CN100366337C - Method for preparing absorbent with phosphor concentration and phosphor reclaim function - Google Patents
Method for preparing absorbent with phosphor concentration and phosphor reclaim function Download PDFInfo
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- CN100366337C CN100366337C CNB2005100301298A CN200510030129A CN100366337C CN 100366337 C CN100366337 C CN 100366337C CN B2005100301298 A CNB2005100301298 A CN B2005100301298A CN 200510030129 A CN200510030129 A CN 200510030129A CN 100366337 C CN100366337 C CN 100366337C
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Abstract
The present invention relates to a method for preparing absorbent with the functions of phosphor concentration and phosphor recovery. Natural inorganic substances are used as raw materials. 100 parts of calcareous raw materials by weight and 80 to 200 parts of siliceous raw materials are uniformly mixed, and then water and synthetic auxiliary agents, such as sodium hydroxide solution or calcium hydrate solution, are added to the raw materials. The mixtures are put in a hydrothermal reaction kettle after standing activation to be heated, pressurized and synthesized. The synthesis temperature is from 120 to 280DEG. C, the synthesis pressure is from 10 to 40MPa, and the synthesis time is from 3 to 24 hours. The hydrothermal synthesized materials are cooled, dried and finely ground or processed into granules to obtain efficient absorbents with the functions of phosphor concentration and phosphor recovery. The calcareous raw materials of the present invention are lime hydrate, burnt lime, shells, etc. The siliceous raw materials are silica dioxide, sodium silicate, silica, diatomite, rice husk ash, etc. The source is wide, and the cost is low. The prepared absorbents have the advantages of large processing quantity of phosphorus of unit weight part, low production cost, easy desorption, phosphorus recovery, etc.
Description
Technical field
The present invention relates to a kind of preparation of adsorbent method with phosphorus enrichment and phosphorus recovery function, being specifically related to a kind of is raw material with inorganic matters such as quick lime and silicas, the preparation method of the synthetic high-efficiency adsorbent with phosphorus enrichment and phosphorus recovery function belongs to water-treatment technology field by hydro-thermal reaction.
Background technology
In recent years, lake, the river eutrophication pollution that too much causes owing to the nutriments such as nitrogen phosphorus in the water body become the great environmental problem that China faces.Scientific research shows, just may break out the blue-green alge wawter bloom when the total phosphorus content in the unhurried current water bodys such as lake and reservoir surpasses 0.02mg/L, causes dissolved oxygen decline in the water body, and water quality is black smelly, animals and plants disappearance, drinking water source severe contamination.On the other hand, the source of students key element that phosphorus is grown up as all things on earth is again extremely valuable resource.Phosphorus is one-way flow in biosphere: after the man-made recovery uses or after natural erosion, the home to return to of phosphorus is to import the sea by the river, land mostly, finally is deposited in the sedimentary deposit at deep-sea, no longer returns.Because occurring in nature phosphorus circulating path irreversible, its consumption will cause serious loss, thereby be a kind of non-renewable, resource of being difficult to substitute, even more valuable more than water and oil.
The content of phosphorus is very high in the sanitary sewage, every cubic metre of nearly 5 gram phosphorus, and the phosphorus that reclaims in the sewage has eutrophication of preventing and treating and the double meaning of laying in phosphor resource.If half phosphorus calculates in the sewage by reclaiming, its quantity is also considerable.With Gaobeidian City, Beijing sewage treatment plant is example, and this is the sewage treatment plant in present China maximum, Asia second, disposes of sewage every day up to 100 ten thousand steres, and recuperable pure phosphorus is up to 2500 kilograms, and this is a huge cornucopia beyond doubt.
Mostly adopt the phosphorus in bioanalysis or chemical method or the absorption method removal sewage at present both at home and abroad.Biological phosphate-eliminating based on activated sludge discharge phosphorus under the anaerobic state, under good oxygen condition absorption phosphorus characteristics and develop, the phosphorus in the sewage finally accumulates in activated sludge, effluxes with dewatered sludge after a series of subsequent treatment such as concentrated, mummification.Because the sludge quantity that this method produces is big, and contains a large amount of organic matters and a certain amount of toxic heavy metal in the mud, is difficult to realize the recovery of phosphorus.Chemical method promptly directly adds phosphorus in chemical agent and the phosphorus reaction generation flocky precipitate removal water at the preliminary sedimentation tank or the second pond of Sewage Plant.But up to the present, selected medicament mostly is conventional aluminium salt or molysite, and its dispensing cost is very high, and the flco that the reaction back produces is small, is difficult to precipitation; Through finding after theoretical calculating and the actual experiment analysis, phosphorus content is a little less than poor efficiency phosphate fertilizer commonly used at present in aluminium salt and the molysite dephosphorization product, only be about 1%～2%, simultaneously since with phosphorus state quite stable after iron, aluminium combine, be utilized as the fertilizer use so also be difficult to be reproduced.The phosphorus removing method of absorption method for coming into one's own in recent years promptly utilizes phosphorus in the direct adsorbed water of specific sorbing material.Activated alumina is to be seen in the maximum phosphorus sorbing material of report at present, and this material only is per kilogram adsorbent 10 gram phosphorus to the adsorbance of phosphorus, and promptly phosphorus content still can not reach the standard of phosphate fertilizer in the product about 1%.Iron-rare earth element compound water treatment adsorbent of reporting among the aqua oxidation lanthanum of report and the Chinese patent CN1094070C in other phosphorus sorbing materials such as the document " experimental study of aqua oxidation lanthanum adsorption and dephosphorization " (environmental science .2003.24 (5) .111-113) or the like, though the phosphorus adsorbance is up to 140mg/g, be that the per kilogram adsorbent absorbs 140 gram phosphorus, but since raw materials used be rare precious metal element, therefore be in tangible inferior position on production cost, whether harmful simultaneously do not have the clear conclusions report as yet yet.
Summary of the invention
The objective of the invention is to deficiency at existing technology, a kind of preparation of adsorbent method with phosphorus enrichment and phosphorus recovery function is provided, raw material sources is extensive, with low cost, but the adsorbent of preparation has that Unit Weight part phosphorus treating capacity is big, the low desorb of production cost, can realize characteristics such as phosphorus recovery.
For realizing this purpose, it is raw material that the present invention adopts natural inorganic matter, after calcareous raw material and siliceous raw material mixed by a certain percentage, add entry and additive synthesis leaves standstill activation, then mixture is dropped in the hydrothermal reaction kettle, heating is pressed into, and cooling oven dry back is levigate or be processed into particle, can obtain having the adsorbent of phosphorus enrichment and phosphorus recovery function.
The composition and the consumption of raw material of the present invention are as follows:
In weight portion: calcareous raw material: 100 parts,
Siliceous raw material: 80～200 parts,
Additive synthesis: 1～10 part,
Water: 100～600 parts.
Calcareous raw material of the present invention is calcium hydroxide, quick lime, and shell etc., siliceous raw material are silica, sodium metasilicate, silica, diatomite, rice hull ash etc., additive synthesis be weight percentage 1% sodium hydroxide solution or aqua calcis.
Method of the present invention specifically comprises the steps:
1. in weight portion, the siliceous raw material of 100 parts calcareous raw materials and 80～200 parts is mixed, add 1～10 part additive synthesis and 100～600 parts water then, leave standstill activation 1～6 hour after the mixing.
2. said mixture being dropped into heats in the hydrothermal reaction kettle is pressed into.Synthesis temperature is at 120～280 ℃, and synthesis pressure is 10～40Mpa, generated time 3～24 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.
Material is levigate or be processed into promptly to make after the graininess and have the high-efficiency adsorbent that phosphorus enrichment and phosphorus reclaim function 3..
Adopt common chemical flocculants such as the synthetic adsorbent of above method and molysite and aluminium salt to compare, the dephosphorization ability is much better than, and settling rate is faster, separates simple; Compare with the adsorbent that activated alumina etc. is commonly used, at normal temperatures with conventional water in phosphorus adsorption capacity under the pH value condition obviously increase, the phosphorus rate of adsorption is obviously accelerated; Compare with the noble metal compound adsorbent, much with low cost, wide material sources many, and nontoxic.
Advantage of the present invention and positive role are embodied in: realize in dephosphorization that phosphorus reclaims 1., Unit Weight phosphorus adsorbance at actual sewage reaches per kilogram adsorbent 70 grams～140 gram phosphorus, reach even exceed phosphorus content in the conventional phosphate fertilizer, this adsorbent can be separated the phosphorus of the sucking-off overwhelming majority in the short time under the condition of pH＜3, so can directly be used as efficient phosphorous fertilizer, perhaps be used for the production of all kinds of phosphorus chemical products.2. have the buffer capacity of meta-alkalescence after this adsorbent drops in the water, effectively the pH scope is very wide, handles back sewage pH and is stabilized between 8～8.5.This adsorbed product particle big, than great, precipitate and separate is easy, disengaging time is in 10 minutes.4. employing wide material sources, with low cost, nontoxic natural material is a raw material, has tangible prices of raw and semifnished materials advantage.
The specific embodiment
Below by specific embodiment technical scheme of the present invention is further described.Enforcement of the present invention is not limited to following examples.
Embodiment 1
In weight portion, raw material adopts 100 parts of calcium hydroxides and 80 parts of silica, after both are mixed, add 100 parts water and 1 part of percentage by weight and be 1% sodium hydroxide solution, leaving standstill activation after 1 hour drops into mixture and is warming up to 120 ℃ in the hydrothermal reaction kettle, be synthetic under the condition of 10Mpa at pressure, generated time 3 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.Make Powdered adsorbent with material is levigate at last.
The phosphorus adsorbent that utilizes above-mentioned technology to make carries out sewage phosphorus and reclaims experiment.Sewage is taken from purification of water quality factory of Shanghai shen village sludge concentration tank, and former water phosphate concn is 25mg/L, and pH is 7.1.Get 3 gram phosphorus adsorbents and drop in this sanitary sewage of 10L, constantly stir, adsorb to staticly settle after 8 hours and isolated adsorbed product in 10 minutes.PH is 8.3 in the mensuration supernatant, and phosphate concn is 1.3mg/L, and tp removal rate is 94.8%, and the phosphorus adsorbance is 79mg/g; Get the adsorbed product 100mg after the oven dry, add in the 100mL distilled water, regulate pH=2.1, desorb after 1 hour the phosphate stripping quantity be 73mg/g, desorption efficiency reaches 92%.
Embodiment 2.
In weight portion, raw material adopts 100 parts of quick limes and 120 parts of sodium metasilicate, after both are mixed, add 200 parts water and 2 parts of percentage by weights and be 1% aqua calcis, leaving standstill activation after 2 hours drops into mixture and is warming up to 140 ℃ in the hydrothermal reaction kettle, be synthetic under the condition of 12Mpa at pressure, generated time 5 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.Make Powdered adsorbent with material is levigate at last.
The phosphorus adsorbent that utilizes above-mentioned technology to make carries out sewage phosphorus and reclaims experiment.Sewage is taken from purification of water quality factory of Shanghai shen village sludge concentration tank, and former water phosphate concn is 25mg/L, and pH is 7.1.Get 2 gram phosphorus adsorbents and drop in this sanitary sewage of 10L, constantly stir, adsorb to staticly settle after 8 hours and isolated adsorbed product in 10 minutes.PH is 8.23 in the mensuration supernatant, and phosphate concn is 1.5mg/L, and tp removal rate is 94%, and the phosphorus adsorbance is 117.5mg/g; Get the adsorbed product 100mg after the oven dry, add in the 100mL distilled water, regulate pH=2.3, desorb after 1 hour the phosphate stripping quantity be 115mg/g, desorption efficiency reaches 97.9%.
Embodiment 3
In weight portion, raw material adopts 100 parts of oyster shells and 150 parts of silicas, after both are mixed, add 300 parts water and 4 parts of percentage by weights and be 1% sodium hydroxide solution, leaving standstill activation after 3 hours drops into mixture and is warming up to 160 ℃ in the hydrothermal reaction kettle, be synthetic under the condition of 17Mpa at pressure, generated time 6 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.Make Powdered adsorbent with material is levigate at last.
The phosphorus adsorbent that utilizes above-mentioned technology to make carries out sewage phosphorus and reclaims experiment.Sewage is taken from purification of water quality factory of Shanghai shen village sludge concentration tank, and former water phosphate concn is 25mg/L, and pH is 7.1.Get 2 gram phosphorus adsorbents and drop in this sanitary sewage of 10L, constantly stir, adsorb to staticly settle after 8 hours and isolated adsorbed product in 10 minutes.PH is 8.3 in the mensuration supernatant, and phosphate concn is 1.5mg/L, and tp removal rate is 94%, and the phosphorus adsorbance is 117.5mg/g; Get the adsorbed product 100mg after the oven dry, add in the 100mL distilled water, regulate pH=2.1, desorb after 1 hour the phosphate stripping quantity be 113mg/g, desorption efficiency reaches 96%.
Embodiment 4
In weight portion, raw material adopts 100 parts of calcium hydroxides and 180 parts of diatomite, after both are mixed, add 400 parts water and 5 parts of percentage by weights and be 1% sodium hydroxide solution, leaving standstill activation after 5 hours drops into mixture and is warming up to 180 ℃ in the hydrothermal reaction kettle, be synthetic under the condition of 20Mpa at pressure, generated time 6 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.Make Powdered adsorbent with material is levigate at last.
The phosphorus adsorbent that utilizes above-mentioned technology to make carries out sewage phosphorus and reclaims experiment.Sewage is taken from purification of water quality factory of Shanghai shen village sludge concentration tank, and former water phosphate concn is 25mg/L, and pH is 7.1.Get 1.5 gram phosphorus adsorbents and drop in this sanitary sewage of 10L, constantly stir, adsorb to staticly settle after 8 hours and isolated adsorbed product in 10 minutes.PH is 8.24 in the mensuration supernatant, and phosphate concn is 3mg/L, and tp removal rate is 88%, and the phosphorus adsorbance is 146mg/g; Get the adsorbed product 100mg after the oven dry, add in the 100mL distilled water, regulate pH=2.5, desorb after 1 hour the phosphate stripping quantity be 127mg/g, desorption efficiency reaches 90.7%.
Embodiment 5
In weight portion, raw material adopts 100 parts of quick limes and 200 parts of rice hull ash, after both are mixed, add 600 parts water and 10 parts of percentage by weights and be 1% aqua calcis, leaving standstill activation after 6 hours drops into mixture and is warming up to 280 ℃ in the hydrothermal reaction kettle, be synthetic under the condition of 40Mpa at pressure, generated time 24 hours.Material with hydro-thermal after synthetic takes out and the cooling oven dry.To make the granular adsorption agent after the material cutting at last.
The phosphorus adsorbent that utilizes above-mentioned technology to make carries out sewage phosphorus and reclaims experiment.Sewage is taken from purification of water quality factory of Shanghai shen village sludge concentration tank, and former water phosphate concn is 25mg/L, and pH is 7.1.Get 3 gram phosphorus adsorbents and drop in this sanitary sewage of 10L, constantly stir, adsorb to staticly settle after 8 hours and isolated adsorbed product in 10 minutes.PH is 8.41 in the mensuration supernatant, and phosphate concn is 1.7mg/L, and tp removal rate is 93.2%, and the phosphorus adsorbance is 116.5mg/g; Get the adsorbed product 100mg after the oven dry, add in the 100mL distilled water, regulate pH=2.5, desorb after 1 hour the phosphate stripping quantity be 109mg/g, desorption efficiency reaches 93.6%.
Claims (2)
1. the preparation of adsorbent method with phosphorus enrichment and phosphorus recovery function is characterized in that comprising the steps:
1) in weight portion, the siliceous raw material of 100 parts calcareous raw materials and 80～200 parts is mixed, add 1～10 part additive synthesis and 100～600 parts water then, leave standstill activation 1～6 hour after the mixing; Described additive synthesis be weight percentage 1% sodium hydroxide solution or aqua calcis;
2) said mixture is dropped into heat in the hydrothermal reaction kettle and be pressed into, synthesis temperature is 120～280 ℃, and synthesis pressure is 10～40Mpa, generated time 3～24 hours, and the material with hydro-thermal after synthetic takes out and the cooling oven dry;
3) material is levigate or be processed into graininess, promptly make and have the adsorbent that phosphorus enrichment and phosphorus reclaim function.
2. according to the preparation of adsorbent method with phosphorus enrichment and phosphorus recovery function of claim 1, it is characterized in that described calcareous raw material is calcium hydroxide, quick lime or shell, described siliceous raw material is silica, sodium metasilicate, silica, diatomite or rice hull ash.
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| CNB2005100301298A CN100366337C (en) | 2005-09-29 | 2005-09-29 | Method for preparing absorbent with phosphor concentration and phosphor reclaim function |
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| CNB2005100301298A CN100366337C (en) | 2005-09-29 | 2005-09-29 | Method for preparing absorbent with phosphor concentration and phosphor reclaim function |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101176839B (en) * | 2007-11-23 | 2010-09-08 | 福州大学 | Raw material prescription and preparing method for preparing recoverable wastewater dephosphorization material using shuck |
| CN102351206B (en) * | 2011-07-04 | 2014-03-19 | 重庆大学 | Carbide slag calcium characteristic-based preparation method of phosphorus recovery material |
| CN103721667B (en) * | 2013-12-17 | 2015-08-26 | 江苏省农业科学院 | A kind of dephosphorization adsorbent and preparation method efficiently |
| CN106629757B (en) * | 2016-11-17 | 2019-08-13 | 黑龙江大学 | Recycling silicon prepares the method that calcium silicates removes nitrogen phosphorus in water removal in a kind of red mud |
| CN106955677A (en) * | 2017-04-20 | 2017-07-18 | 佛山市飞时达新材料科技有限公司 | It is a kind of based on ion liquid modified egg shell/acticarbon and preparation method thereof |
| CN108097205A (en) * | 2017-12-29 | 2018-06-01 | 中国科学院亚热带农业生态研究所 | A kind of method and application that wastewater efficient dephosphorization adsorbent is prepared using bentonite |
| CN108126663B (en) * | 2018-02-26 | 2021-07-02 | 彭万喜 | High-efficiency adsorbent |
| CN109881525B (en) * | 2019-01-31 | 2021-03-19 | 济南盛和纸业有限公司 | Preparation method of indoor air purification paper |
| CN110876917B (en) * | 2019-11-25 | 2023-04-21 | 山东建筑大学 | Superparamagnetic response nano phosphorus adsorbent and preparation method thereof |
| CN115737456B (en) * | 2022-11-22 | 2024-05-17 | 宁波子沐新材料科技有限公司 | Skin cleansing scrub and preparation method thereof |
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| CN1248486A (en) * | 1999-09-29 | 2000-03-29 | 清华大学 | Ferri-rareearth element compound water treatment adsorbent and preparation process thereof |
| JP2002336874A (en) * | 1996-12-28 | 2002-11-26 | Mitsubishi Materials Corp | Dephosphorizing material and method for producing the same |
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| JP2004275896A (en) * | 2003-03-17 | 2004-10-07 | Kyoto Institute Of Technology | Material and method for dephosphorization |
| CN1669632A (en) * | 2004-12-29 | 2005-09-21 | 上海交通大学 | Method for preparing active fly ash phosphorus adsorbent |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002336874A (en) * | 1996-12-28 | 2002-11-26 | Mitsubishi Materials Corp | Dephosphorizing material and method for producing the same |
| CN1248486A (en) * | 1999-09-29 | 2000-03-29 | 清华大学 | Ferri-rareearth element compound water treatment adsorbent and preparation process thereof |
| JP2004249263A (en) * | 2003-02-21 | 2004-09-09 | Mitsubishi Materials Corp | Phosphorus recovering material and its production method |
| JP2004275896A (en) * | 2003-03-17 | 2004-10-07 | Kyoto Institute Of Technology | Material and method for dephosphorization |
| CN1669632A (en) * | 2004-12-29 | 2005-09-21 | 上海交通大学 | Method for preparing active fly ash phosphorus adsorbent |
Non-Patent Citations (1)
| Title |
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| 粉煤灰合成沸石同步去除污水中氮磷的初步研究. 赵统刚，吴德意，孔海南，陈建刚，胡湛波.第二届全国环境化学学术报告会论文集. 2004 * |
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