JPH03197313A - Stabilized synthetic zeolite and its production - Google Patents
Stabilized synthetic zeolite and its productionInfo
- Publication number
- JPH03197313A JPH03197313A JP33922289A JP33922289A JPH03197313A JP H03197313 A JPH03197313 A JP H03197313A JP 33922289 A JP33922289 A JP 33922289A JP 33922289 A JP33922289 A JP 33922289A JP H03197313 A JPH03197313 A JP H03197313A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- acid
- synthetic zeolite
- water
- synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 210
- 239000010457 zeolite Substances 0.000 title claims abstract description 176
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 175
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002253 acid Substances 0.000 claims abstract description 70
- 238000005406 washing Methods 0.000 claims abstract description 62
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 48
- 238000007654 immersion Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 33
- 229910052782 aluminium Inorganic materials 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 238000001914 filtration Methods 0.000 description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 20
- 229910017604 nitric acid Inorganic materials 0.000 description 20
- 238000010828 elution Methods 0.000 description 19
- 238000000926 separation method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 12
- -1 sodium and potassium Chemical class 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Chemical group 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical group 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Chemical group 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011135 tin Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical group 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、水に対して自己崩壊現象のない安定化した合
成ゼオライト及びその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a stabilized synthetic zeolite that does not self-disintegrate in water and a method for producing the same.
［従来の技術］
ゼオライトは、固有の細孔径、表面電場、イオン交換能
、吸着分離能などを持っており、極めて有用な機能性材
料として注目を集めている。とりわけ合成ゼオライトは
、合成物質の特徴である均質な製品が多量に製造出来、
加えて安定に供給可能なことから広範に利用されてきて
いる。[Prior Art] Zeolite has unique pore diameter, surface electric field, ion exchange ability, adsorption separation ability, etc., and is attracting attention as an extremely useful functional material. In particular, synthetic zeolite can be produced in large quantities with the homogeneous properties that are characteristic of synthetic materials.
In addition, it has been widely used because it can be stably supplied.
合成ゼオライトは一般に、ケイ酸ソーダ、アルミン酸ソ
ーダ及び苛性ソーダの溶液を混合、熟成し、生成したゲ
ルをろ別、水洗及び乾燥して作られている。Synthetic zeolites are generally made by mixing and aging solutions of sodium silicate, sodium aluminate, and caustic soda, and filtering the resulting gel, washing with water, and drying.
［発明が解決しようとする課題］
従来市販されている合成ゼオライトは、製造工程の後段
で水洗されているにも拘らず、これを水に分散すると分
散液が強いアルカリ性を呈する。[Problems to be Solved by the Invention] Conventionally commercially available synthetic zeolites are washed with water at a later stage of the production process, but when dispersed in water, the dispersion becomes strongly alkaline.
合成ゼオライトは洗剤のビルグーとして多量に用いられ
ており、この場合には合成ゼオライトがアルカリ性を与
えることはむしろ利点となる。合成ゼオライトは、吸着
剤、触媒、担体、イオン交換材、充填剤などとしても用
いられ、これらの分野のあるものにおいては合成ゼオラ
イトの塩基性は欠点となる。Synthetic zeolites are used in large amounts as building blocks for detergents, and in this case it is rather advantageous that synthetic zeolites provide alkalinity. Synthetic zeolites are also used as adsorbents, catalysts, supports, ion exchange materials, fillers, etc., and the basicity of synthetic zeolites is a drawback in some of these fields.
後記の実施例で述べるように、本発明者及び国内外のゼ
オライト製造業者が作った合成ゼオライトについて調べ
たところ、５０ｇ／Ｊ！の合成ゼオライト分散物を２０
℃で２４時間保持するとｐＨ約８〜１２となり、分散液
中に約１０〜３０１）ｐＨｌのアルミニウムの存在が確
認された。合成ゼオライトを改めて多量の水で洗浄した
後に同様に試験しても、やはり分散液は強いアルカリ性
を示すことが判った。そこで合成ゼオライトを希酸で中
和した後に分離、水洗し、同様に水中に分散すると分散
液はやはりアルカリ性であった。そこで、強いアルカリ
性を示す合成ゼオライト（分散液のｐＨ１）の分散物に
１規定塩酸の一滴（０，０３ｍ１ ＞を滴下したが、２
４時間後にｐＨが１１になった。１規定苛性ソーダをゼ
オライト分散物に滴下した場合にも、２４時間後にｐＨ
が同じ＜１１になった。As described in the Examples below, when we investigated the synthetic zeolite produced by the present inventor and domestic and foreign zeolite manufacturers, we found that it was 50g/J! Synthetic zeolite dispersion of 20
When kept at ℃ for 24 hours, the pH became about 8 to 12, and the presence of aluminum with a pH of about 10 to 301) was confirmed in the dispersion. Even when the synthetic zeolite was washed again with a large amount of water and then tested in the same manner, it was found that the dispersion liquid still showed strong alkalinity. Therefore, when the synthetic zeolite was neutralized with dilute acid, separated, washed with water, and similarly dispersed in water, the dispersion was still alkaline. Therefore, one drop of 1N hydrochloric acid (0.03ml) was added to a dispersion of strongly alkaline synthetic zeolite (dispersion pH 1), but 2
The pH reached 11 after 4 hours. Even when 1N caustic soda is dropped into a zeolite dispersion, the pH changes after 24 hours.
became the same <11.
一方、成る天然ゼオライトを水に分散するとＯＨは６．
８であり、アルミニウム濃度は検出限界（０，５ｐｐｍ
）以下であった。同じゼオライト分散物に１規定塩酸を
滴下するとｐＨは直ちに５．０になり、２４時間後も同
じであった、他方、同じゼオライト分散物に１規定苛性
ソーダを滴下するとｌ）Ｈは直ちに９．０になり、２４
時間後も同じであった。On the other hand, when natural zeolite is dispersed in water, the OH is 6.
8, and the aluminum concentration is below the detection limit (0.5 ppm
) or less. When 1N hydrochloric acid was added dropwise to the same zeolite dispersion, the pH immediately became 5.0 and remained the same after 24 hours; on the other hand, when 1N caustic soda was added dropwise to the same zeolite dispersion, l)H immediately became 9.0. becomes 24
It was the same after hours.
以上の様に、従来の合成ゼオライトは天然ゼオライトと
違って著しいアルカリ性を呈し、合成ゼオライトを慣用
の如く水洗又は中和しても、いぜんとして著しいアルカ
リ性を示す。これは合成ゼオライトが徐々に自己崩壊し
ているか、又は合成ゼオライトの製造時に封じ込められ
たアルカリ性物質が徐々にゼオライトから滲出してくる
ためであると考えられる。しかし天然ゼオライトにおい
ては莫大な時間のうちに、ゼオライトの不安定な構造又
はアルカリ性物質が雨水で洗われるなどして除去されて
しまっているのであろう。As mentioned above, unlike natural zeolites, conventional synthetic zeolites exhibit significant alkalinity, and even if synthetic zeolites are washed with water or neutralized in the conventional manner, they still exhibit significant alkalinity. This is thought to be because the synthetic zeolite gradually self-destructs, or because the alkaline substances that were sealed during the production of the synthetic zeolite gradually ooze out from the zeolite. However, in natural zeolite, the unstable structure of the zeolite or the alkaline substances are likely to have been removed by washing with rainwater or the like over an enormous amount of time.
従って本発明は、合成ゼオライトの水及び空気中の湿気
に対する不安定性を解消し、水に分散したときに分散液
がアルカリ性を呈さないところの合成ゼオライトを提供
することを目的とする。Therefore, an object of the present invention is to provide a synthetic zeolite which eliminates the instability of synthetic zeolite with respect to water and moisture in the air, and whose dispersion does not exhibit alkalinity when dispersed in water.
［課題を解決するための手段］
本発明者は、合成ゼオライトを酸性水性液に浸漬し、浸
漬液のｐＨを約７以下の所定の値に保つように酸を追加
し、もはや酸を追加しなくてもほぼ一定のｐＨを少くと
も１時間持続するまで浸漬を持続し、次に合成ゼオライ
トを洗浄することなくまたは洗液のｐＨが実質的にｐＨ
約６．５を越えない条件で洗浄した後に加熱乾燥するこ
とにより、目的とする安定化された合成ゼオライトが得
られることを見出した。[Means for Solving the Problems] The present inventor immersed a synthetic zeolite in an acidic aqueous solution, added acid to maintain the pH of the immersion solution at a predetermined value of about 7 or less, and added no more acid. Continue soaking until a nearly constant pH is maintained for at least 1 hour without washing the synthetic zeolite or until the pH of the washing solution is substantially at
It has been found that the desired stabilized synthetic zeolite can be obtained by heating and drying after washing under conditions not exceeding about 6.5.
ここで、浸漬液のｐＨが酸を加えずとも７以下で長時間
一定となるまで浸漬を続けること、次に洗浄することな
くまたはもし洗浄するのなら洗液のｐＨが６．５を相当
時間に亘って越えない条件での洗浄を行い、加熱乾燥す
ることが本発明の重要な要件である。従来のように単に
水洗したのでは目的が達成さ゛れないことは勿論であり
、浸漬処理を行っても次に大量の水で洗浄して洗浄液の
ｐＨが６゜５を越えてから（特に中性になってから）加
熱乾燥したのでは本発明の目的は達成されない。−方、
本発明に従い酸処理後に洗浄を行わずにまたは洗液のｐ
Ｈが６．５を実質上越えない条件で洗浄し、加熱乾燥を
一旦行ったあとでは、合成ゼオライトを水洗しても合成
ゼオライト分散液はアルカリ性を呈しない。このことは
全く予測されなかったことである。At this point, continue immersion until the pH of the immersion liquid remains constant at 7 or less for a long time without adding acid, and then continue immersion without washing or if washing, the pH of the washing liquid will remain at 6.5 for a considerable period of time. It is an important requirement of the present invention to perform washing under conditions that do not exceed 100% and then heat and dry. Of course, the purpose cannot be achieved by simply washing with water as in the past, and even if immersion treatment is performed, it is necessary to wash with a large amount of water until the pH of the washing solution exceeds 6.5 (especially if it is neutral). The object of the present invention cannot be achieved if heat-drying is carried out after the temperature is reached. - direction,
According to the invention, after acid treatment without washing or with p.
After washing under conditions where H does not substantially exceed 6.5 and once heating and drying, the synthetic zeolite dispersion does not exhibit alkalinity even if the synthetic zeolite is washed with water. This was completely unexpected.
すなわち本発明は、合成ゼオライトを５０ｇ／ｌの濃度
で蒸留水中に分散し、２０〜２５℃で２４時間保持した
後の分散水のＩ）Ｈが５〜７であることを特徴とする合
成ゼオライトである。That is, the present invention provides a synthetic zeolite characterized in that after dispersing the synthetic zeolite in distilled water at a concentration of 50 g/l and holding it at 20 to 25°C for 24 hours, the I)H of the dispersed water is 5 to 7. It is.
また本発明は、合成ゼオライトを酸性水性液に浸漬し、
浸漬液のｐＨを約７以下の所定の値に保つように酸を追
加し、もはや酸を追加しなくてもはぼ一定のｐＨを少く
とも１時間持続するまで浸漬を持続し、次に合成ゼオラ
イトを洗浄することなくまたは洗液のｐＨが実質的にｐ
Ｈ約６．５を越えない条件で洗浄した後に加熱乾燥する
ことを特徴とする、上記の安定化された合成ゼオライト
の製造法である。In addition, the present invention involves soaking synthetic zeolite in an acidic aqueous solution,
Add acid to maintain the pH of the soaking solution at a predetermined value of about 7 or less, continue soaking until no more acid is added to maintain a more or less constant pH for at least 1 hour, and then synthesize without washing the zeolite or when the pH of the washing solution is substantially p.
The method for producing the above-mentioned stabilized synthetic zeolite is characterized in that it is washed under conditions where H does not exceed about 6.5 and then heated and dried.
本発明において合成ゼオライトは、総ての合成ゼオライ
トを包含する。合成ゼオライトは一般には、Ａ、ｌ！
２ｏ３を基準にしてｘＭ２／。０・Ａ、ｌ１２０３・ｙ
ＳｉＯ２・ｚＨ２０で表わされる。In the present invention, the synthetic zeolite includes all synthetic zeolites. Synthetic zeolites are generally A, l!
xM2/ based on 2o3. 0・A, l1203・y
It is expressed as SiO2.zH20.
Ｍは１価又は２価の金属、特にナトリウム及びカリウム
のようなアルカリ金属であり、ｎはその原子価である。M is a monovalent or divalent metal, especially an alkali metal such as sodium and potassium, and n is its valence.
ｘ、ｙ及びＺは夫々、金属酸化物の係数、二酸化ケイ素
の係数及び結晶水の数を示す。合成ゼオライトは、組成
比、細孔径、比表面積などの責る多種のものが知られて
いる。合成ゼオライトの曲型的なものとしてＡ型ゼオラ
イド（Ｓ ｉ ０２ ／ＡＩ２０３ ＝ １．４〜２．
４）、Ｘ型ゼオライト（ＳｉＯ／Ａｊ２０３＝２〜３）
、Ｙ型ゼオライト（Ｓ ｉ ０２／Ａｎ ２０３ ＝３
〜６）、モルデナイト（Ｓ ｉ ０２ ／ Ａｊ！ ２
０３ ＝ ９〜１０〉などが挙げられる。x, y and Z indicate the coefficient of metal oxide, the coefficient of silicon dioxide and the number of water of crystallization, respectively. Various types of synthetic zeolites are known, depending on composition ratio, pore diameter, specific surface area, etc. A-type zeolide (S i 02 /AI203 = 1.4-2.
4), X-type zeolite (SiO/Aj203=2-3)
, Y-type zeolite (S i 02/An 203 =3
~6), mordenite (S i 02 / Aj! 2)
03 = 9-10>, etc.
上記式中のＭは一般にナトリウム又はカリウムであるが
、Ｍの一部又は全部が鉄、亜鉛、銅、錫、銀、バナジウ
ム、タングステン、ニッケル、モリブデン、アンチモン
、クロムなどの重金属、カルシウム、マグネシウム、リ
チウム、アルミニウムなどの軽金属、又はアンモニウム
イオンにより置換されていてよい。M in the above formula is generally sodium or potassium, but some or all of M is iron, zinc, copper, tin, silver, vanadium, tungsten, nickel, molybdenum, antimony, heavy metals such as chromium, calcium, magnesium, It may be substituted with light metals such as lithium, aluminum, or ammonium ions.
合成ゼオライトを浸漬する酸性水性液は、無機酸及び／
又は有機酸の水性液である。例えば、塩酸、硫酸、硝酸
、燐酸などの無機酸、及び蟻酸、酢酸、シュウ酸、酒石
酸などの有機酸を用いることが出来る。本発明には以上
のように種々の慣用の酸を使用することが出来るが、中
でも弱酸、例えば酢酸、蟻酸、酒石酸、アジピン酸、ホ
ウ酸等が好ましい。ゼオライトを分散させた蒸溜水に例
えば２Ｎ硝酸または２Ｎ酢酸を少量ずつ添加すると、硝
酸を添加した場合には分散液の増粘及びかなりの発泡が
観察されるが、酢酸を添加した場合には少量の発泡があ
るのみであり、しかもゼオライト分散液のｐＨがほぼ一
定になるのが早い。この理由としては、ゼオライトを分
散させた浸漬液に強酸を添加（追加）する場合、撹拌が
不十分だと浸漬液のｐＨが局部的に低くなり、ゼオライ
トの一部が急速に侵される（例えばＡ−型ゼオライドは
ｌ）Ｈ約４以下で急速に侵される）のに対し、酢酸、蟻
酸のような弱酸を使用する場合には浸漬液ｐｕの局部的
低下が小さいのでゼオライトの急激な分解が殆ど起こら
ないこと、また従って添加した弱酸がゼオライトの分解
に費されずに穏やかに本発明の処理を進行させるのであ
ろう。また、ｐＨの局部的変化とは別に、強酸に比べて
弱酸はゼオライトに対して緩慢に作用するので、本発明
の時間をかける浸漬処理においてゼオライトを不都合に
侵す危険性がより小さい。無機酸及び有機酸を併用する
ことも出来、又２種類以上の無機酸又は有機酸を混合使
用してもよい。溶媒は一般に水であり、少量の有機溶媒
及び／または界面活性剤を含んでもよい、更に、必要に
応じては、酸性水性液に可溶な無機塩類または有機塩類
を添加することが出来る。The acidic aqueous liquid in which the synthetic zeolite is immersed contains an inorganic acid and/or
or an aqueous solution of an organic acid. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, oxalic acid, and tartaric acid can be used. Although various conventional acids can be used in the present invention as described above, weak acids such as acetic acid, formic acid, tartaric acid, adipic acid, and boric acid are particularly preferred. For example, when 2N nitric acid or 2N acetic acid is added little by little to distilled water in which zeolite is dispersed, thickening of the dispersion and considerable foaming are observed when nitric acid is added, but a small amount is observed when acetic acid is added. There is only foaming, and the pH of the zeolite dispersion becomes almost constant quickly. The reason for this is that when a strong acid is added to an immersion liquid in which zeolite is dispersed, if the stirring is insufficient, the pH of the immersion liquid will be locally lowered, and part of the zeolite will be rapidly eroded (e.g. A-type zeolide is rapidly attacked by l) H below about 4), whereas when using a weak acid such as acetic acid or formic acid, the local drop in the immersion liquid PU is small, so rapid decomposition of the zeolite is prevented. This is unlikely to occur and therefore the added weak acid is not wasted on decomposing the zeolite and the process of the present invention proceeds gently. Also, apart from local changes in pH, weak acids act more slowly on the zeolite than strong acids, so there is less risk of adversely attacking the zeolite during the time-consuming soaking process of the present invention. An inorganic acid and an organic acid may be used together, or two or more types of inorganic acids or organic acids may be used in combination. The solvent is generally water, which may contain small amounts of organic solvents and/or surfactants; furthermore, if necessary, inorganic or organic salts soluble in the acidic aqueous liquid can be added.
浸漬液の当初のｐＨは７以下、好ましくは４．０〜６．
５、特に４゜５〜６．０とし、浸漬処理の進行につれて
ｐＨが上がるので酸（溶液）によりｐＨを調節する。The initial pH of the immersion liquid is 7 or less, preferably 4.0 to 6.
5. In particular, set the temperature to 4°5 to 6.0, and adjust the pH with an acid (solution) as the pH increases as the immersion process progresses.
浸漬処理法は任意である。たとえば、攪拌機付き容器に
酸性水性液を入れ、攪拌下に合成ゼオライトを徐々に加
えて分散させる。その際に分散液のｐＨは上昇するので
、ｐＨ７以下の所定のｐＨに維持するよう酸を適宜添加
する。総てのゼオライトを分散させた後にも攪拌を続け
ながら、所定のｐＨを維持するよう酸を添加する。もは
や酸を加えなくともｐＨ値がほぼ一定（±０．５、好ま
しくは±０．３）となるのを確認してから浸漬処理を終
える。一般に浸漬処理は、酸を加えなくともＩ）Ｈ値が
ほぼ一定になってから１時間以上、好ましくは３時間以
上続ける。はぼ一定ＤＨになってからの処理時間を長く
すると、製品ゼオライトの安定性がより良くなる。処理
条件を例示すると、最終的に５〜４０重量％の合成ゼオ
ライト固体粒子濃度とし、１００〜２０００ｒＥ）ｌの
緩かな攪拌の下で１０〜５０℃で行う。合成ゼオライト
の濃度を極端に低くし、温度を高めると、処理時間を短
縮できる。攪拌速度は処理時間に少ししか関係しない。The immersion treatment method is arbitrary. For example, an acidic aqueous solution is placed in a container equipped with a stirrer, and synthetic zeolite is gradually added and dispersed while stirring. At this time, the pH of the dispersion increases, so an acid is appropriately added to maintain the pH at a predetermined value of 7 or less. After all the zeolite has been dispersed, acid is added to maintain a predetermined pH while continuing stirring. After confirming that the pH value becomes almost constant (±0.5, preferably ±0.3) without adding any more acid, the immersion treatment is finished. Generally, the immersion treatment is continued for at least 1 hour, preferably for at least 3 hours, after the I)H value becomes approximately constant even without adding an acid. The longer the treatment time after reaching a constant DH, the better the stability of the product zeolite becomes. To illustrate the treatment conditions, the final synthetic zeolite solid particle concentration is 5 to 40% by weight, and the treatment is carried out at 10 to 50°C under gentle stirring at 100 to 2000 rE). By reducing the concentration of synthetic zeolite to an extremely low level and increasing the temperature, processing times can be shortened. Stirring speed has only a small bearing on processing time.
上記とは逆に、予めゼオライトを水に懸濁し、これに酸
を少しずつ添加して浸漬処理することもできる。処理ｐ
Ｈ１時間等は上記と同様である。Contrary to the above, zeolite can be suspended in water in advance, and acid can be added little by little to carry out the immersion treatment. Processing p
H1 time etc. are the same as above.
また、合成ゼオライトの浸漬処理を、合成ゼオライトの
製造工程の最終工程として行うこともできる。すなわち
、ケイ酸ソーダ、アルミン酸ソーダ及び苛性ソーダの水
溶液から生成したゼオライトゲルを含む反応後のスラリ
ーを分別し、生成ゼオライトに酸を添加することにより
、上述のような浸漬処理を行うことができる。好ましく
は、スラリーからゼオライトを分離し、水洗するという
従来の工程を行ったうえで、ゼオライトスラリーを酸性
水に添加して浸漬処理を行う。Moreover, the immersion treatment of the synthetic zeolite can also be performed as the final step of the synthetic zeolite manufacturing process. That is, by separating the slurry after the reaction containing the zeolite gel produced from an aqueous solution of sodium silicate, sodium aluminate, and caustic soda, and adding an acid to the produced zeolite, the immersion treatment as described above can be performed. Preferably, the conventional process of separating the zeolite from the slurry and washing with water is performed, and then the zeolite slurry is added to acidic water and subjected to an immersion treatment.
酸による浸漬処理において重要なことは、通常の中和処
理の如く短時間で終了するのではなく、酸の追加添加な
しで液ＤＨが少くとも１時間、好ましくは少くとも３時
間はぼ一定となるまで、処理を継続することである。な
お、合成ゼオライトの種類及び製造法によって、任意の
ｐＨ値で所定時間一定にならないことがある。そのよう
な場合には、意図するＤＨ値を種々変更して（一般には
より酸性側にして）浸漬処理を行えば、酸添加なしで一
定ＤＩが達成できるｐＨ値が見い出される。What is important in acid immersion treatment is that it does not finish in a short time as in normal neutralization treatment, but that the liquid DH remains almost constant for at least 1 hour, preferably at least 3 hours, without additional addition of acid. The process should continue until the Note that depending on the type of synthetic zeolite and the manufacturing method, the pH value may not be constant for a given period of time. In such a case, by performing the immersion treatment with various changes in the intended DH value (generally making it more acidic), a pH value at which a constant DI can be achieved without addition of acid can be found.
上記のように酸性水性液に合成ゼオライトを十分な時間
浸漬した後に、通常、合成ゼオライトを液から分離する
。分離は、ろ過、デカンテーションなど任意の方法で行
うことができる。After the synthetic zeolite is immersed in the acidic aqueous liquid for a sufficient period of time as described above, the synthetic zeolite is usually separated from the liquid. Separation can be performed by any method such as filtration or decantation.
分離したゼオライトは、洗浄することなく加熱乾燥に付
される。あるいは、任意的に、洗液のｐＨが６．５を実
質上越えない条件下で洗浄することも出来る。洗浄操作
において重要なことは、洗液のｐｕが６．５を実質上越
えない条件下で洗浄を行うことである。ここで、“ｐＨ
が６．５を実質上越えない”とは、洗液の９８が洗浄終
了時に６．５以下となることを意味するものであり、洗
液のｐＨが短時間６．５を越えても、本発明が目的とす
る安定化された合成ゼオライトを得ることが出来る。洗
浄操作には酸性水性液を用いることが出来る。酸として
は、浸漬処理に使用可能ないずれの酸をも使用すること
ができる。酸性水性液のｐＨは、浸漬時のｐＨに近似ま
たはそれ以下であることが好ましいが、より高くなって
も良い。少量の水で洗浄することも出来る。浸漬処理時
のＰｔｆ及び浸漬液からの分離方法によっては（例えば
低い９Ｈにて浸漬処理を行った場合、あるいは浸漬液か
らのゼオライトの分離をデカンテーションにて行った場
合には）、浸漬処理時の酸がゼオライト上にかなり残留
している。The separated zeolite is heated and dried without washing. Alternatively, washing can optionally be carried out under conditions in which the pH of the washing liquid does not substantially exceed 6.5. What is important in the cleaning operation is to perform the cleaning under conditions in which the PU of the cleaning liquid does not substantially exceed 6.5. Here, “pH
``does not substantially exceed 6.5'' means that the pH of the washing liquid is 6.5 or less at the end of washing, and even if the pH of the washing liquid exceeds 6.5 for a short time, The stabilized synthetic zeolite that is the object of the present invention can be obtained.An acidic aqueous solution can be used for the washing operation.As the acid, any acid that can be used for the soaking process can be used. The pH of the acidic aqueous liquid is preferably close to or lower than the pH during immersion, but it may be higher.It can also be washed with a small amount of water.Ptf and immersion liquid during immersion treatment Depending on the method of separation from the zeolite (for example, when the zeolite is immersed at low 9H, or when the zeolite is separated from the immersion liquid by decantation), a considerable amount of the acid during the immersion process may remain on the zeolite. are doing.
従って洗浄操作に比較的少量の水を用いて洗浄終了時に
洗液のＩ）Ｈが６．５以下となり、本発明の目的を達成
することが出来る。洗浄操作自体は、種々の慣用の方法
にて行うことが出来る。例えば分離した合成ゼオライト
を撹拌機付き容器に入れ、洗液を加えて撹拌、洗浄する
。あるいは、分離装置中のゼオライトに洗液を注加して
洗浄する。洗浄操作は通常、ゼオライトに対し０．５〜
１００倍程度の液量の洗液を用い、室温で行われるが、
他の条件下で行うことも可能である。こうした洗浄操作
により、浸漬処理時にゼオライトから生じた不純物の除
去等、製品の品質向上がなされる。Therefore, by using a relatively small amount of water in the washing operation, the I)H of the washing liquid becomes 6.5 or less at the end of washing, and the object of the present invention can be achieved. The washing operation itself can be carried out in a variety of conventional ways. For example, the separated synthetic zeolite is placed in a container equipped with a stirrer, a washing liquid is added thereto, and the container is stirred and washed. Alternatively, the zeolite in the separation device is washed by pouring a washing liquid into the zeolite. The washing operation is usually performed at a concentration of 0.5 to 0.5 for zeolite.
It is carried out at room temperature using about 100 times the amount of washing liquid.
It is also possible to carry out under other conditions. This cleaning operation improves the quality of the product, such as by removing impurities generated from the zeolite during the soaking process.
次に、得られた合成ゼオライトを加熱乾燥する。Next, the obtained synthetic zeolite is dried by heating.
通常、１００℃以上、好ましくは１２０℃以上、特に１
３０℃以上で、１時間以上、好ましくは３時間以上、常
圧下で、所望により減圧下で行う。かかる加熱乾燥によ
り、付着していた酸は通常揮発してしまう。従って、本
発明の合成ゼオライトを水に分散したときに強い塩基性
を示さない理由が、付着酸によるのではないことが明ら
かである。本発明に従い浸漬処理の後に、洗浄を行わず
にまたは規定の洗浄操作を行い、加熱乾燥した場合にの
み、本発明の効果が達成される。浸漬処理に続いて大量
の水で洗浄し、加熱乾燥したのでは目的が達成されない
。一方、本発明に従い出来上がった合成ゼオライトを、
後に大量の水で洗浄しても本発明の効果は失われない。Usually 100°C or higher, preferably 120°C or higher, especially 1
The reaction is carried out at a temperature of 30° C. or higher for 1 hour or more, preferably 3 hours or more, under normal pressure, and optionally under reduced pressure. By such heating and drying, the adhering acid usually evaporates. Therefore, it is clear that the reason why the synthetic zeolite of the present invention does not show strong basicity when dispersed in water is not due to the attached acid. The effects of the invention are achieved only if the soaking treatment according to the invention is followed by heating and drying without washing or with a prescribed washing operation. Soaking followed by washing with large amounts of water and heating and drying will not achieve the objective. On the other hand, the synthetic zeolite produced according to the present invention,
Even after washing with a large amount of water, the effects of the present invention are not lost.
上記の、浸漬−（洗浄）−加熱乾燥の一連の操作を、複
数回繰返してもよい。The series of operations of immersion-(washing)-heat-drying described above may be repeated multiple times.
特定の理論により本発明は限定されないが、まず本発明
に従う酸処理において合成ゼオライトの表面をゾル状物
が覆うと考えられる。すなわち、浸漬処理の間に、ゼオ
ライト結晶構造の欠陥個所から崩壊脱落したケイ素及び
アルミニウム原子団〈イオン基）またはゼオライト内部
に封じ込められたゼオライト原料物質が酸と反応してゼ
オライト表面にゾル状物を形成する。続いて合成ゼオラ
イトを加熱乾燥すると、ゾル状物は脱水して、キセロゲ
ル状になると考えられる。−旦、キセロゲル膜が形成さ
れると、これは水洗によっても脱落しない。しかし、加
熱乾燥する前のゾル状物は弱いので、中性及びアルカリ
性雰囲気下で水洗すると脱落するのであろう。本発明の
合成ゼオライトを水に分散したときにキセロゲル膜はい
わゆる半透膜として働き、ゼオライトからアルミニウム
及びケイ素の原子団などが水中に出てゆくのを防ぐと考
えられる。本発明の合成ゼオライトを酸性水（塩酸、Ｄ
Ｈ２〜３）及びアルカリ性水（水酸化ナトリウム、ｐＨ
１０〜１１）に分散（固液比１：１０）すると、いずれ
の場合でも分散水は同じｐＨ１たとえばｐｉｆ６．８に
なり、しかも合成ゼオライトは崩壊せず、分散水中にア
ルミニウムイオンは検出されない。Although the present invention is not limited by any particular theory, it is believed that a sol-like substance covers the surface of the synthetic zeolite in the acid treatment according to the present invention. That is, during the immersion treatment, silicon and aluminum atomic groups (ionic groups) that disintegrate and fall from defects in the zeolite crystal structure, or zeolite raw materials sealed inside the zeolite, react with acid to form a sol on the zeolite surface. Form. It is thought that when the synthetic zeolite is subsequently heated and dried, the sol-like substance dehydrates and becomes a xerogel-like substance. - Once the xerogel film is formed, it does not fall off even when washed with water. However, since the sol-like material is weak before being heated and dried, it will likely fall off when washed with water in a neutral or alkaline atmosphere. When the synthetic zeolite of the present invention is dispersed in water, the xerogel membrane acts as a so-called semipermeable membrane, and is thought to prevent aluminum and silicon atomic groups from leaving the zeolite into the water. The synthetic zeolite of the present invention is mixed with acidic water (hydrochloric acid, D
H2-3) and alkaline water (sodium hydroxide, pH
10 to 11) (solid-liquid ratio 1:10), the dispersion water has the same pH 1, for example pif 6.8, in all cases, and the synthetic zeolite does not disintegrate, and no aluminum ions are detected in the dispersion water.
以上のように本発明の合成ゼオライトは水中で極めて安
定である。本発明の合成ゼオライトを５０ｇ／ｊｌの濃
度で蒸留水中に分散し、２０〜２５℃で２４時間、好ま
しくは７２時間保持した後に、分散水のｐＨは５〜７、
好ましくは６．０〜６．８の範囲に留る。本発明の合成
ゼオライトが安定であることは、実施例で説明するよう
に分散水中にアルミニウムイオンが検出されないことか
らも確認される。従来の合成ゼオライトの場合には、分
散水のｐＨは２４時間後に強いアルカリ性となり、アル
ミニウムイオンが検出される。As described above, the synthetic zeolite of the present invention is extremely stable in water. After dispersing the synthetic zeolite of the present invention in distilled water at a concentration of 50 g/jl and maintaining it at 20-25°C for 24 hours, preferably 72 hours, the pH of the dispersion water is 5-7,
Preferably it stays within the range of 6.0 to 6.8. The stability of the synthetic zeolite of the present invention is also confirmed by the fact that no aluminum ions are detected in the dispersion water, as explained in Examples. In the case of conventional synthetic zeolite, the pH of the dispersion water becomes strongly alkaline after 24 hours, and aluminum ions are detected.
なお、特開昭５９−２０３７２３号公報に、ゼオライト
に海水中のミネラル成分を担持させ、かつ平衡１）Ｈが
１０．５以下に調整されている改質ゼオライトが記載さ
れ、平衡１）Ｈは好ましくは９．５〜４．５とされ、実
施例に平衡ｐＨ６，５の物が記載されている。しかし、
そこでの平衡ｐＨとは５ ｇ ７１００ ｍｌの水性ス
ラリーの僅か３０分間後のｌ）Ｈ値である。本発明者が
見い出したところによると、３０分間では平衡ｐＨには
達しない。たとえば従来の合成ゼオライトをｐＨ２，５
の塩酸で中和したゼオライトを水に分散すると、分散水
のｐＨは１時間後には６．５であるが２４時間後には８
．９まで著しく上昇する。従って、上記公報における「
平衡１）■」のゼオライトは本願発明を示唆していない
。また上記公報におけるゼオライトの酸処理は、単に「
中和処理」とのみ記載されているので、本発明方法のよ
うに長時間の処理を示唆していない。従来の合成ゼオラ
イトを酸で中和すると、見かけ上はすみやかに中和され
るが、たとえこれを水洗せずに乾燥したとしても、水に
再び分散するとアルカリ性を呈する。In addition, JP-A No. 59-203723 describes a modified zeolite in which zeolite supports mineral components in seawater and whose equilibrium 1) H is adjusted to 10.5 or less, and whose equilibrium 1) H is Preferably, the pH is 9.5 to 4.5, and the example describes an equilibrium pH of 6.5. but,
The equilibrium pH here is the l)H value of a 5 g 7100 ml aqueous slurry after only 30 minutes. According to the findings of the present inventors, equilibrium pH is not reached within 30 minutes. For example, conventional synthetic zeolite has a pH of 2.5.
When zeolite neutralized with hydrochloric acid is dispersed in water, the pH of the dispersed water is 6.5 after 1 hour, but 8 after 24 hours.
．． It rises significantly to 9. Therefore, “
Equilibrium 1) zeolite "■" does not suggest the present invention. In addition, the acid treatment of zeolite in the above publication is simply “
Since it only mentions ``neutralization treatment'', it does not suggest a long treatment like the method of the present invention. When conventional synthetic zeolite is neutralized with acid, it appears to be neutralized quickly, but even if it is dried without being washed with water, it becomes alkaline when it is redispersed in water.
本発明の合成ゼオライトは安定な中性乃至微弱酸性を維
持し、湿潤時にもｐＨが高まることなく安定である。そ
れ故に、体粘膜や皮膚等に接触しても低刺激性を示し、
副作用を呈することがない。The synthetic zeolite of the present invention maintains stable neutrality to slightly acidic properties, and is stable without increasing pH even when wet. Therefore, it exhibits low irritation even when it comes into contact with body mucous membranes, skin, etc.
It does not exhibit any side effects.
従って、医薬、医療、化粧品及び食品関係の原料、用材
に使用できる。各種有機材料、無機材料中に混入複合化
した際にも、長期に亘って構造が安定であるので、材料
の物性や性状の劣化原因とはならない。又、用途に応じ
てイオン交換して変性されたすべての従来の合成ゼオラ
イトにも本発明は適用される。本発明の合成ゼオライト
は多くの場合、従来の合成ゼオライトと事実上同一の機
能を有し、例えば、乾燥剤、吸着剤、イオン交換剤、各
種添加剤、或は触媒、分子フルイなどの成分分離、水処
理用造粒体、担体などとして使用できる。Therefore, it can be used as raw materials and materials for medicine, medical care, cosmetics, and food. Even when mixed into various organic and inorganic materials to form a composite, the structure remains stable over a long period of time, so it does not cause deterioration of the physical properties or properties of the material. The present invention also applies to all conventional synthetic zeolites modified by ion exchange depending on the application. In many cases, the synthetic zeolite of the present invention has virtually the same functions as conventional synthetic zeolites, such as desiccant, adsorbent, ion exchange agent, various additives, or component separation such as catalyst and molecular sieve. , can be used as granules for water treatment, carriers, etc.
本発明の合成ゼオライトを有機高分子体に混合して用い
る場合について特に説明する。ゼオライトに抗菌性金属
イオンを担持させ、これと高分子体とを混合し、成形す
る技術が知られている（特開昭５９−１３３２３５号公
報）。本発明の合成ゼオライトは中性乃至微弱酸性であ
るので、高分子体の劣化をもたらすことがない。高分子
体は、たとえば合成又は半合成の有機高分子体であり、
特にポリエチレン、ポリプロピレン、ポリスチレン、ポ
リ塩化ビニリデン、ポリアミド、ポリエステル、ポリビ
ニルアルコール、ポリカーボネート、ポリアセタール、
ＡＢＳ樹脂、アクリル樹脂、フッ素樹脂、ポリウレタン
エラストマー、ポリエステルエラストマーなどの熱可塑
性合成高分子、フェノール樹脂、ユリア樹脂、メラミン
樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、ウレタ
ン樹脂などの熱硬化性合成高分子、レーヨン、キュプラ
、アセテート、トリアセテートなどの再生又は半合成高
分子などが挙げられる０合成ゼオライトを高分子体に混
入することにより、（変性）ゼオライトの機能、たとえ
ば吸着、乾燥、抗菌などの性質を持つ高分子成形体（塗
装及び接着剤を含め）を得ることができる。The case where the synthetic zeolite of the present invention is mixed with an organic polymer will be particularly explained. A technique is known in which zeolite is made to support antibacterial metal ions, mixed with a polymer, and molded (Japanese Unexamined Patent Publication No. 133235/1983). Since the synthetic zeolite of the present invention is neutral to slightly acidic, it does not cause deterioration of the polymer. The polymer is, for example, a synthetic or semi-synthetic organic polymer,
Especially polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal,
Thermoplastic synthetic polymers such as ABS resin, acrylic resin, fluororesin, polyurethane elastomer, and polyester elastomer; thermosetting synthetic polymers such as phenolic resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, and urethane resin; By mixing synthetic zeolite, which includes regenerated or semi-synthetic polymers such as rayon, cupro, acetate, and triacetate, into a polymer, it has the functions of a (modified) zeolite, such as adsorption, drying, and antibacterial properties. Polymer molded bodies (including coatings and adhesives) can be obtained.
［実 施 例］ 以下で実施例により本発明を更に説明する。[Example] The invention will be further explained below by means of examples.
以下において、ゼオライトを分散した水のＤＨ（簡単の
ためにゼオライトのｐＨと云うことがある）は次のよう
にして測定した。合成ゼオライトを常圧、１０５℃で２
時間乾燥し、室温に冷却後に蒸留水に５０ｇ／ｌの濃度
で分散し、２０〜２５℃で２４時間５ｏｏｒｐ−で攪拌
した後、保証電極を使用して２０℃で測定した。In the following, the DH of water in which zeolite was dispersed (sometimes referred to as zeolite pH for simplicity) was measured as follows. Synthetic zeolite at normal pressure and 105℃
After drying for an hour and cooling to room temperature, it was dispersed in distilled water at a concentration of 50 g/l, stirred at 20-25°C for 24 hours at 5oorp-, and then measured at 20°C using a guarantee electrode.
アルミニウムの溶出の測定は、上記の如＜５０ｇ ／
４１の分散物を２０〜２５℃で２４時間５００ｒｐｍで
攪拌した後に、７２時間静置し、液を０．４５ミクロン
メンブランフィルタ−に通過させて得た分取液について
原子吸光分析方法〔島流製作所製Ａ Ａ −６４０１３
型〕で求めた。検出限界は０．５ｐｐｍである。Measurement of aluminum elution was performed as described above at <50g/
After stirring the dispersion of No. 41 at 500 rpm for 24 hours at 20 to 25°C, it was allowed to stand still for 72 hours, and the liquid was passed through a 0.45 micron membrane filter. Manufactured by Seisakusho A A-64013
[Type] The detection limit is 0.5 ppm.
実施例で用いた原料の合成ゼオライトを第１表に示す。Table 1 shows the synthetic zeolites used as raw materials in the examples.
各合成ゼオライトは必要に応じて粉砕及び分級して、所
望の粒子径とした。表中の含水率は、１０５℃で乾燥し
た物の含水率である。Each synthetic zeolite was pulverized and classified as necessary to obtain a desired particle size. The moisture content in the table is the moisture content of the product dried at 105°C.
対照例
上記の合成ゼオライト（１）〜（８）について、ｌ）Ｈ
及びアルミニウム溶出濃度を調べた。結果を第２表に示
す。Control example Regarding the above synthetic zeolites (1) to (8), l) H
and aluminum elution concentration were investigated. The results are shown in Table 2.
第 ２ 表
ゼオライト
Ａ−型ゼオライ
Ｙ−型ゼオライ
Ｘ−型ゼオライ
Ａ−型ゼオライ
Ａ−型ゼオライ
Ａ−型ゼオライ
Ｙ−型ゼオライ
Ｘ−型ゼオライ
１）Ｈ
１２，２
１０，９
１１，０
１０，９
１１，３
１０，４
１１，０
１０，８
アルミニウムの
溶出濃度、ｐｐｍ
３２．２
１２．４
１０．１
１２．９
１１．６
１５．５
７．３
９．５
実施例 １ａ
上記の８種の合成ゼオライト粒子から、本発明の合成ゼ
オライトを以下の方法で製造した。Table 2 Zeolite A-type zeolite Y-type zeolite X-type zeolite A-type zeolite A-type zeolite A-type zeolite Y-type zeolite 9 11,3 10,4 11,0 10,8 Aluminum elution concentration, ppm 32.2 12.4 10.1 12.9 11.6 15.5 7.3 9.5 Example 1a Above 8 types The synthetic zeolite of the present invention was produced from the synthetic zeolite particles of the following method.
１０％硝酸水溶液を入れた酸添加装置を備えた容量２１
の攪拌装置付反応槽に、イオン交換水１ｐを入れた。イ
オン交換水の初発１）Ｈを４に調整し、温度３０℃、攪
拌速度５００ｒｐｌで攪拌しながら合成ゼオライト固体
粒子１００ｇを徐々に添加して分散させた。その間反応
槽内分散液のｐＨは上昇するのでｐＨ５，５±０．３以
内を保持すべく酸添加装置より酸を継続的に添加して反
応槽内のｔ）Ｈをコントロールし続けた。約２０分で合
成ゼオライト粒子の添加を完結させた後、更に２時間酸
を加えながらｐＨをコントロールした。次に酸を加えな
くともｐＨ＝５．５±０．３の領域に留ることを１時間
確認してから処理を終了した。次にブッフナーろ過装置
を使用して固液分離した後、合成ゼオライトを水洗する
ことなく１３０℃で４時間乾燥して水分を除去し、次い
で局方乳鉢を用いて適度に粉砕して製品とした。Capacity 21 equipped with acid addition device containing 10% aqueous nitric acid solution
1 p of ion-exchanged water was placed in a reaction tank equipped with a stirring device. Initial injection of ion-exchanged water 1) H was adjusted to 4, and 100 g of synthetic zeolite solid particles were gradually added and dispersed while stirring at a temperature of 30° C. and a stirring speed of 500 rpm. During this time, the pH of the dispersion in the reaction tank increased, so t)H in the reaction tank was continuously controlled by continuously adding acid from an acid addition device to maintain the pH within 5.5±0.3. After completing the addition of the synthetic zeolite particles in about 20 minutes, the pH was controlled while adding acid for another 2 hours. Next, it was confirmed that the pH remained in the range of 5.5±0.3 even without addition of acid for 1 hour, and then the treatment was terminated. Next, after solid-liquid separation using a Buchner filtration device, the synthetic zeolite was dried at 130°C for 4 hours without washing with water to remove moisture, and then appropriately ground using a pharmacopoeia mortar to form a product. .
得た本発明の合成ゼオライトを蒸留水に分散させてＩ）
Ｈ及びアルミニウム溶出濃度を測定した。結果は第３ａ
表の通りであって、水に対する安定性はすべで極めて良
好であった。I) The obtained synthetic zeolite of the present invention is dispersed in distilled water.
H and aluminum elution concentrations were measured. The result is 3rd a
As shown in the table, the stability against water was extremely good in all cases.
第 ３ａ 表
ゼオライト
１）Ｈ
アルミニウム
２） Ｙ−型ゼオライド ６□５ 〃３） Ｘ−
型ゼオライド ６．４〃
４） Ａ−型ゼオライド ６．５〃
５） Ａ−型ゼオライド ６．６〃
６） Ａ−型ゼオライド ６．３ ノ１７）
Ｙ−型ゼオライド ６．４〃
実施例 １ｂ
実施例１ａと同じ装置を用い、８種の合成ゼオライト粒
子から本発明の合成ゼオライトを以下の方法で製造した
。Table 3a Zeolite 1) H Aluminum 2) Y-type zeolide 6□5 〃3) X-
Type zeolide 6.4〃 4) A-type zeolide 6.5〃 5) A-type zeolide 6.6〃 6) A-type zeolide 6.3 No.17)
Y-Type Zeolide 6.4 Example 1b Using the same apparatus as in Example 1a, the synthetic zeolite of the present invention was produced from eight types of synthetic zeolite particles in the following manner.
１０％硝酸水溶液を入れた酸添加装置を備えた容量２ｆ
Ｉの攪拌装置付反応槽に、イオン交換水１１を入れな。Capacity 2f equipped with acid addition device containing 10% nitric acid aqueous solution
Pour ion-exchanged water 11 into the reaction tank equipped with a stirrer I.
イオン交換水の初発ｐＨを３，８に調整し、温度３０℃
、攪拌速度５００ｒｐ−で攪拌しながら合成ゼオライト
固体粒子１００．を徐々に添加して分散させた。その間
反応槽内分散液のｐＨは上昇するのでＩ）Ｈ５，Ｏ±０
．３以内を保持すべく酸添加装置より酸を継続的に添加
して反応槽内のｐＨをコントロールし続けた。約２０分
で合成ゼオライト粒子の添加を完結させた後、更に２時
間酸を加えながらｐＨをコントロールした。次に酸を加
えなくともｐＨ＝５．０±０．３の領域に留ることを１
時間確認してから処理を終了した。次にブッフナーろ過
装置を使用して固液分離した後、イオン交換水に１０％
硝酸水溶液を加えてｐＨ３，８とした洗浄液３１をグツ
フナ−濾過装置上のゼオライト分離物に注加し、ゼオラ
イトの洗浄を行った。洗浄処理終了時の洗液のｐＨは約
５であった。次に合成ゼオライトを１３０℃で４時間乾
燥して水分を除去し、次いで局方乳鉢を用いて適度に粉
砕して製品とした。Adjust the initial pH of ion-exchanged water to 3.8, and adjust the temperature to 30°C.
, 100. of synthetic zeolite solid particles while stirring at a stirring speed of 500 rpm. was gradually added and dispersed. During that time, the pH of the dispersion in the reaction tank increases, so I) H5,O±0
．． In order to keep the pH within 3, acid was continuously added from an acid addition device to keep the pH in the reaction tank under control. After completing the addition of the synthetic zeolite particles in about 20 minutes, the pH was controlled while adding acid for another 2 hours. Next, we confirmed that the pH remained in the range of 5.0±0.3 without adding acid.
I finished the process after checking the time. Next, after solid-liquid separation using a Buchner filtration device, 10%
A washing liquid 31 adjusted to pH 3.8 by adding an aqueous nitric acid solution was poured into the zeolite separated material on the Gutzfner filtration apparatus to wash the zeolite. The pH of the washing liquid at the end of the washing process was approximately 5. Next, the synthetic zeolite was dried at 130° C. for 4 hours to remove moisture, and then appropriately ground using a pharmacopoeia mortar to obtain a product.
得た本発明の合成ゼオライトを蒸留水に分散させて９１
１及びアルミニウム溶出濃度を測定した。結果は第３ｂ
表の通りであって、水に対する安定性はすべて極めて良
好であった。The obtained synthetic zeolite of the present invention was dispersed in distilled water and 91
1 and aluminum elution concentration were measured. The result is part 3b
As shown in the table, the stability against water was all very good.
第
ｂ
表
ゼオライト
ｐＨ
１Ａ−型ゼオライド ６．６
２ Ｙ−型ゼオライド ６．４
３ Ｘ−型ゼオライド ６．４
４ Ａ−型ゼオライド ６．３
５ Ａ〜型ゼオライト ６，４
６ Ａ〜型ゼオライト ６．３
７ Ｙ−型ゼオライド ６．３
アルミニウム
の溶出濃度
検出限界以下
〃
〃
！！
ノー
実施例 ２ａ
通常の合成ゼオライト（４）、 （７）及び（８）を用
いて、本発明の合成ゼオライトを製造した。反応装置は
実施例１ａと同一のものを使用した。但し、使用した酸
は１０％酢酸水溶液であった。Table b Zeolite pH 1 A-type zeolide 6.6 2 Y-type zeolide 6.4 3 X-type zeolide 6.4 4 A-type zeolide 6.3 5 A~ type zeolite 6,4 6 A~ type zeolite 6 .3 7 Y-type zeolide 6.3 Aluminum elution concentration below detection limit〃 〃! ! No Example 2a A synthetic zeolite of the present invention was produced using conventional synthetic zeolites (4), (7) and (8). The same reactor as in Example 1a was used. However, the acid used was a 10% acetic acid aqueous solution.
１１のイオン交換水を反応槽に入れ、イオン交換水の初
発ｐＨを５に調整し、温度２５℃、攪拌速度５００ｒｌ
）−で攪拌しながら合成ゼオライト粒子１００ｇを徐々
に添加した分散させた。Put the ion-exchanged water of No. 11 into the reaction tank, adjust the initial pH of the ion-exchanged water to 5, and set the temperature at 25°C and the stirring speed at 500rl.
) - While stirring, 100 g of synthetic zeolite particles were gradually added and dispersed.
その間反応槽内分散液のｐＨは上昇するので、１）Ｈ６
，３土０．３以内を保持すべく酸を継続的に添加して反
応槽内のｐＨをコントロールし続けた。約２０分間で合
成ゼオライトの添加を終え、更に７時間酸を加えながら
ｐＨをコントロールした。次に酸を加えなくともｐＨ＝
６．３±０．３領域で留まることを１時間確認後に処
理を終了しな。During that time, the pH of the dispersion in the reaction tank increases, so 1) H6
, 3 The pH in the reaction tank was continuously controlled by continuously adding acid to maintain the pH within 0.3. The addition of the synthetic zeolite was completed in about 20 minutes, and the pH was controlled while adding acid for another 7 hours. Next, without adding acid, pH =
Do not end the process after confirming that it remains in the 6.3±0.3 area for 1 hour.
ブッフナーろ過装置を使用して固液分離させた後、合成
ゼオライトを水洗することなく１３０℃で４時間乾燥し
て水分を除去し、次いで局方乳鉢を用いて適度に粉砕し
て製品とした。After solid-liquid separation using a Buchner filtration device, the synthetic zeolite was dried at 130° C. for 4 hours to remove moisture without washing with water, and then appropriately ground using a pharmacopoeia mortar to obtain a product.
取得した本発明の合成ゼオライト製品を蒸溜水に分散さ
せてｐＨ及びアルミニウムの溶出濃度を測定した。結果
は第４ａ表の通りであって、水に対する安定性は極めて
良好であった。The obtained synthetic zeolite product of the present invention was dispersed in distilled water, and the pH and elution concentration of aluminum were measured. The results are shown in Table 4a, and the stability to water was extremely good.
第 ４ａ 表
ゼオライト ｐＨアルミニウム
の溶出濃度
（４）Ａ−型ゼオライド ６．９ 検出限界以下（７）
Ｙ−型ゼオライド ６．６ ｎ実施ｆＩＡ２ｂ
通常の合成ゼオライト（４）、 （７）及び（８）を用
いて、本発明の合成ゼオライトを製造した。反応装置は
実施例１ａと同一のものを使用した。但し、使用した酸
は１０％酢酸水溶液であった。Table 4a Zeolite pH Aluminum elution concentration (4) A-type zeolide 6.9 Below detection limit (7)
Y-type zeolide 6.6n Example fIA2b The synthetic zeolite of the present invention was produced using conventional synthetic zeolites (4), (7), and (8). The same reactor as in Example 1a was used. However, the acid used was a 10% acetic acid aqueous solution.
１ｇのイオン交換水を反応槽に入れ、イオン交換水の初
発ＤＩ（を４．０に調整し、温度２５℃、攪拌速度５０
０ｒｐｍで攪拌しながら合成ゼオライト粒子１０（）ｇ
を徐々に添加した分散させた。Put 1 g of ion-exchanged water into a reaction tank, adjust the initial DI of ion-exchanged water to 4.0, and set the temperature at 25°C and the stirring speed at 50°C.
10 () g of synthetic zeolite particles while stirring at 0 rpm.
was gradually added and dispersed.
その間反応槽内分散液のｐＨは上昇するので、Ｉ）Ｈ５
゜８±０．３以内を保持すべく酸を継続的に添加して反
応槽内のｐＨをコントロールし続けた。約２０分間で合
成ゼオライトの添加を終え、更に７時間酸を加えながら
ｐＨをコントロールした。次に酸を加えなくともｐＨ＝
５．８±０．３領域で留まることを１時間確認後に処
理を終了した。During that time, the pH of the dispersion liquid in the reaction tank increases, so I) H5
The pH in the reaction tank was continuously controlled by continuously adding acid to maintain the pH within 8±0.3. The addition of the synthetic zeolite was completed in about 20 minutes, and the pH was controlled while adding acid for another 7 hours. Next, without adding acid, pH =
The treatment was terminated after confirming that it remained in the 5.8±0.3 range for 1 hour.
プッフナーろ過装置を使用して固液分離させた後、イオ
ン交換水に１０％硝酸を加えてｐＨ３，８とした洗浄液
３ｊ！中に、分離した合成ゼオライトを分散させ、３０
分間充分に撹拌洗浄した。洗浄処理終了時の洗浄液のｔ
）Ｈは約５．５であった。再度ブッフナー濾過装置を用
いてゼオライトを分離した後、１３０℃で４時間乾燥し
て水分を除去し、次いで局方乳鉢を用いて適度に粉砕し
て製品とした。After solid-liquid separation using a Puchner filtration device, 10% nitric acid was added to the ion-exchanged water to adjust the pH to 3.8. Separated synthetic zeolite is dispersed in it, and 30
Thoroughly stirred and washed for several minutes. t of cleaning solution at the end of cleaning process
)H was about 5.5. After separating the zeolite using the Buchner filtration device again, it was dried at 130° C. for 4 hours to remove moisture, and then appropriately ground using a pharmacopoeia mortar to obtain a product.
取得した本発明の合成ゼオライト製品を蒸溜水に分散さ
せてｐＨ及びアルミニウムの溶出濃度を測定した。結果
は第４ｂ表の通りであって、水に対する安定性は極めて
良好であった。The obtained synthetic zeolite product of the present invention was dispersed in distilled water, and the pH and elution concentration of aluminum were measured. The results are shown in Table 4b, and the stability against water was extremely good.
第
４ｂ
表
の溶出濃度
（７）Ｙ−型ゼオライド ５，５ Ｊ）実施例
２Ｃ
硝酸及び酢酸を用い、ゼオライト分散液のｐＨの変化を
測定した。Table 4b Elution concentration (7) Y-type zeolide 5,5 J) Example 2C The change in pH of the zeolite dispersion was measured using nitric acid and acetic acid.
撹拌機付き容器二つを用意し、その夫々に蒸溜水１３０
０１１を加え、５００ ｒ、ｐ、ｍ、での撹拌下、（５
）Ａ−型ゼオライド６０ｇずつを分散させた。次に、各
分散液の夫々に、２Ｎ （１２６ｇ／Ｎ ）硝酸、及び
２Ｎ（１２０ｇ／ｆｌ ）酢酸を、５００ ｒ、ｐ、ｍ
、での撹拌下、５分間隔で初めは１．Ｏｍｌずつ、１０
．００１１の添加後は５．０Ｑ１１ずつ、５０．Ｏｍｌ
の添加後は１０ｍ１ずつ加え、その都度衣の添加の直前
に分散液の９１１を測定した。Prepare two containers with stirrers and add 130 ml of distilled water to each container.
011 and stirring at 500 r, p, m, (5
) 60 g of A-type zeolide was dispersed. Next, 2N (126 g/N) nitric acid and 2N (120 g/fl) acetic acid were added to each dispersion at 500 r, p, m.
, at 5 minute intervals, initially at 1. Oml each, 10
．． After adding 0011, 5.0Q11 each, 50. Oml
After adding , 10 ml of the dispersion was added, and 911 of the dispersion was measured each time immediately before adding the batter.
その結果を第１図に示す。酢酸を用いた場合６二（よ、
同じ規定度の硝酸を使用した場合に比べてゼオライト分
散液のｐＨがほぼ一定となるのが早いということが判る
。尚、ｐＨ６，５付近において、各分散液に発泡が見ら
れたが、硝酸を用いた場合には著しい発泡がｐＨ６，８
〜５．１付近まで続いたのに対し、酢酸を使用した場合
にはその発泡が僅かであった。The results are shown in FIG. When using acetic acid, 62 (yo,
It can be seen that the pH of the zeolite dispersion becomes almost constant faster than when nitric acid of the same normality is used. Note that foaming was observed in each dispersion near pH 6.5, but when nitric acid was used, significant foaming occurred at pH 6.8.
However, when acetic acid was used, the foaming was slight.
また、硝酸を使用した場合、ｐＨ９付近で分散液が増粘
し、スターラーが一時的に停止したが、酢酸を用いた場
合にはこのような増粘は観察されなかった。Furthermore, when nitric acid was used, the dispersion thickened at around pH 9 and the stirrer temporarily stopped, but such thickening was not observed when acetic acid was used.
比較例 １ 実施例２ａ、２ｂで用いた合成ゼオライト（４）。Comparative example 1 Synthetic zeolite (4) used in Examples 2a and 2b.
（７）及び（８）を用いて以下の方法で水洗処理又は中
和処理を実施した。Using (7) and (8), water washing or neutralization was carried out in the following manner.
水洗処理
合成ゼオライト粒子１００ｇをＩＪのイオン交換水に加
え、充分に攪拌分散の後、ブッフナーろ過装置を使用し
て固液分離した。更にろ過装置の上部より３１のイオン
交換水を注意深く数回に分割して注入し、ろ液のｐＨが
ほぼ７であることを確認した。水洗を終えたゼオライト
粒子を取り出して１３０℃で４時間乾燥し、適度に粉砕
した。100 g of water-washed synthetic zeolite particles were added to ion-exchanged water in an IJ, and after thorough stirring and dispersion, solid-liquid separation was performed using a Buchner filtration device. Further, 31 ion exchange water was carefully injected into the top of the filtration device in several portions, and it was confirmed that the pH of the filtrate was approximately 7. After washing with water, the zeolite particles were taken out, dried at 130° C. for 4 hours, and pulverized appropriately.
中和処理
合成ゼオライト粒子１００ｇを１１のイオン交換水に加
え、充分に攪拌分散した後、ブツフナーろ過装置を使用
してろ過した。次いで希硝酸を注意深く注ぎ入れ中和し
た。中和水のｐＨが５分間はぼ６．５であることを確認
してから中和を停止し、中和後のゼオライト粒子を取り
出して１３０℃で４時間乾燥し、適度に粉砕した。100 g of neutralized synthetic zeolite particles were added to the ion-exchanged water in Step 11, thoroughly stirred and dispersed, and then filtered using a Büchner filtration device. Dilute nitric acid was then carefully poured in to neutralize. After confirming that the pH of the neutralized water was approximately 6.5 for 5 minutes, neutralization was stopped, and the zeolite particles after neutralization were taken out, dried at 130° C. for 4 hours, and appropriately pulverized.
得たゼオライトを蒸留水に分散させて、ｐＨ及びアルミ
ニウムの溶出濃度を測定した。結果は第５表の如くであ
った。第２ａ、２ｂ表と比べると、ｐＨ値は殆んど改善
されていす、不安定である。そしてその結果と考えられ
るがアルミニウムの溶出も殆んど処理前と変らぬレベル
であり、自己崩壊と認められる状況であった。即ち、水
洗又は中和によりｌ）Ｈを７前後としたにも拘らず、の
ちに水中に分散させた時点で、ｐＨが１０近くになって
しまった。The obtained zeolite was dispersed in distilled water, and the pH and elution concentration of aluminum were measured. The results were as shown in Table 5. Compared to Tables 2a and 2b, the pH value is almost improved but unstable. Perhaps as a result of this, the elution of aluminum was at almost the same level as before treatment, and the situation was recognized as self-destruction. That is, even though the l)H was brought to around 7 by washing or neutralization, the pH became close to 10 when it was later dispersed in water.
実施例 ３ａ
合成ゼオライト粒子（１）に銀イオンをイオン交換によ
り与え、このゼオライト−Ａｇを使用して本発明の合成
ゼオライトを製造した。反応装置は実施例１と同一のも
のを使用した。但し、反応槽に硝酸銀添加装置を更に付
設した。Example 3a Synthetic zeolite particles (1) were provided with silver ions by ion exchange, and the zeolite-Ag was used to produce the synthetic zeolite of the present invention. The same reactor as in Example 1 was used. However, a silver nitrate addition device was additionally attached to the reaction tank.
Ａ型−ゼオライド（１）２００ ｇを反応槽に入れ、こ
の中に添加装置より０．５％硝酸銀水溶液ＩＪ２を添加
した後、温度３０℃、攪拌速度５００ｒｐｍで５時間攪
拌混合させてイオン交換反応を行ない、銀でイオン交換
したゼオライトを形成させた。次に、ろ過、水洗して過
剰の硝酸銀を取り去ると同時にｐＨが中和されたことを
確認し、乾燥、粉砕した。200 g of A-type zeolide (1) was placed in a reaction tank, and after adding 0.5% silver nitrate aqueous solution IJ2 from an addition device, the mixture was stirred and mixed at a temperature of 30°C and a stirring speed of 500 rpm for 5 hours to perform an ion exchange reaction. was carried out to form ion-exchanged zeolite with silver. Next, it was filtered and washed with water to remove excess silver nitrate, and at the same time, it was confirmed that the pH was neutralized, and the product was dried and pulverized.
上記、ゼオライト−Ａ（ｌのほぼ１／２に相当する１０
０ｇについて本発明の方法を適用した。同一の反応槽に
イオン交換水１Ｍを加え、１０％硝酸でＤＨ＝４に調節
した後に３０℃で５００ｒｐｍで攪拌しながらゼオライ
ト−Ａｇ１００ｇを徐々に添加して分散させた。Zeolite-A (10 equivalent to approximately 1/2 of l)
The method of the invention was applied for 0 g. After adding 1 M of ion-exchanged water to the same reaction tank and adjusting DH=4 with 10% nitric acid, 100 g of zeolite-Ag was gradually added and dispersed while stirring at 500 rpm at 30°C.
その間に分散液のｐＨは上昇するがｐＨ６，０±０．３
以内を保持すべく酸を継続的に添加して反応槽内のＩ）
Ｈをコントロールし続けた。約２０分間で分散を終えた
後、更に３時間酸を加えながらｐＨをコントロールした
。次に酸を加えなくともＩ）Ｈ＝ ６．０±０．３領域
で留ることを１時間確認してから反応を終了した。During this time, the pH of the dispersion liquid increases, but the pH is 6.0 ± 0.3.
I) in the reaction tank by continuously adding acid to maintain the
I continued to control H. After dispersion was completed in about 20 minutes, the pH was controlled while adding acid for an additional 3 hours. Next, the reaction was terminated after confirming that I)H remained in the 6.0±0.3 range for 1 hour even without adding acid.
ブッフナーろ過装置を使用して固液分離した後、ゼオラ
イト−ＡＯを水洗することなく １３０’Ｃで４時間乾
燥して水分を除去し、次に局方乳鉢を用いて適度に粉砕
して製品とした。After solid-liquid separation using a Buchner filtration device, the zeolite-AO was dried at 130'C for 4 hours to remove moisture without washing with water, and then crushed appropriately using a pharmacopoeia mortar to form a product. did.
取得した本発明の合成ゼオライト−、Ｊ及び酸浸漬前の
それについてＩ）Ｈ及びアルミニウムの溶出濃度を測定
した。結果は第６表の通りであった。I) Elution concentrations of H and aluminum were measured for the obtained synthetic zeolite of the present invention, J, and the zeolite before acid immersion. The results are shown in Table 6.
水に対する安定性の差は両者間で顕著である。The difference in stability to water is significant between the two.
本発明のゼオライト−ＡｇではｐＨが中性で安定してお
り、アルミニウムの溶出がなく、自己崩壊を認ない極め
て安定な製品であった。The zeolite-Ag of the present invention had a neutral pH and was stable, had no aluminum elution, and was an extremely stable product without self-disintegration.
なお、硝酸銀でのイオン交換の際に硝酸によりイオン交
換液のｐＨを５に保持してイオン交換した後に、ゼオラ
イトを水洗せずに炉別乾燥する実施態様で作った本発明
に従う合成ゼオライトは６．５のｐＨを示した。In addition, the synthetic zeolite according to the present invention made in an embodiment in which the pH of the ion exchange solution was maintained at 5 with nitric acid during ion exchange with silver nitrate and the zeolite was dried in a furnace without washing with water was 6. It showed a pH of .5.
実施例 ３ｂ
実施例３ａと同じ方法で作ったゼオライト−Ａｇ ｔ
ｏｏｇについて、次の操作を行った。Example 3b Zeolite-Ag t made in the same manner as Example 3a
Regarding oog, the following operation was performed.
実施例１ａで用いたのと同じ反応槽にイオン交換水１１
を加え、１０％硝酸でｐ）ｌ＝３．８に調節した後に３
０℃で５００ｒｐｍで攪拌しながらゼオライト−Ａ（Ｉ
＋ １００ｇを徐々に添加して分散させた。Ion-exchanged water 11 was placed in the same reaction tank as used in Example 1a.
was added and adjusted to p)l=3.8 with 10% nitric acid.
Zeolite-A (I
+ 100g was gradually added and dispersed.
その間に分散液のｐＨは上昇するがｐＨ５，５±０．３
以内を保持すべく酸を継続的に添加して反応槽内のＤＨ
をコントロールし続けた。約２０分間で分散を終えた後
、更に３時間酸を加えながらｐＨをコントロールした。During that time, the pH of the dispersion liquid increases, but the pH is 5.5 ± 0.3.
The DH in the reaction tank is adjusted by continuously adding acid to maintain the DH within the reaction tank.
continued to be controlled. After dispersion was completed in about 20 minutes, the pH was controlled while adding acid for an additional 3 hours.
次に酸を加えなくともｐＨ＝ ５．５±０．３領域で留
ることを１時間確認してから反応を終了した。Next, the reaction was terminated after confirming that the pH remained in the 5.5±0.3 range for 1 hour without adding acid.
ブッフナーろ過装置を用いてゼオライトを分離し、イオ
ン交換水０．３１に分散させて、室温で５分間撹拌洗浄
した。洗浄終了後の分散液のｐＨは６．３であった。The zeolite was separated using a Buchner filtration device, dispersed in 0.31% ion-exchanged water, and washed with stirring at room temperature for 5 minutes. The pH of the dispersion after washing was 6.3.
ブッフナーｒ過装置を使用して固液分離した後、ゼオラ
イト−Ａｇを水洗することなく１３０℃で４時間乾燥し
て水分を除去し、次に局方乳鉢を用いて適度に粉砕して
製品とした。After solid-liquid separation using a Buchner filtration device, the zeolite-Ag was dried at 130°C for 4 hours to remove moisture without washing with water, and then crushed appropriately using a pharmacopoeia mortar to form a product. did.
取得した本発明の合成ゼオライト−Ａ（Ｊについて９Ｈ
及びアルミニウムの溶出濃度を測定した。結果は第６表
の通りであった。Obtained synthetic zeolite-A of the present invention (9H for J
and the elution concentration of aluminum was measured. The results are shown in Table 6.
本発明のゼオライト−ＡｐではｐＨが中性で安定してお
り、アルミニウムの溶出がなく、自己崩壊を認ない極め
て安定な製品であった。The zeolite-Ap of the present invention had a neutral pH and was stable, had no aluminum elution, and was an extremely stable product without self-disintegration.
なお、硝酸銀でのイオン交換の際に硝酸によりイオン交
換液のｐＨを５に保持してイオン交換した後に、ブッフ
ナーｒ過装置を用いて固液分離し、これを取り出して以
下上記と同様に行って作った本発明に従う合成ゼオライ
トは６．８のｐＨを示した。In addition, during ion exchange with silver nitrate, after ion exchange by keeping the pH of the ion exchange solution at 5 with nitric acid, solid-liquid separation was performed using a Buchner filtration apparatus, and this was taken out and carried out in the same manner as above. The synthetic zeolite according to the present invention made in this manner exhibited a pH of 6.8.
比較例 ２ 実施例３ａと同一の方法でゼオライト−銀を製造した。Comparative example 2 Zeolite-silver was prepared in the same manner as Example 3a.
次に、ゼオライト−Ａｇのほぼ１／２に相当する１００
ｇについて、浸漬処理俊に水洗を充分に行う方法につ
いて実験した。Next, zeolite-100 which corresponds to approximately 1/2 of Ag
Regarding g, an experiment was conducted on a method of thoroughly rinsing with water after immersion treatment.
酸を加えなくともｐＨ５，５±０．５に止まることを１
時間確認する浸漬処理を施したゼオライト八ｇをブッフ
ナー濾過装置で固液分離した後、３、Ｏｊ！のイオン交
換水に分散、室温下で３０分間攪拌洗浄処理した。この
際、洗浄処理終了時の洗液のｐＨは６．９であった。1. The pH remains at 5.5 ± 0.5 without adding acid.
Check the time After 8 g of soaked zeolite is separated into solid and liquid using a Buchner filtration device, 3. Oj! The sample was dispersed in ion-exchanged water and washed with stirring at room temperature for 30 minutes. At this time, the pH of the washing liquid at the end of the washing process was 6.9.
ゼオライト−Ａｇを再度ブッフナー濾過装置を用いて分
離し、１３０℃で４時間乾燥して水分を除去し、粉砕し
て製品とした。Zeolite-Ag was separated again using the Buchner filtration device, dried at 130° C. for 4 hours to remove moisture, and pulverized to obtain a product.
得られたゼオライト−Ａ（ＩＩは、ＤＨ８，３のアルカ
リ性を示した。The obtained zeolite-A(II) exhibited alkalinity of DH8.3.
残り１／２のゼオライト−Ａｇについて同様に浸漬処理
してプッフナー濾過装置で固液分離した後に、３．（ｌ
のイオン交換水を上から徐々に注いで水洗した以外は上
記と同じ操作を行った。水洗処理の最後の１．ｌ！のイ
オン交換水のＤＨは７．１であった。１ｑられたゼオラ
イト−ＡｔｌｌのｐＨは８．１のアルカリ性を示した。The remaining 1/2 of the zeolite-Ag was immersed in the same manner and subjected to solid-liquid separation using a Puchner filtration device, and then 3. (l
The same operation as above was performed except that ion-exchanged water was gradually poured from above to rinse. The last step in the water washing process. l! The DH of the ion-exchanged water was 7.1. The pH of 1q of zeolite-Atll was alkaline at 8.1.
実施例 ４
通常の合成ゼオライト粒子を製造する過程に本発明の方
法を組入れて本発明の合成ゼオライトを製造した。反応
装置は実施例３と同一のものを用いた。ゼオライトの原
料はすべて和光純薬工業株式会社の市販品であった。Example 4 Synthetic zeolite of the present invention was manufactured by incorporating the method of the present invention into the process of manufacturing conventional synthetic zeolite particles. The same reactor as in Example 3 was used. All zeolite raw materials were commercially available from Wako Pure Chemical Industries, Ltd.
１０％アルミン酸ソーダ水溶液１Ｍを反応槽の中に入れ
、温度６０℃、撹拌速度１１０００ｒｐで撹拌しながら
添加装置より１０％ケイ酸ソーダ水溶液０．９ｊ！を徐
々に１時間にわたって注入した。その間温度及び撹拌速
度はこの条件を保持し続け、添加完結後も引き続き１時
間この状態を継続させた。その後反応槽の温度を８５℃
に昇温すると同時に撹拌速度を５００ｒｐｍに降下させ
、８時間熟成反応を実施して合成ゼオライト粒子を形成
せしめた。冷却後に反応槽から合成ゼオライトを取り出
す訳であるが、反応物を含む分散液の全量的１．９１を
２分割して、一方を（Ａ）通常の方法で処理し、他の一
方を（Ｂ）本発明の方法で処置した。即ち、（Ａ）では
ブッフナーろ過装置を使用して固液分離し、多量のイオ
ン交換水を分注して充分に水洗を施すことにより未反応
物質を除去すると共に過剰の洗浄を行って、ろ過液がほ
ぼ中和となったことを確認後に水洗を停止した。そして
１３０℃で４時間乾燥し、適度に粉砕して製品とした。Pour 1M of 10% sodium aluminate aqueous solution into a reaction tank, and add 0.9j of 10% sodium silicate aqueous solution from the addition device while stirring at a temperature of 60°C and a stirring speed of 11,000 rpm! was gradually injected over 1 hour. During this time, the temperature and stirring speed were maintained at the same conditions, and these conditions were continued for 1 hour even after the addition was completed. After that, the temperature of the reaction tank was increased to 85℃.
At the same time, the stirring speed was lowered to 500 rpm, and an aging reaction was carried out for 8 hours to form synthetic zeolite particles. After cooling, the synthesized zeolite is taken out from the reaction tank, and the total amount of the dispersion containing the reactants (1.91%) is divided into two parts, one of which is treated with (A) in the usual manner, and the other with (B). ) treated with the method of the invention. That is, in (A), solid-liquid separation is performed using a Buchner filtration device, unreacted substances are removed by dispensing a large amount of ion-exchanged water, and thorough washing is performed, as well as excessive washing, followed by filtration. After confirming that the liquid was almost neutralized, water washing was stopped. Then, it was dried at 130°C for 4 hours and pulverized appropriately to obtain a product.
一方、（Ｂ）では、ブッフナーろ過装置を使用して固液
分離し、装置上部より水洗水を加えて未反応物質を除去
した。次いでろ通園相部を少量のイオン交換水でスラリ
ー状とさせてから、イオン交換水ＩＪ２ （硝酸でＤＨ
＝４に調節）を入れた反応槽に徐々に加え本発明の操作
を実施した。反応条件は１０％硝酸使用、常温、攪拌速
度５００ｒｐｍ、保持ｐＨ５，５＋０．３とし、ゼオラ
イトの添加終了後も更に２時間酸を加えながらｐＨをコ
ントロールし、次いで酸を加えなくても該ｐＨに留るこ
とを１時間確認した。次にブッフナーろ過装置を使用し
て固液分離し、１３０℃で４時間乾燥し、次に適度に粉
砕しな。On the other hand, in (B), solid-liquid separation was performed using a Buchner filtration device, and unreacted substances were removed by adding washing water from the top of the device. Next, make a slurry of the filtrate with a small amount of ion-exchanged water, and then slurry it with ion-exchanged water IJ2 (DH with nitric acid).
= 4) was gradually added to a reaction tank containing the mixture, and the operation of the present invention was carried out. The reaction conditions were to use 10% nitric acid, room temperature, stirring speed 500 rpm, and maintain pH 5.5+0.3. After the addition of zeolite, the pH was controlled by adding acid for another 2 hours, and then the pH was maintained without adding acid. I confirmed that it would stay there for an hour. Next, solid-liquid separation was performed using a Buchner filtration device, dried at 130° C. for 4 hours, and then appropriately pulverized.
得たゼオライトの１）１１及びアルミニウムの溶出濃度
を測定した。結果は第７表の通りであった。The elution concentrations of 1) 11 and aluminum in the obtained zeolite were measured. The results were as shown in Table 7.
本発明の製品は水に対する安定性が際だって優れている
ことが明らかである。It is clear that the products according to the invention have outstanding stability towards water.
第 ７ 表
方 法 、■ アルミニウムの
溶出濃度、ｐｐａｔ
（Ａ）従来法１０．１ １６．８
（８）本発明法 ６．８ 検出限界以下実施例 ５
本実施例は、ゼオライトの酸浸漬処理後の洗浄方法が、
本発明にとって重要であることを示すものである。合成
ゼオライト粒子（１）、 （２）及び（３）から本発明
の合成ゼオライトを以下の方法で製造した。Table 7 Method, ■ Elution concentration of aluminum, ppat (A) Conventional method 10.1 16.8 (8) Method of the present invention 6.8 Below the detection limit Example 5 This example shows the results of zeolite after acid immersion treatment. The cleaning method is
This indicates that it is important for the present invention. The synthetic zeolite of the present invention was produced from synthetic zeolite particles (1), (2), and (3) by the following method.
５％リン酸水溶液を入れた酸添加装置を備えた容量２ｇ
の攪拌装置付反応槽にイオン交換水１ｊ！を入れた。イ
オン交換水の初発ｐＨを４に調整し、温度３０℃、攪拌
速度５００ｒｐｍで合成ゼオライト粒子１００ ｇを徐
々に添加して分散させた。その間、反応槽内分散液のｐ
Ｈは上昇するのでｐＨ５，０±０．３以内を保持すべく
酸添加装置より酸を継続的に添加して反応槽内のｐＨを
コントロールし続けた。約３０分で合成ゼオライト固体
粒子の添加を完結させた後、更に２時間酸を加えながら
ｐＨをコントロールした。次にｐＨ＝ ５．０±０．３
の領域に留ることを１時間確認し処理を終了した。Capacity 2g with acid addition device containing 5% phosphoric acid aqueous solution
1 j of ion-exchanged water in a reaction tank with a stirrer! I put it in. The initial pH of the ion-exchanged water was adjusted to 4, and 100 g of synthetic zeolite particles were gradually added and dispersed at a temperature of 30° C. and a stirring speed of 500 rpm. Meanwhile, the p of the dispersion in the reaction tank
Since H increased, acid was continuously added from an acid addition device to keep the pH within the reaction tank under control in order to maintain the pH within 5.0±0.3. After completing the addition of the synthetic zeolite solid particles in about 30 minutes, the pH was controlled while adding acid for another 2 hours. Then pH = 5.0±0.3
After confirming that the sample remained in the area for 1 hour, the treatment was terminated.
ブッフナーろ過装置を使用して固液分離した後、２２０
℃で３時間乾燥して水分を除去し、次いで局方乳鉢を用
いて適度に粉砕して製品とした。After solid-liquid separation using a Buchner filtration device, 220
The mixture was dried at ℃ for 3 hours to remove moisture, and then appropriately ground using a pharmacopoeia mortar to obtain a product.
比較のためブッフナーろ過装置により固液分離した後に
、ｐｔｆ３．８に調整した酢酸水溶液３．０ｆｔを上か
ら徐々に注加して洗浄（洗浄処理における洗液の最後の
１１のｐＨは約５であった）した以外は、上記と同じ処
理を行った合成ゼオライト、及び、同様にイオン交換水
３．ＯＪ！を上から徐々に注加して水洗した合成ゼオラ
イトを製造した。For comparison, after solid-liquid separation using a Buchner filtration device, 3.0 ft of acetic acid aqueous solution adjusted to ptf 3.8 was gradually poured from above for washing (the pH of the last 11 washes in the washing process was approximately 5). Synthetic zeolite was treated in the same way as above, except that 3) ion-exchanged water was used. OJ! A synthetic zeolite was produced by gradually pouring zeolite from above and washing with water.
各合成ゼオライトのｌ）Ｈ及びアルミニウム溶出濃度を
測定した。結果を第８表に示す。水洗を行った比較例と
しての合成ゼオライトは、水に対して不安定であり、一
方、本発明の合成ゼオライトは安定であることが明らか
である。l) The H and aluminum elution concentrations of each synthetic zeolite were measured. The results are shown in Table 8. It is clear that the synthetic zeolite as a comparative example which was washed with water is unstable in water, whereas the synthetic zeolite of the present invention is stable.
第１図はゼオライト分散液のｐＨを、添加した酸の量に
対してプロットしたグラフである。黒丸は酸として酢酸
を用いた際のｐＨを、白丸は硝酸を用いた際のｐＨを示
す。
出
願
人
鐘
紡
株
式FIG. 1 is a graph plotting the pH of the zeolite dispersion versus the amount of acid added. The black circles indicate the pH when acetic acid is used as the acid, and the open circles indicate the pH when nitric acid is used. Applicant Kanebo Co., Ltd.
Claims (1)
散し、２０〜２５℃で２４時間保持した後の分散水のｐ
Ｈが５〜７であることを特徴とする合成ゼオライト。 ２、合成ゼオライトを酸性水性液に浸漬し、浸漬液のｐ
Ｈを約７以下の所定の値に保つように酸を追加し、もは
や酸を追加しなくてもほぼ一定のｐＨを少くとも１時間
持続するまで浸漬を持続し、次に合成ゼオライトを洗浄
することなくまたは洗液のｐＨが実質的にｐＨ約６．５
を越えない条件で洗浄した後に加熱乾燥することを特徴
とする、請求項第１項記載の合成ゼオライトの製造法。 ３、ｐＨ約６．５以下の酸性水性液または少量の水で洗
浄する請求項第２項記載の方法。４、浸漬処理時におい
て酸として弱酸を使用することを特徴とする、請求項第
２項記載の方法。[Claims] 1. Synthetic zeolite is dispersed in distilled water at a concentration of 50 g/l, and the p of the dispersion water is maintained at 20 to 25°C for 24 hours.
A synthetic zeolite characterized in that H is 5 to 7. 2. The synthetic zeolite is immersed in an acidic aqueous solution, and the p of the immersion solution is
Acid is added to keep the H at a predetermined value of about 7 or less, and the soaking is continued until no more acid is added to maintain a nearly constant pH for at least 1 hour, and the synthetic zeolite is then washed. or when the pH of the wash solution is substantially pH 6.5.
2. The method for producing a synthetic zeolite according to claim 1, wherein the synthetic zeolite is heated and dried after washing under conditions not exceeding . 3. The method of claim 2, wherein the washing is performed with an acidic aqueous liquid having a pH of about 6.5 or less or with a small amount of water. 4. The method according to claim 2, characterized in that a weak acid is used as the acid during the dipping treatment.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33922289A JP2826868B2 (en) | 1989-04-24 | 1989-12-27 | Stabilized synthetic zeolite and method for producing the same |
| AU53850/90A AU633073B2 (en) | 1989-04-24 | 1990-04-24 | Stabilized synthetic zeolite and a process for the preparation thereof |
| CA 2015277 CA2015277C (en) | 1989-04-24 | 1990-04-24 | Stabilized synthetic zeolite and a process for the preparation thereof |
| DE1990625088 DE69025088T2 (en) | 1989-04-24 | 1990-04-24 | Stabilized, synthetic zeolite and process for its production |
| EP19900107719 EP0394948B1 (en) | 1989-04-24 | 1990-04-24 | Stabilized synthetic zeolite and a process for the preparation thereof |
| US08/001,415 US5443812A (en) | 1989-04-24 | 1993-01-07 | Stabilized synthetic zeolite and a process for the preparation thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10177289 | 1989-04-24 | ||
| JP1-101772 | 1989-04-24 | ||
| JP33922289A JP2826868B2 (en) | 1989-04-24 | 1989-12-27 | Stabilized synthetic zeolite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03197313A true JPH03197313A (en) | 1991-08-28 |
| JP2826868B2 JP2826868B2 (en) | 1998-11-18 |
Family
ID=26442588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33922289A Expired - Lifetime JP2826868B2 (en) | 1989-04-24 | 1989-12-27 | Stabilized synthetic zeolite and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2826868B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126494A (en) * | 1993-11-02 | 1995-05-16 | Mitsui Petrochem Ind Ltd | Epoxy resin composition, jointing member for airtight sealing coated therewith as adhesive, package for semiconductor device molded therefrom, and semiconductor device using them |
| US6071542A (en) * | 1995-03-16 | 2000-06-06 | Kanebo Ltd. | Antibacterial zeolite causing little discoloration and method of the production thereof |
| KR20150074085A (en) * | 2012-10-18 | 2015-07-01 | 바스프 에스이 | Post-treatment of a zeolitic material |
-
1989
- 1989-12-27 JP JP33922289A patent/JP2826868B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126494A (en) * | 1993-11-02 | 1995-05-16 | Mitsui Petrochem Ind Ltd | Epoxy resin composition, jointing member for airtight sealing coated therewith as adhesive, package for semiconductor device molded therefrom, and semiconductor device using them |
| US6071542A (en) * | 1995-03-16 | 2000-06-06 | Kanebo Ltd. | Antibacterial zeolite causing little discoloration and method of the production thereof |
| KR20150074085A (en) * | 2012-10-18 | 2015-07-01 | 바스프 에스이 | Post-treatment of a zeolitic material |
| JP2015536291A (en) * | 2012-10-18 | 2015-12-21 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Post-treatment of zeolite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2826868B2 (en) | 1998-11-18 |
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