JP2019210207A - Highly wear-resistant zeolite compact and its production method - Google Patents
Highly wear-resistant zeolite compact and its production method Download PDFInfo
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- JP2019210207A JP2019210207A JP2019100631A JP2019100631A JP2019210207A JP 2019210207 A JP2019210207 A JP 2019210207A JP 2019100631 A JP2019100631 A JP 2019100631A JP 2019100631 A JP2019100631 A JP 2019100631A JP 2019210207 A JP2019210207 A JP 2019210207A
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- zeolite
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- compact
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000010457 zeolite Substances 0.000 title claims abstract description 129
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000004927 clay Substances 0.000 claims abstract description 40
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 29
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000465 moulding Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims description 18
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract 2
- 238000005299 abrasion Methods 0.000 description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 229920002678 cellulose Polymers 0.000 description 11
- 239000001913 cellulose Substances 0.000 description 11
- 235000010980 cellulose Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 9
- 238000004513 sizing Methods 0.000 description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052625 palygorskite Inorganic materials 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 235000011008 sodium phosphates Nutrition 0.000 description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical class NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 description 4
- 229960000892 attapulgite Drugs 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 ether carboxylates Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004113 Sepiolite Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 229910052624 sepiolite Inorganic materials 0.000 description 3
- 235000019355 sepiolite Nutrition 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 2
- BRZHSVBNTLQTMN-UHFFFAOYSA-L disodium 2-(carboxymethyl)-2-hydroxypropanedioate Chemical compound C(=O)(O)CC(C(=O)[O-])(O)C(=O)[O-].[Na+].[Na+] BRZHSVBNTLQTMN-UHFFFAOYSA-L 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229960001790 sodium citrate Drugs 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 2
- 229940039790 sodium oxalate Drugs 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000007641 Trefoil Factors Human genes 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- BNVZBQVIMPLFNA-UHFFFAOYSA-L disodium;2-(carboxymethoxy)butanedioate Chemical compound [Na+].[Na+].OC(=O)COC(C([O-])=O)CC([O-])=O BNVZBQVIMPLFNA-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000791 photochemical oxidant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
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 regulation, which is one of the causative substances of suspended particulate matter and photochemical oxidants, has started and attention has been paid to 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 trouble 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 compact having practical wear resistance has not been achieved, and the invention of a zeolite compact having higher wear resistance is desired.
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 compact that is superior in wear resistance to conventional zeolite compacts 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。すなわち、本発明は、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、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高耐摩耗性ゼオライト成形体の製造方法である。 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. That is, the present invention is based on 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 4 molding aids with respect to 100 parts by weight of zeolite. -20 parts by weight, wear resistance strength is 90% or more, and the zeolite has a water adsorption amount of 10 under conditions of Si / Al 2 of 10 or more and 100,000 or less, 25 ° C., and a relative pressure of 0.5. (G / 100g) Highly wear-resistant zeolite compact characterized by containing one or more zeolites, 35 to 70 parts by weight of fibrous clay and 5 to 40 parts by weight of silica sol with respect to 100 parts by weight of zeolite. A mixture containing 0.5 to 10 parts by weight of a water-soluble sodium salt, 4 to 20 parts by weight of a molding aid, and 120 to 180 parts by weight of water, followed by drying. The zeolite is calcined at ˜700 ° C., and the zeolite has a Si / Al 2 of 10 or more and 100,000 or less, a moisture adsorption amount of 10 (g / 100 g) or less under conditions of 25 ° C. and a relative pressure of 0.5. It is a method for producing a highly wear-resistant zeolite compact characterized by containing at least one zeolite.
以下、本発明について説明する。 The present invention will be described below.
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 compact of the present invention is 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 type of zeolite include beta type zeolite, Y type zeolite, L type zeolite, ferrierite type zeolite, mordenite type zeolite, ZSM-5 type zeolite and the like. 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 highly 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. Since abrasion resistance becomes higher, 40-60 weight part is preferable and 45-55 weight part is further more preferable. 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 keep both the wear resistance and the 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 is preferably 5 to 30 nm as an average particle size.
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 the water-soluble sodium salt contained in the highly 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 highly 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. Preferably it is 8-16 weight part. 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 the wear resistance strength is performed in accordance with 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 15-50 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 type of zeolite include beta type zeolite, Y type zeolite, L type zeolite, ferrierite type zeolite, mordenite type zeolite, ZSM-5 type zeolite and the like. 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。 The mixture used in the production method of the present invention includes 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. Since abrasion resistance becomes higher, 40-60 weight part is preferable and 45-55 weight part is further more preferable. 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 keep both the wear resistance and the 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 is preferably 5 to 30 nm as an average particle size. 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, sodium hexametaphosphate, etc. 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 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.
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 and preferably 140 to 160 parts by weight with respect to 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. In addition, 4 to 20 parts by weight of the 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。 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, 0.5 to 10 parts by weight of a water-soluble sodium salt, and a molding aid for 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. A drying temperature can be performed at 50-200 degreeC. 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 is sintered and strength can be developed, and is preferably 400 to 700 ° C. The firing atmosphere can be performed in an air or nitrogen atmosphere under atmospheric pressure.
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、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 the 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
80 parts by weight of Y-type zeolite powder (HSZ (registered trademark) -385HUA: manufactured by Tosoh Corporation (Si / Al 2 : 100, moisture adsorption amount: 2 g / 100 g)), MFI-type 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 (manufactured by Minerals) (1253 g; moisture content 22%), 6 parts by weight (120 g) sodium carboxymethylcellulose, and 6 parts by weight of crystalline cellulose (Seolas (registered trademark) RC-591; manufactured 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. Then, 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. Then, 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. Then, 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. Then, 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. Then, 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 conducting 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 conducting 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 conducting 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 conducting 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 (registered trademark) 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 conducting 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 conducting the abrasion resistance test was 89.6%.
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。 Since the highly wear-resistant zeolite molded article of the present invention is excellent in wear resistance, it can be used in applications such as adsorption separation agents and catalysts without causing equipment trouble or pressure loss.
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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 |
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 |
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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 |
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 |
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