EP0466709A1 - Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials - Google Patents
Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materialsInfo
- Publication number
- EP0466709A1 EP0466709A1 EP90904165A EP90904165A EP0466709A1 EP 0466709 A1 EP0466709 A1 EP 0466709A1 EP 90904165 A EP90904165 A EP 90904165A EP 90904165 A EP90904165 A EP 90904165A EP 0466709 A1 EP0466709 A1 EP 0466709A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silicate
- mixture
- layered silicate
- kenyaite
- compound
- 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.)
- Withdrawn
Links
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 title description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 12
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 12
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 7
- -1 tetraalkylammonium compound Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 4
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 3
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 150000004770 chalcogenides Chemical class 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/049—Pillared clays
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
Definitions
- This invention relates to the synthesis of a Kenyaite-type layered crystalline silicate and to pillaring of the resultant product.
- the fundamental unit of crystalline silicate structures is a tetrahedral complex consisting of the Si cation in a tetrahedral coordination with four oxygens.
- the tetrahedra link to form chains which result in fibrous or needlelike morphologies. Single chains result when SiO ⁇ tetrahedra are joined at two oxygen atoms.
- the tetrahedra are linked in layers or sheets as in mica minerals. Similar arrangements of the tetrahedra are found in clay minerals wherein two types of sheets may exist, one consisting of aluminum, iron or magnesium ions in a six-fold coordination with oxygens.
- the layer or sheet structures result from linking between three corners of each tetrahedron to neighboring tetrahedra. Breck, Zeolite Molecular Sieves, John Wiley . Sons, New York, London, Sydney, Toronto, p.
- Kenyaite-type layered crystalline silicates have, until now, been found in natural deposits (H.P. Eugster, ' ⁇ ydrous Sodium Silicate From Lake Magadii, Kenya; Precursors in Bedded Chert", Science, 157, 1177-1180 (1967)) or have been synthesized from inorganic systems (K. Beneke and G. Lagaly, "Kenyaite-Synthesis and Properties", Amer. Mineralogist, 6 , 818-826 (1983), and WO88/00091).
- the present invention provides an improved, economical and reproducible method for preparing synthetic Kenyaite-type layered crystalline silicate exhibiting high crystallinity and purity, catalytic activity and other valuable properties.
- the invention resides in a method for synthesizing a crystalline Kenyaite-type silicate which comprises (i) preparing a mixture capable of forming said silicate, said mixture comprising sources of alkali metal cations (AM), silica, a non-alkali metal (M) of valence n, water and an organic compound (R) selected from an alkylamilne, a trialkylamine, a tetraalkylammonium compoung and trimethylhexamethylene diamine, said alkyl having 1 to 12 carbon atoms, and having a composition, in terms of mole ratios, within the following ranges:
- AM alkali metal cations
- M non-alkali metal
- R organic compound selected from an alkylamilne, a trialkylamine, a tetraalkylammonium compoung and trimethylhexamethylene diamine, said alkyl having 1 to 12 carbon atoms, and having a composition, in terms of mo
- the invention further resides in a method for pillaring the resulting layered silicate.
- the Kenyaite-type silicate prepared by the method of the invention has a characteristic X-ray diffraction pattern including the lines listed in Table 1 below: Table 1
- X-ray diffraction data were collected with a Rigaku diffraction system, equipped with a graphite diffracted beam monochromator and scintillation counter, using copper K-alpha radiation.
- the diffraction data were recorded by step-scanning at 0.02 degrees of two-theta, where theta is the Bragg angle, and a counting time of 1 second for each step.
- the interplanar spacings, d's were calculated in Angstrom units (A), and the relative intensities of the lines, I/I 0 , where I is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine (or second derivative algorithm).
- the intensities are uncorrected for Lorentz and polarization effects.
- crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in topology of the structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, and thermal and/or hydrothermal history.
- Synthesis of a Kenyaite-type layered silicate according to the invention comprises (i) preparing a mixture capable of forming the layered silicate, said mixture comprising sources of alkali metal cations (AM), silica, non-alkali metal (M), water and an organic compound (R), and having a composition, in terms of mole ratios, within the following ranges:
- n is the valence of M, (ii) maintaining said mixture under sufficient conditions until crystals of said silicate are formed, and (iii) recovering said silicate having a highly crystalline Kenyaite-type layered structure.
- the quantity of OH " is calculated only from inorganic sources of alkali without any organic base contribution.
- Metal M may include any one or more of metals from Periodic Table Groups IVB (e.g. titanium), IIIA (e.g. aluminum, gallium, indium and thallium), VIB (e.g. chromium), IVA (e.g. germanium, tin and lead) and VIII (e.g. iron).
- Organic R may include any organic which acts as a mineralizer to promote crystallization from the above reaction mixture. Examples of such organic agents include alkylamine, trialkylamine, tetraalkylammonium compound wherein alkyl has 1 to about 12 carbon atoms, e.g. tetrapropylammoniura, and trimethylhexamethylene diamine.
- Hydrothermal reaction conditions for crystallizing the present product from the above mixture include heating the reaction mixture to a temperature of 60°C to 250°C for a period of time of 6 hours to 60 days.
- a more preferred temperature range is from 100°C to 200°C with the amount of time at a temperature in such range being from 8 hours to 5 days.
- the reaction is carried out until a fully crystalline product is formed.
- the solid product comprising highly crystalline Kenyaite-type layered silicate is recovered from the reaction medium, such as by cooling the whole to room temperature, filtering and water washing.
- the reaction mixture composition for the synthesis of synthetic crystalline silicate hereby can be prepared utilizing materials which can supply the appropriate oxide.
- Such compositions include metal (M) salts or oxides and, when a separate source of aluminum is desired, aluminates or alumina; and silicates, silica hydrosol, silica gel, silicic acid and hydroxides.
- M metal
- silicates silica hydrosol, silica gel, silicic acid and hydroxides.
- each oxide component utilized in the reaction mixture for preparing the present silicate can be supplied by one or more essential reactants and they can be mixed together in any order.
- any oxide can be supplied by an aqueous solution, sodium hydroxide or by an aqueous solution of a suitable silicate.
- the reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time for the product composition comprising the present silicate will vary with the exact nature of the reaction mixture employed.
- Useful sources of silicon for the reaction mixture of the present invention include solid silicas or silica precursors. Such sources are cost effective and allow high solids loading of the reaction mixture.
- a solid silica e.g. Ultrasil (a precipitated, spray dried silica) or HiSil (a precipitated hydrated Si0 2 containing about 6 weight percent free H-,0 and about 4.5 weight percent bound H 2 0 of hydration and having a particle size of about 0.02 micron) as the oxide of silicon source provides economic synthesis.
- Such solid silica sources are commercially available.
- the silica precursor source of silicon for the present reaction mixture is an amorphous silica precipitate made from a solution of a soluble silica source.
- the solution is an aqueous solution of a pH ranging from 9 to 12.
- the source of silica can be any soluble silicate and is preferably sodium silicate.
- the silica precursor is formed by its continuous precipitation from the solution phase. Accordingly, precipitation comprises initiating precipitation and maintaining said precipitation.
- the composition of the solution of soluble silica source is undertaken by introducing a precipitating reagent.
- the precipitating reagent is a source of acid, conveniently a solution of a mineral acid, such as H 2 S0., HC1, and HNO, typically having a pH ranging from essentially 0 to about 6.
- a mineral acid such as H 2 S0., HC1, and HNO
- precipitation of the silica precursor can be effected by acid neutralization of a basic solution of a silicate.
- the silica can be precipitated alone in the absence of sources of other framework elements, e.g. aluminum. In this fashion, both the precipitating reagent and the solution of silica source can be free of intentionally added alumina or alumina source.
- silica precipitation reaction mixture no aluminum is deliberately added to the silica precipitation reaction mixture, in this embodiment; however, aluminum is ubiquitous and the presence of such a material in minor amounts is due to impurities in the precursors of the reactants or impurities extracted from the reaction vessel.
- the amount of alumina in the silica precursor precipitate will be less than about 0.5 weight percent, and generally less than 0.2 weight percent.
- the amount of alumina in the silica precursor precipitate will be up to about 5 weight percent.
- Silicate precipitation can be coprecipitation in the presence of soluble sources of other framework elements including gallium, indium, boron, iron and chromium.
- the soluble source of these other framework components can be, for example, nitrates.
- the coprecipitation product would be amorphous, for example an amorphous gallosilicate, borosilicate or ferrosilicate.
- Continuous precipitation of the amorphous silica precursor may comprise introducing the solution of silica source and the precipitating reagent to a reaction zone while maintaining a molar ratio of silica source to precipitating reagent substantially constant.
- the precipitating reagent and the silica source are introduced simultaneously into the reaction zone.
- the continuous precipitation of silica precursor effects two results. Firstly, silica gel formation is at least substantially eliminated and secondly, precipitated silica precursor particle size exceeds that at which silica gel formation is possible.
- the precipitated silica precursor comprises agglomerated solids in the shape of microspheres. Suspensions of these particles exhibit low viscosities at high solids loading in the subsequent synthesis reaction mixture of the present invention, even at solids loading equal to or greater than about 20-40%.
- the particle size of the precipitated silica precursor ranges between 1-500 microns, but the average size is 50-100 microns.
- the temperature of the precipitation mixture can range from 80°F to 300°F (27°C to 150°C).
- the time of contact of the solution of silica source and the precipitating reagent can range from 10 minutes to several hours at pH maintained from 6 to 11.
- the silica precursor is processed by isolating it, for example by filtration, and removing soluble contaminants therefrom by washing and/or ion exchange. This stage can be considered a solids consolidation step.
- the Kenyaite-type silicate prepared by the present method has a chemical composition in terms of mole ratios of oxides and in the anhydrous state, as-synthesized, as follows:
- the silicate product of the invention is valuable as a catalyst component, e.g., low activity support, for various chemical conversion processes.
- Such process mechanisms include (1) formation or rupture of carbon-carbon bonds, such as cracking, isomerization, polymerization, alkylation and olefin dismutation; (2) formation or rupture of carbon-hydrogen bonds, such as hydrogenation, dehydrogenation, hydrogen transfer and hydrogenolysis; (3) conversion of oxygenates to other oxygenates or hydrocarbons as well as other reactions involving heteroatom-containing organic compounds; (4) oxidation of alkanes, alkenes and aromatic hydrocarbons; and (5) the reactions of unsaturated hydrocarbons with carbon oxides.
- the layered silicate product of the present invention can be modified to increase its interlayer spacing by introducing material between the layers.
- chalcogenide, and preferably oxide, pillars can be intercalated between the layers to provide a thermally stable, highly porous structure useful as a catalyst or a catalyst support.
- the preferred method for producing such a chalcogenide pillared product is described in detail in US Patent No. 4600503 and EP-A-205711.
- the method involves physically separating the layers by introducing an organic cationic species, typically an organoammonium compound and preferably a C*-, or larger alkylammonium cation, at anionic sites between the layers and then introducing between the separated layers of the resultant "propped" species, an electrically neutral compound, such as an alkoxide, capable of conversion, preferably by hydrolysis, to the required chalcogenide pillars.
- an electrically neutral compound such as an alkoxide
- the hydrolyzable, electrically neutral compound is tetraraethylorthosilicate, tetrapropylorthosilicate or, more preferably, tetraethylorthosilicate.
- Example 1-6 Six separate efforts were made to synthesize Kenyaite-type layered silicate directly under hydrotherraal conditions from reaction mixtures containing an organic agent.
- the organic R added to Example 1 was trimethylhexamethylene diamine. Tetrapropylammonium bromide was the organic R added to the reaction mixtures of Examples 2, 5 and 6.
- Tripropylamine was the organic R added to the Example 3 reaction mixture, and n-propylamine was added to the mixture of Example 4.
- the silica source in Example 1 was Q-brand sodium silicate
- reaction mixtures were stirred at 400 rpm for the reaction duration and maintained at 160°C.
- Each example yielded pure 100% crystalline Kenyaite-type layered silicate.
- Figure 1 is a reproduction of an X-ray diffraction scan of as-synthesized product from Example 3.
- the X-ray diffraction pattern of the Example 3 product is set forth in Table 3.
- the synthetic kenyaite-type product hereof is pillared by the following procedure.
- the pH of the solution is kept at 2 for 24 hours with addition of acid as needed.
- the mixture is then filtered, water-washed and vacuum-dried.
- the dry sample is then treated with a dimethylsulfoxide(DMSO)/n-octylamine mixture at the weight ratio of 1:2:1 (sample:DMS0:amine) at ambient temperature for 24 hours.
- the sample is then filtered and dried in air at ambient temperature.
- the sample is finally suspended in tetraethylorthosilicate (TEOS), 5g TEOS/ lg solid, for 24 hours. After this treatment, the sample is filtered, dried and air calcined at 540°F for 3 hours.
- TEOS tetraethylorthosilicate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1990/000406 WO1991012204A1 (en) | 1990-02-06 | 1990-02-06 | Synthesis of kenyaite-type layered silicate material and pillaring of said material |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0466709A1 true EP0466709A1 (de) | 1992-01-22 |
Family
ID=22220636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90904165A Withdrawn EP0466709A1 (de) | 1990-02-06 | 1990-02-06 | Synthese von schichtsilikatmaterial von kenyait-typ und verbrücken des materials |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0466709A1 (de) |
JP (1) | JPH04504557A (de) |
KR (1) | KR920702852A (de) |
WO (1) | WO1991012204A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2011224043B2 (en) * | 2004-12-10 | 2014-04-17 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69225311T2 (de) * | 1991-01-11 | 1998-08-20 | Mobil Oil Corp., Fairfax, Va. | Schichtenförmige oxide sowie geschwollene und saeulenartige formen dieser materialien |
CA2098395A1 (en) * | 1991-01-11 | 1992-07-12 | Charles Theodore Kresge | Method of preparing a pillared layered oxide material |
NL9202277A (nl) * | 1992-12-29 | 1994-07-18 | Pelt & Hooykaas | Werkwijze ter bereiding van een gelaagd, klei-achtig materiaal alsmede een werkwijze voor het immobiliseerbaar maken van afvalmateriaal. |
FR2865725B1 (fr) * | 2004-01-29 | 2006-03-17 | Inst Francais Du Petrole | Methode de synthese de solides lamellaires a partir d'un structurant organique de type amino-alcool |
FR2909905B1 (fr) * | 2006-12-15 | 2009-02-06 | Inst Francais Du Petrole | Procede de preparation de magdiite ou kenyaite a partir d'un structurant orgnanique comp0rtant deux fonctions alcools terminales. |
FR2909991B1 (fr) | 2006-12-15 | 2009-02-06 | Inst Francais Du Petrole | Procede de preparation de magadiite a partir d'un structurant organique de type diammonium quaternaire. |
FR2918049B1 (fr) | 2007-06-28 | 2009-10-16 | Inst Francais Du Petrole | Procede de preparation de magadiite a partir du structurant n,n,n',n',-tetramethyl-n,n'-dibenzylhexanediammonium. |
EP3467052B1 (de) * | 2017-10-06 | 2022-04-13 | Evonik Operations GmbH | Wässrige dispersion enthaltend siliziumdioxid und trimethyl 1,6-hexamethylendiamin |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD220586A1 (de) * | 1984-01-09 | 1985-04-03 | Univ Halle Wittenberg | Verfahren zur herstellung von kenyait |
US4689207A (en) * | 1985-03-06 | 1987-08-25 | Chevron Research Company | Process for the preparation of crystalline microporous organosilicates using magadiite as a silica source |
DE3669490D1 (de) * | 1985-06-13 | 1990-04-19 | Hoechst Ag | Verfahren zur herstellung von kristallinen alkalischichtsilikaten. |
AU587075B2 (en) * | 1985-11-12 | 1989-08-03 | Mobil Oil Corporation | Layered silicates |
-
1990
- 1990-02-06 KR KR1019910700405A patent/KR920702852A/ko not_active Application Discontinuation
- 1990-02-06 EP EP90904165A patent/EP0466709A1/de not_active Withdrawn
- 1990-02-06 JP JP2504320A patent/JPH04504557A/ja active Pending
- 1990-02-06 WO PCT/US1990/000406 patent/WO1991012204A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9112204A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2011224043B2 (en) * | 2004-12-10 | 2014-04-17 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
Also Published As
Publication number | Publication date |
---|---|
JPH04504557A (ja) | 1992-08-13 |
KR920702852A (ko) | 1992-10-28 |
WO1991012204A1 (en) | 1991-08-22 |
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