WO2019230841A1 - Article moulé en zéolite hautement résistant à l'abrasion et sa méthode de production - Google Patents

Article moulé en zéolite hautement résistant à l'abrasion et sa méthode de production Download PDF

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WO2019230841A1
WO2019230841A1 PCT/JP2019/021398 JP2019021398W WO2019230841A1 WO 2019230841 A1 WO2019230841 A1 WO 2019230841A1 JP 2019021398 W JP2019021398 W JP 2019021398W WO 2019230841 A1 WO2019230841 A1 WO 2019230841A1
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zeolite
weight
parts
sodium
water
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PCT/JP2019/021398
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English (en)
Japanese (ja)
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悠輝 大庭
平野　茂
敬助 徳永
清水　要樹
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東ソー株式会社
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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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a highly wear-resistant zeolite compact and a method for producing the same.
  • the highly wear-resistant zeolite molded body of the present invention is useful for applications such as adsorption separation agents and catalysts.
  • VOC emission regulations which are considered to be one of the causative substances of suspended particulate matter and photochemical oxidants, have begun and attention has been focused on VOC emission countermeasure technology.
  • Zeolite has attracted attention as a VOC adsorbent. Since it is a skeleton made of heat-resistant silicon dioxide, VOC adsorption / desorption at high temperature is easy and high in safety, and has a high specific surface area.
  • stationary phase or fluidized bed adsorption towers are used, but adsorbents are pulverized when they are filled, adsorbed and desorbed, resulting in equipment troubles and pressure loss. For this reason, the adsorbent is required to have high wear resistance, but the invention has not led to the invention of a zeolite molded body having high wear resistance that can be practically used.
  • Patent Document 1 discloses a method of mixing, kneading, and molding A-type or X-type zeolite as zeolite, kaolin clay or hydrous halloysite as binder, and CMC (carboxymethylcellulose) as thickener or water retention agent. .
  • Patent Document 2 discloses a method of using a plurality of types of low silica X-type zeolite as zeolite and kaolin clay, sepiolite clay, attapulgite clay, and bentonite clay as binders.
  • Patent Document 3 discloses a method of mixing, kneading and molding 3A-type zeolite as a zeolite, kaolin clay as a binder, and condensed phosphate as an inorganic dispersant.
  • Japanese Unexamined Patent Publication No. 10-87322 Japanese Unexamined Patent Publication No. 11-314913 Japanese Unexamined Patent Publication No. 2001-226167
  • the present invention provides a zeolite molded body having a higher wear resistance than conventional zeolite molded bodies and a method for producing the same.
  • the high wear-resistant zeolite compact can be used in various adsorption separation applications and catalytic reaction applications.
  • the present inventors have found a production method that uses two types of fibrous clay and silica sol as a binder when producing a zeolite compact, and have completed the present invention. is there.
  • the present invention resides in the following [1] to [3].
  • the wear resistance strength is 90% or more
  • the zeolite has a water adsorption amount of 10 (g / g) under the conditions of Si / Al 2 of 10 to 100,000, 25 ° C., and a relative pressure of 0.5.
  • a high wear-resistant zeolite compact comprising at least one zeolite that is less than or equal to 100 g).
  • the high wear-resistant zeolite compact of the present invention has high wear resistance.
  • it can be usefully used in adsorption separation applications including heating regeneration processes and catalytic reaction applications.
  • the high wear-resistant zeolite molded product of the present invention comprises 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, and 0.5 to 10 parts by weight of water-soluble sodium salt with respect to 100 parts by weight of zeolite. And 4 to 20 parts by weight of a molding aid.
  • the zeolite contained in the highly wear-resistant zeolite compact has a Si / Al 2 content of 10 or more and 100,000 or less, a moisture adsorption amount of 10 (g / 100 g) or less under the conditions of 25 ° C. and a relative pressure of 0.5. It is a zeolite and contains at least one of them.
  • Si / Al 2 is less than 10
  • the wear strength decreases when the moisture adsorption amount exceeds 10 (g / 100 g) under the conditions of 25 ° C. and a relative pressure of 0.5.
  • zeolite examples include beta zeolite, Y zeolite, L zeolite, ferrierite zeolite, mordenite zeolite, ZSM-5 zeolite, and the like.
  • Y zeolite, ZSM-5 zeolite Is preferred.
  • the Si / Al 2 is preferably 50 or more and 10,000 or less, and more preferably 80 or more and 2000 or less.
  • the amount of fibrous clay contained in the high wear-resistant zeolite compact is 35 to 70 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). When the amount is less than 35 parts by weight, the wear resistance is low, and even when the amount is more than 70 parts by weight, no improvement in wear resistance is observed. For higher wear resistance, the amount is preferably 40 to 60 parts by weight, and more preferably 45 to 55 parts by weight.
  • the particle size of the clay is not particularly limited, but is preferably 0.5 to 30 ⁇ m as an average particle size. Examples of the fibrous clay include sepiolite clay, attapulgite clay, and palygorskite clay.
  • the amount of silica sol contained in the high wear-resistant zeolite compact is 5 to 40 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion).
  • the amount is less than 5 parts by weight, the wear resistance is not effective, and as the amount of silica sol is increased, the wear resistance is improved.
  • the amount exceeds 40 parts by weight the extrusion moldability is remarkably deteriorated.
  • 10 to 30 parts by weight is preferable, and 15 to 25 parts by weight is more preferable.
  • the particle size of the silica sol is not particularly limited, but preferably the average particle size is 5 to 30 nm.
  • the amount of water-soluble sodium salt contained in the high wear-resistant zeolite compact is 0.5 to 10 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). If the amount is less than 0.5 parts by weight, the effect is not sufficient, and if the amount is more than 10 parts by weight, the effect does not change. In order not to increase the amount of sodium derived from the water-soluble sodium salt, 0.5 to 8 parts by weight is preferable, and 0.5 to 6 parts by weight is more preferable.
  • the water-soluble sodium salt include inorganic acid sodium and organic acid sodium.
  • the inorganic acid sodium may be a water-soluble sodium salt, and examples thereof include sodium phosphate, sodium silicate, and sodium aluminate. Of these, sodium phosphate is preferred. Examples of sodium phosphate include monobasic sodium phosphate, dibasic sodium phosphate, tribasic sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. Is done.
  • the organic acid sodium may be a water-soluble sodium salt, and examples thereof include general organic carboxylic acids, amino carbonates, ether carboxylates, vinyl polymer sodium salts, and the like.
  • Examples of the general organic carboxylic acid include sodium citrate, sodium gluconate, sodium oxalate, and sodium tartrate.
  • Examples of the amino carbonate include sodium ethylenediaminetetraacetate and sodium diethylenetriaminopentaacetate.
  • the ether carboxylates include sodium carboxymethyl tartronate and sodium carboxymethyl oxysuccinate.
  • the vinyl polymer sodium salt include sodium polyacrylate and acrylic acid / maleic acid copolymer. Examples thereof include a sodium salt of a polymer.
  • the amount of the molding aid contained in the high wear-resistant zeolite compact is 4 to 20 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). When the amount is less than 4 parts by weight, the wear resistance is lowered, and when it exceeds 20 parts by weight, the moldability is significantly lowered.
  • the amount is preferably 8 to 16 parts by weight.
  • the molding aid include cellulose, alcohol, lignin, starch, guar gum and the like. Of these, cellulose and alcohol are preferred. Examples of cellulose include crystalline cellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC), and the like. Examples of the alcohol include polyvinyl alcohol and ethylene glycol.
  • the high wear-resistant zeolite compact of the present invention has a wear resistance strength of 90% or more.
  • the wear resistance strength is less than 90%, it tends to be pulverized and may cause pressure loss.
  • the measurement of wear resistance is performed according to the activated carbon test method of JIS-K-1474 (see ⁇ Abrasion Resistance Test> in Examples).
  • the wear resistance strength is preferably 92% or more, more preferably 95% or more, and particularly preferably 96.5% or more.
  • the method for producing a highly wear-resistant zeolite molded body of the present invention comprises 15 to 50 parts by weight of fibrous clay and 5 parts of silica sol with respect to 100 parts by weight of zeolite. ⁇ 40 parts by weight, 0.5 to 10 parts by weight of water-soluble sodium salt, 4 to 20 parts by weight of molding aid, 120 to 180 parts by weight of water, and then dried, and further obtained zeolite molding The body is fired at 400 to 700 ° C.
  • the zeolite contained in the mixture used in the production method of the present invention has a Si / Al 2 content of 10 or more and 100000 or less, a water adsorption amount of 10 (g / 100 g) under the conditions of 25 ° C. and a relative pressure of 0.5. It is necessary to include one or more of the following zeolites.
  • Si / Al 2 is less than 10
  • moisture adsorption amount exceeds 10 (g / 100 g) under the conditions of 25 ° C. and relative pressure 0.5, it becomes easy to adsorb moisture in the atmosphere and wear strength. Decreases.
  • zeolite examples include beta zeolite, Y zeolite, L zeolite, ferrierite zeolite, mordenite zeolite, ZSM-5 zeolite, and the like.
  • Y zeolite, ZSM-5 zeolite Is preferred.
  • the Si / Al 2 is preferably 50 or more and 10,000 or less, and more preferably 80 or more and 2000 or less.
  • fibrous clay includes various types of clay, but fibrous clay does not block the pores present in the zeolite crystals, so there is no performance degradation.
  • Plate-like crystal clay such as kaolin clay is not preferred because it may block the pores of zeolite crystals.
  • fibrous clay include sepiolite clay, attapulgite clay, and palygorskite clay.
  • the amount of fibrous clay is 35 to 70 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). When the amount is less than 35 parts by weight, the wear resistance is low, and even when the amount is more than 70 parts by weight, no improvement in wear resistance is observed. For higher wear resistance, the amount is preferably 40 to 60 parts by weight, and more preferably 45 to 55 parts by weight.
  • the particle size of the clay is not particularly limited, but is preferably 0.5 to 30 ⁇ m as an average particle size.
  • silica sol included in the mixture used in the production method of the present invention is silica sol.
  • the amount of silica sol is 5 to 40 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). When the amount is less than 5 parts by weight, the wear resistance is not effective, and as the amount of silica sol is increased, the wear resistance is improved. When the amount exceeds 40 parts by weight, the extrusion moldability is remarkably deteriorated. In order to maintain both wear resistance and extrusion moldability at a high level, 10 to 30 parts by weight is preferable, and 15 to 25 parts by weight is more preferable.
  • the particle size of the silica sol is not particularly limited, but preferably the average particle size is 5 to 30 nm.
  • the pH is not particularly limited, but is preferably 7.0 to 10.0.
  • a water-soluble sodium salt included in the mixture used in the production method of the present invention.
  • the water-soluble sodium salt include inorganic acid sodium and organic acid sodium.
  • As a water-soluble sodium salt it is preferable to contain at least one of an inorganic acid sodium or an organic acid sodium.
  • the amount of the water-soluble sodium salt is 0.5 to 10 parts by weight with respect to 100 parts by weight of zeolite (anhydrous conversion). If the amount is less than 0.5 parts by weight, the effect is not sufficient, and if the amount is more than 10 parts by weight, the effect does not change. In order not to increase the amount of sodium derived from the water-soluble sodium salt, 0.5 to 8 parts by weight is preferable, and 0.5 to 6 parts by weight is more preferable.
  • the inorganic acid sodium may be a water-soluble sodium salt, and examples thereof include sodium phosphate, sodium silicate, and sodium aluminate. Of these, sodium phosphate is preferably used because it is easy to handle. Examples of sodium phosphate include monobasic sodium phosphate, dibasic sodium phosphate, tribasic sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. it can.
  • the organic acid sodium may be a water-soluble sodium salt, and examples thereof include general organic carboxylic acids, amino carbonates, ether carboxylates, vinyl polymer sodium salts, and the like.
  • Examples of the general organic carboxylic acid include sodium citrate, sodium gluconate, sodium oxalate, and sodium tartrate.
  • Examples of the amino carbonate include sodium ethylenediaminetetraacetate and sodium diethylenetriaminopentaacetate.
  • the ether carboxylate for example, sodium carboxymethyl tartronate and sodium carboxymethyloxysuccinate can be used
  • the vinyl polymer sodium salt for example, sodium polyacrylate, acrylic acid / maleic acid copolymer A sodium salt of a polymer can be used.
  • Molding aids improve moldability, and examples include cellulose, alcohol, lignin, starch, and guar gum. Of these, cellulose and alcohol are preferred because they are easy to handle. Examples of cellulose include crystalline cellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC), and the like. Examples of the alcohol include polyvinyl alcohol and ethylene glycol.
  • the amount of the molding aid is 4 to 20 parts by weight, preferably 8 to 16 parts by weight, based on 100 parts by weight of zeolite (anhydrous conversion). When the amount is less than 4 parts by weight, the wear resistance is lowered, and when it exceeds 20 parts by weight, the moldability is significantly lowered.
  • the amount of water contained in the mixture used in the production method of the present invention is 120 to 180 parts by weight, preferably 140 to 160 parts by weight, based on 100 parts by weight of zeolite (anhydrous conversion). If it is less than 120 parts by weight or more than 180 parts by weight, molding may be difficult.
  • the mixture used in the production method of the present invention comprises 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, and 0.5 to 10 parts by weight of water-soluble sodium salt with respect to 100 parts by weight of zeolite. Further, 4 to 20 parts by weight of a molding aid and 120 to 180 parts by weight of water are mixed and kneaded.
  • the method of mixing and kneading is not particularly limited, and for example, a roll kneader mix muller, a blade stirring Henschel mixer, a batch type or continuous kneader can be used.
  • the shape of the molded body is not particularly limited, but a spherical shape, a cylindrical shape, an elliptical shape, a saddle shape, a trefoil shape, a ring shape and the like are preferable, and a spherical shape and a cylindrical shape are more preferable.
  • the size of the molded body is not particularly limited, but the average particle diameter is preferably 0.1 to 3 mm.
  • the aspect ratio (ratio of major axis to minor axis) of the molded body is not particularly limited, but is preferably 3 or less.
  • the formed zeolite compact is dried.
  • the drying method is not particularly limited, and for example, a box-type dryer or a continuous dryer can be used.
  • the drying temperature can be 50 to 200 ° C.
  • the drying atmosphere can be performed in an air or nitrogen atmosphere at atmospheric pressure.
  • the dried zeolite compact is classified to a desired size. Classification can also be performed before drying.
  • the dried zeolite compact is fired.
  • the firing method is not particularly limited, and can be performed by an apparatus such as a box muffle furnace, a rotary kiln, or a shaft kiln.
  • the firing temperature may be any temperature at which the fibrous clay can be sintered to develop strength, and is preferably 400 to 700 ° C.
  • the firing atmosphere can be performed in an air or nitrogen atmosphere under atmospheric pressure.
  • the moisture adsorption amount was measured at a temperature of 25 ° C. using a spring balance type adsorption device.
  • ⁇ Abrasion resistance test> The measurement of wear resistance strength in the wear resistance test was performed according to JIS-K-1474. That is, the sample was lightly tapped to a 100 mL mark of a 200 mL graduated cylinder and filled. A sample taken with a graduated cylinder was placed in an abrasion resistance test dish with 15 steel balls each having a diameter of 12.7 mm and a diameter of 9.5 mm. It was attached to a sieve shaker and shaken for 30 minutes. Using a sieve with a half-eye size of the sieve with the most remaining sample and a pan, all the samples except for the steel balls were placed and attached to a sieve shaker. After shaking for 3 minutes, the mass of the sample remaining on the sieve and the pan was weighed to the order of 0.1 g. The abrasion resistance strength was calculated by the following formula 1.
  • H W / S ⁇ 100 (Formula 1)
  • H wear resistance strength (mass fraction%)
  • W mass of the sample remaining on the sieve (g)
  • S total mass (g) of the specimen remaining on the sieve and on the tray.
  • Example 1 Y-type zeolite powder (HSZ (registered trademark) -385HUA: manufactured by Tosoh Corporation (Si / Al 2 : 100, moisture adsorption amount: 2 g / 100 g)) 80 parts by weight (1627 g; moisture content 2%), MFI zeolite powder (HSZ (registered trademark) -891HOA: manufactured by Tosoh Corporation (Si / Al 2 : 1500, moisture adsorption amount: 4 g / 100 g)) 20 parts by weight (413 g; moisture content 3%), attapulgite type clay (minigel MB: active 50 parts by weight (made by Minerals) (1253 g; moisture content 22%), 6 parts by weight (120 g) sodium carboxymethylcellulose, and 6 parts by weight crystalline cellulose (Seolas® RC-591; made by Asahi Kasei Chemicals) (120 g) Weighed and mixed for 5 minutes with a mix muller (manufacture
  • silica sol (Snowtex C-30: manufactured by Nissan Chemical Industries) was added and mixed for 5 minutes.
  • water in which 1.5 parts by weight (30 g) of sodium dihydrogen phosphate (manufactured by Rin Kagaku Kogyo; NaH 2 PO 4 ) was dissolved and mixed for 5 minutes.
  • 960 g of water was further added, and the mixture was stirred and kneaded for 10 minutes to obtain a mixture.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 109 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm.
  • the abrasion resistance strength after the abrasion resistance test was 96.7%.
  • Example 2 Example 1 except that 4 parts by weight (80 g) of sodium carboxymethylcellulose, 4 parts by weight (80 g) of crystalline cellulose (Theolas® RC-591: manufactured by Asahi Kasei Chemicals) and 1350 g of silica sol were added. The same operation was performed to obtain a mixture. The obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 106 parts by weight with respect to 100 parts by weight of zeolite. The obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm.
  • the abrasion resistance strength after the abrasion resistance test was 96.4%.
  • Example 3 A mixture was obtained in the same manner as in Example 1 except that the mix muller was changed to a Henschel mixer and the amount of water added was changed to 1088 g. The obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 106 parts by weight with respect to 100 parts by weight of zeolite. The obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 900 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object. The aspect ratio of the zeolite compact was 1.2.
  • the abrasion resistance strength after the abrasion resistance test was 96.7%.
  • Example 4 A mixture was obtained in the same manner as in Example 1 except that the silica sol was changed to 25 parts by weight.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 101 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 900 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the aspect ratio of the zeolite compact was 1.2.
  • the abrasion resistance strength after the abrasion resistance test was 96.8%.
  • Example 5 A mixture was obtained in the same manner as in Example 1 except that 10 parts by weight (653 g) of silica sol and 1350 g of water to be added were used. The obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 95 parts by weight with respect to 100 parts by weight of zeolite. The obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 900 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object. The aspect ratio of the zeolite compact was 1.2.
  • the abrasion resistance strength after the abrasion resistance test was 96.5%.
  • Example 6 The same operation as in Example 4 was performed to obtain a mixture.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 101 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 600 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the aspect ratio of the zeolite compact was 2.3.
  • the abrasion resistance strength after the abrasion resistance test was 95.0%.
  • Example 7 The same operation as in Example 4 was performed to obtain a mixture.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 101 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 450 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the aspect ratio of the zeolite compact was 2.5.
  • the abrasion resistance strength after the abrasion resistance test was 93.2%.
  • Example 8 The same operation as in Example 4 was performed to obtain a mixture.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 101 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Thereafter, rolling sizing was performed with a Malmerizer (QJ-400: manufactured by Dalton) at a rotation speed of 300 rpm, and the cylindrical molded body was deformed into a spherical shape. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the aspect ratio of the zeolite compact was 3.
  • the abrasion resistance strength after the abrasion resistance test was 90.9%.
  • Comparative Example 1 Without adding silica sol, 4 parts by weight (80 g) of sodium carboxymethylcellulose, 4 parts by weight (80 g) of crystalline cellulose (Theolas® RC-591: manufactured by Asahi Kasei Chemicals), and 1740 g of water to be added Performed the same operation as Example 1 to obtain a mixture.
  • the obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 95 parts by weight with respect to 100 parts by weight of zeolite.
  • the obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the abrasion resistance strength after the abrasion resistance test was 84.9%.
  • Comparative Example 2 The same operation as in Example 1 was performed except that the attapulgite-type clay (Minigel MB: manufactured by Active Minerals) was changed to kaolin clay (plate-like clay), and the silica sol was not added, but the added water was changed to 1400 g. A mixture was obtained. The obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 83 parts by weight with respect to 100 parts by weight of zeolite. The obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the attapulgite-type clay Minigel MB: manufactured by Active Minerals
  • the abrasion resistance strength after the abrasion resistance test was 45.3%.
  • Comparative Example 3 A mixture was obtained in the same manner as in Example 1 except that 25 parts by weight of silica sol, 30 parts by weight of attapulgite-type clay, and 1530 g of water to be added were used. The obtained mixture was measured for loss on ignition at 650 ° C. for 1 hour. As a result, it was 95 parts by weight with respect to 100 parts by weight of zeolite. The obtained mixture was molded into a cylindrical shape having a diameter of 0.6 mm. Then, it dried at 100 degreeC for 12 hours or more, and baked at 650 degreeC for 3 hours, and obtained the zeolite molded object.
  • the abrasion resistance strength after the abrasion resistance test was 89.6%.
  • the high wear-resistant zeolite molded body of the present invention is excellent in wear resistance, and therefore can be used without causing equipment trouble or pressure loss in applications such as adsorption separation agents and catalysts.

Abstract

La présente invention aborde le problème de la fourniture d'un article moulé en zéolite hautement résistant à l'abrasion et sa méthode de production, ledit article moulé ayant une excellente résistance à l'abrasion par comparaison avec des articles moulés en zéolite classiques. L'invention concerne : un article moulé en zéolite hautement résistant à l'abrasion caractérisé en ce qu'il contient 35 à 70 parties en poids d'une argile fibreuse, 5 à 40 parties en poids de sol de silice, 0,5 à 10 parties en poids d'un sel de sodium soluble dans l'eau et 4 à 20 parties en poids d'une aide au moulage par rapport à 100 parties en poids de zéolite, la force de résistance à l'abrasion étant de 90 % ou plus, et ladite zéolite contenant un ou plusieurs types de zéolite dans lesquels Si/Al2 est de 10 à 100 000, et dans lesquels la quantité d'adsorption d'eau est de 10 (g/100g) ou moins dans des conditions à 25°C et une pression relative de 0,5 ; et une méthode de production dudit article moulé en zéolite.
PCT/JP2019/021398 2018-05-31 2019-05-29 Article moulé en zéolite hautement résistant à l'abrasion et sa méthode de production WO2019230841A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09150056A (ja) * 1995-12-01 1997-06-10 Kawata Mfg Co Ltd ハニカム状セラミック体及びその製造方法
JPH1087322A (ja) * 1996-09-13 1998-04-07 Tosoh Corp 高強度低摩耗性ゼオライト粒状物、その製造方法及びそれを用いた吸着分離方法
JPH11314913A (ja) * 1998-05-07 1999-11-16 Tosoh Corp 高強度低摩耗性ゼオライト粒状物及びその製造方法
JP2001226167A (ja) * 1999-12-07 2001-08-21 Tosoh Corp ゼオライトビーズ成形体、その製造方法及びこれを用いた吸着除去方法
WO2012070605A1 (fr) * 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Corps façonné à base de silice, son procédé de fabrication et procédé de fabrication de propylène à l'aide du corps façonné à base de silice

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3738916A1 (de) * 1987-11-17 1989-05-24 Ibs Engineering & Consulting I Grossformatiger oder kleinformatiger molekularsieb-formkoerper und verfahren zu seiner herstellung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09150056A (ja) * 1995-12-01 1997-06-10 Kawata Mfg Co Ltd ハニカム状セラミック体及びその製造方法
JPH1087322A (ja) * 1996-09-13 1998-04-07 Tosoh Corp 高強度低摩耗性ゼオライト粒状物、その製造方法及びそれを用いた吸着分離方法
JPH11314913A (ja) * 1998-05-07 1999-11-16 Tosoh Corp 高強度低摩耗性ゼオライト粒状物及びその製造方法
JP2001226167A (ja) * 1999-12-07 2001-08-21 Tosoh Corp ゼオライトビーズ成形体、その製造方法及びこれを用いた吸着除去方法
WO2012070605A1 (fr) * 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Corps façonné à base de silice, son procédé de fabrication et procédé de fabrication de propylène à l'aide du corps façonné à base de silice

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