CN106807334B - A kind of preparation method and applications of heavy metal ion adsorbing material - Google Patents
A kind of preparation method and applications of heavy metal ion adsorbing material Download PDFInfo
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- CN106807334B CN106807334B CN201710062889.XA CN201710062889A CN106807334B CN 106807334 B CN106807334 B CN 106807334B CN 201710062889 A CN201710062889 A CN 201710062889A CN 106807334 B CN106807334 B CN 106807334B
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28014—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 form
- B01J20/28047—Gels
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention discloses a kind of preparation method and applications of heavy metal ion adsorbing material, by using landfill leachate as raw material, it is subjected to graft copolymerization with the cellulose extracted in cigarette stalk to produce landfill leachate-tobacco stalk fiber element compound, and it will be after landfill leachate-tobacco stalk fiber element compound progress gelation processing, it is regenerated, landfill leachate-tobacco stalk fiber element base aeroge is made after exchange of solvent and vacuum drying, obtained landfill leachate-tobacco stalk fiber element base aerogel material aperture is big, porosity is high, stable structure, and there is excellent chelation to the heavy metal in waste water, adsorption efficiency and adsorbance, using low-cost landfill leachate and cigarette stalk, the cost of heavy mental treatment can not only be reduced, it can also greatly realize the cycling and reutilization of resource, promote the protection of environment.
Description
Technical field
The present invention relates to heavy metal ion adsorbing material field, especially a kind of preparation side of heavy metal ion adsorbing material
Method and its application.
Background technique
With the rapid development of industry, the wastewater discharge generated in industrial processes also increasingly increases, wherein containing
The industrial wastewater of heavy metal ion and organic dyestuff will cause the serious pollution of water body, has jeopardized ecological environment and the mankind are strong
Therefore health has caused the great attention of numerous scientific workers to the processing of industrial wastewater.Usually said heavy metal pollution,
It is primarily referred to as the significant element of the bio-toxicities such as lead, copper, mercury, further includes the element that zinc, tin, cobalt etc. have certain toxicity, due to
Heavy metal and heavy metal compound are widely used in the industries such as chemical industry, plating, leather, as their applications constantly expand, heavy metal
Pollution also increasingly increases, and since heavy metal is difficult to be biodegradable, and has bioconcentration, therefore the pollution caused by it
With duration, heavy metal in water has become one of the environmental problem of most serious in the world today, on the other hand, with weaving
Printing and dyeing, papermaking and the development of printing industry and people are higher and higher to the needs in terms of color, at present organic dye waste water
Discharge amount is continuously increased in the specific gravity of national every profession and trade, and dyestuff type constantly update and increase, it is anti-light solution, it is anti-oxidant and
Antibiont degradation property constantly enhances, so that the processing difficulty of dyestuff waste liquid is significantly promoted.
Currently, the method for processing industrial wastewater mainly has reduction method, absorption method and ion-exchange-resin process.These methods exist
It plays an important role in processing industrial wastewater, wherein absorption method is because easy to operate, and removal efficiency is high, and use scope is wide, ready-made to be
Relatively reliable method for treating waste liquid.
Using the traditional synthesis quasi polymer of biomass portion or replacing whole, the pollutant for repairing in water body is close
One of the hot spot of several years environmental science forward positions research, cellulose and sodium humate are as natural polymer, in nature
In be widely distributed, and have good chemical adsorptivity, preferable reproducibility, biodegradable, moisture-absorption water-retention make
With；And in above-mentioned two classes polymer chemistry structure contain great amount of hydroxy group, carboxylate groups and amino, can with the heavy metal in water from
Suction-operated occurs for son and organic dyestuff, meanwhile, these functional groups can also be crosslinked by chemical modification, form macromolecular
Reticular structure can effectively avoid the shortcomings that sodium humate meets water dissolution, by cellulose and sodium humate both high molecular materials
Advantage concentrate in together, to increase substantially the adsorption capacity of heavy metal ion.
In addition, the yield of municipal refuse also increasingly rises since present people's lives level is gradually increased, handling
A large amount of landfill leachate can be generated during rubbish, due to containing a large amount of humic acid in landfill leachate, by itself and agriculture
Crop cigarette stalk carries out production heavy metal absorbent as raw material, not only low in cost, additionally it is possible to realize the recycling of waste,
It realizes secondary economic value, all there is positive effect to the cost and waste cycling and reutilization that reduce heavy metal processing.
Summary of the invention
In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of low in cost, highly effective and safes, production
The preparation method and applications of the heavy metal ion adsorbing material of simple process.
In order to realize above-mentioned technical purpose, the technical solution of the present invention is as follows: a kind of system of heavy metal ion adsorbing material
It is carried out graft copolymerization with the cellulose extracted in cigarette stalk and landfill leachate-is made by Preparation Method using landfill leachate as raw material
Tobacco stalk fiber compound after carrying out gelation to landfill leachate-tobacco stalk fiber compound, then regenerates it, is molten
Agent exchange and supercritical carbon dioxide are dry, and it is fine to can be prepared by the landfill leachate-tobacco rod for having adsorptivity to heavy metal ion
Tie up plain base aeroge.
Further comprising following steps:
(1) after being filtered, cleaning by landfill leachate, its pH is adjusted to 7~9, coagulant is then added, and utilize
After agitating device stirs 3~5min with 2000~3000rpm, then with 500~650rpm, 10~15min of stirring, after the completion of stirring
Mixed solution is staticly settled, then sediment filter out and is configured to solution, and the solution ph of configuration is adjusted to 7~9；
(2) cigarette stalk is emedullated after core, smashes it through 14~20 meshes, then by after sieving cigarette stalk with by sodium hydrate solid
The sodium hydroxide solution that the mass fraction that grain dissolution is configured to is 2% mixes, and mixed solution is heated to 90~150 DEG C,
After carrying out 1~3h of reaction, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 5~15min after again with toluene washing with Lampen mill and adds it to first
It carries out 4~6h of dipping in the mixed liquor of benzene and epoxychloropropane, after dipping, solid content is filtered out again, and successively use second
Alcohol, distilled water are washed, and are washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 100~300W carries out 2~5h of assisted reaction, after the reaction was completed, solution is stood 3~5h at normal temperature, then by solution
In solid content filter out, washed and impregnated with the sodium hydroxide solution that pH value is 9~11, until leachate is in colourless
Only, it can be prepared by landfill leachate-tobacco stalk fiber element compound；
(5) by landfill leachate obtained above-tobacco stalk fiber element compound under conditions of 60~80 DEG C, vacuum is carried out
After dry 24~48h, then landfill leachate-tobacco stalk fiber element compound is added in ionic liquid, and at 65~85 DEG C
Under the conditions of, 1~3h is stirred to react with the mixing speed of 600~800rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is that freezen protective 12~for 24 hours is carried out in -75~-50 DEG C of ultra low temperature freezer that mold, which is placed in temperature,；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with non solvent liquid and is replaced 3~6 times, then will
It is freeze-dried by the mixture that solvent is replaced, can be prepared by the landfill leachate-that counterweight metal ion has adsorptivity
Tobacco stalk fiber element base aeroge.
Preferably, the addO-on therapy and mass fraction of each step are as follows:
Preferably, the ionic liquid is 1- butyl -3- methylimidazole villaumite or 1- allyl -3- methylimidazole chlorine
Salt.
Preferably, the coagulant is the polymer of molysite, aluminium salt or molysite and aluminium salt.
It preferably, is 40%~60% using the solution solid content that sediment is configured in the step (1).
It preferably, is the cylindrical body of radius 10mm, height 30mm by formed in mould mixture in the step (5).
Preferably, the non solvent liquid is the tert-butyl alcohol or acetone.
A kind of application by heavy metal ion adsorbing material made from above-mentioned preparation method, by heavy metal ion adsorbed material
Material is for heavy metal ion adsorbed in landfill leachate.
Above-mentioned technical solution is used the invention has the benefit that by using landfill leachate as raw material, by itself and cigarette
The cellulose that extracts in stalk carries out graft copolymerization to produce landfill leachate-tobacco stalk fiber element compound, and by landfill leachate-
After tobacco stalk fiber element compound carries out gelation processing, then is regenerated, garbage filter is made after exchange of solvent and vacuum drying
Liquid-tobacco stalk fiber element base aeroge, obtained landfill leachate-tobacco stalk fiber element base aerogel material aperture is big, porosity
High, stable structure and there is excellent chelation, adsorption efficiency and adsorbance to the heavy metal in waste water, using cost
Cheap landfill leachate and cigarette stalk, can not only reduce the cost of heavy mental treatment, additionally it is possible to greatly realize resource
Cycling and reutilization, promote the protection of environment.
Specific embodiment
A kind of preparation method of heavy metal ion adsorbing material, using landfill leachate as raw material, by its with extracted in cigarette stalk
Cellulose carry out graft copolymerization be made landfill leachate-tobacco stalk fiber compound, by multiple to landfill leachate-tobacco stalk fiber
After closing object progress gelation, then it is regenerated, the drying of exchange of solvent and supercritical carbon dioxide, can be prepared by heavy metal
Ion has landfill leachate-cigarette pole fiber element base aeroge of adsorptivity.
Further comprising following steps:
(1) after being filtered, cleaning by landfill leachate, its pH is adjusted to 7~9, coagulant is then added, and utilize
After agitating device stirs 3~5min with 2000~3000rpm, then with 500~650rpm, 10~15min of stirring, after the completion of stirring
Mixed solution is staticly settled, then sediment filter out and is configured to solution, and the solution ph of configuration is adjusted to 7~9；
(2) cigarette stalk is emedullated after core, smashes it through 14~20 meshes, then by after sieving cigarette stalk with by sodium hydrate solid
The sodium hydroxide solution that the mass fraction that grain dissolution is configured to is 2% mixes, and mixed solution is heated to 90~150 DEG C,
After carrying out 1~3h of reaction, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 5~15min after again with toluene washing with Lampen mill and adds it to first
It carries out 4~6h of dipping in the mixed liquor of benzene and epoxychloropropane, after dipping, solid content is filtered out again, and successively use second
Alcohol, distilled water are washed, and are washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 100~300W carries out 2~5h of assisted reaction, after the reaction was completed, solution is stood 3~5h at normal temperature, then by solution
In solid content filter out, washed and impregnated with the sodium hydroxide solution that pH value is 9~11, until leachate is in colourless
Only, it can be prepared by landfill leachate-tobacco stalk fiber element compound；
(5) by landfill leachate obtained above-tobacco stalk fiber element compound under conditions of 60~80 DEG C, vacuum is carried out
After dry 24~48h, then landfill leachate-tobacco stalk fiber element compound is added in ionic liquid, and at 65~85 DEG C
Under the conditions of, 1~3h is stirred to react with the mixing speed of 600~800rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is that freezen protective 12~for 24 hours is carried out in -75~-50 DEG C of ultra low temperature freezer that mold, which is placed in temperature,；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with non solvent liquid and is replaced 3~6 times, then will
It is freeze-dried by the mixture that solvent is replaced, can be prepared by the landfill leachate-that counterweight metal ion has adsorptivity
Tobacco stalk fiber element base aeroge.
Preferably, the addO-on therapy and mass fraction of each step are as follows:
Preferably, the ionic liquid is 1- butyl -3- methylimidazole villaumite or 1- allyl -3- methylimidazole chlorine
Salt.
Preferably, the coagulant is the polymer of molysite, aluminium salt or molysite and aluminium salt.
It preferably, is 40%~60% using the solution solid content that sediment is configured in the step (1).
It preferably, is the cylindrical body of radius 10mm, height 30mm by formed in mould mixture in the step (5).
Preferably, the non solvent liquid is the tert-butyl alcohol or acetone.
A kind of application by heavy metal ion adsorbing material made from above-mentioned preparation method, by heavy metal ion adsorbed material
Material is for heavy metal ion adsorbed in landfill leachate.
Embodiment 1
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 26.97Kg after filtering, cleaning is adjusted to 7, and 0.03Kg tri-chlorination is then added
Iron, and after stir 3min under 2000rpm revolving speed using agitating device, then 10min, stirring completion are stirred with the revolving speed of 600rpm
Mixed solution is staticly settled afterwards, then sediment filter out and is configured to the solution that solid content is 58%, and by solution ph
It is adjusted to 7；
(2) 10Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5Kg hydroxide
The sodium hydroxide solution that the mass fraction that the dissolution of sodium solid particle is configured to is 2% mixes, and mixed solution is heated to 90 DEG C,
After carrying out reaction 1h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out 5min is discongested after again with toluene washing with Lampen mill to add it to by 15Kg
It carries out dipping 4h in toluene and 5Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively use second
Alcohol, distilled water are washed, and are washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 100W carries out assisted reaction 2h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 9, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 60 DEG C
After for 24 hours, then landfill leachate-tobacco stalk fiber element compound is added in 38Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 65 DEG C, 3h is stirred to react with the mixing speed of 600rpm, after the completion of stirring, pours the mixture into molding die
In, and mold is placed in the ultra low temperature freezer that temperature is -75 DEG C and carries out freezen protective 12h, it is shaped to radius 10mm, height
Spend the cylindrical body of 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 6 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Embodiment 2
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 24Kg after filtering, cleaning is adjusted to 8, and 0.05Kg aluminum sulfate is then added, and
It, will after the completion of stirring after stirring 3min under 2100rpm revolving speed using agitating device, then with the revolving speed stirring 10min of 610rpm
Mixed solution staticly settles, then sediment filter out and is configured to solid content as 40% solution, and solution ph is adjusted
To 8；
(2) 10Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5.95Kg hydrogen-oxygen
Change the mass fraction that the dissolution of sodium solid particle is configured to mix for 2% sodium hydroxide solution, and mixed solution is heated to 100
DEG C, after carrying out reaction 5h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 10min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 4h in 15Kg toluene and 5Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively
It is washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 250W carries out assisted reaction 4h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 10, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 70 DEG C
After 36h, then landfill leachate-tobacco stalk fiber element compound is added in 40Kg 1- allyl -3- methylimidazole villaumite, and
Under conditions of 70 DEG C, 2h is stirred to react with the mixing speed of 700rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is that freezen protective 18h is carried out in -70 DEG C of ultra low temperature freezer that mold, which is placed in temperature, be shaped to radius 10mm,
The cylindrical body of height 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with acetone soln and is replaced 6 times, then will be passed through molten
The mixture of agent displacement is freeze-dried, and it is fine to can be prepared by landfill leachate of the counterweight metal ion with adsorptivity-cigarette stalk
Tie up plain base aeroge.
Embodiment 3
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 26Kg after filtering, cleaning is adjusted to 8, and 0.04Kg polyaluminium is then added
Aluminium, and after stir 5min under 2200rpm revolving speed using agitating device, then 12min, stirring completion are stirred with the revolving speed of 500rpm
Mixed solution is staticly settled afterwards, then sediment filter out and is configured to the solution that solid content is 40%, and by solution ph
It is adjusted to 9；
(2) 10.5Kg is emedullated the cigarette stalk after core, smashes it through 16 meshes, then by after sieving cigarette stalk with by 5.46Kg hydrogen
The sodium hydroxide solution that the mass fraction that the dissolution of sodium oxide molybdena solid particle is configured to is 2% mixes, and mixed solution is heated to
150 DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 15min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 6h in 18Kg toluene and 6Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively
It is washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 100W carries out assisted reaction 5h, after the reaction was completed, solution is stood 4h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 11, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 80 DEG C
After for 24 hours, then landfill leachate-tobacco stalk fiber element compound is added in 34Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 75 DEG C, 1h is stirred to react with the mixing speed of 800rpm, after the completion of stirring, pours the mixture into molding die
In, and mold is placed in the ultra low temperature freezer that temperature is -60 DEG C and carries out freezen protective 28h, it is shaped to radius 10mm, height
Spend the cylindrical body of 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with acetone soln and is replaced 5 times, then will be passed through molten
The mixture of agent displacement is freeze-dried, and it is fine to can be prepared by landfill leachate of the counterweight metal ion with adsorptivity-cigarette stalk
Tie up plain base aeroge.
Embodiment 4
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 28Kg after filtering, cleaning is adjusted to 8, and 0.03Kg ferric trichloride is then added,
And after utilizing agitating device to stir 3min under 2300rpm revolving speed, then with the revolving speed stirring 10min of 630rpm, after the completion of stirring
Mixed solution is staticly settled, then sediment filter out and is configured to the solution that solid content is 40%, and by solution ph tune
It saves to 7；
(2) 12Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5Kg hydroxide
The sodium hydroxide solution that the mass fraction that the dissolution of sodium solid particle is configured to is 2% mixes, and mixed solution is heated to 100
DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 5min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 4h in 15.3Kg toluene and 5.1Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and
It is successively washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 300W carries out assisted reaction 2h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 9, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 75 DEG C
After 22h, then landfill leachate-tobacco stalk fiber element compound is added in 34.57Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 90 DEG C, 2h is stirred to react with the mixing speed of 700rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is that freezen protective 18h is carried out in -55 DEG C of ultra low temperature freezer that mold, which is placed in temperature, be shaped to radius 10mm,
The cylindrical body of height 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 4 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Embodiment 5
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 24Kg after filtering, cleaning is adjusted to 9, and 0.03Kg aluminum sulfate is then added, and
It, will after the completion of stirring after stirring 5min under 2400rpm revolving speed using agitating device, then with the revolving speed stirring 15min of 640rpm
Mixed solution staticly settles, then sediment filter out and is configured to solid content as 50% solution, and solution ph is adjusted
To 9；
(2) 15Kg is emedullated the cigarette stalk after core, smashes it through 20 meshes, then by after sieving cigarette stalk with by 6Kg hydroxide
The sodium hydroxide solution that the mass fraction that the dissolution of sodium solid particle is configured to is 2% mixes, and mixed solution is heated to 100
DEG C, after carrying out reaction 3h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 10min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 6h in 15Kg toluene and 5Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively
It is washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 150W carries out assisted reaction 4h, after the reaction was completed, solution is stood 5h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 10, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 80 DEG C
After 48h, then landfill leachate-tobacco stalk fiber element compound is added in 34.97Kg 1- allyl -3- methylimidazole villaumite,
And under conditions of 80 DEG C, 1.5h is stirred to react with the mixing speed of 650rpm and is poured the mixture into after the completion of stirring
In pattern tool, and mold is placed in the ultra low temperature freezer that temperature is -50 DEG C and carries out freezen protective for 24 hours, is shaped to radius
The cylindrical body of 10mm, height 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with acetone soln and is replaced 3 times, then will be passed through molten
The mixture of agent displacement is freeze-dried, and it is fine to can be prepared by landfill leachate of the counterweight metal ion with adsorptivity-cigarette stalk
Tie up plain base aeroge.
Embodiment 6
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 25Kg after filtering, cleaning is adjusted to 8, and 0.03Kg polyaluminium is then added
Aluminium, and after stir 3min under 2500rpm revolving speed using agitating device, then 10min, stirring completion are stirred with the revolving speed of 650rpm
Mixed solution is staticly settled afterwards, then sediment filter out and is configured to the solution that solid content is 40%, and by solution ph
It is adjusted to 7；
(2) 10Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5.4Kg hydrogen-oxygen
Change the mass fraction that the dissolution of sodium solid particle is configured to mix for 2% sodium hydroxide solution, and mixed solution is heated to 150
DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 15min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 6h in 18Kg toluene and 6Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively
It is washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 300W carries out assisted reaction 2h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 10, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 70 DEG C
After 36h, then landfill leachate-tobacco stalk fiber element compound is added in 35.57Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 85 DEG C, 3h is stirred to react with the mixing speed of 600rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is that freezen protective 12h is carried out in -75 DEG C of ultra low temperature freezer that mold, which is placed in temperature, be shaped to radius 10mm,
The cylindrical body of height 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 3 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Embodiment 7
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 27Kg after filtering, cleaning is adjusted to 8, and 0.05Kg ferric trichloride is then added,
And after utilizing agitating device to stir 3min under 2600rpm revolving speed, then with the revolving speed stirring 10min of 640rpm, after the completion of stirring
Mixed solution is staticly settled, then sediment filter out and is configured to the solution that solid content is 40%, and by solution ph tune
It saves to 8；
(2) 11Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5.95Kg hydrogen-oxygen
Change the mass fraction that the dissolution of sodium solid particle is configured to mix for 2% sodium hydroxide solution, and mixed solution is heated to 100
DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out 5min is discongested after again with toluene washing with Lampen mill to add it to by 15Kg
It carries out dipping 4h in toluene and 5Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively use second
Alcohol, distilled water are washed, and are washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 250W carries out assisted reaction 2h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 9, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 65 DEG C
After 28h, then landfill leachate-tobacco stalk fiber element compound is added in 36Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 70 DEG C, 2h is stirred to react with the mixing speed of 700rpm, after the completion of stirring, pours the mixture into molding die
In, and mold is placed in the ultra low temperature freezer that temperature is -65 DEG C and carries out freezen protective 19h, it is shaped to radius 10mm, height
Spend the cylindrical body of 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 5 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Embodiment 8
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 26Kg after filtering, cleaning is adjusted to 8, and 0.04Kg aluminum sulfate is then added, and
It, will after the completion of stirring after stirring 3min under 2900rpm revolving speed using agitating device, then with the revolving speed stirring 10min of 630rpm
Mixed solution staticly settles, then sediment filter out and is configured to solid content as 40% solution, and solution ph is adjusted
To 8；
(2) 10Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5Kg hydroxide
The sodium hydroxide solution that the mass fraction that the dissolution of sodium solid particle is configured to is 2% mixes, and mixed solution is heated to 100
DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out 5min is discongested after again with toluene washing with Lampen mill to add it to by 15Kg
It carries out dipping 5h in toluene and 5Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively use second
Alcohol, distilled water are washed, and are washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 120W carries out assisted reaction 4h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 10, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 60 DEG C
After for 24 hours, then landfill leachate-tobacco stalk fiber element compound is added in 38.96Kg 1- allyl -3- methylimidazole villaumite,
And under conditions of 65 DEG C, 1h is stirred to react with the mixing speed of 800rpm, after the completion of stirring, pours the mixture into molding
In mold, and mold is placed in the ultra low temperature freezer that temperature is -75 DEG C and carries out freezen protective 12h；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 4 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Embodiment 9
A kind of preparation method of heavy metal ion adsorbing material comprising following steps:
(1) the landfill leachate pH by 25Kg after filtering, cleaning is adjusted to 8, and 0.05Kg aluminum sulfate is then added, and
It, will after the completion of stirring after stirring 3min under 3000rpm revolving speed using agitating device, then with the revolving speed stirring 10min of 610rpm
Mixed solution staticly settles, then sediment filter out and is configured to solid content as 60% solution, and solution ph is adjusted
To 7；
(2) 11Kg is emedullated the cigarette stalk after core, smashes it through 14 meshes, then by after sieving cigarette stalk with by 5Kg hydroxide
The sodium hydroxide solution that the mass fraction that the dissolution of sodium solid particle is configured to is 2% mixes, and mixed solution is heated to 150
DEG C, after carrying out reaction 2h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 15min with Lampen mill, after again with toluene washing, add it to by
It carries out dipping 6h in 18Kg toluene and 6Kg epoxychloropropane mixed liquor, after dipping, solid content is filtered out again, and successively
It is washed with ethyl alcohol, distilled water, is washed till until cleaning solution is in neutrality, can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with
The power of 300W carries out assisted reaction 2h, after the reaction was completed, solution is stood 3h at normal temperature, then the solid content in solution is filtered
Out, it is washed and is impregnated with the sodium hydroxide solution that pH value is 10, until leachate is in colourless, can be prepared by rubbish infiltration
Filtrate-tobacco stalk fiber element compound；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 80 DEG C
After for 24 hours, then landfill leachate-tobacco stalk fiber element compound is added in 34.95Kg 1- butyl -3- methylimidazole villaumite, and
Under conditions of 65 DEG C, 1h is stirred to react with the mixing speed of 800rpm, after the completion of stirring, pours the mixture into shaping mould
In tool, and it is to carry out freezen protective for 24 hours in -50 DEG C of ultra low temperature freezer that mold, which is placed in temperature, be shaped to radius 10mm,
The cylindrical body of height 30mm；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution
Until being detected with silver nitrate without precipitating, then solvent is carried out to the mixture after washing with t-butanol solution and is replaced 3 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by landfill leachate-cigarette stalk that counterweight metal ion has adsorptivity
Cellulose base aeroge.
Performance test
Landfill leachate made from 0.5g Examples 1 to 9-tobacco stalk fiber element base aeroge is taken to be added separately to 1L concentration and be
In the lead ion of 50mg/L, copper ion and arsenic ion, after 25 DEG C of shaking tables concussions for 24 hours, detect lead ion in each solution, copper from
Son and arsenic ion residual concentration, and calculate landfill leachate-tobacco stalk fiber element base aeroge to lead ion, copper ion and arsenic from
The adsorption rate of son, acquired results are as follows:
The above is the embodiment of the present invention, for the ordinary skill in the art, religion according to the present invention
Lead, without departing from the principles and spirit of the present invention all equivalent changes done according to scope of the present invention patent, repair
Change, replacement and variant, is all covered by the present invention.
Claims (7)
1. a kind of preparation method of heavy metal ion adsorbing material, it is characterised in that: using landfill leachate as raw material, by itself and cigarette
The cellulose extracted in stalk carries out graft copolymerization and landfill leachate-tobacco stalk fiber compound is made, by landfill leachate-cigarette
After stalk fiber compound carries out gelation, then it is regenerated, the drying of exchange of solvent and supercritical carbon dioxide, be can be prepared by
There is landfill leachate-cigarette pole fiber element base aeroge of adsorptivity to heavy metal ion；Itself the following steps are included:
(1) after being filtered, cleaning by landfill leachate, its pH is adjusted to 7~9, coagulant is then added, and utilize stirring
After device stirs 3~5min with 2000~3000rpm, then with 500~650rpm, 10~15min of stirring, it will be mixed after the completion of stirring
Solution left standstill precipitating is closed, then sediment filter out and is configured to solution, and the solution ph of configuration is adjusted to 7~9；
(2) cigarette stalk is emedullated after core, smashes it through 14~20 meshes, then by after sieving cigarette stalk with by sodium hydrate solid particle
It dissolves the sodium hydroxide solution that the mass fraction being configured to is 2% to mix, and mixed solution is heated to 90~150 DEG C, carry out anti-
After answering 1~3h, the solid content in mixed solution is filtered out；
(3) the above-mentioned solid content filtered out is discongested into 5~15min with Lampen mill, after again with toluene washing, add it to toluene and
Carry out 4~6h of dipping in the mixed liquor of epoxychloropropane, after dipping, solid content filtered out again, and successively with ethyl alcohol, steam
Distilled water is washed, and is washed till until cleaning solution is in neutrality, be can be prepared by tobacco stalk fiber element；
(4) tobacco stalk fiber element obtained above is added in solution made from step (1), and using ultrasonic equipment with 100
The power of~300W carries out 2~5h of assisted reaction and solution is stood 3~5h at normal temperature, then will be in solution after the reaction was completed
Solid content filters out, and is washed and is impregnated with the sodium hydroxide solution that pH value is 9~11, until leachate is in colourless, i.e.,
Landfill leachate-tobacco stalk fiber element compound can be made；
(5) landfill leachate obtained above-tobacco stalk fiber element compound is dried in vacuo under conditions of 60~80 DEG C
After 24~48h, then landfill leachate-tobacco stalk fiber element compound is added in ionic liquid, and in 65~85 DEG C of condition
Under, 1~3h is stirred to react with the mixing speed of 600~800rpm, after the completion of stirring, pours the mixture into molding die
In, and it is that freezen protective 12~for 24 hours is carried out in -75~-50 DEG C of ultra low temperature freezer that mold, which is placed in temperature,；
(6) it by step (5) freezen protective and mixture after molding taking-up, and is washed with deionized water to cleaning solution nitre
Until sour silver detection is without precipitating, then solvent is carried out to the mixture after washing with non solvent liquid and is replaced 3~6 times, then will be passed through
The mixture of solvent displacement is freeze-dried, and can be prepared by the landfill leachate-cigarette stalk for having adsorptivity to heavy metal ion
Cellulose base aeroge；
Wherein, the addO-on therapy and mass fraction of each step are as follows:
Landfill leachate 24%~28%；
Coagulant 0.03%~0.05%；
Cigarette stalk 10%~15%；
Sodium hydroxide 5%~6%；
Toluene 15%~18%；
Epoxychloropropane 5%~6%；
Ionic liquid 34%~40%.
2. a kind of preparation method of heavy metal ion adsorbing material according to claim 1, it is characterised in that: it is described from
Sub- liquid is 1- butyl -3- methylimidazole villaumite or 1- allyl -3- methylimidazole villaumite.
3. a kind of preparation method of heavy metal ion adsorbing material according to claim 1, it is characterised in that: described is mixed
Solidifying agent is the polymer of molysite, aluminium salt or molysite and aluminium salt.
4. a kind of preparation method of heavy metal ion adsorbing material according to claim 1, it is characterised in that: the step
(1) the middle solution solid content configured using sediment is 40%~60%.
5. a kind of preparation method of heavy metal ion adsorbing material according to claim 1, it is characterised in that: the step
(5) pass through the cylindrical body that formed in mould mixture is radius 10mm, height 30mm in.
6. a kind of preparation method of heavy metal ion adsorbing material according to claim 1, it is characterised in that: described is non-
Solvent liquid is the tert-butyl alcohol or acetone.
7. a kind of application of heavy metal ion adsorbing material made from preparation method as described in claim 1, it is characterised in that:
Heavy metal ion adsorbing material is used for heavy metal ion adsorbed in landfill leachate.
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