CN104069792A - Synthetic method of aragonite material for deeply removing phosphorus wastewater - Google Patents
Synthetic method of aragonite material for deeply removing phosphorus wastewater Download PDFInfo
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- CN104069792A CN104069792A CN201310472996.1A CN201310472996A CN104069792A CN 104069792 A CN104069792 A CN 104069792A CN 201310472996 A CN201310472996 A CN 201310472996A CN 104069792 A CN104069792 A CN 104069792A
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Abstract
The invention discloses a method for synthesizing an aragonite type nano adsorbing material. The synthetic method specifically comprises the following steps: (1) adding a 0.9 mol/L calcium acetate (Ca(CH3COO)2) water solution into glycol to prepare a solution A; (2) adding a 3 mol/L Na2CO3 water solution into glycol to prepare a solution B; and (3) quickly mixing the solution A with the solution B for reaction in a water bath at 50 DEG C, thereby obtaining a product after one hour, repeatedly washing the product with absolute ethyl alcohol (AR), taking out and drying at 40 to 60 DEG C. The synthetic material designed in the invention is a nano aragonite (Ca(CO)3) material which can be used for effectively and deeply removing high-concentration phosphorus pollutants from wastewater (for total phosphorus with the concentration of 500 mg/L, the removing rate reaches more than 90%), secondary treatment does not need to be performed on a treatment product, and the product can be used as a phosphatic fertilizer to be directly applied to farmland. A foundation is established for industrial wastewater treatment and resource reuse, and good economic and social benefits are achieved.
Description
Technical field
The present invention relates to a kind of simple inorganic nano material preparation and technical field of sewage, be specifically related to a kind of aragonite (Ca (CO) of degree of depth removal high phosphorus industrial wastewater
3) simple method for synthesizing of mineral material.
Background technology
The eutrophication of water body is threatening the sustainable development of human society.Show according to investigation, in China's rivers and lakes, water quality total phosphorus concentration is 0.018-0.97mg/L, the standard that is generally 0.02mg/L higher than the phosphorus concentration that body eutrophication occurs.It pollutes most and mainly comes from industrial phosphorus-containing wastewater, pollution concentration is far away higher than this standard, as phosphorus concentration in coating wastewater reaches 100mg/L left and right, the concentration that the Phosphorus From Wastewater of some enterprise's discharges pollutes is higher, as the Phosphorus From Wastewater hydrochlorate concentration of industrial production LED can be up to 300mg/L.The method that removal at present used is polluted has use calcite, but its removal effect is not very good, removes phosphorus pollution if do not added the degree of depth effectively, will finally cause the deterioration of water body environment.The many rivers and lakes of China have phosphorus in various degree to pollute, this to fishery fish for, aquaculture causes tremendous economic loss.
Research shows, (main component is CaCO to calcite
3) as a kind of easy acquisition and natural minerals with low cost, there is good development prospect.The mechanism of the phosphorus of calcite removal is simultaneously subject to initial concentration and the impact of pH value of phosphorus.When the concentration of phosphorus is low, calcite is chemisorbed and physical absorption except dephosphorization mainly relies on, and when the concentration of phosphorus is high, the material surface that mainly relies on that calcite is removed phosphorus generates calcium phosphate nucleus.PH value is removed and in the process of phosphorus, is played a part very importantly at calcite in addition, and when the concentration of phosphorus is low, pH value is higher just more favourablely removes dephosphorization.In the time of high phosphorus concentration, when pH value is in 6-7 interval, the efficiency of removing phosphorus by precipitation goes up significantly very much, however along with the increase of pH value step-down to 20%.Therefore under alkali condition, calcite is removed the variation that the efficiency of high concentration phosphorus presents along with the change of pH value, can not reach the object of effective removal phosphorus.
Therefore, the present invention can provide a kind of efficient degree of depth to remove the high concentration phosphorus in industrial wastewater, and the preparation method of the nanometer aragonite material that not contaminated water quality pH value affects has very deep meaning, and environment and harmonious economic development are had to important effect.
Summary of the invention
The object of the invention is to overcome the above problem that prior art exists, a kind of simple process of nano adsorption material of synthetic removal alkaline waste water middle and high concentration phosphorus pollution is provided, the clearance that the present invention pollutes alkaline waste water middle and high concentration phosphorus (concentration is 500mg/L) reaches more than 90%, lay a good foundation for purify waste water environment and resource reutilization, there is good economic and social benefit.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
Remove the aragonitic nano adsorption material that alkaline waste water middle and high concentration phosphorus pollutes, its synthesis technique, comprises the following steps:
Step 1) by 0.9mol/L Ca (CH
3cOO)
2the aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by 3mol/L Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) then rapidly solution A is mixed with solution B, stirred under 50 DEG C of conditions in water-bath, react 1 hour, obtain suspension precipitation;
Step 4) with absolute ethyl alcohol cleaning suspension precipitation, oven dry, obtain synthetic aragonitic sorbing material.
Further described step 1) Ca (CH
3cOO)
2the volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 2) Na
2cO
3the aqueous solution is 2: 3 in the volume ratio of ethylene glycol.
Further described step 4) in bake out temperature scope is set is 40 DEG C to 60 DEG C.
The invention has the beneficial effects as follows:
1, synthetic nanometer aragonite material ubiquity in natural environment in the present invention, itself is a kind of eco-friendly mineral material, has good heat endurance.
2, in the present invention, related synthesis technique is brief, easy to operate, raw material are inexpensive, and efficiency is high, energy consumption is low, be easy to amplify and the feature such as wide material sources.
3, the long service life of aragonitic nano adsorption material, easily stores, and the requirement of the pH value of the concentration of adsorption process to phosphorus and environment is not high, and operation is simple.Coal Gas Washing Cycling Water phosphorus being polluted to the effectively degree of depth and remove, is 4 times of common calcite, has solved to a great extent calcite under alkali condition and has removed the inefficient problem of high concentration phosphorus, therefore has a good application prospect.
4, its end product can not cause secondary pollution to environment, is not only easy to recycle, and can be used as phosphate fertilizer through simple process and be directly applied for and in farmland, promotes crops growth, has good social and economic benefits.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of description, below with better case study on implementation of the present invention and coordinate accompanying drawing to be described in detail as follows.Concrete synthetic method of the present invention and performance test are provided in detail by following examples and accompanying drawing thereof.
Brief description of the drawings
Accompanying drawing described herein is used to provide a further understanding of the present invention, forms the application's a part, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the XRD phenogram of synthetic material in the present invention;
Fig. 2 is the SEM phenogram of synthetic material in the present invention;
Fig. 3 be in the present invention synthetic material to phosphatic isothermal adsorption curve;
Fig. 4 is the comparison diagram that affects that in the present invention, the involutory written stone material of pH and natural calcite are removed phosphorus.
Detailed description of the invention
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
Remove the aragonitic nano adsorption material that alkaline waste water middle and high concentration phosphorus pollutes, its synthesis technique, comprises the following steps:
Step 1) by 0.9mol/L Ca (CH
3cOO)
2the aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by 3mol/L Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) then rapidly solution A and solution B are mixed in container, stirred under 50 DEG C of conditions in water-bath, react 1 hour, obtain suspension precipitation;
Step 4) clean suspension precipitation with absolute ethyl alcohol, and dry in baking oven, obtain synthetic aragonitic sorbing material.
Further described step 1) Ca (CH
3cOO)
2the volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 2) Na
2cO
3the aqueous solution is 2: 3 in the volume ratio of ethylene glycol.
Further described step 4) in bake out temperature scope is set is 40 DEG C to 60 DEG C.
The principle of the present embodiment is as follows:
The mechanism of the phosphorus in calcite removal water is mainly subject to the impact of pH value, near pH=6 time, mainly goes out dephosphorization by precipitation; In the time of pH > 7, it is mainly the chemical reaction effect on solid-liquid surface.This be due to, when pH value is during in 6 left and right, calcium carbonate meeting and H
-there is the dissolving of part, dissolve the Ca
2+p elements in water is combined and is formed slightly solubility calcium precipitation, thereby has reached the object of removing phosphorus; In the time that pH value is greater than 7, calcium carbonate can become slightly solubility material, and the high concentration phosphorus in water is removed in the chemical reaction effect that mainly leans against material surface formation Ca-P type nucleus.
Method of the present invention is synthetic inorganic nano sorbing material-aragonitic sorbing material cheaply, the ratio of percent by volume, calcium acetate and the sodium carbonate of the temperature to reaction, the time of reaction, ethylene glycol has been carried out orthogonal test and has been determined optimum reaction condition, under optimum condition, synthetic aragonitic sorbing material has good phosphorus adsorption efficiency absorption, and adsorption rate is 92.3%.
Embodiment 1
Design orthogonal test method Control experiment condition T (temperature), t (time), V (ethylene glycol percent by volume), C (Ca (CH
3cOO)
2concentration and Na
2cO
3concentration):
T is respectively 25 DEG C, 50 DEG C, 75 DEG C, 100 DEG C;
T is respectively 1h, 2h, 3h, 4h;
V is respectively 20%, 40%, 60%, 80%;
C (Ca (CH
3cOO)
2, Na
2cO
3concentration) (200mL) be respectively 0.15M, 0.5M; 0.3M, 1M; 0.6M, 2M; 0.9M, 3M.
Table 1 is the four factor four horizontal quadrature testing programs (adsorption efficiency) of carrying out in the present invention.Above-mentioned orthogonal test table is carried out to data analysis, use extreme difference formula to show that four factor extreme differences are respectively: T=17.7475, V=81.8, C=14.668, t=15.458
Optimum level factor scheme thus, the condition that obtains the removal efficiency best material synthesized optimum to phosphorus is: temperature 50 C, 1 hour time, the percent by volume 60% of ethylene glycol, Ca (CH
3cOO)
2concentration 0.9M, Na
2cO
3concentration 3M.That Fig. 1 shows is synthesized CaCO
3the XRD phenogram of material, shows that the specific nano material synthesizing in the present invention is pure aragonite (CaCO
3) material.And Fig. 2 can find by SEM (SEM), under this optimal condition, synthetic material has the inclined to one side ball linear structure of the spherical protrusion in stage casing of strip before absorption, closely have certain specific area and be conducive to absorption, experiment case study result backward also confirms this phenomenon.
Table 1
Factor | Temperature (DEG C) | Time (h) | Ethylene glycol volume ratio (%) | Concentration (mol/L) * | Tp removal rate (%) |
1 | 25 | 1 | 20 | 1 | 20.61 |
2 | 25 | 2 | 40 | 2 | 40.2 |
3 | 25 | 3 | 60 | 3 | 41.13 |
4 | 25 | 4 | 80 | 4 | 33.55 |
5 | 50 | 1 | 40 | 3 | 51.38 |
6 | 50 | 2 | 20 | 4 | 41.34 |
7 | 50 | 3 | 80 | 1 | 38.98 |
8 | 50 | 4 | 60 | 2 | 46.16 |
9 | 75 | 1 | 60 | 4 | 53.74 |
10 | 75 | 2 | 80 | 3 | 28.84 |
11 | 75 | 3 | 20 | 2 | 30.02 |
12 | 75 | 4 | 40 | 1 | 21.29 |
13 | 100 | 1 | 80 | 2 | 28.06 |
14 | 100 | 2 | 60 | 1 | 24.78 |
15 | 100 | 3 | 40 | 4 | 38.86 |
16 | 100 | 4 | 20 | 3 | 15.17 |
* 1,2,3,4 represent Ca (CH
3cOO)
2and Na
2cO
3concentration be respectively 0.15M, 0.5M; 0.3M, 1M; 0.6M, 2M; 0.9M, 3M.
Embodiment 2
Under room temperature (25 DEG C), in 16.13mM phosphorus solution, add the sorbing material of 5g/L, be placed on afterwards on impeller and react 15 hours, centrifuging and taking supernatant, the concentration of P in employing uv-spectrophotometric instrument analysis water-like.
What Fig. 3 showed is under pH=10 condition, aragonite material increases along with the increase of phosphorus concentration in solution the adsorbance of phosphorus, and from datagram intuitively, no matter this material is all quite outstanding in low phosphorus concentration or ultrahigh concentration (500mg/L) situation to the removal capacity of phosphorus, can reach more than 90% clearance.
Embodiment 3
Under room temperature (25 DEG C), in 16.13mM phosphorus solution, add the aragonite sorbing material of 5g/L, regulate respectively pH within the scope of 5.5-12, be placed in 15h on 25r/min shaking table, centrifuging and taking supernatant is put lining weighing apparatus pH again, calculate the concentration of phosphorus with ultraviolet-uisible spectrophotometer, draw out the removal efficiency curve of different pH eight-legged essay stone materials to phosphorus.Take the natural calcite material of equivalent, carry out identical phosphorus adsorption experiment, concrete operation step is the same.
Shown in Fig. 4, the aragonite material of synthesized and natural calcite are removed phosphatic pH influence curve figure in water.The overall trend of these 2 kinds of materials is basic identical, but due to the ad hoc structure character of the aragonite material of synthesized, under pH6-9 environment, can reach more than 90% the removal efficiency of phosphorus.Natural material is due to the defect of self, remove efficiency generally lower, particularly in the time of pH=10, be only 25% left and right to the clearance of phosphorus, and synthetic aragonite material can bring up to 80%, improve nearly 4 times, therefore absolutely proved that the aragonite material after the method modification is synthesized has very outstanding performance and the potential quality of preparation of industrialization, can in technology for treating industrial waste water, have actual application value widely.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. the aragonitic nano adsorption material that the removal alkaline waste water middle and high concentration phosphorus that is easy to synthesize pollutes, its synthesis technique: comprise the following steps:
Step 1) by 0.9mo1/L calcium acetate (Ca (CH
3cOO)
2) aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by 3mol/L Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) then rapidly solution A and solution B are mixed in container, be to stir under 50 DEG C of conditions in water-bath, fully react 1 hour, obtain suspension precipitation;
Step 4) with absolute ethyl alcohol cleaning suspension precipitation, oven dry, obtain synthetic aragonitic sorbing material.
2. a kind of aragonitic nano adsorption material that alkaline waste water middle and high concentration phosphorus pollutes, its synthesis technique removed according to claim 1; Described step 1) calcium acetate (Ca (CH
3cOO)
2) volume ratio of the aqueous solution and ethylene glycol is 2:3.
3. a kind of aragonitic nano adsorption material that alkaline waste water middle and high concentration phosphorus pollutes, its synthesis technique: described step 2 removed according to claim 1) Na
2cO
3the volume ratio of the aqueous solution and ethylene glycol is 2:3.
According to claim 1 a kind of remove alkaline waste water middle and high concentration phosphorus pollute aragonitic nano adsorption material, its synthesis technique: described step 4) in bake out temperature scope be 40 DEG C to 60 DEG C.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105056872A (en) * | 2015-05-14 | 2015-11-18 | 苏州科技学院 | Novel calcium aluminum carbonate water purification agent preparation method and phosphorus removal process |
CN105879833A (en) * | 2014-11-11 | 2016-08-24 | 苏州科技学院 | Methods for preparing zeolite loaded nano vaterite type CaCO3 composite material and removing nitrogen and phosphorus in water bodies |
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2013
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CN1641077A (en) * | 2004-01-13 | 2005-07-20 | 中国人民解放军国防科学技术大学 | Method for preparing aragonite type calcium carbonate whisker |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105879833A (en) * | 2014-11-11 | 2016-08-24 | 苏州科技学院 | Methods for preparing zeolite loaded nano vaterite type CaCO3 composite material and removing nitrogen and phosphorus in water bodies |
CN105879833B (en) * | 2014-11-11 | 2018-12-21 | 苏州科技学院 | Zeolite-loaded nanosphere graupel type CaCO3The preparation of composite material and the method for removing water body nitrogen phosphorus |
CN105056872A (en) * | 2015-05-14 | 2015-11-18 | 苏州科技学院 | Novel calcium aluminum carbonate water purification agent preparation method and phosphorus removal process |
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