CN105797693A - Magnetic chaff charcoal for removing lead and cadmium in water and preparation and application method thereof - Google Patents

Magnetic chaff charcoal for removing lead and cadmium in water and preparation and application method thereof Download PDF

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Publication number
CN105797693A
CN105797693A CN201610360584.2A CN201610360584A CN105797693A CN 105797693 A CN105797693 A CN 105797693A CN 201610360584 A CN201610360584 A CN 201610360584A CN 105797693 A CN105797693 A CN 105797693A
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China
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rice husk
magnetic
husk charcoal
charcoal
water body
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Inventor
廖柏寒
周航
曹玮
杜文琪
鲍恒
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Hunan Debao Hengjiang Environmental Protection Biotechnology Co Ltd
Central South University of Forestry and Technology
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Hunan Debao Hengjiang Environmental Protection Biotechnology Co Ltd
Central South University of Forestry and Technology
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Priority to CN201610360584.2A priority Critical patent/CN105797693A/en
Publication of CN105797693A publication Critical patent/CN105797693A/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
    • B01J20/28—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
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
    • 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

The invention discloses magnetic chaff charcoal for removing lead and cadmium in water and a preparation and application method thereof.The preparation method of the magnetic chaff charcoal includes the steps of (1) preparing chaff charcoal; (2) performing acid modification on the chaff charcoal, namely modifying the chaff charcoal through nitric acid to obtain acid-modified chaff charcoal; (3) and magnetizing the acid-modified chaff charcoal to obtain loaded nano Fe3O4 modified chaff charcoal particles (BC-Fe).The magnetic chaff charcoal can remove heavy metals in water, such as Pb and Cd, not only has high removal rate of heavy metals, but also is low in cost without secondary pollution.In addition, the magnetic chaff charcoal can be recycled and widely applied to the field of treatment of wastewater with heavy metals such as Pb and Cd.

Description

A kind of magnetic rice husk charcoal for removing lead cadmium in water body and preparation thereof and application Method
Technical field
The present invention relates to lead cadmium pollution field in water body, a kind of magnetic rice husk for removing lead cadmium in water body is raw Thing charcoal and methods for making and using same thereof.
Background technology
Heavy metal pollution has become a global environmental problem.The toxic heavy-metal elements such as lead (Pb), cadmium (Cd), Animal and plant body, in the environment difficult degradation can be entered by the empty approach such as gas and water, soil, can be endangered by aquatic animals and plants rich absorbent Evil aquatic ecological environment, entering food chain may harm person poultry safety.It addition, directly drink or contact skin is containing a poisonous huge sum of money The water body belonged to all can make it into human body, works the mischief health.
The heavy metal of excess enters after water body, can change the fine structure of water plant cell, the activity of inhibitory enzyme thus Change its nucleic acid constituent so that cell volume changes, grow hindered etc..Research shows, Cd can destroy some The chlorophyll of chlorella, causes photosynthesis to decline, and also its Repiration is produced impact.Heavy metal can also endanger aquatic animal The process such as growth promoter, physiological metabolism.Research finds, Pb, Cd of variable concentrations can affect the fetal development of Tachypleus tridentatus and cause Deformity.Therefore find a kind of method efficient, environmental protection and process containing toxic heavy metal contamination waste water such as Pb, Cd so that it is qualified discharge, Reduce environmental pollution, be to need research and the environmental problem solved badly.
Absorption method is one of main method of current heavy metal containing wastewater treatment, has efficient, easy and selectivity good etc. excellent Point, but the most industrial adsorbent commonly used is expensive, makes the extensively application of absorption method be restricted.Exploitation is cheap, Efficient water treatment absorbent will be an importance of absorption research, and regeneration and the secondary pollution of adsorbent is also to inhale simultaneously Attached method processes the problem that should consider emphatically in heavy metal wastewater thereby.
The charcoal utilizing agricultural wastes to prepare processes heavy metal-containing waste water, is the study hotspot of absorption method in recent years. Charcoal rich surface, containing multiple functional groups such as carboxyl, phenolic hydroxyl group, carbonyl, quinonyls, has substantial amounts of pore structure, is a kind of efficient Adsorbent.According to statistics, the agricultural wastes that China produces every year reach tens million of ton, and these agricultural wastes are lifes cheap and easy to get Thing carbon feedstock.The charcoal of the preparations such as more current research application rice husk, rice straw, corn straw is to Heavy Metals in Waters Adsorption effect and characteristic are studied, and result shows, charcoal surface has more adsorption site, to Pb in water body2+、Cd2+ Preferable etc. the adsorption effect of heavy metal ion.Charcoal is modified or surface is modified and can be significantly improved its adsorption effect.Grind Study carefully and show, adsorbent magnetic iron oxide nanoparticle is carried out surface modification, can not only give up by Adsorption fast and efficiently The heavy metal ion of water, and owing to the magnetic property of its uniqueness also can reclaim by the most additional Magnet, have and well may be used Repeat recycling property, show good application prospect.The most domestic charcoal surface loaded magnetic investigation of materials is still in Initial stage, on the biological carbon materials of neutrality or alkali modification, carried magnetic is easier to realize, and its reason is that composing magnetic needs to exist Carry out under the conditions of alkalescence, and the biological carbon materials that acid is modified is composed magnetic and also there is no relevant report, it is contemplated that a kind of acid of research and development Modification biological charcoal magnetic material, to the Pb in water body2+And Cd2+There is huge adsorption capacity, and can be carried out quickly by magnetic Separating and recycle, this is significant to China's heavy metal containing wastewater treatment.
Summary of the invention
For solving the problems referred to above present in existing charcoal surface loaded magnetic investigation of materials, it is an object of the invention to The heavy metals such as a kind of Pb, Cd that can remove in water body are provided, not only it are had high clearance, and inexpensively dirty without secondary Dye, it is possible to the magnetic rice husk charcoal repeatedly recycled and reused and methods for making and using same thereof.
For achieving the above object, the present invention provides techniques below scheme:
The preparation method of a kind of magnetic rice husk charcoal for removing lead cadmium in water body, comprises the following steps:
(1) rice husk charcoal is prepared
Rice husk material, after high temperature carbonization, cleans removal ash with 0.005 ~ 0.01 mol/L nitric acid by solid-to-liquid ratio 1:10 ~ 1:20, Deionized water is washed till neutrality, dries to constant weight, pulverizes and sieves, obtain rice husk charcoal；
(2) acid of rice husk charcoal is modified
Weigh rice husk charcoal and add 1 ~ 2 mol/L nitric acid with solid-to-liquid ratio 1:8 ~ 1:15, be then heated to 110 DEG C of oxidation reactions 1 ~ 2 h, period stirs mixing once in a while；It is washed with deionized water after heating to neutrality, dries to constant weight, obtain the modified rice husk of acid raw Thing charcoal；
(3) the modified rice husk charcoal of acid composes magnetic
It is the FeCl of 4:1 ~ 2:1 by mass ratio3、FeCl2It is dissolved in the HCl solution of 1.0% ~ 1.3%, then will mix FeCl3、FeCl2Acid solution and the modified rice husk charcoal of acid obtained through step 2 together add in 1.2% ~ 1.4% ammonia spirit, After ul-trasonic irradiation 10 ~ 20 min, staticly settling, pour out supernatant after it precipitates completely, ultra-pure water is cleaned, and is loaded Nanometer Fe3O4Modified rice husk charcoal granule, i.e. magnetic rice husk charcoal (BC-Fe).
Preferably, high temperature carbonization described in step (1) refers under the protection of nitrogen in 300 ~ 700 ° of C carbonization 4 ~ 6 h.
It is prepared as described above the magnetic rice husk charcoal for removing lead cadmium in water body obtained by method.
It is prepared as described above the application process of the magnetic rice husk charcoal for removing lead cadmium in water body obtained by method, bag Include following steps:
(1) measure Pb and Cd content in water body, determine Pb/Cd content ratio in water body；
(2) when Pb/Cd content ratio >=2 in water body, magnetic rice husk charcoal (BC-is added with solid-to-liquid ratio 1:1000 ~ 1:1500 Fe)；As Pb/Cd content ratio ＜ 2 in water body, add magnetic rice husk charcoal (BC-Fe) with solid-to-liquid ratio 1:400 ~ 1:1000；
(3) after having adsorbed, utilize magnetic force to be separated from water body by magnetic rice husk charcoal, obtain the water body of cleaning.
Preferably, above-mentioned steps (2), after adding magnetic rice husk charcoal (BC-Fe), is 100 ~ 180 rad/ at rotating speed Vibrate under min 1 ~ 2 h.
The method have the advantages that (1) is to Pb in polluted-water2+、Cd2+There are higher removal effect, specific surface Amassing is 72.94 m2/ g, unit mass adsorbent is to Pb under optimum conditions2+、Cd2+Adsorbance be respectively 40.6 mg/g and 17.9 mg/g；(2) magnetic bio charcoal can be reused by desorbing absorption regeneration, after five desorbings are adsorbed, right Concentration be 100 mg/L containing Pb2+Waste water, the simulation of 50 mg/L contain Cd2+Waste water clearance remains at about 60.0%；(3) Compare the treatment technology of other Heavy Metals in Waters, and magnetic bio charcoal is a kind of low-cost sorbent, uses simple to operate, and not Secondary pollution can be produced, utilize magnetic force to be prone to carry out solid-liquid separation, can repeatedly recycle, it is adaptable to containing Pb2+、Cd2+Waste water Process.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing In having technology to describe, the required accompanying drawing used does simple introduction, it should be apparent that, the accompanying drawing in describing below is the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to These accompanying drawings obtain other accompanying drawing.
Accompanying drawing 1 be in the embodiment of the present invention 13 kinds of different adsorbents to Pb2+、Cd2+Clearance contrast.
BC-400-Fe is adsorbed Pb for adsorption time in the embodiment of the present invention 2 and initial concentration by accompanying drawing 22+Impact；
BC-400-Fe is adsorbed Cd for adsorption time in the embodiment of the present invention 2 and initial concentration by accompanying drawing 32+Impact；
Accompanying drawing 4 is scanning electron microscope Fig. 1 of BC-Fe in the embodiment of the present invention 2；
Accompanying drawing 5 is scanning electron microscope Fig. 2 of BC-Fe in the embodiment of the present invention 2；
Accompanying drawing 6 is BC-400-Fe Fourier infrared spectrum figure in the embodiment of the present invention 2；
Accompanying drawing 7 is BC-400-Fe XRD diffraction spectrogram in the embodiment of the present invention 2.
Detailed description of the invention
Below by specific embodiment, the present invention is further illustrated.
Embodiment 1
1, preparation magnetic rice husk charcoal (BC-300-Fe)
(1) rice husk raw material is cleaned, dries, under 300 DEG C of condition of nitrogen gas, heat 6 h, after carbonization, pulverized 100 mesh sieves, 0.005 mol/L nitric acid removes ash by the cleaning of solid-to-liquid ratio 1:10, cleans to neutral with ultra-pure water, obtains paddy after 70 DEG C of drying Shell charcoal；
(2) taking a certain amount of carbonization rice husk in solid-liquid ratio is in the nitric acid that 1:20 is placed in 2 mol/L, 110 DEG C of oxidation reactions 1.5 h, period stirs once in a while.Clean with distilled water after cooling until supernatant pH is to neutral, after drying, obtain the modified rice husk of acid Charcoal；
(3) by a certain proportion of FeCl3 6H2O and FeCl2·4H2O mixed dissolution, in the HCl solution of 0.5 mol/L, adds In 0.9 mol/L ammonia spirit, generate the Fe of black3O4Gelatinous precipitate.Add a certain amount of carbonization rice husk, stir 30 min, Standing separation, obtains magnetic rice husk charcoal (BC-300-Fe), collects standby after drying.
2, rice husk charcoal, the modified rice husk charcoal of acid and the actual effect contrast of magnetic rice husk charcoal
Measure 300 DEG C of unmodified rice husk charcoals (BC-300) of 3 kinds of charcoals, 300 DEG C of modified rice husk charcoal (BC-of acid respectively 300-HNO3, 300 DEG C of magnetic rice husk charcoal (BC-300-Fe) are to Pb2+、Cd2+Removal effect, concrete using method is:
(1) measure Pb and Cd content in water body, determine Pb/Cd content ratio in water body；
(2) when Pb/Cd content ratio >=2 in water body, magnetic rice husk charcoal (BC-is added with solid-to-liquid ratio 1:1000 ~ 1:1500 Fe)；As Pb/Cd content ratio ＜ 2 in water body, add magnetic rice husk charcoal (BC-Fe) with solid-to-liquid ratio 1:400 ~ 1:1000；
(3) after having adsorbed, utilize magnetic force to be separated from water body by magnetic rice husk charcoal, obtain the water body of cleaning.
Wherein treatment conditions are under the conditions of pH=5.0, and quantity of sorbent is 2 g/L, and rotating speed is 160 rpm, in temperature 25 At DEG C, the process time is 4 h, and simulation is containing Pb2+Waste water solution initial concentration is 50 mg/L, and simulation is containing Cd2+Waste water solution is initial Concentration is 20 mg/L.
3 kinds of different adsorbents are to Pb2+、Cd2+Clearance to such as accompanying drawing 1, as seen from the figure, in simulation containing Pb2+Waste water is molten Liquid initial concentration is 50 mg/L, containing Cd2+When waste water solution initial concentration is 20 mg/L, utilize 350 DEG C of rice husks fired biological Charcoal (BC-300) is in aqueous to Pb2+、Cd2+Removal effect the best, the modified rice husk charcoal of acid after Nitric Acid Modified (BC-300-NO3) substantially increase the removal effect of its heavy metal ion, to Pb2+、Cd2+Clearance all reached 95% with On.Magnetic rice husk charcoal (BC-300-Fe) slightly raises with acid modification rice husk charcoal phase specific removal rate, can remove this completely Under the conditions of heavy metal ion, clearance has reached 99%.
Embodiment 2
1, preparation magnetic rice husk charcoal (BC-400-Fe)
(1) rice husk raw material is cleaned, dries, under 400 DEG C of condition of nitrogen gas, heat 4 h, after carbonization, pulverized 100 mesh sieves, 0.007 mol/L nitric acid removes ash by the cleaning of solid-to-liquid ratio 1:15, cleans to neutral with ultra-pure water, obtains rice husk after 70 DEG C of drying Charcoal (BC-400)；
(2) taking a certain amount of carbonization rice husk in solid-liquid ratio is in 1: 10 nitric acid being placed in 2 mol/L, 110 DEG C of oxidation reactions 2 H, period stirs once in a while.Clean with distilled water after cooling until supernatant pH is to neutral, obtain the modified rice husk of acid after drying biological Charcoal (BC-400-HNO3)；
(3) by a certain proportion of FeCl3·6H2O and FeCl2·4H2O mixed dissolution, in the HCl solution of 0.4 mol/L, adds In 0.7 mol/L ammonia spirit, generate the Fe of black3O4Gelatinous precipitate.Add a certain amount of carbonization rice husk, stir 30 min, Standing separation, obtains magnetic rice husk charcoal (BC-400-Fe), collects standby after drying.
2, the actual effect contrast of magnetic rice husk charcoal
By magnetic rice husk charcoal (BC-400-Fe) for preparing with solid-to-liquid ratio as 1:500, add to Pb and Cd and be respectively 50 Hes 25 mg/L, 100 and 50 mg/L, 150 and 75 mg/L simulated wastewater in.
Adsorption time and initial concentration are to absorption Pb2+、Cd2+Affect result as shown in accompanying drawing 3, accompanying drawing 3.As seen from the figure, BC-400-Fe is to Pb2+、Cd2+Absorption basically reached adsorption equilibrium when 2 h, unrelated with the initial concentration of solution；Unit The BC-400-Fe of quality is to Pb2+、Cd2+Adsorbance increase along with the increase of heavy metal ions concentration in solution.
As shown in Figure 2, BC-400-Fe is to Pb2+Absorption very fast, reached absorption when adsorption time is 5 min More than the 50% of total amount.Along with the prolongation of adsorption time, BC-400-Fe is to Pb2+Adsorbance be gradually increased, be 2 at adsorption time Adsorption equilibrium is reached during h；Continuing to extend adsorption time, adsorption capacity amplification is less.The BC-400-when high concentration (150 mg/L) Fe is to Pb2+Adsorbance slightly reduce, it may be possible to Pb adsorbed after saturated absorption2+Desorb in solution.Initial at solution When concentration is 50 mg/L, the BC-400-Fe of 0.1g can adsorb the Pb in 50 mL completely2+, equilibrium adsorption capacity is 25 mg/g；Continue Pb in continuous increase solution2+Concentration to 100,150 mg/L time, its equilibrium adsorption capacity is consequently increased 40.6,50.9 mg/g, Basically reach saturated adsorbed state.
From the figure 3, it may be seen that BC-400-Fe is to Cd2+Adsorption process with its to Pb2+Adsorption tendency unanimous on the whole, can be in short-term Between most of heavy metal ion in internal adsorption solution, and reach time of equilibrium adsorption in 1 h.Cd in the solution2+Concentration is relatively low Time (25 mg/L), 0.1 g BC-400-Fe can remove the Cd in this solution of 50 mL completely2+, adsorption capacity is 12.5 mg/g； Along with Cd in solution2+Concentration increases to 50,75 mg/L time, the adsorbance of unit mass BC-400-Fe is consequently increased 17.9,18.0 mg/g, is more or less the same, it can thus be appreciated that unit mass BC-400-Fe is to Cd2+Saturated extent of adsorption be that 18 mg/g are left Right.
3, the phenetic analysis of magnetic rice husk charcoal
(1) SEM scanning analysis
The scanning electron microscope (SEM) photograph of BC-400-Fe is by shown in accompanying drawing 4, accompanying drawing 5, as seen from the figure, BC-400-Fe be irregular spherical, Cylindrical structural, granule is internal and surface distributed substantial amounts of size and differed, the aperture of sub-circular, adds the fluctuating of upper surface not Flat, it is dispersed with substantial amounts of fine particle thing, greatly adds the specific surface area of adsorbent, when this is likely to be carried magnetic, Fe3O4Granule is attached to what the surface of charcoal was caused.These particulate matters are full of between its hole, add the ratio of adsorbent Surface area, is conducive to the absorption of its heavy metal ion.And the edge of BC-400-Fe granule presents large stretch of light tone region, it is Owing to having loaded the reason of magnetic Fe.
(2) BET analyzes
As shown in Table 1, BC-400, BC-400-HNO3And the specific surface area of BC-400-Fe is respectively 2.02 m2/g、1.59 m2/ g and 85.0 m2/g.Obviously, prepare rice husk charcoal specific surface area at 400 DEG C less, account for major part with micropore；Nitric acid changes After property, its specific surface area slightly declines, and reduces its average pore size and make its number cells reduce, and this is likely to be Nitric Acid Modified During charcoal, the strong oxidizing property of nitric acid makes major part micropore cave in, connect and caused.Charcoal is carried out after negative magnetic significantly Add the specific surface area of charcoal, this is because the Fe of load3O4Granule is attached to the surface of adsorbent, causes magnetic bio Carbon surface is rough, adds specific surface area, it is provided that more adsorption site.Obtained by specific surface area and porosity measurement Going out, the micropore specific area proportion of BC-400-Fe is little, is a kind of atresia adsorbent, the most only there occurs that surface is inhaled Attached, adsorption process can be rapidly achieved balance.
The specific surface area of 13 kinds of charcoals of table, pore volume
(3) FTIR infrared spectrum analysis
The FTIR results of IR of BC-400-Fe is as shown in Figure 6.As seen from the figure, at infrared spectrum characteristic spectrum zone, 3680 cm-1Place creates a stronger and sharp peak, and this is the O-H stretching vibration peak of free alcohol and phenol；3378 cm-1Place goes out Show a wider O-H stretching vibration peak；3182cm-1Place occurs that ethylenic unsaturation, the stretching vibration of alkynes C-H absorbs Peak；1806cm-1Place occurs that the stretching vibration absworption peak of C=O in carboxyl；1596 cm-1Occur in that the skeleton of aromatic ring is flexible to shake Dynamic peak；1484 cm-1The peak that place occurs is owing to the bending vibration of c h bond and alcohol and phenol O-H in-plane bending produce.Red External spectrum finger-print region, 1161 cm-1Place occurs in that C-C skeletal vibration absworption peak；And 1084 cm-1That place produces is then Si-O- The antisymmetric stretching vibration peak of Si；859 cm-1Place occurs that the in-plane bending vibration absworption peak of aromatic ring C-H；579 cm-1Left Right appearance peak be Fe3O4Characteristic peak, show that carbonized rice husks successfully loads Fe3O4, there is magnetic.
(4) XRD analysis
As shown in Figure 7, as seen from the figure, the diffraction maximum that the BC-400-Fe synthesized occurs is single for the XRD analysis of BC-400-Fe, Illustrate that it comprises only Fe3O4A kind of crystal structure, and purity is high, complete crystal form.
Principle and the embodiment of the present invention are set forth by specific embodiment used herein, above example Method and the core concept thereof being only intended to help to understand the present invention is described.The above is only the side of being preferable to carry out of the present invention Formula, it is noted that due to the finiteness of literal expression, and objectively there is unlimited concrete structure, for the art For those of ordinary skill, under the premise without departing from the principles of the invention, it is also possible to make some improvement, retouch or change, also Above-mentioned technical characteristic can be combined by rights；These improve retouching, change or combine, or the most improved general is sent out Bright design and technical scheme directly apply to other occasion, are regarded as protection scope of the present invention.

Claims (5)

1. the preparation method being used for removing the magnetic rice husk charcoal of lead cadmium in water body, it is characterised in that include following step Rapid:
(1) rice husk charcoal is prepared
Rice husk material, after high temperature carbonization, cleans removal ash with 0.005-0.01 mol/L nitric acid by solid-to-liquid ratio 1:10 ~ 1:20, Deionized water is washed till neutrality, dries to constant weight, pulverizes and sieves, obtain rice husk charcoal；
(2) acid of rice husk charcoal is modified
Weigh rice husk charcoal and add 1 ~ 2 mol/L nitric acid with solid-to-liquid ratio 1:8 ~ 1:15, be then heated to 110 DEG C of oxidation reactions 1 ~ 2 h, period stirs mixing once in a while；It is washed with deionized water after heating to neutrality, dries to constant weight, obtain acid modification paddy Shell charcoal；
(3) the modified rice husk charcoal of acid composes magnetic
It is the FeCl of 4:1 ~ 2:1 by mass ratio3、FeCl2It is dissolved in the HCl solution of 1.0% ~ 1.3%, then will mix FeCl3、FeCl2Acid solution and the modified rice husk charcoal of acid obtained through step 2 together add in 1.2% ~ 1.4% ammonia spirit, After ul-trasonic irradiation 10 ~ 20 min, staticly settling, pour out supernatant after it precipitates completely, ultra-pure water is cleaned, and is loaded Nanometer Fe3O4Modified rice husk charcoal granule, i.e. magnetic rice husk charcoal (BC-Fe).
The preparation method of the magnetic rice husk charcoal for removing lead cadmium in water body the most according to claim 1, its feature Being, high temperature carbonization described in step (1) refers under the protection of nitrogen in 300-700 DEG C of carbonization 4-6 h.
3. according to the magnetic green rice husk charcoal for removing lead cadmium in water body obtained by the preparation method of claim 1 or 2.
4., according to the application process of magnetic rice husk charcoal for removing lead cadmium in water body of claim 1 or 2, its feature exists In, comprise the following steps:
(1) measure Pb and Cd content in water body, determine Pb/Cd content ratio in water body；
(2) when Pb/Cd content ratio >=2 in water body, magnetic rice husk charcoal (BC-is added with solid-to-liquid ratio 1:1000 ~ 1:1500 Fe)；As Pb/Cd content ratio ＜ 2 in water body, add magnetic rice husk charcoal (BC-Fe) with solid-to-liquid ratio 1:400 ~ 1:1000；
(3) after having adsorbed, utilize magnetic force to be separated from water body by magnetic rice husk charcoal, obtain the water body of cleaning.
The application process of the magnetic rice husk charcoal for removing lead cadmium in water body the most according to claim 4, it is characterised in that Described step (2) is after adding magnetic rice husk charcoal (BC-Fe), and vibrate under rotating speed is 100 ~ 180 rad/min 1 ~ 2 h.
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