rate influence diagram；
Figure 19 be test example 6 in, embodiment 7, the processing method of embodiment 12-21 for ammonia nitrogen removal frank influence diagram；
Figure 20 be test example 6 in, embodiment 7, the processing method of embodiment 12-21 for TOC removal rate influence diagram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Column-shaped active carbon employed in following embodiment is purchased from Henan Huan Shengtan industry Co., Ltd；Those skilled in the art Member is it is appreciated that column-shaped active carbon selects commercial sources to obtain, the above is only source is illustrated, not to technology of the invention Scheme limits.
Other reagents unless otherwise specified, commercially obtain.
Embodiment 1
The present embodiment provides a kind of absorbent charcoal composite materials, are prepared by the following method:
1) 28g column-shaped active carbon is placed in the ferrous sulfate solution that 500mL concentration is 1mol/L and is stirred two hours；
2) it after cleaning active carbon particle obtained by step 1), is placed in 300mL or so ultrapure water and stirs, while being added dropwise dropwise The solution of potassium borohydride of 100mL concentration 1.08mol/L continues stirring for 24 hours, prepared material is then put in freezing after dripping off In drying machine at -80 DEG C be lyophilized 8h to get.
Through characterizing, as shown in Fig. 1-1~Fig. 5:
It is the scanning electron microscope (SEM) photograph of absorbent charcoal composite material of the invention with reference to attached drawing 1-1 and attached drawing 1-2, it is known that, it is described The surface of absorbent charcoal composite material is non-uniform porous structure, and surface is made of multiple element.
With reference to attached drawing 2, by XRD diagram it is found that the peaks that 2 θ are 25.13 ° of appearance represent the amorphous carbon in material, at 43.37 ° The peak of appearance represents amorphous Fe0, the peak that 78.58 ° of whens occur represents Fe3C。
With reference to attached drawing 3, by the full spectrogram of XPS it is found that the ingredient in the absorbent charcoal composite material mainly includes C, O, Fe tri- Kind.
With reference to attached drawing 4, it can be seen that Iron activiation mainly has simple substance Fe, Fe in material by the XPS open score figure of iron2O3、Fe3O4 Three kinds.
With reference to attached drawing 5, the active carbon is answered it can be seen from the FTIR spectrum figure of the absorbent charcoal composite material Condensation material main functional group has-CH2,-C=O and-C-O.
Embodiment 2
The present embodiment provides a kind of absorbent charcoal composite materials, the difference from embodiment 1 is that:
Iron-carbon ratio is 1:2.
Embodiment 3
The present embodiment provides a kind of absorbent charcoal composite materials, the difference from embodiment 1 is that:
Iron-carbon ratio is 3:1.
Embodiment 4
The present embodiment provides a kind of absorbent charcoal composite materials, the difference from embodiment 1 is that:
Iron-carbon ratio is 2:1.
Embodiment 5
The present embodiment provides a kind of absorbent charcoal composite materials, the difference from embodiment 1 is that:
Prepared material is put into 60 DEG C of baking oven drying 8h by step 2).
Embodiment 6
The present embodiment provides a kind of absorbent charcoal composite materials, the difference from embodiment 1 is that:
Step 2) is placed in 300mL or so ethanol solution (30% ethyl alcohol) after cleaning active carbon particle obtained by step 1) Stirring.
Embodiment 7
The present embodiment provides a kind of heterogeneous advanced oxidization methods for handling sewage, use active carbon described in embodiment 1 Composite material is as cleanser.
Specifically comprise the following steps:
S1, persulfate is added in the first sewage, obtains the second sewage；In second sewage, persulfate it is dense Degree is 20mmol/L；
S2, so that second sewage is flowed through adsorption column, the adsorption column be filled with the absorbent charcoal composite material to get.
Wherein, first sewage contains chloride ion and carbanion ion, and the chlorine ion concentration is 5mmol/L, And the pH value for adjusting the first sewage is 3.
Wherein, the first sewage quality data are as shown in the table:
Embodiment 8-11
Embodiment 8-11 provides a kind of heterogeneous advanced oxidization method for handling sewage respectively, and the difference with embodiment 7 exists In: the pH value for adjusting first sewage is respectively 5,7,9,11.
Embodiment 12-21
Embodiment 12-21 provides a kind of heterogeneous advanced oxidization method for handling sewage, the difference point with embodiment 7 respectively Be not: the concentration of the persulfate is respectively 0,3,5,7,10,15,25,30,35,40mmol/L.
Comparative example 1
This comparative example provides a kind of active carbon.The difference from embodiment 1 is that: only with active carbon, not load iron.
Test example 1
This test example verifies the application effect of absorbent charcoal composite material provided by embodiment 1-4 and the active carbon of comparative example 1 Fruit.
Test method: it according to method described in embodiment 7, respectively in the concentration of persulfate in 0-25mmol/L, surveys Surely using ammonia nitrogen removal frank, the total tp removal rate, TOC removal rate after above-mentioned absorbent charcoal composite material.
According to identical test method measurement using comparative example 1 active carbon after ammonia nitrogen removal frank, total tp removal rate and TOC removal rate.
Said determination method does not do special limitation according to the conventional method of this field herein.
Test result:
As shown in attached drawing 6-8.
As it can be seen that under different iron-carbon ratios, different persulfate contents can influence to a certain extent ammonia nitrogen, total phosphorus and The removal rate of TOC.
It is all preferable to the removal effect of ammonia nitrogen in the case of any persulfate concentration when iron-carbon ratio is 3:1.
It is preferable for the removal effect of total phosphorus in the case of the concentration of persulfate is greater than 0 when iron-carbon ratio is 1:2.
It is preferable for the removal effect of TOC when the concentration of persulfate is 0-17mmol/L when iron-carbon ratio is 2:1； When the concentration of persulfate rises to more than 17mmol/L, the removal rate of the absorbent charcoal composite material of iron-carbon ratio 1:2 for TOC It is higher.
Test example 2
This test example provides the application performance test of absorbent charcoal composite material provided by embodiment 1,5.
Mechanical strength is detected according to conventional method in that art, as a result as follows:
Slight change has occurred in the pore structure and mechanical strength of the absorbent charcoal composite material of embodiment 5, and material slightly becomes Loose, mechanical strength is lower than the absorbent charcoal composite material of embodiment 1.
Through detecting, the physical property of the absorbent charcoal composite material of embodiment 1 does not change, and mechanical strength is higher.
Test example 3
This test example provides the application performance test of the absorbent charcoal composite material of embodiment 1, embodiment 6.
Test method:
(1) it according to method described in embodiment 7, is measured respectively when persulfate content is 0-30mmol/L, embodiment 6 (having alcohol solvent) and embodiment 1 (no alcohol solvent) are as total tp removal rate after cleanser.
(2) it according to method described in embodiment 8, measures using embodiment 6 (having alcohol solvent) and embodiment 1 respectively (no alcohol solvent) is as the three-dimensional fluorescence figure under the conditions of cleanser.
Test result:
(1) measurement result is as shown in Fig. 9.
By attached drawing 9 as it can be seen that under the concentration range of any persulfate, embodiment 1 is higher than the removal rate of total phosphorus real Apply example 6.
(2) measurement result is as shown in attached drawing 10-11.
By attached drawing 10-11 as it can be seen that embodiment 1 can remove total phosphorus well under the concentration of lower persulfate；And Embodiment 6 just can reach and the comparable technical effect of embodiment 1 under the concentration of higher persulfate.
As explanation and illustration, in attached drawing 10 and attached drawing 11, " raw water " occurred refers to the sewage without any processing Fluorogram；" 0mmol persulfate " refers to there is no under conditions of persulfate, is answered with active carbon described in embodiment 1 Condensation material adsorbed after water body fluorogram；" 10mmol persulfate ", " 15mmol persulfate ", " 20mmol over cure Hydrochlorate " refers respectively under the persulfate concentration of 10mmol/L, 15mmol/L and 20mmol/L with activity described in embodiment 1 Carbon composite adsorbed after water body fluorogram.
Wherein, in each fluorogram of attached drawing 10 and attached drawing 11, abscissa is launch wavelength (nm), and ordinate is Excitation wavelength (nm).
Test example 4
This test example provides the measure of merit of heterogeneous advanced oxidization method described in embodiment 8-11.
Test method: according to conventional method in that art measurement according to above-mentioned heterogeneous advanced oxidization method treated water body In ammonia nitrogen, total phosphorus, TOC value.
Test result: as shown in attached drawing 12-14.
As shown in Fig. 12, it is seen that pH value is 11, persulfate concentration is in 15mmol/L, for the removal rate of ammonia nitrogen Highest.
As shown in Fig. 13, it is seen that pH value be 7, persulfate content be 7mmol/L when, for total phosphorus removal rate most It is high.
As shown in Fig. 14, it is seen that pH value be 3, persulfate content be 20mmol/L when, for TOC removal rate most It is high.
As can be seen from the above results, weak base and neutrallty condition are suitble to the removal of total phosphorus, and alkaline condition is suitble to going for ammonia nitrogen It removes, acid and neutrallty condition is suitble to the removal of TOC.
Test example 5
This test example provides the number of repetition test of absorbent charcoal composite material provided by embodiment 1.
Test method: it after absorbent charcoal composite material described in method use described in embodiment 7, is rushed with ultrapure water It washes, and after freeze-drying 8h, is continued at -80 DEG C in freeze drier, measure its second and third time handles sewage Application effect.
Test result: as shown in attached drawing 15-17.
By attached drawing 15-17 it is found that with composite material recycling, the removal rate of total phosphorus in sewage is slightly increased Add, the removal rate of ammonia nitrogen and TOC is slightly reduced.
It can be seen that the recycling of material provided by the present invention is high-efficient.
Test example 6
This test example provides embodiment 7 and the treatment effect test of embodiment 12-21.
Test method: being handled according to the method for embodiment 7, embodiment 12-21, and measures the total of treated sewage Phosphorus, ammonia nitrogen, TOC index.
Test result: as shown in attached drawing 18-20.
It can be seen that different persulfate contents has a certain impact for the removal of total phosphorus, ammonia nitrogen, TOC.
For compbined test example 1-6 it is found that absorbent charcoal composite material provided by the present invention, mechanical strength is good, recycling time Number is high, and the cleanser as sewage has biggish advantage.It is used for the absorbent charcoal composite material to handle sewage, can reach to sewage Middle ammonia nitrogen, organic matter, total phosphorus effectively remove.After processing, the content of total organic carbon reduces 40% or more, and fluorescent characteristic obtains Significant removal is arrived, ammonia nitrogen reduces 70% or more, and total phosphorus reduces 80% or more.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Range.

Claims (10)

1. a kind of method for preparing absorbent charcoal composite material, which comprises the steps of:
1) active carbon is added in the solution of ferrous salt and is stirred, obtain active carbon particle；The wherein active carbon: the matter of ferrous salt Amount molar ratio is (17-100) g:1mol；
2) the resulting active carbon particle of step 1) is added in solvent, stirs, is drying to obtain in the presence of a reducing agent.
2. the method according to claim 1, wherein the active carbon: the quality molar ratio of ferrous salt is (30- 80) g:1mol；
Preferably, the active carbon: the quality molar ratio of ferrous salt is 50g:1mol；Or, the concentration of the ferrous salt solution exists 0.5-2mol/L。
3. method according to claim 1 or 2, which is characterized in that the ferrous salt is in ferrous sulfate, frerrous chloride One or two；
Wherein, in terms of the quality of ferro element F and the quality meter of active carbon C, iron-carbon ratio is Fe:C=(1-3): (1-2)；It is preferred that Ground, Fe:C are (2-3): 1 or Fe:C is (1-2): (1-2).
4. method according to claim 1-3, which is characterized in that the solvent is selected from C1-C3Alcohol, ultrapure water One of or at least two；Preferably ultrapure water；
And/or
The reducing agent is potassium borohydride；Preferably, the mole dosage ratio of the reducing agent and the ferrous salt is 1:(300- 600)；
And/or
The drying is freeze-drying；Preferably, the drying is to be freeze-dried 5-10h under the conditions of -80 DEG C.
5. a kind of absorbent charcoal composite material, which is characterized in that be prepared by activated carbon supported Zero-valent Iron, the Zero-valent Iron is at least Including amorphous form, and it is attached to the activated carbon surface；
Preferably, it is prepared by the described in any item methods of claim 1-4.
6. absorbent charcoal composite material described in claim 5 is in the application of sewage treatment field；Preferably, the active carbon is compound Cleanser of the material as sewage.
7. a kind of heterogeneous advanced oxidization method for handling sewage, which comprises the steps of:
S1, persulfate is added in the first sewage, obtains the second sewage；
S2, so that second sewage is in contact with the absorbent charcoal composite material described in claim 5 to get；
Preferably, in second sewage, the concentration of persulfate is 5-50mmol/L；It is highly preferred that the persulfate Concentration is 5-25mmol/L.
8. the method according to the description of claim 7 is characterized in that at least containing following ion: chlorine in first sewage Ion and/or carbanion；
Preferably, concentration of the chloride ion in first sewage is 2-20mmol/L.
9. according to the described in any item methods of claim 7-8, which is characterized in that the pH value of first sewage is 3-11；
Preferably, the content of the persulfate is 10-17mmol/L, pH value 10-11；Or, pH value is 3-4；Or, pH value is 6-8。
10. according to the described in any item methods of claim 7-9, which is characterized in that the iron-carbon ratio is 1:2, the persulfuric acid The dosage of salt is 7-25mmol/L；
Or,
The iron-carbon ratio is 3:1, and the dosage of the persulfate is 10-20mmol/L.
CN201910666059.7A 2019-07-23 2019-07-23 Active carbon composite material and preparation method and application thereof Expired - Fee Related CN110327885B (en)

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JP6165598B2 (en) * 2013-11-13 2017-07-19 水ｉｎｇ株式会社 Regeneration method of plant-based spherical activated carbon and reuse method of the regenerated plant-based spherical activated carbon in water purification treatment
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CN108341480A (en) * 2018-03-27 2018-07-31 北京师范大学 A method of production activation persulfate production chlorine radical removes nitrogen-containing wastewater
CN108439570A (en) * 2018-05-22 2018-08-24 徐建 Charcoal loads nano zero valence iron activation sodium peroxydisulfate system and its preparation and application
CN109999753A (en) * 2019-03-18 2019-07-12 上海交通大学 A kind of high adsorption porous carbon load zeroth order iron catalyst and its preparation method and application

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JP6165598B2 (en) * 2013-11-13 2017-07-19 水ｉｎｇ株式会社 Regeneration method of plant-based spherical activated carbon and reuse method of the regenerated plant-based spherical activated carbon in water purification treatment
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CN108217834A (en) * 2018-03-27 2018-06-29 北京师范大学 The method of production activation persulfate production carbonate radical removal nitrogen-containing wastewater
CN108341480A (en) * 2018-03-27 2018-07-31 北京师范大学 A method of production activation persulfate production chlorine radical removes nitrogen-containing wastewater
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