CN102847519A - Composite absorbing material for removing chlorate in water and preparation method thereof - Google Patents
Composite absorbing material for removing chlorate in water and preparation method thereof Download PDFInfo
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- CN102847519A CN102847519A CN2012103419342A CN201210341934A CN102847519A CN 102847519 A CN102847519 A CN 102847519A CN 2012103419342 A CN2012103419342 A CN 2012103419342A CN 201210341934 A CN201210341934 A CN 201210341934A CN 102847519 A CN102847519 A CN 102847519A
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Abstract
The invention discloses a composite absorbing material for removing chlorate in water and a preparation method thereof and belongs to the field of sewage purification in environmental protection. The method uses activated carbon nanotube load vegetable fibers to remove chlorate in water. The method includes adding 1-1.5g/L absorbing material to the neutral sewage. Concentration of the chlorate is lower than 0.10g/L after absorption, so that chlorate ion in water can be removed effectively. The composite absorbing material has the advantages that the material is simple to operate, low in material cost and high in absorption efficiency, and has huge spaces inside and large specific surface area, part of the material can be recycled after absorption, water discharge is stable, discharged water can reach the standard and the like. Selection range of absorbent for wastewater biotreatment is widened, environment is protected, recycling of wastes is achieved, and fine environmental and economical benefits are achieved.
Description
Technical field
The present invention relates to a kind of composite adsorbing material and tool preparation method who removes chlorate anions in the water; the NEW TYPE OF COMPOSITE sorbing material that is specifically related to utilize vegetable fibers to load on and makes on the CNT is processed the method through the pretreated chloride acid group sewage of traditional physico-chemical process, belongs to the dirty water decontamination handles field in the environmental protection.
Background technology
No matter chloranion in acidity or alkaline solution, has strong oxidisability, and chloranion and common reproducibility ion cannot coexist in a large number.Such as CIO
-And Fe
2 +, S
2 -, HS
-, S0
3 2-, HS0
3 -Deng cannot coexisting in a large number because send out a dirt redox reaction.Chloride acid group waste water is the product of oxidant after being used for a plurality of neighborhood processings such as water treatment, fabric and association with pulp bleaching from chlorine mainly.Chlorate anions has strong oxidizing property, and stability is not high, and chlorate anions is similar to the molecular structure of nitrate anion, is the competitive inhibitor of nitrate reductase, can suppress the reduction process of nitric acid, and the utilization of blocking-up nitrate nitrogen simultaneously, also produces poisonous hypochlorite.
At present, generally use chemical precipitation method or electrolysis to process chloride acid group waste water on the engineering.The heavy catharsis of the chemistry plurality of advantages such as maturation, small investment, processing cost are low, strong adaptability, convenient management, automaticity height that possess skills, it is the conventional treatment method of chloride acid group sewage, but may introduce new ion in the processing procedure, cause secondary pollution.Electrolysis is processed chloride acid group waste water, by electrolysis chlorate anions is dissociated, and flow process is simple, but power consumption is large, is not suitable for a large amount of processing.
In recent years, when the further Improvement of the people development of evil in febrile disease precipitation method are closed electrolysis, turn to gradually bioanalysis, bioanalysis has efficient, energy-conservation, advantages of environment protection, become acid ion and recovered acid radical ions such as from waste water, removing chlorate anions, and will substitute gradually normal processing method, biosorption technology with its have adsorption capacity large, selective strong, efficient is high, consumption is few, can effectively process the sight that plurality of advantages such as containing low-level chlorinated acid group sewage has attracted numerous researchers.
The present invention is for obtaining a kind of non-living body biological adsorption agent of cheap, high adsorption capacity; a kind of NEW TYPE OF COMPOSITE sorbing material that utilizes vegetable fibers to load on to make on the CNT is provided; realized the comprehensive utilization of part house refuse; protected environment; widened the range of choice of biological wastewater treatment process absorption; realize the resource of discarded object, had good Social benefit and economic benefit.
Summary of the invention
The objective of the invention is for overcoming the deficiencies in the prior art, a kind of composite adsorbing material of removing chlorate anions in the water and preparation method thereof is provided, it is that vegetable fibers is foretold through the effect of 4-chloro-2-methyl aniline blowing agent, load on the NEW TYPE OF COMPOSITE sorbing material that makes on the CNT by polymerisation, it is high that the present invention has an adsorption efficiency, simple to operation, cost is low, stable water outlet reaches country's " integrated wastewater discharge standard ", the place is the characteristics such as process non-secondary pollution, take full advantage of the production discarded object, realized the effect of the treatment of wastes with processes of wastes against one another.
The objective of the invention is to be achieved through the following technical solutions:
Sorbing material of the present invention is lived on the CNT to make by the vegetable fibers load.
The CNT preparation method of the present invention's activation is:
(1) take natural gas as raw material, prepares the CNT crude product with the methane chemical vapour deposition technique;
(2) get 30～40g CNT crude product and put into 250mL, in the conical flask, the adding mass concentration is 20%～30%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 2h～3h, leave standstill 20h～24h, then filter, keep filter residue, with distilled water that the residue washing washing is extremely neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grind after the oven dry, obtain the purification of nanocarbon pipe powder;
(3) CNT behind the purifying is foretold calcining 30min～40min at 600 ℃～700 ℃ high temperature, the CNT that obtains activating is with the CNT grind into powder of activation.
The preparation method of vegetable fibers of the present invention is:
(1) take vegetable leaf as raw material, be after 40%～50%NaOH solution soaks 15h, to filter with mass concentration, the vegetable leaf after the immersion is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps thin dish, namely get vegetable fibers;
(2) be 100～100 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers grind into powder.
The method of nano-carbon tube load vegetable fibers of the present invention is: CNT and vegetable fibers are put into the stupid amine aqueous solution of mass concentration 40%～50%4-chloro-2-methyl by 2: 1 mass ratio soak 4h～5h, and constantly stir, then filter, be washed with distilled water to neutrality, be 120 ℃～150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
Described vegetables be Chinese cabbage, green vegetables, romaine lettuce, celery etc. one or several.
The principle of the invention is: the vegetable fibers of CNT area load is rich in hydroxyl, carboxyl isoreactivity group, these groups can provide lone pair electrons and chlorate anions surface to form complex compound and chelate, acid ion in the solution is adsorbed, the CNT internal voids is many, so that the adsorbance of sorbing material is greatly improved, thereby reach the purpose of from sewage, removing chlorate anions.
Tool this application method of the present invention is: the dosage with 1.0～1.5g/L joins composite adsorbing material in the pretreated 1mg/L of containing of traditional physico-chemical process～500mg/L chlorate anions sewage, and regulating pH is 6.0～7.0, standing adsorption 1～2h behind stirring 2～3h; The filtering adsorbent, pulp water separates, and chlorate anions content is lower than 0.10mg/L, effluent reuse or qualified discharge in the rear sewage of absorption; Chloride acid group waste residue can reclaim chlorate anions and CNT.
Beneficial effect of the present invention:
(1) the selected raw material vegetables of the present invention source is wide, and with low cost, processing procedure is simple, and excellent adsorption, removes chloranion efficient high;
Affected by pH little, adsorbance is large, and is water insoluble, can not produce new contaminated ion, and the part material can be recycled.
The specific embodiment
The technical solution used in the present invention is as follows:
(1) take natural gas as raw material, prepares the CNT crude product with the methane chemical vapour deposition technique;
(2) get 30～40g CNT crude product and put into the 250mL conical flask, the adding mass concentration is 20%～30%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 2h～3h, leave standstill 20h～24h, then filter, keep filter residue, with distilled water that the residue washing washing is extremely neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grind after the oven dry, obtain the purification of nanocarbon pipe powder;
(3) CNT behind the purifying is calcined 30min～40min under 600 ℃～700 ℃ high temperature, the nanometer alkali pipe that obtains activating is with the CNT grind into powder of activation;
(4) take vegetable leaf as former section, be after 40%～50%NaOH solution soaks 15h, to filter with mass concentration, the vegetable leaf after soaking is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps vegetables, namely get vegetable fibers;
(5) be 100～110 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers grind into powder;
(6) with CNT and vegetable fibers by 2: the mass ratio of l is put into mass concentration 40%～50%4-chloro-2-methyl aniline solution and is soaked 4h～5h, and constantly stir, then filter, be washed with distilled water to neutrality, be 120 ℃～150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
Described vegetables be Chinese cabbage, green vegetables, romaine lettuce, celery etc. one or several
Below describe again the present invention in detail with 3 embodiment:
Example 1
Take natural gas as raw material, prepare the CNT crude product with the methane chemical vapour deposition technique; Get 30g CNT crude product and put into the 250mL conical flask, the adding mass concentration is 20%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 3h, leave standstill 24h, then filter, keep filter residue, with distilled water residue washing is washed to neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grinding obtains the purification of nanocarbon pipe powder after the oven dry; CNT behind the purifying is calcined 30min under 600 ℃ of high temperature, the CNT that obtains activating is with the CNT grind into powder of activation; Take vegetable leaf as raw material,, filter for after soaking 15h for 40%NaOH Ji liquid with mass concentration, the vegetable leaf after soaking is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps vegetables, namely get vegetable fibers; Be 100～110 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers wood of pulverizing; CNT and vegetable fibers are put into mass concentration 40%4-chloro-2-methyl aniline solution by 2: 1 mass ratio soak 4h, and constantly stir, then filter, be washed with distilled water to neutrality, be 150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
Getting this sorbing material of 0.5g, to put into volume be that 500mL concentration is the waste water that 100mg/L contains chlorate anions, and regulating pH is 6.0～7.0, stirs standing adsorption 1h behind the 2h; , after the absorption in the water chlorate anions contain and be lower than 0.02mg/L most.
Example 2
Take natural gas as raw material, prepare the CNT crude product with the methane chemical vapour deposition technique; Get in the 35g CNT crude product income 250mL conical flask, the adding mass concentration is 25%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 3h, leave standstill 24h, then filter, keep filter residue, with distilled water residue washing is washed to neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grinding obtains the purification of nanocarbon pipe powder after the oven dry; CNT behind the purifying is calcined 30min under 650 ℃ of high temperature, the CNT that obtains activating is received water carbon pipe grind into powder with activation; Take vegetable leaf as raw material, be after 45%NaOH solution soaks 15h, to filter with mass concentration, the vegetable leaf after soaking is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps vegetables, namely get vegetable fibers; Be 100～110 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers grind into powder; With CNT and vegetable fibers by 2: the mass ratio of l is put into mass concentration 40%4-chloro-2-methyl aniline solution and is soaked 5h, and constantly stir, then filter, be washed with distilled water to neutrality, be 150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
Getting this sorbing material of 0.6g, to put into volume be that 500mL concentration is the waste water that 250mg/L contains chlorate anions, and regulating pH is 6.0～7.0, stirs standing adsorption 2h behind the 2h:, after the absorption in the water chlorate anions content be lower than 0.05mg/L
Example 3
Take large right gas as raw material, prepare the CNT crude product with the methane chemical vapour deposition technique: get 40g CNT crude product and put into the 250mL conical flask, the adding mass concentration is 30%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 3h, leave standstill 24h, then filter, keep filter residue, with distilled water that residue washing is extremely neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grind after the oven dry, obtain the purification of nanocarbon pipe powder; CNT behind the purifying is calcined 40min under 700 ℃ of high temperature, the CNT that obtains activating is with the CNT grind into powder of activation; Take vegetable leaf as raw material, be after 50%NaOH solution soaks 15h, to filter with mass concentration, the vegetable leaf after soaking is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps vegetables, namely get vegetable fibers; Be 100～110 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers grind into powder: CNT and vegetable fibers are soaked 5h than putting into mass concentration 50%4-chloro-2-methyl aniline solution by 2: 1 matter, and constantly stir, then filter, be washed with distilled water to neutrality, be 150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
Getting this sorbing material of 0.7g, to put into volume be that 500mL concentration is the waste water that 500mg/L contains chlorate anions, and regulating pH is 6.0～7.0, stirs standing adsorption 2h behind the 3h; , chlorate anions content is lower than 0.03mg/L in the rear water of absorption.
Claims (5)
1. composite adsorbing material of removing chlorate anions in the water and preparation method thereof, it is characterized in that: this sorbing material vegetable fibers loads on the CNT and makes.
2. a kind of composite adsorbing material preparation method who removes chlorate anions in the water according to claim 1 is characterized in that the CNT preparation method who activates is:
(1) take natural gas as raw material, prepares the CNT crude product with the methane chemical vapour deposition technique;
(2) get 30～40g CNT crude product and put into the 250mL conical flask, the adding mass concentration is 20%～30%HNO
3In the solution, with the conical flask sealing, use sonic oscillation 2h～3h, leave standstill 20h～24h, then filter, keep filter residue, with distilled water that the residue washing washing is extremely neutral, filter residue is 105～110 ℃ in temperature dries to constant weight, grind after the oven dry, obtain the purification of nanocarbon pipe powder;
(3) nano-sized carbon behind the purifying is kept a grip under 600 ℃～700 ℃ high temperature and calcined 30min～40min, the CNT that obtains activating is with the CNT grind into powder of activation.
3. a kind of composite adsorbing material preparation method who removes chlorate anions in the water according to claim 1 is characterized in that the vegetable fibers preparation method is:
(1) take vegetable leaf as raw material, be after 40%～50%NaOH solution soaks 15h, to filter with mass concentration, the vegetable leaf after soaking is cleaned in distilled water to neutral, and remove the stem that mesophyll keeps vegetables, namely get vegetable fibers;
(2) be 100～110 ℃ of oven dry with vegetable fibers in temperature, with the vegetable fibers grind into powder.
4. a kind of composite adsorbing material preparation method who removes chlorate anions in the water according to claim 1, the method that it is characterized in that the nano-carbon tube load vegetable fibers is: CNT and vegetable fibers are put into mass concentration 40%～50%4-chloro-2-methyl aniline solution by 2: 1 mass ratio soak 4h～5h, and constantly stir, then filter, be washed with distilled water to neutrality, be 120 ℃～150 ℃ in temperature and dry to constant weight, make the NEW TYPE OF COMPOSITE sorbing material.
5. a kind of composite adsorbing material preparation method who removes chlorate anions in the water according to claim 2, it is characterized in that: described chemical vapour deposition technique refers to utilize gas-phase reaction, under the conditions such as high temperature, plasma or laser assisted, control the factors such as reaction pressure, air-flow velocity, substrate material temperature, thus the nucleating growth process of control nanoparticle film.
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|---|---|---|---|
| CN201210341934.2A CN102847519B (en) | 2012-09-04 | 2012-09-04 | Composite absorbing material for removing chlorate in water and preparation method thereof |
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| CN201210341934.2A CN102847519B (en) | 2012-09-04 | 2012-09-04 | Composite absorbing material for removing chlorate in water and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944009A (en) * | 2017-04-13 | 2017-07-14 | 广西壮族自治区环境保护科学研究院 | A kind of high-efficiency adsorbent and its application in heavy metal wastewater thereby |
| CN109289784A (en) * | 2018-10-22 | 2019-02-01 | 北京科技大学 | Utilize garlic stalk waste production fluorine removal compounding adsorbent material and application method |
| CN109999768A (en) * | 2019-05-05 | 2019-07-12 | 河北工业大学 | A kind of stalk base composite absorbent purified for chlorinated aromatic hydrocarbons in incineration flue gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101601992A (en) * | 2009-06-30 | 2009-12-16 | 同济大学 | A kind of preparation and using method thereof with the CTAB modified absorbing material |
| CN102424448A (en) * | 2011-11-01 | 2012-04-25 | 同济大学 | Method for removing perchlorate in water |
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2012
- 2012-09-04 CN CN201210341934.2A patent/CN102847519B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101601992A (en) * | 2009-06-30 | 2009-12-16 | 同济大学 | A kind of preparation and using method thereof with the CTAB modified absorbing material |
| CN102424448A (en) * | 2011-11-01 | 2012-04-25 | 同济大学 | Method for removing perchlorate in water |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944009A (en) * | 2017-04-13 | 2017-07-14 | 广西壮族自治区环境保护科学研究院 | A kind of high-efficiency adsorbent and its application in heavy metal wastewater thereby |
| CN106944009B (en) * | 2017-04-13 | 2019-10-11 | 广西壮族自治区环境保护科学研究院 | A kind of high-efficiency adsorbent and its application in heavy metal wastewater thereby |
| CN109289784A (en) * | 2018-10-22 | 2019-02-01 | 北京科技大学 | Utilize garlic stalk waste production fluorine removal compounding adsorbent material and application method |
| CN109999768A (en) * | 2019-05-05 | 2019-07-12 | 河北工业大学 | A kind of stalk base composite absorbent purified for chlorinated aromatic hydrocarbons in incineration flue gas |
| CN109999768B (en) * | 2019-05-05 | 2020-01-07 | 河北工业大学 | Straw-based composite adsorbent for purifying chlorinated aromatic hydrocarbons in incineration flue gas |
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| CN102847519B (en) | 2014-05-07 |
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Inventor after: Lei Chunsheng Inventor after: Wang Qing Inventor after: Chen Xingquan Inventor after: Mi Hao Inventor before: Chen Xingquan Inventor before: Lei Chunsheng Inventor before: Mi Hao |
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