CN108079960A - A kind of netted quaternary amine base anion adsorbent - Google Patents
A kind of netted quaternary amine base anion adsorbent Download PDFInfo
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- CN108079960A CN108079960A CN201611038557.XA CN201611038557A CN108079960A CN 108079960 A CN108079960 A CN 108079960A CN 201611038557 A CN201611038557 A CN 201611038557A CN 108079960 A CN108079960 A CN 108079960A
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- quaternary amine
- amine base
- netted
- base anion
- luffa
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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
- B01J20/28042—Shaped bodies; Monolithic structures
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of netted quaternary amine base anion adsorbent, using luffa as raw material, it invents and etherificate crosslinking technology is used to prepare quaternary amine base anion exchange absorbing agent, luffa is by etherificate graft modification, its nitrogen content increases to 4.44% from 0.6%, the optimal adsorption pH that modified product has been successfully introduced into amine groups anion exchange absorbing agent is 3~10, and anion exchange absorbing agent is to NO3 ‑Absorption be monolayer adsorption and the anion exchange absorbing agent that is carried out at the same time of multilayer absorption to NO3 ‑With higher selectivity, the product after adsorbing that has a good application prospect in terms of lake water denitrogenation can be regenerated with the HCl solution of 0.1mol/L, can at least recycled 5 times.
Description
Technical field
The present invention relates to a kind of adsorbent more particularly to a kind of netted quaternary amine base anion adsorbents.
Background technology
Eutrophication is one of severe water pollution problems that the world today faces, and causes river, river and lake storehouse water environment matter
Amount is worsening, and aquatic ecosystem is seriously destroyed.The technology for being presently used for denitrogenation processing mainly has:It is reverse osmosis
Method, electro-osmosis method, chemical reduction method, biological denitrificaion method and absorption method etc..Hyperfiltration and chemical reduction method processing cost are higher;It is raw
Object denitrogenation is easily influenced by influent quality, and operational management is complicated;Absorption denitrogenation rule equipment is simple, stable, small investment,
Thus receive significant attention.
The main component of luffa has cellulose, hemicellulose and lignin, and content of cellulose is up to 65%.Luffa
As natural gauze bio material, there is unique porosity physical arrangement and excellent mechanical strength, utilize this feature
Cellular functional fiber material is can be made into, is not easy to plug as absorption column packing, and easily biological-degradable, regeneration efficiency
Height is recycled conveniently, with good application prospect.Luffa is with not only hydrophilic but also oleophylic amphipathic chemical constitution and solely
Special space physics structure prepares fibrous material using it as matrix with higher researching value.
The content of the invention
The purpose of the invention is to carry out denitrogenation processing, a kind of netted quaternary amine base anion adsorbent is devised.
The technical solution adopted by the present invention to solve the technical problems is:
Netted quaternary amine base anion adsorbent to prepare raw material as follows:Epoxychloropropane, n,N-Dimethylformamide (DMF), second
Diamines (EDA), triethylamine, NaOH and KNO3(top pure grade).
Netted quaternary amine base anion adsorbent to prepare preprocess method as follows:It is by raw material luffa immersion mass fraction
In 10% NaOH solution, cleaned after impregnating 12h with pure water to neutrality, dry drying, the fritter of 1cm × 1cm or so is made, it is standby
With.
The preparation method of netted quaternary amine base anion adsorbent is as follows:Take the luffa weighed, 120mLN, N- dimethyl methyls
In three-necked flask, temperature is controlled at 85 DEG C for amide and 60mL epoxychloropropane, stirs 1h;8mL crosslinking agents are added in, the reaction was continued
Then 1h adds in 10mL amination reagents and carries out graft reaction, pours out product rapidly after reacting 2h, and cleaned with distilled water into water
Without residue, drying in baking oven is placed in, obtains quaternary amine base anion exchange absorbing agent.
The luffa passes through etherificate-graft modification, and nitrogen content increases to 4.44% from 0.6%, modified product
Amine groups are successfully introduced into, the optimal adsorption pH of the anion exchange absorbing agent is 3~10.
The beneficial effects of the invention are as follows:
Netted quaternary amine base anion adsorbent is to NO3 -Absorption be monolayer adsorption and multilayer absorption be carried out at the same time, to NO3 -Tool
There is higher selectivity, therefore it has a good application prospect in terms of lake water denitrogenation, the product after absorption can use 0.1mol/
The HCl solution regeneration of L, can at least recycle 5 times.
Specific embodiment
Case study on implementation 1:
Netted quaternary amine base anion adsorbent to prepare raw material as follows:Epoxychloropropane, n,N-Dimethylformamide (DMF), second
Diamines (EDA), triethylamine, NaOH and KNO3(top pure grade).Netted quaternary amine base anion adsorbent prepares preprocess method such as
Under:Raw material luffa is immersed in the NaOH solution that mass fraction is 10%, cleaned after impregnating 12h with pure water to neutrality, drying is done
It is dry, the fritter of 1cm × 1cm or so is made, it is spare.The preparation method of netted quaternary amine base anion adsorbent is as follows:Take what is weighed
In three-necked flask, temperature is controlled at 85 DEG C for luffa, 120mLN, dinethylformamide and 60mL epoxychloropropane, stirring
1h;8mL crosslinking agents are added in, then the reaction was continued 1h adds in 10mL amination reagents and carries out graft reaction, poured out rapidly after reacting 2h
Product, and cleaned with distilled water into water without residue, drying in baking oven is placed in, obtains quaternary amine base anion exchange absorbing agent.
Case study on implementation 2:
Luffa and product amplify 1000 times after raw material luffa, alkali process, carry out SEM Analysis of Surface Topography.As a result and analyze:
Before alkali process, loofah fiber surface is relatively rough, and surface is also covered with fraction of impurity particle.After alkali process, due to chemistry
Effect eliminates the lignin, hemicellulose and impurity on surface, and luffa surface becomes smooth, and the degree of order of fiber is carried
It is high.Alkali process causes the cellulose in luffa to be exposed, and substantially increases its reactivity.Product shows many small
Hole, this is because the vigorous reaction of crosslinking agent so that luffa surface portion is destructurized.It follows that modified silk
Melon network has bigger difference in states of matter with former luffa, and product has a large amount of apertures, so as to add contact area, is conducive to inhale
It is attached.Its monofilament specific surface area is measured to the luffa after before modified.The result shows that the monofilament specific surface area of raw material luffa is
0.4594m2/g, the monofilament specific surface area of product is 0.2545m2/g.The specific surface area of modified luffa monofilament reduces instead,
This is because graft reaction occurs for modifying agent and the functional group on luffa surface in modifying process, cause the hole knot of luffa
Structure blocks.Luffa before modified after C, H content variation be not it is obvious that but N content change significantly, this is because
During luffa is modified, luffa occurs nucleophilic substitution with aminating agent and introduces amine groups, so that product
N content be significantly increased.FTIR atlas analysis is carried out to the luffa after before modified, luffa raw material is in 3406cm- 1Place has
Strong vibration, and absworption peak is wider, this is-OH vibrations, illustrates to contain more hydroxyl in raw material;Modified loofah sponge exists
2914cm- 1Locate C-H stretching vibrations for saturation;In 1632cm- 1Locate as N-H bending vibrations;In 1401cm- 1Locate to stretch for C-N
Contracting vibration, shows that triethylamine has been grafted on luffa.It is nitrogenous to can be seen that product introduces with reference to FTIR collection of illustrative plates, elemental analysis
Group, by containing quaternary amine base in reaction mechanism map analysis product.There are the tertiary amine group of positively charged in the ion exchange absorbent,
And outside includes one layer of electronegative Cl-, place it in solution, Cl-Gravitation between tertiary amine group is it is possible that be attenuated to
Cl-By the degree that other anion such as nitrate is substituted in solution, at this time since electrostatic attraction is acted on harmful anion such as
Nitrate Adsorption, it is seen that the adsorption process is ion exchange absorption.
Case study on implementation 3:
Test influences of the pH of solution to anion exchange absorbing agent adsorption effect.As a result and analyze:When pH value of solution is increased to by 2
When 3, removal rate increased dramatically by 35% to 84%;When pH is changed to 10 by 3, NO3 -Removal rate variation it is little, but be above 80%;
Afterwards as pH is raised, NO3 -Removal rate drops to 11% instead.Its reason may be:During pH < 3, H+ concentration is higher, product
Effective adsorption potential is by a large amount of H+It occupies, adsorption efficiency is low;As pH is raised, H+Concentration reduces, and effective adsorption potential of product is released
Out, adsorption efficiency improves;When pH is increased to 11, substantial amounts of OH is contained in solution-, OH-And NO3 -Generation competitive Adsorption, leads
Cause NO3 -Removal rate reduces.
Case study on implementation 4:
Under the conditions of investigating different temperatures (20 DEG C, 30 DEG C, 40 DEG C), influence of the anion exchange absorbing agent to the absorption of NO-3.Knot
3 adsorption isotherms of fruit and analysis tend to be steady after Ce is more than 200mg/L, reach maximum.In the low concentration range,
3 curves essentially coincide, and temperature change is for NO3 -Removal effect influence it is little;With the rise of initial concentration, adsorption capacity
It is reduced with the rise of temperature.Ion exchange absorbent is to NO3 -Absorption with Langmuir isotherm models or can both can use
Freundlich isotherm adsorption models describe, and it is that mono layer adsorption and multilayer absorption are simultaneous to illustrate the absorption.
Maximum monolayer adsorption capacity Qmax is reduced with the rise of temperature in Langmuir thermoisopleth parameters, illustrates that the adsorption process is
It is exothermic.
Case study on implementation 5:
In the NO-3 solution for being 2mg/L in initial concentration, add in containing NO2 -And Cl-Solution, make its concentration for 3mg/L, adjust
PH=7 of solution.0.1g products are taken, the coexisting in solution of 200mL is placed in, measures the adsorption rate of each anion respectively, it is right to investigate its
NO is adsorbed in anion exchange absorbing agent3 -The influence of effect.The result shows that anion exchange absorbing agent is to NO3 -、NO2 -And Cl-'s
Removal efficiency is respectively 71.5%, 20.1% and 10.3%, and NO3 -Removal efficiency during individualism is 97%, it is seen that product pair
NO-3 has higher adsorption selectivity, and handling nitrogenous lake water using the ion exchange absorbent, there is certain environment to anticipate
Justice.
Case study on implementation 6:
The anion exchange absorbing agent of adsorption saturation is put into the HCl solution of 30mL0.1mol/L and carries out desorption experiment.
As a result and analyze:It can be seen that after 5 times recycle, adsorption efficiency reduces seldom, drops to 89% from 96%, i.e. the anion exchange
Adsorbent can at least recycle 5 times or more.
Claims (5)
1. a kind of netted quaternary amine base anion adsorbent to prepare raw material as follows:Epoxychloropropane, n,N-Dimethylformamide
(DMF), ethylenediamine (EDA), triethylamine, NaOH and KNO3(top pure grade).
2. netted quaternary amine base anion adsorbent according to claim 1, it is characterized in that preprocess method is as follows:By raw material
Luffa is immersed in the NaOH solution that mass fraction is 10%, is cleaned after impregnating 12h with pure water to neutrality, is dried drying, be made
The fritter of 1cm × 1cm or so, it is spare.
3. netted quaternary amine base anion adsorbent according to claim 1, it is characterized in that preparation method is as follows:Take what is weighed
In three-necked flask, temperature is controlled at 85 DEG C for luffa, 120mLN, dinethylformamide and 60mL epoxychloropropane, stirring
1h;8mL crosslinking agents are added in, then the reaction was continued 1h adds in 10mL amination reagents and carries out graft reaction, poured out rapidly after reacting 2h
Product, and cleaned with distilled water into water without residue, drying in baking oven is placed in, obtains quaternary amine base anion exchange absorbing agent.
4. netted quaternary amine base anion adsorbent according to claim 1, it is characterized in that the luffa process etherificate-
Graft modification, nitrogen content increase to 4.44% from 0.6%, and modified product has been successfully introduced into amine groups.
5. netted quaternary amine base anion adsorbent according to claim 1, it is characterized in that the anion exchange absorbing
The optimal adsorption pH of agent is 3~10.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113210023A (en) * | 2021-04-29 | 2021-08-06 | 黄山学院 | Biochar-based anion exchanger and preparation method and application thereof |
CN113774673A (en) * | 2021-08-23 | 2021-12-10 | 安安(中国)有限公司 | Processing method of super-simulation leather artificial synthetic leather |
CN115672282A (en) * | 2022-10-13 | 2023-02-03 | 青岛科技大学 | Preparation method of simple and reproducible biogas residue-based anion adsorbent |
-
2016
- 2016-11-23 CN CN201611038557.XA patent/CN108079960A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113210023A (en) * | 2021-04-29 | 2021-08-06 | 黄山学院 | Biochar-based anion exchanger and preparation method and application thereof |
CN113774673A (en) * | 2021-08-23 | 2021-12-10 | 安安(中国)有限公司 | Processing method of super-simulation leather artificial synthetic leather |
CN113774673B (en) * | 2021-08-23 | 2023-12-15 | 安安(中国)有限公司 | Processing method of super-imitation leather artificial synthetic leather |
CN115672282A (en) * | 2022-10-13 | 2023-02-03 | 青岛科技大学 | Preparation method of simple and reproducible biogas residue-based anion adsorbent |
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Application publication date: 20180529 |