CN113000007B - Preparation method of defluorination adsorbent and defluorination adsorption filter paper and application thereof - Google Patents

Preparation method of defluorination adsorbent and defluorination adsorption filter paper and application thereof Download PDF

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CN113000007B
CN113000007B CN202110259814.7A CN202110259814A CN113000007B CN 113000007 B CN113000007 B CN 113000007B CN 202110259814 A CN202110259814 A CN 202110259814A CN 113000007 B CN113000007 B CN 113000007B
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defluorination
filter paper
magnesium
preset
prepared
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CN113000007A (en
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柯飞
刘政权
宛晓春
潘安
彭传燚
蔡芸梅
关莹
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Anhui Agricultural University AHAU
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Anhui Agricultural University AHAU
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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
    • B01J20/048—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 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F3/00—Tea; Tea substitutes; Preparations thereof
    • A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
    • A23F3/20—Removing unwanted substances
    • A23F3/205—Using flocculating or adsorbing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/02—Methods of beating; Beaters of the Hollander type
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/14—Making cellulose wadding, filter or blotting paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/08—Filter paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells

Abstract

The application discloses a preparation method of a defluorination adsorbent and defluorination adsorption filter paper and application thereof, belonging to the field of selective removal of fluorine ions. The application provides a preparation method of biomass filter paper for filtering fluorinion in food, wherein a calcium source is provided by recycling waste biological shells, magnesium-doped hydroxyapatite synthesized by doping magnesium ions is taken as an adsorbent, and the biomass filter paper for filtering fluorinion is prepared between two layers of different celluloses. The application is synthesized by a chemical precipitation method which is convenient to prepare, and is attached by a mechanical beating method, thereby playing a role in enhancing and filtering the fluorinion. Compared with the traditional adsorption method, the method has the advantages of simple process and low cost, and accords with practical application.

Description

Preparation method of defluorination adsorbent and defluorination adsorption filter paper and application thereof
Technical Field
The application relates to preparation methods of an adsorbent and adsorption filter paper and applications thereof, in particular to a preparation method of a fluorine removal adsorbent and fluorine removal adsorption filter paper and applications thereof.
Background
Fluorine is one of trace elements necessary for human life activities and has close relation with calcium and phosphorus metabolism. The intake of proper amount of fluorine can enhance the hardness of bones and teeth of the body, promote the metabolism of an enzyme system and help to transfer nerve excitation. However, when the fluorine content exceeds 1.5mg/L, the slight person may cause dental fluorosis, and the serious person may cause osteofluorosis. Tea and diet are important sources of supplementation for the human body to ingest fluorine. Tea is a fluorine-rich plant, and tea drinking type fluorosis caused by long-term drinking of high-fluorine tea is reported at home and abroad; the fish, shrimp and shell products are main marine products in coastal areas, the marine products contain rich nutrient substances, and the fluorine content is several times higher than that of terrestrial animals and other foods; particularly, the antarctic krill is rich in protein and is an important protein resource, but the antarctic krill has high fluorine content, the fluorine content of the dried krill powder can reach 2000-6000 mg/kg, and the long-term eating of the antarctic krill is easy to cause fluorine poisoning; and part of surface water and mineral water in high-fluorine areas, and the fluorine content of the surface water and the mineral water is far higher than the normal standard. How to effectively reduce the excessive fluoride ions in high-fluorine food is always a hotspot and a difficulty of research.
Disclosure of Invention
In order to solve the defects of the prior art, the application provides a preparation method of a defluorination adsorbent, which comprises the following steps: grinding the raw materials of the biological shells to obtain powder to be fired of the biological shells; calcining the biochell powder at a first preset temperature for a first preset time to form powder to be mixed; mixing the powder to be mixed with soluble magnesium salt or/and phosphate, deionized water and ammonia water to form paste with a preset pH value; drying the paste at a second preset temperature to form a dried product; and centrifuging, washing, drying and crushing the dried product to obtain the defluorination adsorbent.
Further, the raw material of the biochells is washed and dried, and then placed in an acid solution of a predetermined concentration and stirred.
Further, the preparation method of the defluorination adsorbent also comprises the following steps: taking out the raw material of the biological shells in the acid solution with the preset concentration, and washing and drying the raw material again.
Further, the step of mixing the powder to be mixed with soluble magnesium salt or/and phosphate and deionized water to form a paste with a preset pH value comprises the following steps: premixing the powder to be mixed, soluble magnesium salt and deionized water into paste, and adding the paste into a reaction kettle to be uniformly stirred; and dropwise adding the prepared phosphate solution and ammonia water into the reaction kettle to obtain the paste with the preset pH value.
Further, the first preset temperature ranges from 600 ℃ to 900 ℃.
Further, the first preset time period ranges from 4 hours to 6 hours.
Further, in the step of mixing the powder to be mixed with soluble magnesium salt or/and phosphate and deionized water to form a paste with a preset pH value, mixing the powder to be mixed with the soluble magnesium salt or/and phosphate and the deionized water according to a preset molar ratio of magnesium element to calcium element, wherein the value range of the preset molar ratio of magnesium element to calcium element is 2-36.
Further, in the step of mixing the powder to be mixed with soluble magnesium salt or/and phosphate and deionized water to form a paste with a preset pH value, the ratio of the sum of the molar numbers of magnesium element and calcium element to the molar number of phosphoric acid ranges from 1.3 to 1.9.
Further, the preset pH value ranges from 8 to 11.
Further, the raw materials of the biological shells comprise: one or more of abalone shell, egg shell, shrimp and crab shell, mussel shell, oyster shell and pearl shell.
As another aspect of the present application, there is also provided a method for preparing a defluorination adsorption filter paper, including: the preparation method is adopted; preparing double-layer filter paper, and arranging the defluorination adsorbent between the double-layer structures of the filter paper.
As another aspect of the present application, there is also provided a use of the defluorination adsorption filter paper prepared as described above in defluorination of liquid drinks, through which the liquid drinks are passed.
As another aspect of the present application, there is also provided a method for preparing the fluorine-removing adsorption filter paper according to the above, wherein the fluorine-removing adsorption filter paper is applied to the fluorine-removing filtration of the tea beverage, and the tea beverage passes through the fluorine-removing adsorption filter paper.
As another aspect of the present application, there is also provided a use of the defluorination adsorbent according to the above in defluorination of food, characterized in that food is mixed with the defluorination adsorbent.
The application has the advantages that: provides a preparation method of a fluorine removal adsorbent and a fluorine removal adsorption filter paper which can remove fluorine element in food with high efficiency and reach food grade, and application thereof.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, serve to provide a further understanding of the application and to enable other features, objects, and advantages of the application to be more apparent. The drawings and the description of the exemplary embodiments of the present application are provided for explaining the present application and do not constitute an undue limitation on the present application. In the drawings:
FIG. 1 is a scanning electron microscope picture of magnesium-doped (molar ratio of calcium to magnesium 9:1) hydroxyapatite prepared in example 1 by recycling of biological shells.
Fig. 2 is a scanning electron microscope picture of commercially available hydroxyapatite.
FIG. 3 is a graph showing the effect of magnesium doped hydroxyapatite (Bio to HAP) with different calcium-magnesium molar ratios on the adsorption of fluoride ions in brick tea prepared in example 2 by recycling of biological shells.
FIG. 4 is a graph showing the effect of different concentrations of coexisting ions of magnesium-doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by recycling the biological shells in example 3 on the adsorption of fluoride ions in brick tea.
FIG. 5 is a graph showing the effect of different dosages of magnesium-doped (Ca-Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared in the reuse of biological shells in example 5 and commercially available hydroxyapatite (Mar to HAP) on the adsorption of fluoride ions in brick tea.
FIG. 6 is a graph showing the effect of different dosages of magnesium-doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by recycling the biological shells in example 5 on the content of catechin and caffeine after adsorption of fluoride ions in brick tea.
FIG. 7 is a graph showing the effect of different mass ratios of magnesium-doped hydroxyapatite (Bio to HAP) heat-seal type tea filter paper prepared by recycling the loaded biological shell in example 6 on the adsorption of fluorine ions in brick tea.
Fig. 8 is a photograph of heat-sealing type tea filter paper (CFs are pure wood pulp fiber filter paper, and HAP is magnesium-doped hydroxyapatite prepared by recycling the biological shells) in which the mass ratio of magnesium-doped hydroxyapatite (Bio to HAP) prepared by recycling the biological shells in example 6 is 10%.
FIG. 9 is a graph showing the effect of different adsorption times of magnesium-doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared in the reuse of biological shells in example 7 and commercially available hydroxyapatite (Mar to HAP) on the adsorption of fluoride ions in brick tea.
FIG. 10 is a second order kinetic fit of the adsorption time of different magnesium doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by the reuse of the biological shell in example 7 and commercially available hydroxyapatite (Mar to HAP) to the adsorption of fluoride ions in brick tea.
Fig. 11 is XRD of magnesium-doped (ca-mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by recycling of the bioshell in example 1 and commercially available hydroxyapatite (Mar to HAP).
FIG. 12 is a graph showing the effect of different adsorption temperatures of magnesium-doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by reusing biological shells in example 8 and commercially available hydroxyapatite (Mar to HAP) on the adsorption of fluoride ions in brick tea.
FIG. 13 is a photograph of a finished heat-seal type tea filter paper product in which the mass ratio of magnesium-doped hydroxyapatite (Bio to HAP) prepared by recycling the biological shell supported in example 4 is 10%.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort shall fall within the protection scope of the present application.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In this application, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings. These terms are used primarily to better describe the present application and its embodiments, and are not used to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meaning of these terms in this application will be understood by those of ordinary skill in the art as appropriate.
Furthermore, the terms "mounted," "disposed," "provided," "connected," and "sleeved" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
The method for efficiently and selectively reducing the fluoride ions in the high-fluoride food uses the magnesium-doped hydroxyapatite prepared by recycling the biological shell for adsorption or supports the biological shell for coating by the prepared magnesium-doped hydroxyapatite filter paper; the high-fluorine food is tea, tea-containing products or antarctic krill enzymatic hydrolysate.
In one embodiment of the present application, the tea leaves are brick tea.
In one embodiment of the present application, the high fluorine food product is tea; the method comprises the steps of mixing magnesium-doped hydroxyapatite particles prepared by recycling biological shells, tea leaves and water, or putting the tea leaves into magnesium-doped hydroxyapatite filter paper prepared by recycling the biological shells, sealing and injecting water, wherein the heating time of the two forms is 1-50 min.
In one embodiment of the application, the mass ratio of the loading amount of the adsorbent in the prepared magnesium-doped hydroxyapatite adsorbent particles or the magnesium-doped hydroxyapatite filter paper prepared by reusing biological shells to the adding amount of the tea leaves is 1:15 to 1: 35.
In one embodiment of the present application, the mass ratio of tea leaves to water is from 1:30 to 1: 70.
In one embodiment of the present application, the high fluorine food is an antarctic krill enzymatic hydrolysate; the method comprises the steps of mixing magnesium-doped hydroxyapatite prepared by recycling biological shells or magnesium-doped hydroxyapatite filter paper prepared by recycling loaded biological shells with antarctic krill enzymatic hydrolysate, and carrying out shock adsorption for 2-12 min at the temperature of 25-35 ℃.
In one embodiment of the application, the mass-to-volume ratio of the loading amount of the adsorbent in the hydroxyapatite or magnesium-loaded hydroxyapatite filter paper prepared by reusing biological shells and magnesium-doped hydroxyapatite or loaded biological shells to the antarctic krill enzymatic hydrolysate is 2 mg/mL.
In one embodiment of the present application, the rotation speed of the oscillating adsorption is 50 to 250 r/min.
In one embodiment of the present application, the preparation method of the antarctic krill enzymatic hydrolysate is: mixing the antarctic krill with water according to a solid-to-liquid ratio of 1:8 to 1:12, adding 2500-3000U/g antarctic krill Alcalase, carrying out enzymolysis for 160-200 min at the pH value of 8-9 and the temperature of 55-65 ℃, and then carrying out enzyme deactivation and centrifugation to obtain the antarctic krill enzymolysis liquid.
In one embodiment of the application, the biological shell is recycled to prepare the magnesium-doped hydroxyapatite defluorination adsorbent, and the magnesium-doped hydroxyapatite defluorination adsorbent has the characteristics of good biological activity and compatibility, and environmental friendliness.
In an embodiment of the application, the biological shell is recycled to prepare the magnesium-doped hydroxyapatite defluorination adsorbent, the synthesis method is mainly a hydrothermal method, the production and use processes and equipment are simple and easy to control, and the large-scale production, popularization and utilization are facilitated.
In one embodiment of the application, the prepared magnesium-doped hydroxyapatite filter paper loaded with the biological shells is reused, and the filter paper has the advantages of light and thin paper surface and high water passing capacity.
In one embodiment of the present application, a specific preparation step of the defluorination adsorbent for biomass recycling is as follows:
(1) cleaning and drying biological shells, dissolving the biological shells in 0.1mol/L hydrochloric acid solution, continuously stirring until no bubbles are generated, cleaning and drying;
(2) crushing and grinding the dried biological shells in the step (1), and screening by using a 200-mesh filter screen to obtain biological shell powder with impurities removed;
(3) calcining the biological shell powder obtained in the step (2) in a muffle furnace for 1 to 6 hours at the calcining temperature of 500 to 900 ℃, and dissolving the obtained white calcium oxide powder in water to be used as a synthetic calcium source;
(4) food-grade soluble phosphate, ammonia water and soluble magnesium salt are adopted as raw materials;
(5) determining the adding quality of the soluble magnesium salt and the calcium source according to the molar ratio of calcium to magnesium (36: 1-2: 1);
(6) mixing soluble magnesium salt and calcium salt with determined adding quality into paste with 50mL of deionized water, adding into a reaction kettle, and stirring to be uniform while adding;
(7) determining the adding amount of phosphoric acid according to the molar ratio (1.3-1.9) of the sum of the moles of the soluble magnesium salt and the calcium source to the moles of phosphate, and preparing a phosphate solution by using 15mL of deionized water;
(8) dropwise adding the prepared phosphate solution into a reaction kettle, and simultaneously adding ammonia water to adjust the pH value of a reaction system in the dropwise adding process;
(9) after the phosphate solution is dripped, stabilizing the pH value at 8-11, and stirring for 30min at normal temperature;
(10) stopping stirring the reaction kettle, placing the reaction kettle into a constant-temperature drying box, and standing and aging at 90 ℃;
(11) and taking out the product, centrifuging, washing, drying and crushing to obtain the magnesium-doped hydroxyapatite defluorination adsorbent prepared by recycling the biomass.
In one embodiment of the present application, in the synthesis method of magnesium-doped hydroxyapatite prepared by recycling the biological shell, the molar ratio of magnesium to calcium is 36:1 to 2: 1.
In one embodiment of the present application, in the synthesis method of magnesium-doped hydroxyapatite prepared by recycling the biological shell, the molar ratio of the sum of the number of moles of the soluble magnesium salt and the calcium source to the phosphoric acid is 1.3 to 1.9.
In one embodiment of the present application, in the method for synthesizing magnesium-doped hydroxyapatite by reusing the biological shell, the pH value of the reaction system is maintained in a range of 8 to 11 in real time.
In one embodiment of the present application, in the method for synthesizing magnesium-doped hydroxyapatite by recycling the biological shell, the biological shell is placed in a constant temperature drying oven, and the biological shell is kept at 90 ℃ for 2 to 10 hours for aging.
In one embodiment of the present application, the aqueous calcium oxide solution required for synthesis of the magnesium-doped hydroxyapatite prepared by recycling the biochells may be: one or more of abalone shell, egg shell, shrimp and crab shell, mussel shell, oyster shell and pearl shell;
the magnesium salt is one or more of magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium hydroxide;
the phosphate is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In one embodiment of the application, the preparation process of the magnesium-doped hydroxyapatite heat-sealing type tea filter paper prepared by reusing biological shells specifically comprises the following steps:
(1) preparing raw materials: the raw materials of the chemical fiber layer comprise the following components in proportion: 20 to 60 percent (mass) of softwood pulp and 40 to 80 percent (mass) of chemical fiber staple fiber form hot-melt fiber pulp; the wood pulp layer comprises the following raw materials in parts by weight: long fiber pulp of natural fibers consisting of 10 to 80% of manila hemp pulp and 20 to 90% of softwood pulp;
(2) pulping: pulping wood pulp of the chemical fiber layer, the chemical fiber and a wet strength agent respectively, wherein the beating degree of the two kinds of pulp is 14-18 ℃, and simultaneously adding prepared magnesium-doped hydroxyapatite which accounts for 5%, 10%, 20% and 40% of the mass ratio of the filter paper into the wood pulp layer;
(3) papermaking: respectively papermaking the two parts of pulp to obtain chemical fiber base paper and wood pulp base paper;
(4) shaping: compounding and shaping the two kinds of base paper into composite paper by adopting a compression roller, wherein the temperature of compounding and shaping is 180-185 ℃, and the pressure is 0.3-0.35 MPa;
(5) and (3) cooling: cooling the shaped composite paper by cooling water within 30s, wherein the cooling temperature is 10-20 ℃;
(6) and (3) drying: drying the shaped composite paper at 55 ℃ for 2-10 h;
(7) surface treatment: soaking the shaped composite paper in a surface treating agent for 2-5 min;
(8) drying: and (3) drying the surface-treated composite paper in vacuum at a low temperature of 40-50 ℃ and a vacuum degree of 0.05-0.07 MPa to obtain a finished product of the heat-seal filter paper.
The filter paper is of a two-layer structure, a wood pulp layer is used as an inner layer, a chemical fiber layer is used as an outer layer, and the filter paper is formed by adopting two raw materials to respectively make paper and then compounding through heat setting. The chemical fiber in the chemical fiber layer can be softened easily when being heated and has viscosity, so that the chemical fiber layer is convenient to be combined with the wood pulp layer.
In one embodiment of the present application, the chemical fiber is polypropylene fiber or polyethylene fiber, the length of the fiber is 3 to 5nm, and the fineness is 3.3 Dtex.
In one embodiment herein, the wet strength agent is a polyamide polyepichlorohydrin resin (PAE) from 0.05 to 0.08 g.
In one embodiment of the present application, the surface treatment agent comprises the following components in parts by weight: 10 to 15 parts of gelatin, 2 to 5 parts of oxidized starch, 1 to 3 parts of calcium carbonate, 10 to 15 parts of chitosan and 100mL of water.
In one embodiment of the present application, the magnesium-doped hydroxyapatite heat-seal type tea filter paper prepared by recycling the bio-shells has a diameter of 10 to 30cm
The following is a detailed description of the present application.
The first embodiment is as follows: preparation of magnesium-doped (calcium-magnesium molar ratio 9:1) hydroxyapatite prepared by recycling biological shells
(1) Cleaning and drying biological shells, dissolving the biological shells in 0.1mol/L hydrochloric acid solution, continuously stirring until no bubbles are generated, cleaning and drying;
(2) crushing and grinding the dried biological shells in the step (1), and screening by using a 200-mesh filter screen to obtain biological shell powder with impurities removed;
(3) calcining the biological shell powder obtained in the step (2) in a muffle furnace for 6 hours at 900 ℃, and dissolving the obtained white calcium oxide powder in water to be used as a synthetic calcium source;
(4) food-grade soluble phosphate, ammonia water and soluble magnesium salt are used as raw materials;
(5) determining the adding mass of the soluble magnesium salt and the calcium source according to the molar ratio of calcium to magnesium of 1: 9;
(6) mixing soluble magnesium salt and calcium salt with determined adding quality into paste with 50mL of deionized water, adding into a reaction kettle, and stirring to be uniform while adding;
(7) determining the adding amount of phosphoric acid according to the molar ratio of the sum of the soluble magnesium salt and the calcium source to the phosphate of 1.85:1, and preparing a phosphate solution by using 15mL of deionized water;
(8) dropwise adding the prepared phosphate solution into a reaction kettle, and simultaneously adding ammonia water to adjust the pH value of a reaction system in the dropwise adding process;
(9) after the phosphate solution is added dropwise, the pH value is stabilized at 11, and stirring is carried out for 30min at normal temperature;
(10) stopping stirring the reaction kettle, placing the reaction kettle into a constant-temperature drying box, and standing and aging at 90 ℃;
(11) and taking out the product, centrifuging, washing, drying and crushing to obtain the magnesium-doped hydroxyapatite defluorination adsorbent prepared by recycling the biomass.
Fig. 1 clearly reveals the morphology structure of magnesium-doped (ca-mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by biological shell recycling, which has a regular long-strip structure size of about 100nm, a very rough surface, and is formed by stacking a large number of nano-sheets; in addition, the commercially available hydroxyapatite (Mar to HAP) has a leaf-like structure with a size of about 150nm, completely different from the magnesium-doped (ca-mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by recycling the bioshell, by comparing the morphologies of the commercially available hydroxyapatite (Mar to HAP) in fig. 2, and it can be observed from fig. 11 that 5 main characteristic peaks (26.13, 32.03, 39.43, 47, 49.74 in 2 θ) of the XRD spectrum of the magnesium-doped (ca-mg molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by recycling the bioshell are matched with the commercially available hydroxyapatite (Mar to HAP).
The second embodiment is as follows: influence of magnesium-doped hydroxyapatite prepared by recycling biological shells and having different calcium-magnesium molar ratios on adsorption of fluoride ions in brick tea
40mg of different calcium-magnesium sources are mixed in a molar ratio of 36:1, 18:1, 9:1, 4:1, 2:1 and adding 25mL of deionized water into magnesium-doped hydroxyapatite (Bio to HAP) and 0.5g of brick tea powder, heating and boiling the mixture in a water bath for 30min under the condition of 373K, filtering the mixed solution, taking out the solution, and measuring the residual fluorine ion concentration.
It can be observed from fig. 3 that the adsorption effect on fluoride ions increases with the increase of the magnesium ion content, and when the molar ratio of calcium to magnesium is 9:1, the adsorption capacity on fluoride ions reaches up to 70mg/L, but when the molar ratio of calcium to magnesium is greater than 9:1, the adsorption effect on fluoride ions of the material decreases, so the molar ratio of the calcium to magnesium source of 9:1 is selected as the optimal molar ratio.
The third concrete implementation mode: under the condition of coexisting anions with different concentrations, the biological shell is reused to prepare magnesium-doped (calcium-magnesium molar ratio 9:1) hydroxyapatite (Bio-HAP) with the adsorption influence on fluoride ions in brick tea
Bicarbonate (HCO) was studied 3 - ) Chloride ion (Cl) - ) Sulfate (SO) 4 2- ) And Nitrate (NO) 3 - ) And (3) the interference of different coexisting ions on the adsorption of fluoride by magnesium-doped (calcium-magnesium molar ratio 9:1) hydroxyapatite (Bio to HAP) prepared by biological shell reuse. The adsorbent (40mg) was suspended in 25mL of a mixed solution containing fluorine (8.5mg/L) and another anion at anion concentrations of 0, 8.5 and 272mg/L, respectively. After shaking at room temperature for 2 hours, the mixed solution was filtered, and the solution was taken out to measure the remaining fluoride ion concentration.
FIG. 4 shows the adsorption effect of magnesium-doped (Ca/Mg molar ratio 9:1) hydroxyapatite (Bio to Hap) prepared by reusing biological shells under different concentrations in the coexistence of anions. Even at high concentrations of HCO 3 - To F - The adsorption efficiency of (A) is reduced by only about 5%, and the adsorption efficiency of (B) is reduced by F under the condition of low concentration of other coexisting anions - The effect of adsorption efficiency of (a) is negligible. At the same time, under the condition of high concentration of other coexisting anions, F is treated - The adsorption efficiency of (a) has only a slight influence. The result shows that the prepared hydroxyapatite has stronger selective adsorption to fluorinion.
The fourth concrete implementation mode: preparation of magnesium-doped hydroxyapatite (Bio-HAP) heat-seal type tea filter paper by reusing biological shell loaded with 10% by mass
(1) Preparing raw materials: the raw materials of the chemical fiber layer comprise the following components in proportion: 60 percent (mass) of softwood pulp and 40 percent (mass) of polypropylene fiber form hot-melt fiber pulp; the wood pulp layer comprises the following raw materials in parts by weight: a long fiber pulp of natural fibers consisting of 70% of manila hemp pulp and 30% of softwood pulp;
(2) pulping: pulping the wood pulp, the chemical fiber and the wet strength agent of the chemical fiber layer respectively, wherein the beating degree of the two kinds of pulp is 18 degrees, and simultaneously adding the prepared magnesium-doped hydroxyapatite which accounts for 10 percent of the mass ratio of the filter paper and is recycled into the wood pulp layer;
(3) papermaking: respectively papermaking the two parts of pulp to obtain chemical fiber base paper and wood pulp base paper;
(4) shaping: compounding and shaping the two kinds of base paper into composite paper by adopting a compression roller, wherein the temperature of compounding and shaping is 185 ℃, and the pressure is 0.35 MPa;
(5) and (3) cooling: cooling the shaped composite paper by cooling water within 30s, wherein the cooling temperature is 10 ℃;
(6) and (3) drying: drying the shaped composite paper at 55 ℃ for 5 h;
(7) surface treatment: soaking the shaped composite paper with a surface treating agent for 5 min;
(8) and (3) drying: and (3) drying the surface-treated composite paper in vacuum at a low temperature of 50 ℃ and a vacuum degree of 0.07MPa to obtain a finished heat-seal filter paper product with the diameter of 22 cm.
It can be observed from fig. 8 that the photographs of the prepared magnesium-doped hydroxyapatite (Bio to Hap) heat-seal type tea filter paper loaded with 10% of the Bio-shell by mass ratio were uniform in thickness and 22cm in diameter. Meanwhile, as can be observed from fig. 13, the finished tea bag product with the weight ratio of 10% of the magnesium-doped hydroxyapatite (Bio to Hap) heat-seal type tea filter paper prepared by reusing the treated loaded biological shell is shown.
The fifth concrete implementation mode is as follows: influence of amount of magnesium-doped hydroxyapatite adsorbent prepared by recycling biological shells on adsorption of fluorine ions in brick tea
Adding 0, 10, 20, 40, 60mg of prepared magnesium-doped hydroxyapatite or commercially available hydroxyapatite and 0.5g of brick tea powder into 25mL of deionized water, heating and boiling in water bath under 373K condition for 30min, filtering the mixed solution, and taking out the solution to measure the residual fluorine ion concentration and the concentrations of tea polyphenol and caffeine.
As can be observed from fig. 5, the adsorption effect of the magnesium-doped hydroxyapatite (Bio to Hap) prepared by recycling the biological shell is obviously improved relative to the commercially available hydroxyapatite (Mar to Hap) with the increase of the adsorbent dosage.When the dosage reaches 2.4g/L, the biological shell reuses the prepared magnesium-doped hydroxyapatite (Bio to HAP) pair F - The adsorption effect is close to saturation, and the adsorption efficiency is up to 90%. Meanwhile, as can be observed from fig. 6, the magnesium-doped hydroxyapatite (Bio to HAP) prepared by recycling the biological shells almost has negligible influence on the content of contents such as catechin and caffeine after adsorbing fluorine ions in brick tea with the increase of the dosage of the adsorbent, and the content loss is less than 5% when the dosage reaches 2.4 g/L.
The sixth specific implementation mode: biological shell loaded and recycled prepared magnesium-doped hydroxyapatite (Bio to HAP) heat-seal type tea filter paper load influences adsorption of fluorine ions in brick tea
Respectively weighing 0.3g of the prepared magnesium-doped hydroxyapatite heat-seal type tea bag with the load biological shells of 5%, 10%, 20% and 40% in mass ratio, filling 0.5g of brick tea for sealing, boiling the tea bag at 373K for 30min, taking out the tea bag, and measuring the initial concentration of fluorine ions in the tea soup through a fluorine ion selective electrode.
As can be observed from fig. 7, the magnesium-doped hydroxyapatite (Bio-Hap) heat-seal type tea filter paper prepared by recycling the loaded biological shell has a significantly increased adsorption effect on fluoride ions in brick tea along with the increase of the loading amount, and the adsorption efficiency is about 80% when the loading amount is 40%.
The seventh embodiment: influence of adsorption time of magnesium-doped hydroxyapatite prepared by recycling biological shells on adsorption of fluorine ions in brick tea
Brick tea soup stock solution: 0.5g of brick tea was dispersed in 25mL of deionized water (1:50g/mL) and boiled at 373K for 30min, and then the mixed solution was filtered to obtain an initial tea soup solution, and the initial concentration of fluorine ions in the tea soup was measured by a fluorine ion selective electrode.
Respectively adding 40mg of biological shell prepared by recycling magnesium-doped hydroxyapatite or commercially available hydroxyapatite into 25mL of brick tea soup stock solution, shaking at constant temperature of 25 ℃, taking out the solution at intervals of 2-120 min, and measuring the residual fluorine ion concentration and the concentrations of tea polyphenol and caffeine by using a fluorine ion selective electrode.
By means of FIG. 9The observation shows that the adsorption quantity and the adsorption efficiency of the magnesium-doped hydroxyapatite (Bio to HAP) prepared by recycling the biological shell are obviously improved along with the increase of the adsorption time; and the adsorption balance is achieved in 40min, and the adsorption efficiency reaches 75%, which shows that the material has the capability of rapidly adsorbing fluorine ions. Compared to commercially available hydroxyapatite (Mar to HAP), the adsorption equilibrium time is shortened and the adsorption capacity is increased. Meanwhile, it can be observed from fig. 10 that the change of the biological shell reutilizing the prepared magnesium-doped hydroxyapatite (Bio to HAP) with the adsorption time follows a quasi-second order kinetic model, balancing the adsorption capacity (q) e ) The value was 3.75 mg/g.
The specific implementation mode is eight: influence of adsorption temperature of magnesium-doped hydroxyapatite prepared by recycling biological shells on adsorption of fluorine ions in brick tea
Respectively adding 40mg of biological shell prepared by reusing magnesium-doped hydroxyapatite into 25mL of brick tea with initial fluorine ion concentrations of 9, 18, 36, 72, 144 and 288mg/L, placing the mixed solution in batches in 298K, 308K and 318K constant-temperature oscillators, oscillating and adsorbing for 60min, filtering and separating, and measuring the residual fluorine ion concentration of the tea soup by using a fluorine ion selective electrode.
As can be observed from fig. 12, at the temperature of 298K, as the initial concentration of fluorine in the tea soup increases, the adsorption capacity of the adsorption material for fluorine ions increases significantly, indicating that the magnesium-doped hydroxyapatite (Bio to HAP) prepared by recycling the biological shell is beneficial to the selective adsorption of fluorine at high concentration, and the maximum saturated adsorption amount is 35 mg/g. When the adsorption temperature is increased to 308K and 318K, the adsorption capacity of the material to fluorine ions in the tea soup is increased to 43mg/g and 52mg/g respectively, which indicates that the process is an endothermic adsorption process. The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (5)

1. A preparation method of defluorination adsorption filter paper comprises the following steps:
(1) preparing raw materials: the raw materials of the chemical fiber layer comprise the following components in proportion: 20 to 60 percent (mass) of softwood pulp and 40 to 80 percent (mass) of chemical fiber staple fiber form hot-melt fiber pulp; the wood pulp layer comprises the following raw materials in parts by weight: long fiber pulp of natural fibers consisting of 10 to 80% of manila hemp pulp and 20 to 90% of softwood pulp;
(2) pulping: pulping wood pulp of a chemical fiber layer, chemical fiber and a wet strength agent respectively, beating the two raw materials, wherein the beating degrees of the two raw materials are 14-18 ℃, and simultaneously adding a magnesium-doped hydroxyapatite defluorination adsorbent prepared by recycling biological shells accounting for 5%, 10%, 20% and 40% of the mass ratio of filter paper into the wood pulp layer;
(3) papermaking: respectively papermaking the two parts of pulp to obtain chemical fiber base paper and wood pulp base paper;
(4) shaping: compounding and shaping the two kinds of base paper into composite paper by adopting a compression roller, wherein the temperature of compounding and shaping is 180-185 ℃, and the pressure is 0.3-0.35 MPa;
(5) and (3) cooling: cooling the shaped composite paper by cooling water within 30s, wherein the cooling temperature is 10-20 ℃;
(6) and (3) drying: drying the shaped composite paper at 55 ℃ for 2-10 h;
(7) surface treatment: soaking the shaped composite paper in a surface treating agent for 2-5 min;
(8) and (3) drying: drying the surface-treated composite paper in vacuum at a low temperature of 40-50 ℃ and a vacuum degree of 0.05-0.07 MPa to obtain a finished product of the heat-seal filter paper;
the preparation method of the defluorination adsorbent comprises the following steps:
grinding the raw materials of the biological shells to obtain powder to be fired of the biological shells;
calcining the biochell powder at a first preset temperature for a first preset time to form powder to be mixed;
mixing the powder to be mixed with soluble magnesium salt or/and phosphate, deionized water and ammonia water to form paste with a preset pH value;
drying the paste at a second predetermined temperature to form a dried product;
centrifuging, washing, drying and crushing the dried product to obtain the defluorination adsorbent;
the preparation method of the defluorination adsorbent also comprises the following steps:
cleaning and drying raw materials of the biological shells, then placing the raw materials in an acid solution with a preset concentration, and then stirring, cleaning and drying the raw materials; the step of mixing the powder to be mixed with soluble magnesium salt or/and phosphate and deionized water to form paste with a preset pH value comprises the following steps:
pre-mixing the powder to be mixed, soluble magnesium salt and deionized water into paste, and adding the paste into a reaction kettle to be uniformly stirred;
dropwise adding the prepared phosphate solution and ammonia water into the reaction kettle to obtain a paste with the preset pH value;
the value range of the first preset temperature is 600-900 ℃;
the value range of the first preset time is 4 to 6 hours;
in the step of mixing the powder to be mixed, soluble magnesium salt or/and phosphate and deionized water to form a paste with a preset pH value, mixing the powder to be mixed with the soluble magnesium salt or/and phosphate and the deionized water according to a preset molar ratio of magnesium element to calcium element, wherein the preset molar ratio of calcium element to magnesium element is 9: 1;
in the step of mixing the powder to be mixed, soluble magnesium salt or/and phosphate and deionized water to form a paste with a preset pH value, the value range of the ratio of the sum of the mole numbers of magnesium element and calcium element to the mole number of phosphoric acid is 1.85;
the preset pH value is 11;
the raw materials of the biological shells comprise: one or more of abalone shell, egg shell, shrimp and crab shell, mussel shell, oyster shell and pearl shell;
the nano-film has a regular long strip structure size of about 100nm, has a very rough surface and is formed by stacking a large number of nano-sheets.
2. The method for preparing the defluorination adsorption filter paper according to claim 1, wherein the filter paper has a two-layer structure, the wood pulp layer is used as an inner layer, the chemical fiber layer is used as an outer layer, the two raw materials are respectively used for papermaking and then are compounded by heat setting, and the chemical fiber in the chemical fiber layer is easy to soften and has viscosity when being heated, so that the chemical fiber can be conveniently combined with the wood pulp layer;
the chemical fiber is polypropylene fiber or polyethylene fiber, the length of the fiber is 3-5 nm, and the titer is 3.3 Dtex;
the wet strength agent is polyamide polyepichlorohydrin resin (PAE);
the surface treating agent comprises the following components in parts by weight: gelatin, oxidized starch, calcium carbonate, chitosan and water.
3. The application of the defluorination adsorption filter paper prepared by the preparation method of claim 2 in defluorination of liquid drinks, which is characterized in that the liquid drinks are made to pass through the defluorination adsorption filter paper.
4. The application of the defluorination adsorption filter paper prepared by the preparation method of claim 2 in defluorination filtration of tea drinks is characterized in that the tea drinks are made to pass through the defluorination adsorption filter paper.
5. Use of the fluorine removing adsorbent prepared by the preparation method according to claim 1 for removing fluorine from food, wherein the food is mixed with the fluorine removing adsorbent.
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