CN104043486A - Granular ammonium ion exchange material and preparation method - Google Patents
Granular ammonium ion exchange material and preparation method Download PDFInfo
- Publication number
- CN104043486A CN104043486A CN201310076457.6A CN201310076457A CN104043486A CN 104043486 A CN104043486 A CN 104043486A CN 201310076457 A CN201310076457 A CN 201310076457A CN 104043486 A CN104043486 A CN 104043486A
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- ammonium ion
- solid
- exchange material
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a granular ammonium ion exchange material and a preparation method. The preparation method includes following steps: a) mixing kaolin, sodium hydroxide, sodium metaaluminate and distilled water with stirring uniformly to obtain a mixed solution; b) heating the mixed solution in water bath, performing heat-insulation, cooling the mixed solution, performing solid-liquid separation, removing the liquid, adding distilled water to the solid for soaking and washing the solid; c) performing heat-treatment on the washed solid, cooling the heat-treated solid to room temperature and carrying out a grinding process and a sieving process to obtain a powder; d) mixing the powder, kaolin, sodium silicate and sodium bicarbonate uniformly and adding distilled water with stirring uniformly to obtain a soft material; e) manufacturing the soft material into granules; and f) heat-treating the granules and cooling the heat-treated granules to room temperature to obtain the granular ammonium ion exchange material. The granular ammonium ion exchange material has an ammonium ion exchange capacity being greater than that of 75 mgNH4<+>-N per gram of the ammonium ion exchange material and is suitable for treating an ammonia-nitrogen wastewater in low-medium concentration. Raw materials of the material are cheap and are easy to obtain. The preparation method is simple and easy. The material is suitable for a large scale industrial production.
Description
Technical field
The invention belongs to technical field of sewage, particularly relate to the preparation that a kind of ammonia nitrogen waste water is processed material.
Background technology
At present, denitrogenation of waste water method has many both at home and abroad.Processing the good technology of practicality mainly contains: biological denitrificaion method; Blow-off method, break point chlorination, ion-exchange.Also there is nitrite anions, nitrate anion and the ammonia nitrogen still with pollution in biological denitrificaion, limited the range of application of biological denitrificaion in the process of processing waste water.The shortcoming of blow-off method maximum is that transfer has just occurred ammonia, and the pollution in water transfers the pollution of atmosphere to, and the only applicable high wastewater treatment of ammonia nitrogen concentration.Break point chlorination ammonia nitrogen removal rate is high, but liquefied ammonia safe handling and memory requirement are high.It is little and entered the advantages such as the impact of variation of water ammonia concentration is very micro-that ion-exchange has strong adaptability, temperature influence.In ion-exchange, the method for typical general is to do denitrogenation material with zeolite, this method cost is low, equipment is little, it is selective preferably that ammonia nitrogen is had, but it is except ammonia effect is undesirable and regeneration expense is high, turned to other to be more easy to get at present and the easily research of the clay material of regeneration.
Kaolin is as a kind of China reserves clay material large and cheap and easy to get, and its particle is trickle has a very large incompleteness surface, interlayer adhesion a little less than, and exist the unsaturated filling distortion of interlayer structure.Kaolinic aperture and acidity have adjustable sex change simultaneously, and these features provide the processing method of Applied Physics or chemistry to change the possibility of its structure, make it aspect ion-exchange, have vast potential for future development.
CN1824386A discloses a kind of preparation method of ammonium ion sieve, and its ammonium ion exchange capacity is preferably more than 65.2mgNH
4 +-N/g, but because it is Powdered, be not suitable for commercial development utilization.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of graininess ammonium ion exchange material is provided.
Second object of the present invention is to provide a kind of graininess ammonium ion exchange material.
Technical scheme of the present invention is summarized as follows:
A preparation method for graininess ammonium ion exchange material, comprises the steps:
A. be in mass ratio (1-3): 3:(1-3): 5 ratio, by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtains mixed liquor;
B. heating water bath mixed liquor is to 80-100 ℃, and insulation 3-5 hour, is cooled to 15-25 ℃, and Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 7-8;
C. the heating rate of the solid after washing being take is heat-treated as 2-3 ℃/min is warming up to 550-700 ℃ of insulation 0.5-3.5h, is cooled to room temperature, grinds, crosses 300 mesh sieves, obtains powder;
D. in mass ratio for the ratio of (5-9): 1:1:1 adds mixture quality 0.2-0.24 times distilled water after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material;
E. described soft material is made to the particle that particle diameter is 0.5-1.5mm;
F. by particle with heating rate 8-15 ℃/min, be warming up to 400-800 ℃ insulation 0.5-3.5h heat-treat, take rate of temperature fall as 1-5 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
Described step a is preferably: for the ratio of 2:3:2:5 is by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtain mixed liquor in mass ratio.
Described step b is preferably: heating water bath mixed liquor to 90 ℃, be incubated 4 hours, and be cooled to 20 ℃, Separation of Solid and Liquid, discards liquid, and solid adding distil water washing by soaking washs to pH value as 7-8.
Described step c is preferably: the solid after washing be take to heating rate and as 2-3 ℃/min is warming up to 600 ℃ of insulation 2.5h, heat-treat, be cooled to room temperature, grind, cross 300 mesh sieves, obtain powder.
Described steps d is preferably: for the ratio of 7:1:1:1 adds 0.22 times of distilled water of mixture quality after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material in mass ratio.
Described step f is preferably: particle, with 10 ℃/min of heating rate, is warming up to 600 ℃ of insulation 2h and heat-treats, take rate of temperature fall as 3 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
Ammonium ion exchange material prepared by said method.
The ammonium ion exchange capacity of graininess ammonium ion exchange material prepared by the present invention is greater than 75mgNH
4 +-N/g, the ammonium ion exchange capacity of material had increased significantly more in the past, can be used for removing of ammonia nitrogen in water treatment procedure.The static ammonia nitrogen removal experiment in chamber by experiment, utilize formula: ammonia nitrogen removal frank (%)=(solution ammonium concentration after original solution ammonium concentration-balance)/original solution ammonium concentration * 100%, the ammonia nitrogen removal frank of ammonium ion exchange material of the present invention ammonia nitrogen waste water under 100mg/L to concentration can reach more than 90%.The raw material of ammonium ion exchange material of the present invention is cheap and easy to get, and preparation method is simple, is applicable to large-scale industrial production, has higher economic benefit.
Accompanying drawing explanation
Fig. 1 is the SEM photo of kaolinic 100000 times of embodiment 1 Raw;
Fig. 2 is the SEM photo of 100000 times of the graininess ammonium ion exchange materials of embodiment 1 preparation;
Fig. 3 is the kaolinic energy of embodiment 1 Raw spectrogram;
Fig. 4 is the energy spectrogram of the graininess ammonium ion exchange material of embodiment 1 preparation;
Fig. 5 is the embodiment 1 kaolinic X-ray powder diffraction of Raw (XRD) collection of illustrative plates;
Fig. 6 is X-ray powder diffraction (XRD) collection of illustrative plates of the graininess ammonium ion exchange material of embodiment 1 preparation.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
A preparation method for graininess ammonium ion exchange material, comprises the steps:
A. be in mass ratio the ratio of 2:3:2:5 by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtain mixed liquor;
B. heating water bath mixed liquor to 90 ℃, is incubated 4 hours, is cooled to 20 ℃, and Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 7.5;
C. the heating rate of the solid after washing being take is heat-treated as 2.5 ℃/min is warming up to 600 ℃ of insulation 2.5h, is cooled to room temperature, grinds, crosses 300 mesh sieves, obtains powder;
D. in mass ratio for the ratio of 7:1:1:1 adds 0.22 times of distilled water of mixture quality after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material;
E. described soft material is made to the particle that particle diameter is 1mm;
F. by particle with 10 ℃/min of heating rate, be warming up to 600 ℃ insulation 2h heat-treat, take rate of temperature fall as 3 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
Through CEC, measure, the ammonium ion exchange capacity of the ammonium ion exchange material making is 76.26mgNH
4 +-N/g ammonium ion exchange material.At 100ml, mass concentration is to add the ammonium ion exchange material that 0.5g is dry containing in ammonia nitrogen solution of 50mg/l, utilize formula: ammonia nitrogen removal frank (%)=(solution ammonium concentration after original solution ammonium concentration-balance)/original solution ammonium concentration * 100% is 94.6% by calculating its ammonia nitrogen removal frank.
Embodiment 2
A preparation method for graininess ammonium ion exchange material, comprises the steps:
A. be in mass ratio the ratio of 1:3:1:5 by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtain mixed liquor;
B. heating water bath mixed liquor to 80 ℃, is incubated 5 hours, is cooled to 15 ℃, and Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 8;
C. the heating rate of the solid after washing being take is heat-treated as 2 ℃/min is warming up to 550 ℃ of insulation 3.5h, is cooled to room temperature, grinds, crosses 300 mesh sieves, obtains powder;
D. in mass ratio for the ratio of 5:1:1:1 adds 0.2 times of distilled water of mixture quality after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material;
E. described soft material is made to the particle that particle diameter is 0.5mm;
F. by particle with 8 ℃/min of heating rate, be warming up to 400 ℃ insulation 3.5h heat-treat, take rate of temperature fall as 1 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
Through CEC, measure, the ammonium ion exchange capacity of the ammonium ion exchange material making is 70.4mgNH
4 +-N/g ammonium ion exchange material.At 100ml, mass concentration is to add the ammonium ion exchange material that 0.5g is dry containing in ammonia nitrogen solution of 50mg/l, utilize formula: ammonia nitrogen removal frank (%)=(solution ammonium concentration after original solution ammonium concentration-balance)/original solution ammonium concentration * 100% is 89.1% by calculating its ammonia nitrogen removal frank.
Embodiment 3
A preparation method for graininess ammonium ion exchange material, comprises the steps:
A. be in mass ratio the ratio of 3:3:3:5 by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtain mixed liquor;
B. heating water bath mixed liquor to 100 ℃, is incubated 3 hours, is cooled to 25 ℃, and Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 7;
C. the heating rate of the solid after washing being take is heat-treated as 3 ℃/min is warming up to 700 ℃ of insulation 0.5h, is cooled to room temperature, grinds, crosses 300 mesh sieves, obtains powder;
D. in mass ratio for the ratio of 9:1:1:1 adds 0.24 times of distilled water of mixture quality after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material;
E. described soft material is made to the particle that particle diameter is 1.5mm;
F. by particle with 15 ℃/min of heating rate, be warming up to 800 ℃ insulation 0.5h heat-treat, take rate of temperature fall as 5 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
Through CEC, measure, the ammonium ion exchange capacity of the ammonium ion exchange material making is 73.8mgNH
4 +-N/g ammonium ion exchange material.At 100ml, mass concentration is to add the ammonium ion exchange material that 0.5g is dry containing in ammonia nitrogen solution of 50mg/l, utilize formula: ammonia nitrogen removal frank (%)=(solution ammonium concentration after original solution ammonium concentration-balance)/original solution ammonium concentration * 100% is 92.1% by calculating its ammonia nitrogen removal frank.
Each embodiment step of the present invention e preferably pharmaceutical extruding-spheronizator makes by soft material the particle that particle diameter is 0.5-1.5mm, wherein, extruded velocity is 15-18r/min, and round as a ball speed and time are first through the round as a ball 1-2min of 1000r/min, then through the round as a ball 2-3min of 1200r/min; Again through step f granulation.Graininess ammonium ion exchange material of the present invention is directly used in to water treatment removal of ammonia and nitrogen, makes Separation of Solid and Liquid easy, improve the practical application performance of material.
Kaolin is highly purified even single-phase water-washed kaoline preferably, the water-washed kaoline that for example Maoming City Xing Huang mining industry Co., Ltd produces.
The heat treatment of step c and f can be carried out in Muffle furnace, also can in heat-treatment furnace, carry out.
As can be seen from Figure 1 kaolin major part is single sheet, and also some is lamination shape, and combination is between layers not tight, is unordered being deposited in together of stratiform.And graininess ammonium ion exchange material laminated structure of the present invention from Fig. 2 disappears, be dispersity, micropore is very flourishing, and particle is tiny, distribution uniform.
Table 1 is the EDAX results of feed kaolin, and table 2 is EDAX results of the graininess ammonium ion exchange material of embodiment 1 preparation.From Fig. 3, Fig. 4 with table 1, table 2, can find out that graininess ammonium ion exchange material compares the content of O, Al, Si and reduce with kaolin, the quality percentage composition of Na is 10.75%.The reduction of O content is removing due to adsorbed water in calcination process and hydroxyl.The reduction of Al, Si may be and Na on the one hand
+ion exchanges, and may be on the other hand under highly basic effect, to react with highly basic to generate the cause that DDGS washes out in later stage cleaning.
As can be seen from Figure 5, the diffraction maximum number of the feed kaolin sample in the present embodiment 1 is many, and peak shape is narrow, sharply symmetrical, well-crystallized.With Jade software analysis presentation of results in this sample main component be kaolinite, and content is high, impurity is few.As can be seen from Figure 6, in the graininess ammonium ion exchange material of the present embodiment 1 preparation, kaolinite composition disappears, and replaces and has formed na-pretreated zeolite, and main component is sodalite and a small amount of quartz, annite and albite.The kaolinic chemical formula providing in software is Al
2(Si
2o
5) (OH)
4, the main chemical formula of na-pretreated zeolite is Na
8(Al
6si
6o
24) (CO
3) 3H
2o, after modification, kaolinic structure is disintegrated, and hydroxyl structure also destroys completely, and a kind of aluminosilicate structure with the sodium of macroion exchange activity forms.
The experiment proved that: the ammonium ion exchange capacity of graininess ammonium ion exchange material of the present invention is (70-85) mgNH
4 +-N/g.Can be applicable to the ammonia nitrogen removal of middle Low Concentration Ammonia Containing Wastewater.
Table 1 feed kaolin EDAX results
| Element | Mass percent % | Atomic percent % |
| C?K | 07.21 | 11.64 |
| O?K | 49.95 | 60.51 |
| Al?K | 18.70 | 13.43 |
| Si?K | 20.35 | 14.05 |
| Au?K | 03.79 | 00.37 |
Table 2 graininess ammonium ion exchange material EDAX results
| Element | Mass percent % | Atomic percent % |
| C?K | 16.53 | 25.25 |
| O?K | 43.12 | 49.45 |
| Na?K | 10.75 | 08.58 |
| Al?K | 11.88 | 08.08 |
| Si?K | 12.50 | 08.16 |
| Au?K | 05.21 | 00.49 |
Claims (7)
1. a preparation method for graininess ammonium ion exchange material, is characterized in that comprising the steps:
A. be in mass ratio (1-3): 3:(1-3): 5 ratio, by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtains mixed liquor;
B. heating water bath mixed liquor is to 80-100 ℃, and insulation 3-5 hour, is cooled to 15-25 ℃, and Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 7-8;
C. the heating rate of the solid after washing being take is heat-treated as 2-3 ℃/min is warming up to 550-700 ℃ of insulation 0.5-3.5h, is cooled to room temperature, grinds, crosses 200-300 mesh sieve, obtains powder;
D. in mass ratio for the ratio of (5-9): 1:1:1 adds mixture quality 0.2-0.24 times distilled water after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material;
E. described soft material is made to the particle that particle diameter is 0.5-1.5mm;
F. by particle with heating rate 8-15 ℃/min, be warming up to 400-800 ℃ insulation 0.5-3.5h heat-treat, take rate of temperature fall as 1-5 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
2. method according to claim 1, is characterized in that described step a is: for the ratio of 2:3:2:5 is by kaolin, NaOH, sodium metaaluminate and distilled water mixing and stirring, obtain mixed liquor in mass ratio.
3. method according to claim 1, is characterized in that described step b is: heating water bath mixed liquor to 90 ℃, be incubated 4 hours, be cooled to 20 ℃, Separation of Solid and Liquid, discards liquid, solid adding distil water washing by soaking, wash to pH value be 7-8.
4. method according to claim 1, is characterized in that described step c is: the solid after washing be take to heating rate and as 2-3 ℃/min is warming up to 600 ℃ of insulation 2.5h, heat-treat, be cooled to room temperature, grind, cross 300 mesh sieves, obtain powder.
5. method according to claim 1, it is characterized in that described steps d is: for the ratio of 7:1:1:1 adds 0.22 times of distilled water of mixture quality after powder, kaolin, sodium metasilicate and sodium acid carbonate are mixed, be stirred into soft material in mass ratio.
6. method according to claim 1, is characterized in that described step f is: particle, with 10 ℃/min of heating rate, is warming up to 600 ℃ of insulation 2h and heat-treats, take rate of temperature fall as 3 ℃/min is down to room temperature, obtain graininess ammonium ion exchange material.
7. the graininess ammonium ion exchange material that prepared by the method for one of claim 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310076457.6A CN104043486A (en) | 2013-03-11 | 2013-03-11 | Granular ammonium ion exchange material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310076457.6A CN104043486A (en) | 2013-03-11 | 2013-03-11 | Granular ammonium ion exchange material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104043486A true CN104043486A (en) | 2014-09-17 |
Family
ID=51497173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310076457.6A Pending CN104043486A (en) | 2013-03-11 | 2013-03-11 | Granular ammonium ion exchange material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104043486A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824386A (en) * | 2006-01-27 | 2006-08-30 | 天津大学 | Ammonium ion sieve, its preparation method and application |
| CN101829608A (en) * | 2010-06-11 | 2010-09-15 | 天津大学 | Preparation method and application of ammonium ion exchange material |
-
2013
- 2013-03-11 CN CN201310076457.6A patent/CN104043486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824386A (en) * | 2006-01-27 | 2006-08-30 | 天津大学 | Ammonium ion sieve, its preparation method and application |
| CN101829608A (en) * | 2010-06-11 | 2010-09-15 | 天津大学 | Preparation method and application of ammonium ion exchange material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102151546B (en) | Modified zeolite as well as preparation method and application thereof | |
| CN107285341B (en) | Method for preparing magnetic P-type molecular sieve by using coal gangue | |
| CN104947176B (en) | A kind of hollow-core construction magnesium titanate potassium crystal whisker materials and preparation method thereof | |
| CN104492372B (en) | A kind of preparation method and applications for adsorbing heavy metal in waste water material | |
| CN107262037A (en) | A kind of preparation and application of sepiolite FeOOH active carbon compound adsorbent | |
| JP2024504492A (en) | Composite type A molecular sieve raw material powder containing radio wave absorbing material, all zeolite molecular sieve, manufacturing method thereof, and use thereof | |
| CN103831080B (en) | For reclaiming nickel slag sorbing material and the preparation thereof of heavy metal ions in wastewater | |
| CN106881071A (en) | A kind of preparation method of modified activated carbon/diatomite adsorbant | |
| CN107970885A (en) | Compound ammonia nitrogen adsorbent prepared by a kind of microwave radiation method and preparation method thereof | |
| CN104607144A (en) | Structure self-growing aqueous phase phosphate radical adsorbing material and preparation method and application thereof | |
| Chen et al. | Pure zeolite Na‐P and Na‐X prepared from coal fly ash under the effect of steric hindrance | |
| CN102874805A (en) | Method for preparing porous carbon for wastewater treatment | |
| CN101757890B (en) | Preparation method of attapulgite filter material for selectively absorbing calcium ions and magnesium ions | |
| CN101474514B (en) | Method for preparing modified ultra-high molecular mass polyethylene micropore filter element | |
| CN108201876B (en) | Method for deeply adsorbing zinc ions by using NaP molecular sieve | |
| CN111545163B (en) | Adsorbent for heavy metal wastewater treatment and preparation method thereof | |
| CN101829608A (en) | Preparation method and application of ammonium ion exchange material | |
| CN108383540A (en) | A kind of modified coal ash ceramics and its preparation method and application | |
| CN104043486A (en) | Granular ammonium ion exchange material and preparation method | |
| CN101875494A (en) | Preparation method of low-titanium and high-purity polycrystalline silicon | |
| CN112108117A (en) | Preparation method and testing device for simultaneously removing multiple radioactive metal carbon-based composite materials | |
| CN102351224A (en) | Process for preparing active alumina from aluminum section industrial wastewater alkaline residues | |
| CN104014300B (en) | Diatomite preparation is with the method for drainage functional beer stabilizing agent | |
| CN103537258A (en) | Preparation method of novel magnetic clay nanometer composite material | |
| CN110565190A (en) | Polyester material for inducing negative oxygen ions and preparation method of functional powder and auxiliary agent thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140917 |