JPH0310568B2 - - Google Patents
Info
- Publication number
- JPH0310568B2 JPH0310568B2 JP56061573A JP6157381A JPH0310568B2 JP H0310568 B2 JPH0310568 B2 JP H0310568B2 JP 56061573 A JP56061573 A JP 56061573A JP 6157381 A JP6157381 A JP 6157381A JP H0310568 B2 JPH0310568 B2 JP H0310568B2
- Authority
- JP
- Japan
- Prior art keywords
- crystalline
- silicic acid
- sio
- compound
- cations
- 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.)
- Expired - Lifetime
Links
- -1 silicic acid compound Chemical class 0.000 claims description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 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 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000005342 ion exchange Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002602 lanthanoids Chemical group 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical group [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Chemical group 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium 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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ゼオライト構造を有する結晶性ケイ
酸化合物に関するものである。更に詳しくは、ラ
ンタニド族稀土類元素をケイ素の一部と置換した
形で結晶格子中に有する、三次元のゼオライト構
造を持つケイ酸化合物に関するものである。
ゼオライトは、結晶性アルミノシリケートであ
り、SiO4及びAlO4とからなる四面体によつて構
成される三次元の網目構造を有している。ケイ素
及びアルミニウムを中心とする四面体は、酸素原
子を共有することによつて結合しており、アルミ
ニウムの原子価は、アルカリ金属、アルカリ土類
金属などのカチオンを結晶に配位することによつ
てバランスを保ち、全体の電気的中性を維持して
いる。これらのカチオンは、通常のイオン交換技
法により他種のカチオンと相互に交換することが
可能である。
ゼオライトは、元来天然に産するものであり、
その特異な触媒活性、吸着能、分子ふるい作用な
どのため、工業的に極めて有用であり、多くの研
究がなされた。その結果、天然には見られない新
種のゼオライトが合成され、現在までに、非常に
数多くの合成ゼオライトが発表されている。これ
ら多くのゼオライトは、全て結晶性アルミノシリ
ケートであるが、ゼオライトの網目構造を形成し
ているアルミニウム、ケイ素を他の元素で置換
し、新規なゼオライト状の立体構造を有する化合
物を合成しようという試みも行なわれており、ア
ルミニウムをガリウム、リン、ベリリウム、ヒ素
で置換した形のゼオライト状の立体構造を持つた
化合物、あるいは、ケイ素をゲルマニウムで置換
した形のゼオライト状の立体構造を持つた化合物
などが既に得られている。例えば、特開昭55−
7598号にはケイ素の結晶格子中にケイ素に対する
置換元素として入るかまたは二ケイ酸塩またはポ
リケイ酸塩として入るクロム、ベリリウム、チタ
ン、バナジウム、マンガンなどの化学元素で変性
した結晶性ケイ素よりなることを特徴とするケイ
素基体合成物質が、また、特開昭55−67521号に
はアルミナを必須成分とした結晶性アルミノシリ
ケートゼオライトが開示されている。
本発明者らは、工業的有用性の高い、新規なゼ
オライト状の立体構造を有する化合物の合成を目
指し、鋭意研究を重ねた結果、通常のゼオライト
のアルミニウムをランタニド族稀土類元素で置換
した構造を持つ、新規な結晶性ケイ酸化合物を合
成することに成功し、この知見を基に本発明に到
達した。
即ち本発明は、下記一般式(1)
（M2O3）・（SiO2）ｘ ……(1)
（式中、Ｍはランタニド族稀土類元素より選ばれ
る少くとも一種の金属、Ｏは酸素、ｘは２〜
10000の数）によつて表わされる組成を必須成分
とし、表−１に記載したＸ線回折パターンを有す
る結晶性ケイ酸化合物を提供するものである。
一般式(1)中のＭはランタニド族稀土類元素であ
るが、工業的応用の面から考え、ランタン、セリ
ウム、プラセオジウム又はネオジウムが好適であ
り、更に好ましいのは、ランタン又はセリウムで
ある。一般式(1)のｘは２〜10000、好ましくは５
〜5000の数である。ｘが２未満の場合はｘが２以
上の場合と異なり、本発明の結晶性ケイ酸化合物
と同一の立体構造の化合物にならない。またｘが
10000を越えると例えば触媒としての活性が著し
く低くなるなどにより工業的有用性に乏しくな
る。
本発明における結晶性ケイ酸化合物の結晶構造
中のランタニド族稀土類元素の原子は電荷にかた
よりを生じ負に帯電した状態になつていると考え
られる。この負電荷に対してはそれぞれカチオン
が配位し全体の電気的中性を保つていると考えら
れ、一般式(1)で示される組成を必須とする結晶性
ケイ酸化合物中には、この配位カチオンが存在す
ることは勿論である。
本発明の結晶性ケイ酸化合物にカチオンが配位
した状態の組成式は下記一般式(2)で表わすことが
できる。
（M2O3）・（SiO2）ｘ・（Y2O）ｙ ……(2)
（Ｍ、Ｏ及びｘは前記と同じ。Ｙは配位カチオ
ン、ｙは0.1〜１の数）この配位カチオンは、水
素カチオン、金属カチオンなどの無機カチオン及
び有機カチオンなどであり、有機カチオンの例と
しては、アンモニウムイオン、アルキルアンモニ
ウムイオンなどが挙げられる。これらの配位カチ
オンは、相互に交換が可能であり、通常のイオン
交換技法により容易に交換することができる。ｙ
は後記する結晶化度によつて異なり、結晶化度
100％の場合はｙ＝１であり結晶化度が10％の場
合はｙ＝0.1である。本発明の結晶性ケイ酸化合
物の前記触媒として使用する場合の活性を考慮す
るとｙは0.4〜１、特に0.7〜１が好ましい。
本発明の結晶性ケイ酸化合物は、表−１に示す
如き一定のＸ線回折パターンを有するものであ
る。表−１に示される回折パターンより本発明の
結晶性ケイ酸化合物はゼオライト状の立体構造を
有していると推定される。
The present invention relates to a crystalline silicic acid compound having a zeolite structure. More specifically, the present invention relates to a silicic acid compound having a three-dimensional zeolite structure in which a rare earth element of the lanthanide group is substituted for a portion of silicon in the crystal lattice. Zeolite is a crystalline aluminosilicate and has a three-dimensional network structure composed of tetrahedra made of SiO 4 and AlO 4 . Tetrahedrons centered on silicon and aluminum are bonded by sharing oxygen atoms, and the valence of aluminum is determined by coordinating cations such as alkali metals and alkaline earth metals to the crystal. balance and maintain overall electrical neutrality. These cations can be interchanged with other types of cations by conventional ion exchange techniques. Zeolite is naturally occurring,
Due to its unique catalytic activity, adsorption ability, molecular sieving action, etc., it is extremely useful industrially and has been the subject of much research. As a result, new types of zeolites not found in nature have been synthesized, and to date, a large number of synthetic zeolites have been announced. Many of these zeolites are all crystalline aluminosilicate, but an attempt was made to synthesize a compound with a new zeolite-like three-dimensional structure by replacing the aluminum and silicon that form the zeolite network structure with other elements. Compounds with a zeolite-like three-dimensional structure in which aluminum is replaced with gallium, phosphorus, beryllium, or arsenic, or compounds with a zeolite-like three-dimensional structure in which silicon is replaced with germanium, etc. has already been obtained. For example, JP-A-55-
No. 7598 includes crystalline silicon modified with chemical elements such as chromium, beryllium, titanium, vanadium, manganese, etc., which enter the silicon crystal lattice as a substitute element for silicon or as a disilicate or polysilicate. JP-A-55-67521 discloses a crystalline aluminosilicate zeolite containing alumina as an essential component. The present inventors aimed to synthesize a compound with a novel zeolite-like three-dimensional structure that is highly useful industrially, and as a result of extensive research, we discovered a structure in which the aluminum of ordinary zeolite is replaced with a rare earth element of the lanthanide group. We have succeeded in synthesizing a new crystalline silicic acid compound having the following properties, and based on this knowledge, we have arrived at the present invention. That is, the present invention provides the following general formula (1) (M 2 O 3 )・(SiO 2 ) Oxygen, x is 2~
The present invention provides a crystalline silicic acid compound having a composition represented by 10,000) as an essential component and having an X-ray diffraction pattern shown in Table 1. M in the general formula (1) is a rare earth element of the lanthanide group, and from the viewpoint of industrial application, lanthanum, cerium, praseodymium or neodymium is preferable, and lanthanum or cerium is more preferable. x in general formula (1) is 2 to 10000, preferably 5
The number is ~5000. When x is less than 2, unlike when x is 2 or more, the compound does not have the same three-dimensional structure as the crystalline silicic acid compound of the present invention. Also x
If it exceeds 10,000, the activity as a catalyst will be significantly lowered, resulting in poor industrial usefulness. It is considered that the atoms of the lanthanide group rare earth element in the crystal structure of the crystalline silicate compound in the present invention have biased charges and are in a negatively charged state. It is thought that each cation coordinates with this negative charge and maintains the overall electrical neutrality, and in the crystalline silicate compound that requires the composition shown by general formula (1), this Of course, there is a coordinating cation. The compositional formula of the crystalline silicic acid compound of the present invention in which a cation is coordinated can be represented by the following general formula (2). (M 2 O 3 )・(SiO 2 )x・(Y 2 O) y ...(2) (M, O and x are the same as above. Y is a coordinating cation, y is a number from 0.1 to 1) Coordinating cations include inorganic cations such as hydrogen cations and metal cations, and organic cations, and examples of organic cations include ammonium ions and alkylammonium ions. These coordinating cations are mutually interchangeable and can be easily exchanged by conventional ion exchange techniques. y
varies depending on the degree of crystallinity, which will be described later.
When the degree of crystallinity is 100%, y=1, and when the degree of crystallinity is 10%, y=0.1. Considering the activity of the crystalline silicic acid compound of the present invention when used as the catalyst, y is preferably 0.4 to 1, particularly preferably 0.7 to 1. The crystalline silicic acid compound of the present invention has a certain X-ray diffraction pattern as shown in Table 1. From the diffraction pattern shown in Table 1, it is estimated that the crystalline silicic acid compound of the present invention has a zeolite-like three-dimensional structure.
【表】
本発明の結晶性ケイ酸化合物は、含有するラン
タニド族稀土類元素の量に対応する酸量を有して
おり、通常のアルミノシリケート・ゼオライトと
同様にイオン交換能を持つている。また、触媒と
して極めて高い活性及び熱安定性を有しており、
種々の有機化合物の転換反応に有効に作用する。
特にメタノールを炭化水素に転換する反応に対し
て高い活性を示し、実用触媒として使用し得る寿
命も有している。また、イソブテンとホルムアル
デヒドよりイソブレン、イソペンテニルアルコー
ルを生成する反応に対しても高い活性を有し、工
業触媒として有用である。
本発明の結晶性ケイ酸化合物は、SiO2源、
M2O3源並びに無機アルカリ及び／若しくは含窒
素化合物の水を媒質とする混合溶液ないしは懸濁
液（以下混合溶液ないしは懸濁液を反応液と記
す）を100〜250℃の温度で反応させ、結晶化させ
ることによつて製造される。
使用されるSiO2源としては、ケイ酸、アルカ
リ金属ないしはアルカリ土類金属のケイ酸塩、水
ガラス、シリカヒゾロゾル、シリカゲル、有機シ
リケートなどがあり、特にアルカリ金属ケイ酸
塩、水ガラス、有機シリケートが好適である。用
いられるアルカリ金属ケイ酸塩の例としては、ケ
イ酸ナトリウム、ケイ酸カリウムなどが挙げら
れ、有機シリケートの例としては、テトラエチル
オルトシリケートなどが挙げられる。これらの
SiO2源は二種以上併用してもよい。SiO2源の使
用量は反応液の媒質である水に対し通常モル数で
１／１０〜1/200であり、特に1/15〜1/60が好ましい。
M2O3源としては、水に可溶性の塩であれば特
に限定はなく、例えば、ランタニド族稀土類元素
の塩化物、臭化物、酢酸塩、硝酸塩、硫酸塩、シ
ユウ酸塩などが挙げられる。これらのM2O3源も
二種以上併用しても良いことは勿論である。
M2O3源の使用量は合成目的物質が合成できるよ
うにSiO2源を基準として適宜決めることができ
る。
無機アルカリとは、アルカリ金属又はアルカリ
土類金属の水酸化物などであり、これらは単独で
あるいは、二種以上を併用して用いられる。アル
カリ金属の水酸化物としては、水酸化ナトリウ
ム、水酸化カリウムが良好に使用され、特に水酸
化ナトリウムが良好に用いられる。またアルカリ
土類金属の水酸化物としては水酸化カルシウムが
好適に用いられる。含窒素化合物としてはアルキ
ルアンモニウム類、アミン類などの有機化合物を
挙げることができ、アルキルアンモニウム類とし
ては、例えば炭素数２〜５のアルキル基を有する
第四級アンモニウム化合物が良好に使用される。
第四級アンモニウムとしてはテトラエチルアンモ
ニウム、テトラプロピルアンモニウム、テトラブ
チルアンモニウム、テトラペンチルアンモニウム
などを挙げることができる。特に、テトラプロピ
ルアンモニウム、テトラブチルアンモニウムが良
好に使用される。アルキルアンモニウム類は水酸
化物、例えばテトラプロピルアンモニウムハイド
ロオキサイド、テトラブチルアンモニウムハイド
ロオキサイドなどとして供給される他、適当な塩
の形式、例えば臭化テトラプロピルアンモニウ
ム、塩化テトラプロピルアンモニウムなどとして
も供給することができる。
アミン類としては、水に可溶なアミン、例えば
エチレンジアミン、トリメチレンジアミン、テト
ラメチレンジアミン、ペンタメチレンジアミン、
ヘキサメチレンジアミンなどが良好に用いられ
る。また、炭素数２〜５のアルキル基を持つ水に
不溶なアルキルアミンなども、適当な溶剤、例え
ば、アセトン、メチルエチルケトンなどと共に用
いれば、使用することが可能である。無機アルカ
リ及び／若しくは含窒素化合物の使用量はSiO2
源に対して化学量論以下で用いることが好まし
く、特にSiO2源１モルに対して0.05〜0.5モル用
いることが好ましい。また本発明の結晶性ケイ酸
化合物の合成において無機アルカリ及び含窒素化
合物を併用することによつて、結晶化が促進され
るため、この両者の併合が望ましい。反応液のPH
は特に限定するものではないが、通常８以上、好
ましくは9.5〜14のアルカリ性で反応を行なう。
また反応液中にアルカリ金属又はアルカリ土類金
属の無機塩、例えば塩化ナトリウム、臭化ナトリ
ウム、塩化カリウム、塩化カルシウムなどの鉱化
剤を添加してもよい。
結晶化を行なわせるためには、前記反応液を
100〜250℃、好ましは120〜200℃にまで加熱し、
0.5〜30日、好ましくは１日〜10日、前記温度に
保持する。
結晶化の過程においては、反応液を撹拌するこ
とが好ましく、これによつてより円滑に結晶化を
進行させることができる。結晶化反応終了後、反
応液をロ過することによつて本発明の結晶性ケイ
酸化合物が得られる。
本発明の結晶性ケイ酸化合物の結晶化度は結晶
化速度と反応時間によつて定まる。すなわち反応
終了時に結晶化していないSiO2及びM2O3は結晶
性ケイ酸化合物を反応後より分離する際に非晶質
のSiO2及び非晶質のM2O3として混入し、本発明
の結晶性ケイ酸化合物の結晶化度を低下させる。
本発明の結晶性ケイ酸化合物は通常結晶化度10〜
100％のものとして得られ、触媒として使用する
場合の活性を考慮すると、結晶化度は40〜100％、
特に70〜100％のものが好ましい。
こうした操作により結晶性ケイ酸化合物が得ら
れるが、通常は得られた結晶性ケイ酸化合物を純
水で洗浄し、乾燥した後、300〜1000℃、好まし
くは400〜850℃で、１〜30時間、好ましくは３〜
20時間焼成し、一般に知られているイオン交換技
法により、結晶中に含有されるアルカリカチオン
の一部又は全部をプロトン、即ちH+に置き換え
て使用する。
イオン交換の一例を述べると、H+を供給し得
る酸、例えば、HCl、HNO3、H2SO4の水溶液と
接触させる方法、あるいはNH4 +を供給し得る
塩、例えばNH4Cl、NH4NO3、NH4OOCH3など
で処理した後、100〜1000℃で焼成するなどの方
法がある。勿論、プロトン以外のカチオンと交換
することも可能であり、容易に各種金属カチオン
を含有する結晶性ケイ酸化合物を得ることができ
る。
前記のようにイオン交換は、いかなるカチオン
でも可能であるが、工業的応用の面から考え、水
素、アルカリ金属、アルカリ土類金属、第族の
金属、銅、銀、亜鉛、カドミウム、マンガン、レ
ニウム、クロム、モリブデン、タングステン、及
び／又は稀土類元素などが本発明の結晶性ケイ酸
化合物に含有させるカチオンとして好適であり、
これらの元素のカチオンを用いてイオン交換する
ことが望しい。この場合のイオン交換技法の例と
しては、上記元素をカチオンとして放出すること
の可能な化合物を水溶液とし、この中に結晶性ケ
イ酸化合物を浸漬する方法などが挙げられる。イ
オン交換の結果、結晶性ケイ酸化合物に含有され
るカチンオンは、単一種である必要はなく、二種
以上であつても良いことは勿論である。
本発明を、以下に示す実施例によつて、更に具
体的に説明する。
実施例 １
水ガラス（SiO236.6重量％含有）41ｇを32ｇの
純水に溶解させる。同時に硫酸ランタン1.36ｇ、
臭化テトラプロピルアンモニウム6.4ｇ、濃硫酸
５mlを純水43ｇに溶解せしめた溶液を調製する。
20重量％のNaCl水溶液80ml中に、前記の両溶液
を滴下させつつ、撹拌を続ける。得られた溶液
を、テフロンシールを施した電磁撹拌式オートク
レーブ中に仕込み、撹拌しつつ、２時間で160℃
まで加熱し、次いで160℃で48時間反応させた。
この時間、撹拌速度は600r.p.mで一定であつた。
得られた反応液をロ過し、約12ｇの白色粉末状結
晶性ランタンシリケーを得た。これを純水で良く
洗浄したのち、80℃、減圧下において一夜乾燥せ
しめ、次いで550℃で６時間焼成した。このもの
の元素含有量を分析した結果、（La2O3）・
（SiO2）112・（Na2O）0.91によつて表わされる組成
を有していることを確認した。
このようにして得られた結晶性ランタンシリケ
ートを、触媒として使用すべく、次の手順に従
い、イオン交換を行つて、Na+を除去し、H+型
とした。イオン交換は、上記結晶性ランタンシリ
ケートを５重量％のNH4Cl水溶液200ml中に浸漬
し、６時間放置した後、上澄液を除去し、再度５
重量％のNH4Cl水溶液200mlを加え、この操作を
５回繰り返すことによつて行つた。このようにし
て得られたプロトン型結晶性ランタンシリケート
を、減圧下、80℃で一夜乾燥させ、550℃で６時
間焼成した。このものの元素分析を行なつた結
果、Naは検出されなかつた。
得られた試料に関するＸ線回折パターンを表−
２に示す。[Table] The crystalline silicate compound of the present invention has an acid content corresponding to the amount of the lanthanide group rare earth element contained, and has an ion exchange ability like a normal aluminosilicate zeolite. It also has extremely high activity and thermal stability as a catalyst.
Effectively acts on conversion reactions of various organic compounds.
In particular, it shows high activity in the reaction of converting methanol to hydrocarbons, and has a lifespan that allows it to be used as a practical catalyst. It also has high activity in reactions that produce isobrene and isopentenyl alcohol from isobutene and formaldehyde, making it useful as an industrial catalyst. The crystalline silicic acid compound of the present invention includes a SiO 2 source,
A mixed solution or suspension of an M 2 O 3 source and an inorganic alkali and/or nitrogen-containing compound in water (hereinafter the mixed solution or suspension is referred to as a reaction solution) is reacted at a temperature of 100 to 250°C. , produced by crystallization. The SiO 2 sources used include silicic acid, alkali metal or alkaline earth metal silicates, water glass, silica hiszosols, silica gels, and organic silicates, especially alkali metal silicates, water glass, and organic silicates. suitable. Examples of alkali metal silicates used include sodium silicate and potassium silicate, and examples of organic silicates include tetraethyl orthosilicate. these
Two or more types of SiO 2 sources may be used in combination. The amount of the SiO 2 source used is usually 1/10 to 1/200, particularly preferably 1/15 to 1/60, of the amount of water that is the medium of the reaction solution. The M 2 O 3 source is not particularly limited as long as it is a water-soluble salt, and examples thereof include chlorides, bromides, acetates, nitrates, sulfates, and oxalates of rare earth elements of the lanthanide group. Of course, two or more of these M 2 O 3 sources may be used in combination.
The amount of the M 2 O 3 source to be used can be appropriately determined based on the SiO 2 source so that the target substance can be synthesized. The inorganic alkali refers to hydroxides of alkali metals or alkaline earth metals, and these may be used alone or in combination of two or more. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferably used, and sodium hydroxide is particularly preferably used. Calcium hydroxide is preferably used as the alkaline earth metal hydroxide. Examples of the nitrogen-containing compound include organic compounds such as alkylammoniums and amines. As the alkylammonium, for example, quaternary ammonium compounds having an alkyl group having 2 to 5 carbon atoms are preferably used.
Examples of quaternary ammonium include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, and tetrapentylammonium. In particular, tetrapropylammonium and tetrabutylammonium are preferably used. Alkylammoniums can be supplied in the form of hydroxides, such as tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc., as well as in the form of appropriate salts, such as tetrapropylammonium bromide, tetrapropylammonium chloride, etc. Can be done. Examples of amines include water-soluble amines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine,
Hexamethylene diamine and the like are preferably used. Furthermore, water-insoluble alkylamines having an alkyl group having 2 to 5 carbon atoms can also be used if they are used with a suitable solvent such as acetone or methyl ethyl ketone. The amount of inorganic alkali and/or nitrogen-containing compound used is SiO 2
It is preferable to use it in a stoichiometric or less amount with respect to the source, and it is particularly preferable to use 0.05 to 0.5 mol per mol of SiO 2 source. Further, since crystallization is promoted by using an inorganic alkali and a nitrogen-containing compound in combination in the synthesis of the crystalline silicate compound of the present invention, it is desirable to combine the two. PH of reaction solution
is not particularly limited, but the reaction is usually carried out at an alkalinity of 8 or higher, preferably 9.5 to 14.
Additionally, mineralizing agents such as inorganic salts of alkali metals or alkaline earth metals, such as sodium chloride, sodium bromide, potassium chloride, and calcium chloride, may be added to the reaction solution. In order to cause crystallization, the reaction solution is
Heating to 100-250℃, preferably 120-200℃,
The temperature is maintained for 0.5 to 30 days, preferably 1 to 10 days. During the crystallization process, it is preferable to stir the reaction solution, thereby allowing the crystallization to proceed more smoothly. After the crystallization reaction is completed, the crystalline silicic acid compound of the present invention is obtained by filtering the reaction solution. The degree of crystallinity of the crystalline silicic acid compound of the present invention is determined by the crystallization rate and reaction time. That is, SiO 2 and M 2 O 3 that are not crystallized at the end of the reaction are mixed as amorphous SiO 2 and amorphous M 2 O 3 when the crystalline silicic acid compound is separated after the reaction, and the present invention decreases the crystallinity of crystalline silicic acid compounds.
The crystalline silicic acid compound of the present invention usually has a crystallinity of 10 to
Obtained as 100% and considering the activity when used as a catalyst, the crystallinity is 40-100%,
Particularly preferred is 70 to 100%. A crystalline silicate compound is obtained by such an operation, but usually the obtained crystalline silicate compound is washed with pure water, dried, and then heated at 300 to 1000°C, preferably 400 to 850°C, for 1 to 30 minutes time, preferably 3~
After calcination for 20 hours, some or all of the alkali cations contained in the crystals are replaced with protons, ie, H + , using commonly known ion exchange techniques. An example of ion exchange is a method of contacting with an aqueous solution of an acid capable of supplying H + , such as HCl, HNO 3 , H 2 SO 4 , or a method of contacting with an aqueous solution of an acid capable of supplying H + , or a method of contacting with an aqueous solution of an acid capable of supplying NH 4 + , such as NH 4 Cl, NH 4 4 There are methods such as treating with NO 3 , NH 4 OOCH 3 , etc., and then firing at 100 to 1000°C. Of course, it is also possible to exchange with cations other than protons, and crystalline silicic acid compounds containing various metal cations can be easily obtained. As mentioned above, ion exchange is possible with any cation, but from the viewpoint of industrial application, hydrogen, alkali metals, alkaline earth metals, group metals, copper, silver, zinc, cadmium, manganese, rhenium , chromium, molybdenum, tungsten, and/or rare earth elements are suitable as cations to be included in the crystalline silicic acid compound of the present invention,
It is desirable to perform ion exchange using cations of these elements. An example of the ion exchange technique in this case is a method in which a compound capable of releasing the above element as a cation is prepared as an aqueous solution, and the crystalline silicate compound is immersed in the aqueous solution. As a result of ion exchange, the cations contained in the crystalline silicic acid compound need not be of a single type, but of course may be two or more types. The present invention will be explained in more detail with reference to the following examples. Example 1 41 g of water glass (containing 36.6% by weight of SiO 2 ) is dissolved in 32 g of pure water. At the same time, 1.36g of lanthanum sulfate,
A solution is prepared by dissolving 6.4 g of tetrapropylammonium bromide and 5 ml of concentrated sulfuric acid in 43 g of pure water.
Both solutions were added dropwise to 80 ml of a 20% by weight NaCl aqueous solution while stirring was continued. The resulting solution was placed in a Teflon-sealed electromagnetic stirring autoclave and heated to 160℃ for 2 hours while stirring.
and then allowed to react at 160°C for 48 hours.
During this time, the stirring speed remained constant at 600 rpm.
The resulting reaction solution was filtered to obtain about 12 g of white powdery crystalline lanthanum silica. After thoroughly washing this with pure water, it was dried at 80°C under reduced pressure overnight, and then calcined at 550°C for 6 hours. As a result of analyzing the elemental content of this material, it was found that (La 2 O 3 )・
It was confirmed that it had a composition represented by (SiO 2 ) 112 ·(Na 2 O) 0.91 . In order to use the thus obtained crystalline lanthanum silicate as a catalyst, ion exchange was performed to remove Na + and convert it into H + form according to the following procedure. For ion exchange, the crystalline lanthanum silicate was immersed in 200 ml of a 5% by weight NH 4 Cl aqueous solution, left for 6 hours, the supernatant liquid was removed, and the crystalline lanthanum silicate was immersed in 5% by weight aqueous NH 4 Cl solution.
This was carried out by adding 200 ml of a wt% aqueous NH 4 Cl solution and repeating this operation five times. The proton type crystalline lanthanum silicate thus obtained was dried under reduced pressure at 80°C overnight and calcined at 550°C for 6 hours. As a result of elemental analysis of this material, no Na was detected. The X-ray diffraction patterns for the obtained samples are shown below.
Shown in 2.
【表】【table】
【表】
表−２中には、最強ピークとのピーク比を％で
示し相対強度とした。本実施例の試料は、結晶中
に含有するカチオンがH+となつているため、格
子面間隔11.13〓に対応するピークが最強ピーク
となつている。固体酸量は0.268meq／ｇ、固体
酸強度の最高値はハメツトの酸度関数値において
−8.2以上であつた。
この結晶性ランタンシリケートを160Kg／cm2の
圧力で加圧成型し、粒度10〜30メツシユの粒子と
した。この粒子1.5ｇを流通式反応管に充填し、
常圧、温度350℃にてメタノールを毎時3.94ｇ供
給した。その結果、表−３に示す如き結果が得ら
れた。[Table] In Table 2, the peak ratio with respect to the strongest peak is expressed as a relative intensity in %. In the sample of this example, since the cation contained in the crystal is H + , the peak corresponding to the lattice spacing of 11.13〓 is the strongest peak. The amount of solid acid was 0.268 meq/g, and the maximum solid acid strength was -8.2 or more in terms of the acidity function value of the hook. This crystalline lanthanum silicate was pressure molded at a pressure of 160 kg/cm 2 to form particles with a particle size of 10 to 30 mesh. Fill 1.5g of these particles into a flow-through reaction tube,
3.94 g of methanol was supplied per hour at normal pressure and temperature of 350°C. As a result, the results shown in Table 3 were obtained.
Claims (1)
る少なくとも一種の金属、Ｏは酸素、ｘは２〜
10000の数）によつて表わされる組成を必須成分
とし、下記表−１に記載したＸ線回折パターンを
有する結晶性ケイ酸化合物。 【表】 【表】 ２ アルカリ金属、アルカリ土類金属、第族の
金属、銅、銀、亜鉛、カドミウム、マンガン、レ
ニウム、クロム、モリブデン、タングステン、稀
土類元素及び水素の群より選ばれた少くとも一種
の元素が、カリオンとして配位している特許請求
の範囲第１項記載の結晶性ケイ酸化合物。[Claims] 1 The following general formula (M 2 O 3 )・(SiO 2 ) x is 2~
10,000) as an essential component, and has an X-ray diffraction pattern shown in Table 1 below. [Table] [Table] 2 A small number selected from the group of alkali metals, alkaline earth metals, group metals, copper, silver, zinc, cadmium, manganese, rhenium, chromium, molybdenum, tungsten, rare earth elements, and hydrogen. 2. The crystalline silicic acid compound according to claim 1, wherein both elements are coordinated as karyons.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56061573A JPS57175722A (en) | 1981-04-23 | 1981-04-23 | Crystalline silicate compound |
| AU82693/82A AU8269382A (en) | 1981-04-23 | 1982-04-16 | Zeolite catalysts, use in organic conversion reactions |
| CA000401448A CA1184739A (en) | 1981-04-23 | 1982-04-22 | Crystalline silicate compounds and process for preparing hydrocarbons or unsaturated alcohols by using said silicate compounds as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56061573A JPS57175722A (en) | 1981-04-23 | 1981-04-23 | Crystalline silicate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57175722A JPS57175722A (en) | 1982-10-28 |
| JPH0310568B2 true JPH0310568B2 (en) | 1991-02-14 |
Family
ID=13174992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56061573A Granted JPS57175722A (en) | 1981-04-23 | 1981-04-23 | Crystalline silicate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57175722A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659127A (en) * | 2012-06-05 | 2012-09-12 | 哈尔滨工业大学 | Method for preparing hydroxyapatite type lanthanum silicate electrolyte powder through low-temperature presintering |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS557598A (en) * | 1978-06-22 | 1980-01-19 | Snam Progetti | Silicon based synthetic substance and method |
| JPS5567521A (en) * | 1978-11-09 | 1980-05-21 | Mobil Oil | Crystalline aluminoosilicateezeolite catalyst* converting organic material by using same* and preparing same catalyst |
-
1981
- 1981-04-23 JP JP56061573A patent/JPS57175722A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS557598A (en) * | 1978-06-22 | 1980-01-19 | Snam Progetti | Silicon based synthetic substance and method |
| JPS5567521A (en) * | 1978-11-09 | 1980-05-21 | Mobil Oil | Crystalline aluminoosilicateezeolite catalyst* converting organic material by using same* and preparing same catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57175722A (en) | 1982-10-28 |
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