WO2024048091A1 - 吸着剤 - Google Patents

吸着剤 Download PDF

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Publication number
WO2024048091A1
WO2024048091A1 PCT/JP2023/025909 JP2023025909W WO2024048091A1 WO 2024048091 A1 WO2024048091 A1 WO 2024048091A1 JP 2023025909 W JP2023025909 W JP 2023025909W WO 2024048091 A1 WO2024048091 A1 WO 2024048091A1
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Prior art keywords
magnesium silicate
silicate compound
alkali metal
adsorbent
amount
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English (en)
French (fr)
Japanese (ja)
Inventor
晴美 高畑
フオン テイ ド
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SETOLAS Holdings Inc
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SETOLAS Holdings Inc
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Priority to KR1020257005355A priority Critical patent/KR20250038765A/ko
Priority to EP23859861.9A priority patent/EP4582178A1/en
Priority to JP2024544009A priority patent/JPWO2024048091A1/ja
Priority to CN202380061207.7A priority patent/CN119744196A/zh
Publication of WO2024048091A1 publication Critical patent/WO2024048091A1/ja
Priority to JP2025026179A priority patent/JP2025071257A/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • 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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/14—Pore volume
    • 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
    • C01P2006/90—Other properties not specified above

Definitions

  • the present invention relates to a novel adsorbent used for adsorbing substances such as alkali metals.
  • Chemical products may contain trace amounts of impurities such as catalysts used during synthesis, unreacted raw materials, and by-products during reactions. From the viewpoint of improving product quality, etc., it is required to efficiently remove these impurities.
  • methods for removing such impurities include methods such as neutralization, distillation, extraction, or adsorption during the manufacturing process of chemical products. Among these, adsorption methods, particularly methods using adsorbents, are often used as simple methods.
  • polyurethane foam is manufactured by polymerizing a polyol component and an isocyanate component, which are raw materials.
  • Polyols used in the production of polyurethane foam include polyether polyols, polymer polyols, polyester polyols, etc., and these are used in any combination depending on the target performance of the polyurethane.
  • polyether polyol is produced by addition polymerizing propylene oxide to glycerin in the presence of an alkali metal-containing basic catalyst, but it is required to have a purity in which the residual catalyst after purification is as close to zero as possible.
  • adsorbents that can adsorb and remove alkali metal-containing basic catalysts are used in the production of polyether polyols.
  • the adsorbents used here are usually synthetic products such as molecular sieves, activated alumina, synthetic magnesium silicate, synthetic aluminum silicate, and activated carbon; natural products; and processed products of natural products such as acid clay and activated clay. Yes, but not particularly limited.
  • an adsorbent capable of adsorbing and removing an alkali metal-containing basic catalyst an amorphous adsorbent whose chemical formula, BET specific surface area, alkali metal content, and average particle size are within specific ranges is used.
  • An adsorbent comprising a synthetic hydrous magnesium silicate compound is disclosed.
  • an object of the present invention is to provide a novel adsorbent that has a high adsorption capacity and can adsorb objects to be adsorbed with a small amount of use.
  • the present inventors found that by using an amorphous magnesium silicate compound with low alkali metal content and high solid acidity as an adsorbent, K + , Na It has been found that the adsorption ability for metal ions such as + and Ni + is improved.
  • the present disclosure has been completed based on this knowledge and includes the following aspects.
  • the first disclosure is an adsorbent made of an amorphous magnesium silicate compound.
  • the magnesium silicate compound has an alkali metal content of 1.20% by mass or less.
  • the magnesium silicate compound has a solid acid amount of 0.70 mmol/g or more.
  • the magnesium silicate compound is a compound represented by the following formula (1).
  • x is a number satisfying 0.1 ⁇ x ⁇ 0.5.
  • m is a number satisfying 0.1 ⁇ m ⁇ 1.5. ]
  • the BET specific surface area of the magnesium silicate compound is 200 m 2 /g to 1000 m 2 /g.
  • the fourth disclosure is the magnesium silicate compound according to any one of the first to third disclosures, wherein the total pore volume of the magnesium silicate compound is 0.40 cm 3 /g to 1.50 cm 3 /g.
  • the fifth disclosure is a method for reducing the alkali metal content in polyether polyols.
  • the reduction method includes contacting a polyether polyol containing an alkali metal-containing basic catalyst with the adsorbent of any one of the first to fourth disclosures.
  • FIG. 1 is a powder method X-ray diffraction diagram of the magnesium silicate compound of Example 2.
  • FIG. 2 is a powder method X-ray diffraction diagram of the magnesium silicate compound of Example 4.
  • the adsorbent according to one embodiment of the present invention is made of an amorphous magnesium silicate compound.
  • This magnesium silicate compound has an alkali metal content of 1.20% by mass or less. Furthermore, this magnesium silicate compound has a solid acid amount of 0.70 mmol/g or more.
  • the adsorbent of this embodiment is made of an amorphous magnesium silicate compound that has a low alkali metal content and high solid acidity as described above, so that it is effective against metal ions such as K + , Na + , and Ni + . It can exhibit excellent adsorption ability. Since its adsorption capacity is much higher than that of conventional adsorbents made of magnesium silicate compounds, the amount of the adsorbent used in this embodiment can be significantly reduced compared to such conventional adsorbents. can be reduced.
  • the adsorbent of the present embodiment is a novel adsorbent that has much higher adsorption capacity than conventional adsorbents made of magnesium silicate compounds and can adsorb objects to be adsorbed with a small amount of use. Furthermore, the adsorbent of this embodiment can contribute to reducing energy consumption and waste disposal, etc., and has the advantage that it can contribute to achieving the SDGs (Sustainable Development Goals) adopted at the United Nations Summit. There is also.
  • SDGs Stustainable Development Goals
  • the adsorbent according to one embodiment of the present invention is made of an amorphous magnesium silicate compound as described above.
  • amorphous magnesium silicate compound means a magnesium silicate compound whose powder X-ray diffraction pattern shows an amorphous form.
  • the alkali metal content of the magnesium silicate compound is 1.20% by mass or less.
  • Such an alkali metal content below a specific amount can be achieved, for example, by adjusting the pH of the reaction slurry to be low during the synthesis of the magnesium silicate compound described below, or by performing heat aging treatment and/or acid treatment after synthesis. You can get it by doing.
  • the alkali metal content can be reduced by lowering the pH of the reaction slurry during synthesis of the magnesium silicate compound.
  • the alkali metal content can be reduced by promoting dissolution precipitation of the magnesium silicate compound.
  • acid treatment is performed after synthesis of the magnesium silicate compound, the alkali metal component contained therein is replaced with acid protons, so that the alkali metal content can be reduced.
  • the alkali metal component means an alkali metal such as sodium or potassium derived from raw materials, for example.
  • the alkali metal content of the magnesium silicate compound is preferably 1.10% by mass or less, more preferably 1.00% by mass or less. Further, the lower limit of the alkali metal content of the magnesium silicate compound is not particularly limited, but may be, for example, 0.001% by mass.
  • the solid acid amount of the magnesium silicate compound is 0.70 mmol/g or more.
  • Such an amount of solid acid exceeding a specific amount can be obtained by the same means as for the alkali metal content described above.
  • the amount of solid acid above a specific amount can be adjusted, for example, by adjusting the pH of the reaction slurry to be low during the synthesis of the magnesium silicate compound described below, or by performing heat aging treatment and/or acid treatment after synthesis. You can get it by doing. For example, by lowering the pH of the reaction slurry during the synthesis of a magnesium silicate compound, the alkali metal content can be reduced and the amount of solid acid can be increased.
  • the solid acid amount of the magnesium silicate compound is preferably 1.00 mmol/g or more, more preferably 1.50 mmol/g or more. Further, the upper limit of the amount of solid acid in the magnesium silicate compound is not particularly limited, but may be, for example, 10.00 mmol/g.
  • the magnesium silicate compound in one embodiment of the present invention has an alkali metal content of not more than the above-mentioned specific amount and a high solid acid content of not less than the above-mentioned specific amount, so that it can absorb various metal ions. It can exhibit very excellent adsorption ability against. As a result, the adsorbent of this embodiment can adsorb various metal ions in a smaller amount than a conventional adsorbent made of a magnesium silicate compound.
  • the magnesium silicate compound is not particularly limited except that it is amorphous, has an alkali metal content equal to or less than the above specified amount, and has a high solid acid amount equal to or more than the above specified amount.
  • a hydrous magnesium silicate compound represented by formula (1) is preferable.
  • x is a number satisfying 0.1 ⁇ x ⁇ 0.5.
  • m is a number satisfying 0.1 ⁇ m ⁇ 1.5. ]
  • magnesium silicate compound is a hydrous magnesium silicate compound represented by the formula (1), the above-mentioned excellent adsorption ability for metal ions can be more reliably exhibited.
  • the preferable range of x is 0.2 ⁇ x ⁇ 0.35.
  • the BET specific surface area of the magnesium silicate compound is preferably 200 m 2 /g to 1000 m 2 /g.
  • the BET specific surface area of the magnesium silicate compound is within such a range, a certain amount or more of adsorption can be ensured, so that the above-mentioned excellent adsorption ability for metal ions can be more reliably exhibited.
  • the BET specific surface area of the magnesium silicate compound is more preferably 220 m 2 /g or more, and even more preferably 250 m 2 /g or more. Further, the BET specific surface area of the magnesium silicate compound is more preferably 900 m 2 /g or less, and even more preferably 800 m 2 /g or less.
  • the BET specific surface area means the specific surface area of a magnesium silicate compound determined by the BET method.
  • a specific method for measuring the BET specific surface area will be explained in Examples below.
  • the total pore volume of the magnesium silicate compound is preferably 0.40 cm 3 /g to 1.50 cm 3 /g.
  • the total pore volume of the magnesium silicate compound is within this range, it is possible to ensure a certain amount of adsorption or more, so the above-mentioned excellent adsorption ability for metal ions can be more reliably demonstrated. .
  • the total pore volume of the magnesium silicate compound is more preferably 0.50 cm 3 /g or more. Further, the total pore volume of the magnesium silicate compound is more preferably 1.20 cm 3 /g or less.
  • the average particle size of the magnesium silicate compound is preferably 2.0 ⁇ m to 60.0 ⁇ m.
  • the specific surface area can be widened and a certain amount of adsorption can be secured, so the above-mentioned excellent adsorption ability for metal ions can be further enhanced. It can definitely be performed.
  • the average particle size of the magnesium silicate compound is more preferably 5.0 ⁇ m or more. Moreover, it is more preferable that the average particle size of the magnesium silicate compound is 50.0 ⁇ m or less.
  • the magnesium silicate compound that can be used as the adsorbent of the present invention is amorphous, has an alkali metal content of not more than the above specified amount, and has a high solid acid content of not less than the above specified amount.
  • the manufacturing method, conditions, etc. are not limited in any way.
  • the above-mentioned hydrous magnesium silicate compound can be synthesized by reacting a water-soluble magnesium compound and a water-soluble silicate compound.
  • water-soluble magnesium compounds include magnesium chloride, magnesium sulfate, and magnesium nitrate.
  • the reaction may be a batch reaction in which a certain amount of a magnesium compound aqueous solution and a certain amount of a silicate compound aqueous solution are simultaneously added to a reaction tank, or a certain amount of a magnesium compound aqueous solution and a certain amount of a silicate compound aqueous solution are added to a reaction tank. It may be a continuous reaction in which a reaction slurry is continuously obtained by continuous addition. Continuous reaction is advantageous in terms of production efficiency.
  • the reaction temperature is not particularly limited, but a temperature of 15°C to 60°C can be employed, for example.
  • the reaction may be carried out by placing a reaction vessel in a constant temperature bath controlled at a constant temperature, or a container containing an aqueous magnesium compound solution and a container containing an aqueous silicate compound solution in a constant temperature bath controlled at a constant temperature. and may be poured into the reaction tank from each container using a metering pump.
  • the reaction pH is, for example, 7 to 10, preferably 8.5 to 9.5.
  • the primary particles of the hydrous magnesium silicate compound after synthesis can be made into fine particles.
  • the specific surface area of the hydrous magnesium silicate compound increases, the number of adsorption sites increases, and the adsorption capacity can be improved.
  • the reaction slurry obtained by the above synthesis step may be aged by heating and stirring.
  • the aging temperature is, for example, 60°C to 120°C, preferably 70°C to 110°C, and more preferably 80°C to 100°C.
  • the aging time is, for example, 0.5 to 18 hours, preferably 1 to 12 hours, and more preferably 2 to 6 hours.
  • the hydrous magnesium silicate compound after synthesis may be acid-treated using an inorganic acid.
  • the alkali metal component in the hydrous magnesium silicate compound after synthesis is replaced with the proton of the inorganic acid, increasing the solid acidity of the hydrous magnesium silicate compound, thereby increasing the adsorption of alkali metal ions. ability can be improved.
  • the alkali metal component is, for example, sodium or potassium derived from the raw material.
  • the inorganic acid that can be used in the acid treatment step is not particularly limited, but examples include sulfuric acid, hydrochloric acid, and nitric acid.
  • a specific method of the acid treatment step includes, for example, solid-liquid separation of the reaction slurry to separate the solids.
  • An example of this method is washing with diluted inorganic acid and then washing with water.
  • Other methods include separating the reaction slurry into solid and liquid, suspending the solid in diluted inorganic acid, stirring for a certain period of time, and washing with water after dehydration.
  • the concentration of the inorganic acid is, for example, 0.01 mol/L to 0.5 mol/L, preferably 0.02 mol/L to 0.2 mol/L.
  • concentration of the diluted inorganic acid is 0.01 mol/L or more, protons in the inorganic acid are sufficiently replaced with alkali metal components.
  • concentration of the diluted inorganic acid is 0.5 mol/L or less, sulfate ions, chloride ions, nitrate ions, and the like of the inorganic acid are difficult to remain as impurities in the solid material.
  • the concentration of the diluted inorganic acid is 0.5 mol/L or less, it becomes difficult for the magnesium in the magnesium silicate to be dissolved by the inorganic acid.
  • the method for drying the hydrous magnesium silicate compound after synthesis is not particularly limited, but includes, for example, a shelf drying method in which the solid after dehydration is placed in a stainless steel vat and dried with hot air.
  • Other drying methods include slurrying the solid material after dehydration to a concentration of 100 g/L to 500 g/L in terms of solid content, and optionally adjusting the shape of the dried material using a ball mill, colloid mill, SC mill, dyno mill, etc.
  • Examples include a spray drying method in which the material is processed using a wet pulverizer and then dried using a spray dryer.
  • the drying method it is preferable to employ a spray drying method since it is easy to granulate the hydrous magnesium silicate compound into spherical shapes.
  • Granulating a hydrous magnesium silicate compound into spherical shapes has the advantage that it can be easily separated and removed after adsorption treatment.
  • the magnesium silicate compound obtained by the above production method is amorphous and has an alkali metal content below the above specified amount due to the reaction conditions during synthesis and the heat aging step and/or acid treatment step after synthesis. Moreover, it has a high solid acid amount exceeding the above-mentioned specific amount.
  • Such a magnesium silicate compound can be used, for example, as an adsorbent for various industrial purposes, but as mentioned above, it can be used to adsorb and remove alkali metal-containing basic catalysts when producing polyether polyols. It is particularly useful as an adsorbent for
  • Another embodiment of the invention is a method of reducing alkali metal content in polyether polyols.
  • the reduction method includes adding an amorphous magnesium silicate having an alkali metal content of not more than the above specified amount and a high solid acid content of not less than the above specified amount to a polyether polyol containing an alkali metal-containing basic catalyst. contacting an adsorbent comprising a compound.
  • the adsorbent has an extremely excellent adsorption ability capable of adsorbing various metal ions with a small amount used, so it is possible to increase the yield of polyether polyol, and further, The amount of waste generated after purification can be reduced.
  • the above-mentioned magnesium silicate compound is added to the polyether polyol as an adsorbent, mixed, and then the adsorption Examples include a method of separating and removing the agent.
  • the amount of the adsorbent added depends on the amount of the residual alkali metal-containing basic catalyst, but is, for example, 0.1% to 10.0% by mass based on the mass of the polyether polyol, preferably 0.5% by mass. The mass is ⁇ 5.0% by mass.
  • the adsorption treatment can be performed under stirring, at a treatment temperature of 70° C. to 150° C., and a treatment time of 5 minutes to 120 minutes.
  • Water may be added during the adsorption treatment. In that case, it is preferable to add 0.5% to 3.0% by mass of water based on the mass of the polyether polyol.
  • an antioxidant may be added to the polyether polyol to prevent deterioration.
  • the adsorbent before adding the adsorbent to the polyether polyol, at least one of inorganic acids, inorganic acid salts, and organic acids such as phosphoric acid, sulfuric acid, sodium hydrogen pyrophosphate, and oxalic acid is added to cause a neutralization reaction. may be caused. In that case, the adsorbent is added after the neutralization reaction has finished.
  • the present invention is not limited to the above-described embodiments or the examples described below, and can be appropriately combined, substituted, and changed within the scope of the purpose and gist of the present invention.
  • SiO 2 /MgO molar ratio and alkali metal content were measured using a scanning fluorescent X-ray analyzer “ZSX Primus IV” manufactured by Rigaku Corporation.
  • BET specific surface area and total pore volume The BET specific surface area and total pore volume of the magnesium silicate compound were measured using a high precision critical area/pore distribution measuring device "BELsorp-max" manufactured by Microtrac Bell Co., Ltd.
  • the liquid pH of the magnesium silicate compound was measured as follows. 2.0 g of dried magnesium silicate compound and 40 mL of ion-exchanged water were placed in a beaker, stirred for 5 minutes using a magnetic stirrer, and then mixed with No. It was filtered using 5C filter paper, and the pH of the filtrate was measured. The pH of this filtrate was defined as the liquid pH of the magnesium silicate compound.
  • ⁇ Solid acid amount> 0.1 g of a dried magnesium silicate compound was placed in an Erlenmeyer flask with a stopper, and 5 mL of benzene (Wako reagent special grade) was added. 1 mL of a 0.1% by weight benzene solution of methyl orange was added as an indicator with pKa 4.8, and the dried particles were colored red. Titration was performed with a 0.1 mol/L n-butylamine-benzene solution until the dried particles turned yellow, and the amount of n-butylamine-benzene solution required for titration was defined as A (mL).
  • the average particle diameter of the magnesium silicate compound was measured using a particle size distribution measuring device "MICROTRAC MT3000II series" manufactured by Nikkiso Co., Ltd. Specifically, first, 70 mL of a 2.0 g/L sodium hexametaphosphate aqueous solution was added to 0.7 g of a dried magnesium silicate compound, and the mixture was stirred with a magnetic stirrer. 2 to 4 mL of the dispersion was added to a 2.0 g/L aqueous sodium hexametaphosphate solution, the dispersion was circulated for 1 minute, and then the particle size distribution was measured using the above particle size distribution measuring device. The average particle diameter was determined from the obtained 50% cumulative (median diameter).
  • Example 1 (Synthesis test) A constant amount of a 1.17 mol/L magnesium sulfate aqueous solution and a No. 3 water glass aqueous solution consisting of 0.46 mol/L Na 2 O and 1.44 mol/L SiO 2 were continuously poured into a continuous reaction tank. , a coprecipitation reaction was carried out. The reaction temperature was 40°C. The pH of the resulting reaction slurry was 8.9. Further, the average particle size of the reactant particles was 8.2 ⁇ m. Furthermore, this reaction slurry was dehydrated by suction filtration using a Nutsche filter, and the solid matter was washed with ion-exchanged water in an amount 20 times the weight of the solid matter. The obtained solid was slurried to a concentration of 250 g/L and spray-dried using a spray dryer.
  • the SiO 2 /MgO molar ratio of the magnesium silicate compound of Example 1 was 3.5.
  • the alkali metal content of the magnesium silicate compound of Example 1 was 1.00% by mass.
  • the BET specific surface area of the magnesium silicate compound of Example 1 was 295 m 2 /g.
  • the total pore volume of the magnesium silicate compound of Example 1 was 0.47 cm 3 /g.
  • the liquid pH of the magnesium silicate compound of Example 1 was 9.8.
  • the amount of solid acid in the magnesium silicate compound of Example 1 was 0.73 mmol/g.
  • the average particle size of the magnesium silicate compound of Example 1 was 42.2 ⁇ m.
  • the powder method X-ray diffraction pattern of the magnesium silicate compound of Example 1 showed that it was amorphous.
  • Adsorption test 1 In advance, 160 g of polypropylene glycol (degree of polymerization: 3,000) in which potassium hydroxide had been dissolved so that the potassium concentration was 1400 ppm was placed in a four-necked round-bottomed flask, and the flask was heated and stirred with a mantle heater while purging with nitrogen. When the liquid temperature reached 85°C, 1.6 mL of ion-exchanged water was added, and after the liquid temperature reached 90°C, 0.4 g of an adsorbent made of a synthesized magnesium silicate compound was added. The mixture was heated and stirred for 30 minutes.
  • Adsorption test 2 In advance, 160 g of polypropylene glycol (degree of polymerization: 3,000) in which potassium hydroxide had been dissolved so that the potassium concentration was 1400 ppm was placed in a four-necked round-bottomed flask, and the flask was heated and stirred with a mantle heater while purging with nitrogen. When the liquid temperature reached 85°C, 1.6 mL of ion-exchanged water was added, and after the liquid temperature reached 90°C, 0.56 g of an adsorbent made of a synthesized magnesium silicate compound was added. The mixture was heated and stirred for 30 minutes.
  • the treated solution was immediately filtered under suction at a suction pressure of 0.02 MPa to obtain a filtrate.
  • This filtrate was subjected to potentiometric titration with 0.01N hydrochloric acid to determine the potassium concentration in the filtrate, which was found to be 128 ppm.
  • the treated solution was immediately filtered under suction at a suction pressure of 0.02 MPa to obtain a filtrate.
  • This filtrate was subjected to potentiometric titration with 0.01N hydrochloric acid to determine the potassium concentration in the filtrate, which was found to be 38 ppm.
  • Example 2 (Synthesis test) A constant amount of a 1.17 mol/L magnesium sulfate aqueous solution and a No. 3 water glass aqueous solution consisting of 0.46 mol/L Na 2 O and 1.44 mol/L SiO 2 were continuously poured into a continuous reaction tank. , a coprecipitation reaction was carried out. The reaction temperature was 40°C. The pH of the resulting reaction slurry was 8.9. Further, the average particle size of the reactant particles was 8.2 ⁇ m.
  • this reaction slurry was dehydrated by suction filtration using a Nutsche filter, and the solid was washed with 0.05 mol/L sulfuric acid, which was 15 times the weight of the solid, and the sodium in the solid was ion-exchanged. Thereafter, it was washed with 20 times the amount of ion-exchanged water in the same manner.
  • the obtained solid was slurried to a concentration of 250 g/L and spray-dried using a spray dryer.
  • the SiO 2 /MgO molar ratio of the magnesium silicate compound of Example 2 was 3.9.
  • the alkali metal content of the magnesium silicate compound of Example 2 was 0.17% by mass.
  • the BET specific surface area of the magnesium silicate compound of Example 2 was 259 m 2 /g.
  • the total pore volume of the magnesium silicate compound of Example 2 was 0.56 cm 3 /g.
  • the liquid pH of the magnesium silicate compound of Example 2 was 9.1.
  • the amount of solid acid in the magnesium silicate compound of Example 2 was 0.90 mmol/g.
  • the average particle size of the magnesium silicate compound of Example 2 was 43.8 ⁇ m.
  • the powder method X-ray diffraction diagram of the magnesium silicate compound of Example 2 showed that it was amorphous as shown in FIG.
  • Adsorption test 2 An adsorption test was conducted in exactly the same manner as adsorption test 2 in Example 1, and the potassium concentration in the filtrate was 104 ppm.
  • Example 3 (Synthesis test) A constant amount of a 1.17 mol/L magnesium sulfate aqueous solution and a No. 3 water glass aqueous solution consisting of 0.46 mol/L Na 2 O and 1.44 mol/L SiO 2 were continuously poured into a continuous reaction tank. , a coprecipitation reaction was carried out. The reaction temperature was 40°C. The pH of the resulting reaction slurry was 8.9. Further, the average particle size of the reactant particles was 8.2 ⁇ m. Furthermore, this reaction slurry was heated and stirred at 90° C. for 2 hours.
  • this slurry was dehydrated by suction filtration using a Nutsche filter, and the solid matter was washed with ion-exchanged water in an amount 20 times the weight of the solid matter.
  • the obtained solid was slurried to a concentration of 250 g/L and spray-dried using a spray dryer.
  • the SiO 2 /MgO molar ratio of the magnesium silicate compound of Example 3 was 3.4.
  • the alkali metal content of the magnesium silicate compound of Example 3 was 0.98% by mass.
  • the BET specific surface area of the magnesium silicate compound of Example 3 was 714 m 2 /g.
  • the total pore volume of the magnesium silicate compound of Example 3 was 1.05 cm 3 /g.
  • the liquid pH of the magnesium silicate compound of Example 3 was 9.6.
  • the amount of solid acid in the magnesium silicate compound of Example 3 was 1.65 mmol/g.
  • the average particle size of the magnesium silicate compound of Example 3 was 39.8 ⁇ m.
  • the powder method X-ray diffraction pattern of the magnesium silicate compound of Example 3 showed that it was amorphous.
  • Adsorption test 2 An adsorption test was conducted in exactly the same manner as adsorption test 2 in Example 1, and the potassium concentration in the filtrate was 70 ppm.
  • Example 4 (Synthesis test) A constant amount of a 1.17 mol/L magnesium sulfate aqueous solution and a No. 3 water glass aqueous solution consisting of 0.46 mol/L Na 2 O and 1.44 mol/L SiO 2 were continuously poured into a continuous reaction tank. , a coprecipitation reaction was carried out. The reaction temperature was 40°C. The pH of the resulting reaction slurry was 8.9. Further, the average particle size of the reactant particles was 8.2 ⁇ m. Furthermore, this reaction slurry was heated and stirred at 90° C. for 2 hours.
  • this slurry was dehydrated by suction filtration using a Nutsche filter, and the solid matter was washed with 0.05 mol/L sulfuric acid, which was 15 times the weight of the solid matter, and the sodium in the solid matter was ion-exchanged. , and washed in the same manner with 20 times the amount of ion-exchanged water.
  • the obtained solid was slurried to a concentration of 250 g/L and spray-dried using a spray dryer.
  • the SiO 2 /MgO molar ratio of the magnesium silicate compound of Example 4 was 4.0.
  • the alkali metal content of the magnesium silicate compound of Example 4 was 0.08% by mass.
  • the BET specific surface area of the magnesium silicate compound of Example 4 was 702 m 2 /g.
  • the total pore volume of the magnesium silicate compound of Example 4 was 1.07 cm 3 /g.
  • the liquid pH of the magnesium silicate compound of Example 4 was 8.4.
  • the amount of solid acid in the magnesium silicate compound of Example 4 was 1.62 mmol/g.
  • the average particle size of the magnesium silicate compound of Example 4 was 39.8 ⁇ m.
  • the powder method X-ray diffraction diagram of the magnesium silicate compound of Example 4 showed that it was amorphous as shown in FIG.
  • Adsorption test 2 An adsorption test was conducted in exactly the same manner as adsorption test 2 in Example 1, and the potassium concentration in the filtrate was 78 ppm.
  • Comparative example 1 (Synthesis test) A fixed amount of a 1.35 mol/L magnesium sulfate aqueous solution and a No. 3 water glass aqueous solution consisting of 0.55 mol/L Na 2 O and 1.73 mol/L SiO 2 were continuously poured into a continuous reaction tank. , a coprecipitation reaction was carried out. The reaction temperature was 40°C. The pH of the resulting reaction slurry was 9.3. Further, the average particle size of the reactant particles was 12.8 ⁇ m. Furthermore, this reaction slurry was dehydrated by suction filtration using a Nutsche filter, and the solid matter was washed with ion-exchanged water in an amount 20 times the weight of the solid matter. The obtained solid was slurried to a concentration of 250 g/L and spray-dried using a spray dryer.
  • the SiO 2 /MgO molar ratio of the magnesium silicate compound of Comparative Example 1 was 3.6.
  • the alkali metal content of the magnesium silicate compound of Comparative Example 1 was 1.60% by mass.
  • the BET specific surface area of the magnesium silicate compound of Comparative Example 1 was 126 m 2 /g.
  • the total pore volume of the magnesium silicate compound of Comparative Example 1 was 0.24 cm 3 /g.
  • the liquid pH of the magnesium silicate compound of Comparative Example 1 was 10.1.
  • the amount of solid acid in the magnesium silicate compound of Comparative Example 1 was 0.61 mmol/g.
  • the average particle size of the magnesium silicate compound of Comparative Example 1 was 40.6 ⁇ m.
  • the powder method X-ray diffraction diagram of the magnesium silicate compound of Comparative Example 1 showed that it was amorphous.
  • Adsorption test 2 An adsorption test was conducted in exactly the same manner as adsorption test 2 of Example 1, and the potassium concentration in the filtrate was 283 ppm.
  • the adsorbents made of the magnesium silicate compounds of Examples 1 to 4 had a small amount of residual K in the adsorption test and could exhibit very excellent adsorption performance for alkali metals.
  • the adsorbent made of the magnesium silicate compound of Comparative Example 1 had a large amount of residual K in the adsorption test, and was found to have insufficient adsorption performance for alkali metals.
  • the adsorbent of the present invention has a much higher adsorption capacity than conventional adsorbents made of magnesium silicate compounds, and can adsorb objects with a small amount of use, so it can be used as an adsorbent for various industrial applications, for example. It can be suitably used.
  • the adsorbent of the present invention is particularly useful as an adsorbent for adsorbing and removing an alkali metal-containing basic catalyst when producing a polyether polyol.

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JP2004075674A (ja) * 2002-06-18 2004-03-11 Kyowa Chem Ind Co Ltd 粗製ポリエーテルの精製方法および吸着剤
JP2020513048A (ja) * 2017-03-23 2020-04-30 ザ ダラス グループ オブ アメリカ，インコーポレイテッド 酸官能化シリカ及び金属ケイ酸塩を用いた粗ポリアルキレンオキシドポリマーの精製

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JP2020513048A (ja) * 2017-03-23 2020-04-30 ザ ダラス グループ オブ アメリカ，インコーポレイテッド 酸官能化シリカ及び金属ケイ酸塩を用いた粗ポリアルキレンオキシドポリマーの精製

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