WO2020135720A1 - Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof - Google Patents

Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof Download PDF

Info

Publication number
WO2020135720A1
WO2020135720A1 PCT/CN2019/129225 CN2019129225W WO2020135720A1 WO 2020135720 A1 WO2020135720 A1 WO 2020135720A1 CN 2019129225 W CN2019129225 W CN 2019129225W WO 2020135720 A1 WO2020135720 A1 WO 2020135720A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxyapatite
molding method
aqueous solution
mixed
ion
Prior art date
Application number
PCT/CN2019/129225
Other languages
French (fr)
Chinese (zh)
Inventor
樊斯斯
徐金铭
黄延强
段洪敏
张涛
黄庆连
洪万墩
陈玉振
吴建慧
郑雅文
温明宪
张朝钦
黄朝晟
廖于涵
葉律真
Original Assignee
中国科学院大连化学物理研究所
台湾塑胶工业股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院大连化学物理研究所, 台湾塑胶工业股份有限公司 filed Critical 中国科学院大连化学物理研究所
Publication of WO2020135720A1 publication Critical patent/WO2020135720A1/en

Links

Images

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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present application relates to a method for forming spherical hydroxyapatite, spherical hydroxyapatite and applications, and belongs to the field of porous material preparation.
  • hydroxyapatite also has a strong adsorption capacity. It is precisely because of these characteristics that hydroxyapatite has emerged in the field of catalysis and adsorption, becoming a new type of hydroxyapatite-based catalytic and adsorption material.
  • hydroxyapatite itself is very brittle, difficult to form, and slightly soluble in water. At present, there are few reports on the formation of hydroxyapatite, which greatly limits its application.
  • a method for forming spherical hydroxyapatite is provided.
  • the method can greatly improve the mechanical strength of the hydroxyapatite pellets, and the preparation process is safe and simple.
  • a molding method of spherical hydroxyapatite includes at least the following steps:
  • Alginate is a by-product of the extraction of iodine and mannitol from brown algae kelp or Sargassum. Its molecules are composed of ⁇ -D-mannuronic acid and ⁇ -L-guluronic acid ( ⁇ -L-guluronic , G) Press (1 ⁇ 4) to connect.
  • cations such as Ca 2+ and Ba 2+
  • the Na + plasma on the carboxylate undergoes an ion exchange reaction with the multivalent cation to form a cross-linked network structure, thereby forming a hydrogel.
  • the use of alginate has unique properties, that is, in the presence of multivalent metal cations, such as Ca 2+ , a sol-gel transition can occur. Therefore, the addition of alginate to hydroxyapatite to assist in molding can greatly improve the mechanical properties of the ball Strength, and the preparation process is safe and simple.
  • step S100 includes:
  • An aqueous solution containing calcium ions and an aqueous solution containing phosphate groups are mixed to obtain a precipitate, and the precipitate is directly dispersed in water to obtain the hydroxyapatite suspension.
  • the aqueous solution containing calcium ions may be an aqueous solution of soluble calcium salts such as calcium chloride, calcium nitrate, and calcium hydroxide.
  • the aqueous solution containing phosphate radicals may be an aqueous solution of ammonium dihydrogen phosphate or an aqueous solution of ammonium orthophosphate.
  • a calcium chloride aqueous solution and an ammonium dihydrogen phosphate aqueous solution are mixed to obtain a precipitate, and the precipitate is directly dispersed in water to obtain the hydroxyapatite suspension.
  • step S100 ammonia water needs to be added during the mixing process to control the PH value to 10-12; the stirring temperature is 80-100°C; the stirring time is 1-4 hours; cooled to room temperature, the aging time is 10-24 hours .
  • the molar concentration of Ca 2+ is 0.1 to 0.5 mol/L;
  • the PO 4 3- molar concentration is 0.05 to 0.3 mol/L;
  • the Ca 2+ molar concentration is 0.1 to 0.5 mol/L;
  • the PO 4 3- molar concentration is 0.05 to 0.3 mol/L;
  • the mass fraction of the hydroxyapatite in the suspension is 25 to 35 wt%.
  • the soluble alginate includes at least one of sodium alginate, potassium alginate, ammonium alginate, lithium alginate, and magnesium alginate.
  • the mass fraction of the hydroxyapatite in the mixed floating slurry is 0.5-25 wt%; the mass fraction of the soluble alginate in the mixed floating slurry is 0.05 ⁇ 4wt%.
  • the upper limit of the mass fraction of the hydroxyapatite in the mixed floating slurry is independently selected from 5wt%, 15wt%, 25wt%; the hydroxyapatite in the mixed floating slurry
  • the lower limit of the mass fraction is independently selected from 0.5wt%, 5wt%, and 15wt%.
  • the upper limit of the mass fraction of the soluble alginate in the floating slurry is independently selected from 0.8wt%, 1.4wt%, 1.7wt%, 4wt%; the soluble alginate in the floating slurry
  • the lower limit of the mass fraction in the material is independently selected from 0.05wt%, 0.8wt%, 1.4wt%, 1.7wt%.
  • the step S300 includes: dropping the mixed floating slurry into a metal salt solution to form a gel ball.
  • the volume ratio of the mixed floating slurry to the metal salt solution is 0.1-10.
  • the metal salt contains a metal cation
  • the metal cation includes at least one of calcium ion, strontium ion, barium ion, iron ion, cobalt ion, nickel ion, manganese ion, copper ion, zinc ion, and aluminum ion.
  • the concentration of the metal cation substance in the metal salt solution is 0.01-3 mol/L.
  • the upper limit of the concentration of the amount of the metal cation substance is independently selected from 0.1 mol/L, 0.2 mol/L, 0.5 mol/L, 2 mol/L, 3 mol/L; the lower limit of the concentration of the amount of the metal cation substance Independently selected from 0.01 mol/L, 0.1 mol/L, 0.2 mol/L, 0.5 mol/L, 2 mol/L.
  • the molding method of spherical hydroxyapatite includes the following steps:
  • the aqueous solution containing calcium ions includes any one of calcium chloride aqueous solution, calcium nitrate aqueous solution, and calcium hydroxide aqueous solution;
  • the phosphate-containing aqueous solution includes any one of ammonium dihydrogen phosphate aqueous solution and ammonium orthophosphate aqueous solution.
  • the pH of the alkaline environment is 10-12; the stirring temperature is 80-100°C; the stirring time is 1-4h; and the aging time is 10-24h.
  • the aging time of the gel ball is 0.1-24 hours.
  • the upper limit of the gel ball aging time is selected from 1h, 2h, 10h, 15h, 24h; the lower limit of the gel ball aging time is selected from 0.1h, 1h, 2h, 10h, 15h.
  • the drying conditions are: drying temperature 20-150°C; drying time 0.5-48h.
  • the drying temperature is 20 to 150° C., and the time is 0.5 to 48 hours.
  • the firing conditions are as follows: firing temperature 300 ⁇ 700°C; firing time 1 ⁇ 15h.
  • firing is started at a firing temperature of 300 to 700°C for a time of 1 to 15 hours.
  • the upper limit of the calcination temperature is independently selected from 350°C, 500°C, 600°C, and 700°C; the lower limit of the calcination temperature is independently selected from 300°C, 350°C, 500°C, and 600°C.
  • the upper limit of the calcination time is independently selected from 2h, 3h, and 15h; the lower limit of the calcination time is independently selected from 1h, 2h, and 3h.
  • the molding method of spherical hydroxyapatite includes the following steps:
  • a spherical hydroxyapatite obtained by the molding method described in any one of the above.
  • the diameter of the spherical hydroxyapatite is 1 to 5 mm.
  • the upper limit of the diameter of the spherical hydroxyapatite is independently 2 mm, 2.5 mm, and 5 mm; the lower limit of the diameter of the spherical hydroxyapatite is independently 1 mm, 2 mm, and 2.5 mm.
  • the spherical hydroxyapatite contains a porous structure, the average pore diameter is 2-10 nm, the total pore volume is 0.1-1 cm 3 /g, and the specific surface area is 80-200 m 2 /g.
  • spherical hydroxyapatite obtained by the molding method described above and/or the spherical hydroxyapatite described above in the field of catalysts, adsorption separation materials or bioengineering Application in the field.
  • the present application provides a method for forming spherical hydroxyapatite assisted by sodium alginate.
  • the hydroxyapatite precipitate is prepared by the precipitation method, and then the hydroxyapatite precipitate is dissolved in water and dispersed to obtain a suspension.
  • the alginate aqueous solution and the hydroxyapatite suspension are mixed to form a floating slurry, and then mixed
  • the floating slurry is dropped into a solution of multivalent metal ions, and the hydroxyapatite solidifies into a gel ball, and after drying and roasting, a spherical hydroxyapatite is obtained.
  • the method for forming spherical hydroxyapatite which uses soluble alginate to assist the formation of spherical hydroxyapatite, can greatly improve the mechanical strength of the hydroxyapatite ball, and solves the problem of the hydroxyapatite itself It is very brittle and difficult to form, and retains the characteristics of hydroxyapatite with high adsorption performance and porous structure.
  • the precipitate is filtered without washing, and is directly dissolved in deionized water to prepare a suspension.
  • the impurities in the filter cake are mainly ammonia and ammonium chloride, they can be directly volatilized during the subsequent heating and roasting treatment. Therefore, when the precipitation amount is relatively large, the problem that the filter cake is thick and the filter is filtered is very slow.
  • the molding method of spherical hydroxyapatite provided in this application can obtain hydroxyapatite balls with a diameter of 1-5mm through the method of drop ball molding.
  • the process is simple and controllable. By controlling the size of the drop hole, different Ball of particle size.
  • the spherical hydroxyapatite provided in this application has high spherical sphericity, uniform particle size, and high strength. It can be used as a carrier for preparing catalysts or directly as a catalyst, adsorption material, and separation material. It is widely used in catalytic reactions. Catalysts or carriers, adsorption separation materials or bioengineering and other fields.
  • Figure 1 is a photograph of spherical hydroxyapatite obtained in Example 1 of this application.
  • Example 2 is a photograph of spherical hydroxyapatite obtained in Example 2 of this application.
  • FIG. 3 is a photograph of spherical hydroxyapatite obtained in Example 3 of the present application.
  • FIG. 4 is an isotherm diagram of adsorption and desorption of spherical hydroxyapatite in Example 1 of the present application under STP conditions.
  • FIG. 1 The physical picture is shown in Figure 1.
  • the outer surface of the ball is smooth and spherical, with a uniform particle size and a diameter of 2mm.
  • Mechanical strength is measured by DLIII-500 type strength tester. The average mechanical strength can reach 152N/piece.
  • FIG. 2 The physical picture is shown in Figure 2.
  • the outer surface of the ball is smooth and spherical, with a uniform particle size and a diameter of 2.5mm.
  • Mechanical strength is measured by DLIII-500 type strength tester. The average mechanical strength can reach 148N/piece.
  • hydroxyapatite suspension Take 6g of hydroxyapatite suspension and add it to 30g of 2% sodium alginate solution, stir and disperse for 180min to obtain a mixed floating slurry of hydroxyapatite.
  • the mass fraction of hydroxyapatite in the mixed slurry is 5wt %
  • the mass fraction of sodium alginate in the floating slurry is 1.7% by weight.
  • Mechanical strength is measured by DLIII-500 type strength tester, and the average mechanical strength can reach 162N/piece.
  • hydroxyapatite suspension 8g was added to 40g of 1% sodium alginate solution, and the mixture was stirred and dispersed for 30 minutes to obtain a mixed floating slurry of hydroxyapatite.
  • hydroxyapatite is the same as that of Example 1, except that the above suspension is taken dropwise into 300 mL of 0.01 M ferric nitrate solution.
  • the samples in Examples 1 to 11 were tested using Quadrasorb evoTM automatic specific surface and porosity analyzers respectively.
  • the test results show that the spherical hydroxyapatite contains a porous structure with an average pore size of 2-10 nm and a total pore volume of 0.1-1cm 3 /g, specific surface area is 80-200m2/g.
  • test results of the sample in Example 1 are as follows: the specific surface area is 158 m 2 /g, the average pore diameter is 5.4 nm, and the pore volume is 0.36 cm 3 /g;
  • test results of the sample in Example 2 are as follows: specific surface area is 110 m 2 /g, average pore diameter is 4.8 nm, and pore volume is 0.26 cm 3 /g;
  • test results of the sample in Example 3 are as follows: the specific surface area is 138 m 2 /g, the average pore diameter is 5.6 nm, and the pore volume is 0.24 cm 3 /g;
  • FIG. 4 is the absorption-desorption isotherm diagram of the sample. From this figure, it can be seen that the sample has a mesoporous structure and a specific surface area of 158 m 2 /g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Combustion & Propulsion (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Disclosed are a method for forming spherical hydroxyapatite, spherical hydroxyapatite and a use thereof. A method for forming spherical hydroxyapatite, which at least comprises the following steps: S100. obtaining a hydroxyapatite suspension; S200. obtaining a mixed and suspended slurry containing the hydroxyapatite suspension and a soluble alginate; S300. mixing the mixed and suspended slurry with a metal salt solution to obtain gel spheres; and S400. aging and roasting the gel spheres to obtain spherical hydroxyapatite. The method can greatly improve the mechanical strength of hydroxyapatite spheres, and has a safe, simple and convenient preparation process.

Description

球形羟基磷灰石的成型方法及球形羟基磷灰石和应用Forming method of spherical hydroxyapatite, spherical hydroxyapatite and application 技术领域Technical field
本申请涉及一种球形羟基磷灰石的成型方法及球形羟基磷灰石和应用，属于多孔材料制备领域。The present application relates to a method for forming spherical hydroxyapatite, spherical hydroxyapatite and applications, and belongs to the field of porous material preparation.
背景技术Background technique
羟基磷灰石(HAP)是动物骨骼的主要无机成分，具有优良的生物相容性和生物活性。同时羟基磷灰石具有独特的离子交换性质，其结构中的阴阳离子位置都可以被其它离子所取代。同时羟基磷灰石形成过程中也可以生成Ca 2+缺乏的形式，形成非化学计量比的羟基磷灰石(Ca/P＝1.4～1.67)，从而调节羟基磷灰石的表面酸碱性。羟基磷灰石结构稳定，1200℃焙烧依然能够维持完美的HAP结构。此外，羟基磷灰石还具有很强的吸附能力，正是由于这些特性，羟基磷灰石在催化和吸附领域崭露头角，成为一种新型的羟基磷灰石基催化和吸附材料。 Hydroxyapatite (HAP) is the main inorganic component of animal bones and has excellent biocompatibility and bioactivity. At the same time, hydroxyapatite has unique ion exchange properties, and the anion and cation positions in its structure can be replaced by other ions. At the same time, during the formation of hydroxyapatite, Ca 2+ deficient form can also be formed, forming non-stoichiometric ratio of hydroxyapatite (Ca/P=1.4～1.67), thereby adjusting the surface acidity and alkalinity of hydroxyapatite. The structure of hydroxyapatite is stable, and calcination at 1200℃ can still maintain the perfect HAP structure. In addition, hydroxyapatite also has a strong adsorption capacity. It is precisely because of these characteristics that hydroxyapatite has emerged in the field of catalysis and adsorption, becoming a new type of hydroxyapatite-based catalytic and adsorption material.
然而，羟基磷灰石本身很脆，不易成型，微溶于水，目前有关羟基磷灰石成型的报道较少，这在很大程度上限制了它的应用。However, hydroxyapatite itself is very brittle, difficult to form, and slightly soluble in water. At present, there are few reports on the formation of hydroxyapatite, which greatly limits its application.
发明内容Summary of the invention
根据本申请的一个方面，提供了一种球形羟基磷灰石的成型方法，该方法可以大大提高羟基磷灰石小球的机械强度，且制备过程安全简便。According to one aspect of the present application, a method for forming spherical hydroxyapatite is provided. The method can greatly improve the mechanical strength of the hydroxyapatite pellets, and the preparation process is safe and simple.
一种球形羟基磷灰石的成型方法，至少包括以下步骤：A molding method of spherical hydroxyapatite includes at least the following steps:
S100、获得羟基磷灰石悬浊液；S100. Obtain a hydroxyapatite suspension;
S200、获得含有所述羟基磷灰石悬浊液与可溶性海藻酸盐的混浮浆料；S200. Obtain a floating slurry containing the hydroxyapatite suspension and soluble alginate;
S300、将所述混浮浆料与金属盐溶液混合，得到凝胶球；S300. Mix the mixed-floating slurry with a metal salt solution to obtain a gel ball;
S400、将所述凝胶球经老化、焙烧，得到球形羟基磷灰石。S400. After aging and roasting the gel balls, spherical hydroxyapatite is obtained.
海藻酸盐是从褐藻类的海带或马尾藻中提取碘和甘露醇之后的副产物，其分子由β-D-甘露糖醛酸和α-L-古洛糖醛酸(α-L- guluronic，G)按(1→4)键连接而成。当有Ca 2+、Ba 2+等阳离子存在时，羧酸根上的Na +等离子与多价阳离子发生离子交换反应，形成交联网络结构，从而形成水凝胶。利用海藻酸盐具有独特的性质，即在多价金属阳离子，比如Ca 2+存在时可以发生溶胶一凝胶转变，因此在羟基磷灰石中加入海藻酸盐辅助成型，可以大大提高球的机械强度，且制备过程安全简便。 Alginate is a by-product of the extraction of iodine and mannitol from brown algae kelp or Sargassum. Its molecules are composed of β-D-mannuronic acid and α-L-guluronic acid (α-L-guluronic , G) Press (1→4) to connect. When cations such as Ca 2+ and Ba 2+ are present, the Na + plasma on the carboxylate undergoes an ion exchange reaction with the multivalent cation to form a cross-linked network structure, thereby forming a hydrogel. The use of alginate has unique properties, that is, in the presence of multivalent metal cations, such as Ca 2+ , a sol-gel transition can occur. Therefore, the addition of alginate to hydroxyapatite to assist in molding can greatly improve the mechanical properties of the ball Strength, and the preparation process is safe and simple.
可选地，所述步骤S100包括：Optionally, the step S100 includes:
将含有钙离子的水溶液和含有磷酸根的水溶液混合，得到沉淀物，直接将所述沉淀物分散到水中，得到所述羟基磷灰石悬浊液。An aqueous solution containing calcium ions and an aqueous solution containing phosphate groups are mixed to obtain a precipitate, and the precipitate is directly dispersed in water to obtain the hydroxyapatite suspension.
本申请中，含有钙离子的水溶液可以为氯化钙、硝酸钙、氢氧化钙等可溶性钙盐的水溶液。In the present application, the aqueous solution containing calcium ions may be an aqueous solution of soluble calcium salts such as calcium chloride, calcium nitrate, and calcium hydroxide.
本申请中，含有磷酸根的水溶液可以为磷酸二氢铵水溶液、正磷酸铵水溶液。In the present application, the aqueous solution containing phosphate radicals may be an aqueous solution of ammonium dihydrogen phosphate or an aqueous solution of ammonium orthophosphate.
例如：将氯化钙水溶液和磷酸二氢铵水溶液混合，得到沉淀物，直接将所述沉淀物分散到水中，得到所述羟基磷灰石悬浊液。For example, a calcium chloride aqueous solution and an ammonium dihydrogen phosphate aqueous solution are mixed to obtain a precipitate, and the precipitate is directly dispersed in water to obtain the hydroxyapatite suspension.
具体地，在步骤S100中，混合过程中需加入氨水控制PH值至10-12；搅拌温度为80-100℃；搅拌时间为1-4小时；冷却至室温，陈化时间为10-24小时。Specifically, in step S100, ammonia water needs to be added during the mixing process to control the PH value to 10-12; the stirring temperature is 80-100°C; the stirring time is 1-4 hours; cooled to room temperature, the aging time is 10-24 hours .
可选地，在所述含有钙离子的水溶液中，Ca 2+摩尔浓度为0.1～0.5mol/L； Optionally, in the aqueous solution containing calcium ions, the molar concentration of Ca 2+ is 0.1 to 0.5 mol/L;
在所述含有磷酸根的水溶液中，PO 4 3-摩尔浓度为0.05～0.3mol/L； In the phosphate-containing aqueous solution, the PO 4 3- molar concentration is 0.05 to 0.3 mol/L;
所述含有钙离子的水溶液与所述含有磷酸根的水溶液按照摩尔比Ca/P＝1.67的比例混合The calcium ion-containing aqueous solution and the phosphate-containing aqueous solution are mixed in a molar ratio Ca/P=1.67
具体地，在所述氯化钙水溶液中，Ca 2+摩尔浓度为0.1～0.5mol/L； Specifically, in the calcium chloride aqueous solution, the Ca 2+ molar concentration is 0.1 to 0.5 mol/L;
在所述磷酸二氢铵水溶液中，PO 4 3-摩尔浓度为0.05～0.3mol/L； In the aqueous solution of ammonium dihydrogen phosphate, the PO 4 3- molar concentration is 0.05 to 0.3 mol/L;
氯化钙和磷酸二氢铵按照摩尔比Ca/P＝1.67的比例混合。Calcium chloride and ammonium dihydrogen phosphate are mixed in a molar ratio Ca/P=1.67.
可选地，在步骤S100中，所述羟基磷灰石在悬浊液中的质量分数为25～35wt％。Optionally, in step S100, the mass fraction of the hydroxyapatite in the suspension is 25 to 35 wt%.
可选地，在步骤S200中，所述可溶性海藻酸盐包括海藻酸钠、海藻酸钾、海藻酸铵、海藻酸锂、海藻酸镁中的至少一种。Optionally, in step S200, the soluble alginate includes at least one of sodium alginate, potassium alginate, ammonium alginate, lithium alginate, and magnesium alginate.
可选地，在步骤S200中，所述羟基磷灰石在所述混浮浆料中的质量分数为0.5～25wt％；所述可溶性海藻酸盐在所述混浮浆料中的质量分数为0.05～4wt％。Optionally, in step S200, the mass fraction of the hydroxyapatite in the mixed floating slurry is 0.5-25 wt%; the mass fraction of the soluble alginate in the mixed floating slurry is 0.05～4wt%.
具体地，所述羟基磷灰石在所述混浮浆料中的质量分数的上限独立的选自5wt％、15wt％、25wt％；所述羟基磷灰石在所述混浮浆料中的质量分数的下限独立的选自0.5wt％、5wt％、15wt％。Specifically, the upper limit of the mass fraction of the hydroxyapatite in the mixed floating slurry is independently selected from 5wt%, 15wt%, 25wt%; the hydroxyapatite in the mixed floating slurry The lower limit of the mass fraction is independently selected from 0.5wt%, 5wt%, and 15wt%.
所述可溶性海藻酸盐在所述混浮浆料中的质量分数的上限独立的选自0.8wt％、1.4wt％、1.7wt％、4wt％；所述可溶性海藻酸盐在所述混浮浆料中的质量分数的下限独立的选自0.05wt％、0.8wt％、1.4wt％、1.7wt％。The upper limit of the mass fraction of the soluble alginate in the floating slurry is independently selected from 0.8wt%, 1.4wt%, 1.7wt%, 4wt%; the soluble alginate in the floating slurry The lower limit of the mass fraction in the material is independently selected from 0.05wt%, 0.8wt%, 1.4wt%, 1.7wt%.
可选地，所述步骤S300包括：将所述混浮浆料滴入到金属盐溶液中，形成凝胶球。Optionally, the step S300 includes: dropping the mixed floating slurry into a metal salt solution to form a gel ball.
可选地，所述混浮浆料与金属盐溶液的体积比为0.1-10。Optionally, the volume ratio of the mixed floating slurry to the metal salt solution is 0.1-10.
可选地，在步骤S300中，所述金属盐中含有金属阳离子；Optionally, in step S300, the metal salt contains a metal cation;
所述金属阳离子包括钙离子、锶离子、钡离子、铁离子、钴离子、镍离子、锰离子、铜离子、锌离子、铝离子中至少一种。The metal cation includes at least one of calcium ion, strontium ion, barium ion, iron ion, cobalt ion, nickel ion, manganese ion, copper ion, zinc ion, and aluminum ion.
可选地，在所述金属盐溶液中，金属阳离子的物质的量的浓度为0.01～3mol/L。Optionally, the concentration of the metal cation substance in the metal salt solution is 0.01-3 mol/L.
具体地，金属阳离子的物质的量的浓度的上限独立地选自0.1mol/L、0.2mol/L、0.5mol/L、2mol/L、3mol/L；金属阳离子的物质的量的浓度的下限独立地选自0.01mol/L、0.1mol/L、0.2mol/L、0.5mol/L、2mol/L。Specifically, the upper limit of the concentration of the amount of the metal cation substance is independently selected from 0.1 mol/L, 0.2 mol/L, 0.5 mol/L, 2 mol/L, 3 mol/L; the lower limit of the concentration of the amount of the metal cation substance Independently selected from 0.01 mol/L, 0.1 mol/L, 0.2 mol/L, 0.5 mol/L, 2 mol/L.
可选地，球形羟基磷灰石的成型方法包括以下步骤：Optionally, the molding method of spherical hydroxyapatite includes the following steps:
(1)将含有钙离子的水溶液和含有磷酸根的水溶液在碱性环境中搅拌混合均匀，静置陈化，过滤后得到沉淀物，直接将沉淀物分散到去离子水中得到羟基磷灰石悬浊液；(1) Stir and mix the aqueous solution containing calcium ions and the aqueous solution containing phosphate radicals in an alkaline environment, let stand and age, and obtain a precipitate after filtration. Disperse the precipitate directly into deionized water to obtain hydroxyapatite suspension Turbid liquid
(2)将羟基磷灰石悬浊液与可溶性海藻酸盐的水溶液充分混合制成混浮浆料；(2) The hydroxyapatite suspension and the aqueous solution of soluble alginate are fully mixed to make a floating slurry;
(3)将混浮浆料滴入到金属盐溶液中，形成凝胶球；(3) Drop the mixed slurry into the metal salt solution to form a gel ball;
(4)将凝胶球老化后取出，用去离子水洗涤，干燥，焙烧后制 得球形羟基磷灰石。(4) Take out the gel spheres after aging, wash with deionized water, dry, and calcinate to obtain spherical hydroxyapatite.
可选地，所述含有钙离子的水溶液包括氯化钙水溶液、硝酸钙水溶液、氢氧化钙水溶液中的任一种；Optionally, the aqueous solution containing calcium ions includes any one of calcium chloride aqueous solution, calcium nitrate aqueous solution, and calcium hydroxide aqueous solution;
所述含有磷酸根的水溶液包括磷酸二氢铵水溶液、正磷酸铵水溶液中的任一种。The phosphate-containing aqueous solution includes any one of ammonium dihydrogen phosphate aqueous solution and ammonium orthophosphate aqueous solution.
可选地，在步骤(1)中，所述碱性环境的pH值为10～12；所述搅拌温度为80～100℃；搅拌时间为1～4h；陈化时间为10～24h。Optionally, in step (1), the pH of the alkaline environment is 10-12; the stirring temperature is 80-100°C; the stirring time is 1-4h; and the aging time is 10-24h.
可选地，在步骤(4)中，所述凝胶球老化时间为0.1～24h。Optionally, in step (4), the aging time of the gel ball is 0.1-24 hours.
具体地，在步骤S400中，凝胶球老化时间的上限选自1h、2h、10h、15h、24h；凝胶球老化时间的下限选自0.1h、1h、2h、10h、15h。Specifically, in step S400, the upper limit of the gel ball aging time is selected from 1h, 2h, 10h, 15h, 24h; the lower limit of the gel ball aging time is selected from 0.1h, 1h, 2h, 10h, 15h.
所述干燥的条件为：干燥温度20～150℃；干燥时间为0.5～48h。The drying conditions are: drying temperature 20-150°C; drying time 0.5-48h.
具体地，凝胶球老化后，用去离子水洗涤，干燥，干燥温度为20到150℃，时间为0.5到48小时。Specifically, after the aging of the gel ball, it is washed with deionized water and dried, and the drying temperature is 20 to 150° C., and the time is 0.5 to 48 hours.
所述焙烧的条件为：焙烧温度300～700℃；焙烧时间1～15h。The firing conditions are as follows: firing temperature 300～700℃; firing time 1～15h.
具体地，干燥后，开始焙烧，焙烧温度为300到700℃，时间为1到15小时。Specifically, after drying, firing is started at a firing temperature of 300 to 700°C for a time of 1 to 15 hours.
焙烧温度的上限独立地选自350℃、500℃、600℃、700℃；焙烧温度的下限独立地选自300℃、350℃、500℃、600℃。The upper limit of the calcination temperature is independently selected from 350°C, 500°C, 600°C, and 700°C; the lower limit of the calcination temperature is independently selected from 300°C, 350°C, 500°C, and 600°C.
焙烧时间的上限独立地选自2h、3h、15h；焙烧时间的下限独立地选自1h、2h、3h。The upper limit of the calcination time is independently selected from 2h, 3h, and 15h; the lower limit of the calcination time is independently selected from 1h, 2h, and 3h.
可选地，球形羟基磷灰石的成型方法包括以下步骤：Optionally, the molding method of spherical hydroxyapatite includes the following steps:
(1)将氯化钙水溶液和磷酸二氢铵水溶液在碱性环境中搅拌混合均匀，静置陈化，过滤后得到沉淀物，直接将沉淀物分散到去离子水中得到羟基磷灰石悬浊液；(1) The calcium chloride aqueous solution and the ammonium dihydrogen phosphate aqueous solution are stirred and mixed in an alkaline environment, allowed to stand and age, and the precipitate is obtained after filtration, and the precipitate is directly dispersed into deionized water to obtain hydroxyapatite suspension liquid;
(2)将羟基磷灰石悬浊液与可溶性海藻酸盐的水溶液充分混合制成混浮浆料；(2) The hydroxyapatite suspension and the aqueous solution of soluble alginate are fully mixed to make a floating slurry;
(3)将混浮浆料滴入到金属盐溶液中，形成凝胶球；(3) Drop the mixed slurry into the metal salt solution to form a gel ball;
(4)将凝胶球老化后取出，用去离子水洗涤，干燥，焙烧后制得球形羟基磷灰石。(4) Take out the gel ball after aging, wash it with deionized water, dry it, and prepare spherical hydroxyapatite after roasting.
下面介绍一种可能的球形羟基磷灰石的成型方法的制备方法，具体步骤为：The following describes a preparation method of a possible spherical hydroxyapatite molding method. The specific steps are:
(1)将氯化钙和磷酸二氢铵配置成水溶液，按照摩尔比Ca/P＝1.67将二者搅拌混合均匀，混合过程中加入氨水调节PH值至10～12；继续在80～100℃下，搅拌1～4小时后静置陈化，陈化时间为10～24小时；过滤后得到沉淀物，直接将沉淀物分散到去离子水中得到羟基磷灰石悬浊液；(1) Dispose calcium chloride and ammonium dihydrogen phosphate into an aqueous solution, stir and mix the two according to the molar ratio Ca/P=1.67, add ammonia to adjust the PH value to 10-12 during the mixing process; continue at 80-100℃ Under stirring, after 1 to 4 hours of stirring, let stand and age for 10 to 24 hours; after filtration, a precipitate is obtained, and the precipitate is directly dispersed in deionized water to obtain a hydroxyapatite suspension;
(2)将羟基磷灰石与可溶性海藻酸盐的水溶液充分混合制成混浮浆料；(2) The hydroxyapatite and soluble alginate aqueous solution are thoroughly mixed to make a floating slurry;
(3)将混浮浆料滴入到金属盐的溶液中，形成凝胶球；(3) Drop the mixed slurry into the metal salt solution to form a gel ball;
(4)将凝胶球老化后取出，用去离子水洗涤，干燥，焙烧后制得球形羟基磷灰石。(4) Take out the gel ball after aging, wash it with deionized water, dry it, and prepare spherical hydroxyapatite after roasting.
根据本申请的另一方面，还提供了一种球形羟基磷灰石，该球形羟基磷灰石通过上述任一项所述的成型方法得到。According to another aspect of the present application, there is also provided a spherical hydroxyapatite obtained by the molding method described in any one of the above.
可选地，所述球形羟基磷灰石的直径为1～5mm。Optionally, the diameter of the spherical hydroxyapatite is 1 to 5 mm.
具体地，球形羟基磷灰石的直径的上限独立地为2mm、2.5mm、5mm；球形羟基磷灰石的直径的下限为独立地为1mm、2mm、2.5mm。Specifically, the upper limit of the diameter of the spherical hydroxyapatite is independently 2 mm, 2.5 mm, and 5 mm; the lower limit of the diameter of the spherical hydroxyapatite is independently 1 mm, 2 mm, and 2.5 mm.
可选地，所述球形羟基磷灰石含有多孔结构，平均孔径为2-10nm,总孔容为0.1-1cm 3/g，比表面积为80-200㎡/g。 Optionally, the spherical hydroxyapatite contains a porous structure, the average pore diameter is 2-10 nm, the total pore volume is 0.1-1 cm 3 /g, and the specific surface area is 80-200 m 2 /g.
根据本申请的又一方面，还提供了上述任一项所述的成型方法得到的球形羟基磷灰石和/或上述所述的球形羟基磷灰石在催化剂领域、吸附分离材料领域或生物工程领域中的应用。According to yet another aspect of the present application, there is also provided spherical hydroxyapatite obtained by the molding method described above and/or the spherical hydroxyapatite described above in the field of catalysts, adsorption separation materials or bioengineering Application in the field.
本申请提供一种海藻酸钠辅助球形羟基磷灰石的成型方法。先通过沉淀法制得羟基磷灰石沉淀物，然后将羟基磷灰石沉淀物溶于水中分散得到悬浮液，将海藻酸盐水溶液与羟基磷灰石悬浮液混合成混浮浆料，再把混浮浆料滴入到多价金属离子的溶液中，羟基磷灰石凝固成凝胶球，经干燥焙烧后得到球形的羟基磷灰石。The present application provides a method for forming spherical hydroxyapatite assisted by sodium alginate. The hydroxyapatite precipitate is prepared by the precipitation method, and then the hydroxyapatite precipitate is dissolved in water and dispersed to obtain a suspension. The alginate aqueous solution and the hydroxyapatite suspension are mixed to form a floating slurry, and then mixed The floating slurry is dropped into a solution of multivalent metal ions, and the hydroxyapatite solidifies into a gel ball, and after drying and roasting, a spherical hydroxyapatite is obtained.
本申请能产生的有益效果包括：The beneficial effects of this application include:
1)本申请所提供的球形羟基磷灰石的成型方法，该方法利用可溶性海藻酸盐辅助球形羟基磷灰石成型，可以大大提高羟基磷灰石球的机械强度，解决了羟基磷灰石本身很脆，不易成型的问题，而且保留了羟基磷灰石高吸附性能、多孔结构的特点。1) The method for forming spherical hydroxyapatite provided by this application, which uses soluble alginate to assist the formation of spherical hydroxyapatite, can greatly improve the mechanical strength of the hydroxyapatite ball, and solves the problem of the hydroxyapatite itself It is very brittle and difficult to form, and retains the characteristics of hydroxyapatite with high adsorption performance and porous structure.
2)本申请所提供的球形羟基磷灰石的成型方法，在羟基磷灰石的制备过程中沉淀物过滤后无需洗涤，直接溶于去离子水中配成悬浊液。因为滤饼中的杂质主要为氨水和氯化铵，在后续加热焙烧处理时可以直接挥发，因此解决了当沉淀量比较大时，过滤洗涤滤饼较厚过滤非常慢的问题。2) In the method for forming spherical hydroxyapatite provided in this application, during the preparation of hydroxyapatite, the precipitate is filtered without washing, and is directly dissolved in deionized water to prepare a suspension. Because the impurities in the filter cake are mainly ammonia and ammonium chloride, they can be directly volatilized during the subsequent heating and roasting treatment. Therefore, when the precipitation amount is relatively large, the problem that the filter cake is thick and the filter is filtered is very slow.
3)本申请所提供的球形羟基磷灰石的成型方法，通过滴球成型的方法，得到直径1-5mm的羟基磷灰石球，该过程简单可控，通过控制滴孔的大小，得到不同粒径的球。3) The molding method of spherical hydroxyapatite provided in this application can obtain hydroxyapatite balls with a diameter of 1-5mm through the method of drop ball molding. The process is simple and controllable. By controlling the size of the drop hole, different Ball of particle size.
4)本申请所提供的球形羟基磷灰石，球球形度高、粒径大小均匀、强度大，可用作制备催化剂的载体或直接作为催化剂、吸附材料、分离材料，广泛应用于催化反应的催化剂或载体、吸附分离材料或生物工程等领域。4) The spherical hydroxyapatite provided in this application has high spherical sphericity, uniform particle size, and high strength. It can be used as a carrier for preparing catalysts or directly as a catalyst, adsorption material, and separation material. It is widely used in catalytic reactions. Catalysts or carriers, adsorption separation materials or bioengineering and other fields.
附图说明BRIEF DESCRIPTION
图1为本申请中实施例1得到球形羟基磷灰石的照片。Figure 1 is a photograph of spherical hydroxyapatite obtained in Example 1 of this application.
图2为本申请中实施例2得到球形羟基磷灰石的照片。2 is a photograph of spherical hydroxyapatite obtained in Example 2 of this application.
图3为本申请中实施例3得到球形羟基磷灰石的照片。FIG. 3 is a photograph of spherical hydroxyapatite obtained in Example 3 of the present application.
图4为本申请中实施例1中的球形羟基磷灰石在STP条件下的吸脱附等温线图。FIG. 4 is an isotherm diagram of adsorption and desorption of spherical hydroxyapatite in Example 1 of the present application under STP conditions.
具体实施方式detailed description
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.
如无特别说明，本申请的实施例中的原料均通过商业途径购买。Unless otherwise specified, the raw materials in the examples of this application are purchased through commercial channels.
实施例1Example 1
取无水氯化钙74.8g与磷酸二氢铵52.8g分别溶于1600mL水中，机械搅拌下将氯化钙溶液和磷酸二氢铵溶液混合，并用氨水将溶液pH值调至10.4。继续搅拌15min，放入90℃水浴锅中继续搅拌加热2h，室温冷却静置老化12小时，将得到的沉淀用布氏漏斗减压过滤。取沉淀6.69g溶于15.61g去离子水中，得到22.3g质量分数30％的羟基磷灰石悬浊液。Dissolve 74.8 g of anhydrous calcium chloride and 52.8 g of ammonium dihydrogen phosphate in 1600 mL of water, mix the calcium chloride solution and the ammonium dihydrogen phosphate solution under mechanical stirring, and adjust the pH of the solution to 10.4 with ammonia water. Stirring was continued for 15 min, placed in a 90°C water bath and stirred and heated for 2 h, cooled at room temperature and allowed to stand for aging for 12 hours. The resulting precipitate was filtered under reduced pressure using a Buchner funnel. Take 6.69 g of the precipitate and dissolve in 15.61 g of deionized water to obtain 22.3 g of 30% hydroxyapatite suspension.
将22.3g羟基磷灰石悬浊液加入20g 3％的海藻酸钠溶液，用磁力搅拌分散30min，得到含有羟基磷灰石的混浮浆料，羟基磷灰石在混浮浆料中的质量分数为15.8wt％，海藻酸钠在混浮浆料中的质量分数为1.4wt％。Add 22.3g of hydroxyapatite suspension to 20g of 3% sodium alginate solution, and stir and disperse with magnetic force for 30min to obtain a floating slurry containing hydroxyapatite. The quality of hydroxyapatite in the floating slurry The fraction is 15.8 wt%, and the mass fraction of sodium alginate in the floating slurry is 1.4 wt%.
取上述悬浮液滴入到300mL 0.2M的硝酸钙水溶液中(混浮浆料与金属盐溶液的体积比为0.1)，在硝酸钙溶液中老化2h后，取出室温下25℃干燥48h，600℃焙烧2h，得到球形羟基磷灰石。Take the above suspension droplets into 300mL 0.2M calcium nitrate aqueous solution (the volume ratio of the floating slurry to the metal salt solution is 0.1), after aging in the calcium nitrate solution for 2h, take it out at room temperature and dry at 25℃ for 48h, 600℃ After calcination for 2h, spherical hydroxyapatite was obtained.
实物照片见图1，由图1可以看出，小球外表面光滑，呈圆球状，粒径大小均一，直径2mm。The physical picture is shown in Figure 1. As can be seen from Figure 1, the outer surface of the ball is smooth and spherical, with a uniform particle size and a diameter of 2mm.
机械强度采用DLIII-500型强度测定仪测定机械强度，平均机械强度可以达到152N/颗。Mechanical strength is measured by DLIII-500 type strength tester. The average mechanical strength can reach 152N/piece.
实施例2Example 2
羟基磷灰石制备步骤同实施例1，不同之处在于：The preparation steps of hydroxyapatite are the same as in Example 1, except that:
取8g羟基磷灰石悬浊液加入到40g 1％的海藻酸钠溶液，搅拌分散30min，得到含有羟基磷灰石的混浮浆料；羟基磷灰石在混浮浆料中的质量分数为5wt％，海藻酸钠在混浮浆料中的质量分数为0.8wt％。Add 8g of hydroxyapatite suspension to 40g of 1% sodium alginate solution, stir and disperse for 30min to obtain a mixed floating slurry containing hydroxyapatite; the mass fraction of hydroxyapatite in the mixed floating slurry is 5wt%, the mass fraction of sodium alginate in the floating slurry is 0.8wt%.
取上述混浮浆料用滴入到300ml 0.5M的硝酸钙溶液中(混浮浆料与金属盐溶液的体积比为10)，在硝酸钙溶液中老化10h后，取出室温下60℃干燥24h，500℃焙烧3h，得到球形羟基磷灰石。Take the above floating slurry into 300ml 0.5M calcium nitrate solution (volume ratio of mixed floating slurry to metal salt solution is 10), after aging in calcium nitrate solution for 10h, take it out at room temperature and dry at 60℃ for 24h , Calcined at 500℃ for 3h to obtain spherical hydroxyapatite.
实物照片见图2，由图2可以看出，小球外表面光滑，呈圆球状，粒径大小均一，直径2.5mm。The physical picture is shown in Figure 2. As can be seen from Figure 2, the outer surface of the ball is smooth and spherical, with a uniform particle size and a diameter of 2.5mm.
机械强度采用DLIII-500型强度测定仪测定机械强度，平均机械 强度可以达到148N/颗。Mechanical strength is measured by DLIII-500 type strength tester. The average mechanical strength can reach 148N/piece.
实施例3Example 3
羟基磷灰石制备步骤同实施例1，不同之处在于：The preparation steps of hydroxyapatite are the same as in Example 1, except that:
取6g羟基磷灰石悬浊液加入到30g 2％的海藻酸钠溶液，搅拌分散180min，得到羟基磷灰石的混浮浆料，羟基磷灰石在混浮浆料中的质量分数为5wt％，海藻酸钠在混浮浆料中的质量分数为1.7wt％。Take 6g of hydroxyapatite suspension and add it to 30g of 2% sodium alginate solution, stir and disperse for 180min to obtain a mixed floating slurry of hydroxyapatite. The mass fraction of hydroxyapatite in the mixed slurry is 5wt %, the mass fraction of sodium alginate in the floating slurry is 1.7% by weight.
取上述混浮浆料用滴入到300mL 2M的硝酸钙溶液中(混浮浆料与金属盐溶液的体积比为2)，在硝酸钙溶液中老化1h后，取出室温下120℃干燥8h，700℃焙烧1h，得到球形羟基磷灰石。Take the above floating slurry into 300mL 2M calcium nitrate solution (the volume ratio of floating slurry to metal salt solution is 2), after aging in calcium nitrate solution for 1h, take it out at room temperature and dry at 120℃ for 8h. Sintered at 700℃ for 1h to obtain spherical hydroxyapatite.
实物照片如图3，由图3可以看出，小球外表面光滑，小颗粒呈圆球状，大颗粒呈椭圆球状，直径为2～5mm。The physical picture is shown in Figure 3. It can be seen from Figure 3 that the outer surface of the small ball is smooth, the small particles are spherical, and the large particles are elliptical, with a diameter of 2 to 5 mm.
机械强度采用DLIII-500型强度测定仪测定机械强度，平均机械强度可以达到162N/颗。Mechanical strength is measured by DLIII-500 type strength tester, and the average mechanical strength can reach 162N/piece.
实施例4Example 4
羟基磷灰石制备步骤同实施例1，不同之处在在于：The preparation steps of hydroxyapatite are the same as in Example 1, except that:
取22.3g30％羟基磷灰石悬浊液，加入20g3％的海藻酸铵溶液，用磁力搅拌分散30min，得到羟基磷灰石的混浮浆料；羟基磷灰石在混浮浆料中的质量分数为15.8wt％，海藻酸铵在混浮浆料中的质量分数为1.4wt％。Take 22.3g of 30% hydroxyapatite suspension, add 20g of 3% ammonium alginate solution, and disperse with magnetic stirring for 30min to obtain a mixed floating slurry of hydroxyapatite; the quality of hydroxyapatite in the mixed slurry The fraction is 15.8% by weight, and the mass fraction of ammonium alginate in the floating slurry is 1.4% by weight.
取上述混浮浆料滴入到200mL 0.1M的硝酸钡水溶液中，在硝酸钡溶液中老化15h后，取出室温下80℃干燥12h，600℃焙烧2h，得到钡掺杂的球形羟基磷灰石。Take the above mixed floating slurry into 200mL 0.1M barium nitrate aqueous solution, after aging in barium nitrate solution for 15h, take it out at room temperature and dry at 80℃ for 12h, roast at 600℃ for 2h to obtain barium doped spherical hydroxyapatite .
实施例5Example 5
羟基磷灰石制备步骤同实施例1，不同之处在在于：The preparation steps of hydroxyapatite are the same as in Example 1, except that:
取8g羟基磷灰石悬浊液加入到40g1％的海藻酸钠溶液，搅拌分 散30min，得到羟基磷灰石的混浮浆料。8g of hydroxyapatite suspension was added to 40g of 1% sodium alginate solution, and the mixture was stirred and dispersed for 30 minutes to obtain a mixed floating slurry of hydroxyapatite.
取上述混浮浆料用滴入到300mL 0.5M的硫酸铜溶液中，在硫酸铜溶液中老化10h后，取出室温下60℃干燥36h，350℃焙烧15h，得到铜掺杂的球形羟基磷灰石。Take the above mixed floating slurry and drop it into 300mL 0.5M copper sulfate solution, after aging in copper sulfate solution for 10h, take it out at room temperature, dry at 60℃ for 36h, and bake at 350℃ for 15h to obtain copper-doped spherical hydroxyapatite stone.
实施例6Example 6
羟基磷灰石制备步骤同实施例1，不同之处在于：取上述悬浮液用滴入到300mL 0.01M的硝酸铁溶液中。The preparation procedure of hydroxyapatite is the same as that of Example 1, except that the above suspension is taken dropwise into 300 mL of 0.01 M ferric nitrate solution.
实施例7～9Examples 7-9
羟基磷灰石制备步骤同实施例1，不同之处在于见表1。The preparation steps of hydroxyapatite are the same as those in Example 1, except that Table 1 shows the difference.
表1Table 1
Figure PCTCN2019129225-appb-000001
Figure PCTCN2019129225-appb-000001
实施例10～11Examples 10 to 11
羟基磷灰石制备步骤同实施例1，不同之处在于见表2。The preparation steps of hydroxyapatite are the same as in Example 1, except that Table 2 shows the difference.
表2Table 2
Figure PCTCN2019129225-appb-000002
Figure PCTCN2019129225-appb-000002
Figure PCTCN2019129225-appb-000003
Figure PCTCN2019129225-appb-000003
实施例13Example 13
利用Quadrasorb evoTM全自动比表面和孔隙度分析仪分别对实施例1至11中的样品进行进行测试，测试结果表明，球形羟基磷灰石含有多孔结构，平均孔径为2-10nm,总孔容为0.1-1cm 3/g，比表面积为80-200㎡/g。 The samples in Examples 1 to 11 were tested using Quadrasorb evoTM automatic specific surface and porosity analyzers respectively. The test results show that the spherical hydroxyapatite contains a porous structure with an average pore size of 2-10 nm and a total pore volume of 0.1-1cm 3 /g, specific surface area is 80-200㎡/g.
实施例1中的样品的测试结果为：比表面积为158㎡/g，平均孔径为5.4nm，孔容为0.36cm 3/g； The test results of the sample in Example 1 are as follows: the specific surface area is 158 m 2 /g, the average pore diameter is 5.4 nm, and the pore volume is 0.36 cm 3 /g;
实施例2中的样品的测试结果为：比表面积为110㎡/g，平均孔径为4.8nm，孔容为0.26cm 3/g； The test results of the sample in Example 2 are as follows: specific surface area is 110 m 2 /g, average pore diameter is 4.8 nm, and pore volume is 0.26 cm 3 /g;
实施例3中的样品的测试结果为：比表面积为138㎡/g，平均孔径为5.6nm，孔容为0.24cm 3/g； The test results of the sample in Example 3 are as follows: the specific surface area is 138 m 2 /g, the average pore diameter is 5.6 nm, and the pore volume is 0.24 cm 3 /g;
以实施例1中的样品为典型代表，图4为样品的吸脱附等温线图，由该图可以看出该样品为介孔结构，比表面积为158㎡/g。Taking the sample in Example 1 as a typical representative, FIG. 4 is the absorption-desorption isotherm diagram of the sample. From this figure, it can be seen that the sample has a mesoporous structure and a specific surface area of 158 m 2 /g.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few examples of this application, and are not intended to limit this application in any way. Although this application is disclosed in the above with preferred embodiments, it is not intended to limit this application. Any person skilled in the art, Without departing from the scope of the technical solution of the present application, making slight changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case and belongs to the scope of the technical solution.

Claims (18)

  1. 一种球形羟基磷灰石的成型方法，其特征在于，至少包括以下步骤：A molding method of spherical hydroxyapatite, characterized in that it includes at least the following steps:
    S100、获得羟基磷灰石悬浊液；S100. Obtain a hydroxyapatite suspension;
    S200、获得含有所述羟基磷灰石悬浊液与可溶性海藻酸盐的混浮浆料；S200. Obtain a floating slurry containing the hydroxyapatite suspension and soluble alginate;
    S300、将所述混浮浆料与金属盐溶液混合，得到凝胶球；S300. Mix the mixed-floating slurry with a metal salt solution to obtain a gel ball;
    S400、将所述凝胶球经老化、焙烧，得到球形羟基磷灰石。S400. After aging and roasting the gel balls, spherical hydroxyapatite is obtained.
  2. 根据权利要求1所述的成型方法，其特征在于，所述步骤S100包括：The molding method according to claim 1, wherein the step S100 includes:
    将含有钙离子的水溶液和含有磷酸根的水溶液混合，得到沉淀物，直接将所述沉淀物分散到水中，得到所述羟基磷灰石悬浊液。An aqueous solution containing calcium ions and an aqueous solution containing phosphate groups are mixed to obtain a precipitate, and the precipitate is directly dispersed in water to obtain the hydroxyapatite suspension.
  3. 根据权利要求2所述的成型方法，其特征在于，在所述含有钙离子的水溶液中，Ca 2+摩尔浓度为0.1～0.5mol/L； The molding method according to claim 2, characterized in that, in the calcium ion-containing aqueous solution, the Ca 2+ molar concentration is 0.1 to 0.5 mol/L;
    在所述含有磷酸根的水溶液中，PO 4 3-摩尔浓度为0.05～0.3mol/L； In the phosphate-containing aqueous solution, the PO 4 3- molar concentration is 0.05 to 0.3 mol/L;
    所述含有钙离子的水溶液与所述含有磷酸根的水溶液按照摩尔比Ca/P＝1.67的比例混合。The calcium ion-containing aqueous solution and the phosphate-containing aqueous solution are mixed in a molar ratio Ca/P=1.67.
  4. 根据权利要求1所述的成型方法，其特征在于，在步骤S100中，所述羟基磷灰石在悬浊液中的质量分数为25～35wt％。The molding method according to claim 1, wherein in step S100, the mass fraction of the hydroxyapatite in the suspension is 25 to 35 wt%.
  5. 根据权利要求1所述的成型方法，其特征在于，在步骤S200中，所述可溶性海藻酸盐包括海藻酸钠、海藻酸钾、海藻酸铵、海藻酸锂、海藻酸镁中的至少一种。The molding method according to claim 1, wherein in step S200, the soluble alginate comprises at least one of sodium alginate, potassium alginate, ammonium alginate, lithium alginate, and magnesium alginate .
  6. 根据权利要求1所述的成型方法，其特征在于，在步骤S200中，所述羟基磷灰石在所述混浮浆料中的质量分数为 0.5～25wt％；The molding method according to claim 1, characterized in that, in step S200, the mass fraction of the hydroxyapatite in the mixed floating slurry is 0.5-25 wt%;
    所述可溶性海藻酸盐在所述混浮浆料中的质量分数为0.05～4wt％。The mass fraction of the soluble alginate in the mixed floating slurry is 0.05-4 wt%.
  7. 根据权利要求1所述的成型方法，其特征在于，所述步骤S300包括：将所述混浮浆料滴入到金属盐溶液中，形成凝胶球。The molding method according to claim 1, wherein the step S300 comprises: dropping the mixed floating slurry into a metal salt solution to form a gel ball.
  8. 根据权利要求7所述的成型方法，其特征在于，所述混浮浆料与金属盐溶液的体积比为0.1-10。The molding method according to claim 7, wherein the volume ratio of the mixed floating slurry to the metal salt solution is 0.1-10.
  9. 根据权利要求1所述的成型方法，其特征在于，在步骤S300中，所述金属盐中含有金属阳离子；The molding method according to claim 1, wherein in step S300, the metal salt contains a metal cation;
    所述金属阳离子包括钙离子、锶离子、钡离子、铁离子、钴离子、镍离子、锰离子、铜离子、锌离子、铝离子中至少一种。The metal cation includes at least one of calcium ion, strontium ion, barium ion, iron ion, cobalt ion, nickel ion, manganese ion, copper ion, zinc ion, and aluminum ion.
  10. 根据权利要求9所述的成型方法，其特征在于，在所述金属盐溶液中，金属阳离子的物质的量的浓度为0.01～3mol/L。The molding method according to claim 9, wherein the concentration of the amount of the metal cation substance in the metal salt solution is 0.01 to 3 mol/L.
  11. 根据权利要求1所述的成型方法，其特征在于，包括以下步骤：The molding method according to claim 1, comprising the following steps:
    (1)将含有钙离子的水溶液和含有磷酸根的水溶液在碱性环境中搅拌混合均匀，静置陈化，过滤后得到沉淀物，直接将沉淀物分散到去离子水中得到羟基磷灰石悬浊液；(1) Stir and mix the aqueous solution containing calcium ions and the aqueous solution containing phosphate radicals in an alkaline environment, let stand and age, and obtain a precipitate after filtration. Disperse the precipitate directly into deionized water to obtain hydroxyapatite suspension Turbid liquid
    (2)将羟基磷灰石悬浊液与可溶性海藻酸盐的水溶液充分混合制成混浮浆料；(2) The hydroxyapatite suspension and the aqueous solution of soluble alginate are fully mixed to make a floating slurry;
    (3)将混浮浆料滴入到金属盐溶液中，形成凝胶球；(3) Drop the mixed slurry into the metal salt solution to form a gel ball;
    (4)将凝胶球老化后取出，用去离子水洗涤，干燥，焙烧后制得球形羟基磷灰石。(4) Take out the gel ball after aging, wash it with deionized water, dry it, and prepare spherical hydroxyapatite after roasting.
  12. 根据权利要求11所述的成型方法，其特征在于，所述含有 钙离子的水溶液包括氯化钙水溶液、硝酸钙水溶液、氢氧化钙水溶液中的任一种；The molding method according to claim 11, wherein the aqueous solution containing calcium ions includes any one of an aqueous calcium chloride solution, an aqueous calcium nitrate solution, and an aqueous calcium hydroxide solution;
    所述含有磷酸根的水溶液包括磷酸二氢铵水溶液、正磷酸铵水溶液中的任一种。The phosphate-containing aqueous solution includes any one of ammonium dihydrogen phosphate aqueous solution and ammonium orthophosphate aqueous solution.
  13. 根据权利要求11所述的成型方法，其特征在于，在步骤(1)中，所述碱性环境的pH值为10～12；所述搅拌温度为80～100℃；搅拌时间为1～4h；陈化时间为10～24h。The molding method according to claim 11, characterized in that in step (1), the pH value of the alkaline environment is 10-12; the stirring temperature is 80-100°C; and the stirring time is 1-4h ; The aging time is 10 ~ 24h.
  14. 根据权利要求11所述的成型方法，其特征在于，在步骤(4)中，所述凝胶球老化时间为0.1～24；The molding method according to claim 11, characterized in that, in step (4), the aging time of the gel ball is 0.1 to 24;
    所述干燥的条件为：干燥温度20～150℃；干燥时间为0.5～48h；The drying conditions are: drying temperature 20-150°C; drying time 0.5-48h;
    所述焙烧的条件为：焙烧温度300～700℃；焙烧时间1～15h。The firing conditions are as follows: firing temperature 300～700℃; firing time 1～15h.
  15. 一种球形羟基磷灰石，其特征在于，所述球形羟基磷灰石通过权利要求1至14任一项所述的成型方法得到。A spherical hydroxyapatite, characterized in that the spherical hydroxyapatite is obtained by the molding method according to any one of claims 1 to 14.
  16. 根据权利要求15所述的球形羟基磷灰石，其特征在于，所述球形羟基磷灰石的直径为1～5mm。The spherical hydroxyapatite according to claim 15, wherein the diameter of the spherical hydroxyapatite is 1 to 5 mm.
  17. 根据权利要求15所述的球形羟基磷灰石，其特征在于，所述球形羟基磷灰石含有多孔结构，平均孔径为2～10nm，总孔容为0.1～1cm 3/g，比表面积为80～200m 2/g。 The spherical hydroxyapatite according to claim 15, wherein the spherical hydroxyapatite has a porous structure, an average pore diameter of 2 to 10 nm, a total pore volume of 0.1 to 1 cm 3 /g, and a specific surface area of 80 ~200m 2 /g.
  18. 权利要求1至14任一项所述的成型方法得到的球形羟基磷灰石和/或权利要求15至17任一项所述的球形羟基磷灰石在催化剂领域、吸附分离材料领域或生物工程领域中的应用。The spherical hydroxyapatite obtained by the molding method according to any one of claims 1 to 14 and/or the spherical hydroxyapatite according to any one of claims 15 to 17 in the field of catalysts, adsorption separation materials, or bioengineering Application in the field.
PCT/CN2019/129225 2018-12-27 2019-12-27 Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof WO2020135720A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811608743.1A CN111375432B (en) 2018-12-27 2018-12-27 Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof
CN201811608743.1 2018-12-27

Publications (1)

Publication Number Publication Date
WO2020135720A1 true WO2020135720A1 (en) 2020-07-02

Family

ID=71128728

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/129225 WO2020135720A1 (en) 2018-12-27 2019-12-27 Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof

Country Status (2)

Country Link
CN (1) CN111375432B (en)
WO (1) WO2020135720A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121581A (en) * 2020-09-23 2020-12-25 苏州云式环境科技有限公司 Industrial tail gas treatment system
CN112403470B (en) * 2020-11-25 2023-07-14 陕西榆大科技发展有限公司 Catalyst for preparing synthetic gas by reforming methane and carbon dioxide and application thereof
CN113145176B (en) * 2021-05-07 2023-06-30 中国平煤神马能源化工集团有限责任公司 Cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof
CN113952970A (en) * 2021-11-10 2022-01-21 中国科学院山西煤炭化学研究所 Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof
CN114471636A (en) * 2022-01-13 2022-05-13 南京师范大学 Preparation method and application of supported nickel-based catalyst
CN115518652A (en) * 2022-06-13 2022-12-27 安徽理工大学 Silicon-cerium composite microporous material packaged metal catalyst and preparation method and application thereof
CN115350718A (en) * 2022-08-06 2022-11-18 南京师范大学 Method for preparing second-generation biodiesel by using Ni-Fe/HAP catalytic grease hydrogenation
CN116273090A (en) * 2022-12-29 2023-06-23 广西大学 Preparation method and application of methane dry reforming catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006199810A (en) * 2005-01-20 2006-08-03 Yokohama National Univ Composite particle and method for producing the same
CN102020777A (en) * 2010-11-29 2011-04-20 同济大学 Method for preparing nano hydroxyl apatite calcium alginate injectable hydrogel and application thereof
CN102718241A (en) * 2012-06-28 2012-10-10 天津大学 Method for preparing spherical alumina particles by alginic acid auxiliary forming method
CN104477953A (en) * 2014-11-12 2015-04-01 中国海洋石油总公司 Spherical alumina shaping method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106694015B (en) * 2016-11-17 2018-01-12 陕西师范大学 High dispersive nickel oxygen cluster modifies the simple preparation method of carbonitride hydrogen production by water decomposition photochemical catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006199810A (en) * 2005-01-20 2006-08-03 Yokohama National Univ Composite particle and method for producing the same
CN102020777A (en) * 2010-11-29 2011-04-20 同济大学 Method for preparing nano hydroxyl apatite calcium alginate injectable hydrogel and application thereof
CN102718241A (en) * 2012-06-28 2012-10-10 天津大学 Method for preparing spherical alumina particles by alginic acid auxiliary forming method
CN104477953A (en) * 2014-11-12 2015-04-01 中国海洋石油总公司 Spherical alumina shaping method

Also Published As

Publication number Publication date
CN111375432B (en) 2023-03-28
CN111375432A (en) 2020-07-07

Similar Documents

Publication Publication Date Title
WO2020135720A1 (en) Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof
CN111217598B (en) Hydroxyapatite forming method, hydroxyapatite and application
JP7036924B2 (en) High-voltage lithium nickel cobalt manganese oxide precursor and its manufacturing method, and high voltage lithium nickel cobalt manganese oxide positive electrode material manufacturing method
CN107376827B (en) Zirconium dioxide coated manganese lithium ion sieve and preparation method and application thereof
CN102702518B (en) Method for preparing composite material of stannic oxide/polyaniline
RU2336946C2 (en) Sorbent for heavy metals, method of its production and method of water purification
WO2024027044A1 (en) Preparation method for high-adsorption-capacity granular aluminum salt lithium extraction adsorbent
Ryu et al. Lithium ion adsorption characteristics of porous Li1. 33Mn1. 67O4 adsorbent prepared using petroleum-based pitch as a binder
CN106167270A (en) A kind of preparation method of mesoporous θ aluminium oxide ball type carrier
CN115301196A (en) Titanium-doped modified manganese-based lithium ion sieve and preparation method thereof
CN101973538A (en) Method for preparing iron phosphate
CN114698646A (en) Preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder
CN116654967B (en) Preparation method of spherical nano barium carbonate easy for solid-liquid separation
CN107986253B (en) Ball shape ferric phosphate and its preparation method and application
WO2023083062A1 (en) Method for preparing titanium-based lithium ion exchanger
JP6835319B2 (en) Adsorbent carrier
CN116159531A (en) Preparation method of hollow fiber membrane lithium ion adsorbent
CN112275258B (en) Rare earth modified aluminum-based adsorbent and preparation method and application thereof
Wang et al. Electrochemical properties and controlled-synthesis of hierarchical β-Ni (OH) 2 micro-flowers and hollow microspheres
CN105366700A (en) Method for synthesizing petal-shaped magnesium-aluminum spinel nano empty sphere with high specific surface
CN104058468A (en) Compact spherical cobalt oxide and preparation method thereof
JP4721979B2 (en) Anion adsorbent and method for producing the same
CN104399426A (en) Production method of aluminum-doped hydroxyapatite defluorinating filter material
CN105006550A (en) Nanocrystalline iron oxide coating stereoplasm carbon microsphere composite material and preparing method and application thereof
CN103466582A (en) High-activity nanoscale iron phosphate and synthesis method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19903597

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19903597

Country of ref document: EP

Kind code of ref document: A1