CN110575821B - Hydroxyapatite/chitosan composite material and preparation method and application thereof - Google Patents
Hydroxyapatite/chitosan composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a hydroxyapatite/chitosan composite material and a preparation method and application thereof, the composite material is composed of layered chitosan and lamellar hydroxyapatite, the hydroxyapatite is uniformly adhered between layers and on the surface of the chitosan to form a composite layer of the hydroxyapatite and the chitosan, and the distance between the composite layers is 50-300 mu m. The invention uses chitosan, common calcium salt and carbonate as raw materials, which is not only cheap and easily available and widely available, but also is environment-friendly and harmless, has simple process and short preparation period; the hydroxyapatite/chitosan composite material is of a layered porous structure, has high porosity and large specific surface area, and the layered structure is favorable for adsorption of heavy metal ions, can be recycled and is easy to separate from wastewater; the hydroxyapatite/chitosan composite material has proper mechanical properties and good processing performance, and can be widely applied to the field of removing heavy metal ions in water.
Description
Technical Field
The invention relates to the fields of high polymer materials, inorganic non-metallic materials and removal of heavy metals in water, in particular to a hydroxyapatite/chitosan composite material and a preparation method and application thereof.
Background
In recent years, environmental pollution has increased, and serious threats to ecological balance, human health and social and economic sustainable development are formed. Environmental decontamination has received worldwide attention. Among many pollutants, the difficulty in removing heavy metal ions from water has been the focus of environmental purification. The wastewater containing heavy metal ions is the most serious environmental hazard and has the greatest harm to human beings. The five most dangerous substances in the ecological environment are mercury, lead, cadmium, dichlorodiphenyl and polychlorinated biphenyl, and the heavy metals of mercury, cadmium, lead, chromium, arsenic and the like are 'five toxins'. These heavy metal wastes are discharged to the environment through soil, water, air, and in particular certain heavy metal waste waters and their compounds, which can accumulate in fish and other aquatic organisms and crop tissues through drinking water and food chain and biological accumulation of organisms. Heavy metals are often acutely or chronically toxic to organisms, or may poison the body in a more complex manner, for example causing cancer or indirectly causing certain diseases. It is therefore necessary to investigate how to remove heavy metal ions from water. In the past, people use reverse osmosis, membrane filtration, electrochemical treatment and the like to remove heavy metal ions in water. But they are not widely used due to their high cost. Fortunately, researchers have found that adsorption separation is an economical and effective method for removing heavy metal ions from water. These include magnetic mesoporous materials, carbon nanotubes, activated carbon, chitosan, hydroxyapatite, graphene oxide, and the like. The ideal adsorbent can efficiently adsorb heavy metal ions while not polluting the environment.
Clockhair et al (CN108298669A) discloses a method for treating wastewater, which comprises the steps of removing COD with titanium dioxide and an oxidizing agent, removing phosphorus with a water-soluble magnesium salt, and removing heavy metals with a coagulant. Zhoukong et al (CN10828144A) disclose a lead-zinc beneficiation wastewater treatment device and a treatment method, and the lead-zinc beneficiation wastewater treatment device comprises a pretreatment tank for adjusting the pH value of lead-zinc beneficiation wastewater to remove heavy metal ions by sedimentation and an aerobic biological reaction tank for reducing the COD value of the effluent of the pretreatment tank. The adsorption method is a method for removing heavy metal ions in wastewater by using various porous adsorption materials. The core of the adsorption method is the selection of an adsorbent, and the traditional adsorbent is activated carbon. The active carbon has strong adsorption capacity and high removal rate, but has low regeneration efficiency and high price and is limited in application. Therefore, many scholars at home and abroad have recently turned their attention to finding alternative adsorbent materials. Van Jie Ping et al (CN109351210A) use cyclodextrin, chitosan and polyvinyl alcohol solution as spinning solution, use electrostatic spinning technology to spin, make nanometer fiber membrane, the nanometer fiber membrane has very high specific surface area and mechanical strength, and the adsorption ability is strong, easy to regenerate.
Apatite is the main inorganic component of natural bone, and the corresponding synthetic hydroxyapatite has environmental protection property. Hydroxyapatite has been widely used as an effective absorbent for the long-term treatment of heavy metals in the past decades due to its high adsorption capacity, low water solubility and low cost. In addition, chitosan produced by the alkaline deacetylation of chitin has been widely used as an adsorbent for removing heavy metal ions such as copper, lead, mercury, cadmium and chromium, and amine groups in chitosan have a strong affinity for heavy metals. However, it is difficult to separate chitosan and hydroxyapatite particles from wastewater, limiting their industrial applications.
Bionic materials are an emerging material which is researched more in recent years. It is a material developed by inspiring or imitating the characteristics of living things. The bionic shell structure material is inspired by mussels.
Based on the hydroxyapatite/chitosan composite material, the hydroxyapatite/chitosan composite material has high adsorption performance, is environment-friendly, can be recycled, and is easy to separate from waste water.
Disclosure of Invention
The invention aims to solve the technical problem of providing a hydroxyapatite/chitosan composite material which has a layered porous structure, a large specific surface area, good adsorption performance, environmental friendliness, recyclability and easy separation from wastewater.
The invention also provides a preparation method of the hydroxyapatite/chitosan composite material, the preparation process is simple, the preparation period is short, the production cost is low, the obtained material is of a layered structure of a bionic shell, the wastewater can be filtered layer by layer in multiple stages, and the removal effect of the material on heavy metal ions in water can be improved.
The invention also provides application of the hydroxyapatite/chitosan composite material in removing heavy metal ions in water.
The invention is realized by the following technical scheme:
the hydroxyapatite/chitosan composite material consists of layered chitosan and flaky hydroxyapatite, the hydroxyapatite is uniformly adhered among layers and on the surface of the chitosan to form a composite layer of the hydroxyapatite and the chitosan, and the distance between the composite layers is 50-300 mu m.
Preferably, the mass ratio of the hydroxyapatite to the chitosan in the hydroxyapatite/chitosan composite material is (1-10): 1.
a preparation method of a hydroxyapatite/chitosan composite material comprises the following steps:
(1) dissolving chitosan powder in acid liquor to prepare chitosan slurry, placing the chitosan slurry in a mold, heating to 40-60 ℃, preserving heat for 10-20 min, and then drying and forming to prepare a layered chitosan material;
(2) repeatedly and alternately immersing the obtained layered chitosan material into a calcium salt solution and a carbonate solution to obtain a calcium carbonate/chitosan layered porous composite material;
(3) and (3) immersing the obtained calcium carbonate/chitosan material into a phosphate buffer solution to obtain the hydroxyapatite/chitosan composite material.
Preferably, the acid solution in the step (1) is an aqueous solution of acetic acid, nitric acid and hydrochloric acid, and the volume fraction of the acid solution is 0.5-10%.
Preferably, the concentration of the chitosan slurry in the step (1) is 0.010 g/L-saturated solution, the temperature is 40-60 ℃, and more preferably, the concentration of the chitosan slurry is 1 g/L-200 g/L.
Preferably, the drying in the step (1) is freeze drying, the freeze drying temperature is-85 ℃ to-60 ℃, the vacuum degree is 10Pa to 100Pa, and the time is 24h to 120 h.
Preferably, the concentration of the calcium salt solution in the step (2) is 0.010M-saturated solution, the temperature is 10-30 ℃, and the soaking time is 4-24 h each time; preferably, the concentration of the calcium salt solution is 0.01-1M.
Preferably, the concentration of the carbonate solution in the step (2) is 0.010M-saturated solution, the temperature is 10-30 ℃, and the soaking time is 4-24 h each time; preferably, the concentration of the carbonate solution is 0.01-1M.
Preferably, the repetition frequency of the step (2) is 10-20 times.
Preferably, the calcium salt in step (2) is any one of calcium nitrate and calcium chloride, and the carbonate is any one of sodium carbonate and potassium carbonate.
Preferably, the concentration of the phosphate buffer solution in the step (3) is 0.010M to saturation concentration, the temperature is 25 ℃ to 70 ℃, the soaking time is 1min to 240h, the pH of the phosphate buffer solution is 7.2 to 7.6, the preferred soaking time is 24 to 240h, more preferably 96 to 240h, and the preferred concentration of the phosphate buffer solution is 0.1M to 1.0M.
The invention also provides application of the hydroxyapatite/chitosan composite material in removing heavy metal ions in water.
The invention also provides an adsorbent for removing heavy metal ions in water, which contains the hydroxyapatite/chitosan composite material. The hydroxyapatite/chitosan composite material is a bionic shell layered structure material, not only well combines hydroxyapatite and chitosan together, but also the layered structure acts as a tower plate effect, so that wastewater is adsorbed to a certain extent when passing through each layer, and the purpose of removing Pd in water in a multi-stage layer-by-layer manner is achieved 2+ 、Cd 2+ 、Hg 2+ The effect of the heavy metal ions is improved, so that the effect of the material on the metal ions in the water can be improvedThe ability to be removed.
Compared with the prior art, the invention has the advantages that:
(1) the hydroxyapatite/chitosan composite material prepared by the invention uses chitosan, common calcium salt and carbonate as raw materials, is cheap and easily available, has wide material sources, is environment-friendly and harmless, and has the advantages of simple process, short preparation period and low production cost.
(2) The hydroxyapatite/chitosan composite material prepared by the invention has a layered porous structure and high porosity; the macroporous structure has larger specific surface area, and the layered special structure is favorable for the adsorption of heavy metal ions, thereby being favorable for removing the heavy metal ions in water, and the macroporous structure is environment-friendly, can be recycled and is easy to separate from wastewater.
(3) The hydroxyapatite/chitosan composite material prepared by the invention has proper mechanical properties and good processing performance, does not cause secondary pollution to the environment when adsorbing heavy metal ions in water, and can be widely applied to the field of removing the heavy metal ions in water.
Drawings
Fig. 1 is a scanning electron microscope image (SEM), wherein fig. 1a is a chitosan material, fig. 1b is a partial enlarged view of fig. 1a, fig. 1c is a calcium carbonate/chitosan material, fig. 1d is a partial enlarged view of fig. 1c, fig. 1e is a hydroxyapatite/chitosan material, and fig. 1f is a partial enlarged view of fig. 1 e;
FIG. 2 is an XRD pattern of a hydroxyapatite/chitosan composite material prepared in example 1;
fig. 3 is a graph of an adsorption capacity curve of the hydroxyapatite/chitosan composite material prepared in example 1 after an experiment for adsorbing lead ions in water is performed;
fig. 4a is a graph of an adsorption rate of the hydroxyapatite/chitosan composite material prepared in example 1 after an experiment for adsorbing lead ions in water is performed, and fig. 4b is a graph of an instantaneous lead ion concentration of the hydroxyapatite/chitosan composite material prepared in example 1 after an experiment for adsorbing lead ions in water is performed;
fig. 5 is a graph of an adsorption amount curve of the hydroxyapatite/chitosan composite material prepared in example 1 after an experiment for adsorbing other heavy metal ions in water is performed;
fig. 6a is a graph of a mechanical property test performed on the calcium carbonate/chitosan layered porous composite material prepared in example 1, and fig. 6b is a graph of a mechanical property test performed on the hydroxyapatite/chitosan composite material prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
(1) Accurately weighing 2.0g chitosan (Shanghai Runjie chemical reagent Co., Ltd.) and placing in 50mL acetic acid solution with volume fraction of 2.0%, stirring at 50 deg.C until chitosan is completely dissolved in acetic acid solution, and removing bubbles by ultrasonic wave;
(2) transferring the prepared chitosan slurry into a mold, heating to 50 ℃, preserving heat for 10min, transferring into a freeze dryer, and freeze-drying at-63 ℃ and 40Pa for 72h to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.10M calcium chloride solution and 0.10M sodium carbonate solution, and alternating the process for 22 times, namely soaking each solution for 11 times, and soaking each time for 6 hours at the soaking temperature of 25 ℃, so as to obtain the calcium carbonate/chitosan layered porous composite material;
(4) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.20M phosphate buffer solution for 168 h; the temperature of the phosphate buffer solution is 60 ℃, and the pH value of the phosphate buffer solution is 7.4, thus obtaining the hydroxyapatite/chitosan composite material.
The morphology and composition of the composite material prepared in example 1 were characterized, and the obtained scanning electron microscope image (SEM) and wide angle ray diffraction pattern (XRD) are shown in fig. 1 and 2, respectively.
As shown in SEM figure 1, the obtained hydroxyapatite/chitosan composite material has a multilayer layered structure, and the distance between layers is 50-300 μm. The generated calcium carbonate and hydroxyapatite are uniformly distributed on the surface of the chitosan material; the calcium carbonate formed in the high power lens is a blocky structure, and the hydroxyapatite formed by conversion is a sheet structure. According to the XRD spectrum 2, the synthesized material is a composite material of hydroxyapatite and chitosan. The mass ratio of hydroxyapatite to chitosan in the hydroxyapatite/chitosan composite material prepared by the embodiment is 7: 1.
example 2
(1) Accurately weighing 10g of chitosan, placing the chitosan into 50mL of hydrochloric acid solution with the volume fraction of 1.0%, stirring at 40 ℃ until the chitosan is completely dissolved in the hydrochloric acid solution, and removing bubbles by ultrasonic waves;
(2) transferring the prepared chitosan slurry into a mold, heating to 40 ℃, preserving heat for 12min, transferring into a freeze dryer, and freeze-drying for 48h under the conditions of-60 ℃ and 60Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.010M calcium nitrate solution and 0.010M potassium carbonate solution, and alternating the process for 20 times, namely soaking each solution for 10 times, wherein the soaking time is 4 hours, and the soaking temperature is 15 ℃, so that the calcium carbonate/chitosan layered porous composite material can be obtained;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.30M phosphate buffer solution for 96 hours, wherein the temperature of the phosphate buffer solution is 70 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of hydroxyapatite to chitosan in the hydroxyapatite/chitosan composite material prepared by the embodiment is 2: 1, the structure is the same as that of example 1.
Example 3
(1) Accurately weighing 1.0g of chitosan, placing the chitosan in 100mL of nitric acid solution with the volume fraction of 2.0%, stirring at 60 ℃ until the chitosan is completely dissolved in the nitric acid solution, and removing bubbles by ultrasonic;
(2) transferring the prepared chitosan slurry into a mold, heating to 60 ℃, preserving heat for 15min, transferring into a freeze dryer, and freeze-drying for 120h at-53 ℃ under 20Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.15M calcium chloride solution and 0.15M potassium carbonate solution, and alternating the process for 26 times, namely soaking each solution for 13 times, and soaking each time for 8 hours at the soaking temperature of 30 ℃, so as to obtain the calcium carbonate/chitosan layered porous composite material;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.50M phosphate buffer solution for 240 hours, wherein the temperature of the phosphate buffer solution is 60 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of hydroxyapatite to chitosan in the hydroxyapatite/chitosan composite material prepared by the example is 9: 1, the structure is the same as that of example 1.
Example 4
(1) Accurately weighing 2.0g of chitosan, placing the chitosan into 100mL of acetic acid solution with volume fraction of 10%, stirring the chitosan at 55 ℃ until the chitosan is completely dissolved in the acetic acid solution, and removing bubbles by ultrasonic waves;
(2) transferring the prepared chitosan slurry into a mold, heating to 55 ℃, preserving heat for 16min, transferring into a freeze dryer, and freeze-drying for 120h at-70 ℃ under 100Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.15M calcium chloride solution and 0.15M sodium carbonate solution, and performing the process alternately for 30 times, wherein each solution is soaked for 15 times, each time is soaked for 6 hours, and the soaking temperature is 10 ℃, so that the calcium carbonate/chitosan layered porous composite material can be obtained;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.50M phosphate buffer solution for 168 hours, wherein the phosphate buffer temperature is 60 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of the hydroxyapatite to the chitosan in the hydroxyapatite/chitosan composite material prepared by the embodiment is 8: 1, the structure is the same as in example 1.
Example 5
(1) Accurately weighing 5.0g of chitosan, placing the chitosan in 100mL of acetic acid solution with the volume fraction of 2.0%, stirring at 45 ℃ until the chitosan is completely dissolved in the acetic acid solution, and removing bubbles by ultrasonic;
(2) transferring the prepared chitosan slurry into a mold, heating to 45 ℃, preserving heat for 20min, transferring into a freeze dryer, and freeze-drying for 72h at-63 ℃ under 10Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.20M calcium nitrate solution and 0.20M sodium carbonate solution, and alternating the process for 26 times, namely soaking each solution for 13 times, wherein the soaking time is 12 hours, and the soaking temperature is 25 ℃, so that the calcium carbonate/chitosan layered porous composite material can be obtained;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.50M phosphate solution for 148h, wherein the temperature of the phosphate buffer solution is 60 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of the hydroxyapatite to the chitosan in the hydroxyapatite/chitosan composite material prepared by the embodiment is 6: 1, the structure is the same as in example 1.
Example 6
(1) Accurately weighing 10g of chitosan, placing the chitosan into 100mL of acetic acid solution with the volume fraction of 2.0%, stirring at 60 ℃ until the chitosan is completely dissolved in the acetic acid solution, and removing bubbles by ultrasonic;
(2) transferring the prepared chitosan slurry into a mold, heating to 60 ℃, preserving heat for 14min, transferring into a freeze dryer, and freeze-drying for 24h at-40 ℃ and 55Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.10M calcium chloride solution and 0.10M sodium carbonate solution, and alternating the process for 20 times, namely soaking each solution for 10 times, and soaking each time for 24 hours at the soaking temperature of 20 ℃, so as to obtain the calcium carbonate/chitosan layered porous composite material;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 0.20M phosphate buffer solution for 120h, wherein the temperature of the phosphate buffer solution is 60 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of hydroxyapatite to chitosan in the hydroxyapatite/chitosan composite material prepared by the example is 3: 1, the structure is the same as that of example 1.
Example 7
(1) Accurately weighing 10g of chitosan, placing the chitosan into 100mL of acetic acid solution with the volume fraction of 2.0%, stirring at 50 ℃ until the chitosan is completely dissolved in the acetic acid solution, and removing bubbles by ultrasonic;
(2) transferring the prepared chitosan slurry into a mold, heating to 50 ℃, preserving heat for 17min, transferring into a freeze dryer, and freeze-drying for 108h at-83 ℃ and 65Pa to obtain a layered chitosan material;
(3) respectively soaking the prepared layered chitosan material in 0.10M calcium chloride solution and 0.10M sodium carbonate solution, and alternating the process for 30 times, namely soaking each solution for 15 times, and soaking each time for 4 hours at the soaking temperature of 25 ℃, so as to obtain the calcium carbonate/chitosan layered porous composite material;
(4) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into 1.0M phosphate buffer solution for 168 hours, wherein the temperature of the phosphate buffer solution is 80 ℃, and the pH value of the phosphate buffer solution is 7.4, so as to obtain the hydroxyapatite/chitosan composite material.
The mass ratio of hydroxyapatite to chitosan in the hydroxyapatite/chitosan composite material prepared by the example is 1: 1, the structure is the same as in example 1.
Performance testing
The hydroxyapatite/chitosan composite material obtained in example 1 is used for the experiment of adsorbing lead ions in water:
(1) the hydroxyapatite/chitosan composite material obtained in example 1 was taken, and simulated wastewater containing lead was pumped through the hydroxyapatite/chitosan composite material by a peristaltic pump. The temperature of the experimental conditions is ensured to be 25 ℃, the hydroxyapatite/chitosan composite material is 0.4g, the pH value of the simulated lead solution is 7.4, and the speed of the peristaltic pump is controlled to be 0.25 mL/min.
(2) And taking out the adsorbed simulated solution every 1h, 2h, 6h, 12h, 24h, 48h, 72h, 96h, 120h and 144h, and measuring the concentration of the adsorbed lead ions by an EDTA titration method. All tests were repeated 3 times, averaged and the results of the repeated experiments were within the allowed error range (+ -5%).
The data obtained by the experiment for adsorbing the lead ions in the water are drawn and analyzed, and the lead ion adsorption curve chart is shown in fig. 3, so that the adsorption capacity of the hydroxyapatite/chitosan composite material is improved along with the increase of the lead ion concentration. We also measured the instantaneous concentration of lead ions at different times and the adsorption rate of the material to lead ions, and the results are shown in fig. 4. It can be seen that the material has better adsorption effect on lead ions in the first 12 hours, and the material gradually loses the removal effect on the lead ions along with the consumption of hydroxyapatite along with the prolonging of time.
In the same way we are dealing with other heavy metal ions such as Cd 2+ ，Hg 2+ The ions were subjected to an elimination experiment. The results of the experiment are shown in FIG. 5. The result shows that the hydroxyapatite/chitosan composite material also has certain adsorption capacity to other heavy metal ions.
The hydroxyapatite/chitosan composite material obtained in the embodiments 2 to 7 is detected by the same method, and the result shows that the adsorption capacity is improved along with the increase of the concentration of heavy metal ions.
The hydroxyapatite/chitosan composite material obtained in example 1 was used to perform mechanical property experiments. The experimental result is shown in fig. 6, and it can be seen that the mechanical properties of the calcium carbonate/chitosan layered porous composite material are obviously improved after the calcium carbonate/chitosan layered porous composite material is converted into the hydroxyapatite/chitosan porous composite material. This can be attributed to its unique layered structure, which is slowly destroyed with displacement as the external force changes.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention. The terms appearing in the present invention are used for illustration and understanding of the technical aspects of the present invention, and do not constitute limitations of the present invention. The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (7)
1. The hydroxyapatite/chitosan composite material is characterized by comprising layered chitosan and lamellar hydroxyapatite, wherein the hydroxyapatite is uniformly attached between layers and on the surface of the chitosan to form a composite layer of the hydroxyapatite and the chitosan, and the distance between the composite layers is 50-300 mu m;
the mass ratio of the hydroxyapatite to the chitosan is (1-10): 1;
the preparation method comprises the following steps:
(1) dissolving chitosan powder in acid liquor to prepare chitosan slurry, placing the chitosan slurry in a mould and heating, and then drying and forming to prepare a layered chitosan material;
(2) repeatedly and alternately immersing the obtained layered chitosan material into a calcium salt solution and a carbonate solution to obtain a calcium carbonate/chitosan layered porous composite material;
(3) and (3) immersing the obtained calcium carbonate/chitosan layered porous composite material into a phosphate buffer solution to obtain the hydroxyapatite/chitosan composite material.
2. The hydroxyapatite/chitosan composite material according to claim 1, wherein the acid solution in step (1) is an aqueous solution of acetic acid, nitric acid and hydrochloric acid, and the volume fraction of the acid solution is 0.5-10%.
3. The hydroxyapatite/chitosan composite material according to claim 1, wherein the chitosan slurry of step (1) has a concentration ranging from 0.010g/L to a saturated solution and a temperature ranging from 40 ℃ to 60 ℃.
4. The hydroxyapatite/chitosan composite material according to claim 1, wherein the drying in the step (1) is freeze drying, the freeze drying temperature is-85 ℃ to-60 ℃, the vacuum degree is 10Pa to 100Pa, and the time is 24h to 120 h.
5. The hydroxyapatite/chitosan composite material according to claim 1, wherein the calcium salt solution in the step (2) has a concentration of 0.010M to a saturated solution, a temperature of 10 ℃ to 30 ℃, and a soaking time of 4 to 24 hours each time, and the carbonate solution has a concentration of 0.010M to a saturated solution, a temperature of 10 ℃ to 30 ℃, and a soaking time of 4 to 24 hours each time.
6. The hydroxyapatite/chitosan composite material according to claim 1, wherein the concentration of the phosphate buffer solution in the step (3) is 0.010M to saturated concentration, the temperature is 25 ℃ to 70 ℃, the soaking time is 1min to 240h, and the pH of the phosphate buffer solution is 7.2 to 7.6.
7. Use of a hydroxyapatite/chitosan composite according to any one of claims 1 to 6 for removing heavy metal ions from water.
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