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WO2011091766A1 - Procédé pour préparer des particules micronisées modifiées - Google Patents

Procédé pour préparer des particules micronisées modifiées Download PDF

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Publication number
WO2011091766A1
WO2011091766A1 PCT/CN2011/070751 CN2011070751W WO2011091766A1 WO 2011091766 A1 WO2011091766 A1 WO 2011091766A1 CN 2011070751 W CN2011070751 W CN 2011070751W WO 2011091766 A1 WO2011091766 A1 WO 2011091766A1
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Prior art keywords
oxide
barium
hydroxide
phosphate
lead
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Chinese (zh)
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张颖
刘刚
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Priority claimed from CN201010103394A external-priority patent/CN101792167A/zh
Priority claimed from CN201010183854XA external-priority patent/CN101862273B/zh
Application filed by Individual filed Critical Individual
Priority to US13/575,963 priority Critical patent/US20130015398A1/en
Publication of WO2011091766A1 publication Critical patent/WO2011091766A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties

Definitions

  • the invention relates to the technical field of chemical industry, in particular to a preparation method of modified micronized particles.
  • the water-insoluble micronized particles tend to have a strong interaction between each other during the chemical reaction of nucleation and growth, so that the micronized particles can only have a particle size of several micrometers or even several micrometers in subsequent use.
  • the size distribution in the filled substrate has extremely poor monodispersity (secondary particle size), and there is a significant difference in application performance compared with micronized particle particles distributed in submicron or even nanometer order.
  • micro-particles of various materials are not well treated, or the modification is not good, it is not only difficult to uniformly disperse into the matrix material, but also tends to reduce the overall performance of the matrix material. Under microscopic observation, at this time, there is a gap region between the micronized particles and the matrix material, which shows an obvious two-phase separation phenomenon. This kind of example is hard to come by.
  • the surface modification effect of the particles is much more important than the particle size.
  • the modified micronized particles can be well dispersed into the parent material, water. But we know that when it comes to the final application, the properties of the parent material and water to which it is added often vary greatly, for example, plastics, fibers, and so on. In order to adapt to the changing parent material, only the modification is carried out at this time.
  • the enrichment of the above-mentioned micronized particles is extremely difficult in the conventional preparation process. Since the surface of the micronized particles is modified to a high degree of hydrophilicity by a small molecule dispersing agent, and the particles are small, it is difficult to be filtered, and it is difficult to separate the micronized particles from the reaction mother liquid, and there is a problem that the micronized particles are lost during the separation process.
  • the present invention provides a method for preparing modified micronized particles, which comprises the steps of: coprecipitation reaction between a freezing point and a boiling point of an aqueous solution in an aqueous solution to form a micronized particle or a micronized particle precursor Mixed precipitation of bulk and inorganic precipitates.
  • the mixed precipitate of the precipitated and inorganic precipitate of the micronized or micronized particle precursor is 0.1%-50%, most preferably 0.5%-10% in the mother liquor after the reaction; and the micronized or micronized
  • the mass ratio of the precipitation of the particle precursor to the inorganic precipitation is from 1000:1 to 1:100,000, and less preferably from 100:1 to 1:1000, most preferably from 10:1 to 1:100.
  • the coprecipitation reaction is carried out under conventional agitation or under high speed agitation/mixing/shearing/friction conditions, further under supergravity conditions.
  • the pH of the reaction solution is controlled at 3 to 14, most preferably 7-14.
  • the micronized or micronized particle precursor is an inorganic or organic substance that is poorly soluble in water and does not chemically react with water, and a mixture therebetween.
  • the inorganic substance is selected from the elemental substance, and further selected are zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, silver, antimony, palladium, Platinum, gold, carbon, silicon, tungsten, boron, antimony, selenium, sulfur or iodine, and mixtures thereof.
  • the inorganic substance is selected from the group consisting of hydroxides, and further selected are barium hydroxide, palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, Barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide, aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II , IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide,
  • the inorganic substance is selected from the group consisting of oxides, and further selected are cerium oxide, palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide. , cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), cerium oxide (III) , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, cerium oxide, chromium oxide, cobalt oxide, molybdenum oxide (III, IV
  • the inorganic substance is selected from the group consisting of inorganic salts, and further selected are barium arsenate, barium carbonate, barium chromate, barium ferrocyanide, barium fluorosilicate, barium fluoride, barium hydrogen phosphate, barium iodate, sulfuric acid.
  • the inorganic substance is selected from the group consisting of organic metal salts, and further selected are lanthanum, cerium, calcium, lithium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, magnesium, lanthanum, cerium, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, antimony, An optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylate of cobalt, nickel, molybdenum, tin, lead, copper, ruthenium, osmium, mercury, silver, ruthenium, palladium, platinum or gold ions.
  • the organic substance has at least one of the following elements:
  • the decomposition temperature is higher than its melting point
  • any liquid or liquid composition other than water is further selected to dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 °C.
  • the present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or a portion thereof to a water-soluble substance, and washing and concentrating the remaining precipitate.
  • the purifying agent is a water-soluble inorganic or organic acid, and may be selected from one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acetic acid or phosphoric acid, or a mixture thereof.
  • the present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or its after-swept body into a water-soluble substance, and washing and concentrating the remaining precipitate.
  • the invention further comprises: mixing/reacting the purified mixed precipitate with the surface modifier to obtain modified micronized particles.
  • the surface modifier refers to a compound capable of forming adsorption with the surface of the microparticles, including an anionic compound, a cationic compound, a nonionic surfactant, a water-insoluble organic liquid, a coupling agent, or a parent material to which it is added, and Their composition.
  • the average particle diameter d50 of the secondary particle diameter of the modified micronized particles is less than 10 ⁇ m, further preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm.
  • the present invention further comprises: in the presence of an inorganic precipitate in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, which can be converted into a water-soluble substance, and subjected to a precipitation reaction of the micronized particles or the micronized particle precursor.
  • the inorganic precipitate which can be converted into a water-soluble substance has a solubility of less than 1 gram per 100 grams of water at the reaction temperature, and is further selected to be less than 0.01 gram; and the cationic portion of the inorganic precipitate is selected from the group consisting of ruthenium, osmium, calcium, and lithium.
  • the anion portion of the inorganic precipitate is cyanide ion, halide ion, sulfuric acid (hydrogen) ion, nitrite ion, carbonic acid (hydrogen) ion, sulfuric acid (hydrogen) ion, Dichromate ion, phosphoric acid (hydrogen)
  • the surface active material is added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater.
  • a method for preparing modified micro-barium sulfate comprises the following steps:
  • the step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, removing the inorganic salt precipitate completely, and washing and concentrating the remaining precipitate.
  • the step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, partially removing the inorganic salt precipitate, and washing and concentrating the remaining precipitate.
  • the preparation method of the modified micronized particles of the present invention restricts the adhesion of the micronized particles during formation, growth and ripening by adding an inorganic precipitate which can be separated, and obtains particles having a desired micronized particle size. Moreover, such micronized or micronized particle precursor precipitated particles are easily separated from the reaction mother liquor under conventional equipment conditions. Next, selectively and different surface modifiers can be used to obtain modified micro-particles with excellent secondary particle size suitable for different materials and high specificity, and the secondary particle size can reach nano-scale distribution.
  • the present invention effectively overcomes the contradiction between the prior modification of the micro-particles of the modified micro-particles and the surface modification, and the difficulty in separating the micro-particles from the reaction mother liquid, and can conveniently obtain the performance and the fine change of the secondary particle size.
  • the micronized particles can realize the industrial production of nano-micronized particles.
  • the degree of removal of the inorganic precipitate of the present invention is elastic, and the inorganic precipitate can be removed, partially removed or completely removed according to the specific application and the type of inorganic precipitation, the application is flexible, and the application performance of the micro-particles can be enriched, and the time is saved.
  • a method for preparing a modified micronized particle of the present invention comprises the steps of: coprecipitating a reaction between a freezing point and a boiling point of a reaction mother liquid in an aqueous solution to form a mixed precipitate of a micronized particle or a micronized particle precursor and an inorganic precipitate.
  • a purifying agent is added to the mixed precipitate, and the inorganic precipitate or a portion thereof is converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
  • a purifying agent is added to the mixed precipitate, and the inorganic precipitate or its after-swept body is completely converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
  • the method for preparing a modified micronized particle of the present invention further comprises: mixing/reacting the purified mixed precipitate with a surface modifier to obtain modified micronized particles.
  • the preparation method of a modified micronized particle of the invention is carried out in the presence of an inorganic precipitate which can be converted into a water-soluble substance in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, and the precipitation reaction of the micronized particle or the micronized particle precursor is carried out. .
  • the precipitation reaction referred to in the present invention is carried out in an aqueous solution
  • the aqueous solution is not excluded from further containing other liquid components such as an organic solvent such as ethanol.
  • the reaction carried out in the aqueous solution can also be understood to be carried out between the state in which the reaction mother liquid is not frozen and boiled under reflux.
  • pure water is a solid below 0 ° C at the freezing point, and a gas above 100 ° C above its boiling point.
  • the fluctuations in freezing point and boiling point value exist objectively.
  • the variation of the freezing point and the boiling point value of the reaction mother liquid is more remarkable. General chemical technicians have a good understanding of this.
  • the mixed precipitation formed by the coprecipitation reaction is a time-consistent mixed reaction process, which includes both the reaction process of micronizing or micronizing the precipitation of the particle precursor, and the reaction process of synthesizing the inorganic precipitation, due to The speed of response between the two cannot be absolutely identical. Therefore, there is bound to be a problem of being unsynchronized one after the other. Accordingly, the judgment of the concept of the process time of the coprecipitation reaction should include the entire process of nucleation, growth and ripening of the micronized or micronized particle precursor. The introduction of previously removable inorganic precipitation reactions at any stage of the process is considered to be within the scope of this patent.
  • the introduction of such a removable inorganic precipitate objectively reduces the particle size of the micronized particles, and the determination of such results can be easily achieved by instruments such as a laser particle size analyzer.
  • the precipitation reaction of the micronized particles or the micronized particle precursor is carried out. Since this method also reduces the particle size of the micronized particles, this embodiment is also within the protection scope of the patent.
  • the inorganic precipitate obtained in the process of the present invention is characterized in that it can be conveniently converted into a water-soluble substance by our usual inorganic or organic acid. Separation with micronized particle precipitation is achieved by using an electrodeless precipitate in which the stability of the acid in the aqueous solution is worse than that of the micronized particle or a higher pH is required to stabilize. But this separation does not necessarily require that it be necessary or thorough.
  • aluminum hydroxide is often used in plastic articles to improve its flame retardancy. Based on this, calcium carbonate and inorganic precipitated aluminum hydroxide can be added to a plastic article without being separately dispersed or modified.
  • the aging treatment is preferred.
  • the length of the aging time can be selected within the range of 0 to 24 hours depending on the curing temperature.
  • the degree of purification of the mixed precipitate is elastic, that is, it is optional to use no treatment, partial treatment or total treatment with a purifying agent, and the degree of elasticity is selected according to the specific application requirements and the type of inorganic precipitation. If purification treatment is required, the order of purification treatment and washing concentration can also be interchanged, either by first treating with a purifying agent, then by concentration, or by concentrating and then treating with a purifying agent.
  • Gravity sedimentation, vacuum suction filtration, centrifugal filtration or centrifugal sedimentation may be adopted in the solid-liquid separation in each treatment stage, and specifically, a gravity sedimentation tank, a filtration or sedimentation three-leg centrifuge and a plate and frame filter press may be employed.
  • the micronized particle precursor or the inorganic precipitated precursor is a generalized technique for preparing the micronized particles, for example, in the preparation of copper simple substance by coprecipitation reaction of copper sulfate and magnesium chloride, which is formed in the previous stage.
  • Copper oxide is the precursor of the final prepared pure copper element.
  • the formed calcium oxide is a precursor of the previously coprecipitated calcium hydroxide after dehydration by heating. This can be fully understood under the conditions of the prior art.
  • the anion portion of the inorganic precipitate is further selected as a hydroxide ion, an oxygen ion, a sulfur (hydrogen) ion, a sulfuric acid (hydrogen) ion, a phosphoric acid (hydrogen) ion or a hydrogen (hydrogen) root.
  • the anion donor may be a salt of a direct form, for example, sodium carbonate or the like, or may be a gas method.
  • ammonia gas is dissolved in water to form hydroxide
  • carbon dioxide is dissolved in water and sodium hydroxide to form sodium carbonate, and the like.
  • anions such as basic carbonates can be understood as a mixture of carbonates and hydroxides and are considered to be within the scope of this patent.
  • the volume average particle diameter d50 of the secondary particle diameter of the modified micronized particles obtained by the method of the present invention is less than 10 ⁇ m, more preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm.
  • the determination of the specific particle diameter can be carried out by a laser particle size analyzer, an electron scanning electron microscope (SEM) or the like.
  • the coprecipitation reaction of the present invention can be carried out under conventional stirring conditions, for example, in an enamel reactor commonly used in chemical production. More preferably, it is carried out under high-speed stirring/mixing/shearing/friction conditions, for example, a coprecipitation reaction is carried out under high-speed stirring in a GFJ type disperser (Shandong Laizhou Shenglong Chemical Machinery Factory). Most preferably, it is carried out under supergravity conditions, for example, in a supergravity reaction apparatus based on the principle of supergravity, and their specific form can be found in the book "Supergravity Technology and Applications" by the Chemical Industry Press.
  • a surface active material may also be added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater.
  • Preferred surface active materials are further selected as anionic alkyl or aryl organics including alkyl or aryl sulfates, sulfonic acids, phosphates or carboxylic acids and salts thereof, and mixtures thereof. It is added in an amount of from 0.05% to 100%, more preferably from 0.05% to 40%, most preferably from 0.1% to 10%, based on the weight of the precipitate of the micronized or micronized particle precursor.
  • the physical and/or chemical adsorption produced by such addition contributes to the further miniaturization of the precipitated particle size of the micronized or micronized particle precursor, the improvement of the lipophilic properties of the inorganic particles and the particles.
  • the controllability of the morphology changes.
  • this addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater: that is, under the established formulation, the turbidity of the mother liquor cannot be increased after the mixed precipitate is separated from the mother liquor, and the wastewater contains no adsorbed particles.
  • Surfactants do not increase the difficulty of wastewater treatment, which can be easily determined at the state of the art.
  • linoleic acid oleic acid
  • stearic acid sodium stearyl ether ether
  • dioctyl sulfosuccinate dioctyl sulfosuccinate
  • butylnaphthalene sulfonate a butylnaphthalene sulfonate
  • An anionic alkyl or aryl organic compound such as a salt, a polymerized alkylnaphthalenesulfonate, a dodecylbenzene phosphate, a polycarboxylate or a heavy naphthenate.
  • the surface active material may further include inorganic anionic compounds such as sodium polyphosphate and sodium hypophosphite; they may also include ethanol, lauryl betaine, octadecyl ammonium salt, fatty alcohol polyoxyethylene ether, and the like.
  • inorganic anionic compounds such as sodium polyphosphate and sodium hypophosphite; they may also include ethanol, lauryl betaine, octadecyl ammonium salt, fatty alcohol polyoxyethylene ether, and the like.
  • Other types of surface active materials may also include organic polymer compounds such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, and the like. They can be used either singly or in combination. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
  • the optional surface modifier comprises a compound capable of forming an adsorption with the surface of the micronized particle, including an anionic compound, a cationic compound, a nonionic surfactant, an organic solvent, a coupling agent, and a parent to which it is added. Materials, and combinations thereof.
  • the micro-particles exist only in a weak physical adhesion (also known as soft agglomeration), and then through the mixing/reaction with the surface modifier, they can be converted into monodisperse micros which meet the requirements of modification. The particles are then conveniently added to the parent material.
  • a weak physical adhesion also known as soft agglomeration
  • the nanometer calcium carbonate prepared by the method needs other complicated treatment, and can be directly agglomerated and dispersed in an aqueous solution containing the formaldehyde phthalate sulfonate dispersant MIGHTY150, and can be directly agglomerated and dispersed in liquid paraffin containing oleic acid.
  • Direct deagglomeration is dispersed in an aqueous solution containing oleic acid and penetrant JFC, and can be directly deagglomerated and dispersed in an aqueous solution containing anionic organic dye fluorescent yellow and nonionic surfactant penetrant JFC, which can be directly deagglomerated and dispersed in 3% acrylic acid.
  • the micro-calcium carbonate prepared by the method reserves a variety of modification space for its later application.
  • modifiers are very rich for different application purposes, they include:
  • Anionic compounds which are classified into anionic inorganic substances and anionic organic substances. Generally, these anionic compounds can form an ionic bond-based chemical adsorption with the exposed metal ions on the surface of the micronized particles, and more specifically include:
  • A an anionic inorganic substance such as fluoride ion, silicate, phosphate, and the like.
  • Anionic organic matter including:
  • a surfactant/dispersant having an anionic group of a sulfonic acid group, a phosphoric acid group or a carboxyl group for example, a polycarboxylate dispersing agent, stearic acid, oleic acid, a polymeric naphthalenesulfonate dispersing agent, and the like. Their specific forms can be found in the book "The Principles of Surfactant Applications” by China Chemical Industry Press.
  • a chelating agent including sodium tripolyphosphate, sodium polyphosphate, EDTA-2Na, maleic acid, citric acid, sodium pyrithione, oxalic acid, triethanolamine, and the like.
  • Such high polymers may be water soluble or water soluble or oil soluble.
  • Cationic compounds which are classified into cationic inorganic substances and cationic organic substances:
  • A cationic inorganic substances, including strontium ions, magnesium ions, calcium ions, aluminum ions, etc.
  • the addition of the above ions can enhance the anionic dye or Adsorption stability of the pigment.
  • the addition of the above ions can improve the adsorption stability of sodium carboxymethylcellulose.
  • cationic organic matter including alkyl ammonium chloride, aryl ammonium chloride, polyethylene imine, cationic guar gum and the like. Their specific forms can be found in the book “The Principles of Surfactant Applications” by China Chemical Industry Press.
  • Nonionic surfactants including alkyl polyglycol ethers, aryl polyglycol ethers, polyethylene glycol-polypropylene glycol ethers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene wax emulsions, and the like. Their specific forms can be found in the book “The Principles of Surfactant Applications” by China Chemical Industry Press.
  • Water-insoluble organic liquid including all organic liquids which can dissolve up to 0.1 gram per 100 gram of water at 25 ° C, which may be a single component or a mixed component.
  • Carriers suitable for this purpose include all of the micronized particles listed in this patent.
  • the coupling agent includes a silane coupling agent such as vinyltrichlorosilane (A-150), vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), ⁇ . —(2,3-epoxypropoxy)propyltrimethoxysilane (A-187, KH-560), etc.; titanate coupling agent, for example, isopropyl tris(dioctyl pyrophosphate) titanium Acid ester (KR-38S), isopropyl tris(isostearyl) titanate (KR-TTS), isopropyl tris(dodecylbenzenesulfonyl) titanate (KR-9S), different Propyl tris(n-ethylamino-ethylamino) titanate (KB-44), etc.; aluminate coupling agent and the like.
  • silane coupling agent such as vinyltrichlorosilane (A-150),
  • parent material include plastics, rubber, fibers, coatings, inks, metals, ceramics, and the like.
  • the calcium carbonate produced by the process can be added directly to a universal pure acrylic emulsion with 3% acrylic groups.
  • the surface modifier may be used singly or in combination of two or more.
  • treatments such as heating, calcination or drying during or after the modification are also essential. These can be applied skillfully under the existing knowledge conditions.
  • the modification or dispersion of the present invention can be accomplished under optional conventional equipment conditions, for example, an emulsifying machine, a dispersing machine, a vertical horizontal sand mill, a stirred mixing kettle, and the like.
  • an emulsifying machine for example, an emulsifying machine, a dispersing machine, a vertical horizontal sand mill, a stirred mixing kettle, and the like.
  • other finer dispersion, grinding or modification means are also available.
  • the modified micronized particles according to the present invention are inorganic substances and organic substances which are hardly soluble in water and do not chemically react with water.
  • poorly soluble in water or insoluble in water is a general quantitative chemical concept.
  • the present invention is intended to solve the problems of miniaturization and surface modification of the above substances by suitable introduction of inorganic precipitation, and is characterized in that a mixed precipitate of the above substances and inorganic precipitates is formed.
  • the process of forming such a mixed precipitate may be physical, chemical, or a mixture of the two.
  • dispersing iodine dissolved in ethanol into a calcium phosphate precipitate is a physical precipitation reaction process.
  • the process in which the molten organic matter is dispersed into the inorganic precipitation liquid to form the micronized organic particles is also a physical precipitation reaction process.
  • the synthetic micro-organisms and the modified micro-particles of oxides, hydroxides, inorganic salts, other inorganic salts, some organic metal salts and some organic substances are chemical precipitation processes, and the obvious characteristics before and after the reaction process are compared.
  • the preparation techniques of modified micronized particles of simple substances, hydroxides, oxides, inorganic salts, other inorganic substances, metal organic salts and organic substances according to the present invention are known, and their preparation methods are often various. Diverse. The variety of preparation methods is not only reflected in the selection of raw materials, for example, aluminum sulfate and sodium hydroxide can react to synthesize aluminum hydroxide, aluminum sulfate and sodium sulfide can also be synthesized into aluminum hydroxide, and also in the preparation process. Change in conditions. For example, ⁇ -alumina (also known as corundum) can be obtained by calcining aluminum hydroxide at 1200 ° C or hydrothermally synthesized under high pressure and high basicity. The use of these known synthetic methods and the use of the patented technology are not contradictory. By using the patented technology, the particles synthesized by the known synthetic methods can be improved in microfabrication and surface modification by coprecipitation reaction.
  • micronized particles of zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin and lead which can be selected by hydrogen reduction of a mixture of the corresponding oxide and calcium oxide
  • preparation of copper , micronized particles of ruthenium, osmium, silver, iridium, palladium, platinum, gold and ruthenium which can be selected by reducing the corresponding oxides in aqueous solution by using a hydrazine hydrazine reducing agent
  • preparing silver, ruthenium, palladium, platinum and Gold micronized particles can also be selected by heating a mixture of their corresponding oxides and calcium carbonate
  • micronized particles for preparing carbon simple substances can be selected.
  • micronized particles of silicon, tungsten and boron It is obtained by mixing and incompletely burning calcium stearate and calcium carbonate, and preparing micronized particles of silicon, tungsten and boron.
  • the mixed precipitation of their corresponding hydrated oxides and barium sulfate can be reduced by metal magnesium powder.
  • the method of obtaining selenium, sulfur and iodine elemental micronized particles can be selected from the organic solution by physical precipitation.
  • hydroxide micronized particles can be carried out by reacting their corresponding water-soluble metal salts with water-soluble bases.
  • water soluble bases include sodium hydroxide, potassium hydroxide, aqueous ammonia, and ammonia.
  • hydroxides capable of double hydrolysis for example, aluminum hydroxide, sodium carbonate, ammonium carbonate, sodium hydrogencarbonate, sodium sulfide are also optional.
  • hydroxides include barium hydroxide and palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide , aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II, IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide
  • the metal oxide micronized particles can be prepared by hydrothermal decomposition of a mixed precipitate of the corresponding hydroxide and calcium hydroxide (inorganic precipitate), which includes cerium oxide and palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide, cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), yttrium oxide (III , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, ce
  • the preparation conditions are also very different. For example, for gold oxide, it can be obtained directly without heating.
  • the choice of calcination method is also optional.
  • the corresponding hydroxide prepared by the prior method is washed and concentrated, and then dispersed in an alcohol solvent having a boiling point higher than water, particularly a polyhydric alcohol such as 1,2-propanediol. Then heat and evaporate.
  • the preparation of the inorganic salt micronized particles can be carried out by coprecipitation reaction by selecting a corresponding water-soluble metal salt and a corresponding mixture of water-soluble acid groups and hydroxides/carbonates. In addition, it is also an option to react with an insoluble hydroxide or carbonate of the corresponding metal ion and an acid of the corresponding acid.
  • the inorganic micronized particles for preparing tungsten carbide, silicon carbide, boron carbide, silicon nitride, and boron nitride are also obtained by reducing the mixed precipitation with carbon or nitrogen (ammonia gas) on the basis of the coprecipitation reaction.
  • the preparation of the organometallic salt micronized particles can be selected in the same manner as the preparation of the inorganic salt micronized particles, including strontium, barium, calcium, lithium, strontium, barium, strontium, barium, strontium, strontium, barium, strontium, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, An optional alkyl or aryl sulfate of gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, mercury, silver, antimony, palladium, platinum or gold ions, Sulfonic acid, phosphate or carboxylate.
  • the optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylic acid or a salt thereof can also be coprecipitated by dissolving in a water-miscible solvent such as ethanol.
  • a water-miscible solvent such as ethanol. The way of the water emulsion is to participate in the coprecipitation reaction.
  • the present invention also discloses a method of micronizing a solid organic substance that is poorly soluble in water.
  • Carriers suitable for this purpose include all of the micronized particles recited in this patent, with inorganic micronized particles prepared by the present patent technology being particularly preferred.
  • the poorly water-soluble solid organic substance has at least a liquid or liquid composition which has a decomposition temperature higher than its melting point or below its thermal decomposition temperature and can be dissolved in water other than water, and has a solubility of not less than 1 g/100 g.
  • a liquid or liquid composition which has a decomposition temperature higher than its melting point or below its thermal decomposition temperature and can be dissolved in water other than water, and has a solubility of not less than 1 g/100 g.
  • a reaction mode of an aqueous solution and a gas When a solid organic substance which is hardly soluble in water can be reacted by an aqueous solution and an aqueous solution, a reaction mode of an aqueous solution and a gas, a reaction mode of an aqueous solution and a water-insoluble liquid, and a reaction mode of a water-insoluble liquid and a gas can be used. Chemical precipitation reaction process.
  • the water-insoluble solid organic matter can be melted to achieve this physical precipitation reaction process.
  • the water-insoluble solid organic matter can also participate in the coprecipitation reaction in a solution manner.
  • This process generally involves two physical precipitation reactions, adsorption and precipitation.
  • the precipitation process is basically a physical adsorption process; when the solvent is miscible with water, the precipitation process is basically a precipitation process.
  • a more preferable precipitation process is a precipitation process in a precipitation mode. Therefore, when the water-insoluble solid organic substance participates in the coprecipitation reaction in a solution manner, it is preferred that any liquid or liquid composition dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 ° C.
  • solvent Handbook edited by Cheng Nenglin, China Chemical Industry Press.
  • the water-insoluble solid organic substance participates in the coprecipitation reaction in the form of a (aqueous) suspension or a (water) suspension emulsion.
  • the water-insoluble solid organic matter can be classified into drugs, pesticides, veterinary drugs, pigments, dyes (pigments), flavors, bactericides, fungicides, catalysts, polymer resins or organic dyes.
  • the specific names of organic substances suitable for the scope of this patent can be found in the Chinese Pharmacopoeia 2010, the Chinese Pesticide Code, and the Fine Chemicals Handbook.
  • insoluble organic matter has important application significance. For example, for drugs, more than 40% of the drugs are insoluble in water. Therefore, it is obvious that the miniaturization of these drugs is effective for improving the dissolution rate of the drug and improving the efficacy.
  • the compatibility between the inorganic substance and the organic substance is generally poor, it is generally difficult to obtain a desired result by dispersing the organic substance supported by the inorganic particle as a carrier.
  • the inorganic micronized particles involved in the patent have the advantages of flexible surface modification space, free hydrophilic-lipophilic adjustment, and the like, so that the compatibility can be maximized, thereby obtaining an ideal micro-insoluble organic matter.
  • the rich modification space reserved for the micro-particles also provides convenience for the drug coating, and provides a basis for drug sustained-release control.
  • the suspension containing the precipitation of calcium carbonate and calcium hydroxide was filtered.
  • the resulting filter cake was placed in a 50 ml beaker.
  • the magnetic stirrer was turned on, and 8 ml of a 0.1 mol/L aqueous hydrochloric acid solution was slowly added under vigorous stirring. After 30 minutes, it was filtered again, then washed with about 10 ml of water, then filtered, and washed again, three times.
  • the water-soluble calcium chloride in the filtrate and the wash water can be treated by a soda ash recovery method.
  • the washed calcium carbonate precipitation slurry was placed in a 50 ml plastic beaker, and 30 ml of DEMOL containing 2% dispersant was added.
  • the GF1110 laboratory disperser (Shandong Shenglong Machinery Factory) was opened and the solution was forcedly dispersed for 20 minutes at 1200 rpm.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 30 nm.
  • Example 2 The same experiment as in Example 1 was repeated, and the obtained calcium carbonate was dispersed in 30 ml of liquid paraffin containing 0.1% oleic acid; dispersed in 30 ml of an aqueous solution containing 0.1% oleic acid and 0.1% penetrant JFC; In a 30 ml aqueous solution containing 0.1% anionic organic dye fluorescent yellow and 0.1% nonionic surfactant penetrant JFC; dispersed in a pure acrylic emulsion called AT-150 with 3% acrylic group (Zhongshan An Texa Chemical Co., Ltd.).
  • Calcium carbonate in the above liquid can be well dispersed, and the deagglomeration effect of calcium carbonate is substantially the same as in the first embodiment.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of a 0.1 mol/L suspension of calcium oxide water was added to a 50 ml closed flask, and then the reaction was stopped by introducing carbon dioxide gas to about pH 10.5. After aging, the pH was adjusted to about 9 with hydrochloric acid. Then wash repeatedly and then disperse.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 80 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride. After heating at 80 ° C for two hours and standing for 24 hours, 10 ml of 0.2 mol / L hydrochloric acid was further added. Then wash repeatedly and then disperse.
  • aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate a mixture of water glass and sodium carbonate
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter precipitated by calcium silicate (hydrated calcium oxide and silica complex) has a volume average particle diameter d50 of about 50 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1.
  • 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride.
  • 10 ml of 0.2 mol/L of calcium chloride After heating at 80 ° C for two hours and standing for 24 hours, 0.5 g of finely ground ultrafine carbon powder (above 200 mesh) was further added. After thorough dispersion, it is washed, concentrated and dried. It is placed in a corundum boat with a content of more than 99%.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the silicon carbide precipitate has a volume average particle diameter d50 of about 900 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of ferric chloride and 0.02 mol/L of calcium chloride was added, followed by addition of 5 ml of 0.7 mol/L of sodium hydroxide for coprecipitation. Not acidified, disperse after washing.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the precipitate of the ferric hydroxide colloid has a volume average particle diameter d50 of about 30 nm.
  • the mixture of the previously washed iron hydroxide and calcium hydroxide was sufficiently dispersed with 10 ml of 1,2-propylene glycol, dried by heating, placed in a muffle furnace, and calcined at 500 ° C to obtain a micronized iron oxide.
  • the iron oxide was reduced with carbon monoxide in a DC-R tubular high temperature furnace (tubular furnace) at 450 ° C to obtain magnetic ferroferric oxide.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of an aqueous solution of 0.1 mol/L of aluminum chloride and 0.02 mol/L of calcium chloride was added to a 50 ml closed flask, and then 5 ml of 0.7 mol/L of sodium hydroxide was added to carry out a coprecipitation reaction. After the mixed precipitate was aged, it was acidified with 10 ml of 0.06 mol/L hydrochloric acid, and then washed and concentrated. The obtained aluminum hydroxide precipitate was sufficiently dispersed in 10 ml of a 1,2-propanediol solution, and then dried in an oven at 300 °C. The dried product was again placed in a muffle furnace and calcined at 1000 ° C for 3 hours.
  • alumina also called corundum
  • ⁇ -alumina also called corundum
  • the secondary particle diameter of alumina has a volume average particle diameter d50 of about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L aluminum nitrate and 0.05 mol/L silver nitrate to a 50 ml beaker, heat to 60 ° C, and then add 5 ml of 1.4 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g. Hydrazine hydrate (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, then acidified with 9.5 ml of 0.7 mol/L nitric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver has a volume average particle diameter d50 of about 160 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium chloride and 0.05 mol/L copper sulfate in a 50 ml beaker, heat to 80 ° C, and then add 5 ml of 2 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g of hydrazine hydrate. (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, and then acidified with 9.5 ml of 1 mol/L hydrochloric acid, followed by washing and concentration.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of copper has a volume average particle diameter d50 of about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium sulfate and 0.05 mol/L copper sulfate was added to a 50 ml beaker, and after heating to 80 ° C, 10 ml of 1 mol/L sodium hydroxide was added dropwise to carry out a reaction mixture precipitation for 24 hours, and then matured. After concentration and washing, it was acidified with 9.5 ml of 1 mol/L hydrochloric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the copper oxide has a volume average particle diameter d50 of about 50 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.1 mol/L silver nitrate aqueous solution and 0.1 mol/L aluminum nitrate aqueous solution to a 50 ml beaker, and add 10 ml of a mixed aqueous solution of 0.3 mol/L sodium hydroxide and 0.1 mol/L sodium chloride (containing 0.015). The oleic acid is reacted. After concentrated washing and aging, it was acidified with 9.5 ml of 0.3 mol/L nitric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver chloride has a volume average particle diameter d50 of about 320 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 5 ml of a 0.2 mol/L aqueous solution of calcium chloride was added to a 25 ml beaker, and 5 ml of 0.12 mol/L sodium phosphate and 0.04 mol/L sodium hydroxide were added dropwise. Then, when heated to 80 ° C, 0.01 g of stearic acid was added to carry out the reaction under vigorous stirring. After the incubation was continued for ten minutes, it was cooled to room temperature with vigorous stirring. After concentration and washing, it was acidified by adding 5 ml of a 0.1 mol/L hydrochloric acid aqueous solution and then dispersed.
  • the obtained calcium phosphate and calcium stearate were mixed and precipitated for dispersion, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the mixed precipitate has a volume average particle diameter d50 of about 350 nm.
  • cod liver oil 0.01 g was added dropwise to the above dispersion, and after vigorous stirring, an aqueous suspension emulsion of cod liver oil was obtained, and the volume average particle diameter d50 of the secondary particle diameter was also about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.2 mol/L calcium chloride aqueous solution to a 50 ml beaker, add 10 ml of a mixed aqueous solution of 0.07 mol/L sodium phosphate and 0.1 mol/L sodium carbonate, and then add 0.1 g of 10% IPBC. A solution of (iodopropynyl carbamate, an excellent industrial antifungal agent) in methanol. After aging, it was acidified with 10 ml of 0.2 mol/L hydrochloric acid, concentrated and washed, and then dispersed.
  • the obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is also about 300 nm.
  • the IPBC of the thirteenth embodiment was replaced with 0.1 g of a 10% content of a solution of Ganbaosu 1,2-propanediol and 0.1 g of a 10% ketoconazole methanol solution.
  • the other operations were similar, and the excellent water of the two drugs was also obtained.
  • the volume average particle diameter d50 of the dispersion and the secondary particle diameter was about 300 nm.
  • the dispersant containing DEMOL in Examples 14 and 15 The aqueous solution of N is replaced with an aqueous solution containing 1% concentration of sodium carboxymethyl cellulose (Zhangjiagang Sanhui Chemical Co., Ltd., having a carboxyl group substitution degree of about 0.7) of ICM-7 type. Other operations are as good as the above mixed precipitation. Dispersions.
  • the obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is about 360 nm.
  • the above aqueous solutions of A and B are at a single flow rate of not more than 200 L/H, and the flow rate molar ratio is about 1: 1.1, simultaneously pumped into the supergravity reactor for synthesis.
  • the supergravity reactor was rotated at 1000 rpm; the synthetic slurry of A and B was placed in a 100 liter polypropylene plastic bucket, and the GFJ-8 type disperser was started, and the rotation speed was adjusted to 1000 rpm.
  • C was added to the synthetic slurry of A and B over 10 minutes.
  • the obtained slurry was treated in the same manner as in Example 1.
  • the centrifugal separation equipment uses an ordinary sedimentation type three-legged centrifuge.
  • the dispersing agent was selected from the Japanese Kao Company formaldehyde phthalate sulfonate dispersing agent DEMOLN.
  • the modified micro-purinated zinc pyrithione obtained in this example was subjected to particle size analysis by scanning electron microscopy (SEM), and it was found that the particle diameter of the particles was substantially less than 300 nm.
  • Example 2 5 ml of each of an aqueous solution of calcium chloride and sodium carbonate having a concentration of 0.1 mol/L was separately disposed, and treated in the same manner as in Example 1.
  • the obtained calcium carbonate dispersion obtained by the non-patent method is a laser particle size analyzer (beckman) Coulter) was tested with a d50 of about 8.5 microns. It can be seen that inorganic precipitation of calcium hydroxide can effectively improve the secondary particle size of calcium carbonate.
  • the above aqueous solution of zinc sulphate and sodium 2-pyridyl pyridine oxide solution were separately pumped into a supergravity reactor at a single flow rate of not more than 200 L/H at a flow ratio of about 1.05:1.
  • the supergravity reactor was rotated at 1000 rpm.
  • the obtained slurry was filtered with a quantitative filter paper, and as a result, a large amount of modified micro-pyridinium oxychloride zinc particles penetrated the filter paper, and the separation of the modified micro-pyridyl pyridine oxide zinc particles from the reaction mother liquid could not be achieved by this method.
  • the obtained slurry was centrifuged at 3000 rpm for 20 minutes using a bench-top low-speed centrifuge 80-2T (Shanghai Surgical Instrument Factory). As a result, a large amount of modified micronization was still contained in the centrifuged mother liquor. The zinc pyrithione particles and the DEMOLN dispersant still do not provide good separation of the reaction product from the reaction mother liquor.

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Abstract

La présente invention concerne un procédé pour préparer des particules micronisées modifiées, qui comprend les étapes suivantes : conduite d'une réaction de coprécipitation dans une solution aqueuse à une température comprise entre le point de congélation et le point d'ébullition du liquide de réaction pour obtenir un précipité mélangé de particules micronisées ou précurseur de particules micronisées et un autre précipité inorganique. Le procédé résout efficacement le conflit entre la micronisation et la modification de surface des particules et résout le problème dû au fait qu'il est difficile de séparer les particules micronisées du liquide de réaction parent.
PCT/CN2011/070751 2010-01-29 2011-01-28 Procédé pour préparer des particules micronisées modifiées Ceased WO2011091766A1 (fr)

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CN112374859A (zh) * 2020-11-03 2021-02-19 景德镇卓之艺陶瓷有限公司 一种养生陶瓷制品及其制造工艺
CN113540446A (zh) * 2021-07-05 2021-10-22 武汉钜能科技有限责任公司 一种锂离子电池负极材料及其制备方法
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CN114760743A (zh) * 2022-04-02 2022-07-15 民吉科技服务(重庆)有限公司 一种多面体离子化合物复合陶瓷及其制备方法和应用以及氧鎓离子激发器
CN116515321A (zh) * 2023-05-09 2023-08-01 西安电子科技大学 一种无溶剂钆基流体及其制备方法
CN117867290A (zh) * 2023-12-25 2024-04-12 武汉理工大学 一种共沉淀高效同步去除溶液中钾铊的方法
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CN111704164A (zh) * 2020-07-01 2020-09-25 洛阳理工学院 一种钼酸钡花状晶体的制备方法
CN111704164B (zh) * 2020-07-01 2023-01-24 洛阳理工学院 一种钼酸钡花状晶体的制备方法
CN112374859A (zh) * 2020-11-03 2021-02-19 景德镇卓之艺陶瓷有限公司 一种养生陶瓷制品及其制造工艺
CN113540446A (zh) * 2021-07-05 2021-10-22 武汉钜能科技有限责任公司 一种锂离子电池负极材料及其制备方法
CN113540446B (zh) * 2021-07-05 2022-10-25 常德昆宇新能源科技有限公司 一种锂离子电池负极材料及其制备方法
CN113860346A (zh) * 2021-10-08 2021-12-31 江西华明纳米碳酸钙有限公司 一种改性纳米碳酸钙的制备方法
CN114480883A (zh) * 2021-12-16 2022-05-13 成都先进金属材料产业技术研究院股份有限公司 一种镍离子协同去除钒溶液中硅和铬以制备高纯五氧化二钒的方法
CN114480883B (zh) * 2021-12-16 2023-11-21 成都先进金属材料产业技术研究院股份有限公司 一种镍离子协同去除钒溶液中硅和铬以制备高纯五氧化二钒的方法
CN114760743A (zh) * 2022-04-02 2022-07-15 民吉科技服务(重庆)有限公司 一种多面体离子化合物复合陶瓷及其制备方法和应用以及氧鎓离子激发器
CN116515321A (zh) * 2023-05-09 2023-08-01 西安电子科技大学 一种无溶剂钆基流体及其制备方法
CN117867290A (zh) * 2023-12-25 2024-04-12 武汉理工大学 一种共沉淀高效同步去除溶液中钾铊的方法
CN118179532A (zh) * 2024-04-03 2024-06-14 安徽大学 一种珊瑚状CuO/Ag催化剂的制备方法

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