Insoluble adsorption defluorination composite material particles, a preparation method thereof, application and a defluorination package

Abstract

The present application belongs to the technical field of adsorptive fluorine removal, and particularly relates to insoluble adsorptive fluorine removal composite material particles, a preparation method, application and fluorine removal package thereof. The method comprises the following steps: 1) dissolving ethyl cellulose in anhydrous ethanol to form a uniform colloid; 2) adding food additive calcium phosphate while stirring to obtain a uniform mixed material; 3) slowly adding the mixed material into water under high-speed operation of a homogenizer, and forming a film of ethyl cellulose when meeting water, and obtaining the composite material particles through homogenization; 4) placing the composite material particles on a 60-mesh screen, washing with water, and screening the composite material and un-composite calcium phosphate powder with particle size above 60 meshes; and 5) collecting the sieve residue, drying to obtain the insoluble adsorptive fluorine removal composite material particles. The composite material is a water-insoluble particle material, can be made into various specifications of fluorine removal packages, can very conveniently and quickly remove fluorine in water or tea soup, and has less influence on the pH value of water or tea soup.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of adsorbing and removing fluorine, and particularly relates to an insoluble adsorbing and removing fluorine composite material particle, a preparation method, application and fluorine removal package thereof. BACKGROUND

[0002] Brick tea has the effects of antioxidant, weight loss and lipid reduction, and gastrointestinal regulation. Fluorine is a major risk factor affecting the safety of brick tea drinking. Long-term consumption of brick tea with high fluorine content increases the risk of "tea fluorosis", mainly manifested as dental and skeletal disorders. Fluorine mainly accumulates in the leaves of tea trees, generally showing mature leaves > tender leaves. Since brick tea is usually made by fermenting and pressing the rough old branches and leaves of tea trees, the fluorine content is relatively high. Therefore, how to effectively reduce the fluorine content of green brick tea is a technical problem to be solved.

[0003] Currently, the techniques for reducing the fluorine content in brick tea mainly involve adding fluorine removal agents during the production of brick tea. Patent CN99115669.2 uses pearl calcium or persimmon leaf powder or bone charcoal powder as a fluorine reduction additive to develop low-fluorine brick tea. Patent CN02138955.1 discloses a method for preparing low-fluorine brick tea powder by adding fluorine removal agents such as bone carbon, hydroxyapatite or tricalcium phosphate to brick tea, followed by boiling, filtering and drying. Patent CN200410081249.6 involves high-temperature calcination of serpentine, cooling and crushing it into powder, and then adding it to brick tea for boiling to reduce the fluorine content in brick tea water. Patent CN200910058301.9 controls the fluorine content by adding an iron salt solution during tea making. Patent CN201910342534.5 prepares low-fluorine brick tea by uniformly spraying the tea leaves with a water extract of highland barley and allowing them to ferment naturally at room temperature. Patent CN200710050384.8 realizes the preparation of low-fluorine brick tea by adding EM complex microbial agents or GM microbial agents during the fermentation process. Patent CN201410043191.X produces low-fluorine brick tea by adding a mixture of calcium citrate and calcium carbonate as a fluorine reduction agent to the brick tea raw materials. The above-mentioned fluorine reduction techniques mainly involve adding fluorine removal materials during the preparation of brick tea. The materials are mostly powders and are difficult to separate from the raw materials or tea soup, which may affect the fermentation of the raw materials or damage the original quality of the brick tea. In addition, non-food raw materials are used, and it is unknown whether new safety risks are introduced.

[0004] In addition, although calcium phosphate is a good fluorine removal material that can effectively remove fluorine ions from water or tea soup, it cannot be directly made into a fluorine removal package for convenient fluorine removal in water or tea soup due to its small particle size. Moreover, the addition of calcium phosphate directly to an aqueous solution has a significant impact on the pH value of the water or tea soup. SUMMARY

[0005] In order to solve the problems of the prior art, the application provides a kind of insoluble adsorption defluorination composite material particle and its preparation method, application and defluorination bag.The composite material is prepared by mixing calcium phosphate, ethyl cellulose and anhydrous ethanol in a certain proportion, and is a particle material insoluble in water, which can be made into various specifications of defluorination bag, can very conveniently and quickly remove fluorine in water or tea soup, has little influence on the pH value of water or tea soup, and the preparation method is simple and easy to realize.

[0006] The technical solution provided by the application is as follows:

[0007] A preparation method of a kind of insoluble adsorption defluorination composite material particle, comprising the following steps:

[0008] 1) Dissolve ethyl cellulose in anhydrous ethanol to form a uniform colloid;

[0009] 2) Add food additive calcium phosphate to the colloid obtained in step 1) while stirring to obtain a uniform mixed material;

[0010] 3) Slowly add the mixed material obtained in step 2) to water under high-speed operation of a homogenizer, and the ethyl cellulose forms a film when it comes into contact with water, and the composite material particles are obtained by homogenization;

[0011] 4) Place the composite material particles obtained in step 3) on a 60-mesh screen, wash with water, and screen out the composite material particles with a particle size above 60 mesh and the un-combined calcium phosphate powder;

[0012] 5) Collect the clean screened composite material particles obtained in step 4), dry them, and obtain the insoluble adsorption defluorination composite material particles.

[0013] The above technical solution mixes calcium phosphate, ethyl cellulose and anhydrous ethanol in a certain proportion to prepare a composite material. The composite material can be made into a defluorination bag.

[0014] The above technical solution dissolves ethyl cellulose in anhydrous ethanol, stirs thoroughly, obtains a colloid of ethyl cellulose mixed with anhydrous ethanol, adds food additive calcium phosphate to the colloid, stirs thoroughly, and mixes them evenly. Pour the mixed ethyl cellulose-anhydrous ethanol-calcium phosphate mixture into water, and homogenize it with a homogenizer while pouring; screen, separate and dry the product to obtain adsorption defluorination composite materials of different specifications.

[0015] The adsorption-defluorination composite material prepared by this invention is a water-insoluble particulate material with a surface rich in hydroxyl active groups. The material is stable and safe, and can be made into defluorination bags, filter media, filter cartridges, etc., for direct use in tea infusions and drinking water for defluorination. Using a dosage of 40 g / L, it can remove fluoride from water or tea infusions with concentrations of 5 mg / L to 15 mg / L within 30 minutes, achieving a defluorination rate of over 85% and meeting the drinking water standard of below 1 mg / L.

[0016] Specifically, in step 1), the weight ratio of ethyl cellulose to anhydrous ethanol is 6:100 to 18:100. Preferably, it is 18:100.

[0017] Specifically, in step 2), the weight ratio of ethyl cellulose to calcium phosphate is 18:10 to 18:100. Preferably, it is 18:50.

[0018] Specifically, in step 3), the rotational speed for homogenization is 8000–12000 rpm. Preferably, it is 10000 rpm.

[0019] Specifically, in step 5), the drying temperature is 100–110°C, preferably 105°C. The drying time is 4–6 hours.

[0020] The present invention also provides insoluble adsorption and defluorination composite material particles prepared according to the above preparation method.

[0021] Specifically, its particle size ranges from 0.25 mm to 2 mm.

[0022] Specifically, its solubility is less than 0.01g / 100g.

[0023] Specifically, when the weight ratio of ethyl cellulose to calcium phosphate is 18:50, the adsorption capacity of fluorine in the composite material particles is 4.90 mg / g (room temperature) and 7.87 mg / g (95℃).

[0024] This invention also provides the application of insoluble adsorption defluorination composite material particles for the preparation of defluorination bags or defluorination agents.

[0025] The present invention also provides a fluoride removal package, comprising a sealed bag and insoluble adsorbent fluoride removal composite material particles filled inside the bag.

[0026] The beneficial effects of this invention are as follows:

[0027] Compared with existing brick tea defluoridation technologies, this invention uses only food-grade raw materials, achieving the goal of effectively reducing fluoride in brick tea water without changing the production process of brick tea or traditional tea drinking habits.

[0028] In addition to being used for defluoridation of brick tea and water, the defluoridation material of this invention can also be used as a novel adsorbent material for defluoridation in the deep processing of tea products and defluoridation of drinking water, and has broad application prospects.

[0029] The technical solution of the present invention is convenient and easy to implement. Attached Figure Description

[0030] Figure 1 This is a scanning electron microscope image of the insoluble adsorption and fluoride removal composite material particles provided in Example 3. Detailed Implementation

[0031] The principles and features of the present invention are described below. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0032] Unless otherwise specified, the testing methods used in the embodiments of this invention are conventional methods; and the raw materials used, unless otherwise specified, are commercially available.

[0033] Example 1

[0034] The preparation of insoluble adsorption and defluorination composite material particles includes the following steps:

[0035] Step 1: Weigh out ethyl cellulose and anhydrous ethanol in a weight ratio of 18:100. First, pour all the anhydrous ethanol into a beaker (or similar vessel), then add the ethyl cellulose to the beaker while stirring continuously until the ethyl cellulose is completely dissolved (in winter when the room temperature is low, you can heat it slowly). Continue until the ethyl cellulose and anhydrous ethanol form a uniform colloidal mixture.

[0036] Step 2: Add 30 parts of food additive calcium phosphate to the system from Step 1 while stirring until the entire system is completely mixed.

[0037] Step 3: Slowly add the mixed material from Step 2 into a beaker filled with water (the water volume is one-third to two-thirds of the container's capacity). While adding the water, homogenize the mixture using a high-performance homogenizer at a speed of 10,000 rpm. Ethyl cellulose forms a film upon contact with water. After homogenization, composite material particles are obtained.

[0038] Step 4: Place the homogenized material from Step 3 onto a 60-mesh sieve and wash it with water (running water is acceptable) to remove composite materials with a particle size larger than 60 mesh and uncomposite calcium phosphate powder.

[0039] Step 5: Collect the cleaned composite material from Step 4 and dry it in an oven at 105°C for about 5 hours.

[0040] Example 2

[0041] The preparation of insoluble adsorption and defluorination composite material particles includes the following steps:

[0042] Step 1: Weigh out ethyl cellulose and anhydrous ethanol in a 18:100 weight ratio. First, pour all the anhydrous ethanol into a beaker, then add the ethyl cellulose while stirring until the ethyl cellulose is completely dissolved. Continue stirring until a homogeneous colloidal mixture of ethyl cellulose and anhydrous ethanol forms.

[0043] Step 2: Add 40 parts of food additive calcium phosphate to the system from Step 1 while stirring until the entire system is completely mixed.

[0044] Step 3: Slowly add the mixed material from Step 2 into a beaker filled with water (the water volume is one-third to two-thirds of the container's capacity). While adding the water, homogenize the mixture using a high-performance homogenizer at a speed of 10,000 rpm. Ethyl cellulose forms a film upon contact with water. After homogenization, composite material particles are obtained.

[0045] Step 4: Place the homogenized material from Step 3 onto a 60-mesh sieve, wash it with water, and remove composite materials with a particle size larger than 60 mesh and uncomposite calcium phosphate powder.

[0046] Step 5: Collect the cleaned composite material from Step 4 and dry it in an oven at 105°C for about 5 hours.

[0047] Example 3

[0048] The preparation of insoluble adsorption and defluorination composite material particles includes the following steps:

[0049] Step 1: Weigh out ethyl cellulose and anhydrous ethanol in a 18:100 weight ratio. First, pour all the anhydrous ethanol into a beaker, then add the ethyl cellulose while stirring until the ethyl cellulose is completely dissolved. Continue stirring until a homogeneous colloidal mixture of ethyl cellulose and anhydrous ethanol forms.

[0050] Step 2: Add 50 parts of food additive calcium phosphate to the system from Step 1 while stirring until the entire system is completely mixed.

[0051] Step 3: Slowly add the mixed material from Step 2 into a beaker filled with water (the water volume is one-third to two-thirds of the container's capacity). While adding the water, homogenize the mixture using a high-performance homogenizer at a speed of 10,000 rpm. Ethyl cellulose forms a film upon contact with water. After homogenization, composite material particles are obtained.

[0052] Step 4: Place the homogenized material from Step 3 onto a 60-mesh sieve, wash it with water, and remove composite materials with a particle size larger than 60 mesh and uncomposite calcium phosphate powder.

[0053] Step 5: Collect the cleaned composite material from Step 4 and dry it in an oven at 105°C for about 5 hours.

[0054] like Figure 1 The image shows a scanning electron microscope (SEM) image of the insoluble adsorption-defluorination composite material particles. As can be seen from the left side of the image, the adsorption-defluorination composite material particles prepared in this invention have a rough and porous surface. These structures give the material a high specific surface area and pore volume, which is beneficial for improving its adsorption performance. The right side of the image shows the energy dispersive spectroscopy (EDS) analysis of the SEM, which reveals the distribution of calcium elements in the particles, proving that calcium phosphate is uniformly loaded into the ethyl cellulose membrane.

[0055] Example 4

[0056] The preparation of insoluble adsorption and defluorination composite material particles includes the following steps:

[0057] Step 1: Weigh out ethyl cellulose and anhydrous ethanol in a 18:100 weight ratio. First, pour all the anhydrous ethanol into a beaker, then add the ethyl cellulose while stirring until the ethyl cellulose is completely dissolved. Continue stirring until a homogeneous colloidal mixture of ethyl cellulose and anhydrous ethanol forms.

[0058] Step 2: Add 60 parts of food additive calcium phosphate to the system from Step 1 while stirring until the entire system is completely mixed.

[0059] Step 3: Slowly add the mixed material from Step 2 into a beaker filled with water (the water volume is one-third to two-thirds of the container's capacity). While adding the water, homogenize the mixture using a high-performance homogenizer at a speed of 10,000 rpm. Ethyl cellulose forms a film upon contact with water. After homogenization, composite material particles are obtained.

[0060] Step 4: Place the homogenized material from Step 3 onto a 60-mesh sieve, wash it with water, and remove composite materials with a particle size larger than 60 mesh and uncomposite calcium phosphate powder.

[0061] Step 5: Collect the cleaned composite material from Step 4 and dry it in an oven at 105°C for about 5 hours.

[0062] Example 5

[0063] The preparation of insoluble adsorption and defluorination composite material particles includes the following steps:

[0064] Step 1: Weigh out ethyl cellulose and anhydrous ethanol in a 18:100 weight ratio. First, pour all the anhydrous ethanol into a beaker, then add the ethyl cellulose while stirring until the ethyl cellulose is completely dissolved. Continue stirring until a homogeneous colloidal mixture of ethyl cellulose and anhydrous ethanol forms.

[0065] Step 2: Add 70 parts of food additive calcium phosphate to the system from Step 1 while stirring until the entire system is completely mixed.

[0066] Step 3: Slowly add the mixed material from Step 2 into a beaker filled with water (the water volume is one-third to two-thirds of the container's capacity). While adding the water, homogenize the mixture using a high-performance homogenizer at a speed of 10,000 rpm. Ethyl cellulose forms a film upon contact with water. After homogenization, composite material particles are obtained.

[0067] Step 4: Place the homogenized material from Step 3 onto a 60-mesh sieve, wash it with water, and remove composite materials with a particle size larger than 60 mesh and uncomposite calcium phosphate powder.

[0068] Step 5: Collect the cleaned composite material from Step 4 and dry it in an oven at 105°C for about 5 hours.

[0069] Example of effect

[0070] Defluorination tests were conducted using insoluble adsorption defluorination composite material particles from each embodiment. The defluorination rate was calculated using the following formula:

[0071]

[0072] The results are as follows:

[0073] Table 1: Fluoride removal effect in tea infusion at a composite material particle dosage of 40 g / L (95℃)

[0074]

[0075] As can be seen from the table above, the defluorination effect of the adsorption defluorination composite material prepared by the present invention is significant. When the amount of defluorination composite material particles used reaches 40 g / L, Examples 1-5 all have good defluorination effects when defluorinating tea soup with a fluoride concentration of 4.76 mg / L.

[0076] Table 2: Defluorination effect of composite material particles at a concentration of 10 g / L in sodium fluoride aqueous solution (95℃)

[0077]

[0078] As can be seen from the table above, the fluoride removal composite material particles prepared by the present invention have a significant fluoride removal effect. When the amount of fluoride removal composite material used reaches 10 g / L, Examples 1-5 all have good fluoride removal effects when removing fluoride from a sodium fluoride aqueous solution with a fluoride concentration of 4.86 mg / L.

[0079] After the experiment, the tea soup and water were filtered separately, and the insoluble adsorption and fluoride removal composite material particles were collected, dried, and weighed. The weight was basically consistent with the original weight of the insoluble adsorption and fluoride removal composite material particles.

[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing insoluble adsorption and defluorination composite material particles, characterized in that, Includes the following steps: 1) Dissolve ethyl cellulose in anhydrous ethanol to form a homogeneous colloid; 2) Add food additive calcium phosphate to the colloid obtained in step 1) while stirring to obtain a uniform mixture; 3) Under the high-speed operation of the homogenizer, the mixed material obtained in step 2) is slowly added to water. Ethyl cellulose forms a film upon contact with water, and after homogenization, composite material particles are obtained. 4) Place the composite material particles obtained in step 3) on a 60-mesh sieve, wash with water, and remove composite material particles with a particle size greater than 60 mesh and uncomposite calcium phosphate powder. 5) Collect the sieve residue obtained in step 4), dry it, and obtain the insoluble adsorption and defluorination composite material particles; In step 1), the weight ratio of ethyl cellulose to anhydrous ethanol is 6:100 to 18:100; In step 2), the weight ratio of ethyl cellulose to calcium phosphate is 18:10 to 18:

100.

2. The method for preparing insoluble adsorption and defluorination composite material particles according to claim 1, characterized in that: In step 3), the rotational speed for homogenization is 8000–12000 rpm.

3. The method for preparing insoluble adsorption and defluorination composite material particles according to any one of claims 1 to 2, characterized in that: In step 5), the drying temperature is 100-110℃ and the drying time is 4-6 hours.

4. An insoluble adsorption-removing fluoride composite material particle prepared by the preparation method according to any one of claims 1 to 3.

5. The insoluble adsorption and defluorination composite material particles according to claim 4, characterized in that: The particle size is 0.25mm to 2mm.

6. The insoluble adsorption and defluorination composite material particles according to claim 4, characterized in that: Solubility is less than 0.01g / 100g; When the weight ratio of ethyl cellulose to calcium phosphate is 18:50, the adsorption capacity of the composite material particles for fluorine is: 4.90 mg / g at room temperature; 7.87 mg / g at 95℃.

7. The application of insoluble adsorption and defluorination composite material particles according to any one of claims 4 to 6, characterized in that: Used to prepare defluorination bags or defluorination agents.

8. A defluorination bag, characterized in that: Includes sealed bags, and insoluble adsorbent fluoride-removing composite material particles as described in any one of claims 4 to 6 filled inside the bags.

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