CN101376531A - MAP (guano) crystal precipitating stuffing and preparation thereof - Google Patents
MAP (guano) crystal precipitating stuffing and preparation thereof Download PDFInfo
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- CN101376531A CN101376531A CNA2007101308541A CN200710130854A CN101376531A CN 101376531 A CN101376531 A CN 101376531A CN A2007101308541 A CNA2007101308541 A CN A2007101308541A CN 200710130854 A CN200710130854 A CN 200710130854A CN 101376531 A CN101376531 A CN 101376531A
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- map
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- struvite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention relates to a pre-filming MAP filler which can improve the crystallization sedimentation performance of MAP (struvite) and a preparation method. The pre-filming MAP filler and the preparation method are characterized in that porous particles such as waste zeolite, waste active carbon, coke, fly ashes, etc. are used as carriers, magnesium, phosphate and ammonia-nitrogen are used as raw materials, the mol ratio among N, P and Mg is 1:1:1.0 to 2.0, and an MAP film is formed on the surface of the carriers through fluidized reaction. The filler is put in ammonia-containing phosphorus wastewater, so the crystallization sedimentation performance of the MAP (struvite) on the surface of the pre-filming filler can be enhanced obviously; the test shows that the crystal nucleus growth velocity is increased about 20 percent compared with a common amorphous filler carriers. In addition, the carriers are pre-filmed, thereby being beneficial for the MAP film-forming and increasing the firmness of the film. The pre-filming MAP filler and the preparation method adopt external circulation fluidized reaction to prepare the pre-film, and the friction between the carriers is reduced, thereby being also beneficial for the film-forming on the carriers. Air is added before reaction for pressurizing, thereby being beneficial for the formation of the porous pre-filmed MAP carriers and increasing the porosity of the pre-filmed carriers obviously.
Description
Technical field
The present invention relates to a kind of pre-film MAP filler and preparation method that can improve MAP (struvite) crystalline deposit performance.
Background technology
Struvite (MAP), molecular formula MgNH
4PO
46H
2O is a kind of white crystal that is insoluble in water, and the solubility product under the normal temperature in water is 25 * 10
-13By adding for example magnesium sources such as magnesium chloride, magnesium oxide, magnesium hydroxide of chemical reagent, can make the ammonia phosphorus in the waste water form the struvite crystalline deposit, realize removal to nitrogen and phosphorus pollutants, the struvite of recovery can be used as slow release fertilizer.It is that the MAP crystal growth is slow that there is a major issue in MAP crystalline deposit method, and the crystal nucleation time is long, and feasible to be used for the sewage disposal processing efficiency low, and the treating water residence time is long, and it is low to hold back nitrogen phosphorus efficient, and recovering effect is poor.Prior art takes to change change pH values, the proportioning of nitrogen, phosphorus, magnesium, and adjust the precipitin reaction condition, add as grain things such as sand grains, Wingdales continuously, improve crystalline growth velocity.But see on the whole, change change pH values, the proportioning of nitrogen, phosphorus, magnesium, and adjust the degree of supersaturation that the precipitin reaction condition need be bigger, and the by product increase, not obvious to improving the MAP sedimentation effect.Therefore general the employing adds non-MAP crystal in the prior art, and this non-parent crystal kind nucleation selectivity is relatively poor, and not only the space of crystal growth is less, and the particle diameter of crystal growth, uniformity coefficient are difficult to control.Secondly, owing to contain various particulate matters in the waste water, the required degree of supersaturation of nucleation process is than low under the homogeneous phase condition, if there are other particulate matters, when then MAP does not also form, may just form a large amount of magnesium hydroxides or trimagnesium phosphate precipitation, denitrification effect reduces, mother crystal is difficult for obtaining, and nucleation rate and nucleation nucleus number are difficult to control.Above-mentionedly cause forming a large amount of tiny MAP particles, crystalline particle is inhomogeneous, not only be difficult to reclaim, and the MAP inferior quality that reclaims.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of cost low, can quicken struvite crystalline deposit performance, MAP (struvite) the crystalline deposit filler that gained struvite crystalline quality is good.
Another object of the present invention is to provide a kind of preparation method of above-mentioned filler.
The present invention's first purpose realizes, the measure of taking is that porous particles such as the useless zeolite of employing, waste active carbon, coke, flyash are carrier, with magnesium, phosphoric acid salt, ammonia nitrogen is raw material, form one deck struvite film at carrier surface, thereby form pre-film MAP particulate vector, overcome the deficiencies in the prior art, realize the object of the invention.Specifically, MAP of the present invention (struvite) crystalline deposit filler is characterized in that being raw material at porous particles carriers such as useless zeolite, waste active carbon, coke, flyash with magnesium, phosphoric acid salt, ammonia nitrogen, with the N:P:Mg mol ratio is 1:1:1.0-2.0, forms one deck MAP film at carrier surface.
The porousness of carrier granule among the present invention, the one, help improving the fastness that combines of pre-film MAP and carrier, two also help forming the porousness of pre-film MAP.For making filler have enough specific surface areas, and the recovery that takes into account crystallisate, carrier of the present invention better adopts the ball-like structure carrier of particle diameter at 1-30mm.
The preparation of MAP of the present invention (struvite) crystalline deposit filler, it is characterized in that the porous particles carriers such as zeolite, waste active carbon, coke, flyash that to give up, place the smooth wall streaming tank, apply with the magnesium source earlier or the immersion carrier, obtain being loaded with the carrier in magnesium source, carrier of separating and residue magnesium source, oven dry; But in fluidized-bed, add water, ammonia nitrogen, phosphoric acid salt to fluidized state, control pH9-10, and bubbling air pressurization, add the magnesium source, making the N:P:Mg mol ratio is 1:1:1.0-2.0, by the outer circulation fluidisation, makes fluidisation intensity reach carrier rate of expansion 10%, end loop, dehydration and bubbling air seasoning.
Smooth wall streaming tank of the present invention can be glass or enamel or stainless steel streaming tank, and slick wall can prevent that crystallization from depositing at wall.
Pressurization makes magnesium source, phosphorus source, ammonia nitrogen ciculation fluidized among the present invention, and a MAP who helps forming infiltrates in the carrier hole, can improve the fastness that combines of MAP and carrier, the two MAP formation vesicular structures that help forming when release of pressure.The present invention's pressurization, test shows that pressure range is preferably 3-4 normal atmosphere, hypotony or too high all can influence pre-film quality, but pressure range of the present invention is not the mathematics exact value, suitably departs from equally and can realize, or slightly influential to film quality.
Carrier surface MAP film thickness of the present invention can realize that wherein pre-thicknesses of layers is preferably 0.5-5mm by control carrier particle diameter, density, reaction times and nitrogen phosphorus magnesium dosage.In addition, can also control crystalline nucleation rate and growth speed, improve MAP (struvite) in filling surface crystalline deposit performance by asynchronous stirring velocity.
In the inventive method, phosphatic adding, a kind of mixture that adopts phosphoric acid salt and magnesium that is preferably helps keeping preferably the stability of reaction system pH, and can obviously reduce side reaction speed.
MAP of the present invention (struvite) crystalline deposit filler, because by being coated with the MAP crystal seed at non-parent crystal filling surface, thereby make common waste material become pre-membrane carrier, put into and contain ammonia phosphorus waste water, can obviously improve MAP (struvite) in pre-film filling surface crystalline deposit performance, improve crystalline deposit speed and water treatment efficiency, test shows that the more common amorphous filling carrier of nucleus growth speed improves about 20%.And the pre-film of carrier, the stability that helps the MAP film forming and improve film.Secondly, the even porous of seed particles can be controlled crystal nucleation speed preferably in the wastewater treatment reaction system, bigger crystal growth space is provided.Outer circulation fluidized reaction of the present invention prepares pre-film, and friction reduces between carrier, also helps the carrier film forming.Add air pressurized before the reaction, help the formation of the pre-film MAP of porous carrier, can obviously improve the porousness of pre-membrane carrier.The use of mixed phosphate, more single phosphoric acid salt can better be kept the pH stability of reaction system, and can obviously reduce side reaction speed.The pre-film filler of the present invention, starting material are cheap and easy to get, and manufacture craft is simple, and the pre-film filler making phase is short, can finish in reactor early stage in the sewage disposal operation.
Below in conjunction with two embodiments, further specify the present invention, but concrete parameter or name of material among the embodiment should not be construed as to concrete qualification of the present invention, some all belong to protection domain of the present invention in technician's simple replacement.
Embodiment
Embodiment 1: adding median size in the enamel streaming tank is the useless Zeolite support of 20mm, and 10% magnesium hydroxide thin mud, behind the continuously stirring 4h, get rid of unnecessary magnesium hydroxide thin mud, the limit feeds the warm air limit and stirs, and until carrier drying, forms precoating magnesium source carrier.In containing precoating carrier streaming tank, add entry, ammonia nitrogen (bicarbonate of ammonia) again to the carrier energy fluidizing, control pH9-10, bubbling air is forced into 3-4 normal atmosphere, add sodium phosphate and magnesium chloride mixture solution with charge pump, making nitrogen magnesium phosphorus mol ratio is 1:1:2.0, adopt the outer circulation pump ciculation fluidized, reaction times 30-180min, make fluidisation intensity reach carrier rate of expansion 10%, stop ciculation fluidizedly, get rid of solution in the streaming tank, feed the normal temperature air seasoning, get pre-film MAP filler, record pre-thicknesses of layers 2.0mm.
In fluidized-bed, put into above-mentioned filler, will be through pretreated ammonia nitrogen and the soluble phosphate sewage (SS is below 50mg/L) of containing, and magnesium chloride solution, enter by fluidized-bed bottom water distribution uniformity, make the current of nitrogenous magnesium phosphorus carry out crystalline deposit through pre-film MAP packing area, sewage is residence time 2-3h in fluidized-bed, and treating water is by the water outlet of fluidized-bed top.A large amount of nitrogen phosphorus are trapped and form struvite crystallization recovery in the water, and ammonia nitrogen removal frank is 90%, and tp removal rate is 95%.
Embodiment 2: at the coke granule carrier of stainless steel fluidisation tank body adding 15mm, and saturated magnesium chloride solution, soak and mechanical stirring, through behind the 4h, get rid of unnecessary magnesium chloride solution, the limit feeds the warm air limit and stirs, until carrier drying, form precoating magnesium source carrier.Carry and add entry, ammonia nitrogen (ammonium chloride) in the jar to containing precoating to the carrier energy fluidizing, control pH9-10, bubbling air is forced into 3-4 normal atmosphere, add SODIUM PHOSPHATE, MONOBASIC and magnesium chloride mixture solution with charge pump, making nitrogen magnesium phosphorus mol ratio is 1:1:1.2, adopt the outer circulation pump ciculation fluidized, reaction times 30-180min, make fluidisation intensity reach carrier rate of expansion 10%, stop ciculation fluidizedly, get rid of solution in the streaming tank, the bubbling air seasoning, obtain pre-film MAP filler, record pre-thicknesses of layers 3.5mm.
Comparative example: under laboratory condition, by using pre-film MAP coke packing (particle diameter 5mm) and not pre-film coke (3-4mm) to compare experiment, experimental result is found, under the condition of initial ammonia nitrogen, phosphate concn unanimity, hydraulic detention time is 2h, use the reactive system of pre-film MAP coke packing, ammonia nitrogen removal frank reaches 96%, tp removal rate reaches 87%, and in using the reactive system of pre-film filler not, ammonia nitrogen removal frank only is 83%, and tp removal rate is 80%, the result shows, uses pre-film MAP filler can obviously improve MAP crystalline deposit performance.
In addition, magnesium can also adopt magnesium oxide among the present invention; Phosphoric acid salt can also adopt mixed form, for example sodium phosphate and SODIUM PHOSPHATE, MONOBASIC mixing salt; Ammonia nitrogen can also adopt other to contain the ammonia nitriding compound.
Claims (7)
1, MAP (struvite) crystalline deposit filler, it is characterized in that at porous particles carriers such as useless zeolite, waste active carbon, coke, flyash, with magnesium, phosphoric acid salt, ammonia nitrogen is raw material, is 1:1:1.0-2.0 with the N:P:Mg mol ratio, forms one deck MAP film at carrier surface.
2,, it is characterized in that described carrier particle diameter is 1-30mm according to the described MAP of claim 1 (struvite) crystalline deposit filler.
3, according to claim 1 or 2 described MAP (struvite) crystalline deposit fillers, it is characterized in that described carrier is ball-like structure.
4, the preparation of MAP (struvite) crystalline deposit filler is characterized in that porous particles carriers such as useless zeolite, waste active carbon, coke, flyash are placed the smooth wall streaming tank, apply with the magnesium source earlier or the immersion carrier, obtain being loaded with the carrier in magnesium source, carrier of separating and residue magnesium source, oven dry; But in fluidized-bed, add water, ammonia nitrogen, phosphoric acid salt to fluidized state, control pH9-10, and bubbling air pressurization, add the magnesium source, making the N:P:Mg mol ratio is 1:1:1.0-2.0, by the outer circulation fluidisation, makes fluidisation intensity reach carrier rate of expansion 10%, end loop, dehydration and bubbling air seasoning.
5,, it is characterized in that moulding pressure is 3-4 normal atmosphere according to the preparation of the described MAP of claim 4 (struvite) crystalline deposit filler.
6, according to the preparation of the described MAP of claim 4 (struvite) crystalline deposit filler, phosphoric acid salt and magnesium add with form of mixtures when it is characterized in that fluidized reaction.
7, according to claim 4,5 or 6 described MAP (struvite) crystalline deposit fillers, it is characterized in that pre-film is to thickness 0.5-5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101308541A CN101376531B (en) | 2007-08-27 | 2007-08-27 | MAP (guano) crystal precipitating stuffing and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101308541A CN101376531B (en) | 2007-08-27 | 2007-08-27 | MAP (guano) crystal precipitating stuffing and preparation thereof |
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| Publication Number | Publication Date |
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| CN101376531A true CN101376531A (en) | 2009-03-04 |
| CN101376531B CN101376531B (en) | 2010-09-01 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804324A (en) * | 2010-04-16 | 2010-08-18 | 南京大学 | Modified molecular sieve with high selectivity to ammonia nitrogen in waste water and preparation method thereof |
| CN102690001A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for treating sewage with high ammonia, nitrogen and phosphorus contents in livestock and poultry farms by chemical precipitation |
| CN103523769A (en) * | 2013-10-08 | 2014-01-22 | 中国农业大学 | Composite charcoal, and preparation method and application thereof |
| CN104016459A (en) * | 2014-06-18 | 2014-09-03 | 无锡市政设计研究院有限公司 | Preparation method and application of filter chamber filter material replacing struvite mineral |
| WO2015004031A1 (en) | 2013-07-10 | 2015-01-15 | Again Nutrient Recovery Ab | Nutrient recovery |
| CN105316002A (en) * | 2015-11-27 | 2016-02-10 | 同济大学 | Preparation method of multifunctional repair agent used for governing heavy metal contaminated soil |
| WO2016070754A1 (en) * | 2014-11-04 | 2016-05-12 | 钱春香 | Method for concreting loose sand particles through biological phosphate and carbonate composite cementing material |
| CN107162139A (en) * | 2017-06-02 | 2017-09-15 | 北京大学 | A kind of flocculant of simultaneous removing ammonia nitrogen and phosphorus and its preparation method and application |
| CN108103839A (en) * | 2017-12-08 | 2018-06-01 | 四川理工学院 | A kind of preparation method of modified calcium sulfate crystal whisker papermaking filler |
| CN108976040A (en) * | 2018-09-12 | 2018-12-11 | 郑忆依 | A method of using coal ash for manufacturing for slow-release fertilizer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004290862A (en) * | 2003-03-27 | 2004-10-21 | Ebara Corp | Method and apparatus for recovering nitrogen and phosphorus |
| CN1623924A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院生态环境研究中心 | Process for removing ammonia of treating waste water containing high contentrition ammonia |
-
2007
- 2007-08-27 CN CN2007101308541A patent/CN101376531B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804324B (en) * | 2010-04-16 | 2012-06-20 | 南京大学 | Modified molecular sieve with high selectivity to ammonia nitrogen in waste water and preparation method thereof |
| CN101804324A (en) * | 2010-04-16 | 2010-08-18 | 南京大学 | Modified molecular sieve with high selectivity to ammonia nitrogen in waste water and preparation method thereof |
| CN102690001A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for treating sewage with high ammonia, nitrogen and phosphorus contents in livestock and poultry farms by chemical precipitation |
| CN102690001B (en) * | 2012-06-06 | 2013-10-30 | 广西大学 | Method for treating sewage with high ammonia, nitrogen and phosphorus contents in livestock and poultry farms by chemical precipitation |
| WO2015004031A1 (en) | 2013-07-10 | 2015-01-15 | Again Nutrient Recovery Ab | Nutrient recovery |
| CN103523769A (en) * | 2013-10-08 | 2014-01-22 | 中国农业大学 | Composite charcoal, and preparation method and application thereof |
| CN104016459A (en) * | 2014-06-18 | 2014-09-03 | 无锡市政设计研究院有限公司 | Preparation method and application of filter chamber filter material replacing struvite mineral |
| CN104016459B (en) * | 2014-06-18 | 2015-12-09 | 无锡市政设计研究院有限公司 | A kind of preparation method of filter of alternative struvite ore and application thereof |
| WO2016070754A1 (en) * | 2014-11-04 | 2016-05-12 | 钱春香 | Method for concreting loose sand particles through biological phosphate and carbonate composite cementing material |
| CN105316002A (en) * | 2015-11-27 | 2016-02-10 | 同济大学 | Preparation method of multifunctional repair agent used for governing heavy metal contaminated soil |
| CN105316002B (en) * | 2015-11-27 | 2018-05-08 | 同济大学 | A kind of preparation method for the multi-functional renovation agent administered for heavy-metal contaminated soil |
| CN107162139A (en) * | 2017-06-02 | 2017-09-15 | 北京大学 | A kind of flocculant of simultaneous removing ammonia nitrogen and phosphorus and its preparation method and application |
| CN107162139B (en) * | 2017-06-02 | 2020-11-10 | 北京大学 | Flocculant for synchronously removing ammonia nitrogen and phosphorus and preparation method and application thereof |
| CN108103839A (en) * | 2017-12-08 | 2018-06-01 | 四川理工学院 | A kind of preparation method of modified calcium sulfate crystal whisker papermaking filler |
| CN108103839B (en) * | 2017-12-08 | 2020-03-20 | 四川理工学院 | Preparation method of modified calcium sulfate whisker papermaking filler |
| CN108976040A (en) * | 2018-09-12 | 2018-12-11 | 郑忆依 | A method of using coal ash for manufacturing for slow-release fertilizer |
| CN108976040B (en) * | 2018-09-12 | 2021-07-06 | 郑忆依 | Method for preparing slow release fertilizer by using fly ash |
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| CN101376531B (en) | 2010-09-01 |
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Granted publication date: 20100901 Termination date: 20190827 |