CN107413319A - Method of the preparation of corncob modified magnetic heavy-metal adsorption material with removing heavy metal in water removal - Google Patents

Method of the preparation of corncob modified magnetic heavy-metal adsorption material with removing heavy metal in water removal Download PDF

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CN107413319A
CN107413319A CN201710337735.7A CN201710337735A CN107413319A CN 107413319 A CN107413319 A CN 107413319A CN 201710337735 A CN201710337735 A CN 201710337735A CN 107413319 A CN107413319 A CN 107413319A
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corncob
heavy
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CN107413319B (en
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范拴喜
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Baoji University of Arts and Sciences
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid 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
    • B01J20/28009Magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0225Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229Compounds of Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

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

Abstract

The magnetic material preparation for removing removing heavy metals and the minimizing technology of heavy metal in water are modified the invention discloses a kind of corncob, magnetic heavy metal adsorbent is prepared into by carrying out physical and chemical modified to agricultural wastes corncob, there is higher removal ability to heavy metal in dirty (useless) water, realize agricultural wastes recycling, with the purpose for pollution treatment of giving up, while overcome the difficulty for being difficult to after conventional absorbtion materials application remove.The invention raw material sources enrich, method simple possible, and to heavy metals removal significant effect in water and stably, and preparation and absorption cost are cheap, have preferable application value.

Description

The preparation of corncob modified magnetic heavy-metal adsorption material is with removing heavy metal in water removal Method
Technical field
The invention belongs to containing heavy metal-polluted (useless) Water warfare field, be modified in particular to a kind of corncob and remove weight The magnetic material of metal prepares the minimizing technology with heavy metal in water.
Background technology
With the fast development of industrial society, material processing, chemical production, Metal mining production with develop and it is daily The discharge capacity of heavy metal-containing waste water is increasing during production and living, and environmental pollution getting worse, human health receives sternly The threat of weight.How the endangering and effectively reclaim heavy metal in waste water of heavy metal is eliminated, and this is current environmental protection work In face one very prominent, and problem in urgent need to solve.
Corncob measures big and generally existing, farm or peasant household are typically made as the discarded object in agricultural production process Burn or discard for fuel, either which kind of mode can all pollute to environment.If being reclaimed, it is developed into Surrounding purifying material, then agricultural wastes recycling is realized, with the purpose for pollution treatment of giving up.At present.Original is used as using corncob To develop the technology of sorbent treatment heavy metal wastewater thereby, someone studies material, entitled《A kind of corncob is material modified and its makes Preparation Method and application》, in Publication No. CN104874361A patent document, disclose by the use of corncob and be used as heavy metal ion The preparation method of adsorbent, this method place into maize cob meal after the pretreatment of sodium hydroxide solution and salpeter solution is soaked Soaked in water, then add after initiator for reaction certain time and purified to obtain that corncob is material modified, to the Cu in waste water2 +、Cd2+、Pb2+Although ion has certain absorption property, but the deficiencies of adsorption efficiency is low, and adsorbent is difficult to recovery be present. CN105854834A discloses a kind of preparation method of modified corn core adsorbent, comprises the following steps:1) corncob is dried, Crush, obtain maize cob meal;2) maize cob meal and silicate solution are mixed, while is passed through nitrogen up to the oxygen in exclusion system Gas, 0.5~1h is stirred, then cool the temperature to less than 30 DEG C, added ammonium ceric nitrate and methyl acrylate progress graft copolymerization is anti- 1~2h is answered, hydroquinones stopped reaction is added, filtering, filter cake is washed with acetone, dried, as graft copolymer;3) to dry Sodium hydroxide solution is added in dry graft copolymer, is entered under 60~70 DEG C, the Hz of ultrasonic wave 50,000~100,000,200~500MPa Row 10~15h of saponification process, cooling, pH to 6~7 is adjusted, filtering, filter cake is washed with acetone, is dried, as modified corn core Adsorbent.However, this method needs graft copolymerization and row saponification process, preparation method is cumbersome, be unfavorable for it is extensive it is low into This production adsorbent.
The present invention, as raw material, is changed using the agricultural wastes corncob being easily obtained by carrying out physical chemistry to it Property, obtain to containing Pb2+、Cu2+、Cd2+、Cr2+、Zn2+There is the magnetic absorption material of excellent removal ability etc. heavy metal ion Material, has reached utilization of waste as resource, with the purpose for pollution treatment of giving up, reduces water process expense, while overcome sorbing material Difficult problem is reclaimed, in addition wastewater treatment process non-secondary pollution risk, meet the environmental protection concept of the treatment of wastes with processes of wastes against one another, had well Social benefit and environmental benefit.
The content of the invention
For the processing of current heavy metal polluted waste water material the defects of and deficiency, it is an object of the invention to using being easy to The agricultural wastes corncob of collection is raw material, and by physical and chemical modified, it is to Pb2+、Cu2+、Cd2+、Cr2+、Zn2+Deng a huge sum of money Category ion is respectively provided with higher removal efficiency, and clearance adsorbs up to more than 98% after removing heavy metal ions in wastewater Material recovery is convenient, and can effectively reclaim the heavy metal in waste water.
In order to realize the purpose of the present invention, inventor is finally obtained as follows by lot of experiments research and unremitting effort Technical scheme:A kind of preparation method of corncob modified magnetic heavy-metal adsorption material, this method comprise the following steps:
(1) corncob is cleaned, dried, crushed, cross 60~80 mesh sieves, it is standby;
(2) step (1) pretreated maize cob meal and water are pressed 1:2~1:4 weight adjusts pH extremely than mixing with acid solution 3.7~4.5,1~1.5h of stirring or vibration, it is 10.5~11.5 to be then adjusted to pH with alkali lye, continues to stir or vibrates 2.5-3.5 hours, centrifugation or elimination moisture, and neutrality is alternately washed till with water and ethanol, and in 60~80 DEG C of drying;
(3) by step (2) drying intermediate under inert gas shielding, in 450~550 DEG C keep 1~2h, after treat temperature Degree is down to room temperature taking-up, obtains modified corn core powder intermediate;
(4) the modified corn core powder intermediate for obtaining step (3) is by 1:2~1:3 weight stirs than adding water in band With the closed of inert gas shielding and can be in heating in water bath for reaction system, under inert gas shielding, bath temperature is maintained at 50 ~60 DEG C, uniform stirring, magnesium chloride is added by 18%~24% of weight among modified corn core powder, stirring reaction 5~ After 8min, molysite and ferrous salt are added, adjusts pH after stirring reaction 4-6min immediately after 10~11,0.4~0.5h of reaction, will Bath temperature rises to 75~85 DEG C and continues centrifugation or filtering after cooling down after 1.3~2.0h of reaction, neutrality is washed till, at 60~80 DEG C Lower drying, it is stand-by;
(5) product after step (4) is dried keeps 1.5~2.5h under inert gas shielding, in 430~480 DEG C, i.e., Obtain corncob modified magnetic heavy-metal adsorption material.
It is further preferred that the preparation method of corncob modified magnetic heavy-metal adsorption material as described above, wherein step (1) pre-treatment step is specially:Corncob is rinsed well with clear water, filters off moisture in 60 DEG C~80 DEG C drying, mistake after crushing 60~80 mesh sieves.
It is further preferred that the preparation method of corncob modified magnetic heavy-metal adsorption material as described above, wherein step (2) acid solution described in is the salpeter solution of mass fraction 2%~5%, and described alkali lye is the hydrogen of mass fraction 5%~10% Potassium oxide solution.
It is further preferred that the preparation method of corncob modified magnetic heavy-metal adsorption material as described above, wherein step (2) speed when in from stirring is 400~500 turns/min, is 200~260 turns/min from speed when vibrating.
It is further preferred that the preparation method of corncob modified magnetic heavy-metal adsorption material as described above, wherein step (4) speed of stirring is 500~700 turns/min in.
It is further preferred that the preparation method of corncob modified magnetic heavy-metal adsorption material as described above, wherein step (4) total amount of molysite and ferrous salt is 30%~40% of weight among modified corn core powder in, and ferrous ion and iron from Sub- mol ratio 1:(2.0~2.3).
In addition, by the present invention obtain corncob modified magnetic heavy-metal adsorption material by it is a certain amount of be separately added into it is leaded, In heavy metal-polluted (useless) water such as zinc, cadmium, chromium, copper, pH under certain condition, after stirring and adsorbing reaction certain time, utilizes magnet Reclaim the sorbing material.Method simple possible, to the removal effect of phosphorus in dirty (useless) water significantly and stably, recovery is convenient, nothing two Secondary pollution, reach with the purpose for pollution treatment of giving up.
Therefore, weight in water removal is removed using above-mentioned corncob modified magnetic heavy-metal adsorption material present invention also offers one kind The method of metal, specifically, this method comprises the following steps:The corncob modified magnetic heavy-metal adsorption material is pressed 2.0g/L~2.5g/L dosage, which adds, to be contained in heavy metal containing sewage, is adjusted pH to 2~6,2~2.5h of stirring and adsorbing, is then added magnetic Iron reclaims the sorbing material.It is further preferred that described heavy metal includes the one or more in lead, zinc, cadmium, chromium and copper. Still further preferably, when heavy metal is lead, zinc, cadmium, chromium, copper in going to remove water, regulation pH value is respectively 5,2,6,4,4.
The corncob modified magnetic heavy-metal adsorption material that the present invention is obtained and one kind of Gong sage and Zhou Xinhua inventions are beautiful Core is material modified compares for rice:The modified preparation process of the present invention does not need initiator and monomer, therefore preparation process is simple to operation; Secondly, the present invention obtain corncob modified magnetic heavy-metal adsorption material absorption to lead, zinc, cadmium, chromium, copper saturated extent of adsorption Respectively 74~76mg/g, 73~74mg/g, 49~50mg/g, 49~50mg/g and 49~50mg/g, and to lead, zinc, cadmium, Chromium, copper clearance for 98.00%~99.99% and its more than, and the sorbing material that Gong Yu is holy and Zhou Xinhua is obtained to lead, Copper, the saturated extent of adsorption of cadmium are respectively 7.2~7.7mg/g, therefore sorbing material its adsorbance that the present invention obtains is significantly larger than Gong The material of holy and Zhou Xinhua inventions;3rd, the corncob modified magnetic heavy-metal adsorption material that the present invention obtains removes weight in water removal Additional magnet is recyclable after metal reaction is complete, therefore is easily recycled, can be thoroughly by heavy metals removal in water.
The corncob modified magnetic heavy-metal adsorption material that the present invention is obtained and the modified corn of Xie Songfen inventions wick Attached dose and its preparation method and application is compared:The modified preparation process of the present invention is not required to graft copolymerization and row saponification process, therefore Preparation process is simple, and reaction is easily controllable;Secondly, the corncob modified magnetic heavy-metal adsorption material absorption pair that the present invention obtains Leaded, zinc, cadmium, chromium, the optimal initial concentration of copper are respectively 150mg/L, 150mg/L, 100mg/L, 100mg/L and 100mg/L, Optimal pH is respectively 5,2,6,4 and 4, sorbing material optimal addn 2.000g/L~2.500g/L, and what Xie Songfen was invented changes Property corncob adsorbent to lead, zinc, copper, nickel, cobalt initial concentration be respectively 2.51mg/L, 12.3mg/L, 5.8mg/L, 10.1mg/L and 15.3mg/L, the amount for adding adsorbent just reaches 2.0g/L, therefore the absorption of the sorbing material of the invention obtained is imitated Fruit is better than the modified corn core adsorbent of Xie Songfen inventions;3rd, the corncob modified magnetic heavy metal adsorption that the present invention obtains It is i.e. recyclable that material goes in water removal heavy metal react additional magnet afterwards, therefore is easily recycled, can be thoroughly by heavy metals removal in water.
Compared with prior art, the present invention is prepared into magnetic by carrying out physical and chemical modified to agricultural wastes corncob Heavy metal absorbent, there is higher removal ability to heavy metal in dirty (useless) water, realize agricultural wastes recycling, With the purpose for pollution treatment of giving up, while overcome the difficulty for being difficult to after conventional absorbtion materials application remove.The invention raw material sources are rich Richness, preparation method simple possible, to heavy metals removal significant effect in water and stably, and preparation and absorption cost are cheap, have Preferable application value.
Embodiment
Below by absorption of the specific embodiment to corncob modified magnetic heavy-metal adsorption material heavy metal of the present invention Performance is clearly and completely described, and the following example is merely to illustrate the present invention, and should not be regarded as limiting the model of the present invention Enclose.In addition, unreceipted particular technique operating procedure or condition person in embodiment, the skill described by according to document in the art Art or condition are carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, are that can pass through city Purchase the conventional products obtained.
Embodiment 1:The preparation of corncob modified magnetic heavy-metal adsorption material
1st, the corncob of collection is rinsed well, filters off moisture and cross 60~80 mesh sieves after 60 DEG C~80 DEG C drying, crushing, It is standby.
2nd, pretreated maize cob meal in step 1 and water are pressed 1:2~1:3 mass ratio (ensures maize cob meal quilt Water all soaks) it is fitted into the reaction vessel of belt stirrer or in appropriate containers, its pH is adjusted to 4 with 5% nitric acid, Vibration (260 turns/min) 1.2h in oscillator is stirred or be placed under 450 turns/min speed, is then adjusted with 10% potassium hydroxide It is 11.0 to pH, continues to stir (450 turns/min) or vibrate (260 turns/min) 3 hours, then centrifuge or filter off moisture, And neutrality is alternately washed till with water and ethanol, and dried in an oven in 60~80 DEG C of temperature.
3rd, by the chemical modification corncob intermediate after the final drying in step 2 in the inert gas such as nitrogen or argon gas Treat that temperature is down to room temperature and taken out after keeping 1.5h in 480 DEG C under protection, it is stand-by.
4th, modified corn core powder intermediate obtained in step 3 is pressed 1:2~1:3 mass ratio adds water, is stirred in band Mix and stir the closed of inert gas shielding and can in heating in water bath for reaction system, under the inert gas shielding such as nitrogen or argon gas, Bath temperature is maintained at 52 DEG C, and mixing speed keeps 600 turns/min uniform stirrings, by weight among modified corn core powder After 20% adds magnesium chloride stirring reaction 5min, then add molysite and ferrous salt, molysite and ferrous salt total amount account for modified corn The 33% of weight among core powder, and ensure ferrous ion and iron ion mol ratio 1:2 ratio, after stirring reaction 5min immediately Adjust pH in the range of 10~11, react 0.5h after, by its temperature rise to 80 DEG C continue react 1.5h after cool down after centrifugation or Filtering, lotion to neutrality, is dried at 60~80 DEG C, stand-by.
5th, by the product after being dried in step 4 under the inert gas shielding such as nitrogen or argon gas, after 430 DEG C keep 2h Obtain corncob modified magnetic heavy-metal adsorption material.
Embodiment 2:The removal of heavy metal in dirty (useless) water
By embodiment 1 obtain corncob modified magnetic heavy-metal adsorption material by it is a certain amount of be separately added into leaded, zinc, In heavy metal-polluted (useless) water such as cadmium, chromium, copper, under certain condition, after stirring and adsorbing reaction certain time, additional magnet reclaims pH The sorbing material.
Experimental result shows, the corncob modified magnetic heavy-metal adsorption material that the present invention is obtained, leaded, zinc, cadmium, Chromium, copper optimal initial concentration are respectively 150mg/L, 150mg/L, 100mg/L, 100mg/L and 100mg/L, and Optimal pH is respectively 5th, 2,6,4 and 4, optimal use temperature is normal temperature, stir speed (S.S.) 300~400 turns/min, 2~2.5h of uniform stirring, sorbing material Optimal addn 2.000g/L~2.500g/L, clearance up to 98.00%~99.99%, distinguish by maximum saturation adsorbance For 74~76mg/g, 73~74mg/g, 49~50mg/g, 49~50mg/g and 49~50mg/g, optimal and most economical use Temperature is normal temperature, to the clearance of lead, zinc, cadmium, chromium, copper for 98.00%~99.99% and its more than.
Comparative example 1:The preparation of corncob modified magnetic heavy-metal adsorption material
1st, the corncob of collection is rinsed well, filters off moisture and cross 60~80 mesh sieves after 60 DEG C~80 DEG C drying, crushing, It is standby.
2nd, pretreated maize cob meal in step 1 and water are pressed 1:2~1:3 mass ratio (ensures maize cob meal quilt Water all soaks) it is fitted into the reaction vessel of belt stirrer or in appropriate containers, being adjusted to pH with 10% potassium hydroxide is 11.0, continue to stir (450 turns/min) or vibrate (260 turns/min) 3 hours, its pH is then adjusted to 4 with 5% nitric acid, Vibration (260 turns/min) 1.2h in oscillator is stirred or is placed under 450 turns/min speed, then centrifugation or elimination water Point, and neutrality is alternately washed till with water and ethanol, and dried in an oven in 60~80 DEG C of temperature.
Step 1,3,4,5 are final to obtain corncob modified magnetic heavy-metal adsorption material with embodiment 1.
Experimental result:Compared with sorbing material prepared by embodiment 1, the corncob modified magnetic heavy metal of program preparation Sorbing material, only preferable to the removal effect of lead, clearance can reach more than 99%, and to zinc, cadmium, chromium, copper removal effect phase To poor, its clearance is between 75%~90%.
Comparative example 2:The preparation (step 3 low temperature) of corncob modified magnetic heavy-metal adsorption material
Steps 1 and 2,4,5 are the same as embodiment 1;
3rd, by the chemical modification corncob intermediate after the final drying in step 2 in the inert gas such as nitrogen or argon gas Under protection, treat that temperature is down to room temperature and taken out after keeping 1.5h in 420 DEG C, it is stand-by.
Experimental result:Compared with sorbing material prepared by embodiment 1, the corncob modified magnetic heavy metal of program preparation Sorbing material, it is the 1/2~3/4 of embodiment 1 to the saturated extent of adsorption of leaded, zinc, cadmium, chromium, copper under the same terms.
Comparative example 3:The preparation (not having inert gas shielding) of corncob modified magnetic heavy-metal adsorption material
Steps 1 and 2,3 are the same as embodiment 1;
4th, modified corn core powder intermediate obtained in step 3 is pressed 1:2~1:3 mass ratio adds water, is stirred in band Mix closed and can be in heating in water bath for reaction system, bath temperature is maintained at 52 DEG C, and mixing speed keeps 600 turns/min uniformly to stir Mix, after adding magnesium chloride stirring reaction 5min by 20% of weight among modified corn core powder, then add molysite and ferrous iron Salt, molysite and ferrous salt total amount account for 33% of weight among modified corn core powder, and ensure ferrous ion and iron ion mole Than 1:2 ratio, pH is adjusted immediately in the range of 10~11 after stirring reaction 5min, after reacting 0.5h, its temperature is risen to 80 DEG C continue to react cool down after 1.5h after centrifugation or filtering, lotion to neutrality, dried at 60~80 DEG C, it is stand-by.
5th, corncob modified magnetic heavy metal adsorption is obtained after the product after being dried in step 4 being kept into 2h in 430 DEG C Material.
Experimental result:With embodiment 1 prepare sorbing material compared with, the program prepare corncob modified absorbing material without Magnetic, therefore sorbing material is difficult to reclaim after adsorption applications.
Comparative example 4:The preparation of corncob modified magnetic heavy-metal adsorption material (step 4 is not added with magnesium chloride)
Steps 1 and 2,3,5 are the same as embodiment 1;
4th, modified corn core powder intermediate obtained in step 3 is pressed 1:2~1:3 mass ratio adds water, is stirred in band Mix and stir the closed of inert gas shielding and can in heating in water bath for reaction system, under the inert gas shielding such as nitrogen or argon gas, Bath temperature is maintained at 52 DEG C, and mixing speed keeps 600 turns/min uniform stirrings, adds molysite and ferrous salt, molysite and ferrous iron Salt total amount accounts for 33% of weight among modified corn core powder, and ensures ferrous ion and iron ion mol ratio 1:2 ratio, is stirred PH is adjusted immediately in the range of 10~11 after mixing reaction 5min, after reacting 0.5h, its temperature is risen to 80 DEG C and continues to react 1.5h Centrifugation or filtering, lotion to neutrality, are dried at 60~80 DEG C after cooling down afterwards, stand-by.
Experimental result:With embodiment 1 prepare sorbing material compared with, the program prepare sorbing material to lead, zinc, cadmium, When chromium, copper heavy metal adsorption, under equal conditions, adsorbent most preferably adds 2~4 times that dosage is embodiment 1, and its saturation is inhaled Attached amount is also 1/2~3/4 times of embodiment 1.
Comparative example 5:The preparation (step 5 high temperature) of corncob modified magnetic heavy-metal adsorption material
Steps 1 and 2,3,4 are the same as embodiment 1;
5th, by the product after being dried in step 4 under the inert gas shielding such as nitrogen or argon gas, after 550 DEG C keep 2h Obtain corncob modified magnetic heavy-metal adsorption material.
Experimental result:Compared with sorbing material prepared by embodiment 1, the magnetic of sorbing material prepared by the program is weaker than reality Apply the sorbing material in example 1 so that absorption is more difficult using magnet recovery adsorbent after terminating.

Claims (9)

1. a kind of preparation method of corncob modified magnetic heavy-metal adsorption material, it is characterised in that this method includes following step Suddenly:
(1) corncob is cleaned, dried, crushed, cross 60~80 mesh sieves, it is standby;
(2) step (1) pretreated maize cob meal and water are pressed 1:2~1:4 weight adjusts pH to 3.7 than mixing with acid solution ~4.5,1~1.5h of stirring or vibration, it is 10.5~11.5 to be then adjusted to pH with alkali lye, continues to stir or vibrate 2.5- 3.5 hours, moisture is centrifuged or filtered off, and neutrality is alternately washed till with water and ethanol, and in 60~80 DEG C of drying;
(3) by step (2) drying intermediate under inert gas shielding, in 450~550 DEG C keep 1~2h, after treat temperature drop Taken out to room temperature, obtain modified corn core powder intermediate;
(4) the modified corn core powder intermediate for obtaining step (3) is by 1:2~1:3 weight is than adding water, in band stirring and lazy Property gas shield closed and can be in heating in water bath for reaction system, under inert gas shielding, bath temperature is maintained at 50~60 DEG C, uniform stirring, magnesium chloride is added by 18%~24% of weight among modified corn core powder, after 5~8min of stirring reaction, Molysite and ferrous salt are added, pH is adjusted after stirring reaction 4-6min immediately 10~11, after reacting 0.4~0.5h, by water-bath temperature Degree rises to 75~85 DEG C and continues centrifugation or filtering after cooling down after 1.3~2.0h of reaction, is washed till neutrality, is dried at 60~80 DEG C It is dry, it is stand-by;
(5) product after step (4) is dried keeps 1.5~2.5h under inert gas shielding, in 430~480 DEG C, that is, obtains Corncob modified magnetic heavy-metal adsorption material.
2. the preparation method of corncob modified magnetic heavy-metal adsorption material according to claim 1, it is characterised in that step (1) pre-treatment step is specially:Corncob is rinsed well with clear water, filters off moisture in 60 DEG C~80 DEG C drying, mistake after crushing 60~80 mesh sieves.
3. the preparation method of corncob modified magnetic heavy-metal adsorption material according to claim 1, it is characterised in that step (2) acid solution described in is the salpeter solution of mass fraction 2%~5%, and described alkali lye is the hydrogen of mass fraction 5%~10% Potassium oxide solution.
4. the preparation method of corncob modified magnetic heavy-metal adsorption material according to claim 1, it is characterised in that step (2) speed when in from stirring is 400~500 turns/min, is 200~260 turns/min from speed when vibrating.
5. the preparation method of corncob modified magnetic heavy-metal adsorption material according to claim 1, it is characterised in that step (4) speed of stirring is 500~700 turns/min in.
6. the preparation method of corncob modified magnetic heavy-metal adsorption material according to claim 1, it is characterised in that step (4) total amount of molysite and ferrous salt is 30%~40% of weight among modified corn core powder in, and ferrous ion and iron from Sub- mol ratio 1:(2.0~2.3).
7. one kind utilizes any corncob modified magnetic heavy-metal adsorption material in claim 1-6 to remove heavy metal in water removal Method, it is characterised in that this method comprises the following steps:The corncob modified magnetic heavy-metal adsorption material is pressed 2.0g/L~2.5g/L dosage, which adds, to be contained in heavy metal containing sewage, is adjusted pH to 2~6,2~2.5h of stirring and adsorbing, is then added magnetic Iron reclaims the sorbing material.
8. go according to claim 7 water removal in heavy metal method, it is characterised in that described heavy metal include lead, zinc, One or more in cadmium, chromium and copper.
9. go according to claim 7 water removal in heavy metal method, it is characterised in that when go water removal in heavy metal be lead, When zinc, cadmium, chromium, copper, regulation pH value is respectively 5,2,6,4,4.
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