CN105056872A - Novel calcium aluminum carbonate water purification agent preparation method and phosphorus removal process - Google Patents
Novel calcium aluminum carbonate water purification agent preparation method and phosphorus removal process Download PDFInfo
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- CN105056872A CN105056872A CN201510243582.0A CN201510243582A CN105056872A CN 105056872 A CN105056872 A CN 105056872A CN 201510243582 A CN201510243582 A CN 201510243582A CN 105056872 A CN105056872 A CN 105056872A
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Abstract
The present invention discloses a preparation method for synthesizing a spherical calcium aluminum carbonate phosphorus-removal water purification agent. The specific synthesis steps comprise: 1) adding a calcium acetate (Ca(CH3COO)2) aqueous solution to ethylene glycol to prepare a solution A; 2) adding a Na2CO3 aqueous solution to ethylene glycol to prepare a solution B; 3) adding a certain amount of aluminum chloride to the solution A, carrying out stirring dissolving, and rapidly carrying out a mixing reaction of the solution A and the solution B at a temperature of 75 DEG C; 4) after 1 h, obtaining a product, repeatedly rinsing with absolute alcohol, taking out, and drying at a temperature of 40-60 DEG C; 5) making the water purification agent act in the wastewater treatment for 2 h; and 6) standing for a certain time to make the synthesized calcium aluminum carbonate water purification material particles be precipitated so as to achieve the deep phosphorus removal purpose. According to the present invention, the calcium aluminum carbonate material is designed and prepared, the removal efficiency on the phosphorus pollution in the wastewater achieves 99% and is not affected by the pH value of the wastewater, the process time is short, the energy source consumption is low, the operation is simple and easy to control, the preparation process is environmental pollution and pollution-free, the new approach and method is provided for the phosphorus-containing industrial wastewater treatment, and the potential good social and economic benefits are provided.
Description
Technical field
The present invention relates to a kind of simple inorganic material preparation and sewage disposal technology, be specifically related to the simple method for synthesizing that a kind of novel degree of depth removes the calcium aluminum carbonate water-purifying material of phosphor contaminant in industrial wastewater.
Background technology
Industrialization is while propelling Development of Human Civilization, and also bring a large amount of development problems, environmental pollution is exactly one of accessory substance of industrialization development.Water is Source of life, but large water gaging is heavily polluted at present.Wherein, water eutrophication turns to one of its main form, and phosphorus pollutes, and as the main cause that body eutrophication produces, has caused the extensive concern of people at present.Now, use new technologies and materials to carry out effective removal to the phosphorus in water body to be widely studied.
Research finds, when phosphorus concentration in water is more than 0.02mg/L, will cause body eutrophication.But while phosphate is widely used as important basic chemical industry raw material, the discharge of its refuse, concerning many factories, does not strictly observe the relevant regulations of country, brings a large amount of industrial phosphorus-containing waste water thus.Specifically as phosphorus concentration in coating wastewater reaches about 100mg/L, the concentration that the Phosphorus From Wastewater of some enterprises discharge pollutes is higher, and the phosphate in waste water concentration produced in LED production process can up to 300mg/L.Current people use natural minerals calcite to remove phosphate, and it is crystal type the most stable in calcium carbonate, and because its specific area is low, adsorption site is few, directly causes its removal effect undesirable.Therefore improve sorbing material performance, efficiently remove phosphate, become very urgent at present.
Research shows, calcite (CaCO
3) itself be the phosphatic mineral material of a kind of excellent removal.Because calcite easily obtains and with low cost, extensively studied at present, and be considered to have good development prospect.But the efficiency of calcite removal phosphorus is low, and the factor impact being subject to pH value of waste water is very large: low pH is physical and chemical adsorption method, and high pH forms calcium phosphate crystal by chemical reaction.When high phosphorus concentration, when pH value is in 6-7 interval, the efficiency being removed phosphorus by precipitation increases significantly; But after pH value of solution enters alkaline environment, the Adsorption efficiency of calcite to phosphorus first reduces and then rises again, and it is about 9.5-11.5 that its minimum adsorption efficiency appears at pH, and now solution Phosphate Sorption efficiency only has an appointment 20%, then can along with the rising of pH value of solution environment, adsorption efficiency and then rises.Thus, under alkali condition, calcite can not effectively dephosphorization.
Remove the deficiency of phosphorus based on above-mentioned calcite, the invention provides a kind of method that efficient degree of depth removes industrial wastewater middle and high concentration phosphorus, its removal efficiency does not affect by water pH value.The proposition of this synthetic method, for removal phosphate anion, suppress body eutrophication, creating policy, friendly environment society are of far-reaching significance.
Summary of the invention
The object of the invention is to the deficiency overcoming the existence of existing dephosphorization technique, provide a kind of and efficiently can remove the synthetic method that industrial wastewater middle and high concentration phosphorus pollutes sorbing material, and do not affect by the pH value of water.The method technique is simple, and with low cost, therefore application prospect is extensive.Research shows, the present invention can make the clearance of Coal Gas Washing Cycling Water phosphor contaminant reach more than 99%, can slow down and suppress body eutrophication, because its synthesis is simple, with low cost, therefore has applications well prospect.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
2, be easy to synthesize novel calcium carbonate aluminium preparation technology and can the degree of depth remove various pH waste water phosphorus pollute a method, comprise the following steps:
Step 1) by a certain amount of calcium acetate (Ca (CH
3cOO)
2) aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by a certain amount of Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) a certain amount of aluminium chloride is joined solution A, and stirring and dissolving;
Step 4) then rapid solution A and solution B are mixed in container, stir under water-bath is 75 DEG C of conditions, fully reaction 1 hour, obtain suspension precipitation;
Step 5) by washes of absolute alcohol suspension precipitation, dry, obtain calcium aluminum carbonate sorbing material.
Step 6) containing in phosphorus waste water at various pH, add synthetic calcium carbonate aluminium adsorbent;
Step 7) stir 2 hours under normal temperature, leave standstill predetermined time, the particle in solution is precipitated, thus remove the phosphorus in waste water.
Further described step 1) calcium acetate (Ca (CH
3cOO)
2) volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 2) Na
2cO
3the volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 1) and step 2) calcium acetate and Na
2cO
3molar ratio be 2: 1.
Further described step 3) aluminium/calcium mol ratio of the aluminium chloride that adds and calcium acetate is 1: 2.
Further described step 5) in bake out temperature to arrange scope be 40 DEG C to 60 DEG C.
Further described step 6) in the pH value range of phosphorus-containing wastewater be 5-12.
The invention has the beneficial effects as follows:
1) this tests the simple and easy to get and low price of synthetic raw material used.
2) synthesis technique involved by is brief, small investment, easy to operate, efficiency is high, energy consumption is low, be easy to amplify and the features such as wide material sources.
3) directly can carry out in water processing reactor, convenient and simple for operation easy, in addition because the absorption of this material is not by the impact of pH value of solution environment, therefore its range of application widely.
4) the calcium aluminum carbonate sample synthesized, compared to the calcite ore material (CaCO3) that occurring in nature exists, synthetic material is removed phosphatic performance and is improved significantly, and treatment time of water also shortens to 2 hours greatly.
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, coordinates accompanying drawing to be described in detail as follows below with better case study on implementation of the present invention.Concrete synthetic method of the present invention and performance test are provided in detail by following examples and accompanying drawing thereof.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide a further understanding of the present invention, and form a application's part, schematic description and description of the present invention, 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 the calcium aluminum carbonate water purification agent synthesized in the present invention;
Fig. 2 is the SEM phenogram of the calcium aluminum carbonate water purification agent synthesized in the present invention;
Fig. 3 is that the calcium aluminum carbonate that synthesizes in the present invention is to phosphatic adsorption isothermal curve;
Fig. 4 is the comparison diagram that in the present invention, pH goes dephosphorization efficiency to affect on calcium aluminum carbonate and natural calcite.
Detailed description of the invention
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
Be easy to synthesize novel calcium carbonate aluminium preparation technology and can the degree of depth remove various pH waste water phosphorus pollute a method, comprise the following steps:
Step 1) by a certain amount of calcium acetate (Ca (CH
3cOO)
2) aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by a certain amount of Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) a certain amount of aluminium chloride is joined solution A, and stirring and dissolving;
Step 4) then rapid solution A and solution B are mixed in container, stir under water-bath is 75 DEG C of conditions, fully reaction 1 hour, obtain suspension precipitation;
Step 5) by washes of absolute alcohol suspension precipitation, dry, obtain calcium aluminum carbonate sorbing material.
Step 6) containing in phosphorus waste water at various pH, add synthetic calcium carbonate aluminium adsorbent;
Step 7) stir 2 hours under normal temperature, leave standstill predetermined time, the particle in solution is precipitated, thus remove the phosphorus in waste water.
Further described step 1) calcium acetate (Ca (CH
3cOO)
2) volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 2) Na
2cO
3the volume ratio of the aqueous solution and ethylene glycol is 2: 3.
Further described step 1) and step 2) calcium acetate and Na
2cO
3molar ratio be 2: 1.
Further described step 3) aluminium/calcium mol ratio of the aluminium chloride that adds and calcium acetate is 1: 2.
Further described step 5) in bake out temperature to arrange scope be 40 DEG C to 60 DEG C.
Further described step 6) in the pH value range of phosphorus-containing wastewater be 5-12.
The principle of the present embodiment is as follows:
The dominant mechanism that calcium aluminum carbonate removes phosphorus in water is: aluminium ion in calcium aluminum carbonate water purification agent, and atomic weight is little, and ioni valence electricity number is high, increases the electropositive of material surface like this, can provide the adsorption site of more multi-phosphate ion, improves sample calcium carbonate dephosphorization efficiency.When pH value is about 6 time, calcium aluminum carbonate material can the dissolving of generating portion, dissolves the Ca
2+with the P elements in water in combination with forming slightly solubility calcium precipitation thus be separated minimizing phosphorus from water body; When pH value is greater than 7, there is chemical reaction and form the object that calcium-phosphate type nucleus reaches phosphorus in removal water in sorbing material surface.
Embodiment 1
Under room temperature (25 DEG C), with the dosage of 5g/L sorbing material in 1-20mM phosphorus solution, react centrifugal extraction supernatant after 2 hours, finally adopt the concentration of phosphorus in UV detector analysis water-like.
As shown in Figure 1, displaying be synthesis calcium aluminum carbonate material XRD characterize, the main diffraction peak of this XRD collection of illustrative plates show sample meets CaCO
3principal character peak, and peak roughness is large, this illustrate because in material structure the existence of aluminium atom to cause the crystal morphology of sample not obvious.The SEM of what Fig. 2 showed the is calcium aluminum carbonate material of synthesis characterizes, and as can be seen from SEM phenogram, the calcium aluminum carbonate nanometer spherical particle of synthesis is mostly broken and be bonded together, and is approximately unformed pattern.Comprehensive XRD characterizes and SEM characterizes, and thinks that the sample of synthesis is for approximate unformed calcium aluminum carbonate material.
What Fig. 3 showed is under pH=9.5 condition, and show adsorption time 2 hours by adsorption experiment, the calcium aluminum carbonate adsorbent of synthesis reaches adsorption equilibrium to phosphate in water.The sunykatuib analysis of result by experiment, the absorption of calcium aluminum carbonate adsorbent to phosphorus of synthesis meets Fruendlich model, matching degree of correlation R
2be 0.99.Can find that the Adsorption ability of water purification agent to phosphorus that we are condensed into increases along with the increase of phosphorus concentration in water body by simulation, namely show quick, superpower removal ability.
Embodiment 2
Under room temperature (25 DEG C), under 6.5mM phosphorus solution, calcium aluminum carbonate sorbing material is added with the dosage of 5g/L, regulate pH value of solution at 5.5-12, react centrifugal extraction supernatant after 2 hours, and using ultraviolet-uisible spectrophotometer to calculate the concentration of phosphorus, when drawing out different pH, calcium aluminum carbonate is to the removal efficiency curve of phosphorus.Solution containing phosphate pH environment is on the impact of natural calcite removal efficiency, and the process of its phosphorus adsorption experiment is with process is the same above, and concrete operation step as above.
Fig. 4 is the curve map that in the calcium aluminum carbonate material and natural calcite removal solution synthesized, phosphatic removal efficiency changes with pH.Analyze and find, the overall trend of these 2 kinds of materials has notable difference.As can be seen from Figure 4, in experiment pH scope 5-12, the clearance of calcium aluminum carbonate water purification agent to phosphorus of synthesis has almost no change, and all remains on more than 94%.And natural material is general lower to the clearance of phosphorus, pH is to the clearance obvious effect of natural calcite to phosphorus, along with the enhancing of alkalescence, the clearance of natural calcite to phosphorus reduces gradually, when pH is about 9.5-11.5, the clearance of natural calcite to phosphorus is only about 25%, and the calcium aluminum carbonate water purification agent of synthesis can reach more than 95% to the clearance of phosphorus under identical pH condition, improves nearly 4 times.Therefore, the calcium aluminum carbonate water purification agent of this method synthesis improves the clearance of natural calcite to phosphorus, and the efficiency overcoming natural calcite adsorption and dephosphorization affects change this shortcoming large by pH.
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 done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. be easy to synthesize novel calcium carbonate aluminium preparation technology and can the degree of depth remove various pH waste water phosphorus pollute a method, comprise the following steps:
Step 1) by a certain amount of calcium acetate (Ca (CH
3cOO)
2) aqueous solution joins wiring solution-forming A in ethylene glycol;
Step 2) by a certain amount of Na
2cO
3the aqueous solution joins wiring solution-forming B in ethylene glycol;
Step 3) a certain amount of aluminium chloride is joined solution A, and stirring and dissolving;
Step 4) then rapid solution A and solution B are mixed in container, stir under water-bath is 75 DEG C of conditions, fully reaction 1 hour, obtain suspension precipitation;
Step 5) by washes of absolute alcohol suspension precipitation, dry, obtain calcium aluminum carbonate sorbing material.
Step 6) containing in phosphorus waste water at various pH, add synthetic calcium carbonate aluminium adsorbent;
Step 7) stir 2 hours under normal temperature, leave standstill predetermined time, the particle in solution is precipitated, thus remove the phosphorus in waste water.
2. a kind of novel calcium carbonate aluminum Preparation Method being easy to synthesize according to claim 1, is characterized in that; 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 novel calcium carbonate aluminum Preparation Method being easy to synthesize according to claim 1, is characterized in that: described step 2) Na
2cO
3the volume ratio of the aqueous solution and ethylene glycol is 2: 3.
4. a kind of novel calcium carbonate aluminum Preparation Method being easy to synthesize according to claim 1, is characterized in that: described step 1) and step 2) calcium acetate and Na
2cO
3molar ratio be 2: 1.
5. a kind of novel calcium carbonate aluminum Preparation Method being easy to synthesize according to claim 1, is characterized in that: described step 3) aluminium/calcium mol ratio of the aluminium chloride that adds and calcium acetate is 1: 2.
6. according to claim 1 a kind of be easy to synthesize novel calcium carbonate aluminum Preparation Method, it is characterized in that: described step 5) in bake out temperature scope be 40 DEG C to 60 DEG C.
7. the method that the phosphorus that the novel calcium aluminum carbonate degree of depth according to claim 1 removes various pH waste water pollutes, is characterized in that: described step 6) in the pH value range of phosphorus-containing wastewater be 5-12.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574058A (en) * | 2019-01-18 | 2019-04-05 | 天水师范学院 | A kind of homogeneous precipitation preparation method of calcium carbonate |
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| CN101913674A (en) * | 2010-08-04 | 2010-12-15 | 南京信息工程大学 | Method for removing phosphorus in water by adopting aluminum salt modified eggshell |
| CN101921009A (en) * | 2010-08-04 | 2010-12-22 | 南京信息工程大学 | Method for removing phosphorus in water by using modified abandoned eggshells |
| CN103130357A (en) * | 2013-03-04 | 2013-06-05 | 苏州科技学院 | Method for removing high concentration phosphor pollution in alkali wastewater |
| CN104069792A (en) * | 2013-10-11 | 2014-10-01 | 苏州科技学院 | Synthetic method of aragonite material for deeply removing phosphorus wastewater |
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2015
- 2015-05-14 CN CN201510243582.0A patent/CN105056872A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN101913674A (en) * | 2010-08-04 | 2010-12-15 | 南京信息工程大学 | Method for removing phosphorus in water by adopting aluminum salt modified eggshell |
| CN101921009A (en) * | 2010-08-04 | 2010-12-22 | 南京信息工程大学 | Method for removing phosphorus in water by using modified abandoned eggshells |
| CN103130357A (en) * | 2013-03-04 | 2013-06-05 | 苏州科技学院 | Method for removing high concentration phosphor pollution in alkali wastewater |
| CN104069792A (en) * | 2013-10-11 | 2014-10-01 | 苏州科技学院 | Synthetic method of aragonite material for deeply removing phosphorus wastewater |
Non-Patent Citations (1)
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| CN109574058A (en) * | 2019-01-18 | 2019-04-05 | 天水师范学院 | A kind of homogeneous precipitation preparation method of calcium carbonate |
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Application publication date: 20151118 |