CN109550489A - The preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water - Google Patents
The preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water Download PDFInfo
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- CN109550489A CN109550489A CN201811467524.6A CN201811467524A CN109550489A CN 109550489 A CN109550489 A CN 109550489A CN 201811467524 A CN201811467524 A CN 201811467524A CN 109550489 A CN109550489 A CN 109550489A
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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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
- B01J20/28023—Fibres or filaments
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
Abstract
The present invention relates to a kind of preparation methods of the ion-exchange fibre of ammonia nitrogen in absorption waste water, include the following steps: that the plant Zea mays fruit after 1) normal growth is mature, by corn rod threshing, becomes corncob after natural air drying or drying.Corncob is put into baking oven to complete dehydration, the cylindric of 5cm or so is cut into, obtains the column corncob of uniform specification.2) the column corncob got ready is pre-processed with method in attached drawing；3) it activates；4) modified；5) it is grafted；6) cleaning, drying obtains ion-exchange fibre.Compared with the preparation approach of existing ion-exchange fibre, raw material are conveniently easy to get, and preparation process is simple and clear, and time-consuming short, energy consumption is few, and preparation cost is low, and product absorption property is good, are suitble to commercial introduction.
Description
Technical field
The present invention relates to a kind of preparation method of the ion-exchange fibre of ammonia nitrogen in absorption waste water, in particular to a kind of utilizations
The method that agricultural by product corncob prepares natural plants ion-exchange fibre.
Background technique
Ion-exchange fibre (ion exchange fibers, IEF) is the adsorption and separation material of a fibre-like
Material, the exchangeable ion and certain same sex ions dissociated mainly by the surface active groups of fiber or fibrous polymer into
Row exchange, compared with traditional ion exchange resin, IEF has large specific surface area, and chemical stability is higher, mass transfer apart from short,
Absorption and desorption rate are fast, and adsorptive selectivity is strong (to the absorption with higher such as metal ion, small organic molecule, pernicious gas
Selectivity), thoroughly, elution and power of regeneration are strong for purification, many advantages, such as low energy consumption, and fluid resistance is small and bioactivity is high.It is existing
It is widely used to water process, the isolation of purified of gas, the recycling of precious metal ion, the separation of drug and extraction and life
The fields such as materialization work, are the rapid new high-tech industries of Developing, constantly bringing forth new ideas and improving with preparation method, IEF's
Application prospect is more wide.
In addition, the special feature that ion-exchange fibre also has development and application various informative, can be made fiber, short fibre
The forms such as dimension, fabric, non-woven cloth, felt, net, therefore can be applied to the ion exchange process of various different conditions.CN
1262706C reports a kind of preparation method of ion-exchange fibre and its fabric in closed reactor, and fabric product has
The ability and power of regeneration of superpower absorption pernicious gas (sulfur dioxide, ammonia, hydrogen fluoride, hydrogen chloride), have good economy
With social benefit.101736525 A of CN discloses a kind of method of non-woven cloth by ion-exchange fibre preparation, this is non-to knit
Cotton material is made applied in the absorbent device of super absorbent polymer, the water absorbent rate of super absorbent polymer can be greatly improved, into
And the usage amount of super absorbent polymer in absorbent device is reduced, economic benefit and actual benefit significantly improve.CN
101036897A is disclosed using crop waste fiber rice straw, corn stover, useless flax silk, waste cotton and is prepared anionite
Method, preparation process is simple, low raw-material cost, be particularly suitable for be used to handle anion-containing waste water.
Research for ion-exchange fibre, in west, American-European countries, Japan, the former Soviet Union are research hotspots, have been possessed
Many research reports and achievement.Wherein the research of the Japanese and former Soviet Union is relatively early and research is more, such as Japanese TIN and Russia
VION, FIBAN etc. formd the product including seriations such as anion, cation, both sexes, chelatings.In RU1658444
In, be prepared for the Fibriform adsorbents containing carboxyl and diazanyl, in gas ammonia and ammonium nitrate have higher purification efficiency.In state
Interior, the seventies begin to expand the development of ion exchange fiber material and using work, Zhongshan University, Beijing Institute of Technology, river
The mechanisms such as southern fine chemistry industry key lab, Beijing Institute of Clothing Tech have successively developed a variety of different ion-exchange fibres
Material, and have some products practical application in each different field.As CN 1112257C relates to a kind of use
The method that sweller and free radical protective agent produce ion-exchange fibre, product exchange capacity are up to 3.0~5.0 mMs often
Gram, at low cost, long service life and no pollution to the environment.CN 105688835A is disclosed a kind of to be gone using cotton stem as raw material
Except the adsorbent material and preparation method thereof of ammonia nitrogen in solution, the biological carbon adsorbent of this method production, the suction to ammonia nitrogen in solution
Attached amount is up to 209.4mg/g, and by the modified adsorbent of aqueous slkali, ammonia nitrogen absorption amount can achieve 518.9mg/g.But it should
It is costly that method carries out anoxic firing to cotton stem, and easily pollutes the environment during the high temperature treatment process.CN
105561935A and CN 105561936A is proposed respectively using lotus leaf and sweet osmanthus leaf as cellulosic material, in isopropanol, NaOH solution
Under the modification of citric acid solution, be prepared into plant cellulose modified absorbing material absorption waste water in heavy metal.The preparation work
Skill is simple, high production efficiency, but it is mainly for the processing of heavy metal in waste water, aldehyde radical, hydroxyl and mercaptan etc. in the material
There is also absorption and complexing, this method not to refer to the ammonia nitrogen in waste water for functional group.
The major processes of ion-exchange fibre are prepared currently with natural plants raw material or composite fibre materials
Identical as above-mentioned process or compound use is further improved on the basis of these methods.Wherein utilize natural plants
Raw material prepare the raw material of natural plants base ion-exchange fibre just like agricultural product, agricultural and sideline product, agricultural wastes, other plant
Deng, such as stalk, rice husk, pericarp, linen-cotton etc..Their main component is cellulose, also contains hemicellulose, lignin and fruit
Glue.
In practical applications, though preparation keeps the technique simplicity of the ion-exchange fibre of complete physical structure, it is handed over
The utilization efficiency for changing capacity and product is lower than graininess ion-exchanger and powdered ion exchange material, and industrial applications are deposited
Certain restricted, further decrease research and development preparation cost and further increase the service efficiency of product and service life be from
The developing direction of sub- exchange fiber.
Corn (Classification system: Zea mays L.) is grass family Zea annual herb plant.Alias: maize,
Ear of maize, maize, corn, corn, maize, maize, maize, luxuriant reed, big sorgo, belong to annual tall and big draft.
Corncob also known as corncob, to be commonly called as " ear of maize bone, " be core remained by corn threshing.It is processed into powder, is had
There are stronger frictional property, nontoxicity, chemical stability, quality harder and high resilience, biodegradability, therefore can be used to
The dry products such as metal or plastics are wiped, can be ground more bright；It can be used for feed industry；Be a kind of fabulous medicine,
Chemical industry carrier；It can also be applied to rubber industry.Most importantly it has adsorptivity, is that one kind has expansionary active carbon very much
Resource.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of the ion-exchange fibre of ammonia nitrogen in absorption waste water, this method
Have the characteristics that at low cost, absorption property is good.
To achieve the above object, the technical solution used in the present invention is: a kind of ion exchange for adsorbing ammonia nitrogen in waste water
The preparation method of fiber, includes the following steps:
1) the plant Zea mays fruit after normal growth is mature, by corn rod threshing, makes it after natural air drying or drying
As corncob；Corncob is put into baking oven to complete dehydration, is cut into the column corncob of uniform specification (preferably
5cm's or so is cylindric)；
2) the cylindric corncob got ready is pre-processed with two methods of one of following methods:
A) by the cylindric corncob got ready crush crusher machine, obtain powdered corncobs, by corncob
Powder, which is dipped into distilled water, stirs 45min, removes the sundries on corncob powder surface, then dries it in 50~70 DEG C of baking ovens
Dry 3-6h, obtains the completely corncob powder without floating dust；
B) the cylinder corncob got ready is sawn into the fan-shaped cylinder that height is 2~3cm, obtains fan-shaped corncob
Axis places it in 6~8h of immersion in distilled water；It is then placed into 60~80 DEG C of baking ovens and dries 12h, obtain the dry corn of fritter
Cob；
3) it activates: weighing 10g corncob powder, place it in 50~75ml n,N-Dimethylformamide (DMF) and 20-
In the mixed solution of 80ml epoxychloropropane, 0.5~1h is stirred under 40~90 DEG C of condition of water bath heating；
4) modified: 20~50ml pyridine solution is added and makees modifying agent, continues 40~90 DEG C of 0.5~1h of heating water bath；
5) it is grafted: 20~40ml glycidyl methacrylate (GMA) monomer (concentration 20vol.%) is added, continue
80~100 DEG C of 6~8h of heating water bath, the maize cob meal (preliminary product) after being grafted；
6) it cleans:
A) maize cob meal after grafting is cooling (being cooled to 20 DEG C or less), 2~3 are eluted with the liquid alkaline solution of 0.2mol/L
It is secondary, then be placed in the liquid alkaline solution that 200ml concentration is 0.1mol/L, heating water bath 20min and strength under the conditions of 40~45 DEG C
It stirs (removing removal of residue, part carbohydrate and protein)；
B) by above-mentioned steps 6) a) obtained maize cob meal is eluted 2~3 times with 0.2mol/L hydrochloric acid solution, then is placed in
In 200ml, 0.1mol/L hydrochloric acid solution, heating water bath 20min and strong stirring under the conditions of 40~45 DEG C adjust pH into
Property；
C) by above-mentioned steps 6) b) obtained maize cob meal with concentration be 30wt% ethanol solution elute 2~3 times, then
It is placed in 200ml, in the ethanol solution that concentration is 30wt%, simultaneously strong stirring 10min (is gone heating water bath under the conditions of 40~45 DEG C
Except remaining organic reactant in preceding step)；
D) by above-mentioned steps 6) c) obtained maize cob meal is eluted 2~3 times with 0.01mol/L sodium chloride solution, then is set
Enter in 500ml, 0.01mol/L sodium chloride solution, heating water bath and 5~10min of strong stirring, obtain under the conditions of 40~45 DEG C
Maize cob meal after cleaning；
7) by the maize cob meal after cleaning in drying 6~12h under the conditions of 65~75 DEG C, powdered/blocky ion is obtained
Exchange fiber (final products are sealed in drier, spare).
The beneficial effects of the present invention are: in the plantation substantial amounts of China's corn, and corncob belongs in peasant's eye
Discarded object, therefore ion-exchange fibre is prepared to develop for raw material using corncob, with existing ion-exchange fibre system
Standby raw material has the characteristics of (waste utilization) at low cost, materials convenient and environmentally friendly (no pollution to the environment) compared with technology.
Natural plants ion-exchange fibre is prepared as raw material using the waste corncob of crops, has opened up natural plants
Ion-exchange fibre prepares the type and preparation approach of raw material, compared with the preparation approach of existing ion-exchange fibre, prepares work
Skill is simple and clear, and time-consuming short, energy consumption is few, and preparation cost is low, and absorption property is good, is suitble to commercial introduction.
Further, the strong stirring refers to that speed of agitator is 300~400r/min.
Product is cleaned in the way of the progress simultaneously of heating water bath electric stirring or heating water bath and magnetic agitation
Decolourize de- slag.
Further, in lessivation, glass apparatus sand core funnel or filter funnel, preferred sand core leakage is utilized
Bucket.
Detailed description of the invention
Fig. 1 is the preparation method process flow chart of the ion-exchange fibre of ammonia nitrogen in the absorption waste water of the embodiment of the present invention.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
Embodiment 1:
As shown in Figure 1, a kind of preparation method for adsorbing the ion-exchange fibre of ammonia nitrogen in waste water, it includes the following steps:
1) the plant Zea mays fruit after normal growth is mature, by corn rod threshing, makes it after natural air drying or drying
As corncob.Corncob is put into baking oven to complete dehydration, the cylindric of 5cm or so is cut into, obtains uniform specification
Column corncob.
2) the cylindric corncob got ready is pre-processed: with crusher machine is crushed, obtains powdered corncobs, it will
Corncob powder be dipped into distilled water and stir 45min, the sundries on corncob powder surface is removed, then by it in 50~70
3-6h is dried in DEG C baking oven, obtains the completely corncob powder without floating dust；
3) it activates: weighing the dry maize cob meal of 10g, be put into the tool plug flask with three necks,round bottom of 1L, two sides of three-necked flask
Mouth is clogged with glass stopper and (note: only opens plug when needing to be added drug, continue beyond the Great Wall after adding drug, entirely react
So operation in the process), electric mixer is protruded into from the main mouth of three-necked flask, is added from the small glass funnel of three-necked flask side port
50ml n,N-Dimethylformamide (DMF) solution, 30ml epoxychloropropane solution, unlatching electric stirring are persistently stirred molten
Liquid (reacts, revolving speed stirs in 60~80r/min, entire reaction process not to be stopped) so that maize cob meal comes into full contact with reagent
0.5~1h of heating water bath under the conditions of 75 DEG C；
4) modified: 20ml pyridine solution is added and makees modifying agent, heating water bath 0.5h under the conditions of 80 DEG C；
5) it is grafted: 20ml glycidyl methacrylate (GMA) monomer (concentration 20vol.%) is added, continue 80 DEG C
Heating water bath 6h, the maize cob meal (preliminary product) after being grafted；
6) it cleans:
A) by the maize cob meal after grafting it is cooling (it is pour out preliminary product from three-necked flask online to clean fine ga(u)ge screen,
20 DEG C are cooled to hereinafter, transferring in sand core funnel), it is eluted 2~3 times with the liquid alkaline solution of 0.5L, 0.2mol/L, then will
It is transferred in 500ml large beaker, pours into the liquid alkaline solution of 200ml, 0.1mol/L, the heating water bath and strong under the conditions of 40 DEG C
Power stirring 20min (removes removal of residue, par-tial polysaccharide substance and protein, the strong stirring refers to that speed of agitator is 300-
400r/min, same as below)；
B) by above-mentioned steps 6) a) obtained maize cob meal 0.2mol/L hydrochloric acid solution elution 2~3 times, it then will be beautiful
Rice core powder is transferred in 500ml large beaker, is poured into 200ml, 0.2mol/L hydrochloric acid solution, and heating water bath is simultaneously under the conditions of 40 DEG C
Strong stirring 20min adjusts pH to neutrality；
C) by above-mentioned steps 6) b) obtained maize cob meal with concentration be 30wt% ethanol solution elute 2~3 times, so
After transfer them in 500ml large beaker, pour into 200ml, concentration be 30wt% ethanol solution in, under the conditions of 40~45 DEG C
Heating water bath and strong stirring 10min (removal residual organic reactant)；
D) by above-mentioned steps 6) c) obtained maize cob meal 0.01mol/L sodium chloride solution elution 2~3 times, then
Maize cob meal is transferred in 500ml large beaker, is poured into 500ml, 0.01mol/L sodium-chloride water solution, in 40~45 DEG C of items
Heating water bath and 5~10min of strong stirring under part, the maize cob meal after being cleaned (purpose is thorough wash off product)；
7) maize cob meal after cleaning is gone to below sieve and pads upper evaporating dish, dried 12h under the conditions of 60~65 DEG C, obtain
To the ion-exchange fibre prepared by corncob (final products are sealed in drier, spare).
In order to preferably show the performance and effect of this ion-exchange fibre, absorption property is carried out to the ammonia nitrogen in water with it
Test, specific experimental method is as follows:
More parts of 1 products obtained therefroms of 1g embodiment are weighed, is respectively put into the iodine flask of clean 250ml, pours into 50ml
30mg/L
The aqueous ammonium chloride solution of (referred to herein as ammonium ion concentration), covers lid, shakes under temperature (20 ± 1 DEG C)
It swings, oscillation intensity 100r/min, vibrates 60min.Ammonia nitrogen concentration Two N-ammoniacal Measurements shown in HI535-2009 carry out
Measurement, related experiment result such as table 1.
Influence of the 1 product dosage of table to removal rate
| Product dosage (g/L) | Ammonia nitrogen removal frank (%) |
| 1 | 74.10 |
| 2 | 90.44 |
| 3 | 94.86 |
| 4 | 96.67 |
Embodiment 2:
The preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water, it includes the following steps:
1) the plant Zea mays fruit after normal growth is mature, by corn rod threshing, makes it after natural air drying or drying
As corncob.Corncob is put into baking oven to complete dehydration, the cylindric of 5cm or so is cut into, obtains uniform specification
Column corncob.
2) the cylindric corncob got ready is pre-processed: with crusher machine is crushed, obtains powdered corncobs, it will
Corncob powder be dipped into distilled water and stir 45min, the sundries on corncob powder surface is removed, then by it in 50~70
3-6h is dried in DEG C baking oven, obtains the completely corncob powder without floating dust；
3) it activates: weighing the dry maize cob meal of 10g, be put into the tool plug flask with three necks,round bottom of 1L, two sides of three-necked flask
Mouth is clogged with glass stopper and (note: only opens plug when needing to be added drug, continue beyond the Great Wall after adding drug, entirely react
So operation in the process), electric mixer is protruded into from the main mouth of three-necked flask, is added from the small glass funnel of three-necked flask side port
60ml n,N-Dimethylformamide (DMF) solution, 80ml epoxychloropropane solution, unlatching electric stirring are persistently stirred molten
Liquid (reacts, revolving speed stirs in 60~80r/min, entire reaction process not to be stopped) so that maize cob meal comes into full contact with reagent
0.5~1h of heating water bath under the conditions of 75 DEG C；
4) modified: 20ml pyridine solution is added and makees modifying agent, heating water bath 0.5h under the conditions of 80 DEG C；
5) it is grafted: 20ml glycidyl methacrylate (GMA) monomer (concentration 20vol.%) is added, continue 80 DEG C
Heating water bath 6h, the maize cob meal (preliminary product) after being grafted；
6) it cleans:
A) by the maize cob meal after grafting it is cooling (it is pour out preliminary product from three-necked flask online to clean fine ga(u)ge screen,
20 DEG C are cooled to hereinafter, transferring in sand core funnel), it is eluted 2~3 times with the liquid alkaline solution of 0.5L, 0.2mol/L, then will
It is transferred in 500ml large beaker, pours into the liquid alkaline solution of 200ml, 0.1mol/L, the heating water bath and strong under the conditions of 40 DEG C
Power stirring 20min (removes removal of residue, par-tial polysaccharide substance and protein, the strong stirring refers to that speed of agitator is 300-
400r/min, same as below)；
B) by above-mentioned steps 6) a) obtained maize cob meal 0.2mol/L hydrochloric acid solution elution 2~3 times, it then will be beautiful
Rice core powder is transferred in 500ml large beaker, is poured into 200ml, 0.2mol/L hydrochloric acid solution, and heating water bath is simultaneously under the conditions of 40 DEG C
Strong stirring 20min adjusts pH to neutrality；
C) by above-mentioned steps 6) b) obtained maize cob meal with concentration be 30wt% ethanol solution elute 2~3 times, so
After transfer them in 500ml large beaker, pour into 200ml, concentration be 30wt% ethanol solution in, under the conditions of 40~45 DEG C
Heating water bath and strong stirring 10min (removal residual organic reactant)；
D) by above-mentioned steps 6) c) obtained maize cob meal 0.01mol/L sodium chloride solution elution 2~3 times, then
Maize cob meal is transferred in 500ml large beaker, is poured into 500ml, 0.01mol/L sodium-chloride water solution, in 40~45 DEG C of items
Heating water bath and 5~10min of strong stirring under part, the maize cob meal after being cleaned (purpose is thorough wash off product)；
7) maize cob meal after cleaning is gone to below sieve and pads upper evaporating dish, dried 12h under the conditions of 60~65 DEG C, obtain
To the ion-exchange fibre prepared by corncob (final products are sealed in drier, spare).
Embodiment 2 exchanges effect (eliminating rate of absorption) such as table 2, and experimental method experiment condition is the same as embodiment 1.
Influence of the 2 product dosage of table to removal rate
| Product dosage (g) | Ammonia nitrogen removal frank (%) |
| 1 | 76.40 |
| 2 | 90.31 |
| 3 | 93.76 |
| 4 | 95.84 |
Embodiment 3:
The preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water, it includes the following steps:
1) the plant Zea mays fruit after normal growth is mature, by corn rod threshing, makes it after natural air drying or drying
As corncob.Corncob is put into baking oven to complete dehydration, the cylindric of 5cm or so is cut into, obtains uniform specification
Column corncob.
2) the cylindric corncob got ready is pre-processed: with crusher machine is crushed, obtains powdered corncobs, it will
Corncob powder, which is dipped into distilled water, stirs 45min, the sundries on corncob powder surface is removed, then by it in 50~70 DEG C
3-6h is dried in baking oven, obtains the completely corncob powder without floating dust；
3) it activates: weighing 10g corncob powder, place it in 60ml n,N-Dimethylformamide (DMF) and 50ml epoxy
In the mixed solution of chloropropane, 0.5~1h is stirred under 40~90 DEG C of condition of water bath heating；
4) modified: 20ml pyridine solution is added and makees modifying agent, heating water bath 0.5h under the conditions of 80 DEG C；
5) it is grafted: 20ml glycidyl methacrylate (GMA) monomer (concentration 20vol.%) is added, continue 80 DEG C
Heating water bath 6h, the maize cob meal (preliminary product) after being grafted；
6) it cleans:
A) maize cob meal after grafting is cooling (being cooled to 20 DEG C or less), 2~3 are eluted with the liquid alkaline solution of 0.2mol/L
It is secondary, then be placed in the liquid alkaline solution that 200ml concentration is 0.1mol/L, heating water bath 20min and strength under the conditions of 40~45 DEG C
It stirs (removing removal of residue, part carbohydrate and protein)；
B) by above-mentioned steps 6) a) obtained maize cob meal is eluted 2~3 times with 0.2mol/L hydrochloric acid solution, then is placed in
In 200ml, 0.1mol/L hydrochloric acid solution, heating water bath 20min and strong stirring under the conditions of 40 DEG C adjust pH to neutrality；
C) by above-mentioned steps 6) b) obtained maize cob meal with concentration be 30wt% ethanol solution elute 2~3 times, then
It is placed in 200ml, in the ethanol solution that concentration is 30wt%, simultaneously strong stirring 10min (is gone heating water bath under the conditions of 40~45 DEG C
Except remaining organic reactant in preceding step)；
D) by above-mentioned steps 6) c) obtained maize cob meal is eluted 2~3 times with 0.01mol/L sodium chloride solution, then is set
Enter in 500ml, 0.01mol/L sodium chloride solution, heating water bath and 5~10min of strong stirring, are cleaned under the conditions of 40 DEG C
Maize cob meal afterwards；
7) by the maize cob meal after cleaning in drying 6h under the conditions of 65~75 DEG C, powdered/blocky ion exchange is obtained
Fiber (final products are sealed in drier, spare).
The experimental method experiment condition of 3 eliminating rate of absorption of embodiment is as a result same as Example 1 with embodiment 1.
Embodiment 4:
It is substantially the same manner as Example 2, the difference is that the bath temperature of three reaction steps is successively are as follows: 60 DEG C, 60 DEG C,
90℃。
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 5: it is substantially the same manner as Example 2, the difference is that finally clean the 0.01mol/L in product stage
NaCl solution replaces with deionized water.
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 6: it is substantially the same manner as Example 2, the difference is that: 2) the cylinder corncob got ready is sawn into
Height is the fan-shaped cylinder of 2~3cm, obtains fan-shaped corncob, places it in 6~8h of immersion in distilled water；Then it places
12h is dried into 60~80 DEG C of baking ovens, obtains the dry corncob of fritter；
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 7: it is substantially the same manner as Example 2, the difference is that: it is modified: 30ml pyridine solution is added and makees modifying agent,
Continue 80 DEG C of heating water bath 0.5h.
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 8: it is substantially the same manner as Example 2, the difference is that: it is modified: 30ml pyridine solution is added and makees modifying agent,
Continue 70 DEG C of heating water bath 1h.
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 9: it is substantially the same manner as Example 2, the difference is that: it is sweet that 40ml Glycidyl methacrylate grafting: is added
Grease (GMA) monomer (concentration 20vol.%), continues 80 DEG C of heating water bath 6h, and the maize cob meal after being grafted is (preliminary to produce
Product)；
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
Embodiment 10: it is substantially the same manner as Example 2, the difference is that: it is sweet that 20ml Glycidyl methacrylate grafting: is added
Grease (GMA) monomer (concentration 20vol.%), continues 80 DEG C of heating water bath 8h, and the maize cob meal after being grafted is (preliminary to produce
Product)；
The experimental method experiment condition of eliminating rate of absorption is as a result same as Example 2 with embodiment 2.
In order to preferably compare ammonia nitrogen removal effect of the invention, with other invention preparation material with it is prepared by the present invention
Material comparison, specific ammonia nitrogen absorption Contrast on effect situation are as shown in table 3 below:
3 difference of table prepares material to ammonia nitrogen absorption Contrast on effect
It can be seen from the data in the table that the material of the embodiment of the present invention 1~10 prepared using corncob as raw material is to ammonia nitrogen
Absorption property is preferable, is suitble to commercial introduction.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformation or modification within the scope of the claims, have no effect on
Substantive content of the invention.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, similarly include
In scope of patent protection of the invention.
Claims (3)
1. the preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water, which comprises the steps of:
1) the plant Zea mays fruit after normal growth is mature, by corn rod threshing, becomes after natural air drying or drying
Corncob；Corncob is put into baking oven to complete dehydration, is cut into the column corncob of uniform specification；
2) the cylindric corncob got ready is pre-processed with one of following two methods:
A) by the cylindric corncob got ready crush crusher machine, obtain powdered corncobs, by corncob powder soak
It steeps and stirs 45min in distilled water, remove the sundries on corncob powder surface, it is then dried into 3- in 50~70 DEG C of baking ovens
6h obtains the completely corncob powder without floating dust；
B) the cylinder corncob got ready is sawn into the fan-shaped cylinder that height is 2~3cm, obtains fan-shaped corncob,
Place it in 6~8h of immersion in distilled water；It is then placed into 60~80 DEG C of baking ovens and dries 12h, obtain the dry corncob of fritter
Axis；
3) it activates: weighing 10g corncob powder, the mixing for placing it in 50~75ml DMF and 20-80ml epoxychloropropane is molten
In liquid, 0.5~1h is stirred under 40~90 DEG C of condition of water bath heating；
4) modified: 20~50ml pyridine solution is added and makees modifying agent, continues 40~90 DEG C of 0.5~1h of heating water bath；
5) it is grafted: 20~40ml GMA monomer solution is added, the concentration of GMA is 20vol.% in the GMA monomer solution, is continued
6~8h, the maize cob meal after being grafted are heated in 80~100 DEG C of water-baths；
6) it cleans:
A) maize cob meal after grafting is cooling (being cooled to 20 DEG C or less), it is eluted 2~3 times with the liquid alkaline solution of 0.2mol/L,
It is placed in the liquid alkaline solution that 200ml concentration is 0.1mol/L, heating water bath 20min and is strongly stirred under the conditions of 40~45 DEG C again
It mixes；
B) by above-mentioned steps 6) a) obtained maize cob meal with 0.2mol/L hydrochloric acid solution elute 2~3 times, then be placed in 200ml,
In 0.1mol/L hydrochloric acid solution, heating water bath 20min and strong stirring under the conditions of 30~40 DEG C adjust pH to neutrality；
C) by above-mentioned steps 6) b) obtained maize cob meal is eluted 2~3 times with the ethanol solution that concentration is 30wt%, then is placed in
In 200ml, the ethanol solution that concentration is 30wt%, heating water bath and strong stirring 10min under the conditions of 40~50 DEG C；
D) by above-mentioned steps 6) c) obtained maize cob meal is eluted 2~3 times with 0.01mol/L sodium chloride solution, then is placed in
In 500ml, 0.01mol/L sodium chloride solution, heating water bath and 5~10min of strong stirring, are washed under the conditions of 30~50 DEG C
Maize cob meal after net；
7) by the maize cob meal after cleaning in drying 6~12h under the conditions of 65~75 DEG C, powdered/blocky ion exchange is obtained
Fiber.
2. the preparation method of the ion-exchange fibre of ammonia nitrogen in absorption waste water according to claim 1, it is characterised in that: institute
It states and is cut into the cylindric of 5cm or so in step 1).
3. the preparation method of the ion-exchange fibre of ammonia nitrogen in absorption waste water according to claim 1, it is characterised in that: institute
It states strong stirring and refers to that speed of agitator is 300~400r/min.
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|---|---|---|---|---|
| CN102614852A (en) * | 2012-04-16 | 2012-08-01 | 武汉理工大学 | Preparation method for spongy ion exchange fiber |
| CN103223354A (en) * | 2013-03-29 | 2013-07-31 | 武汉理工大学 | Preparation method of biomass-based anion exchange fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102614852A (en) * | 2012-04-16 | 2012-08-01 | 武汉理工大学 | Preparation method for spongy ion exchange fiber |
| CN103223354A (en) * | 2013-03-29 | 2013-07-31 | 武汉理工大学 | Preparation method of biomass-based anion exchange fiber |
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Application publication date: 20190402 |