A kind of dephosphorization adsorbent and preparation method thereof
Technical field
The present invention relates to sewage dephosphorization technical fields, and in particular to a kind of dephosphorization adsorbent and preparation method thereof.
Background technique
The eutrophication problem of the natural water bodies such as river, lake is very universal at present, and phosphate leads to eutrophication
Critical nutrients element.Therefore, the phosphate radical for removing excessive concentrations in water body is particularly critical.
For biological cell, phosphate radical is the important composition ingredient of molecule in cell, constitutes phosphatide, nucleotide, nucleic acid
And the skeleton of coenzyme.Therefore phosphate radical is restrictive nutrient, its content in water body is exceeded to be will lead in water body
Algae and other biological mass propagation, and then lead to that the decline of water body dissolved oxygen amount, aquatile are dead and water body is smelly
A succession of reactions such as deterioration.
The method of the phosphate radical in removal water body has biological phosphate-eliminating technology and physical chemistry dephosphorization technique etc. at present.These sides
Method has been applied to the improvement field of polluted-water.In the above method, the absorption of physical chemistry dephosphorization technique scope is belonged to
Method with its low cost, high efficiency, can recycle the features such as phosphor resource and receive significant attention.
Efficient dephosphorization agent is researched and developed as extremely urgent demand.Metalliferous dephosphorization agent has height due to the removal to phosphorus
The characteristics of selectivity and high efficiency, has been increasingly becoming the hot spot of people's research.In recent years, due to its optics, catalysis and antibiotic property
Matter, nano-titanium dioxide are widely used in the fields such as catalyst, cosmetics, paint, suncream and plastics.In addition to this, by
In titania nanoparticles size, small, large specific surface area, surface energy height and surface atom proportion are big, as adsorbent material
Also it enjoys great popularity.
The patent specification of Publication No. CN108355619A discloses a kind of for removing the nano adsorption of water pollutant
Material contains following component: 30~40 parts by weight of nano-titanium dioxide, 30~40 parts by weight of nano zine oxide, 5~10 weight of starch
Part, 1~2 parts by weight of 8~25 parts by weight of modified activated carbon, 1~8 parts by weight of resin and chitosan.Above-mentioned nano adsorption material
Preparation method be simple blend.
The patent specification of Publication No. CN108773870A discloses a kind of active carbon base water purification agent, by following parts by weight
Substance be made: 80~150 parts by weight of coconut skin, 20~40 parts by weight of chitosan, 5~6 parts by weight of monoxone, polyhydroxy-alcohol 30
~60 parts by weight, 5~10 parts by weight of Methacrylamide, 1~3 parts by weight of initiator, 0.1~0.5 parts by weight of organosilicon acid esters,
10~30 parts by weight of organic titanate, 2~6 parts by weight of silane coupling agent, 50~60 parts by weight of solvent.Above-mentioned active carbon base water purification
Agent is compound by porous charcoal, grafting amphoteric chitosan and modifying titanium dioxide progress, so that water purification agent is had both absorption, flocculates and urge
Change the functions such as degradation to be integrated.But the patent specification is not directed to the effect in terms of dephosphorization.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of preparation method of dephosphorization adsorbent, using receiving
Rice titanium dichloride load overcomes common adsorbents adsorption effect and owes on adsorbent based on by active carbon and chitosan
Good, common adsorbents self-strength is insufficient, is not easy to remove, easily causes the deficiencies of secondary pollution, improves the adsorption capacity of adsorbent,
Selected materials economic cost is low, and the phosphate anion in energy efficient absorption water body effectively improves wastewater treatment capacity, realizes environment-
Economic benign cycle.
A kind of preparation method of dephosphorization adsorbent, comprising:
(1) by mass ratio be 1:(1~10) chitosan and active carbon be added in acetum, obtain mixed liquor;
(2) by sodium hydroxide solution and dehydrated alcohol with volume ratio 1:(10~20) mixing, obtain fixer;
(3) mixed liquor is added drop-wise in fixer, by sediment washing, is dried to obtain carrier adsorption agent;
(4) it is added to the water nano-titanium dioxide and dispersing agent to obtain dispersion liquid, carrier adsorption agent is added to dispersion liquid
In loaded after, filter to take solid, washing, it is dry after in 300~600 DEG C of 2~3h of roasting obtain dephosphorization adsorbent.
In step (1), it is preferable that the mass ratio of the chitosan and active carbon be 1:(5~10), active carbon ratio compared with
Height, adsorption effect are preferable.
The effect of acetum is to provide acidic environment, it is preferable that the mass concentration of the acetum be 1%~
8%, the ratio between acetum quality and the gross mass of chitosan and active carbon are (10~80): 1.Acetum is excessive, Zhi Houxu
The alkali wanted also can be more, cause to waste.
The mixed liquor is thick shape.
In step (2), the mixed solution of dehydrated alcohol and sodium hydroxide is inorganic fixatives.
The sodium hydroxide solution is provided with the effect of alkaline environment, it is preferable that the matter of the sodium hydroxide solution
Measuring concentration is 25%~45%.
Distilled water or deionized water can be used in washing described in step (3) and step (4), and room temperature can be used in the drying
Air-dry 12~for 24 hours or 105 DEG C of 2~4h of drying of baking oven.
In step (4), it is preferable that the partial size of the nano-titanium dioxide is 50~80nm, has preferable absorption effect
Fruit.
Minimum environmental hazard is taken into account while in order to reach preferable adsorption effect, it is preferable that receive in the dispersion liquid
The mass concentration of rice titanium dioxide is 1%~2%.
The concentration of dispersing agent can be 0.01~0.03mg/L in the dispersion liquid.
The dispersing agent can be neopelex.
In order to obtain preferable dispersion effect and load effect, it is preferable that the matter of the carrier adsorption agent and dispersion liquid
Amount is than being 1:(10~30).
In order to accelerate load efficiency, improve load effect, heating can be used and the mode stirred is loaded, described adds
Heat can be heating water bath, and preferably heating temperature is 50~70 DEG C.Preferably, the time of the stirring is 12~36h, stirring
The length of time determines the length of load-reaction time, and not exclusively, mixing time is too long not to be had the too short load of mixing time yet
It is necessary.
In step (4), it is preferable that the pH of the solid after washing is 7~7.5, to ensure that impurity is all washed dry
Only.
Preferably, the temperature of the roasting is 350~450 DEG C, maintains preferable adsorption effect.
The dephosphorization adsorbent that the preparation method for the dephosphorization adsorbent that the present invention also provides a kind of according to is prepared.
The dephosphorization adsorbent is by being fixed on carrier adsorption agent surface for nano-titanium dioxide, to improve dephosphorization suction
Attached dose of adsorption capacity, nano-titanium dioxide mainly pass through chelation, covalent bond or coordinate bond and are fixed in conjunction with phosphate radical
Dephosphorization adsorbent surface.Above each substance synergistic effect increases the phosphor-removing effect of dephosphorization adsorbent.
Compared with prior art, the present invention major advantage includes: that the dephosphorization adsorbent overcomes common adsorbents suction
Attached less effective, adsorbent itself intensity are insufficient, are not easy to remove, easily cause the deficiencies of secondary pollution, and preparation method is simply steady
Fixed, graininess formed body intensity is good, and selected materials economic cost is low, and the phosphate anion in energy efficient absorption water body effectively mentions
High wastewater treatment capacity realizes the benign cycle of environment-economy.
Detailed description of the invention
Fig. 1 is the preparation flow figure of dephosphorization adsorbent of the invention;
Fig. 2 is the dephosphorization efficiency of each the carrier adsorption agent and dephosphorization adsorbent of Examples 1 to 3.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
Embodiment 1
(1) as shown in Figure 1A, 1B, the chitosan and Mixture of Activated Carbon that 3g mass ratio is 1:3 is weighed, it is dense to be added to quality
In the acetum that degree is 1.2%, the mixed liquor of thick shape is obtained;
(2) mass concentration is mixed for 40% sodium hydroxide solution and dehydrated alcohol with volume ratio 1:10, obtains alkalinity
Fixer;
(3) as shown in Figure 1 C, mixed liquor is added drop-wise in 80mL fixer, obtains pellets, be washed with distilled water
Grain bead is dried to obtain carrier adsorption agent to neutrality;
(4) as shown in figure iD, nano-titanium dioxide and neopelex are added to the water to obtain dispersion liquid, are dispersed
The mass concentration of nano-titanium dioxide is 1% in liquid, and the concentration of neopelex is 0.017mol/L, by carrier adsorption
Agent is added in dispersion liquid, 60 DEG C of heating water baths, maintains magnetic agitation for 24 hours, and magneton revolving speed is 300rpm;
(5) it as shown in Fig. 1 E, 1F, is filtered after stirring, is washed with distilled water to neutrality, is put into Muffle furnace after dry
In 400 DEG C of roasting 2h, cooling obtains dephosphorization adsorbent.
Embodiment 2
(1) chitosan and Mixture of Activated Carbon that 3g mass ratio is 1:5 are weighed, the vinegar that mass concentration is 1.2% is added to
In acid solution, the mixed liquor of thick shape is obtained;
(2) mass concentration is mixed for 40% sodium hydroxide solution and dehydrated alcohol with volume ratio 1:15, obtains alkalinity
Fixer;
(3) mixed liquor is added drop-wise in 100mL fixer, obtains pellets, be washed with distilled water pellets into
Property, it is dried to obtain carrier adsorption agent;
(4) nano-titanium dioxide and neopelex are added to the water to obtain dispersion liquid, nanometer two in dispersion liquid
The mass concentration of titanium oxide is 2%, and the concentration of neopelex is 0.03mol/L, and carrier adsorption agent is added to point
In dispersion liquid, 50 DEG C of heating water baths maintain magnetic agitation 12h, and magneton revolving speed is 350rpm;
(5) it is filtered after stirring, is washed with distilled water to neutrality, is put into Muffle furnace after dry and is roasted at 400 DEG C
2.5h, cooling obtain dephosphorization adsorbent.
Embodiment 3
(1) chitosan and Mixture of Activated Carbon that 3g mass ratio is 1:7 are weighed, the vinegar that mass concentration is 1.2% is added to
In acid solution, the mixed liquor of thick shape is obtained;
(2) mass concentration is mixed for 40% sodium hydroxide solution and dehydrated alcohol with volume ratio 1:20, obtains alkalinity
Fixer;
(3) mixed liquor is added drop-wise in 110mL fixer, obtains pellets, be washed with distilled water pellets into
Property, it is dried to obtain carrier adsorption agent;
(4) nano-titanium dioxide and neopelex are added to the water to obtain dispersion liquid, nanometer two in dispersion liquid
The mass concentration of titanium oxide is 1.5%, and the concentration of neopelex is 0.01mol/L, and carrier adsorption agent is added to
In dispersion liquid, 70 DEG C of heating water baths maintain magnetic agitation 36h, and magneton revolving speed is 400rpm;
(5) it is filtered after stirring, is washed with distilled water to neutrality, is put into Muffle furnace after dry in 450 DEG C of roasting 2h,
Cooling obtains dephosphorization adsorbent.
Application examples
The dephosphorization adsorbent that Examples 1 to 3 is obtained is as experimental group, and carrier adsorption agent is as a control group.
The sample for weighing 0.0325g experimental group and control group respectively, is put into the centrifuge tube for filling potassium dihydrogen phosphate,
Phosphorus concentration in potassium dihydrogen phosphate is 50mg/L.Three Duplicate Samples are arranged in each sample.
Centrifuge tube is put into constant temperature oscillation case, 12h is vibrated under conditions of 25 DEG C, 180rpm, then by centrifuge tube 4
DEG C, be centrifuged 5 minutes under conditions of 10000rpm.Supernatant is taken after centrifugation, it is dense using P elements in molybdate method measurement water
Degree, as a result as shown in Figure 2.
It can be seen that the dephosphorization adsorbent of experimental group is significantly larger than the carrier adsorption agent of control group to the removal efficiency of phosphorus,
The phosphate anion in dephosphorization adsorbent energy efficient absorption water body after showing load nano-titanium dioxide, significantly improves absorption
Performance.
The usual adsorption effect of common adsorbents is poor, self-strength is insufficient, it is easy to wear, fall powder, and then lead to water body
In common adsorbents be not easy to remove, cause secondary pollution etc..Dephosphorization adsorbent intensity of the invention is higher, is pellets
Shape, it is not easy to wear or fall powder, it not will cause secondary pollution, and the raw material used will not pollute, and can effectively improve
Wastewater treatment capacity realizes the benign cycle of environment-economy.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.