JPH03503881A - Synthesis of crystalline molecular sieves - Google Patents
Synthesis of crystalline molecular sievesInfo
- Publication number
- JPH03503881A JPH03503881A JP1505001A JP50500189A JPH03503881A JP H03503881 A JPH03503881 A JP H03503881A JP 1505001 A JP1505001 A JP 1505001A JP 50500189 A JP50500189 A JP 50500189A JP H03503881 A JPH03503881 A JP H03503881A
- Authority
- JP
- Japan
- Prior art keywords
- al2o3
- mixture
- reaction mixture
- aluminum
- section
- 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.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 claims description 75
- 239000011541 reaction mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 150000001768 cations Chemical group 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- -1 Sb6+ Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- VHLDQAOFSQCOFS-UHFFFAOYSA-M tetrakis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CCO)(CCO)CCO VHLDQAOFSQCOFS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 11
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims 4
- 230000001939 inductive effect Effects 0.000 claims 2
- 239000000047 product Substances 0.000 description 33
- 239000013078 crystal Substances 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 229940024548 aluminum oxide Drugs 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000012265 solid product Substances 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 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 5
- 239000002178 crystalline material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000411 inducer Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000005039 Brassica rapa var. dichotoma Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 240000001781 Xanthosoma sagittifolium Species 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical group [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 244000130745 brown sarson Species 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960003857 proglumide Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- MRKAVJXPGLUQKP-UHFFFAOYSA-N tetrakis(2-hydroxyethyl)azanium Chemical compound OCC[N+](CCO)(CCO)CCO MRKAVJXPGLUQKP-UHFFFAOYSA-N 0.000 description 1
- OZAPNNUDYHYFTO-UHFFFAOYSA-N tetrakis(hydroxymethyl)azanium Chemical class OC[N+](CO)(CO)CO OZAPNNUDYHYFTO-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229910052649 zeolite group Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 結晶性分子ふるいの合成 本発明は、孔径が１０人より大きい、例えば１２人より大きい細孔開口を有する 結晶性分子ふるいを合成する方法に関する。[Detailed description of the invention] Synthesis of crystalline molecular sieves The present invention has a pore opening with a pore size greater than 10, such as greater than 12. This invention relates to a method for synthesizing crystalline molecular sieves.
天然および合成の両方のゼオライト物質が、種々の炭化水素の転化に触媒特性を 有することがこれまで示されている。ゼオライト物質は、Ｘ線回折により決めら れる一定の結晶構造を有する規則正しい多孔質結晶性アルミノシリケートであり 、その内部にはチャンネルまたは細孔により連結され得る空隙が存在する。これ らの空隙および細孔は特定のゼオライト材料中ではきざが一定である。この細孔 の大きさは、ある大きさの分子は吸着するがそれより大きい分子は排除するよう な大きさであることから、これらの物質は「分子ふるい」として知られるように なり、上記特性を利用する種々の方法で利用される。Both natural and synthetic zeolite materials exhibit catalytic properties for the conversion of various hydrocarbons. It has been shown to have. Zeolite materials are determined by X-ray diffraction. It is a regular porous crystalline aluminosilicate with a certain crystal structure. , within which there are voids that can be connected by channels or pores. this These voids and pores are uniform in size in a particular zeolite material. This pore The size of is such that molecules of a certain size will be adsorbed, but molecules larger than that will be excluded. Because of their large size, these materials have become known as "molecular sieves." It is used in various ways that take advantage of the above characteristics.
そのような分子ふるいは、天然および合成のいずれのものも、多くの種類の陽イ オン含有結晶性アルミノシリケートを含む。アルミノシリケートは、アルミニウ ムおよび珪素原子の合計対酸素原子の比が１＝２であるように酸素原子を共有す ることにより四面体が結合されているＳｉｎ、およびＡＱＯ，の剛質三次元構造 であると表すことができる。アルミニウム含有四面体の電子価は、例えばアルカ リ金属またはアルカリ土類金属カチオンようなカチオンを結晶内に含ませること により均衡がとられる。これは、アルミニウム対、Ｃａ／２、Ｓｒ／２、Ｎａ％ ＫまたはＬｉのような種々のカチオンの数の比が１に等しい場合に適用され得る 。一つの種類のカチオンは、常套の方法を用いたイオン交換技術により他の種類 のカチオンにより完全にまたは部分的に交換することができる。そのようなカチ オン交換を用いて、カチオンを適当に選択することにより所定のアルミノシリケ ートの特性を変えることができる。Such molecular sieves can be used in many types of positive sieves, both natural and synthetic. Contains on-containing crystalline aluminosilicate. Aluminosilicate is aluminum Oxygen atoms are shared such that the ratio of total silicon atoms to oxygen atoms is 1=2. Rigid three-dimensional structures of Sin and AQO, in which the tetrahedrons are connected by It can be expressed as The electron valence of the aluminum-containing tetrahedron is, for example, Inclusion of cations such as metal or alkaline earth metal cations within the crystal Balance is achieved by This is aluminum vs. Ca/2, Sr/2, Na% may be applied when the ratio of the numbers of various cations, such as K or Li, is equal to 1 . One type of cation can be transferred to another type by ion exchange techniques using conventional methods. can be completely or partially replaced by the cation of such a tick By using on-exchange, a given aluminosilicate can be prepared by appropriately selecting the cation. The characteristics of the card can be changed.
従来技術により非常の多くの種類の合成ゼオライトが形成されている。ゼオライ トは、ゼオライトＡ（米国特許第２．８８２．２４３号）、ゼオライトｘ（米国 特許第２．８８２，２４４号）、ゼオライトＹ（米国特許第３．１３０．００７ 号）、ゼオライトＺＫ−５（米国特許８３．２４７．１９５号）、ゼオライトＺ Ｋ−４（米国特許第３，３１４．７５２号）、ゼオライ）、ＺＳＭ−５（米国特 許第３，７０２，８８６号）、ゼオライトＺＳＭ−１１（米国特許第３．７０９ ，９７９号）、ゼオライトＺＳＭ−１２（米国特許第３，８３２．４４９号）、 −ゼオライ）ＺＳＭ−２０（米国特許第３．９７２，９８３号）、ゼオライトＺ ＳＭ−３５Ｃ米ｒ５ｎｌｒ許１１４．Ｏ１２，２４５号）、ゼオラ４トＺＳＭ− ３８（米国特許第４，０４６，８５９号）およびゼオライｌ−ＺＳＭ−２３（米 国特許第４．０７６．８４２号）により示されるように、文字または他の便利な 符号を用いて表されるようになった。A large variety of synthetic zeolites have been formed by the prior art. Zeolai Zeolite A (U.S. Pat. No. 2.882.243), Zeolite No. 2.882,244), Zeolite Y (U.S. Pat. No. 3.130.007) No.), Zeolite ZK-5 (U.S. Patent No. 83.247.195), Zeolite Z K-4 (U.S. Pat. No. 3,314.752), Zeolite), ZSM-5 (U.S. Pat. No. 3,702,886), Zeolite ZSM-11 (U.S. Pat. No. 3,709) , 979), Zeolite ZSM-12 (U.S. Patent No. 3,832.449), -zeolite) ZSM-20 (U.S. Patent No. 3,972,983), Zeolite Z SM-35C US r5nlr permission 114. O12,245), Zeola 4T ZSM- 38 (U.S. Pat. No. 4,046,859) and Zeolite l-ZSM-23 (U.S. Pat. 4.076.842), letters or other convenient Now expressed using symbols.
多孔質アルミノホスフェートおよび有機誘導剤を用いたその合成法が、米国特許 第４，３１０．４４０号および同第４，３８５．９９４号に開示されており、種 々の構造のシリコホスホアルミネートの合成法が米国特許第４，４４０．８７１ 号および同第４，６７３．５５９号に開示されている。結晶性メタロアルミノホ スフェートの合成法が米国特許第４．７１３，２２７号に開示されている。Porous aluminophosphate and its synthesis using organic derivatives have been awarded a U.S. patent. No. 4,310.440 and No. 4,385.994; A method for synthesizing silicophosphoaluminates with various structures is disclosed in U.S. Pat. No. 4,440.871. No. 4,673.559. Crystalline metalloaluminophore A method for synthesizing sphates is disclosed in US Pat. No. 4,713,227.
本発明は、 （Ｄアルミニウム、燐および要すればアルミニウムまたは燐以外の一種またはそ れ以上の元素（Ｍ）の酸化物源、水および誘導剤（ｄｉｒｅｃｔｉｎｇ ａｇｅ ｎｔ）（ＤＡ）を含んでなり、下記範囲のモル組成二Ｍ／ＡＩ２，０３ ０〜０．５Ｐ ｇｏ ｓ／ ＡＱｚＯｓ Ｏ−５〜１．２５Ｈ ，Ｏ／ＡＱ！０３ １０〜ｌ ＯＯＤ Ａ／ ＡＩ２＊Ｏｓ Ｏ−５〜１．５（ＤＡは、式： （式中、Ｒ％Ｒ′、Ｒ”およびＲ″′は同じまたは異なって−ＣＨ５Ｘおよび− ＣＨ２ＣＨ！Ｘから選択され、Ｘはカチオンを表す。） で示される化合物を表す。〕 を有する混合物を調製し、 （ｉｉ）該混合物を１００〜１４５°Ｃの温度を含む条件下に８０時間まで維持 し、および （ｉｉｉ）工程（ｉｉ）からｎｏ結晶性生成物を回収することからなる、第１Ａ 表に示すラインを有するＸ線回折パターンを示す結晶性分子ふるいを合成する方 法である。The present invention (D Aluminum, phosphorus and, if necessary, one or more other than aluminum or phosphorus) oxide source of element (M), water and directing agent nt) (DA), with a molar composition in the following range 2M/AI2,03 0~0.5P go s/AQzOs O-5~1.25H ,O/AQ! 03 10~l OOD A/AI2*Os O-5 to 1.5 (DA is the formula: (In the formula, R%R', R" and R"' are the same or different and -CH5X and - CH2CH! selected from X, where X represents a cation. ) Represents a compound represented by ] prepare a mixture having (ii) maintaining the mixture under conditions comprising a temperature of 100-145°C for up to 80 hours; and (iii) recovering no crystalline product from step (ii); How to synthesize a crystalline molecular sieve that exhibits an X-ray diffraction pattern with the lines shown in the table It is the law.
本発明の方法により製造された結晶性分子ふるいは、１１０℃またはそれ以上に 加熱された後でも、下記第１Ａ表のラインを有する特徴的なＸ線回折パターン、 特に下記第１Ｂ表の特徴、より特別には下記第１ｃ表の特徴を示す骨格位相を有 する。The crystalline molecular sieve produced by the method of the present invention can be heated to 110°C or higher. Even after being heated, a characteristic X-ray diffraction pattern having the lines of Table 1A below, In particular, it has a skeletal topology exhibiting the characteristics of Table 1B below, and more particularly the characteristics of Table 1C below. do.
１６．４±０．２ ｖｓ８．２±０．Ｉ Ｗ ４．７４±０．０５ Ｗｌ ６．４：ｌ：０．２ ＶＳ８．２±０．１ Ｗ５．４８±０．０５ Ｗ４．７４±０．０５ Ｗ第１Ｃ表 １６．４ｆＯ，２ＶＳ ８．２±０．１ ｗ ５．４８±ｏ、ｏｓ ｗ４．７４±０．０５ ｗ ４．１０±０．０４ Ｗ４．０５±０．０４ ｗ ３．７６±０．０３ ｗ３．２８±０．０３ ｗ 第１Ａ表、第１Ｂ表および第１Ｃ表のＸ線回折ラインは、１８員環の大きな細孔 開口を示す組成物の結晶骨格位相を同定する。細孔の直径は少なくとも１０人、 例えば少なくとも１２人、例えば１２〜１３人である。これらのラインは、この 位相を他の結晶性アルミノシリケート、アルミノホスフェートおよびシリコアル ミノポスフェート構造から識別する。本組成物のＸ線パターンには最も大きなｄ −間隔に対して顕著な相対強度を示す１３．６〜１３．３人のｄ−間隔が存在し ないことに注目すべきである。この範囲のｄ−間隔が本組成物のサンプル中に現 れる場合、それは不純物によるものであり弱い相対強度を有する。16.4±0.2 vs8.2±0. I W 4.74±0.05 Wl 6.4:l:0.2 W5.48±0.05 W4.74±0.05 W Table 1C 16.4fO, 2VS 8.2±0.1 w 5.48±o, os w4.74±0.05 w 4.10±0.04 W4.05±0.04 w 3.76±0.03 w3.28±0.03 w The X-ray diffraction lines in Table 1A, Table 1B, and Table 1C represent large pores of 18-membered rings. Identify the crystal skeletal phase of the composition that exhibits apertures. The diameter of the pores is at least 10 people, For example, at least 12 people, such as 12-13 people. These lines are like this phase to other crystalline aluminosilicates, aluminophosphates and silicoal Identification from the minophosphate structure. The X-ray pattern of this composition has the largest d - There are 13.6 to 13.3 d-intervals that exhibit significant relative strength to the It should be noted that there is no This range of d-spacings is present in samples of the present composition. If it is, it is due to impurities and has a weak relative strength.
これらのＸ線回折のデータは鋼のに一アルファ放射線を用いた一般的なＸ線系に より集められる。２倍シータ（角度）（シータはブラッグ角）で表されるピーク の位置は２倍シータをスキャンすることにより決められる。眉間間隔ｄ（人で測 定）およびバックグラウンドを差し引いたラインの相対強度Ｉ／Ｌ（Ｉｏは最も 強いラインの強度の１００分の１の値である。）を得た。相対強度は下記符号で 表す：ＶＳ 非常に強い（７５〜１００％）Ｓ 強（５０〜７ ４％） ｍ 中（２５〜４９％） Ｗ 弱（０〜２４％） このＸｗＡ回折は全ての種類の本発明の組成物を特徴付けると解すべきである。These X-ray diffraction data are based on a typical X-ray system using alpha radiation for steel. more collected. Peak expressed in double theta (angle) (theta is Bragg angle) The position of is determined by scanning double theta. Glabella distance d (measured by humans) ) and the relative intensity of the background-subtracted line I/L (Io is the most The value is 1/100 of the intensity of the strong line. ) was obtained. The relative strength is indicated by the sign below. Represents: VS Very strong (75-100%) S Strong (50-7 4%) m Medium (25-49%) W Weak (0-24%) This XwA diffraction is to be understood as characterizing all types of compositions according to the invention.
カチオンを他のイオンとイオン交換すると層間間隔およす組成物が得られる。個 々のラインの最も強いラインに対する相対強度は、組成物を希酸処理のような化 学的処理に付すると変化することもある。サンプルの組成成分比および熱処理温 度により他の変化が起こり得る。ラインの相対強度は、水、炭化水素または他の 成分のチャンネル構造内吸着のような要因による変化にも影響を受は易い。さら に、Ｘ線回折装置の光学素子が、特に角度の低い領域において強度に大きな影響 を与え得る。強度は選択的な結晶配向によっても影響を受は得る。Ion exchange of cations with other ions results in compositions with increased interlayer spacing. Individual The relative strength of each line to the strongest line can be determined by It may change when subjected to scientific treatment. Sample composition ratio and heat treatment temperature Other changes may occur depending on the degree. The relative strength of the lines is determined by water, hydrocarbons or other It is also susceptible to changes due to factors such as adsorption of components within the channel structure. Sara In addition, the optical elements of the X-ray diffraction device have a large influence on the intensity, especially in the low-angle region. can be given. Strength can also be affected by selective crystal orientation.
特に、本発明の方法により製造されｔ；分子ふるいは、Ａｌ２Ｏ２、ＰＯ８およ び要すればＭＯ，（Ｍはアルミニウムまたは燐以外の少なくとも一種の元素を表 す。）の四面体単位からなる三次元骨格構造を有する。元素Ｍが存在しない場合 、分子ふるいは下記の酸化物モル比の組成を有する： Ａｇ２Ｏ３： ｘＰｚ０６： ｎＨ２Ｏ〔式中、Ｘは０．５〜１．５を表し、ｎ は０〜１００、好ましくは０〜ｌＯである。〕 Ｍが存在する場合、Ｍは珪素単独が好ましく、その場合、分子ふるいは下記の酸 化物モル比の組成を有する。In particular, the molecular sieves produced by the method of the invention include Al2O2, PO8 and and, if necessary, MO, (M represents at least one element other than aluminum or phosphorus). vinegar. ) has a three-dimensional skeletal structure consisting of tetrahedral units. If element M does not exist , the molecular sieve has the following oxide molar ratio composition: Ag2O3: xPz06: nH2O [wherein, X represents 0.5 to 1.5, n is from 0 to 100, preferably from 0 to lO. ] When M is present, M is preferably silicon alone, in which case the molecular sieve is It has a composition of chemical compound molar ratio.
Ａｌ２１０３： ＸＰ！Ｏ，： ＦＳｉＯ，： ｎＨ２゜〔式中、Ｘは０．５〜 １．５、ｙは０．０１−０．５を表し、ｎは０−１００、好ましくは０〜ｌＯで ある。〕また、Ｍが珪素以外の元素を含む場合、アルミニウムと燐の合計はＭｊ Ｋ子の数を纏え、分子ふるいは、下記酸化物モル比の無水物組成： （Ａ（２０＊−）＋−−： （Ｐ Ｏｘつｒ−： （ＭＯｚ”一つ、ヤ。Al2103: XP! O,: FSiO,: nH2゜ [wherein, X is 0.5 to 1.5, y represents 0.01-0.5, n is 0-100, preferably 0-1O be. ] Also, if M contains an element other than silicon, the sum of aluminum and phosphorus is Mj The molecular sieve has an anhydride composition with the following oxide molar ratio: (A(20*-)+--: (P Ox two r-: (MOz" one, ya.
［式中、ｍはＭの価数（または重量平均価数）、Ｘおよびｙは下記の関係： ２讃ｙ−ｘ＋（４＋ｍ）・（ｘ＋ｙ）を満たし、Ｚは−１より大きくｌより 小さい。］を有し、電気的中性にするのに必要なアニオン及び／又はカチオンを 含む、２が０より大きい場合、分子ふるいは酸性触媒として使用することができ るカチオン交換物質として作用する。２が０より小ニオン交換物質として作用す る。ある場合には、珪素：非珪素原子の比が１より小さい、好ましくは０．５よ り小さくなるように珪素が存在してもよい。[In the formula, m is the valence (or weight average valence) of M, and X and y have the following relationship: 2) satisfies y-x+(4+m)・(x+y), and Z is greater than -1 and less than l small. ] and the anions and/or cations necessary to make it electrically neutral. Including, when 2 is greater than 0, the molecular sieve can be used as an acidic catalyst. It acts as a cation exchange material. 2 acts as a small ion exchange substance than 0. Ru. In some cases, the silicon:non-silicon atom ratio is less than 1, preferably greater than 0.5. Silicon may also be present so that it becomes smaller.
この態様における元素Ｍは、＋２〜＋６の酸化数および０．１５〜０，７３のイ オン「半径比」を有するが、Ｍの酸化数が＋２の場合は元素Ｍの半径比は０．５ ２〜０．６２である。The element M in this embodiment has an oxidation number of +2 to +6 and an ionic number of 0.15 to 0.73. If the oxidation number of M is +2, the radius ratio of element M is 0.5. It is 2 to 0.62.
「半径比」は、元素Ｍの結晶イオン半径の厳素アニオンｏ２−の結晶イオン半径 に対する比として定義される。"Radius ratio" is the crystal ionic radius of the strict anion o2- of the crystal ionic radius of element M. defined as the ratio to
原子Ｍの結晶イオン半径 半径比−□ ｏ２−の結晶イオン半径 元素の結晶イオン半径のリストが、シーアールシー・ハンドブック・オブ・ケミ ストリー・アンド・フィジックス（ＣＲＣＨａｎｄ−ｂｏｏｋ ｏｆ Ｃｈｅｍ ｉｓｔｒｙ ａｎｄ Ｐｈｙｓｉｃｓ）、６１版、シーアールシープレス社（Ｃ ＲＣＰ ｒｅｓｓ、 Ｉ ｎｃ、）、１９８０年、Ｆ−２１６−Ｆ−２１７頁に 記載されている。半径比を決める際、同じ方法により測定したＭＷ子および際素 アニオン（０ト）の結晶イオン半径を用いるこ必要である。Crystal ionic radius of atom M Radius ratio −□ crystal ionic radius of o2- A list of crystal ionic radii for elements is available in the CRC Handbook of Chemistry. Story and Physics (CRCHand-book of Chem) istry and Physics), 61st edition, CRC Press (C RCP ress, I nc, ), 1980, pages F-216-F-217 Are listed. When determining the radius ratio, use the MW element and the radial element measured using the same method. It is necessary to use the crystal ionic radius of the anion (0).
ここで有用な元素Ｍの例を以下に示す：鼠 価数 半径比Ｂｉ ＋３ ０．７３Ｆｅ ＋２ ０−５６Ｆｅ ＋３ ０．４８Ｇｅ ＋２ ０．５５ｃｅ ＋４ ０．４０Ｉｎ ＋３ ０．６１Ｍｎ ＋２ ° ０．６１ Ｚｎ ＋２ ０．５６本発明のＭとして含まれ ない元素の例は下記元素を含む二原子 価数 生 呈皮Ｂ ＋Ｉ Ｏ，２６Ｂａ ＋１ １．１６Ｂａ ＋２ １．０２Ｃｅ ＋３ ０．７８Ｃｄ ＋ｌ Ｏ，８６ｃｄ ＋２ ０．７３Ｃｒ ＋１ ０．６１Ｃｒ ＋２ ０．６７Ｍｇ ＋］ ０ ．６２Ｍｇ ＋２ ０．５０Ｍｏ ＋］、 ０．７０Ｓｎ ＋２ ０．７０Ｓｒ ＋２ ０．８５Ｔｈ ＋４ ０．７ ７Ｚｎ ＋Ｉ Ｏ，６７合成した 結晶性組成物は、通常、骨格アルミニウム、燐および元素Ｍを含み、Ｍ／（アル ミニウム＋燐）Ｗ子比が１より小さく０より大きい、一般的に０．００１〜０． ９９である。合成したそのような物質の燐／アルミニウム原子比は０．０１−１ ００．０で変化し得る。An example of an element M that is useful here is shown below: Rat Valence Radius ratio Bi +3 0.73Fe +2 +2 0-56Fe +3 +3 0.48Ge +2 0.55ce +4 +4 0.40In 0.61Mn 0.61 Zn +2 0.56 Included as M in the present invention Examples of elements that do not have the following elements are diatomic atoms containing the following elements: Skin presentation B +I O, 26Ba 1.16Ba 1.16Ba +2 +3 1.02Ce 0.78Cd ＋l O, 86cd +2 0.73Cr +1 +2 0.61Cr 0.67Mg ＋] 0.67Mg ．． 62Mg +2 0.50Mo +], 0.70Sn +2 +2 0.70Sr 0.85Th 0.7 7Zn +I O,67 synthesized Crystalline compositions typically include skeletal aluminum, phosphorus, and the element M, with M/(aluminum minium + phosphorus) W ratio is less than 1 and greater than 0, generally 0.001 to 0. It is 99. The phosphorus/aluminum atomic ratio of such a material synthesized is 0.01-1 00.0.
燐酸アルミニウムは、燐酸アルミニウム厚子比が約１であり、本質的に元素Ｍを 含まないと解される。また、「アルミノシリコホスフェートＪと称されることの ある燐置換ゼオライト組ＩＲ＃！Ｊは、珪素／アルミニウム原子比が一般的に１ より大きく、通常、０．６６〜８．０であり、燐／アルミニウム原子比が１より 小さく、通常０〜ｌである。Aluminum phosphate has an aluminum phosphate Atsuko ratio of approximately 1 and essentially contains element M. It is understood that it does not include. Also, the fact that it is called “alumino silicophosphate J” A certain phosphorus-substituted zeolite group IR#! J generally has a silicon/aluminum atomic ratio of 1 larger, usually between 0.66 and 8.0, with a phosphorus/aluminum atomic ratio of less than 1 Small, usually 0-1.
本発明によれば、上記分子ふるいは、アルミニウム源、燐源および要すればアル ミニウムまたは燐以外の元素Ｍ源、有機誘導剤および水を含んでなり、下記モル 比範囲の組成を有する反応混合物ヒドロゲルから合成される： 広い範囲 好ましい範囲 最も好ましい範囲Ｐ２０．／Ａらｏｓ ｏ、５〜１ ．２５ ０．９〜１．１ ０．９〜１．１Ｈｈｏ／ｐ、ａ、ｏｓ １０−１００ ２０〜８０ ３０〜６０Ｄ Ａ ／ Ａ Ｑｚ Ｏ ｓ Ｏ−２〜０．８ ０．３〜０．７ ０．４〜０．６原子Ｍが存 在するとき、 Ｍ／ ＡＱｘＯｓ ０−０１〜０゜５ ０．０１〜０．２ ０． ０１〜０．１誘導剤ＤＡは式： ［式中、Ｒ，Ｒ’、Ｒ′″およびＲ″′は同じまたは異なって−ＣＨ５Ｘおよび −ＣＨ，ＣＨ２Ｘから選択され、Ｘはヒドロキシドまたはハライド（例えばクロ ライドまたはプロミド）のようなカチオンを表す、］ で示される化合物である。これらの化合物の好ましい例は、テトラキス（２−ヒ ドロキシエチル）アンモニウムヒドロキシド、テトラキス（２−タロロエチル） アンモニウムクロライドおよびテトラキス（ヒドロキシメチル）アンモニウムプ ロミドを含む。According to the invention, the molecular sieve comprises an aluminum source, a phosphorus source and optionally an aluminum source. containing an element M source other than phosphorus or phosphorus, an organic inducer, and water, and the following molar Synthesized from reaction mixture hydrogels with compositions in the ratio range: Wide range Preferred range Most preferred range P20. /A et os o, 5-1 ．． 25 0.9~1.1 0.9~1.1Hho/p, a, os 10-100 20-80 30-60D A / A Qz O s O-2~0.8 0.3~0.7 0.4~0.6 atoms M exist When there is M/ AQxOs 0-01~0゜5 0.01~0.2 0. 01-0.1 Inducer DA has the formula: [In the formula, R, R', R'' and R'' are the same or different and -CH5X and -CH, CH2X, where X is a hydroxide or halide (e.g. chloride). ] represents a cation such as ride or promide) This is a compound represented by Preferred examples of these compounds are tetrakis(2-hyperoxyalpha) Droxyethyl) ammonium hydroxide, tetrakis(2-taloloethyl) Ammonium chloride and tetrakis(hydroxymethyl)ammonium salts Contains Lomid.
反応条件は、上記反応混合物を１００℃〜１４５℃の温度で１時間〜８０時間加 熱することを含む。より好ましい温度は１３０〜１４５℃であり、その温度での 時間は１０時間〜３０時間である。温度が１４５°Ｃより高い場合及び／又は時 間が８０時間を越える場合、第１Ａ表、第１Ｂ表および第１Ｃ表のＸ線回折パタ ーンにより特徴付けられる所望の細孔の大きな結晶を生成物が含む量が少なくな る。The reaction conditions were to heat the above reaction mixture at a temperature of 100°C to 145°C for 1 hour to 80 hours. Including heating. A more preferable temperature is 130 to 145°C, and at that temperature The time is 10 hours to 30 hours. If and/or when the temperature is higher than 145°C If the time period exceeds 80 hours, the X-ray diffraction patterns in Tables 1A, 1B and 1C The product contains fewer large crystals with the desired pores characterized by Ru.
反応混合物中のＰ ｘ Ｏｓ／ Ａ ａｔ Ｏｓ比も合成手順において重要であ る。The PxOs/AatOs ratio in the reaction mixture is also important in the synthesis procedure. Ru.
Ｐ ｘ Ｏｓ／ Ａ （２２Ｏｓ比が約１．２５より大きい場合、特に温度が１ ４５℃より高いと、生成物に含まれる所望の結晶性物質の量が少なくなる。P x Os/ A (22Os ratio is greater than about 1.25, especially when the temperature is 1. Above 45°C, the product contains less of the desired crystalline material.
全体を室温に冷却し、濾過し、水洗することにより、所望の分子ふるいを含む固 体生成物が反応媒体から回収される。通常の焼成手順により生成物から誘起誘導 剤を除去することができる。The solid containing the desired molecular sieve is obtained by cooling the whole to room temperature, filtering and washing with water. The product is recovered from the reaction medium. Induced from the product by normal calcination procedure agent can be removed.
本発明の合成方法は、生成物の結晶構造を有する種結晶が反応混合物中に存在す ることにより促進される。反応混合物中に少なくとも全体の重量に対して０．０ １％、好ましくは０．１０％、より好ましくは１％の結晶性物質の種結晶を含む ことにより本方法の結晶化が促進される。The synthesis method of the present invention is characterized in that seed crystals having the crystal structure of the product are present in the reaction mixture. This is facilitated by At least 0.0 based on the total weight in the reaction mixture Contains 1%, preferably 0.10%, more preferably 1% seed crystals of crystalline material This facilitates crystallization in the method.
いて調製される。有用な酸化アルミニウム源の例は、限定しないが、酸化アルミ ニウムまｔ；は水酸化アルミニウム、有機まｔ；は無機塩または化合物、例えば アルミナおよびアルミン酸塩を含む。そのような酸化アルミニウム源は、プソイ ド−ベーマイトおよびアルミニウムテトラアルコキシドを含む。有用な酸化燐源 の例は、限定しないが、任意の既知の形態の燐酸まｔ；は酸化燐、燐酸塩および 亜燐酸塩、および燐の有機誘導体である。有用な元素Ｍ源の例は、限定しないが 、任意の既知の形態の非アルミニウム原子、非燐原子、例えば金属、その酸化物 、水素化物または塩、アルコキシまたは他のＭ含有有機化合物を含む。It is prepared by Examples of useful aluminum oxide sources include, but are not limited to, aluminum oxide aluminum or aluminum hydroxide, organic or inorganic salts or compounds, e.g. Contains alumina and aluminate. Such aluminum oxide sources are Contains doboehmite and aluminum tetraalkoxide. Useful phosphorus oxide source Examples include, but are not limited to, any known form of phosphoric acid; Phosphites and organic derivatives of phosphorus. Examples of useful elemental M sources include, but are not limited to: , non-aluminum atoms, non-phosphorus atoms in any known form, e.g. metals, their oxides , hydrides or salts, alkoxy or other M-containing organic compounds.
反応混合物中で利用される各酸化物成分は一種またはそれ以上の必須反応体から 供給され、任意の順序で混合することができると解される。例えば、水溶液によ り任意の酸化物を供給することができる。反応混合物はバッチ式または連続式に 調製することができる。Each oxide component utilized in the reaction mixture is derived from one or more essential reactants. It is understood that the ingredients can be supplied and mixed in any order. For example, in an aqueous solution Any oxide can be supplied. The reaction mixture can be batchwise or continuously It can be prepared.
所望のメタロアルミノホスフェートを含む生成物の結晶寸法および結晶化時間は 、上記制限内で用いる反応混合物の性質により変化する。The crystal dimensions and crystallization time of the desired metalloaluminophosphate-containing product are , will vary within the above limits depending on the nature of the reaction mixture used.
本発明の分子ふるいは広範囲の有機化合物、例えば炭化水素化合物における吸着 剤または転化反応の触媒成分として用いることができるが、クラッキング、水素 化クラッキング、異性化および改質における触媒として特に有用である。本発明 の組成物を触媒として用いることのできる他の転化方法は、例えば脱ロウを含む 。The molecular sieves of the present invention can be used for adsorption on a wide range of organic compounds, such as hydrocarbon compounds. It can be used as an agent or a catalyst component in conversion reactions, but it can also be used as a catalyst for cracking, hydrogen It is particularly useful as a catalyst in chemical cracking, isomerization and reforming. present invention Other conversion methods in which compositions of can be used as catalysts include, for example, dewaxing. .
本発明により調製される結晶性分子ふるいは、合成した状態で、。The crystalline molecular sieves prepared according to the present invention are as synthesized.
水素機で、または他の一価もしくは多価カチオン型で使用することができる。こ の分子ふるいは、タングステン、バナジウム、モリブデン、レニウム、ニッケル 、コバルト、クロム、マンガンのような水素化成分、または、水素化−脱水素機 能を発揮する白金またはパラジウムのような貴金属と均一に混合して使用するこ ともできる。It can be used in hydrogen machines or in other monovalent or polyvalent cationic forms. child Molecular sieves include tungsten, vanadium, molybdenum, rhenium, nickel , cobalt, chromium, manganese, or hydrogenation-dehydrogenation equipment. It can be used evenly mixed with precious metals such as platinum or palladium, which exhibits Can also be done.
そのような成分は、組成物中に交換、組成物に含浸または物理的に組成物と均一 混合することができる。そのような成分は、結晶性組成物中またはその表面に含 浸させることができ、例えば白金の場合はその材料を白金金属含有イオンで処理 することにより含浸させることができる。この目的のために適当な白金化合物は 、クロロ白金酸、塩化白金および白金アミン錯体を含む種々の化合物を含む。金 属およびその導入方法は組み合わせて使用することもできる。Such components may be exchanged into, impregnated into, or physically homogeneous with the composition. Can be mixed. Such components may be included in or on the surface of the crystalline composition. For example, in the case of platinum, the material can be treated with platinum metal-containing ions. It can be impregnated by doing this. Platinum compounds suitable for this purpose are , chloroplatinic acid, platinum chloride and a variety of compounds including platinum amine complexes. Money The genera and their methods of introduction can also be used in combination.
本発明の組成物は、吸着剤として使用する場合も炭化水素転化方法において触媒 として使用する場合も、少なくとも部分的に脱水すべきである。これは、常圧ま たは減圧下、空気および窒素のような不活性雰囲気中、６５〜３１５℃の範囲の 温度で、１〜４８時間加熱することにより行うことができる。脱水は、ゼオライ トを減圧下に置きさえすれば、より低い温度で行うことができるが、所定の脱水 度を得るためにはより長い時間が必要とされる。新規合成組成物の熱分解生成物 は、２００〜５５０°Ｃの温度で１〜４８時間加熱することにより調製すること ができる。The compositions of the present invention, when used as adsorbents, also serve as catalysts in hydrocarbon conversion processes. It should also be at least partially dehydrated when used as This is normal pressure or or under reduced pressure in an inert atmosphere such as air and nitrogen at temperatures ranging from 65 to 315°C. It can be carried out by heating at a temperature of 1 to 48 hours. Zeolite for dehydration This can be done at lower temperatures as long as the sample is placed under reduced pressure, but Longer time is required to gain strength. Pyrolysis products of new synthetic compositions may be prepared by heating at a temperature of 200 to 550°C for 1 to 48 hours. Can be done.
上述したように、本発明により調製した合成メタロアルミノホスフェートは、そ こに組み込まれている最初のカチオンを、当業者に良く知られた技術により広範 囲の他のカチオンで置換することができる。典型的な置換カチオンは、水素、ア ンモニウムおよび金属カチオンおよびそれらの混合物を含む。置換金属カチオン のうちで特に好ましいものは、希土類金属および元素周期表のＩ［ＡＳｍＡ、ｒ ＶＡ、ＩＢ、ｎＢ、Ｉ［［Ｂ、ＩＶＢ、ＶＩＢおよび■族の金属、特にＭｎ。As mentioned above, the synthetic metalloaluminophosphate prepared according to the present invention has The initial cation incorporated therein can be broadly modified by techniques well known to those skilled in the art. Other cations in the brackets can be substituted. Typical substituted cations are hydrogen, a Including ammonium and metal cations and mixtures thereof. substituted metal cations Particularly preferred among these are rare earth metals and I[ASmA, r VA, IB, nB, I[[B, IVB, VIB and group II metals, especially Mn.
Ｃａ、Ｍｇｓ Ｚｎ％Ｃｄ、Ｐｄ１Ｎｉ、Ｃｕ、Ｔｉ１１Ｘ、５ｎＳＦｅおよび Ｃｏのカチオンである。Ca, Mgs Zn%Cd, Pd1Ni, Cu, Ti11X, 5nSFe and It is a Co cation.
典型的なイオン交換技術は、合成物質と所望の置換カチオンとの接触である。広 範囲の塩を使用することができるが、特ｌこ好ましいのは塩化物、硝酸塩および 硫酸塩である。A typical ion exchange technique is contacting a synthetic material with the desired substituted cation. Wide Although a range of salts can be used, particularly preferred are the chlorides, nitrates and It is a sulfate.
触媒として使用する場合、本発明の分子ふるいに有機物転化方法において使用す る温度および他の条件に耐性のある別の物質を組み込むことが望ましい。そのよ うなマトリックス材料は活性および不活性物質および合成まＩ；は天然産ゼオラ イトならびにクレー、シリカ及び／又は金属酸化物、例えばアルミナのような無 機物質を含む。When used as a catalyst, the molecular sieve of the present invention may be used in an organic matter conversion method. It is desirable to incorporate other materials that are resistant to the temperatures and other conditions involved. That's it The matrix material consists of active and inert substances and synthetic or naturally occurring zeola. clays, silica and/or metal oxides, e.g. alumina. Contains mechanical substances.
後者は、天然産のものでも、シリカと金属酸化物の混合物を含むゼラチン状沈澱 物、ゾルまたはゲルであってよい。活性物質を本発明の分子ふるいと一緒に用い る、すなわち組み合わせると、特定の有機転化プロセスの転化率及び／又は選択 率が向上する。不活性物質は、反応速度制御のための他の手段を用いることなく 生成物を経済的かつ一定量で得ることができるように、所定の方法における転化 量を制御するための希釈剤として好適に役立つ。結晶性触媒物質は、天然産りし ・−１例えばベントナイトおよびカオリンに組み込まれることが多い。これらの 物質、すなわちクレー、酸化物等は、触媒のバインダーとしての機能も有する。The latter, although naturally occurring, is a gelatinous precipitate containing a mixture of silica and metal oxides. It may be a solid, sol or gel. Using an active substance together with the molecular sieve of the invention i.e., in combination, the conversion rate and/or selection of a particular organic conversion process. rate will improve. Inert substances can be used without other means to control the reaction rate. Conversion in a given process so that the product can be obtained economically and in constant quantities It suitably serves as a diluent to control the amount. Crystalline catalyst materials are naturally occurring -1 is often incorporated into bentonite and kaolin, for example. these The substances, ie clays, oxides, etc., also function as binders for the catalyst.
石油精製において、触媒はしばしば雑に取り扱われ、それにより触媒が破壊され て粉末状物質になる傾向があり、プロセスにおいて問題が生じるので、高い圧潰 強さを有する触媒を提供することが望ましい。In oil refining, catalysts are often handled roughly, which can destroy them. high crushing, as they tend to form a powdery material and cause problems in the process. It is desirable to provide a catalyst that has strength.
本発明の分子ふるいと組み合わせることのできる天然産クレーは、サブベントナ イトおよび主鉱物成分がバクサイト、カオリナイト、ディッカイ）・、ナタライ トまＩ；はアナウキサイトである通常ディキシ−、マクナメーおよびフロリダク レー等として知られているカオリンを含むモンモリロナイトおよびカオリン族を 含む。そのようなりレーは、採掘した原料状態で、または最初に焼成し、酸処理 または化学的変性して使用することができる。The naturally occurring clay that can be combined with the molecular sieve of the present invention is The main mineral components are bacsite, kaolinite, dickai), natalai Toma I; is anauxisite, usually Dixie, McNamee and Floridakite. Montmorillonite and kaolin family containing kaolin known as leh etc. include. Such rays can be produced either in the mined raw state or by first firing and acid treatment. Alternatively, it can be used after being chemically modified.
ここで合成された結晶は、前記物質に加えて、シリカ−アルミナ、シリカ−マグ ネシア、シリカージルフニア、シリカ−トリア、シリカ−ベリリア、シリカ−チ タニア、ならびにシリカ−アルミナ−トリア、シリカ−アルミナ−ジルコニア、 シリカ−アルミナ−マグネジ７ＨＪ：びシリカ−マグネシア−ジルコニアのよう な三元物質のような多孔質マトリックス物質と複合させることができる。マトリ ックスはコゲル状であってよい。これらの成分の混合物を使用することもできる 。In addition to the above substances, the crystals synthesized here include silica-alumina, silica-mag nesia, silica dilphnia, silica toria, silica beryllia, silica chi Tania, as well as silica-alumina-thoria, silica-alumina-zirconia, Silica-alumina-magnetic screw 7HJ: like silica-magnesia-zirconia can be combined with porous matrix materials such as ternary materials. Matri The box may be in the form of a cogel. Mixtures of these ingredients can also be used .
微粉砕結晶性物質とマトリックスの割合は、複合物中の結晶性物質含量で１〜９ ０重量％、より一般的には２〜５０重量％の広範囲に変化する。The ratio of finely ground crystalline material to matrix is between 1 and 9 with respect to the crystalline material content in the composite. It varies over a wide range from 0% by weight, more commonly from 2 to 50% by weight.
水素化成分を含む本発明の分子ふるいを含む触媒を使用すると、４５０〜５５０ ℃の温度で改質用原料を改質することができる。圧力は４４５〜３５３０ｋＰａ （５０−５００ｐｓｉ）であり得るが、好ましくは８９０−２１７０ｋＰａ（１ ００−３００ｐｓｉ）である。液体時間空間速度は通常０．１〜１０／時間、好 ましくは１〜４／時間であり、水素対炭化水素モル比は通常１〜１０、好ましく は３〜５である。When using a catalyst containing a molecular sieve of the present invention containing a hydrogenation component, 450 to 550 The raw material for reforming can be reformed at a temperature of °C. Pressure is 445-3530kPa (50-500psi), but preferably 890-2170kPa (1 00-300psi). The liquid hourly space velocity is usually 0.1 to 10/hour, preferably preferably 1 to 4/hour, and the molar ratio of hydrogen to hydrocarbon is usually 1 to 10, preferably is 3-5.
本発明の組成物を含む触媒は、水素化成分、例えば白金が提供されれば、ｎ−パ ラフィンの水素異性化に用し゛ることもできる。水素異性化は、２５０〜４５０ ℃、好ましくは３００〜４２５℃の温度、０．１−１０／時間、好ましくは０． ５〜４／時間の液体時間空間速度で、水素対炭化水素モル比が１−１０であるよ うに水素を用いて行うことができる。さらに、０〜５５０℃の温度で、触媒を用 いてオレフィンまたは芳香族化合物を異性化することができる。Catalysts containing the compositions of the invention can be used if a hydrogenation component, such as platinum, is provided. It can also be used for hydroisomerization of raffins. Hydroisomerization is 250-450 ℃, preferably 300-425℃, 0.1-10/hour, preferably 0. At a liquid hourly space velocity of 5-4/hr, the hydrogen to hydrocarbon molar ratio is 1-10. This can be done using sea urchin hydrogen. Furthermore, the catalyst is used at a temperature of 0 to 550°C. It is possible to isomerize olefins or aromatic compounds.
本発明の分子ふるいを含む触媒は、軽油の流動点を低下させるｔ；めに使用する こともできる。この方法は、０．１〜５／時間の液体時間空間速度および３００ 〜４２５℃の温度で行われる。The catalyst containing the molecular sieve of the present invention is used to lower the pour point of light oil. You can also do that. This method uses a liquid hourly space velocity of 0.1 to 5/hour and a It is carried out at a temperature of ~425°C.
本発明を実施例および添付の図面を参照にしてより詳細に説明する。第１〜８図 は、それぞれ実施例１〜８の焼成生成物のＸ線回折パターンである。The invention will be explained in more detail with reference to examples and the accompanying drawings, in which: FIG. Figures 1-8 are the X-ray diffraction patterns of the fired products of Examples 1 to 8, respectively.
実施例１ ８５％オルト燐酸（Ｈｓ Ｐ○、）１０３．５ｇを水１５５ｇ中に含む混合物を 酸化アルミニウム源（プソイド−ベーマイト）５０．８ｇと混合した。混合物を 撹拌下、８０℃で１時間加熱した。この混合物に、テトラキス（２−ヒドロキシ エチル）アンモニウムハイドライド（ＤＡ）ｌ Ｏ５，５ｇの水１５０ｇ中混合 物音添加し、下記組成からなる反応混合物を得た： Ｐ ２０ ｓ／ ＡＱｘＯｓ ｌ −２６Ｈｔｏ／ ＡＬＯｓ −５２ Ｄ Ａ／ ＡＱｚＯｓ −０、７反応混合物を１０００ｃｃオートクレ ーブに仕込んだ。オートクレーブ内で、２１７０ｋＰａ（３００ｐｓｉｇ）の窒 素雰囲気下、１４０℃で１６時間結晶化を行った。固体生成物を濾過、洗浄およ び乾燥した。Example 1 A mixture containing 103.5 g of 85% orthophosphoric acid (Hs P○) in 155 g of water was prepared. Mixed with 50.8 g of aluminum oxide source (pseudo-boehmite). mixture The mixture was heated at 80° C. for 1 hour while stirring. Add tetrakis (2-hydroxy) to this mixture. Ethyl) ammonium hydride (DA) mixed with 5.5 g of O in 150 g of water A reaction mixture was obtained with the following composition: P 20 s/ AQxOs -26Hto/ ALOs -52 D A/ AQzOs -0,7 The reaction mixture was placed in a 1000cc autoclave. I put it in a tube. Nitrogen at 2170 kPa (300 psig) in an autoclave. Crystallization was performed at 140° C. for 16 hours in an elementary atmosphere. Filter, wash and remove solid products. and dried.
ソックスレー装置により水で抽出することにより洗浄を行った。生成物を空気中 ５３８℃で１０時間焼成した。Washing was carried out by extraction with water in a Soxhlet apparatus. product in the air It was baked at 538°C for 10 hours.
焼成生成物は、Ｘ線粉末回折により分析すると結晶であることがわかり、第２表 および第１図のパターンを示しＩ；。The fired product was found to be crystalline when analyzed by X-ray powder diffraction, and is shown in Table 2. and shows the pattern of FIG.
簾１表 １９．６２６３３ ４．５０２ 、 ２．０１６ ．５０８３７ ５．３５４ １００．０１１．９ ５３０１１１ ７．３９６ ７．１ｇ、２４６ ３４ １０．７２Ｂ ２７．２６．２０３８１ １４．２７７ １２．９４．７４０９５ １ｇ、７１７ １２．７４．３３９３５ ２０． ４６７ １．４４．１９０８７ ２１．２００ ４．５４．０８６９０ ２１．７４６ ５７．１４．０６７９９ ２１．８４８ ６７．２３．９６９１４ ２２．３９９ ４２．０３．９５０９８ ２２．５０４ ４ ６．０３．７９４０５ ２３．４４７ １３．３ ３．７７００９ ２３．５９８ ２４．３３．５ｇ ５６３ ２４．８３１ ５．７３．５０２２２ ２５．４３３ ０．４３．４７５５３ ２５．６３１ １４３．４３４ｇ４ ２ ５．９４０ ２．２３．４１０７６ ２６．１２ ６ １．０３．２８２１４ ２７． ＋６９ ３２．２３．１７００８ ２８．＋４９ ４．９３．１５５０＋ ２８．２８７ ４．４３．０８６７０ ２８．９２６ １ ４．２３．０８１１７ ２８．９７９ １１．１３ ．０３３５１ ２９．４４５ ２．３２．９５４６ １ ３（＋２４９ ９．２２．９５０８６ ３０．２８９ １０．４２．９１４５６ ３０ ．６７５ １．４２．８１５１８ ３１．７８６ ０．９２．７３７８６ ３２．７０９ １２．７２．７３１４５ ３２．７８８ ７．４抽出しｔ；実施例１の生成物の化学分析結果を以下に示す：、１ １９．６３重量％ Ｐ ２１．０４重量％ Ｓ ｉ Ｏ，０２６重量％ Ｎａ Ｏ，０２９重量％ 実施例２ ８５％オルト燐酸（ＨｘＰＯａ）１１５ｇの水１５５ｇ中混合物音７１ｇの酸化 アルミニウム源（プソイド−ベーマイト）と混合した。混合物を撹拌下、８０℃ で３時間加熱した。この混合物に、テトラキス（２−ヒドロキシエチル）アンモ ニウムヒドロキシド（ＤＡ）１０５．５ｇの水１５０ｇ中混合物音添加して、下 記組成を存する反応混合物を得た。1 blind screen 19.62633 4.502, 2.016 ．． 50837 5.354 100.011.9 530111 7.396 7.1g, 246 34 10.72B 27.26.20381 14.277 12.94.74095 1g, 717 12.74.33935 20. 467 1.44.19087 21.200 4.54.08690 21.746 57.14.06799 21.848 67.23.96914 22.399 42.03.95098 22.504 4 6.03.79405 23.447 13.3 3.77009 23.598 24.33.5g 563 24.831 5.73.50222 25.433 0.43.47553 25.631 143.434g4 2 5.940 2.23.41076 26.12 6 1.03.28214 27. +69 32.23.17008 28. +49 4.93.1550+ 28.287 4.43.08670 28.926 1 4.23.08117 28.979 11.13 ．． 03351 29.445 2.32.9546 1 3 (+249 9.22.95086 30.289 10.42.91456 30 ．． 675 1.42.81518 31.786 0.92.73786 32.709 12.72.73145 32.788 7.4 Extracted; The chemical analysis results of the product of Example 1 are shown below: 1 19.63% by weight P 21.04% by weight S O,026% by weight Na O, 029% by weight Example 2 Oxidation of 71 g of a mixture of 115 g of 85% orthophosphoric acid (HxPOa) in 155 g of water Mixed with aluminum source (pseudo-boehmite). The mixture was heated to 80°C under stirring. It was heated for 3 hours. Add tetrakis(2-hydroxyethyl)ammo to this mixture. A mixture of 105.5 g of sodium hydroxide (DA) in 150 g of water was added to the bottom. A reaction mixture having the above composition was obtained.
Ｐｘｏｉ／ＡＱｘＯ３−１ Ｈ，Ｏ／ＡらＯｓ ＝ ４０Ｄ Ａ／ Ａｌ２ｚＯ３＝ ０．５反応混合物を１０００ｃｃのオートクレーブ中に仕込んだ。オートクレー ブ内で２１７０ｋＰａ（３００ｐｓｉｇ）の窒素圧下、１４２℃で１７時間結晶 化を行った。固体生成物を濾過し、洗浄し乾燥した。ソックスレー装置により水 で抽出することにより洗浄を完了した。生成物を空気中、５３０℃で１０時間焼 成した。Pxoi/AQxO3-1 H, O/A et Os = 40D A/Al2zO3= 0.5 reaction mixture was charged into a 1000 cc autoclave. autoclay Crystallize for 17 hours at 142°C under 2170 kPa (300 psig) nitrogen pressure in a vacuum chamber. . The solid product was filtered, washed and dried. Water by Soxhlet device Washing was completed by extraction with The product was baked in air at 530°C for 10 hours. accomplished.
焼成した生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり、 第３表および第２図のパターンを示した。As a result of X-ray powder diffraction analysis, the calcined product was found to be crystalline. The patterns shown in Table 3 and FIG. 2 are shown.
反応混合物をオートクレーブ中Ｉ；仕込んだ。オートクレーブ内で２１７０ｋＰ ａ（３００ｐｓｉｇ）の窒素圧下、１３８℃で１４時間結晶化を行っＩ；。固体 生成物を濾過し、洗浄し、乾燥した。ソックスレー装置により水で抽出すること により洗浄を完了した。生成物を空気中、５３０℃で１０時間＃！成した。The reaction mixture was charged into an autoclave. 2170kP in autoclave Crystallization was carried out at 138° C. for 14 hours under nitrogen pressure of a (300 psig) I; solid The product was filtered, washed and dried. Extraction with water by Soxhlet apparatus Cleaning was completed. The product was heated in air at 530°C for 10 hours #! accomplished.
焼成した生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり、 Ｍ４表および第３図のパターンを示した。As a result of X-ray powder diffraction analysis, the calcined product was found to be crystalline. The M4 table and the pattern in Figure 3 are shown.
８．２１３９６ １０゜７７１ ２３．９６．１６ ３６７ １４．３７０ １３．９４．７３７６９ １８．７３０ １２．８３．７７３３８ ２３．５７８ １Ｂ、３３．４２６７９ ２６．００ ２ １．９３．２８０００ ２７．１８８ ３０．３３．１９７１８ ２７．９０６ １ ．１３．１６２２３ ２８．２２１ ５．３３．０ ７９１２ ２ｇ、９９９ １２．３２．９５１９４ ３０．２７７ １０．７２．９４７８５ ３０．３２０ １２．１２．８９３６９ ３０．９ ０２ ３．２２．７３４６４ ３２．７４８ １３．５２．５８８２２ ３４．６５８ ０．６抽出しＩ；実施例２の生成物の化学的分析結果は下記組成を示した。8.21396 10゜771 23.96.16 367 14.370 13.94.73769 18.730 12.83.77338 23.578 1B, 33.42679 26.00 2 1.93.28000 27.188 30.33.19718 27.906 1 ．． 13.16223 28.221 5.33.0 7912 2g, 999 12.32.95194 30.277 10.72.94785 30.320 12.12.89369 30.9 02 3.22.73464 32.748 13.52.58822 34.658 0.6 Extracted I; Chemical analysis of the product of Example 2 showed the following composition.
ＡＱ １９．４６重量％ Ｐ １６．６３重量％ Ｓ ｉ ０．０４６重量％Ｎａ ’ ０．０３３重量％ 東裏！１ ８５％オルト燐酸（Ｈ３ＰＯ４）５７．５ｇの水７７．５ｇ中混合物を３５．５ ｇの酸化アルミニウム源（プソイド−ベーマイト）と混合した。AQ 19.46% by weight P 16.63% by weight Si 0.046% by weight Na 0.033% by weight East back! 1 A mixture of 57.5 g of 85% orthophosphoric acid (H3PO4) in 77.5 g of water was g of an aluminum oxide source (pseudo-boehmite).
混合物を撹拌下、８０℃で１時間加熱した。この混合物に、テトラキス（２−ヒ ドロキシエチル）アンモニウムヒドロキシド（ＤＡ）５２゜７５ｇの水７５ｇ中 混合物を添加して、下記組成を有する反応混合物を得た。The mixture was heated at 80° C. for 1 hour while stirring. Add tetrakis(2-hyperoxychloride) to this mixture. Droxyethyl) ammonium hydroxide (DA) 52° in 75 g of water The mixture was added to obtain a reaction mixture having the following composition.
Ｐ ｚ Ｏｓ／ Ａ （ｌｘ Ｏｓ ｌＨ２Ｏ／ＡＬＯｓ −４１ Ｄ Ａ／ ＡＱｚＯ３−０、５ 反応混合物をオートクレーブに仕込んだ。オートクレーブ内で２１７０ｋＰａ（ ３００ｐｓｉｇ）の窒素圧下、１３８℃で１４時間結晶化を行った。固体生成物 を濾過し、洗浄し、乾燥した。ソックスレー装置により水で抽出することにより 洗浄を完了した。生成物を空気中、５３０℃で１０時′間焼成した。PzOs/A(lxOs lH2O/ALOs -41 D A/ AQzO3-0, 5 The reaction mixture was charged into an autoclave. 2170kPa in an autoclave ( Crystallization was carried out at 138° C. for 14 hours under nitrogen pressure (300 psig). solid product was filtered, washed and dried. By extraction with water in a Soxhlet apparatus Cleaning completed. The product was calcined in air at 530°C for 10 hours.
焼成した生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり、 第４表および第３図のパターンを示した。As a result of X-ray powder diffraction analysis, the calcined product was found to be crystalline. The patterns shown in Table 4 and FIG. 3 are shown.
罠ｔ！ １６．３３１４７ ５．４１１ １００．０８． １９１６１ １０．８００ ２４．４６．１５８ ４７ １４．３ｇ２ １３．７４．７３２６０ １８．７５０ １３．５４．４６９９４ １９，８６３ １．１４．０７９ｇ４ ２１ ．７８４ ５４．７４．０５９３３ ２１．８９ ５ ６１．４３．９５０５６ ２２．５０９ ３８．３３．９３８３９ ２２．５７６ ３９．４３．７７２２４ ２３．５８５ １６．９３．７６２１７ ２３．６４９ ２ ３．５３．６２８０９ ２４．５３６ ８．９ ３．５８４７３ ２４．８３８ ８．０３．２ ７４７５ ２７．２３２ ３４．８３．１６２１ ９ ２８．２２１ ｇ、４３．０７７３６ ２９．０１６ １４．９３．０２６５３ ２９．５１４ ８．７２．９４６８０ ３０．３３１ １６．９２．８９６６６ ３ ０．８６９ ８．４２．８８６３２ ３０．９ ８３ ９．２２．７４２６１ ３２．６５０ １１．０２．７３３１９ ３２．７６６ １２．４２．７２９８７ ３２．８０７ ９．７抽出した実施例３の生成物の化学的分析結果は下記組成を示し た。Trap! 16.33147 5.411 100.08. 19161 10.800 24.46.158 47 14.3g2 13.74.73260 18.750 13.54.46994 19,863 1.14.079g4 21 ．． 784 54.74.05933 21.89 5 61.43.95056 22.509 38.33.93839 22.576 39.43.77224 23.585 39.43.77224 23.585 16.93.76217 23.649 2 3.53.62809 24.536 8.9 3.58473 24.838 8.03.2 7475 27.232 34.83.1621 9 g, 43.07736 28.221 g, 43.07736 29.016 14.93.02653 29.514 8.72.94680 30.331 16.92.89666 3 0.869 8.42.88632 30.9 83 9.22.74261 32.650 11.02.73319 32.766 12.42.72987 32.807 9.7 The chemical analysis results of the extracted product of Example 3 showed the following composition: Ta.
Ａｌ１ ２１．３３重量％ Ｐ ２ＣＬ１３重量％ Ｓｉ ０．０２８重量％ Ｎａ Ｏ，０２１重量％ 実施例４（比較例） ８５％オルト燐酸（ＨＩＰＯ，）６１．５ｇの水９２．１ｇ中混合物物音０．２ ｇの酸化アルミニウム源（プソイド−ベーマイト）と混合した。Al1 21.33% by weight P 2CL13% by weight Si 0.028% by weight Na O, 021% by weight Example 4 (comparative example) Mixture of 85% orthophosphoric acid (HIPO,) 61.5 g in 92.1 g water Sound volume 0.2 g of an aluminum oxide source (pseudo-boehmite).
混合物を撹拌下、８０°Ｃで１時間加熱した。この混合物に、テトラキス（２− ヒドロキシエチル）アンモニウムヒドロキシド（ＤＡ）６２゜７ｇの水８９−２ ｇ中混合物物音加して、下記組成を有する反応混合物を得た。The mixture was heated under stirring at 80°C for 1 hour. Tetrakis (2- Hydroxyethyl) ammonium hydroxide (DA) 62°7g water 89-2 A reaction mixture having the following composition was obtained by adding the mixture in g.
Ｐ、Ｏ５／Ａ１２２０３ １．２８Ｈ，Ｏ／ＡＩ２．０． − ５２ＤＡ／ＡＱ２０． − ０．７１１反応混物をオ ートクレーブに仕込んだ。オートクレーブ内で２１７０ｋＰａ（３００ｐｓｉｇ ）の窒素圧下、１６０℃で５時間結晶化を行った。固体生成物を濾過し、水洗し 、乾燥した。P, O5/A12203 1.28H, O/AI2.0. - 52DA/AQ20. - 0.711 Turn the reaction mixture over I put it in a tank. 2170 kPa (300 psig) in an autoclave ) under nitrogen pressure at 160° C. for 5 hours. Filter the solid product and wash with water , dried.
生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり、第５表お よび第４図のパターンを示した。As a result of analysis by X-ray powder diffraction, the product was found to be a crystal, and Table 5 and and the pattern shown in Figure 4.
１１．８３９４７ ７．４６７ ５６．４６．８３２ ７７ １２．９５７ ９．２５．９１５３１ １４．９７７ ２３．９４．４６９７５ １９．８６３ ５７．５４．２３４７０ ２０．９７８ ４７．９３．５９７１６ ２４．７５０ ５．１３ ．４１３７９ ２６．１０３ ３６．８３．３００７２ ２７．０１４ ０．０２．９５５８０ ３０ ．２３７ ２１．４２．６５６０８ ３３．７４６ ５．０２．５８０５１ ３１１．７６５ １７．１上記反応混合物から１６０°Ｃで結晶させｊ：実施例４の生成物は、主 にＡＱＰＯ，−”であり、本発明の合成法による細孔の大きなアルミノホスフェ ート結晶はほとんど含まれないことがわかった。11.83947 7.467 56.46.832 77 12.957 9.25.91531 14.977 23.94.46975 19.863 57.54.23470 20.978 47.93.59716 24.750 5.13 ．． 41379 26.103 36.83.30072 27.014 0.02.95580 30 ．． 237 21.42.65608 33.746 5.02.58051 311.765 5.02.58051 311.765 17.1 Crystallized at 160°C from the above reaction mixture: The product of Example 4 was mainly AQPO,-”, which is a large-pore aluminophosphorus synthesized by the synthesis method of the present invention. It was found that almost no carbonate crystals were included.
実施例５ ８５％オルト燐酸（ＨｓＰＯ４）５Ｂ−４ｇの水７７．５ｇ中混合物を３５．５ ｇの酸化アルミニウム源（例えば、プソイド−ベーマイト）および０，６ｇの酸 化珪素源（例えばＨ４ＳｉＭ）と混合した。混合物を撹拌下、８０℃で１時間加 熱した。この混合物に、テトラキス（２−ヒドロキシエチル）アンモニウムヒド ロキシド（ＤＡ、）５２．７５ｇの水７５ｇ中混合物を添加して、下記組成を有 する反応混合物を得た。Example 5 A mixture of 85% orthophosphoric acid (HsPO4) 5B-4g in 77.5g water was prepared at 35.5% g of aluminum oxide source (e.g. pseudo-boehmite) and 0.6 g of acid mixed with a silicon oxide source (eg H4SiM). The mixture was heated at 80°C for 1 hour under stirring. It was hot. Add tetrakis(2-hydroxyethyl)ammonium hydride to this mixture. A mixture of 52.75 g of Roxid (DA) in 75 g of water was added to have the following composition: A reaction mixture was obtained.
ＳｉＯ□／Ａｌ２２０３ − ０．０４Ｐ ｓｏ ｓ／ Ａｌ２２０ ｓ −１ＨｚＯ／ＡＬＯｓ −４１ Ｄ Ａ／ ＡＱ、ｏ ｓ −０−５反応混合物を３００ｃｃのオート クレーブに仕込んだ。オートクレーブ内で２１７０ｋＰａ（３００ｐｓｉｇ）の 窒素圧下、１４２℃で１７時間結晶化を行った。固体生成物を濾過し、洗浄し、 乾燥した。ソックスレー装置により水で抽出することにより洗浄を完了した。生 成物を空気中、５３０°Ｃで１０時間焼成した。SiO□/Al2203 - 0.04P sos/Al220 s -1HzO/ALOs -41 D A/ AQ, os -0-5 The reaction mixture was placed in a 300cc auto I put it in the creve. 2170 kPa (300 psig) in an autoclave Crystallization was carried out at 142° C. for 17 hours under nitrogen pressure. Filter and wash the solid product; Dry. Washing was completed by extraction with water using a Soxhlet apparatus. Living The product was calcined in air at 530°C for 10 hours.
焼成しＩ：生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり 、第６表および第５図のパターンを示した。Calcined I: As a result of X-ray powder diffraction analysis, the product was found to be crystalline. , the patterns in Table 6 and FIG. 5 were shown.
８．８９２１２ ９．９４７ ７．３８．１７０５ ８ １０．８２８ ２０．６６．１３７８４ １４．４３１ １１．１５．４６３５３ １６．２２３ １．８４．０５０５５ ２１．９４３ ５３．７３．７５８７３ ２３．６７１ １６．２ ３．６２６５７ ２４．５４７ ３．４３．３３６６ ７ ２６．７１７ ２．３３．３１３５２ ２６．９０７ ２．４３．２７９９４ ２７．１８８ ２１．１３．２６９２１ ２７．２７９ ２３．０３．１５５０４ ２Ｂ、２８６ ３．８３．０７７１８ ２９．０１８ ８． ４３．０２８７２ ２９．４９２ ２．４３、Ｏ ］、３４６ ２９．６４５ １．２２．９８１１ ３ ２９．９７４ ０．４２．９５１６５ ３０．２８０ ６−５２．９４１００ ３ ０．３９３ ９．０２．８２５１４ ３１．６７ １ ０．０２．７５９０３ ３２．４５１ ２．０抽出した実施例５の生成物の化学的分析結果は下記組成を 示した。8.89212 9.947 7.38.1705 8 10.828 20.66.13784 14.431 11.15.46353 16.223 1.84.05055 21.943 53.73.75873 23.671 16.2 3.62657 24.547 3.43.3366 7 26.717 2.33.31352 26.907 2.43.27994 27.188 21.13.26921 27.279 23.03.15504 2B, 286 3.83.07718 29.018 8. 43.02872 29.492 2.43, O ], 346 29.645 1.22.9811 3 29.974 0.42.95165 30.280 6-52.94100 3 0.393 9.02.82514 31.67 1 0.02.75903 32.451 2.0 The chemical analysis results of the extracted product of Example 5 have the following composition: Indicated.
ＡＱ２２．０９重量％ Ｐ １８．８４重量％ Ｓｉ ０．２９重量％ Ｎａ Ｏ，０４重量％ 筈施例６（比較例） ８５％オルト燐酸（Ｈ３ＰＯｔ）５５．８ｇの水７７．５ｇ中混合物を３５．５ ｇの酸化アルミニウム源（例えば、グツイド−ベーマイト）およびｌｏｇの酸化 珪素源（例えばＨｉＳｉｆｆ）と混合した。混合物を撹拌下、８０℃で１時間加 熱した。この混合物に、テトラキス（２−ヒドロキシエチル）アンモニウムヒド ロキシド（ＤＡ）５２．７５ｇの水７５ｇ中混合物を添加して、下記組成を有す る反応混合物を得た。AQ22.09% by weight P 18.84% by weight Si 0.29% by weight Na O, 04% by weight Example 6 (comparative example) A mixture of 55.8 g of 85% orthophosphoric acid (H3POt) in 77.5 g of water was g of aluminum oxide source (e.g. gtuido-boehmite) and log oxidation mixed with a silicon source (eg HiSiff). The mixture was heated at 80°C for 1 hour under stirring. It was hot. Add tetrakis(2-hydroxyethyl)ammonium hydride to this mixture. A mixture of 52.75 g of Roxid (DA) in 75 g of water was added to have the following composition: A reaction mixture was obtained.
Ｓ ｉｏ ２／ ＡＱｘＯ３０，０６８Ｐ ！Ｏｓ／ ＡＱｚＯｓ ｌＨ！Ｏ／ＡＩ２！０３ − ４１Ｄ Ａ／ ＡＱｘＯｓ −０−５反応混合物を３００ｃｃオートクレーブに仕込んだ。オートクレ ーブ内で２１７０ｋＰａ（３００ｐｓｉｇ）の窒素圧下、１５１”ｏで２０時間 結晶化を行った。固体生成物を濾過し、１６時間窒素を流しｔ：。固体生成物を 濾過し、洗浄し、１１０℃で１７時間乾燥した。S io 2/AQxO30,068P! Os／ AQzOs lH! O/AI2!03 - 41D A/AQxOs -0-5 The reaction mixture was charged into a 300cc autoclave. autocle 20 hours at 151”o under 2170 kPa (300 psig) nitrogen pressure in the chamber Crystallization was performed. The solid product was filtered and flushed with nitrogen for 16 hours. solid product Filtered, washed and dried at 110° C. for 17 hours.
生成物は、Ｘ線粉末回折による分析の結果、結晶であることがわかり、第７表お よび第６図のパターンを示した。As a result of analysis by X-ray powder diffraction, the product was found to be a crystal, and Table 7 and and the pattern shown in FIG.
第７表 １１．８７３５７ ７．４４５ ５６．６６．８４８８７ １２．９２６ ９．５５．９２４０２ １４． ９５５ ２６．１４．４７５１３ １９．８３９ ６０．８４．２２８７９ ２１．００８ ５７．８３．９ ５６６２ ２２．４７１ １００．０３．５９５６９ ２４．７６１ ４．９３．４１７４４ ２６．０７４ ３５−１３．２５８６５ ２７．３６９ ０ ．５３．０７０５０ ２９．０ｇ２ １５．８２．９５９５ ２ ３０．１９８ １９．３２．６５７８４ ３ ３．７２２ ５．０２．５８３０１ ３４．７３０ １５．４上記反応混合物から１５１ ’Ｃで２０時間結晶させた実施例 ６の生成物は、主に５ＡＰＯ−５であり、本発明の合成法による細孔の大きなシ リコアルミノホスフェート結晶はほとんど含まれないことがわかった。Table 7 11.87357 7.445 56.66.84887 12.926 9.55.92402 14. 955 26.14.47513 19.839 60.84.22879 21.008 57.83.9 5662 22.471 100.03.59569 24.761 4.93.41744 26.074 35-13.25865 27.369 0 ．． 53.07050 29.0g2 15.82.9595 2 30.198 19.32.65784 3 3.722 5.02.58301 34.730 15.4 Example of crystallizing the above reaction mixture at 151'C for 20 hours The product of No. 6 is mainly 5APO-5, which is a large-pore silicone produced by the synthesis method of the present invention. It was found that almost no licoaluminophosphate crystals were contained.
実施例７ ８５％オルト燐酸（ＨｓＰＯａ）５６．６ｇの水７７．５ｇ中混合物を００４６ ｇの五酸化バナジウム（Ｖ２０ｓ）と混合した。五酸化バナジウムが完全に溶け るまで、混合物を撹拌下、５０°Ｃで３０分間加熱した。Example 7 A mixture of 56.6 g of 85% orthophosphoric acid (HsPOa) in 77.5 g of water g of vanadium pentoxide (V20s). Vanadium pentoxide is completely dissolved. The mixture was heated under stirring at 50° C. for 30 minutes until the mixture was mixed.
次に３５．５ｇの酸化アルミニウム源（例えばプソイド−ベーマイト）を添加し 、混合物を８０℃で１時間加熱した。この混合物に、テトラキス（２−ヒドロキ シエチル）アンモニウムヒドロキシド（ＤＡ）５２．７５ｇの水７５ｇ中混合物 を添加して、下記組成を有する反応混合物を得た。Then add 35.5 g of an aluminum oxide source (e.g. pseudo-boehmite). , the mixture was heated at 80° C. for 1 hour. Add tetrakis (2-hydroxy) to this mixture. A mixture of 52.75 g of ethyl)ammonium hydroxide (DA) in 75 g of water was added to obtain a reaction mixture having the following composition.
Ｍ／Ａａ＊ｏｓ −０，０１Ｐ、Ｏ，／、１２０３ − １Ｈｘ Ｏ／ Ａ （ｂ Ｏｓ 寓 ４０Ｄ Ａ／ＡＱ！０３ 諺 ０．５反応混合物を３００ｃｃオートクレーブ に仕込んだ。オートクレーブ内で自生圧下、１４２℃で１７時間結晶化を行った 。固体生成物を濾過し、洗浄し、乾燥しｔ；。ソックスレー装置により水で抽出 することにより洗浄を完了した。生成物を空気中、５３０℃で１０時間焼成した 。M/Aa*os -0,01P,O,/,1203 - - 1Hx O/A (b Os Fable 40D A/AQ!03 Progress 0.5 Reaction mixture 300cc auto crave I prepared it in. Crystallization was performed in an autoclave under autogenous pressure at 142°C for 17 hours. . The solid product was filtered, washed and dried. Extracted with water using a Soxhlet apparatus Cleaning was completed by doing this. The product was calcined in air at 530°C for 10 hours. .
焼成生成物は、Ｘ線粉末回折による分析の結果、結晶であること第８表 １４．１０３６１ ６．２６７ ２．６８．２４７６２ １０．７２７ ９．０６．１６９８７ １４．３５ ６ ６．１５．７０７３７ １５．５２６ ４．１５．４９２５６ １６．１３７ １．８５．１３ ７４３ １７．２６１ １．５４．８３７４６ １ ８．３４０ １．８４．６３３７５ １９．１５４ ０．５４．４８４８６ １９．７９６ ７．２ ４．４４２１７ １９．９８８ ３．４４．３８９４０ ２０．２３１ ０．２４．０９６８１ ２１．６９ ３ １００．０３．９５９７９ ２２．４５３ ４４．６３．９３８３４ ２２．５７７ ５６．９３．９ ２０４６ ２２．６８１ ３８．３３．５５４１６ ２５．０５５ ８．４３．５２７３１ ２５．２４９ ４．２３．４５６０６ ２５．７７８ ０． ９３．４３０９０ ２５．９７０ ０．６３．４０６８１ ２６．１５７ １．７３．３２６９５ ２６ ．７９７ ６．０３．２８９００ ２７．１ １２ １５．８３．２６９４８ ２７．２７７ １８．３３．１５９６２ ２８．２４４ ０．８３．０９６７２ ２８．８３０ ４．９３．０８９５８ ２８．８９８ ６．３３．０８１３５ ２８．９７７ ７．０３．０２６９１ ２９．５１０ ９．７ ２．９８８４０ ２９．８９９ ５．１２． ９５６８０ ３０．２２６ １．５２．９４ ６４４ ３０．３３５ ０．４２．９０２２ ３ ３０．８０９ ２．４２．８２７９２ ３１．６３９ ２．４２．７７３１８ ３２．２８１ ２．２２．７３９１８ ３２．６９２ ５．５２．７２４２６ ３２ ．８７７ ２．３２．６７４８３ ３３．５ ０２ ０．７２．６００６５ ３４．４８７ １．１２．５７５５８ ３４．８３３ ０．３抽出した実施例７の生成物の化学分析結果を以下に 示す：Ａｃｔ １８．７５重量％Ｐ １７．３ ９重量％Ｖ Ｏ，１９重量％Ｓｉ ０．１ ７重量％実施例８（比較例） ８５％オルト燐酸（Ｈ，ＰＯ，）５６．６ｇの水７７．５ｇ中混合物を０゜４６ ｇの五酸化バナジウム（ｖｘｏｓ）と混合した。五酸化バナジウムが完全に溶解 するまで、混合物を撹拌下、５０°Ｃで３０分間加熱した。混合物に３５．５ｇ の酸化アルミニウム［（例えばプソイド−ベーマイト）を添加し、８０℃で１時 間加熱した。この混合物に、テトラキス（２−ヒドロキシエチル）アンモニウム ヒドロキシド（ＤＡ）５２．７５ｇの水７５ｇ５ｇ中混を添加して、下記組成を 有する反応混合物を得た。As a result of analysis by X-ray powder diffraction, the fired product is crystalline Table 8 14.10361 6.267 2.68.24762 10.727 9.06.16987 14.35 6 6.15.70737 15.526 4.15.49256 16.137 1.85.13 743 17.261 1.54.83746 1 8.340 1.84.63375 19.154 0.54.48486 19.796 7.2 4.44217 19.988 3.44.38940 20.231 0.24.09681 21.69 3 100.03.95979 22.453 44.63.93834 22.577 56.93.9 2046 22.681 38.33.55416 25.055 8.43.52731 25.249 4.23.45606 25.778 0. 93.43090 25.970 0.63.40681 26.157 1.73.32695 26 ．． 797 6.03.28900 27.1 12 15.83.26948 27.277 18.33.15962 28.244 0.83.09672 28.830 4.93.08958 28.898 4.93.08958 28.898 6.33.08135 28.977 7.03.02691 29.510 9.7 2.98840 29.899 5.12. 95680 30.226 1.52.94 644 30.335 0.42.9022 3 30.809 2.42.82792 31.639 2.42.77318 32.281 2.22.73918 32.692 5.52.72426 32 ．． 877 2.32.67483 33.5 02 0.72.60065 34.487 1.12.57558 34.833 0.3 The chemical analysis results of the extracted product of Example 7 are shown below. Shown: Act 18.75% by weight P 17.3 9% by weight V O, 19% by weight Si 0.1 7% by weight Example 8 (comparative example) A mixture of 56.6 g of 85% orthophosphoric acid (H, PO,) in 77.5 g of water was heated to 0°46 g of vanadium pentoxide (vxos). Vanadium pentoxide completely dissolved The mixture was heated under stirring at 50° C. for 30 minutes until the mixture was stirred. 35.5g in the mixture of aluminum oxide (e.g. pseudo-boehmite) and heated at 80°C for 1 hour. It was heated for a while. Add tetrakis(2-hydroxyethyl)ammonium to this mixture. Add 52.75 g of hydroxide (DA) mixed with 75 g of water and 5 g to make the following composition. A reaction mixture was obtained.
Ｍ／ｐ、ａｚｏｓ −０，０１Ｐ ｔｏ ｓ／ Ａ（１２０ｓ ＩＨ，Ｏ／Ａ（２１Ｏ３−４０ ＤＡ／Ａらｏｓ −０，５ 反応混合物を３００ｃｃオートクレーブに仕込んだ。オートクレーブ内で自生圧 下、１４７℃で１７時間結晶化を行った。固体生成物を濾過し、洗浄し１１０℃ で１７時間乾燥した。M/p, azos -0,01P to s/A (120s IH, O/A (21O3-40 DA/A et os −0,5 The reaction mixture was charged into a 300cc autoclave. Autogenous pressure in autoclave Crystallization was performed at 147° C. for 17 hours. The solid product was filtered and washed at 110°C. It was dried for 17 hours.
かり、第９表および第８図のパターンを示しｔ；。This shows the patterns in Table 9 and Figure 8.
１１．８６３１４ ７．４５２ ５６．５６．８４４０ ４ １２．９３５ １０．０５．９２５１５ １４．９５２ ２４・７４．４７６０２ １９．８３ ５ ５７．１４．２０６１７ ２１．１２２ ５１．４３．９５３６３ ２２．４８８ １００．０ ３．５８４４６ ２４．８４０ ３．１３．４１８７７ ２６．０６４ ３４．６３．１９０７５ ２７．９６３ ０．４３．０６３１６ ２９．２５３ １４−７２．９８０１δ ３０．１９１ １７．９２．６５３９０ ３３．７７４ ４．４２．５ ８４３２ ３４．７１２ １３．７実施例８の生成物は 、主にＡｌ２Ｐ Ｏ、−ｓの構造を有する結晶からなり、本発明の細孔の大きな メタロアルミノホスフェート結晶は微量にしか含まれなかった。11.86314 7.452 56.56.8440 4 12.935 10.05.92515 14.952 24.74.47602 19.83 5 57.14.20617 21.122 51.43.95363 22.488 100.0 3.58446 24.840 3.13.41877 26.064 34.63.19075 27.963 0.43.06316 29.253 14-72.9801δ 30.191 14-72.9801δ 17.92.65390 33.774 4.42.5 8432 34.712 13.7 The product of Example 8 is , mainly consists of crystals having the structure of Al2P O,-s, and the large pores of the present invention Metalloaluminophosphate crystals were only contained in trace amounts.
国際調査報告 ＵＳ ！１９０１３６６ ＳＡ ２８３２１international search report US! 1901366 SA 28321
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/179,175 US5141728A (en) | 1988-04-08 | 1988-04-08 | Synthesis of crystalline aluminophosphate composition |
| US179,344 | 1988-04-08 | ||
| US179,175 | 1988-04-08 | ||
| US07/179,344 US5169614A (en) | 1988-04-08 | 1988-04-08 | Synthesis of crystalline silicoaluminophosphate composition |
| US179,341 | 1988-04-08 | ||
| US07/179,341 US5147525A (en) | 1983-12-19 | 1988-04-08 | Synthesis of crystalline metalloaluminophosphate composition |
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| EP (1) | EP0442879A1 (en) |
| JP (1) | JPH03503881A (en) |
| KR (1) | KR900700385A (en) |
| AU (1) | AU3549189A (en) |
| DK (1) | DK279590D0 (en) |
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| WO2013176227A1 (en) * | 2012-05-24 | 2013-11-28 | 東ソー株式会社 | Silicoaluminophosphate, method for producing same, and solid acid catalyst comprising same |
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| DK0464249T3 (en) * | 1990-07-05 | 1994-04-25 | Leuna Werke Gmbh | Process for the preparation of a large pore crystalline molecular sieve |
| FR2671790B1 (en) * | 1991-01-18 | 1993-04-16 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF ALUMINOPHOSPHATE COMPOUNDS AND SUBSTITUTED DERIVATIVES OF THE VFI STRUCTURAL TYPE INVENTION OF: JEAN-FRANCOIS JOLY, HERVE CAUFFRIEZ AND JEAN-LOUIS GUTH. |
| GB0222477D0 (en) * | 2002-09-27 | 2002-11-06 | British Nuclear Fuels Plc | Novel ion-exchange materials |
| CN102530987A (en) | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
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| WO1989001912A1 (en) * | 1987-08-28 | 1989-03-09 | The Dow Chemical Company | Crystalline aluminumphosphate compositions |
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- 1989-03-31 AU AU35491/89A patent/AU3549189A/en not_active Abandoned
- 1989-03-31 JP JP1505001A patent/JPH03503881A/en active Pending
- 1989-03-31 EP EP89905323A patent/EP0442879A1/en not_active Withdrawn
- 1989-03-31 KR KR1019890702290A patent/KR900700385A/en not_active Application Discontinuation
- 1989-03-31 WO PCT/US1989/001366 patent/WO1989009749A1/en not_active Application Discontinuation
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| WO2013176227A1 (en) * | 2012-05-24 | 2013-11-28 | 東ソー株式会社 | Silicoaluminophosphate, method for producing same, and solid acid catalyst comprising same |
| JP2014141385A (en) * | 2012-05-24 | 2014-08-07 | Tosoh Corp | Silicoaluminophosphate, method for producing the same, and solid acid catalyst comprising the same |
| US9637392B2 (en) | 2012-05-24 | 2017-05-02 | Tosoh Corporation | Silicoaluminophosphate, method for producing the same, and solid acid catalyst comprising the same |
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| Publication number | Publication date |
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| NZ228425A (en) | 1990-11-27 |
| DK279590A (en) | 1990-11-23 |
| DK279590D0 (en) | 1990-11-23 |
| EP0442879A1 (en) | 1991-08-28 |
| AU3549189A (en) | 1989-11-03 |
| KR900700385A (en) | 1990-08-13 |
| WO1989009749A1 (en) | 1989-10-19 |
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