CN113353904B - Oyster shell hydroxyapatite microspheres and preparation method and application thereof - Google Patents
Oyster shell hydroxyapatite microspheres and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of oyster shell hydroxyapatite microspheres which do not produce secondary pollution and have high-efficiency adsorption performance on dyes. The microsphere takes waste oyster shells as a main raw material, sodium ascorbate and sodium citrate as template agents, hydroxyapatite microspheres are formed by hydrothermal synthesis self-assembly, and the hydroxyapatite microspheres are used as an adsorbent to be applied to the adsorption of aqueous solution dye, so that the microsphere shows good adsorbability. The preparation method is simple and convenient, realizes high-valued utilization of the waste oyster shells, achieves the aim of changing waste into valuables, has simple process, low cost and easy popularization, and has good economic benefit and ecological benefit.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of oyster shell hydroxyapatite microspheres which do not produce secondary pollution and can effectively adsorb dye.
Background
In recent years, with the rapid development of industries such as textile, papermaking and printing, dyes are continuously discharged into natural environment by people, and serious pollution is caused to the environment. The dye pollutant has certain irritation, is difficult to degrade in nature, has toxicity and carcinogenicity, and can be accumulated in organisms to cause serious harm to human bodies. Dye contamination has become one of the most harmful environmental pollutants. Therefore, the treatment of waste water dye is always a hot problem of people, and the waste water treatment technologies such as a chemical method, a solvent extraction method, an adsorption method and the like have been developed. The adsorption method has the advantages of large adsorption capacity, high efficiency, high speed, simple and convenient operation and the like, and is an effective method for removing the dye in the wastewater. The traditional adsorbent is activated carbon, which has strong adsorption capacity and high removal rate, but has low regeneration efficiency and high price, so the industrial application of the activated carbon is limited. The research on efficient, low-cost and environment-friendly adsorbents is receiving more and more attention from researchers.
China is waterIn large producing and breeding countries, oysters play an important role in aquaculture industry in China. In 2019, the yield of the oyster mariculture in China reaches 522.5595 ten thousand tons. According to statistics, 300-700 g of waste shells are generated every 1000g of shells are processed, and the utilization rate of the oyster shells is low at present, and the added value is low, so that the oyster shells are regarded as an intractable waste. In the oyster shell treatment and utilization process, only a small amount of oyster shells are used as soil conditioner, feed additive and the like, most of oyster shells are randomly piled up or transported to a garbage disposal station to be buried as common garbage, a large amount of land resources are occupied, if the oyster shells cannot be properly treated for a long time, the meat residues on the shells are easy to breed mosquitoes, flies and microorganisms, and the microorganisms can decompose salt attached to the oyster shells into NH3、H2S and other gases cause odor in accumulated or landfill sites, pollute air and cause great threat to the health of residents in surrounding living areas.
The sodium ascorbate is a main intermediate product in the production process of the vitamin C, is also an important food additive, is used as an antioxidant, can prevent the discoloration and the taste change of foods and beverages, is widely used for fresh-keeping and color fixing of ham, sausage and cake and mildew prevention of moon cakes, is added into cosmetics for crease resistance, aging resistance and whitening, has double functions of supplementing the vitamin C and enhancing the absorption of calcium, and has stable performance. Meanwhile, the sodium ascorbate can participate in the metabolism and the oxidation-reduction process of sugar in the body, the generation of intercellular substance and the coagulation process of blood, and the brittleness of capillary vessels is reduced; has effects in clearing away toxic materials, and improving resistance to infection; can promote folic acid to form tetrahydrofolic acid in vivo and increase iron absorption in intestinal tract. Sodium citrate is one of the most commonly used citrates, is mainly produced by fermenting starch substances to generate citric acid, and then neutralizing with alkali substances, is safe and nontoxic, has the characteristics of biodegradability, dissolubility, pH buffering property and the like, and is widely applied to the fields of food, medicine, chemical industry and the like.
Hydroxyapatite (HA), a naturally mineralized product of calcium apatite, of the general formula Ca10(PO4)6(OH)2. Compared with the traditional adsorbent, the hydroxyapatite has excellent ion exchange performance and adsorption capacity, so that the hydroxyapatite can be used for adsorbing the ionMost heavy metal ions, anions, dyes and organic pollutants have good adsorption and fixation effects, and secondary pollution can not be caused in the sewage treatment process.
From the viewpoint of solving the pollution of waste oyster shells and waste water dye, the method takes oyster shells as a calcium source, takes disodium hydrogen phosphate as a phosphorus source, selects sodium ascorbate and sodium citrate as double templates, prepares hydroxyapatite microspheres under hydrothermal conditions, has larger specific surface area and more and larger pore structures, shows good adsorption capacity on various dyes such as crystal violet, congo red, coomassie brilliant blue and the like, and is expected to become a novel environment-friendly functional material.
Disclosure of Invention
The invention aims to solve the problems of great oyster shell waste, low utilization rate and added value and waste water dye pollution, and provides a preparation method of oyster shell hydroxyapatite microspheres with high-efficiency dye adsorption performance, which has the advantages of simple preparation process, low cost and good dye adsorption effect. The microspheres are porous spherical structures, have the diameter of 5-10 mu m and have good adsorption effect on the dye in water.
The method comprises the following steps:
(1) flushing oyster shells with running water, removing substances on the surface layers of the oyster shells, and then naturally drying;
(2) crushing, grinding and screening the air-dried oyster shells to obtain oyster shell powder;
(3) dissolving oyster shell powder in acetic acid solution, stirring until no bubbles are generated, and then centrifuging to obtain supernatant;
(4) fixing the volume of the supernatant obtained in the step (3) to 100ml, adding disodium hydrogen phosphate into the supernatant, and stirring for 20 min;
(5) adding sodium ascorbate, sodium citrate and urea into the solution stirred in the step (4), and continuously stirring for 30min until the sodium ascorbate, the sodium citrate and the urea are completely dissolved;
(6) pouring the reaction liquid prepared in the step (5) into a high-pressure reaction kettle, and placing the reaction liquid into a constant-temperature drying box for hydrothermal reaction;
(7) and after the reaction is finished, naturally cooling to room temperature, centrifugally washing with water, washing with ethanol, and drying to obtain the oyster shell hydroxyapatite microspheres.
The technological parameters of each step are as follows:
in the step (3), the concentration of the acetic acid solution is 10-30 vol.%, the centrifugal rotation number is 4000rpm, and the centrifugal time is 20-30 min.
The consumption of the oyster shell powder in the step (3) and the disodium hydrogen phosphate in the step (4) needs to ensure that the molar ratio of Ca to P is n (Ca2+)/n(PO4 3-) 1.67: 1 addition.
The dosage of the sodium ascorbate in the step (5) is 0.015g, the dosage of the sodium citrate is 0.09 g-0.18 g, and the dosage of the urea is 4-6 g.
The hydrothermal reaction temperature in the step (6) is 100-120 ℃, and the time is 24 h.
In the step (7), the centrifugal revolution is 4000rpm, and the centrifugal time is 20-30 min; washing for 3-5 times by using deionized water, and washing for 1-2 times by using absolute ethyl alcohol; the drying temperature is 60 ℃, and the drying time is 2 h.
The application of the oyster shell hydroxyapatite microspheres in dye adsorption specifically comprises the following steps:
(1) preparing 100mg/L aqueous solution containing dye at room temperature;
(2) accurately measuring 10mL of the aqueous solution containing the dye in the step (1) at room temperature, adding 0.01g of the oyster shell hydroxyapatite microspheres into the solution, and placing the solution in a constant temperature oscillator of 180r/min for oscillation;
(3) standing and filtering the turbid liquid subjected to adsorption in the step (2) at room temperature, and determining the concentration of the residual dye in the obtained filtrate by using an ultraviolet-visible spectrophotometer;
(4) the adsorption rate was calculated from the dye concentrations in the solution before and after adsorption.
The invention has the following remarkable advantages:
(1) the method takes waste oyster shells as a calcium source, disodium hydrogen phosphate as a phosphorus source, and sodium ascorbate and sodium citrate as double templates to prepare the hydroxyapatite microspheres under hydrothermal conditions. Under hydrothermal conditions, PO4 3-Can be mixed with Ca2+Polymerizing to form a calcium phosphate precursor, sodium ascorbate being bound to phosphoric acid via its hydroxyl groupOn the calcium precursor, the hydrophobic part of the sodium ascorbate can block the formation of hydroxyapatite crystals in the sodium ascorbate butt joint region, and meanwhile, the residual hydroxyl groups of the sodium ascorbate can be continuously combined with other calcium carbonate precursors, so that the lamellar hydroxyapatite is formed. Then, due to the thermal denaturation and the enhancement of thermal motion of the sodium ascorbate in the hydrothermal environment and the addition of the sodium citrate, the sodium ascorbate is separated from the hydroxyapatite sheet layer, so that the hydroxyapatite sheet layer becomes thin. Ca in hydroxyapatite sheet layer2+Can be polymerized with-COO groups in sodium citrate molecules to form a micro-polymer structure to promote the self-assembly of the hydroxyapatite microspheres. Meanwhile, electrostatic repulsion exists between the nano hydroxyapatite sheet layers, and when the assembly effect and the electrostatic repulsion are balanced, the hydroxyapatite microspheres with regular shapes are formed. Therefore, the surface layer of the hydroxyapatite microspheres is covered by the hydroxyapatite sheet layer, the surface pore structure is good, and the adsorption performance of the hydroxyapatite microspheres can be effectively improved.
(2) The raw materials of the invention have wide sources, develop the high added value utilization of the waste oyster shells, achieve the aim of changing waste into valuable, recycle the waste oyster shells and have good economic and ecological benefits;
(3) the preparation process is simple, the hydroxyapatite microspheres obtained by using the hydrothermal synthesis method and the double-template method have good structure and good crystallinity, no agglomeration is generated in the reaction process, high-temperature burning treatment is not needed, the shape and the appearance of the hydroxyapatite can be regulated and controlled by adjusting the proportion of the template, and the reaction time is only 24 hours. The dye in the aqueous solution has good adsorption capacity;
(4) the oyster shell hydroxyapatite microspheres prepared by the invention can not be absorbed and scattered in water, can be recycled, and can not cause secondary pollution to water. The adsorption of the oyster shell hydroxyapatite microspheres to the dye conforms to the Langmuir isotherm, the dye is single-layer chemical adsorption, and the dye is mainly adsorbed on the spherical surface of the dye. During adsorption, the dye can be preferentially adsorbed in the pores between the spherical surface nanosheet layers, so that the large and numerous pore structures can effectively improve the adsorption effect of the oyster shell hydroxyapatite microspheres. Under the condition of lower concentration, dye is adsorbed on the surface of the hydroxyapatite microspheres, and the dye adsorbed on the surface of the hydroxyapatite microspheres is increased along with the increase of the concentration until the hydroxyapatite microspheres are completely covered. The spherical structure gives larger surface area to the hydroxyapatite dye microsphere, so that more sites on the surface can absorb the dye, more dyes can be covered, and the hydroxyapatite microsphere has higher adsorption rate.
Drawings
FIG. 1 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA1 prepared in example 1;
FIG. 2 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA2 prepared in example 1;
FIG. 3 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA3 prepared in example 1;
FIG. 4 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA4 prepared in example 1;
FIG. 5 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA5 prepared in example 1;
FIG. 6 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA6 prepared in example 1;
FIG. 7 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite HA7 prepared in example 1;
FIG. 8 is an X-ray diffraction pattern of HA5 of oyster shell hydroxyapatite microspheres prepared in example 1;
FIG. 9 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite microspheres HA5 obtained in example 1 after 50mg/L Coomassie Brilliant blue adsorption;
FIG. 10 is a scanning electron microscope chromatogram of oyster shell hydroxyapatite microspheres HA5 obtained in example 1 after 100mg/L Coomassie Brilliant blue adsorption;
FIG. 11 is a Fourier infrared spectrum of the oyster shell hydroxyapatite microspheres HA5 prepared in example 1;
FIG. 12 shows the change of the adsorption effect of the oyster shell hydroxyapatite microspheres HA5 prepared in example 1 with the pH of the initial solution;
FIG. 13 shows the change of the adsorption effect of HA5 on the oyster shell hydroxyapatite microspheres prepared in example 1 with the concentration of the dye;
FIG. 14 shows the change of the adsorption effect of the oyster shell hydroxyapatite microspheres HA5 prepared in example 1 with the reaction temperature.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the following examples are only examples of the present invention and do not represent the scope of the present invention defined by the claims.
Example 1
(1) Pulverizing cleaned and air dried Concha Ostreae, grinding, and sieving with 200 mesh filter screen to obtain Concha Ostreae powder;
(2) dissolving oyster shell powder 0.30g with 20ml 20 vol.% acetic acid solution, stirring continuously until no bubbles are generated, centrifuging at 4000rpm for 30min, and collecting supernatant;
(3) diluting the supernatant with deionized water to 100ml, adding 0.8g disodium hydrogen phosphate, and stirring for 20 min;
(4) after stirring, 6g of urea and sodium citrate and sodium ascorbate in different proportions are added into the mixed solution, and stirring is continued for 30min until the mixture is completely dissolved, so that the influence of the template agents in different proportions on the appearance of the hydroxyapatite is researched. The sample and the template agent are proportioned as follows: HA1(0.015g sodium ascorbate, 0g sodium citrate); HA2(0.015g sodium ascorbate, 0.015g sodium citrate); HA3(0.015g sodium ascorbate, 0.045g sodium citrate); HA4(0.015g sodium ascorbate, 0.09g sodium citrate); HA5(0.015g sodium ascorbate, 0.15g sodium citrate); HA6(0.015g sodium ascorbate, 0.18g sodium citrate); HA7(0g sodium ascorbate, 0.15g sodium citrate);
(5) transferring the reaction liquid obtained in the step (4) into a high-pressure reaction kettle, putting the reaction liquid into an oven, and carrying out hydrothermal reaction at 100 ℃ for 24 hours;
(6) after the reaction is finished, taking out the oyster shell hydroxyapatite from the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging for 20min at 4000rpm, washing for 3 times by using deionized water, washing for 1 time by using absolute ethyl alcohol, pumping and filtering the washed sample, and drying for 2h at 60 ℃ to obtain the oyster shell hydroxyapatite;
(7) FESEM analysis is carried out on 7 obtained hydroxyapatite samples, when the addition amount of sodium ascorbate is 0.015g, the appearance of hydroxyapatite is obviously changed along with the addition of sodium citrate, and the hydroxyapatite is changed into a spherical structure from a lamellar structure. When only sodium ascorbate is added, the hydroxyapatite is in a sheet layer shape; when the content of the sodium citrate is 0.015g, the appearance of the hydroxyapatite sheet layer begins to become thin and soft, because the addition of the sodium citrate accelerates the separation of the sodium ascorbate from the hydroxyapatite sheet layer, the attraction and the connection force between the hydroxyapatite sheet layers are reduced; starting from HA3, the hydroxyapatite lamella layer started to appear to aggregate significantly and had a tendency to become spherical; HA4 and HA5 both have a more regular spherical structure, but HA4 HAs a more disordered crystal morphology; HA5 HAs a regular spherical structure because the self-assembly effect of hydroxyapatite platelet layers is optimally balanced with the repulsive force between the platelets when the sodium ascorbate and sodium citrate content is 0.015g and 0.15g, respectively; in the HA6 sample, the spherical structure begins to deform, probably because the addition of excessive sodium citrate destroys the original optimal balance state between the interlayer assembly effect and the repulsion force of the hydroxyapatite sheet, the hydroxyapatite microspheres deform, and the spherical structure of the hydroxyapatite is damaged; when only sodium citrate is added and sodium ascorbate is not added (HA7), the hydroxyapatite is also spherical, but the spheres are different in size. Therefore, we chose HA5 for subsequent adsorption experiments.
(8) Preparing 100mg/L of water solution containing Coomassie brilliant blue at room temperature;
(9) accurately measuring 10mL of the aqueous solution containing the dye in the step (8) at room temperature, adding 0.01g of the prepared oyster shell hydroxyapatite dye microspheres into the solution, and placing the solution in a water bath constant temperature oscillator of 180r/min for oscillation;
(10) exploring the change of the adsorption effect of the oyster shell hydroxyapatite microspheres with the pH of the initial solution, wherein the pH is 1, 2, 3, 4, 5, 6 and 7; oscillating for 4 h; the temperature is 25 ℃;
(11) when the adsorption effect of the oyster shell hydroxyapatite microspheres is researched to change along with the reaction temperature, the reaction temperature is respectively 25 ℃, 30 ℃, 35 and 40 ℃; oscillating for 4 h; pH 5.
(12) When the change of the adsorption effect of the oyster shell hydroxyapatite microspheres with the Coomassie brilliant blue concentration is researched, the initial Coomassie brilliant blue concentrations are respectively 25, 50, 75, 100, 150 and 200 mg/L; oscillating for 4 h; pH 5.
(13) Standing and filtering the turbid liquid after the adsorption in the step at the room temperature, and measuring the concentration of the residual dye in the obtained filtrate by using an ultraviolet-visible spectrophotometer;
example 2
(1) Pulverizing cleaned and air dried Concha Ostreae, grinding, and sieving with 200 mesh filter screen to obtain Concha Ostreae powder;
(2) dissolving oyster shell powder 0.20g with 20ml 20 vol.% acetic acid solution, stirring continuously until no bubbles are generated, centrifuging at 4000rpm for 20min, and collecting supernatant;
(3) diluting the supernatant with deionized water to 100ml, adding 0.6g disodium hydrogen phosphate, and stirring for 20 min;
(4) after stirring, adding 0.09g of sodium citrate, 0.015g of sodium ascorbate and 4g of urea into the mixed solution, and continuously stirring for 30min until the sodium citrate, the sodium ascorbate and the urea are completely dissolved;
(5) transferring the reaction liquid obtained in the step (4) into a high-pressure reaction kettle, putting the reaction liquid into an oven, and carrying out hydrothermal reaction for 24 hours at 100 ℃;
(6) after the reaction is finished, taking out the reaction kettle, naturally cooling to room temperature, centrifuging for 30min at 4000rpm, washing for 4 times by using deionized water, washing for 1 time by using absolute ethyl alcohol, pumping and filtering the washed sample, and drying for 2h at 60 ℃ to obtain oyster shell hydroxyapatite microspheres;
(7) preparing 100mg/L of water solution containing crystal violet at room temperature;
(8) accurately measuring 10mL of the crystal violet-containing aqueous solution obtained in the step (7) at room temperature, adding 0.01g of the prepared oyster shell hydroxyapatite microspheres into the solution, and placing the solution in a water bath constant temperature oscillator of 180r/min for oscillation;
(9) exploring the change of the adsorption effect of the oyster shell hydroxyapatite microspheres with the pH of the initial solution, wherein the pH is 1, 2, 3, 4, 5, 6 and 7; oscillating for 4 h; the temperature is 25 ℃;
(10) when the adsorption effect of the oyster shell hydroxyapatite microspheres is researched to change along with the reaction temperature, the reaction temperature is respectively 25 ℃, 30 ℃, 35 and 40 ℃; oscillating for 4 h; pH 5.
(11) The initial crystal violet concentrations are respectively 25, 50, 75, 100, 150 and 200mg/L when the adsorption effect of the oyster shell hydroxyapatite microspheres is changed along with the crystal violet concentration; oscillating for 4 h; pH 5.
(12) Standing and filtering the turbid liquid after the adsorption in the step at the room temperature, and measuring the concentration of the residual dye in the obtained filtrate by using an ultraviolet-visible spectrophotometer;
example 3
(1) Pulverizing cleaned and air dried Concha Ostreae, grinding, and sieving with 200 mesh filter screen to obtain Concha Ostreae powder;
(2) dissolving oyster shell powder 0.40g with 20ml 20 vol.% acetic acid solution, stirring continuously until no bubbles are generated, centrifuging at 4000rpm for 30min, and collecting supernatant;
(3) diluting the supernatant with deionized water to 100ml, adding 1g disodium hydrogen phosphate, and stirring for 20 min;
(4) after stirring, adding 0.18g of sodium citrate, 0.015g of sodium ascorbate and 6g of urea into the mixed solution, and continuously stirring for 30min until the sodium citrate, the sodium ascorbate and the urea are completely dissolved;
(5) transferring the reaction liquid obtained in the step (4) into a high-pressure reaction kettle, putting the reaction liquid into an oven, and carrying out hydrothermal reaction for 24 hours at 100 ℃;
(6) after the reaction is finished, taking out the reaction kettle, naturally cooling the reaction kettle to room temperature, centrifuging the reaction kettle for 30min at 4000rpm, washing the reaction kettle for 5 times by using deionized water, washing the reaction kettle for 2 times by using absolute ethyl alcohol, pumping and filtering the washed sample, and drying the sample for 2h at 60 ℃ to obtain oyster shell hydroxyapatite microspheres;
(7) preparing 100mg/L of a Congo red-containing aqueous solution at room temperature;
(8) accurately measuring 10mL of the aqueous solution containing congo red in the step (7) at room temperature, adding 0.01g of the prepared oyster shell hydroxyapatite microspheres into the solution, and placing the solution in a water bath constant temperature oscillator of 180r/min for oscillation;
(9) exploring the change of the adsorption effect of the oyster shell hydroxyapatite microspheres with the pH of the initial solution, wherein the pH is 1, 2, 3, 4, 5, 6 and 7; oscillating for 4 h; the temperature is 25 ℃;
(10) the change of the adsorption effect of the oyster shell hydroxyapatite microspheres with the reaction temperature is explored, and the reaction temperature is respectively 25 ℃, 30 ℃, 35 and 40 ℃; oscillating for 4 h; pH 5.
(11) The initial Congo red concentrations are 25, 50, 75, 100, 150 and 200mg/L respectively when the adsorption effect of the oyster shell hydroxyapatite microspheres is changed along with the Congo red concentration; oscillating for 4 h; pH 5.
(12) Standing and filtering the turbid liquid after the adsorption in the step at room temperature, and measuring the concentration of the residual dye in the obtained filtrate by using an ultraviolet-visible spectrophotometer;
as shown in fig. 8, characteristic diffraction peaks were detected at 25.85 °,31.74 °,32.10 °,32.86 °,34.00 °,39.72 °,46.56 °,49.40 °,53.20 °,63.84 ° positions, which completely correspond to the (002), (211), (112), (300), (202), (310), (222), (213), (004) and (304) crystal planes of standard HA (JCPDS No.09-0432), indicating that the prepared sample was hydroxyapatite and that the addition of sodium ascorbate and sodium citrate did not change the purity of the sample.
As shown in fig. 9, when the concentration of the dye is low, the HA microsphere prepared by the present invention only partially adsorbs the dye on the surface.
As shown in fig. 10, when the concentration of the dye is higher, the surface of the HA microsphere prepared by the present invention is completely covered by the dye, and the HA microsphere is saturated in adsorption.
As shown in fig. 11, at 877, 1453 and 1544cm-1Characteristic peak of (A) corresponds to CO3 2-This is probably due to the adsorption of CO from the shell meal during HA production3 2-Or atmospheric carbon dioxide. At 1760cm-1The absence of the C ═ O peak means that sodium ascorbate was not present in the HA, indicating that sodium ascorbate was released from the HA before the end of the preparation reaction. 1645cm-1The tensile vibration of (A) may be due to adsorption of H2Caused by O. At 1032cm-1The absorption peak at (A) belongs to P-O tensile vibration. At 3423cm-1The absorption peak at (A) may be caused by O-H stretching vibration. 950-960 cm-1The small absorption peak in between is caused by C-H tensile vibration,this is probably due to the adsorption of sodium citrate by HA, which is highly consistent with the proposed mechanism of preparation.
As shown in FIG. 12, all pH values contributed to the removal of Coomassie Brilliant blue at pH values of 1-7. Although HA HAs a good effect on adsorbing Coomassie brilliant blue when the pH is less than 3, the color change of the Coomassie brilliant blue dye is obvious, and the experimental result is seriously influenced. When the pH is increased from 3 to 5, the adsorption capacity of HA to coomassie brilliant blue dye is increased, and when the pH is increased from 5 to 7, the adsorption capacity of HA to coomassie brilliant blue dye is decreased, so that the optimal amount of HA is pH 5, at which the adsorption capacity of HA to coomassie brilliant blue dye is strongest. Therefore all experiments in this study were performed at pH 5. Subsequently, the adsorption capacity of hydroxyapatite to coomassie brilliant blue decreases.
As shown in fig. 13, when the coomassie brilliant blue concentration is low, the adsorption capacity gradually increases as the coomassie brilliant blue concentration increases due to the concentration-driving force. When the adsorption amount reached the maximum adsorption amount of 70.7323mg/g, the adsorption capacity was not changed any more.
As shown in fig. 14, the morphology of the HA microspheres did not substantially change with increasing temperature. When the temperature was increased from 298 to 313K, the adsorption amount of Coomassie Brilliant blue was increased from 70.5446 to 83.8169 mg/g. Calculated by adsorption thermodynamics, positive Δ H0And Δ S0The values show that the adsorption process of the HA to the dye is an endothermic process and the degree of freedom of the adsorption reaction increases. Negative Δ G0The values indicate that the adsorption of the dye is a spontaneous process, and Δ G0Becomes negative with increasing temperature, indicating that higher temperatures favor the adsorption reaction.
Claims (6)
1. A preparation method of oyster shell hydroxyapatite microspheres is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) flushing oyster shells with running water, removing substances on the surface layers of the oyster shells, and then naturally drying;
(2) crushing, grinding and screening the air-dried oyster shells to obtain oyster shell powder;
(3) dissolving oyster shell powder in an acetic acid solution, stirring until no bubbles are generated, and then centrifuging to obtain a supernatant;
(4) fixing the volume of the supernatant obtained in the step (3) to 100mL, adding disodium hydrogen phosphate into the supernatant, and stirring for 20 min;
(5) adding sodium ascorbate, sodium citrate and urea into the solution stirred in the step (4), and continuously stirring for 30min until the sodium ascorbate, the sodium citrate and the urea are completely dissolved;
(6) pouring the reaction liquid prepared in the step (5) into a high-pressure reaction kettle, and placing the reaction liquid into a constant-temperature drying box for hydrothermal reaction;
(7) after the reaction is finished, naturally cooling to room temperature, centrifugally washing with water, washing with ethanol, and drying to obtain the oyster shell hydroxyapatite microspheres;
the using amount of the oyster shell powder in the step (3) is 0.30 g; in the step (5), the dosage of the sodium ascorbate is 0.015g, the dosage of the sodium citrate is 0.15g, and the dosage of the urea is 6 g.
2. The method for preparing oyster shell hydroxyapatite microspheres according to claim 1, wherein the method comprises the following steps: in the step (3), the concentration of the acetic acid solution is 10-30 vol.%, the centrifugal rotation number is 4000rpm, and the centrifugal time is 20-30 min.
3. The method for preparing oyster shell hydroxyapatite microspheres according to claim 1, wherein the method comprises the following steps: the consumption of the oyster shell powder in the step (3) and the disodium hydrogen phosphate in the step (4) needs to ensure that the molar ratio of Ca to P is n (Ca2+）/n（PO4 3-) = 1.67: 1 addition.
4. The method for preparing oyster shell hydroxyapatite microspheres according to claim 1, wherein the method comprises the following steps: the hydrothermal reaction temperature in the step (6) is 100-120 ℃, and the time is 24 h.
5. The method for preparing oyster shell hydroxyapatite microspheres according to claim 1, wherein the method comprises the following steps: in the step (7), the centrifugal revolution is 4000rpm, and the centrifugal time is 20-30 min; washing for 3-5 times by using deionized water, washing for 1-2 times by using absolute ethyl alcohol, wherein the drying temperature in the step (7) is 60 ℃, and the drying time is 2 hours.
6. The use of the oyster shell hydroxyapatite microspheres obtained by the preparation method according to claim 1 in dye adsorption.
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