CN115254042B - 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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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 150000002500 ions Chemical class 0.000 title claims abstract description 44
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- 239000003463 adsorbent Substances 0.000 claims abstract description 11
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- 238000009835 boiling Methods 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 11
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- 238000010025 steaming Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- 239000001110 calcium chloride Substances 0.000 abstract description 3
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- 239000008187 granular material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 239000002351 wastewater Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 7
- 239000002639 bone cement Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
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- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
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- 241001474374 Blennius Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 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
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of preparation of heavy metal ion adsorbents, and discloses preparation and application of modified sodium alginate composite spheres for removing heavy metal ions in water. The preparation method comprises the following steps: preparing bone powder: preparing bone meal raw materials from fresh bovine bones through different preparation modes; preparation of modified sodium alginate: grinding sodium alginate and the obtained bone meal raw materials, and preparing modified sodium alginate by different preparation modes; preparation of composite hydrogel: and (3) dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball. According to the invention, bone meal modified sodium alginate is adopted, and the bone meal modified sodium alginate is crosslinked with calcium chloride to form granules, so that the sodium alginate has wide sources and low cost, and the prepared modified sodium alginate composite ball has good adsorption performance and good capability of removing 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 modified sodium alginate composite spheres for removing heavy metal ions in water.
Background
Heavy metal contamination is a serious problem for human health and life. Heavy metal contamination is the result of numerous activities in chemical manufacturing, paint and coating, mining, refining metallurgy, nuclear and other industries. These metals have deleterious effects on the flora of lakes and streams. Among them, cadmium (Cd) is one of the heavy metals with extremely strong toxicity, and is recognized as the most harmful element to the safety of crops, and is also the most movable element with biological activity. The removal of toxic metals is typically performed 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 recommended to find new technologies.
The method for removing heavy metal ions in water mainly comprises a chemical precipitation method, a coagulating precipitation 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 of high efficiency, low energy consumption, simple operation, etc.
For the adsorbent in the adsorption method, na+ ions on the structural unit of the sodium alginate can react with divalent cations such as Ca2+ or Sr2+ in the aqueous solution under a milder condition to form a crosslinked reticular structure, so that the composite sphere adsorbent for obtaining the sodium alginate can be prepared. Compared with the traditional powder adsorbent, the sodium alginate composite ball has the advantages of difficult loss, easy 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 sphere adsorbent has low capability of removing heavy metal ions in water, and can not meet the ideal requirement of heavy metal ion wastewater treatment. Therefore, the sodium alginate is modified by selecting a proper modifier, which is one of the hot problems of the current domestic and foreign researches.
Through the above analysis, the problems and defects existing in 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 capability of removing heavy metal ions in water.
Disclosure of Invention
In order to overcome the problems in the related art, the embodiment of the invention discloses 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 bone powder as reinforcing filler to improve the porous structure of sodium alginate beads and remove Cd ions in aqueous solution.
The innovation point of the invention is that: the bone powder 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: the preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water comprises the following steps:
step one, preparing bone powder: preparing bone meal raw materials from fresh bovine bones through different preparation modes;
step two, preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw materials, and preparing modified sodium alginate by different preparation modes;
preparing composite hydrogel: and (3) dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball.
In one embodiment, in step one, the preparing bone meal raw material in different modes of manufacture comprises:
making the whole bovine bone into crushed bone, putting the crushed bone into a pot, adding water, boiling at 100 ℃, adding a proper amount of quicklime and plant ash into the boiling, boiling while removing fat and colloid until the bone is basically free of grease, and sun-drying and crushing; boiling for 3-8 hr, removing partial oil and bone glue, draining water, stoving at 100-140 deg.c and crushing to obtain the final product. Wherein the bone meal comprises the following components in percentage by mass: quicklime: plant ash= (2-12) kg: (1-6) kg: (1-6) kg.
In one embodiment, in the first step, the preparing bone meal raw material in different modes 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, fishing out grease floating on the water surface after the beasts and birds are separated for one night, taking out bones, drying in the sun, and grinding into bone powder.
In one embodiment, in the first step, the preparing bone meal raw material in different modes further comprises: placing animal bones in a high-pressure tank, removing most of grease and bone glue by high temperature, high pressure and steam to prepare defatted bone powder; knocking dry bones into blocks, putting the blocks into an autoclave, adding water to submerge the blocks, and then tightly covering and heating; when the temperature reaches 120 ℃, the mixture is steamed for 24 hours, the upper fat is removed after the pot is opened in the next day, and the bones are fished out, dried and crushed.
In one embodiment, in step two, preparing the modified sodium alginate by different manufacturing methods comprises:
adding sodium alginate into water at room temperature and normal pressure, dissolving in a water bath at 100deg.C, and heating for 5-8 hr; stirring thoroughly until sodium alginate is dissolved to obtain transparent and uniform gelatinous substance. Providing a uniform medium for the preparation of the hydrogel; fully grinding the bone meal raw material obtained in the step one, sieving with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, fully oscillating for 4-8 hours in an oscillating machine, fully uniformly mixing the bone meal in a sodium alginate colloid, and obtaining 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.
In one embodiment, in the second step, the preparing modified sodium alginate by different manufacturing methods further includes: under the conditions of room temperature and normal pressure, fully grinding the bone meal raw material obtained in the step one, sieving with a 100-mesh sieve, adding the bone meal raw material and sodium alginate into water, placing the mixture into an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by sound waves with the frequency of 40khz for 4-8 hours, fully and uniformly mixing the bone meal in sodium alginate colloid, and obtaining a modified transparent 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 preparing modified sodium alginate by different manufacturing methods further includes: under the conditions of room temperature and normal pressure, adding sodium alginate and bone meal obtained in the step one after fully grinding the bone meal raw material and sieving the bone meal with a 100-mesh sieve into water, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is regulated to 40-100 ℃ and the stirring time is 6-12h; obtaining a transparent and uniform sodium alginate solution after modification; 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, the preparation of the composite hydrogel in the step three specifically includes:
preparing a calcareous solution under the condition of room temperature and normal pressure, wherein the calcareous solution comprises CaCl 2 A solution; dropwise adding the modified sodium alginate solution prepared in the second step into CaCl 2 In the solution, a magnetic stirrer is adopted for fully and uniformly stirring, the temperature of the magnetic stirrer is adjusted to 35-100 ℃, and the stirring time is 5-14h; sodium alginate particles are formed in the dripping process, and after standing for 10-15 hours, the sodium alginate particles are washed by water and soaked in distilled water, so that the modified sodium alginate composite ball with the particle size of 2-6mm is prepared.
In one embodiment, caCl 2 The 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 an 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 in the prior art and the difficulty in solving the problems, the technical problems solved by the technical proposal of the invention are analyzed in detail and deeply by tightly combining the technical proposal to be protected, the results and data in the research and development process, and the like, and some technical effects brought after the problems are solved have creative technical effects. The specific description is as follows:
the modified sodium alginate composite sphere adsorbent provided by the invention is used for removing heavy metal ions in water, and solves the problem that the unmodified seaweed composite sphere adsorbent has low capability of removing heavy metal ions in water.
According to the preparation method of the modified sodium alginate composite ball, bone meal modified sodium alginate is adopted to obtain the modified sodium alginate composite material which has more surface functional groups and coarser 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 diffusion of heavy metal ions into the hydrogel. In addition, the pores have larger specific surface area and a large number of active centers, which is beneficial to the adsorption of heavy metal ions. The sodium alginate composite ball used in the invention has wide sources and low price, and compared with the unmodified sodium alginate composite ball, the prepared modified sodium alginate composite ball has more surface functional groups, has good capability of removing heavy metal ions in water, overcomes the defect of low capability of removing heavy metal ions in water of the unmodified sodium alginate composite ball, increases the possibility of applying the composite ball to actual heavy metal ion wastewater treatment, and has very wide application prospect in the aspect of treating water pollution.
The traditional sodium alginate-based hydrogel has inherent defects in aspects of composition, gel process, architecture and the like. Therefore, the bone powder 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 invention has the key point that the bone powder is used as reinforcing filler to improve the porous structure of the sodium alginate beads and remove Cd ions in the aqueous solution.
The invention prepares the novel adsorption material by using the low-cost biodegradable raw material, efficiently solves the problem of heavy metal pollution in wastewater, and provides possibility for recycling the adsorption material.
Secondly, the technical scheme is regarded as a whole or from the perspective of products, and the technical scheme to be protected has the following technical effects and advantages:
according to the invention, bone meal is adopted to modify sodium alginate, and the sodium alginate modified by the bone meal is crosslinked with calcium chloride to form particles, so that the sodium alginate has wide sources and low cost, the prepared modified sodium alginate composite ball has good adsorption performance and good capability of removing heavy metal ions in water, the defect of low capability of removing heavy metal ions in water of the unmodified alginic acid composite ball is overcome, and the possibility of applying the composite ball to actual heavy metal ion wastewater treatment is increased.
Thirdly, as inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
(1) The expected benefits and commercial values after the technical scheme of the invention is converted are as follows: low cost and high income.
(2) The technical scheme of the invention fills the technical blank in the domestic and foreign industries: fills the blank of bone powder as an adsorption synthetic material.
(3) The technical scheme of the invention solves the technical problems that people are always desirous of solving but are not successful all the time: solves the difficult problem of preparing a biodegradable and easily recycled heavy metal adsorption material.
(4) The technical scheme of the invention overcomes the technical bias: overcomes the prejudice of lower adsorption efficiency of the sodium alginate hydrogel.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of a preparation method of modified sodium alginate composite spheres for removing heavy metal ions in water, which is provided by the embodiment of the 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 modified sodium alginate composite sphere prepared in example 1 of the present invention; wherein fig. 4 (a) is a physical diagram of the composite ball; FIG. 4 (b) is a surface SEM image before modification; FIGS. 4 (c) and 4 (d) are surface SEM images of the modified composite spheres;
fig. 5 is a fourier infrared spectrum (FTIR) diagram of an unmodified alginic acid and modified sodium alginate composite sphere prepared in accordance with an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
1. Explanation of the examples:
as shown in fig. 1, the preparation method of the modified sodium alginate composite sphere (the preparation method of the modified sodium alginate composite sphere for removing heavy metal ions in water) provided by the embodiment of the invention comprises the following steps:
s101, preparing bone meal: preparing bone meal raw materials from fresh bovine bones through different preparation modes;
s102, preparing modified sodium alginate: grinding sodium alginate and the obtained bone meal raw materials, and preparing modified sodium alginate by different preparation modes;
s103, preparation of composite hydrogel: and (3) dripping the prepared modified sodium alginate into a calcareous solution to prepare the modified sodium alginate composite ball.
In the embodiment of the invention, the preparation of the bone meal in the step S101 comprises the following steps: fresh bovine bone was prepared by several methods:
(1) The bone powder can be generally divided into decocted bone powder, crude bone powder (raw bone powder) and steamed bone powder (degummed and defatted bone powder) according to the preparation method. Firstly, the whole bovine bone is made into broken bone, the boiling method is to put the broken bone into a pot, water is added into the pot to be boiled at 100 ℃, and germs in the bone meal can be killed at high temperature. Adding appropriate amount of quicklime, plant ash, etc., decocting while removing fat and colloid until bone is substantially free of oil, sun drying, and pulverizing; boiling for 3-8 hr, removing partial oil and bone glue, draining water, stoving at 100-140 deg.c and crushing to obtain the final product. Wherein the bone meal comprises the following components in percentage by mass: quicklime: 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 grease and bone glue, oven drying, and pulverizing; at ordinary times, the bones of the livestock and poultry are collected, dried in the sun and stored, the bones are firstly broken into small blocks when being manufactured, then the small blocks are put into a pot, water is added for boiling, germs are killed, grease floating on the water surface is fished out after the whole night, and then the bones are taken out, dried in the sun and ground into bone powder.
(3) Or degreasing bone powder is prepared by placing animal bone in a high-pressure tank, and removing most of grease and bone glue by high temperature, high pressure and steam. Bone meal is generally an off-white powder that is insoluble in water, wherein the phosphorus contained therein is more difficult to utilize by plants, but is more readily available in acidic soils, which can be mixed into compost or manure for fermentation and then applied as a base fertilizer, and can also be used as animal feed. Knocking dry bones into blocks, putting the blocks into an autoclave, adding water to submerge the blocks, and then tightly covering the blocks and heating. When the temperature reaches 120 ℃, the mixture can be boiled for 24 hours to extinguish, the upper fat is removed after the boiler is opened the next day, and the bones are fished out, dried and crushed.
The prepared bovine bone powder raw material contains more proteins and minerals, and has the characteristics of looseness and porosity. Provides conditions for long-term preservation and transportation. The content of the hydroxyapatite and the better mechanical property thereof are well preserved, and conditions are provided for adsorbing heavy metals 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 and normal pressure, dissolving in water bath at 100deg.C, and heating for 5-8 hr. Stirring thoroughly until sodium alginate is dissolved to obtain transparent and uniform gelatinous substance. Providing a uniform medium for the preparation of the hydrogel. And (3) fully grinding the bone meal raw material obtained in the step (S101), sieving with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, and fully oscillating for 4-8 hours in an oscillating machine to fully mix the bone meal in sodium alginate colloid to obtain a modified sodium alginate solution.
(2) Under the condition of room temperature and normal pressure, fully grinding the bone meal raw material obtained in the step S101, sieving with a 100-mesh sieve, adding the bone meal raw material and sodium alginate into water, placing the mixture into an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by sound waves with the frequency of 40khz for 4-8 hours, fully and uniformly mixing the bone meal in the sodium alginate colloid, and obtaining the modified transparent uniform sodium alginate solution.
(3) And (3) under the condition of room temperature and normal pressure, adding the sodium alginate and the bone powder raw material obtained by the method in the step (S101) after being fully ground and sieved by a 100-mesh sieve into water, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to 40-100 ℃ and the stirring time is 6-12 h. And obtaining the transparent and uniform sodium alginate solution after modification.
The prepared modified sodium alginate raw material fully maintains the original physical characteristics of bone meal, so that the original heavy metal adsorption capacity is maintained while the mechanical property of sodium alginate is enhanced. The sodium alginate can be fully and completely dissolved in water by heating to obtain a uniform and stable adsorption carrier, thereby creating better conditions for the composite bone powder. The porous and water-absorbing properties of the composite material are fully maintained.
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 pressure 2 A solution; dropwise adding any modified sodium alginate solution in the step S102 in 1-3 into CaCl 2 And (3) in the solution, sodium alginate particles are formed in the dripping process, and after standing for 10-15h, the sodium alginate particles are washed by water and soaked in distilled water, so that the modified sodium alginate composite spheres with the particle size of 2-6mm are prepared.
(2) In the step S102, the dosage ratio of sodium alginate, bone meal and water is (6-48) g: (0.5-4) g: (300-2400) mL.
(3)CaCl 2 The solution is prepared by adding anhydrous calcium chloride into water and stirring uniformly, 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 sphere is 2-4 mm.
(5) The modified sodium alginate composite sphere is applied as a heavy metal ion adsorbent. The heavy metal ions include Cd (II) ions.
Example 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: the bone powder raw material obtained by the preparation of the bone powder in the embodiment is fully ground and then passes through a 100-mesh sieve, 0.5g of the bone powder raw material and 6g of sodium alginate are weighed and added into 300ml of water together, the mixture is placed into an ultrasonic generator, the temperature is adjusted to 70 ℃, the mixture is vibrated by sound waves with the frequency of 40khz for 6 hours, and the bone powder is fully and uniformly mixed in the sodium alginate colloid, so that the modified transparent and uniform sodium alginate solution is obtained.
(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 the mixture was dissolved by stirring with a magnetic stirrer.
(3) And (3) dropwise adding the modified sodium alginate solution in the step (1) into CaCl2 solution, forming sodium alginate particles in the dropwise adding process, standing for 5-14h, 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 physical diagram and the Scanning Electron Microscope (SEM) diagram of the modified sodium alginate composite ball are shown in fig. 4, wherein fig. 4 (a) is a physical diagram of the composite ball; FIG. 4 (b) is a surface SEM image before modification; fig. 4 (c) and 4 (d) are surface SEM images of the modified composite sphere.
(5) As shown in fig. 5, which is a Fourier Transform Infrared (FTIR) chart of modified sodium alginate composite spheres and unmodified sodium alginate, 2 new absorption peaks appear in the modified sodium alginate composite spheres at 2900 and 2988cm-1 compared with the unmodified sodium alginate, and the 2 new absorption peaks can be respectively summarized into c=o telescopic vibration of bone powder and-OH telescopic vibration of bone powder, so that the experimental result shows that the bone powder is successfully modified with 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, weighing 1g of bone powder which is obtained by fully grinding 12g of sodium alginate and the bone powder raw material prepared by the bone powder preparation method in the embodiment and sieving the bone powder with a 100-mesh sieve, adding the bone powder into 600ml of water, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to 40-100 ℃, and the stirring time is 6-12 h. And obtaining the transparent and uniform sodium alginate solution after modification.
(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 the mixture was dissolved by stirring with a magnetic stirrer.
(3) Dropwise adding the modified sodium alginate solution (1) into CaCl 2 And (3) in the solution, sodium alginate particles are formed in the dripping process, and after standing for 5-14h, the sodium alginate particles are washed by water and soaked in distilled water, so that the modified sodium alginate composite spheres with the particle size of 2-4 mm are prepared.
Example 3
The preparation method of the modified sodium alginate composite ball provided by the embodiment of the invention comprises the following steps:
(1) At room temperature and normal pressure, 18g of sodium alginate is added into 900ml of water, dissolved in a water bath at 100 ℃ and heated for 5-8 hours. Stirring thoroughly until sodium alginate is dissolved to obtain transparent and uniform gelatinous substance. Providing a uniform medium for the preparation of the hydrogel. The bone powder raw material obtained by the preparation of the bone powder in the embodiment is fully ground, then is sieved by a 100-mesh sieve, 1.5g of the bone powder raw material is weighed and added into a uniform sodium alginate medium, and the bone powder is fully vibrated in a vibrating machine for 4-8 hours, so that the bone powder is fully and uniformly mixed in the sodium alginate colloid, and the modified sodium alginate solution is obtained.
(2) 75.0000g of anhydrous calcium chloride and 1500mL of ultrapure water were added to a 2000mL beaker at room temperature under normal pressure, and the mixture was dissolved by stirring with a magnetic stirrer.
(3) Dropwise adding the modified sodium alginate solution (1) into CaCl 2 And (3) in the solution, sodium alginate particles are formed in the dripping process, and after standing for 5-14h, the sodium alginate particles are washed by water and soaked in distilled water, so that the modified sodium alginate composite spheres with the particle size of 2-4 mm are prepared.
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 sphere prepared in example 1 or 2 or 3 was added to a 50 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 measuring the concentration of the simulated heavy metal ion wastewater by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the modified sodium alginate composite ball with the adsorption efficiency of 70%, 86%, 83%, 84%, 83% and 83% on Cd (II) respectively. (the adsorption rate of the unmodified sodium alginate composite spheres is lower than 50 percent). The maximum adsorption amount reaches 202mg/g.
(2) Adsorption efficiency pairs are shown in fig. 2, for example.
(3) Fig. 3 is a modified sodium alginate composite Langmuir fitted curve.
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 sphere prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. By CdCl 2 Preparing 50mg/L of heavy metal cadmium ion Cd (II) solution. The pH value is adjusted by 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 values of 2,4,6 and 8, placing the wastewater in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180 minutes, sampling, and measuring the concentration of the simulated heavy metal ion wastewater by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the modified sodium alginate composite ball, wherein the adsorption efficiency of the modified sodium alginate composite ball on the Cd (II) is 70%, 81%, 82% and 79% respectively. (the adsorption rate of the unmodified sodium alginate composite spheres is lower than 50 percent).
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 sphere prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. By CdCl 2 Preparing 50mg/L of heavy metal cadmium ion Cd (II) solution. The solution ion concentration was adjusted with NaCl. 20ml of heavy metal cadmium ion Cd (II) wastewater with the concentration of 50mg/L and the concentration of 40, 60, 80 and 100mM NaCl is taken and placed on a horizontal shaking table at the constant temperature of 25 DEG CUnder the condition of continuous oscillation for 180min, sampling, and measuring the concentration of the simulated heavy metal ion wastewater by using an inductively coupled plasma mass spectrometer (ICP-MS), so as to obtain the modified sodium alginate composite sphere with the adsorption efficiency of 71%, 69%, 65% and 60% on Cd (II) respectively. (the adsorption rate of the unmodified sodium alginate composite spheres is lower than 50 percent).
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 sphere prepared in example 1 or 2 or 3 was added to a 50ml centrifuge tube. By CdCl 2 Preparing 50mg/L of heavy metal cadmium ion Cd (II) solution. By CaCl 2 The ion concentration of the solution was adjusted. Taking 20ml of CaCl with concentration of 50mg/L 2 And (3) placing the 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 180 minutes, sampling, and measuring the concentration of the simulated heavy metal ion wastewater by using an inductively coupled plasma mass spectrometer (ICP-MS) to obtain the modified sodium alginate composite ball with the adsorption efficiencies of 59%, 56%, 46% and 40% on the Cd (II) respectively. (the adsorption rate of the unmodified sodium alginate composite spheres is lower than 30 percent).
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and in part, not described or illustrated in any particular embodiment, reference is made to the related descriptions of other embodiments.
2. Application examples:
application example
5g of the modified sodium alginate composite sphere prepared in example 1 or 2 or 3 was added to a 50 centrifuge tube. Taking 20ml of polluted river wastewater, placing the polluted river wastewater in a horizontal shaking table at the constant temperature of 25 ℃, continuously oscillating for 180min, sampling, and measuring the concentration of the polluted river wastewater before and after treatment by using an inductively coupled plasma mass spectrometer (ICP-MS), so as to obtain the modified sodium alginate composite sphere, wherein the adsorption efficiency of the modified sodium alginate composite sphere on Cd (II) is 83%. (the adsorption rate of the unmodified sodium alginate composite sphere in the prior art is lower than 50%).
While the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (3)
1. The preparation method of the modified sodium alginate composite ball for removing heavy metal ions in water is characterized by comprising the following steps of:
step one, preparing bone powder: preparing bone meal raw materials from fresh bovine bones through different preparation modes; the bone meal raw materials prepared by different preparation modes are as follows:
preparing crushed bovine bone, decocting the crushed bovine bone in water at 100deg.C for 3-8 hr, adding quicklime and plant ash, decocting while removing fat and colloid until the bone does not contain oil, sun drying, and pulverizing; wherein the bone meal comprises the following components in percentage by mass: quicklime: plant ash= (2-12) kg: (1-6) kg: (1-6) kg;
or putting the dried bones into small pieces, adding water into a pot, boiling, fishing out grease floating on the water surface after one night, taking out bones, drying in the sun, and grinding into bone powder;
or knocking dry bones into blocks, putting the blocks into an autoclave, adding water to submerge the blocks, and then tightly covering and heating; when the temperature reaches 120 ℃, steaming and boiling for 24 hours, removing upper fat after boiling in the next day, fishing out bones, sun-drying and crushing;
step two, preparing modified sodium alginate: the modified sodium alginate is prepared by different preparation methods:
adding sodium alginate into water at room temperature and normal pressure, dissolving in a water bath at 100deg.C, and heating for 5-8 hr; fully and uniformly stirring until sodium alginate is dissolved to obtain transparent uniform gelatinous substances, and providing uniform medium for preparing hydrogel; fully grinding the bone meal raw material obtained in the step one, sieving with a 100-mesh sieve, adding the ground bone meal raw material into a uniform sodium alginate medium, fully oscillating for 4-8 hours in an oscillating machine, fully uniformly mixing the bone meal in a sodium alginate colloid, and obtaining 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;
or, under the condition of room temperature and normal pressure, fully grinding the bone meal raw material obtained in the step one, sieving with a 100-mesh sieve, adding the bone meal raw material and sodium alginate into water, placing the mixture into an ultrasonic generator, adjusting the temperature to 40-70 ℃, vibrating the mixture by sound waves with the frequency of 40kHz for 4-8 hours, and fully and uniformly mixing the bone meal in the sodium alginate colloid to obtain a modified transparent 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;
or, fully grinding sodium alginate and the bone meal raw material obtained in the step one, sieving with a 100-mesh sieve, adding the bone meal into water under the condition of room temperature and normal pressure, and adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to 40-100 ℃, and the stirring time is 6-12h; obtaining a transparent and uniform sodium alginate solution after modification; 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;
preparing a calcareous solution under the condition of room temperature and normal pressure, wherein the calcareous solution comprises CaCl 2 A solution; dropwise adding the modified sodium alginate solution prepared in the second step into CaCl 2 Fully and uniformly stirring the solution by adopting a magnetic stirrer, wherein the temperature of the magnetic stirrer is adjusted to 35-100 ℃, and the stirring time is 5-14h; sodium alginate particles are formed in the dripping process, and after standing for 10-15 hours, the sodium alginate particles are washed by water and soaked in distilled water, so as to prepare the modified sodium alginate composite ball with the particle size of 2-6 mm.
2. The method for preparing modified sodium alginate composite spheres for removing heavy metal ions in water according to claim 1, wherein the method is characterized by CaCl 2 The solution is prepared by adding anhydrous calcium chloride into water and stirring uniformly, wherein the dosage ratio of the anhydrous calcium chloride to the water is (5-100) g (100-2000) mL.
3. Use of a modified sodium alginate composite sphere prepared by the method for preparing the modified sodium alginate composite sphere for removing heavy metal ions in water according to any one of claims 1-2 as a heavy metal ion adsorbent in water treatment.
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