WO2020135720A1 - Procédé de formation d'hydroxyapatite sphérique, hydroxyapatite sphérique et son utilisation - Google Patents

Procédé de formation d'hydroxyapatite sphérique, hydroxyapatite sphérique et son utilisation Download PDF

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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
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hydroxyapatite
molding method
aqueous solution
mixed
ion
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PCT/CN2019/129225
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Chinese (zh)
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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
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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
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Publication of WO2020135720A1 publication Critical patent/WO2020135720A1/fr

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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
    • 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.

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Abstract

L'invention concerne un procédé de formation d'hydroxyapatite sphérique, l'hydroxyapatite sphérique et son utilisation. Un procédé de formation d'hydroxyapatite sphérique comprend au moins les étapes suivantes : S100, l'obtention d'une suspension d'hydroxyapatite ; S200, l'obtention d'une bouillie mixte et en suspension contenant la suspension d'hydroxyapatite et un alginate soluble ; S300, le mélange de la bouillie mixte et en suspension avec une solution de sel métallique pour obtenir des sphères de gel ; et S400, le vieillissement et la torréfaction des sphères de gel pour obtenir une hydroxyapatite sphérique. Le procédé peut améliorer considérablement la résistance mécanique des sphères d'hydroxyapatite et présente un processus de préparation sûr, simple et pratique.
PCT/CN2019/129225 2018-12-27 2019-12-27 Procédé de formation d'hydroxyapatite sphérique, hydroxyapatite sphérique et son utilisation WO2020135720A1 (fr)

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