WO2013018742A1 - アルカリ土類金属炭酸塩の製造方法、チタン酸バリウムおよびチタン酸ストロンチウム - Google Patents

アルカリ土類金属炭酸塩の製造方法、チタン酸バリウムおよびチタン酸ストロンチウム Download PDF

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WO2013018742A1
WO2013018742A1 PCT/JP2012/069268 JP2012069268W WO2013018742A1 WO 2013018742 A1 WO2013018742 A1 WO 2013018742A1 JP 2012069268 W JP2012069268 W JP 2012069268W WO 2013018742 A1 WO2013018742 A1 WO 2013018742A1
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earth metal
carbonate
alkaline earth
metal carbonate
barium
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French (fr)
Japanese (ja)
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博幸 泉川
鈴木　孝
雅幸 麻田
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Sakai Chemical Industry Co Ltd
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Sakai Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/186—Strontium or barium carbonate
    • C01F11/187—Strontium carbonate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/186—Strontium or barium carbonate
    • C01F11/188—Barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a method for producing alkaline earth metal carbonates such as barium carbonate and strontium carbonate, and further relates to barium carbonate obtained by the method and barium titanate and strontium titanate produced from strontium carbonate as raw materials.
  • the present invention relates to a method for producing an alkaline earth metal carbonate in which particle growth due to heat is suppressed, and to barium titanate and strontium titanate produced using barium carbonate and strontium carbonate obtained by the method as raw materials.
  • Alkaline earth metal carbonates in particular barium carbonate and strontium carbonate, are useful as raw materials for dielectrics.
  • barium carbonate is barium titanate (BaTiO 3 ) used for dielectric layers of ceramic ceramic capacitors. It is widely used as a starting material.
  • Barium titanate is generally produced by a solid-phase synthesis method. In this solid-phase synthesis method, barium carbonate (BaCO 3 ) powder and titanium oxide (TiO 2 ) powder are mixed in a wet manner, and after drying, the mixed powder is 900 It is fired at a temperature of about ⁇ 1200 ° C (see, for example, Patent Document 1).
  • the present invention has been made in view of the above points, and provides a method for producing an alkaline earth metal carbonate in which particle growth due to heat is suppressed, and uniform and fine barium titanate and strontium titanate. With the goal.
  • the present inventors have conducted intensive research, and as a result, by treating the surface of alkaline earth metal carbonate such as barium carbonate with a titanium compound, the alkaline earth metal carbonate particles are treated.
  • the present inventors have found that particle growth due to heat can be suppressed and completed the present invention. That is, in the method for producing an alkaline earth metal carbonate of the present invention, the surface of the alkaline earth metal carbonate is treated with a titanium compound.
  • the alkaline earth metal carbonate is preferably barium carbonate or strontium carbonate
  • the titanium compound is preferably titanium hydroxide, but may be hydrous titanium oxide or titanium oxide.
  • the treatment with the titanium compound is preferably a treatment in which, for example, titanium hydroxide is adsorbed on the surface of the alkaline earth metal carbonate.
  • the titanium hydroxide which is a titanium compound is preferably produced by neutralizing an aqueous titanium tetrachloride solution with a basic substance such as ammonia.
  • a step of adding an aqueous solution of titanium tetrachloride and an alkaline solution to the slurry of the alkaline earth metal carbonate is included.
  • the method further includes the step of separating the alkaline earth metal carbonate from the alkaline earth metal carbonate slurry to which the aqueous titanium tetrachloride solution and the alkaline solution are added in the adding step. It is a waste.
  • the detailed mechanism is unknown by surface treatment with a titanium compound such as titanium hydroxide, but titanium adsorbed on the surface of the alkaline earth metal carbonate particles. By the compound, the contact between the alkaline earth metal carbonate particles is inhibited, and the particle growth of the alkaline earth metal carbonate particles due to heat can be suppressed.
  • the barium titanate of the present invention is produced using an alkaline earth metal carbonate produced by the production method of the present invention as a starting material, and the starting material is barium carbonate.
  • the alkaline earth metal carbonate produced by the production method of the present invention, which is the starting material is preferably a powder, but may be in a slurry state.
  • the method for producing barium titanate is not particularly limited as long as it uses barium carbonate produced by the production method of the present invention as a starting material, and a known production method can be applied.
  • the strontium titanate of the present invention is produced using an alkaline earth metal carbonate produced by the production method of the present invention as a starting material, and the starting material is strontium carbonate.
  • the method for producing strontium titanate is not particularly limited as long as strontium carbonate produced by the production method of the present invention is used as a starting material, and a known production method can be applied.
  • an alkaline earth metal carbonate such as barium carbonate or strontium carbonate in which particle growth due to heat is suppressed can be obtained. Therefore, the barium titanate of the present invention produced using the barium carbonate obtained by the production method of the present invention as a starting material has the result that the particle growth due to the heat of the barium carbonate particles is suppressed during the temperature rising process during the production.
  • the barium carbonate particles can be reacted in a state where they are uniformly mixed with the fine titanium oxide and fine particles. Barium titanate can be obtained.
  • the strontium titanate of the present invention produced using strontium carbonate obtained by the production method of the present invention as a starting material is a result of suppressing the particle growth due to heat of the strontium carbonate particles during the temperature rising process during the production.
  • Strontium carbonate particles can be reacted in a finely mixed state with fine titanium oxide in a finely mixed state, and the variation in characteristics such as particle size of the produced strontium titanate is reduced, resulting in uniform and fine Barium titanate and strontium titanate can be obtained.
  • an alkaline earth metal carbonate such as barium carbonate or strontium carbonate
  • a titanium compound such as titanium hydroxide
  • FIG. 1 is an SEM photograph showing the size and shape of the particles of Example 1 in the upper stage (a), the middle stage (b), and the lower stage (c), respectively.
  • the upper stage (a) is the middle stage (b) before firing. Shows the shape after firing at 500 ° C. for 30 minutes, and the lower stage (c) shows the shape after firing at 800 ° C. for 30 minutes.
  • FIG. 2 is an SEM photograph showing the size and shape of the particles of Example 2 in the upper stage (a), the middle stage (b), and the lower stage (c).
  • the upper stage (a) is the middle stage (b) before firing. Shows the shape after firing at 500 ° C. for 30 minutes, and the lower stage (c) shows the shape after firing at 800 ° C. for 30 minutes.
  • FIG. 1 is an SEM photograph showing the size and shape of the particles of Example 1 in the upper stage (a), the middle stage (b), and the lower stage (c), respectively.
  • the upper stage (a) is the middle stage (b) before firing
  • FIG. 3 is an SEM photograph showing the size and shape of the particles of Comparative Example 1 in the upper stage (a), the middle stage (b), and the lower stage (c).
  • the upper stage (a) is the middle stage (b) before firing. Shows the shape after firing at 500 ° C. for 30 minutes, and the lower stage (c) shows the shape after firing at 800 ° C. for 30 minutes.
  • 4 is an SEM photograph of Comparative Example 1 corresponding to the lower part (c) of FIG. 3 having a lower magnification than that of FIG.
  • FIG. 5 is a schematic view showing the structure of the reaction apparatus.
  • FIG. 6 is an SEM photograph showing the size and shape of the particles of Example 3 in the upper stage (a) and the lower stage (b).
  • FIG. 7 is an SEM photograph showing the size and shape of the particles of Example 4 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 8 is an SEM photograph showing the size and shape of the particles of Comparative Example 2 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 7 is an SEM photograph showing the size and shape of the particles of Example 4 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 7 is an SEM photograph showing the size and shape of the particles of Example 4 in the upper stage (a) and the lower stage
  • FIG. 9 is an SEM photograph showing the size and shape of the particles of Example 5 in the upper stage (a), the middle stage (b), and the lower stage (c).
  • the upper stage (a) is the middle stage (b) before firing. Shows the shape after baking at 550 ° C. for 30 minutes, and the lower stage (c) shows the shape after baking at 800 ° C. for 30 minutes.
  • FIG. 10 is an SEM photograph showing the size and shape of the particles of Comparative Example 3 in the upper stage (a), the middle stage (b), and the lower stage (c).
  • the upper stage (a) is the middle stage (b) before firing. Shows the shape after baking at 550 ° C. for 30 minutes, and the lower stage (c) shows the shape after baking at 800 ° C. for 30 minutes.
  • FIG. 11 is an SEM photograph showing the size and shape of the particles of Example 6 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 12 is an SEM photograph showing the size and shape of the particles of Example 7 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 13 is an SEM photograph showing the size and shape of the particles of Comparative Example 4 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C.
  • FIG. 14 is an SEM photograph showing the size and shape of the particles of Example 8 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • FIG. 15 is an SEM photograph showing the size and shape of the particles of Comparative Example 5 in the upper (a) and lower (b), respectively.
  • the upper (a) is before firing, and the lower (b) is 800 ° C. ⁇ 30.
  • FIG. 16 is an SEM photograph showing the size and shape of the particles of Example 9 in the upper stage (a) and the lower stage (b).
  • FIG. 17 is an SEM photograph showing the size and shape of the particles of Example 10 in the upper stage (a) and the lower stage (b).
  • the upper stage (a) is before firing, and the lower stage (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • FIG. 18 is an SEM photograph showing the size and shape of the particles of Comparative Example 6 in the upper (a) and lower (b), respectively.
  • the upper (a) is before firing, and the lower (b) is 800 ° C. ⁇ 30.
  • the shapes after partial firing are shown.
  • the manufacturing method of the alkaline earth metal carbonate of this invention is demonstrated in detail.
  • the surface of the alkaline earth metal carbonate is treated with a titanium compound.
  • the alkaline earth metal carbonate barium carbonate or strontium carbonate is preferable.
  • the particle diameter of the alkaline earth metal carbonate whose surface is treated with the titanium compound is preferably about 10 nm to 2000 nm, and 50 nm to 1000 nm as measured by an electron micrograph. Is more preferable.
  • the particle diameter of strontium carbonate is preferably about 10 nm to 2000 nm, and more preferably 50 nm to 1000 nm.
  • Barium carbonate and strontium carbonate are known to have a needle shape depending on the production method, and the major diameter corresponds to the particle diameter in that case.
  • the titanium compound is preferably titanium hydroxide, but may be hydrous titanium oxide or titanium oxide. Barium carbonate and strontium carbonate may be produced by a conventionally known method, and the production method is not particularly limited.
  • the treatment of the surface of the alkaline earth metal carbonate with the titanium compound is preferably performed by adsorbing titanium hydroxide on the surface of the alkaline earth metal carbonate.
  • the adsorption amount of titanium hydroxide is preferably 0.3 wt% to 20 wt%, and more preferably 0.7 wt% to 15 wt%. If the adsorption amount of titanium hydroxide is less than 0.3 wt%, the effect of suppressing particle growth due to heat cannot be obtained, and conversely if it exceeds 20 wt%, the proportion of titanium oxide contained in barium carbonate increases. The influence on the properties of the finally obtained barium titanate is increased. Titanium hydroxide is preferably produced by a reaction between a water-soluble titanium compound and a basic substance. For example, titanium hydroxide is preferably produced by neutralizing an aqueous titanium tetrachloride solution with ammonia water or the like.
  • the method for producing an alkaline earth metal carbonate according to the present invention preferably includes a step of adding an aqueous solution of titanium tetrachloride and an alkaline solution to the slurry of the alkaline earth metal carbonate. Further, in the step of adding, It is preferable to include a step of separating the alkaline earth metal carbonate from the aqueous titanium chloride solution and the alkaline earth metal carbonate slurry to which the alkaline solution is added.
  • the slurry of the alkaline earth metal carbonate to which the titanium tetrachloride aqueous solution and the alkali solution are added in the adding step can be used as it is, for example, as a barium carbonate raw material of solid phase barium titanate.
  • the order in which the titanium tetrachloride solution and the alkali solution are added to the alkaline earth metal carbonate slurry is not particularly limited.
  • Ammonia water is added to the alkaline earth metal carbonate slurry, and then added to the mixed solution.
  • a titanium chloride solution is added so that the pH is 6 to 11, more preferably 8 to 9.
  • the titanium tetrachloride aqueous solution and the alkali solution are simultaneously added to the alkaline earth metal carbonate slurry while maintaining the pH of 6 to 10
  • more preferably the titanium tetrachloride aqueous solution and the alkali solution are simultaneously added while maintaining the pH of 7 to 9.
  • alkaline earth metal carbonate can be treated regardless of the concentration of alkaline earth metal carbonate in the slurry of alkaline earth metal carbonate, but when the viscosity, productivity, and workability of the slurry are taken into consideration.
  • the concentration of the alkaline earth metal carbonate in the slurry is preferably 10 g / L to 400 g / L, more preferably 50 g / L to 200 g / L.
  • the titanium tetrachloride aqueous solution added to the slurry preferably has a titanium concentration of 5 g / L to 200 g / L, and more preferably 15 g / L to 30 g / L.
  • the concentration is preferably 1 wt% to 30 wt%, and more preferably 5 wt% to 25 wt%.
  • the treatment temperature when treating the surface of the alkaline earth metal carbonate by adding a titanium tetrachloride aqueous solution and an alkali solution to the slurry is preferably 5 ° C to 100 ° C, and preferably 10 ° C to 40 ° C. More preferably.
  • a step of aging the slurry to which the both solutions are added is provided.
  • the slurry to which the both solutions are added is provided. Is preferably stirred. The aging is preferably performed at a temperature of about 5 ° C. to 100 ° C. for about 5 minutes to 1 hour, more preferably at a temperature of 10 ° C. to 40 ° C. for about 10 minutes to 30 minutes.
  • the separation is performed using a suction filter, a pressure filter, a centrifuge, or the like. Is preferred.
  • the barium titanate of the present invention is produced using barium carbonate produced by the production method of the present invention as a starting material, and the production method is not particularly limited, and a conventionally known method can be used.
  • the strontium titanate of the present invention is produced using strontium carbonate produced by the production method of the present invention as a starting material, and is not particularly limited, and a conventionally known method can be used.
  • examples of the present invention will be described together with comparative examples. However, the present invention is not limited to these examples.
  • an Example and a comparative example are made to respond
  • Example 1 barium carbonate before the surface was treated with titanium hydroxide was produced as follows. That is, barium chloride dihydrate was dissolved in pure water and adjusted to a concentration of 400 g / L. The liquid temperature at this time is adjusted to 60 ° C., and this barium chloride aqueous solution is used as the raw material A. Next, carbon dioxide was absorbed into the ammonia water to prepare a 44 g / L ammonium carbonate solution as the CO 2 concentration. The liquid temperature at this time is adjusted to 30 ° C., and this ammonium carbonate solution is used as a raw material B.
  • Example 1 barium carbonate whose surface was treated with titanium hydroxide was produced in the same manner except that the amount of ammonia water added was 1 ml and the amount of TiCl 4 added was 44 ml. Obtained.
  • Comparative Example 1 barium carbonate was produced by adding the aqueous ammonia and TiCl 4 , but otherwise performing the same operation, that is, without treating the surface with titanium hydroxide. Obtained.
  • the thermal stability confirmation tests of Examples 1 and 2 and Comparative Example 1 were performed as follows. That is, about 5 g of each sample is put in an alumina crucible, put in an electric furnace preheated to each set temperature, and ignited as it is for 30 minutes.
  • Example 1 After 30 minutes, the sample was taken out and allowed to cool, and the size and shape of the particles were confirmed with a scanning electron microscope (SEM).
  • the ignition temperature was 500 ° C and 800 ° C.
  • the amount of titanium hydroxide adsorbed on the surface of barium carbonate in Examples 1 and 2 was calculated from the amount of titanium tetrachloride added.
  • the adsorption amounts of titanium hydroxide in Examples 1 and 2 were 1.5 wt% and 0.7 wt%, respectively, with respect to Comparative Example 1 in which titanium hydroxide was not adsorbed.
  • 1 to 3 show SEM photographs of Examples 1 and 2 and Comparative Example 1 at a magnification of 10,000 times, respectively, in a thermal stability confirmation test.
  • FIG. 4 shows a state in which small particles are attached to the surface of large particles that are too large to fit on the screen.
  • FIG. 4 in which the magnification in the lower part (c) of FIG. 3 is 1/10, in Comparative Example 1, even if the magnification is 1/10, the particles are larger than those in Examples 1 and 2. You can see that That is, in Examples 1 and 2, it can be seen that the particle growth due to heat is suppressed as compared with Comparative Example 1.
  • barium carbonate before the surface was treated with titanium hydroxide was produced as follows. That is, barium hydroxide octahydrate was dissolved in pure water, and 50 L of a barium hydroxide aqueous solution having a concentration of 75 g / L was prepared. The liquid temperature at this time is adjusted to 40 ° C., and this barium hydroxide aqueous solution is used as the raw material C. This raw material C was mixed with carbon dioxide using the reactor 1 shown in FIG. 5 to synthesize barium carbonate.
  • P1, P2 and P3 are pumps of the first stage, the second stage and the third stage, and the configuration of the pumps P1 to P2 of each stage is as follows.
  • First stage pump P1 centrifugal pump (manufactured by Lhasa Corporation), suction port diameter 1.5 inches, discharge port diameter 1 inch, discharge amount 170 L / min, impeller rotation speed 2080 rpm
  • Second stage pump P2 Centrifugal pump (manufactured by Rasa Shoji Co., Ltd.), suction port diameter 1 inch, discharge port diameter 3/4 inch, discharge rate 30 L / min, impeller rotation speed 1420 rpm
  • Third stage pump P3 centrifugal pump (manufactured by Taiheiyo Metal Co., Ltd.), suction port diameter 1 inch, discharge port diameter 3/4 inch, discharge amount 30 L / min, impeller rotation speed 1420 rpm, specific method for synthesizing barium carbonate Feeds the raw material C and carbon dioxide into the first-stage pump P1 using a double pipe.
  • the flow rate of the raw material C is 12 L / min, and the flow rate of carbon dioxide gas is 300 L / min.
  • the citric acid solution adjusted to a concentration of 25 g / L is continuously added to the third stage pump P3 from the citric acid charging point in FIG. 5 using a double pipe at a flow rate of 1.2 L / min.
  • a barium carbonate slurry was obtained.
  • the surface of barium carbonate dispersed in the slurry was treated with titanium hydroxide as follows.
  • the slurry was separated by filtration using 5C filter paper with Nutsche, and subsequently washed with pure water. The washing was performed until the conductivity of the washing water became 100 ⁇ s or less.
  • the cake after washing with water was dried for 12 hours with a box dryer heated to 110 ° C. to obtain barium carbonate whose surface was treated with titanium hydroxide. The dried barium carbonate was crushed with a small pulverizer to prepare a sample.
  • Example 3 barium carbonate whose surface was treated with titanium hydroxide was manufactured in the same manner except that the amount of TiCl 4 added was changed to 810 ml, and a sample was obtained.
  • Comparative Example 2 barium carbonate was produced by adding the aqueous ammonia and TiCl 4 and performing all the same operations, that is, without treating the surface with titanium hydroxide. Obtained.
  • These Examples 3 and 4 and Comparative Example 2 were subjected to the same thermal stability confirmation test as described above. The ignition temperature was 800 ° C.
  • the adsorption amount of titanium hydroxide of Examples 3 and 4 calculated in the same manner as in Examples 1 and 2 was 1.4 wt% and 3.6 wt%, respectively.
  • Example 5 barium carbonate before the surface was treated with titanium hydroxide was produced as follows. That is, 3.7 kg of a 50 wt% gluconic acid solution, 6 kg of barium hydroxide octahydrate and pure water are mixed to prepare a 50 L barium hydroxide aqueous solution. The temperature of the aqueous solution at this time is adjusted to 40 ° C., and this barium hydroxide aqueous solution is used as the raw material D. This raw material D and carbon dioxide gas are fed into the first stage pump P1 of the reactor 1 of FIG. 5 using a double pipe. At this time, the flow rate of the raw material D is 12 L / min, and the flow rate of the carbon dioxide gas is 300 L / min.
  • the citric acid solution whose concentration was adjusted to 12.5 g / L was continuously added to the third stage pump P3 using a double pipe from the citric acid charging point in the figure at a rate of 1.2 L / min.
  • a slurry of barium carbonate was obtained.
  • the barium carbonate slurry was filtered and separated with a Nutsche using 5C filter paper, and then washed with pure water. The washing was performed until the conductivity of the washing water became 100 ⁇ s or less.
  • the cake washed with water was repulped into pure water to prepare 22 L of a 67.5 g / L slurry as a solid content of barium carbonate.
  • the surface of the barium carbonate of this slurry was treated with titanium hydroxide as follows. That is, 324 ml of a TiCl 4 aqueous solution adjusted to a Ti concentration of 18.8 g / L was added to this slurry over 30 minutes. Simultaneously with the addition of TiCl 4 , ammonia water having a concentration of 25 wt% was added to the slurry, and the pH of the slurry was adjusted to 8.5 ⁇ 0.2. During the addition, stirring was continued at a stirring speed of 300 rpm using a stirrer equipped with a stainless steel 10 mm ⁇ 6-blade stirring blade. After completion of the addition, stirring was continued for 30 minutes, and aging was performed.
  • Example 3 barium carbonate was produced by performing the same operation without adding ammonia water and TiCl 4 , that is, without treating the surface with titanium hydroxide, and obtaining a sample thereof. It was.
  • Example 5 and Comparative Example 3 were subjected to the same thermal stability confirmation test as described above.
  • the ignition temperature was 550 ° C and 800 ° C.
  • the adsorption amount of the titanium hydroxide of Example 5 was 1.0 wt%.
  • FIG. 9 and FIG. 10 show SEM photographs of Example 5 and Comparative Example 3 at a magnification of 10,000 times in the thermal stability confirmation test, respectively.
  • the lower part (c) of FIG. 9 showing the particles of Example 5 ignited at 800 ° C. for 30 minutes is compared with the lower part (c) of FIG. 10 showing the particles of Comparative Example 3 similarly ignited at 800 ° C. for 30 minutes.
  • the particle size is small and particle growth due to heat is suppressed.
  • Example 6 high purity barium carbonate BW-KHR manufactured by Sakai Chemical Industry Co., Ltd. was used as the barium carbonate before the surface was treated with titanium hydroxide.
  • the surface of this barium carbonate BW-KHR was treated with titanium hydroxide as follows. That is, barium carbonate BW-KHR was mixed with pure water and stirred at a rotation speed of 300 rpm using a stirrer equipped with a 75 mm Teflon (registered trademark) stirring blade to prepare 5 L of a slurry having a concentration of 10 g / liter. To the slurry, 12.8 ml of an aqueous TiCl 4 solution adjusted to a Ti concentration of 18.8 g / L was added over 30 minutes.
  • Ammonia water having a concentration of 25 wt% was continuously added so that the slurry pH during the addition of the TiCl 4 aqueous solution was 8.5 ⁇ 0.2. TiCl 4 and the mixture was stirred at the end of the addition after 30 minutes of intact state. All reactions were performed at room temperature. After 5 minutes, the slurry was filtered and separated with Nutsche using 5C filter paper, and then washed with pure water. The washing was performed until the conductivity of the washing water became 100 ⁇ s or less. The cake after washing with water was dried for 12 hours with a box dryer heated to 110 ° C. to obtain barium carbonate whose surface was treated with titanium hydroxide. The dried barium carbonate was crushed with a small pulverizer to prepare a sample.
  • Example 6 the surface was treated with titanium hydroxide in the same manner except that the amount of the 18.8 g / L TiCl 4 aqueous solution added to the barium carbonate slurry was increased to 25.6 ml. Barium carbonate was produced and a sample was obtained.
  • Comparative Example 4 As a comparative sample in which the surface treatment with titanium hydroxide was not performed, high purity barium carbonate BW-KHR manufactured by Sakai Chemical Industry Co., Ltd. was used as Comparative Example 4. About these Example 6, Example 7, and Comparative Example 4, the same thermal stability confirmation test as the above-mentioned was done. The ignition temperature was 800 ° C.
  • Example 6 and Example 7 show SEM photographs of Example 6, Example 7, and Comparative Example 4, respectively, at a magnification of 10,000 by a thermal stability confirmation test.
  • the particles of Comparative Example 4 which were also ignited at 800 ° C. for 30 minutes were shown.
  • the particle size is small and the particle growth due to heat is suppressed.
  • Example 6 except that the barium carbonate used was changed to Sakai Chemical Industry Co., Ltd. high purity barium carbonate BW-KH30, all the same operations were performed to produce barium carbonate whose surface was treated with titanium hydroxide. And got that sample.
  • Comparative Example 5 As a comparative sample in which the surface treatment with titanium hydroxide was not performed, high purity barium carbonate BW-KH30 manufactured by Sakai Chemical Industry Co., Ltd. was used as Comparative Example 5. These Example 8 and Comparative Example 5 were subjected to the same thermal stability confirmation test as described above. The ignition temperature was 800 ° C. The adsorption amount of titanium hydroxide of Example 8 was 1.2 wt%.
  • Example 15 show SEM photographs of Example 8 and Comparative Example 5 at a magnification of 5,000 by a thermal stability confirmation test, respectively.
  • the lower part (b) of FIG. 14 showing the particles of Example 8 ignited at 800 ° C. for 30 minutes is compared with the lower part (b) of FIG. 15 showing the particles of Comparative Example 5 similarly ignited at 800 ° C. for 30 minutes. It can be seen that the particle size is clearly small and the particle growth due to heat is suppressed. [About strontium carbonate]
  • strontium carbonate before the surface was treated with titanium hydroxide was produced as follows. That is, dissolved strontium chloride (SrCl 2 ⁇ 1H 2 O) of pure water and adjusted to a concentration of 200 g / L. The liquid temperature at this time is adjusted to 60 ° C., and this strontium chloride aqueous solution is used as the raw material E. Next, carbon dioxide gas was absorbed into the ammonia water to prepare a 44 g / L ammonium carbonate solution as the CO 2 concentration. The liquid temperature at this time is adjusted to 30 ° C., and this ammonium carbonate solution is used as the raw material F.
  • Example 9 except that the addition amount of TiCl 4 was changed to 180 ml, all the same operations were performed to produce strontium carbonate whose surface was treated with titanium oxide, and a sample was obtained.
  • Comparative Example 6 strontium carbonate was produced by performing the same operation except that TiCl 4 and aqueous ammonia were not added, that is, without treating the surface with titanium hydroxide, and a sample was obtained. It was.
  • These Examples 9 and 10 and Comparative Example 6 were subjected to the same thermal stability confirmation test as described above. The ignition temperature was 800 ° C. Moreover, the adsorption amounts of titanium hydroxide in Examples 9 and 10 were 2.0 wt% and 4.9 wt%, respectively.

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JP2019189493A (ja) * 2018-04-26 2019-10-31 堺化学工業株式会社 炭酸バリウムの製造方法
CN111072065A (zh) * 2019-12-17 2020-04-28 西安交通大学 一种[111]取向的钛酸锶模板材料及其制备方法
JP2020158365A (ja) * 2019-03-27 2020-10-01 堺化学工業株式会社 アルカリ土類金属炭酸塩の製造方法

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JPH10273316A (ja) * 1997-03-27 1998-10-13 Agency Of Ind Science & Technol 被覆炭酸カルシウム粒子の製造方法
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JP2019189493A (ja) * 2018-04-26 2019-10-31 堺化学工業株式会社 炭酸バリウムの製造方法
WO2019208622A1 (ja) * 2018-04-26 2019-10-31 堺化学工業株式会社 炭酸バリウムの製造方法
CN112041270A (zh) * 2018-04-26 2020-12-04 堺化学工业株式会社 碳酸钡的制造方法
KR20210003184A (ko) * 2018-04-26 2021-01-11 사카이 가가쿠 고교 가부시키가이샤 탄산바륨의 제조 방법
KR102678032B1 (ko) 2018-04-26 2024-06-24 사카이 가가쿠 고교 가부시키가이샤 탄산바륨의 제조 방법
JP2020158365A (ja) * 2019-03-27 2020-10-01 堺化学工業株式会社 アルカリ土類金属炭酸塩の製造方法
WO2020195261A1 (ja) * 2019-03-27 2020-10-01 堺化学工業株式会社 アルカリ土類金属炭酸塩の製造方法
JP7200797B2 (ja) 2019-03-27 2023-01-10 堺化学工業株式会社 アルカリ土類金属炭酸塩の製造方法
CN111072065A (zh) * 2019-12-17 2020-04-28 西安交通大学 一种[111]取向的钛酸锶模板材料及其制备方法
CN111072065B (zh) * 2019-12-17 2021-05-28 西安交通大学 一种[111]取向的钛酸锶模板材料及其制备方法

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