CN103962104A - Composite phosphorous removal adsorbent as well as preparation method and application thereof - Google Patents
Composite phosphorous removal adsorbent as well as preparation method and application thereof Download PDFInfo
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- CN103962104A CN103962104A CN201410213954.0A CN201410213954A CN103962104A CN 103962104 A CN103962104 A CN 103962104A CN 201410213954 A CN201410213954 A CN 201410213954A CN 103962104 A CN103962104 A CN 103962104A
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Abstract
The invention belongs to the sewage treatment field and relates to a composite phosphorous removal adsorbent as well as a preparation method and application thereof. The composite phosphorous removal adsorbent is prepared from the following ingredients in percentage by weight: 74-94% of kaolin, 5-25% of oyster and 1-2% of sesbania powder. The preparation method comprises the following steps of adding 100g of mixed powder of kaolin, oyster and sesbania powder with 50-60mL of dilute nitric acid with weight percentage of not more than 1% to be mixed, adding dilute nitric acid with weight percentage of not more than 1%, and stirring into paste; extruding, molding and air drying naturally; and heating at 800-900 DEG C to prepare the composite phosphorous removal adsorbent. The composite phosphorous removal adsorbent has wide raw material source, low cost and reclamation of wastes; the preparation method is simple and has remarkable energy-saving effect; the prepared composite phosphorous removal adsorbent is used for phosphorous removal in waste water and is used for natural water eutrophication treatment and repairing.
Description
Technical field
The invention belongs to sewage treatment area, be specifically related to a kind of composite dephosphorization adsorbent, preparation method and application in sewage treatment area taking kaolin, oyster shell as raw material.
Background technology
Oyster shell derives from the discarded object of the male whetstone production and consumption in seashore, is mainly made up of the organic matter such as mineral matter and protein, polysaccharide, wherein CaCO
3content is more than 90%.According to statistics, the annual oyster shell output in China's Coastal Areas is about 1,000,000 tons, and major part directly abandons as discarded object, causes environmental pollution and the wasting of resources.The kaolin resource of China is abundant, cheap, has been widely used at present the fields such as rubber, plastics, coating, papermaking and PETROLEUM PROCESSING.Kaolin also more and more comes into one's own in the application in environmental improvement field in recent years, but also less in the application of dephosphorization adsorbing domain.
China lake and basin body eutrophication constantly aggravate, and phosphorus is one of principal element of body eutrophication formation, prevent that body eutrophication dephosphorization from being crucial.In water body, the removal method of phosphorus mainly contains chemical precipitation method, bioanalysis and absorption method at present.Chemical precipitation method phosphor-removing effect is good, but cost is higher, easily produces secondary pollution; Bioanalysis sludge output is large, fluctuation of service; Absorption method has high selectivity, low energy consumption because of it, can realize water treatment and resource receives much concern in one.The features such as the key of absorption method dephosphorization is the selection of adsorbent, and it is low that dephosphorization adsorbent should possess production cost, and adsorption capacity is large, and raw material sources are wide.Conventional adsorbent is mainly the three major types such as natural material and waste residue, activated alumina and modifier thereof and artificial synthetic adsorbent at present.Natural material and activated alumina because of its adsorption capacity little, cost is high, easily produces the application such as secondary pollution and is restricted, now artificial synthetic dephosphorization adsorbent more comes into one's own.
The Nie Jin of the Guangdong University of Technology rising sun, Tang Wen extensively waits (Nie Jinxu, Tang Wenguang, Liu Lifan, Ruan Caiqun. the preparation of microwave reinforced modified alta-mud and to phosphorus Study on adsorption properties [J]. nonmetallic ore, 2010,33 (3): 74-76.) by levigate bentonite to the add water water slurry of furnishing 20% of 200 orders, then carry out after 4 grades of sortings 105-110 DEG C of oven dry, be ground to 200 orders; By bentonite and FeSO
4, soak with certain proportioning, then dry porphyrize through suction filtration, washing and be placed in 480w micro-wave oven and heat 5min, cooling 200 mesh sieves that ground obtain iron modified alta-mud.This modified alta-mud is joined to pH is 6, stirs and leave standstill 2h after 15min and measure in the waste water of phosphorous 50mg/L with 180rpm, and tp removal rate is 98%, and modified alta-mud is 4.9mg/g to the unit adsorbance of phosphorus.These adsorbent raw material sources are extensive, price is relatively low, and dephosphorization efficiency by using is high, speed is fast, in preparation technology without high-temperature calcination process, Energy Intensity Reduction.But preparation process adopts heating using microwave, is difficult in industrial applications accomplished.
CN101176839A relates to a kind of oyster shell and clay of utilizing and prepares composition of raw materials and the preparation method of dephosphorization material for raw material, this method is after 500 DEG C of pre-burning fragmentations of oyster shell, to mix by a certain percentage to mud shape material with clay, by compressing mud shape material (granular or tubulose), 50-100 DEG C dry, then after 650-800 DEG C of calcination is cooling, obtains dephosphorization material.This dephosphorization material (granular) is added to 1% quality in the waste water of 10L, phosphorous 5mg/L, and after 10-60h, in solution, the concentration of phosphorus is reduced to 1mg/L, and tp removal rate is 80%.This technology has adopted wide material sources, cheap oyster shell and clay, and cost is low, has realized utilization of waste as resource, and this adsorbent can be regenerated and to be reused.But adsorbent dosage is large in application process, dephosphorization cost is high.
CN1803274A relates to and utilizes granularity for 60-100 object powdered zeolite, diatomite or aluminium oxide, after washing and drying, join by a certain percentage in rare earth (lanthanum and cerium) hydroxide solution, stir 0.75-1h, dipping 15-20h, filtration obtains filter cake, and filter cake is sieved and obtains dephosphorization adsorbent after 300-600 DEG C of roasting 0.5-2h.This adsorbent can be removed yin, yang ion simultaneously, and adsorption capacity is large, and the adsorption capacity of phosphorus is reached to 22-25mg/g, and adsorbent can be resolved regeneration.This material is better to the adsorption effect of phosphorus, but complicated process of preparation, energy consumption is high, and raw material have adopted rare earth element hydroxide and aluminium oxide, and price is high, and rare earth element easily enrichment in food chain, and ecological safety and health are existed to potential risk.
Dalian University of Technology's period-luminosity red (period-luminosity is red. several solid waste adsorption and dephosphorization performances and Exploration of Mechanism [D] thereof. Dalian University of Technology's master thesis, 2010.) by the processing for phosphorus-containing wastewater after oyster shell washing, oven dry, grinding, tp removal rate is 98.3%.This adsorbent adopts discarded object oyster shell, and raw material sources are wide, realized changing waste into resources; The production process of adsorbent only relates to crushing process, and technique is simple, and energy consumption is low; But range request temperature higher (35 DEG C) is crossed in dephosphorization, reaches time of equilibrium adsorption long, and adsorption capacity is lower, needs to heat in practical application, and limitation is higher.Therefore need the new compound adsorbent of exploitation taking oyster shell as raw material, (25 DEG C) have higher adsorption efficiency and larger adsorption capacity at a lower temperature.
Summary of the invention
For shortcomings and deficiencies of the prior art, the object of the invention has been to provide a kind of preparation method taking kaolin and oyster shell as the composite dephosphorization adsorbent of raw material.Preparation process is simple, and raw material is easy to get, production cost is low, and is conducive to realize the dual purpose of environmental protection and the treatment of wastes with processes of wastes against one another.
A kind of composite dephosphorization adsorbent, its raw material comprises kaolin, oyster shell, sesbania powder and rare nitric acid, is by mass percentage:
Kaolin 74-94%;
Oyster shell 5-25%;
Sesbania powder 1-2%;
Kaolin, oyster shell and the sesbania powder mixed-powder of every 100g, add mass percent to be not more than rare nitric acid 50-60mL of 1%.
Described oyster shell is the oyster shell after fragmentation, and oyster shell is 100-200 order.
Of the present inventionly prepare the sesbania powder of composite dephosphorization adsorbent in raw materials used and mass percent to be not more than 1% rare nitric acid be binding agent, for assistant formation.
A preparation method for composite dephosphorization adsorbent, step is as follows:
1. according to the above ratio kaolin, oyster shell and sesbania powder are mixed;
2. add mass percent to be not more than rare nitric acid of 1% to the mixed-powder 1. obtaining, stir into mud shape;
3. the mud shape sample extruded moulding 2. step being obtained, natural air drying;
4. 3. gained bar shaped sample, through heating, makes composite dephosphorization adsorbent.
The sample length that 3. step obtains extruded moulding is 10-20mm, diameter 1.5-2.5mm.
The step heat time under 800-900 DEG C of condition is 4. 2-3h.
With described dephosphorization adsorbent treatment of simulated waste water, test result shows, in water body, the clearance of phosphorus, more than 95%, has proved that this adsorbent can be widely used in waste water treatment plant's dephosphorization, also can be used for that eutrophication of natural water is administered and the field such as reparation.
Beneficial effect of the present invention: composite dephosphorization adsorbent prepared by the present invention is taking oyster shell and kaolin as main component, wide material sources, cost is low, has realized changing waste into resources simultaneously; Preparation method is simple, and energy-saving effect is obvious; This adsorbent can be used for waste water treatment plant's dephosphorization process, also can be used for eutrophication of natural water improvement and repair simulated wastewater test showing, after the solution that is 5mg/L to phosphorus content absorption 6h, in its water body, the clearance of phosphorus is more than 95%.
Detailed description of the invention
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1
1. the preparation of kaolin-oyster shell composite dephosphorization adsorbent
By discarded seashore rubbish oyster shell deionized water washes clean, 80 DEG C of oven dry, ground after 100 mesh sieves, acquisition oyster shell powder, is placed in air-tight bottle and preserves.Kaolin is crossed 325 mesh sieves, 80 DEG C of oven dry, and sealing is preserved.Take 90g kaolin, 10g oyster shell and 2g sesbania powder mixing and stirring, add 1% salpeter solution, stir into mud shape, be crushed to strip, after natural air drying, be ground into the cylindrical particle that length is 10-20mm.Gained cylindrical particle is laid in to crucible bottom, puts into Muffle furnace at 800-900 DEG C of heating 2h.
2. the effect assessment of kaolin-oyster shell composite dephosphorization adsorbent
1.0g dephosphorization adsorbent is joined by analyzing pure KH
2pO
4in the 100mL solution that is 5mg/L containing phosphorus concentration of preparation, be 6-7 with the pH of 10%Na0H regulator solution, the speed with 150rpm at 25 DEG C is carried out constant temperature oscillation.After 6h, sampled 0.45 μ m filter membrane, and measured the phosphorus concentration in filtrate with molybdenum-antimony anti-spectrophotometric method, in solution, tp removal rate is 98.5%.
Embodiment 2
1. the preparation of kaolin-oyster shell composite dephosphorization adsorbent
By discarded seashore rubbish oyster shell deionized water washes clean, 80 DEG C of oven dry, ground after 100 mesh sieves, acquisition oyster shell powder, is placed in air-tight bottle and preserves.Kaolin is crossed 325 mesh sieves, 80 DEG C of oven dry, and sealing is preserved.Take 80g kaolin, 20g oyster shell and 2g sesbania powder mixing and stirring, all the other steps are identical with embodiment 1.
2. the effect assessment of kaolin-oyster shell composite dephosphorization adsorbent
1.0g dephosphorization adsorbent is joined by analyzing pure KH
2pO
4, preparation containing being 6-7 with the pH of 10%NaOH regulator solution in the phosphorus concentration 100mL solution that is 50mg/L, the speed with 150rpm at 25 DEG C is carried out constant temperature oscillation.After 6h, sampled 0.45 μ m filter membrane, and measured the phosphorus concentration in filtrate, in solution, tp removal rate is 91.2%.
Claims (5)
1. a composite dephosphorization adsorbent, is characterized in that, the raw material of composite dephosphorization adsorbent comprises kaolin, oyster shell, sesbania powder and rare nitric acid, is by mass percentage:
Kaolin 74-94%;
Oyster shell 5-25%;
Sesbania powder 1-2%;
Kaolin, oyster shell and the sesbania powder mixed-powder of every 100g, add mass percent to be not more than rare nitric acid 50-60mL of 1%;
Described oyster shell is the oyster shell after fragmentation, and oyster shell is 100-200 order.
2. the preparation method of composite dephosphorization adsorbent claimed in claim 1, is characterized in that, step is as follows:
1. according to the above ratio kaolin, oyster shell and sesbania powder are mixed;
2. add mass percent to be not more than rare nitric acid of 1% to the mixed-powder 1. obtaining, stir into mud shape;
3. the mud shape sample extruded moulding 2. step being obtained, natural air drying;
4. 3. gained bar shaped sample heats 2-3h through under 800-900 DEG C of condition, makes composite dephosphorization adsorbent.
3. the preparation method of composite dephosphorization adsorbent according to claim 1 and 2, is characterized in that, the sample length that 3. described step obtains extruded moulding is 10-20mm, diameter 1.5-2.5mm.
4. the application of the composite dephosphorization adsorbent described in claim 1 or 2, is characterized in that, described composite dephosphorization adsorbent is removed for the phosphorus of waste water or administered and repair for body eutrophication.
5. the application of the composite dephosphorization adsorbent that prepared by preparation method claimed in claim 3, is characterized in that, described composite dephosphorization adsorbent is removed for the phosphorus of waste water or administered and repair for body eutrophication.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554372A (en) * | 2018-05-04 | 2018-09-21 | 南京信息工程大学 | The method that phosphorus in water removal is gone using aluminum salt modified clay |
| CN110732317A (en) * | 2019-09-27 | 2020-01-31 | 浙江海洋大学 | preparation method of natural adsorbent for treating phosphorus-containing wastewater |
| CN110756171A (en) * | 2019-11-06 | 2020-02-07 | 福建师范大学 | Method for preparing oyster shell powder-based sewage treatment device |
| CN112390387A (en) * | 2020-11-13 | 2021-02-23 | 程佳霖 | Water quality modifier, detergent containing water quality modifier and preparation method of water quality modifier |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176839A (en) * | 2007-11-23 | 2008-05-14 | 福州大学 | Raw material prescription and preparing method for preparing recoverable wastewater dephosphorization material using shuck |
-
2014
- 2014-05-19 CN CN201410213954.0A patent/CN103962104A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176839A (en) * | 2007-11-23 | 2008-05-14 | 福州大学 | Raw material prescription and preparing method for preparing recoverable wastewater dephosphorization material using shuck |
Non-Patent Citations (1)
| Title |
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| 翟由涛等: "改性高岭土对废水中磷的吸附性能及机理研究", 《土壤》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554372A (en) * | 2018-05-04 | 2018-09-21 | 南京信息工程大学 | The method that phosphorus in water removal is gone using aluminum salt modified clay |
| CN110732317A (en) * | 2019-09-27 | 2020-01-31 | 浙江海洋大学 | preparation method of natural adsorbent for treating phosphorus-containing wastewater |
| CN110756171A (en) * | 2019-11-06 | 2020-02-07 | 福建师范大学 | Method for preparing oyster shell powder-based sewage treatment device |
| CN112390387A (en) * | 2020-11-13 | 2021-02-23 | 程佳霖 | Water quality modifier, detergent containing water quality modifier and preparation method of water quality modifier |
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Application publication date: 20140806 |