CN115254042A - Preparation and application of modified sodium alginate composite ball for removing heavy metal ions in water - Google Patents
Preparation and application of modified sodium alginate composite ball for removing heavy metal ions in water Download PDFInfo
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- sodium alginate
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical class O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention belongs to the technical field of preparation of heavy metal ion adsorbents, and discloses preparation and application of a modified sodium alginate composite ball for removing heavy metal ions in water. The preparation method comprises the following steps: preparing bone meal: preparing bone meal raw materials from fresh bovine bones by different preparation methods; preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw materials, and preparing modified sodium alginate in different preparation modes; preparation of composite hydrogel: and dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball. According to the invention, the bone meal modified sodium alginate is adopted, and the bone meal modified sodium alginate and calcium chloride are crosslinked to form particles, so that the sodium alginate has wide sources and low price, and the prepared modified sodium alginate composite ball has good adsorption performance and good removal capability on heavy metal ions in water.
Description
Technical Field
The invention belongs to the technical field of preparation of heavy metal ion adsorbents, and particularly relates to preparation and application of a modified sodium alginate composite ball for removing heavy metal ions in water.
Background
Heavy metal pollution is a serious problem for human health and life. Contamination with heavy metals is the result of a variety of activities such as chemical manufacturing, painting and coating, mining, refining metallurgy, nuclear and other industries. These metals have a deleterious effect on the animal and plant community of lakes and streams. Cadmium (Cd) is one of heavy metals with extremely strong toxicity, is recognized as the largest safety hazard to crops, and is also an element with the strongest mobility and biological activity. The removal of toxic metals is usually carried out by redox processes, filtration, electrochemical treatment, evaporation, ion exchange or reverse osmosis. However, these methods have the disadvantages of high energy consumption, high chemical requirements, low efficiency and generally large amounts of sludge. In this respect, it is strongly suggested to find new technologies.
The method for removing heavy metal ions in water mainly comprises a chemical precipitation method, a coagulating sedimentation method, an adsorption method, a flocculation method, a reverse osmosis technology and the like. Among them, the adsorption method is widely used because of its advantages such as high efficiency, low energy consumption and simple operation.
For the adsorbent in the adsorption method, under a relatively mild condition, na + ions on the structural unit of the sodium alginate can perform an ion exchange reaction with divalent cations such as Ca2+ or Sr2+ in an aqueous solution to form a cross-linked network structure, so that the composite ball adsorbent for the sodium alginate can be prepared. Compared with the traditional powder adsorbent, the sodium alginate composite ball has the advantages of low possibility of loss, easiness in separation from water, good recovery performance and the like in the aspect of adsorbing heavy metal ions in water.
However, the unmodified sodium alginate composite ball adsorbent has low capacity of removing heavy metal ions in water, and cannot meet the ideal requirement of heavy metal ion wastewater treatment. Therefore, the selection of a proper modifier for modifying the sodium alginate is one of the hot problems of the current domestic and foreign researches.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) The modified sodium alginate composite ball prepared by the prior art has high manufacturing cost and complex process.
(2) The sodium alginate composite ball prepared by the prior art has poor adsorption performance and low removal capability on heavy metal ions in water.
Disclosure of Invention
In order to overcome the problems in the related art, the disclosed embodiment of the invention provides a preparation method and application of a modified sodium alginate composite ball for removing heavy metal ions in water. In particular to an application of removing Cd ions in an aqueous solution by using bone meal as a reinforcing filler to improve the porous structure of sodium alginate beads.
The innovation points of the invention are as follows: the bone meal and sodium alginate are combined for the first time to prepare the hydrogel for adsorbing heavy metal ions, and the hydrogel is applied.
The technical scheme is as follows: a preparation method of a modified sodium alginate composite ball for removing heavy metal ions in water comprises the following steps:
step one, preparing bone meal: preparing a bone meal raw material from fresh bovine bones by different preparation methods;
step two, preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw material, and preparing modified sodium alginate by different preparation modes;
step three, preparing the composite hydrogel: and dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball.
In one embodiment, in the first step, the preparation of the bone meal raw material by different preparation methods comprises the following steps:
preparing whole ox bone into broken bone, decocting the broken bone in water at 100 deg.C, adding appropriate amount of calx and plant ash, decocting while removing fat and colloid until the bone is substantially free of oil, sun drying, and pulverizing; boiling for 3-8 hours, removing part of grease and bone glue, draining water, drying at 100-140 ℃, and crushing to obtain the finished product. Wherein the bone meal is prepared from the following components in percentage by mass: quicklime: plant ash = (2 to 12) kg: (1-6) kg: (1-6) kg.
In one embodiment, in the step one, the preparation of the bone meal raw material by different preparation methods further comprises:
crushing and boiling animal bones, removing part of oil and bone glue, drying and crushing to obtain crude bone powder; placing the beasts and birds bones which are knocked into small pieces and dried in the sun into a pot, adding water, boiling, taking out grease floating on the water surface after a night, taking out bones, drying in the sun, and grinding into bone powder.
In one embodiment, in the step one, the preparation of the bone meal raw material by different preparation methods further comprises: placing animal bone in a high pressure tank, removing most of oil and bone glue under high temperature and high pressure and steam to obtain defatted bone powder; knocking the dried bones into blocks, putting the blocks into a pressure cooker, adding water to submerge the blocks, and then tightly covering the pressure cooker and heating the blocks; when the temperature reaches 120 ℃, steaming for 24 hours, boiling the pot the next day, removing the upper fat layer, fishing out the bones, drying in the sun and crushing.
In one embodiment, in the second step, the preparation of the modified sodium alginate by different preparation methods comprises:
adding sodium alginate into water at room temperature under normal pressure, dissolving in water bath at 100 deg.C, and heating for 5-8 hr; fully and uniformly stirring until the sodium alginate is dissolved to obtain a transparent and uniform colloidal substance. Providing a uniform medium for the preparation of the hydrogel; fully grinding the bone meal raw material obtained in the step one, sieving the bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, and fully vibrating the bone meal raw material in a vibrating machine for 4 to 8 hours to fully and uniformly mix the bone meal in a sodium alginate colloid to obtain a modified sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5 to 4) g: (300-2400) mL.
In one embodiment, in the second step, the preparation of the modified sodium alginate by different preparation methods further comprises: fully grinding the bone meal raw material obtained in the step one under the conditions of room temperature and normal pressure, sieving the ground bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material and sodium alginate into water together, placing the mixture in an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by using sound waves with the frequency of 40khz for 4-8 hours to ensure that the bone meal is fully and uniformly mixed in the sodium alginate jelly to obtain a modified transparent and uniform sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5-4) g: (300-2400) mL.
In one embodiment, in the second step, the preparation of the modified sodium alginate by different preparation methods further comprises: under the conditions of room temperature and normal pressure, adding the sodium alginate and the bone meal raw material obtained in the step one into water after fully grinding and sieving with a 100-mesh sieve, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to be 40-100 ℃, and the stirring time is 6-12 hours; obtaining a modified transparent and uniform sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5 to 4) g: (300-2400) mL.
In one embodiment, the preparation of the step three composite hydrogel specifically comprises:
preparing a calcareous solution at room temperature and normal pressure, wherein the calcareous solution comprises CaCl2A solution; dropwise adding the modified sodium alginate solution prepared in the second step into CaCl2In the solution, a magnetic stirrer is adopted for fully and uniformly stirring, the temperature of the magnetic stirrer is adjusted to be 35-100 ℃, and the stirring time is 5-14 hours; sodium alginate particles are formed in the dropping process, the mixture is kept stand for 10 to 15 hours, then is washed by water and is soaked into distilled water, and the modified sodium alginate composite ball with the particle size of 2 to 6mm is prepared.
In one embodiment, caCl2The solution is prepared by adding anhydrous calcium chloride into water and uniformly stirring, wherein the dosage ratio of the anhydrous calcium chloride to the water is (5-100) g, (100-2000) mL.
The invention also aims to provide application of the modified sodium alginate composite ball prepared by the preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water as a heavy metal ion adsorbent in water treatment.
By combining all the technical schemes, the invention has the advantages and positive effects that:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with the technical scheme to be protected and the results and data in the research and development process, and some creative technical effects brought after the problems are solved are analyzed in detail and deeply. The specific description is as follows:
the modified sodium alginate composite ball adsorbent provided by the invention is used for removing heavy metal ions in water, and overcomes the problem that the capacity of an unmodified seaweed composite ball adsorbent for removing the heavy metal ions in water is low.
The preparation method of the modified sodium alginate composite ball disclosed by the invention adopts bone meal to modify sodium alginate to obtain a modified sodium alginate composite material which has more surface functional groups and a rougher surface compared with the original sodium alginate, and the novel material is a porous structure with various pore diameters. The porous structure is favorable for swelling and heavy metal ions to diffuse into the hydrogel. In addition, the pores have larger specific surface area and a large number of active centers, which are beneficial to the adsorption of heavy metal ions. The sodium alginate used in the invention has wide sources and low price, and the prepared modified sodium alginate composite ball has more surface functional groups compared with the unmodified sodium alginate composite ball, has good removal capability on heavy metal ions in water, overcomes the defect of low removal capability of the unmodified sodium alginate composite ball on the heavy metal ions in the water, increases the possibility of applying the composite ball to the actual treatment of the heavy metal ion wastewater, and has very wide application prospect in the aspect of treating water pollution.
The traditional sodium alginate-based hydrogel still has inherent defects in the aspects of composition, gel process, system structure and the like. Therefore, the bone meal is used as the reinforcing filler of the sodium alginate matrix to prepare the novel porous sodium alginate-based composite hydrogel for removing cadmium in water.
The method is characterized in that the porous structure of the sodium alginate beads is improved by using bone meal as a reinforcing filler, and Cd ions in an aqueous solution are removed.
The invention uses low-cost biodegradable raw materials to prepare the novel adsorption material, efficiently solves the problem of heavy metal pollution in the wastewater, and provides possibility for the recovery of the adsorption material.
Secondly, considering the technical solution as a whole or from the perspective of products, the technical effects and advantages of the technical solution to be protected by the present invention are specifically described as follows:
according to the invention, the bone meal modified sodium alginate is adopted, and the bone meal modified sodium alginate and calcium chloride are crosslinked to form particles, so that the sodium alginate has wide sources and low price, the prepared modified sodium alginate composite ball has good adsorption performance, has good removing capability for heavy metal ions in water, overcomes the defect of low removing capability for the heavy metal ions in water of the unmodified alginate composite ball, and increases the possibility of applying the composite ball to actual treatment of the heavy metal ion wastewater.
Third, as an inventive supplementary proof of the claims of the present invention, there are also presented several important aspects:
(1) The expected income and commercial value after the technical scheme of the invention is converted are as follows: low cost investment and high income benefit.
(2) The technical scheme of the invention fills the technical blank in the industry at home and abroad: fills the blank of using bone meal as an adsorption synthetic material.
(3) The technical scheme of the invention solves the technical problems which are always desired to be solved but are not successfully achieved: solves the problem of preparing a biodegradable and easily recycled heavy metal adsorbing material.
(4) The technical scheme of the invention overcomes the technical prejudice whether: overcomes the prejudice that the sodium alginate hydrogel has lower adsorption efficiency.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of the preparation of a modified sodium alginate composite sphere for removing heavy metal ions from water according to an embodiment of the present invention;
FIG. 2 is a graph of adsorption efficiency provided by an embodiment of the present invention;
FIG. 3 is a Langmuir fitting curve diagram of the modified sodium alginate composite material provided by the embodiment of the invention;
FIG. 4 is a physical diagram and a Scanning Electron Microscope (SEM) diagram of the prepared modified sodium alginate composite ball provided in example 1 of the invention; wherein, fig. 4 (a) is a real object diagram of the composite ball; FIG. 4 (b) is a surface SEM image before modification; fig. 4 (c) and 4 (d) are SEM images of the surface of the modified composite sphere;
fig. 5 is a fourier transform infrared spectroscopy (FTIR) plot of unmodified alginic acid and modified sodium alginate composite spheres prepared as provided in the examples of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
1. Illustrative examples are illustrated:
as shown in fig. 1, a preparation method of a modified sodium alginate composite ball (a preparation method of a modified sodium alginate composite ball for removing heavy metal ions in water) provided by the embodiment of the present invention includes the following steps:
s101, preparing bone meal: preparing bone meal raw materials from fresh bovine bones by different preparation methods;
s102, preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw material, and preparing modified sodium alginate by different preparation modes;
s103, preparing the composite hydrogel: and dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball.
In the present embodiment, the preparation of the bone meal in step S101 comprises: fresh bovine bone was prepared by several methods:
(1) Generally, bone meal can be divided into decocted bone meal, crude bone meal (raw bone meal) and steamed bone meal (degummed, defatted bone meal) according to the preparation method. Firstly, the whole ox bone is made into broken bone, the boiling method is that the broken bone is put into a pot and boiled by adding water at 100 ℃, and the germ in the bone powder can be killed by high temperature. Adding appropriate amount of calx and plant ash while decocting, removing fat and colloid until bone contains no oil, sun drying, and pulverizing; boiling for 3-8 hr, removing part of oil and bone glue, draining, stoving at 100-140 deg.c and crushing to obtain the product. Wherein the bone meal is prepared from the following components in percentage by mass: quick lime: plant ash = (2-12) kg: (1-6) kg: (1-6) kg.
(2) The crude bone powder is prepared by crushing and boiling animal bone, removing part of oil and bone glue, oven drying, and pulverizing; the livestock and poultry bones are collected, dried in the sun and stored at ordinary times, the livestock and poultry bones are firstly knocked into small pieces during preparation, then the small pieces are put into a pot and boiled with water to kill germs, grease floating on the water surface is fished out after one night, then the bones are taken out, dried in the sun and ground into bone powder.
(3) Or defatted bone powder is prepared by placing animal bone in a high pressure tank, and removing most of oil and bone glue under high temperature, high pressure and steam. The bone meal is generally grey white powder which is insoluble in water, contains phosphorus which is difficult to utilize by plants, but can be quickly utilized in acid soil, and can be mixed into compost or stable manure for fermentation and then used as a base fertilizer. Knocking the dried bones into blocks, putting the blocks into a pressure cooker, adding water to submerge the blocks, and then tightly covering the pressure cooker and heating the blocks. Steaming at 120 deg.C for 24 hr, extinguishing fire, boiling the pot the next day, removing upper fat, taking out bone, sun drying, and pulverizing.
The prepared bovine bone meal raw material contains more protein and mineral substances and has the characteristics of looseness and porosity. Provides conditions for long-term storage and transportation. The content of hydroxyapatite and better mechanical property thereof are well preserved, and conditions are provided for adsorbing heavy metal and enhancing the mechanical property of sodium alginate.
In the embodiment of the present invention, the preparation of the modified sodium alginate in step S102 includes:
(1) Adding sodium alginate into water at room temperature under normal pressure, dissolving in water bath at 100 deg.C, and heating for 5-8 hr. Fully and uniformly stirring until the sodium alginate is dissolved to obtain a transparent and uniform colloidal substance. Provides a uniform medium for preparing the hydrogel. And (4) fully grinding the bone meal raw material obtained in the step (S101), sieving the ground bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, and fully shaking the ground bone meal raw material in a shaking machine for 4-8 hours to fully and uniformly mix the bone meal in sodium alginate jelly to obtain a modified sodium alginate solution.
(2) And (2) fully grinding the bone meal raw material obtained in the step (S101) under the conditions of room temperature and normal pressure, sieving the ground bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material and sodium alginate into water together, placing the mixture in an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by using sound waves with the frequency of 40khz for 4-8 hours to ensure that the bone meal is fully and uniformly mixed in the sodium alginate jelly to obtain a modified transparent and uniform sodium alginate solution.
(3) And (3) adding the bone meal which is obtained by fully grinding sodium alginate and the bone meal raw material obtained in the step (S101) and then sieving with a 100-mesh sieve into water at room temperature and normal pressure, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to be 40-100 ℃, and the stirring time is 6-12 hours. Obtaining the modified transparent and uniform sodium alginate solution.
The prepared modified sodium alginate raw material fully retains the original physical characteristics of the bone meal, so that the mechanical property of the sodium alginate is enhanced, and the original heavy metal adsorption capacity is retained. Heating to make sodium alginate fully and completely dissolved in water to obtain uniform and stable adsorption carrier, and creating better condition for composite bone powder. Fully maintains the porous and water-absorbing characteristics of the composite material.
In the embodiment of the present invention, the preparation of the composite hydrogel in step S103 includes:
(1) Preparing CaCl under the conditions of room temperature and normal pressure2A solution; dropwise adding any one of the modified sodium alginate solutions 1-3 in the step S102 into CaCl2And (3) in the solution, sodium alginate particles are formed in the dropping process, the solution is kept stand for 10 to 15 hours, then is washed by water and is soaked into distilled water, and the modified sodium alginate composite ball with the particle size of 2 to 6mm is prepared.
(2) In step S102, the dosage ratio of sodium alginate, bone meal and water is (6-48) g: (0.5-4) g: (300-2400) mL.
(3)CaCl2The solution is prepared by adding anhydrous calcium chloride into water and uniformly stirring, wherein the dosage ratio of the anhydrous calcium chloride to the water is (5-100) g, (100-2000) mL.
(4) The preparation method of the modified sodium alginate composite ball adopts a magnetic stirrer for fully and uniformly stirring, the temperature of the magnetic stirrer is adjusted to 35-100 ℃, and the stirring time is 5-14 h. The particle size of the modified sodium alginate composite ball is 2-4 mm.
(5) The modified sodium alginate composite ball is applied as a heavy metal ion adsorbent. The heavy metal ions include Cd (II) ions.
Examples 1
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) Under the conditions of room temperature and normal pressure, the reaction steps are as follows: fully grinding the bone meal raw material obtained by preparing the bone meal in the embodiment, sieving the ground bone meal with a 100-mesh sieve, weighing 0.5g of the ground bone meal raw material, adding the ground bone meal raw material and 6g of sodium alginate into 300ml of water, placing the water and the sodium alginate into an ultrasonic generator, adjusting the temperature to 70 ℃, vibrating the water and the sodium alginate by sound waves with the frequency of 40khz for 6 hours to fully and uniformly mix the bone meal in the colloidal sodium alginate to obtain a modified transparent and uniform sodium alginate solution.
(2) 50.0000g of anhydrous calcium chloride and 1000mL of ultrapure water were added to a 2000mL beaker at room temperature under normal pressure, and dissolved by stirring with a magnetic stirrer.
(3) Dropwise adding the modified sodium alginate solution in the step (1) into a CaCl2 solution, forming sodium alginate particles in the dropwise adding process, standing for 5-14 h, washing with water, and soaking into distilled water to obtain the modified sodium alginate composite spheres with the particle size of 2-4 mm.
(4) The real object image and Scanning Electron Microscope (SEM) image of the modified sodium alginate composite sphere are shown in FIG. 4, wherein FIG. 4 (a) is the real object image of the composite sphere; FIG. 4 (b) is a surface SEM image before modification; fig. 4 (c) and 4 (d) are SEM images of the surface of the modified composite sphere.
(5) Fig. 5 is a fourier transform infrared spectroscopy (FTIR) graph of the modified sodium alginate composite bead and the unmodified sodium alginate, and fig. 5 shows that 2 new absorption peaks appear at 2900 and 2988cm < -1 > of the modified sodium alginate composite bead compared with the unmodified sodium alginate, and the 2 new absorption peaks can be respectively summarized as C = O stretching vibration of bone meal and-OH stretching vibration of the bone meal, so that the experimental result shows that the bone meal successfully modifies the sodium alginate.
EXAMPLE 2
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) Under the condition of room temperature and normal pressure, 1g of bone meal which is obtained by fully grinding 12g of sodium alginate and the bone meal raw material prepared by the bone meal of the embodiment and then passes through a 100-mesh sieve is weighed and added into 600ml of water, a magnetic stirrer is adopted, the temperature of the magnetic stirrer is adjusted to be 40-100 ℃, and the stirring time is 6-12 h. Obtaining the modified transparent and uniform sodium alginate solution.
(2) 20.0000g of anhydrous calcium chloride and 400mL of ultrapure water were added to a 500mL beaker at room temperature under normal pressure, and dissolved by stirring with a magnetic stirrer.
(3) Dropwise adding the modified sodium alginate solution (1) into CaCl2And (3) dropwise adding the solution to form sodium alginate particles, standing for 5-14 h, washing with water, and soaking in distilled water to obtain the modified sodium alginate composite spheres with the particle size of 2-4 mm.
EXAMPLE 3
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) Adding 18g of sodium alginate into 900ml of water at room temperature and normal pressure, dissolving in a water bath at 100 ℃, and heating for 5-8 hours. Fully and uniformly stirring until the sodium alginate is dissolved to obtain a transparent and uniform colloidal substance. Provides a uniform medium for preparing the hydrogel. Fully grinding the bone meal raw materials obtained by preparing the bone meal in the embodiment, sieving the ground bone meal with a 100-mesh sieve, weighing 1.5g of the ground bone meal raw materials, adding the weighed bone meal raw materials into a uniform sodium alginate medium, and fully shaking the bone meal raw materials in a shaking machine for 4-8 hours to fully and uniformly mix the bone meal in sodium alginate jelly to obtain a modified sodium alginate solution.
(2) In a 2000mL beaker, 75.0000g of anhydrous calcium chloride and 1500mL of ultrapure water were added at room temperature under normal pressure, and dissolved by stirring with a magnetic stirrer.
(3) Dropwise adding the modified sodium alginate solution (1) into CaCl2And (3) dropwise adding the solution to form sodium alginate particles, standing for 5-14 h, washing with water, and soaking in distilled water to obtain the modified sodium alginate composite spheres with the particle size of 2-4 mm.
EXAMPLE 4
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) 5g of the modified sodium alginate composite beads prepared in example 1 or 2 or 3 was added to a 50-inch centrifuge tube. Taking 20ml of heavy metal cadmium ion Cd (II) wastewater with the concentration of 10, 20, 30, 40, 50, 60, 70 and 80mg/L respectively, placing the wastewater in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and determining the concentration of the simulated heavy metal ion wastewater after treatment by using an inductively coupled plasma mass spectrometer (ICP-MS), so as to obtain the modified sodium alginate composite spheres with the adsorption efficiencies of 70%, 86%, 83%, 84%, 83% and 83% on Cd (II). (the adsorption rate of the unmodified sodium alginate composite spheres is lower than 50 percent). The maximum adsorption capacity reaches 202mg/g.
(2) The adsorption efficiency ratio is shown in fig. 2.
(3) FIG. 3 is a Langmuir fitting curve of the modified sodium alginate composite material.
EXAMPLE 5
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) 5g of the modified sodium alginate composite beads prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. With CdCl2Preparing 50mg/L heavy metal cadmium ion Cd (II) solution. The pH was adjusted with dilute hydrochloric acid and dilute sodium hydroxide. Taking 20ml of heavy metal cadmium ion Cd (II) wastewater with the concentration of 50mg/L and the pH value of 2,4,6 and 8 respectively, placing the wastewater in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and simulating the heavy metal ion wastewater by using an inductively coupled plasma mass spectrometer (ICP-MS)And (3) measuring the concentration of the treated water to obtain the adsorption efficiencies of the modified sodium alginate composite ball to Cd (II) of 70%, 81%, 82% and 79% respectively. (the adsorption rate of the unmodified sodium alginate composite balls is lower than 50%).
EXAMPLE 6
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) 5g of the modified sodium alginate composite beads prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. With CdCl2Preparing 50mg/L heavy metal cadmium ion Cd (II) solution. The solution ion concentration was adjusted with NaCl. Taking 20ml of heavy metal cadmium ion Cd (II) wastewater with the NaCl concentration of 50mg/L of 40, 60, 80 and 100mM, placing the wastewater in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and measuring the concentration of the simulated heavy metal ion wastewater after treatment by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the adsorption efficiencies of the modified sodium alginate composite spheres to Cd (II) of 71%, 69%, 65% and 60% respectively. (the adsorption rate of the unmodified sodium alginate composite balls is lower than 50%).
EXAMPLE 7
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) 5g of the modified sodium alginate composite beads prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. With CdCl2Preparing 50mg/L heavy metal cadmium ion Cd (II) solution. With CaCl2And adjusting the ion concentration of the solution. Taking 20ml CaCl with concentration of 50mg/L2Placing heavy metal cadmium ion Cd (II) wastewater with the concentration of 40, 60, 80 and 100mM in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and determining the concentration of the simulated heavy metal ion wastewater after treatment by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the modified sodium alginate composite spheres with the adsorption efficiencies of 59%, 56%, 46% and 40% for Cd (II). (the adsorption rate of the unmodified sodium alginate composite balls is lower than 30%).
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and reference may be made to the related descriptions of other embodiments for parts that are not described or illustrated in a certain embodiment.
2. The application example is as follows:
application example
5g of the modified sodium alginate composite beads prepared in example 1 or 2 or 3 was added to a 50-inch centrifuge tube. Taking 20ml of polluted river wastewater, placing the polluted river wastewater in a horizontal shaking table at a constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and measuring the concentrations before and after the polluted river wastewater is treated by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the modified sodium alginate composite spheres with the adsorption efficiency of Cd (II) of 83%. (the adsorption rate of the unmodified sodium alginate composite ball in the prior art is lower than 50 percent).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention disclosed herein, which is within the spirit and principle of the present invention, should be covered by the present invention.
Claims (10)
1. A preparation method of a modified sodium alginate composite ball for removing heavy metal ions in water is characterized by comprising the following steps:
step one, preparing bone meal: preparing bone meal raw materials from fresh bovine bones by different preparation methods;
step two, preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw material, and preparing modified sodium alginate by different preparation modes;
step three, preparing the composite hydrogel: and dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball.
2. The preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water according to claim 1, wherein in the first step, the preparation of bone meal raw materials in different preparation modes comprises:
preparing whole ox bone into broken bone, placing the broken bone into a pot, adding water, decocting at 100 deg.C, adding quicklime and plant ash, decocting while removing fat and colloid until the bone is substantially free of oil, sun drying, and pulverizing; boiling for 3-8 hours, removing grease and bone glue, draining water, drying at 100-140 ℃, and crushing to obtain a finished product; wherein the bone meal is prepared from the following components in percentage by mass: quick lime: plant ash = (2-12) kg: (1-6) kg: (1-6) kg.
3. The preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water as claimed in claim 1, wherein in the first step, the preparation of the bone meal raw material by different preparation methods further comprises:
crushing and boiling animal bones, removing part of grease and bone glue, drying and crushing to obtain crude bone powder; placing the beasts and birds bones which are knocked into small pieces and dried in the sun into a pot, adding water, boiling, taking out grease floating on the water surface after a night, taking out bones, drying in the sun, and grinding into bone powder.
4. The preparation method of the modified sodium alginate composite sphere for removing heavy metal ions in water as claimed in claim 1, wherein in the first step, the preparation of the bone meal raw material by different preparation methods further comprises: placing animal bone in a high pressure tank, removing most of oil and bone glue under high temperature and high pressure and steam to obtain defatted bone powder; knocking the dried bones into blocks, putting the blocks into a pressure cooker, adding water to submerge the blocks, and then tightly covering the pressure cooker and heating the blocks; when the temperature reaches 120 ℃, steaming for 24 hours, boiling the pot the next day, removing the upper fat layer, fishing out the bones, drying in the sun and crushing.
5. The preparation method of the modified sodium alginate composite ball for removing the heavy metal ions in the water as claimed in claim 1, wherein in the second step, the preparation of the modified sodium alginate by different preparation methods comprises the following steps:
adding sodium alginate into water at room temperature under normal pressure, dissolving in water bath at 100 deg.C, and heating for 5-8 hr; fully and uniformly stirring until the sodium alginate is dissolved to obtain a transparent and uniform colloidal substance, thereby providing a uniform medium for the preparation of the hydrogel; fully grinding the bone meal raw material obtained in the step one, sieving the bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, and fully vibrating the bone meal raw material in a vibrating machine for 4 to 8 hours to fully and uniformly mix the bone meal in a sodium alginate colloid to obtain a modified sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5-4) g: (300-2400) mL.
6. The preparation method of the modified sodium alginate composite sphere for removing heavy metal ions in water as claimed in claim 1, wherein in the second step, the preparation of the modified sodium alginate through different preparation methods further comprises: fully grinding the bone meal raw material obtained in the step one under the conditions of room temperature and normal pressure, sieving the ground bone meal raw material with a 100-mesh sieve, adding the ground bone meal raw material and sodium alginate into water together, placing the mixture in an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by using sound waves with the frequency of 40khz for 4-8 hours to ensure that the bone meal is fully and uniformly mixed in the sodium alginate jelly to obtain a modified transparent and uniform sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5 to 4) g: (300-2400) mL.
7. The preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water as claimed in claim 1, wherein in the second step, the preparation of the modified sodium alginate by different preparation methods further comprises: under the conditions of room temperature and normal pressure, adding the sodium alginate and the bone meal raw material obtained in the step one into water after fully grinding and sieving with a 100-mesh sieve, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to be 40-100 ℃, and the stirring time is 6-12 hours; obtaining a modified transparent and uniform sodium alginate solution; the dosage ratio of the sodium alginate to the bone meal to the water is (6-48) g: (0.5 to 4) g: (300-2400) mL.
8. The preparation method of the modified sodium alginate composite sphere for removing heavy metal ions in water according to claim 1, wherein the preparation of the composite hydrogel in the third step specifically comprises the following steps:
preparing a calcareous solution at room temperature and normal pressure, wherein the calcareous solution comprises CaCl2A solution; dropwise adding the modified sodium alginate solution prepared in the second step into CaCl2In the solution, a magnetic stirrer is adopted for fully and uniformly stirring, the temperature of the magnetic stirrer is adjusted to be 35-100 ℃, and the stirring time is 5-14 h; sodium alginate particles are formed in the dropping process, the mixture is kept stand for 10 to 15 hours, then is washed by water and is soaked into distilled water, and the modified sodium alginate composite ball with the particle size of 2 to 6mm is prepared.
9. The method for preparing the modified sodium alginate composite spheres for removing the heavy metal ions in the water as claimed in claim 8, wherein the CaCl is added2The solution is prepared by adding anhydrous calcium chloride into water and uniformly stirring, wherein the dosage ratio of the anhydrous calcium chloride to the water is (5-100) g (100-2000) mL.
10. The application of the modified sodium alginate composite ball prepared by the preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water according to any one of claims 1 to 9 as a heavy metal ion adsorbent in water treatment.
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