WO2019230841A1 - Highly abrasion-resistant zeolite moulded article and method for producing same - Google Patents

Highly abrasion-resistant zeolite moulded article and method for producing same Download PDF

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Publication number
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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French (fr)
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

The present invention addresses the problem of providing a highly abrasion-resistant zeolite moulded article and a method for producing the same, said moulded article having excellent abrasion resistance in comparison with conventional zeolite moulded articles. Provided are: a highly abrasion-resistant zeolite moulded article characterised by containing 35-70 parts by weight of a fibrous clay, 5-40 parts by weight of silica sol, 0.5-10 parts by weight of a water-soluble sodium salt and 4-20 parts by weight of a moulding aid in relation to 100 parts by weight of zeolite, wherein the abrasion resistance strength is 90% or more, and said zeolite contains one or more types of zeolite in which Si/Al2 is 10-100,000, and in which the water adsorption amount is 10 (g/100g) or less under conditions of 25°C and relative pressure of 0.5; and a method for producing said zeolite moulded article.

Description

高耐摩耗性ゼオライト成形体及びその製造方法High wear-resistant zeolite molded body and method for producing the same
　本発明は、高耐摩耗性ゼオライト成形体及びその製造方法に関する。本発明の高耐摩耗性ゼオライト成形体は、例えば、吸着分離剤、触媒などの用途に有用である。 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.
　近年、浮立粒子状物質や光化学オキシダントの原因物質の一つとされているＶＯＣの排出規制が始まり、ＶＯＣ排出の対策技術に注目が集まっている。ＶＯＣ吸着剤としてはゼオライトが注目されている。熱に強い二酸化ケイ素からなる骨格であるため、高温でのＶＯＣの吸脱着が容易かつ安全性が高く、高比表面積である。一方で、工場などでＶＯＣを吸着する際、固定相または流動層の吸着塔が利用されるが、それらへの充填や吸脱着の際に吸着剤が粉化してしまい、設備トラブルや圧力損失の原因となるため、吸着剤には高い耐摩耗性が要求されているが、実用可能な高い耐摩耗性を有するゼオライト成形体の発明には至っていない。 In recent years, 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. On the other hand, when adsorbing VOCs at factories and the like, 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.
　ゼオライト成形体の強度を強くする手段として、いくつかの方法が知られている。例えば、特許文献１には、ゼオライトとしてＡ型又はＸ型ゼオライト、バインダーとしてカオリン粘土あるいは加水ハロイサイト、増粘剤または保水剤としてＣＭＣ（カルボキシメチルセルロース）を混合、混練、成形する方法が開示されている。 Several methods are known as means for increasing the strength of the zeolite compact. For example, 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. .
　特許文献２には、ゼオライトとして低シリカＸ型ゼオライト、バインダーとしてカオリン系粘土、セピオライト系粘土、アタパルジャイト系粘土、ベントナイト系粘土を複数種類使用する方法が開示されている。 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.
　特許文献３には、ゼオライトとして３Ａ型ゼオライト、バインダーとしてカオリン粘土、無機系分散剤として縮合リン酸塩を混合、混練、成形する方法が開示されている。 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.
　いずれの特許文献においても、実用性のある耐摩耗性を有するゼオライト成形体の発明には至っておらず、より高い耐摩耗性を有してゼオライト成形体の発明が望まれている。 In any of the patent documents, the invention of a zeolite molded body having practical wear resistance has not been achieved, and the invention of a zeolite molded body having higher wear resistance is desired.
日本国特開平１０－８７３２２号公報Japanese Unexamined Patent Publication No. 10-87322 日本国特開平１１－３１４９１３号公報Japanese Unexamined Patent Publication No. 11-314913 日本国特開２００１－２２６１６７号公報Japanese Unexamined Patent Publication No. 2001-226167
　本発明は、従来のゼオライト成形体よりも耐摩耗性に優れたゼオライト成形体及びその製造方法を提供するものである。高耐摩耗性ゼオライト成形体は、様々な吸着分離用途、触媒反応用途で使用することができる。 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.
　本発明者らは、上記課題を解決するために鋭意検討した結果、ゼオライト成形体を製造する時にバインダーとして繊維状粘土およびシリカゾルの二種類を使用する製造方法を見出し、本発明を完成したものである。 As a result of intensive studies to solve the above problems, 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.
　すなわち、本発明は以下の［１］乃至［３］に存する。 That is, the present invention resides in the following [1] to [3].
　［１］　ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部含み、かつ、耐摩耗強度が９０％以上であり、当該ゼオライトが、Ｓｉ／Ａｌ２が１０以上１０００００以下、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）以下であるゼオライトを一種以上含むことを特徴とする高耐摩耗性ゼオライト成形体。 [1] 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, and 4 to 20 parts by weight of molding aids per 100 parts by weight of zeolite And the wear resistance strength is 90% or more, and 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. 100 g) A high wear-resistant zeolite compact comprising at least one zeolite that is less than or equal to 100 g).
　［２］　ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部、水を１２０～１８０重量部含む混合物を成形した後に乾燥し、さらに得られたゼオライト成形体を４００～７００℃で焼成するものであり、当該ゼオライトが、Ｓｉ／Ａｌ２が１０以上１０００００以下で、２５℃、相対圧０．５の条件で、水分吸着量が１０（ｇ／１００ｇ）以下であるゼオライトを一種以上含むことを特徴とする上記［１］に記載の高耐摩耗性ゼオライト成形体の製造方法。 [2] 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, and 4 to 20 parts by weight of molding aids per 100 parts by weight of zeolite A mixture containing 120 to 180 parts by weight of water and then dried, and the obtained zeolite compact is calcined at 400 to 700 ° C., and the zeolite has Si / Al 2 of 10 or more and 100,000 or less. The high wear-resistant zeolite molding according to the above [1], comprising at least one zeolite having a moisture adsorption amount of 10 (g / 100 g) or less under conditions of 25 ° C. and a relative pressure of 0.5. Body manufacturing method.
　［３］　当該ゼオライトが、ベータ型ゼオライト、Ｙ型ゼオライト、Ｌ型ゼオライト、フェリエライト型ゼオライト、モルデナイト型ゼオライト、ＺＳＭ－５型ゼオライトの少なくとも一種を含むことを特徴とする上記［２］に記載の高耐摩耗性ゼオライト成形体の製造方法。 [3] The above-mentioned [2], wherein the zeolite contains at least one of beta zeolite, Y zeolite, L zeolite, ferrierite zeolite, mordenite zeolite, and ZSM-5 zeolite. A method for producing a highly wear-resistant zeolite compact.
　本発明の高耐摩耗性ゼオライト成形体は、耐摩耗性が高い。特に、加熱再生プロセスを含む吸着分離用途、触媒反応用途で有用に使用することができる。 The high wear-resistant zeolite compact of the present invention has high wear resistance. In particular, it can be usefully used in adsorption separation applications including heating regeneration processes and catalytic reaction applications.
　以下、本発明について説明する。 Hereinafter, the present invention will be described.
　本発明の高耐摩耗性ゼオライト成形体は、ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部含むものである。 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.
　高耐摩耗性ゼオライト成形体に含まれるゼオライトは、Ｓｉ／Ａｌ２が１０以上１０００００以下で、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）以下であるゼオライトであり、これを一種以上含むものである。Ｓｉ／Ａｌ２が１０未満の場合、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）を超える場合には、摩耗強度が低下する。ゼオライトの種類としては、例えば、ベータ型ゼオライト、Ｙ型ゼオライト、Ｌ型ゼオライト、フェリエライト型ゼオライト、モルデナイト型ゼオライト、ＺＳＭ－５型ゼオライトなどが例示されるが、Ｙ型ゼオライト、ＺＳＭ－５型ゼオライトが好ましい。Ｓｉ／Ａｌ２は、５０以上１００００以下が好ましく、８０以上２０００以下がさらに好ましい。 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. When 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. Examples of the types of zeolite 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.
　高耐摩耗性ゼオライト成形体に含まれる繊維状粘土の量は、ゼオライト１００重量部（無水換算）に対して３５～７０重量部である。３５重量部未満の場合は耐摩耗性が低くなり、７０重量部より多くした場合でも、耐摩耗性の向上は認められない。耐摩耗性がより高くなるため、４０～６０重量部が好ましく、４５～５５重量部がさらに好ましい。粘土の粒径は特に制限されないが、好ましくは平均粒径として０．５～３０μｍである。繊維状粘土としては、例えば、セピオライト粘土、アタパルジャイト粘土、パリゴルスカイト粘土などがあげられる。 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 μm as an average particle size. Examples of the fibrous clay include sepiolite clay, attapulgite clay, and palygorskite clay.
　高耐摩耗性ゼオライト成形体に含まれるシリカゾルの量はゼオライト１００重量部（無水換算）に対して５～４０重量部である。５重量部未満の場合、耐摩耗性には効果がなく、シリカゾルの添加量を増加させるにつれて、耐摩耗性も向上していくが、４０重量部を超える場合、押し出し成形性が著しく悪化する。耐摩耗性と押し出し成形性をいずれも高い水準で保持するためには１０～３０重量部が好ましく、１５～２５重量部がさらに好ましい。シリカゾルの粒径は特に制限されないが、好ましくは平均粒径として５～３０ｎｍである。 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). 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.
　高耐摩耗性ゼオライト成形体に含まれる水溶性ナトリウム塩の量は、ゼオライト１００重量部（無水換算）に対して０．５～１０重量部である。０．５重量部未満ではその効果が十分でなく、１０重量部より多くしてもその効果は変化しない。水溶性ナトリウム塩に由来するナトリウムの量を増やさないため、０．５～８重量部が好ましく、０．５～６重量部がさらに好ましい。水溶性ナトリウム塩としては、例えば、無機酸ナトリウム、有機酸ナトリウムなどが例示される。 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. Examples of the water-soluble sodium salt include inorganic acid sodium and organic acid sodium.
　無機酸ナトリウムとしては水溶性のナトリウム塩であればよく、例えば、リン酸ナトリウム、ケイ酸ナトリウム、アルミン酸ナトリウムなどが例示される。これらのうち、リン酸ナトリウムが好ましい。リン酸ナトリウムとしては、例えば、第一リン酸ナトリウム、第二リン酸ナトリウム、第三リン酸ナトリウム、ピロリン酸ナトリウム、酸性ピロリン酸ナトリウム、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ヘキサメタリン酸ナトリウムなどが例示される。 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.
　有機酸ナトリウムとしては水溶性のナトリウム塩であればよく、例えば、一般有機カルボン酸、アミノカーボネート、エーテルカルボン酸塩、ビニル型高分子ナトリウム塩などが例示される。一般有機カルボン酸としては、例えば、クエン酸ナトリウム、グルコン酸ナトリウム、シュウ酸ナトリウム、酒石酸ナトリウムなどが例示され、アミノカーボネートとしては、例えば、エチレンジアミン四酢酸ナトリウム塩、ジエチレントリアミノ五酢酸ナトリウムなどが例示され、エーテルカルボン酸塩としては、例えば、カルボキシメチルタルトロン酸ナトリウム、カルボキシメチルオキシコハク酸ナトリウムなどが例示され、ビニル型高分子ナトリウム塩としては、例えば、ポリアクリル酸ナトリウム、アクリル酸／マレイン酸共重合体のナトリウム塩などが例示される。 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. Examples of the ether carboxylates include sodium carboxymethyl tartronate and sodium carboxymethyl oxysuccinate. Examples of the vinyl polymer sodium salt include sodium polyacrylate and acrylic acid / maleic acid copolymer. Examples thereof include a sodium salt of a polymer.
　高耐摩耗性ゼオライト成形体に含まれる成形助剤の量は、ゼオライト１００重量部（無水換算）に対して４～２０重量部である。４重量部未満の場合は耐摩耗性が低下し、２０重量部を超える場合は成形性が著しく低下する。好ましくは８～１６重量部である。成形助剤としては、例えば、セルロース、アルコール、リグニン、スターチ、グァーガムなどが例示される。これらのうち、セルロース、アルコールが好ましい。セルロースとしては、例えば、結晶性セルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロースナトリウム（ＣＭＣ）などが例示される。アルコールとしては、例えば、ポリビニルアルコール、エチレングリコールなどが例示される。 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. Examples of 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.
　本発明の高耐摩耗性ゼオライト成形体は、耐摩耗強度が９０％以上である。耐摩耗強度が９０％未満の場合は、粉化しやすく圧力損失などを引き起こしやすくなるおそれがある。ここに、耐摩耗強度の測定は、ＪＩＳ－Ｋ－１４７４の活性炭試験法に準じて行うものである（実施例の＜耐摩耗性試験＞を参照）。耐摩耗強度は、９２％以上が好ましく、９５％以上がさらに好ましく、９６．５％以上が特に好ましい。 The high wear-resistant zeolite compact of the present invention has a wear resistance strength of 90% or more. When the wear resistance strength is less than 90%, it tends to be pulverized and may cause pressure loss. Here, 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.
　本発明の高耐摩耗性ゼオライト成形体の製造方法（以下、「本発明の製造方法」ともいう。）は、ゼオライト１００重量部に対して、繊維状粘土を１５～５０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部、水を１２０～１８０重量部含む混合物を成形した後に乾燥し、さらに得られたゼオライト成形体を４００～７００℃で焼成することを特徴とするものである。 The method for producing a highly wear-resistant zeolite molded body of the present invention (hereinafter also referred to as “the production method 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.
　本発明の製造方法で使用される混合物に含まれるゼオライトは、Ｓｉ／Ａｌ２が１０以上１０００００以下で、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）以下であるゼオライトを一種以上含む必要がある。Ｓｉ／Ａｌ２が１０未満の場合、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）を超える場合には、大気中の水分を吸着しやすくなり摩耗強度が低下する。ゼオライトの種類としては、例えば、ベータ型ゼオライト、Ｙ型ゼオライト、Ｌ型ゼオライト、フェリエライト型ゼオライト、モルデナイト型ゼオライト、ＺＳＭ－５型ゼオライトなどが例示されるが、Ｙ型ゼオライト、ＺＳＭ－５型ゼオライトが好ましい。Ｓｉ／Ａｌ２は、５０以上１００００以下が好ましく、８０以上２０００以下がさらに好ましい。 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. When Si / Al 2 is less than 10, when the 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. Examples of the types of zeolite 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.
　本発明の製造方法で使用される混合物に含まれるのは繊維状粘土である。粘土には様々な種類があるが、繊維状粘土はゼオライト結晶に存在する細孔をふさぐことがないため性能低下がない。カオリン粘土の様な板状結晶の粘土はゼオライト結晶の細孔をふさぐ恐れがあり、好ましくない。繊維状粘土としては、例えば、セピオライト粘土、アタパルジャイト粘土、パリゴルスカイト粘土などが例示される。繊維状粘土の量としては、ゼオライト１００重量部（無水換算）に対して３５～７０重量部である。３５重量部未満の場合は耐摩耗性が低くなり、７０重量部より多くした場合でも、耐摩耗性の向上は認められない。耐摩耗性がより高くなるため、４０～６０重量部が好ましく、４５～５５重量部がさらに好ましい。粘土の粒径は特に制限されないが、好ましくは平均粒径として０．５～３０μｍである。 Included in the mixture used in the production method of the present invention is fibrous clay. There are 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. Examples of the 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 μm as an average particle size.
　本発明の製造方法で使用される混合物に含まれるのはシリカゾルである。シリカゾルの量としてはゼオライト１００重量部（無水換算）に対して５～４０重量部である。５重量部未満の場合、耐摩耗性には効果がなく、シリカゾルの添加量を増加させるにつれて、耐摩耗性も向上していくが、４０重量部を超える場合、押し出し成形性が著しく悪化する。耐摩耗性と押し出し成形性をいずれも高い水準で保持するためには１０～３０重量部が好ましく、１５～２５重量部がさらに好ましい。シリカゾルの粒径は特に制限されないが、好ましくは平均粒径として５～３０ｎｍである。また、ｐＨは特に制限はされないが、好ましくは７．０～１０．０である。 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.
　本発明の製造方法で使用される混合物に含まれるのは水溶性ナトリウム塩である。水溶性ナトリウム塩としては、例えば、無機酸ナトリウム、有機酸ナトリウムなどが例示される。水溶性ナトリウム塩としては、無機酸ナトリウム又は有機酸ナトリウムの少なくとも１種を含むことが好ましい。理由は定かではないが、水溶性ナトリウム塩を使用することで耐摩耗性は著しく高くなる。水溶性ナトリウム塩の量としては、ゼオライト１００重量部（無水換算）に対して、０．５～１０重量部である。０．５重量部未満ではその効果が十分でなく、１０重量部より多くしてもその効果は変化しない。水溶性ナトリウム塩に由来するナトリウムの量を増やさないため、０．５～８重量部が好ましく、０．５～６重量部がさらに好ましい。 Included in the mixture used in the production method of the present invention is a water-soluble sodium salt. Examples of 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. Although the reason is not clear, the wear resistance is remarkably increased by using a water-soluble sodium salt. 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.
　無機酸ナトリウムとしては水溶性のナトリウム塩であればよく、例えば、リン酸ナトリウム、ケイ酸ナトリウム、アルミン酸ナトリウムなどが例示される。これらのうち、取り扱いが容易のため、リン酸ナトリウムが好ましく使用できる。リン酸ナトリウムとしては、例えば、第一リン酸ナトリウム、第二リン酸ナトリウム、第三リン酸ナトリウム、ピロリン酸ナトリウム、酸性ピロリン酸ナトリウム、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ヘキサメタリン酸ナトリウムなどが使用できる。 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.
　有機酸ナトリウムとしては水溶性のナトリウム塩であればよく、例えば、一般有機カルボン酸、アミノカーボネート、エーテルカルボン酸塩、ビニル型高分子ナトリウム塩などが例示される。一般有機カルボン酸としては、例えば、クエン酸ナトリウム、グルコン酸ナトリウム、シュウ酸ナトリウム、酒石酸ナトリウムなどが使用でき、アミノカーボネートとしては、例えば、エチレンジアミン四酢酸ナトリウム塩、ジエチレントリアミノ五酢酸ナトリウムなどが使用でき、エーテルカルボン酸塩としては、例えば、カルボキシメチルタルトロン酸ナトリウム、カルボキシメチルオキシコハク酸ナトリウムなどが使用でき、ビニル型高分子ナトリウム塩としては、例えば、ポリアクリル酸ナトリウム、アクリル酸／マレイン酸共重合体のナトリウム塩などが使用できる。 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. As the ether carboxylate, for example, sodium carboxymethyl tartronate and sodium carboxymethyloxysuccinate can be used, and as the vinyl polymer sodium salt, for example, sodium polyacrylate, acrylic acid / maleic acid copolymer A sodium salt of a polymer can be used.
　本発明の製造方法で使用される混合物に含まれるのは成形助剤である。成形助剤としては、成形性を改善するものであり、例えば、セルロース、アルコール、リグニン、スターチ、グァーガムなどが例示される。これらのうち、取り扱いが容易であるため、セルロース、アルコールが好ましい。セルロースとしては、例えば、結晶性セルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロースナトリウム（ＣＭＣ）などが例示される。アルコールとしては、例えば、ポリビニルアルコール、エチレングリコールなどが例示される。成形助剤の量としては、ゼオライト１００重量部（無水換算）に対して、４～２０重量部であり、好ましくは８～１６重量部である。４重量部未満の場合は耐摩耗性が低下し、２０重量部を超える場合は成形性が著しく低下する。 Included in the mixture used in the production method of the present invention is a molding aid. 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.
　本発明の製造方法で使用される混合物に含まれる水の量としては、ゼオライト１００重量部（無水換算）に対して、１２０～１８０重量部であり、１４０～１６０重量部が好ましい。１２０重量部未満の場合も、１８０重量部より多い場合も成形が困難になる場合がある。 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.
　本発明の製造方法で使用される混合物は、ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部、水を１２０～１８０重量部を混合して混練することで得られるものである。混合して混練する方法としては特に制限はなく、例えば、ロール式混練機のミックスマーラー、羽根撹拌式であるヘンシェルミキサー、バッチ式又は連続式のニーダーなどが使用できる。 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.
　本発明の製造方法は、ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部、水を１２０～１８０重量部含む混合物を成形するものである。成形する方法としては特に制限はなく、例えば、転動造粒、撹拌造粒、押出し成形、噴霧造粒、これらの方法を２種以上組み合わせた方法等により成形することができる。成形体の形状は特に制限ないが、球状、円柱状、楕円状、俵型、三つ葉型、リング状などが好ましく、球状、円柱状がさらに好ましい。成形体の大きさは特に制限ないが、平均粒子径として０．１～３ｍｍが好ましい。成形体のアスペクト比(長径と短径の比)は特に制限はないが、３以下が好ましい。 In the production method of the present invention, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of a water-soluble sodium salt, and a molding aid are added to 100 parts by weight of zeolite. A mixture containing 4 to 20 parts by weight and 120 to 180 parts by weight of water is formed. There is no restriction | limiting in particular as a method to shape | mold, For example, it can shape | mold by the method of combining 2 or more types, such as rolling granulation, stirring granulation, extrusion molding, spray granulation, these methods. 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.
　成形されたゼオライト成形体は乾燥される。乾燥方法は特に制限なく、例えば、箱型乾燥機、連続式乾燥機などが使用できる。乾燥温度は５０～２００℃で行うことができる。乾燥雰囲気は大気圧下で空気又は窒素雰囲気で行うことができる。乾燥されたゼオライト成形体は、所望の大きさに分級される。分級は乾燥の前に行うこともできる。 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.
　乾燥されたゼオライト成形体は焼成される。焼成方法は特に制限なく、例えば、箱型マッフル炉、ロータリーキルン、シャフトキルンなどの装置で行うことができる。焼成温度は繊維状粘土が焼結されて強度が発現できる温度であればよく、４００～７００℃が好ましい。焼成雰囲気は大気圧下で空気又は窒素雰囲気で行うことができる。 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.
　以下、実施例により本発明をさらに具体的に説明する。しかしながら、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
　＜水分吸着量の測定＞
　水分吸着量は、スプリングバランス型の吸着装置を使用して、温度２５℃にて測定した。 <Measurement of moisture adsorption amount>
The moisture adsorption amount was measured at a temperature of 25 ° C. using a spring balance type adsorption device.
　＜耐摩耗性試験＞
　耐摩耗性試験における耐摩耗強度の測定は、ＪＩＳ－Ｋ－１４７４に準じて行った。すなわち、試料を２００ｍＬのメスシリンダーの１００ｍＬの標線まで軽くたたいて充填した。メスシリンダーではかりとった試料を直径１２．７ｍｍおよび９．５ｍｍの鋼球それぞれ１５個とともに耐摩耗性試験用皿に入れた。ふるい振とう機に取り付け、３０分間振とうした。最も試料が残ったふるいの半分の目の大きさのふるいおよび受け皿を用い、鋼球を除いた試料を全部いれ、ふるい振とう機に取り付けた。３分間振とうした後、ふるい上および受け皿に残った試料の質量をそれぞれ０．１ｇの桁まではかりとった。耐摩耗強度は次の式１によって算出した。 <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　　…（式１）
　ここで、Ｈ：耐摩耗強度（質量分率％）、Ｗ：ふるい上に残った試料の質量（ｇ）、Ｓ：ふるい上及び受け皿に残った試料の質量の合計（ｇ）とした。 H = W / S × 100 (Formula 1)
Here, H: wear resistance strength (mass fraction%), W: mass of the sample remaining on the sieve (g), and S: total mass (g) of the specimen remaining on the sieve and on the tray.
　実施例１
　Ｙ型ゼオライト粉末（ＨＳＺ（登録商標）－３８５ＨＵＡ：東ソー製（Ｓｉ／Ａｌ２：１００、水分吸着量：２ｇ／１００ｇ））を８０重量部（１６２７ｇ；水分含有量２％）、ＭＦＩ型ゼオライト粉末（ＨＳＺ（登録商標）－８９１ＨＯＡ：東ソー製（Ｓｉ／Ａｌ２：１５００、水分吸着量：４ｇ／１００ｇ））を２０重量部（４１３ｇ；水分含有量３％）、アタパルジャイト型粘土（ミニゲルＭＢ：アクティブミネラルズ製）を５０重量部（１２５３ｇ；水分含有量２２％）、カルボキシメチルセルロースナトリウムを６重量部（１２０ｇ）、結晶性セルロース（セオラス（登録商標）ＲＣ－５９１；旭化成ケミカルズ製）を６重量部（１２０ｇ）量り取り、ミックスマーラー（新東工業製）で５分間混合した。シリカゾル（スノーテックスＣ－３０：日産化学製）１６３９ｇを添加し、５分間混合した。水１０００ｇにリン酸二水素ナトリウム（燐化学工業製；ＮａＨ２ＰＯ４）を１．５重量部（３０ｇ）溶解した水を添加し、５分間混合した。その後、更に９６０ｇの水を添加して、１０分間撹拌混練し、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０９重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数９００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は１．２であった。 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 (manufactured by Shinto Kogyo). 1639 g of silica sol (Snowtex C-30: manufactured by Nissan Chemical Industries) was added and mixed for 5 minutes. To 1000 g of water was added 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. Thereafter, 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. 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. It dried at 100 degreeC for 12 hours or more, baked at 650 degreeC for 3 hours, and obtained the zeolite molded object. The aspect ratio of the zeolite compact was 1.2.
　耐摩耗性試験を行った後の耐摩耗強度は９６．７％であった。 The abrasion resistance strength after the abrasion resistance test was 96.7%.
　実施例２
　カルボキシメチルセルロースナトリウムを４重量部（８０ｇ）、結晶性セルロース（セオラス（登録商標）ＲＣ－５９１：旭化成ケミカルズ製）を４重量部（８０ｇ）、シリカゾルの添加量を１３５０ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０６重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数９００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は１．２であった。 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. 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.
　耐摩耗性試験を行った後の耐摩耗強度は９６．４％であった。 The abrasion resistance strength after the abrasion resistance test was 96.4%.
　実施例３
　ミックスマーラーをヘンシェルミキサーに変更し、添加する水を１０８８ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０６重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数９００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は１．２であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９６．７％であった。 The abrasion resistance strength after the abrasion resistance test was 96.7%.
　実施例４
　シリカゾルを２５重量部とした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０１重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数９００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は１．２であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９６．８％であった。 The abrasion resistance strength after the abrasion resistance test was 96.8%.
　実施例５
　シリカゾルを１０重量部（６５３ｇ）、添加する水を１３５０ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して９５重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数９００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は１．２であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９６．５％であった。 The abrasion resistance strength after the abrasion resistance test was 96.5%.
　実施例６
　実施例４と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０１重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数６００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は２．３であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９５．０％であった。 The abrasion resistance strength after the abrasion resistance test was 95.0%.
　実施例７
　実施例４と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０１重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数４５０ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は２．５であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９３．２％であった。 The abrasion resistance strength after the abrasion resistance test was 93.2%.
　実施例８
　実施例４と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して１０１重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、マルメライザー（ＱＪ－４００：ダルトン製）で回転数３００ｒｐｍで転動整粒を行い、円柱状の成形体を球状に変形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。ゼオライト成形体のアスペクト比は３であった。 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.
　耐摩耗性試験を行った後の耐摩耗強度は９０．９％であった。 The abrasion resistance strength after the abrasion resistance test was 90.9%.
　比較例１
　シリカゾルを添加しないで、カルボキシメチルセルロースナトリウムを４重量部（８０ｇ）、結晶性セルロース（セオラス（登録商標）ＲＣ－５９１：旭化成ケミカルズ製）を４重量部（８０ｇ）、添加する水を１７４０ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して９５重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。 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.
　耐摩耗性試験を行った後の耐摩耗強度は８４．９％であった。 The abrasion resistance strength after the abrasion resistance test was 84.9%.
　比較例２
　アタパルジャイト型粘土（ミニゲルＭＢ：アクティブミネラルズ製）からカオリン粘土（板状粘土）に変更し、シリカゾルを添加しないで、添加する水を１４００ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して８３重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。 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.
　耐摩耗性試験を行った後の耐摩耗強度は４５．３％であった。 The abrasion resistance strength after the abrasion resistance test was 45.3%.
　比較例３
　シリカゾルを２５重量部、アタパルジャイト型粘土を３０重量部、添加する水を１５３０ｇとした以外は、実施例１と同様の操作を行い、混合物を得た。得られた混合物を６５０℃、１時間の条件で強熱減量を測定した結果、ゼオライト１００重量部に対して９５重量部であった。得られた混合物を直径０．６ｍｍの円柱状に成形した。その後、１００℃で１２時間以上乾燥して、６５０℃、３時間の焼成を行い、ゼオライト成形体を得た。 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.
　耐摩耗性試験を行った後の耐摩耗強度は８９．６％であった。 The abrasion resistance strength after the abrasion resistance test was 89.6%.
　なお、２０１８年５月３１日に出願された日本特許出願２０１８－１０４７３０号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2018-104730 filed on May 31, 2018 are cited herein as disclosure of the specification of the present invention. Incorporated.
　本発明の高耐摩耗性ゼオライト成形体は、耐摩耗性に優れるため、吸着分離剤、触媒などの用途において、設備トラブルや圧力損失などを引き起こすことなく使用することができる。 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.

Claims (3)

  1. ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部含み、かつ、耐摩耗強度が９０％以上であり、当該ゼオライトが、Ｓｉ／Ａｌ２が１０以上１０００００以下、２５℃、相対圧０．５の条件で、水分吸着量が、１０（ｇ／１００ｇ）以下であるゼオライトを一種以上含むことを特徴とする高耐摩耗性ゼオライト成形体。 It contains 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of a water-soluble sodium salt, and 4 to 20 parts by weight of a molding aid with respect to 100 parts by weight of zeolite. In addition, the wear resistance strength is 90% or more, and the zeolite has a moisture adsorption amount of 10 (g / 100 g) or less under conditions of Si / Al 2 of 10 or more and 100,000 or less, 25 ° C., and a relative pressure of 0.5. A high wear-resistant zeolite compact comprising one or more zeolites.
  2. ゼオライト１００重量部に対して、繊維状粘土を３５～７０重量部、シリカゾルを５～４０重量部、水溶性ナトリウム塩を０．５～１０重量部、成形助剤を４～２０重量部、水を１２０～１８０重量部含む混合物を成形した後に乾燥し、さらに得られたゼオライト成形体を４００～７００℃で焼成するものであり、当該ゼオライトが、Ｓｉ／Ａｌ２が１０以上１０００００以下で、２５℃、相対圧０．５の条件で、水分吸着量が１０（ｇ／１００ｇ）以下であるゼオライトを一種以上含むことを特徴とする請求項１に記載の高耐摩耗性ゼオライト成形体の製造方法。 Based on 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, 4 to 20 parts by weight of molding aid, water After forming a mixture containing 120 to 180 parts by weight, the mixture is dried, and the obtained zeolite compact is calcined at 400 to 700 ° C., and the zeolite has Si / Al 2 of 10 to 100,000, 2. The method for producing a highly wear-resistant zeolite compact according to claim 1, comprising at least one zeolite having a moisture adsorption amount of 10 (g / 100 g) or less under the conditions of 0 ° C. and a relative pressure of 0.5. .
  3. 当該ゼオライトが、ベータ型ゼオライト、Ｙ型ゼオライト、Ｌ型ゼオライト、フェリエライト型ゼオライト、モルデナイト型ゼオライト、ＺＳＭ－５型ゼオライトの少なくとも一種を含むことを特徴とする請求項２に記載の高耐摩耗性ゼオライト成形体の製造方法。 3. The high wear resistance according to claim 2, wherein the zeolite contains at least one of beta zeolite, Y zeolite, L zeolite, ferrierite zeolite, mordenite zeolite, and ZSM-5 zeolite. A method for producing a zeolite compact.
PCT/JP2019/021398 2018-05-31 2019-05-29 Highly abrasion-resistant zeolite moulded article and method for producing same WO2019230841A1 (en)

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Citations (5)

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JPH09150056A (en) * 1995-12-01 1997-06-10 Kawata Mfg Co Ltd Honeycomb-type ceramic form and manufacture thereof
JPH1087322A (en) * 1996-09-13 1998-04-07 Tosoh Corp High strength and low wear zeolite granule, its production and adsorption separation method using same
JPH11314913A (en) * 1998-05-07 1999-11-16 Tosoh Corp High strength low wear zeolite granule and its production
JP2001226167A (en) * 1999-12-07 2001-08-21 Tosoh Corp Zeolite formed bead, production process of the same and adsorption/removal process using the same
WO2012070605A1 (en) * 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3738916A1 (en) * 1987-11-17 1989-05-24 Ibs Engineering & Consulting I Large-sized or small-sized molecular sieve shaped body and process for the production thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09150056A (en) * 1995-12-01 1997-06-10 Kawata Mfg Co Ltd Honeycomb-type ceramic form and manufacture thereof
JPH1087322A (en) * 1996-09-13 1998-04-07 Tosoh Corp High strength and low wear zeolite granule, its production and adsorption separation method using same
JPH11314913A (en) * 1998-05-07 1999-11-16 Tosoh Corp High strength low wear zeolite granule and its production
JP2001226167A (en) * 1999-12-07 2001-08-21 Tosoh Corp Zeolite formed bead, production process of the same and adsorption/removal process using the same
WO2012070605A1 (en) * 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body

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